Effect of Alloying Elements On Steels Rev.B

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Inspector Knowledge Series 04-B
Effect of steel Alloying Elements
材料基础-钢材合金元素图文简易教材
Descriptive approach
Mok Chek Min 莫泽民
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REVISION HISTORY
01 01.10.2008 For Approval Charlie C. CM Mok

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莫泽民 CM MOK cmmok128@yahoo.com
Chapter One:
Theory of Strengthening
The Mechanism of Strengthening.

Elastic and Plastic Deformation.
Slide show on plastic deformation: Mechanical Testing
Understanding Dislocation.
The Nature of Dislocation.
"Atomistic" of edge and screw dislocation motions.
Origins of Strength from Dislocation Dynamics.
Deformation and strengthening Mechanisms.
Crystal Defects.
Point Defects
Linear Defects
Planar Defects.
Bulk Defects.
Pinning Overview.
Methods of Strengthening.
Works or Strain Hardening.
Strain Hardening and Annealing
Dislocation and plastic deformation
Grain Boundary Strengthening.
Effect of Microstructure Refinement on the Strength and Toughness of low alloy
martensitic steel
Effect of microstructure and notches on the fracture toughness of medium CS
The influence of austenite grain size on hot ductility of steel
Dispersion Strengthening.
Mechanical Alloying.
Solid Solution Strengthening.
Precipitation Hardening.
Chapter Two:
Effects of Alloying Elements on Iron Carbon Alloy
Introduction
Contributing factors to strength of steel.
Ways of improving strength of alloy steels.
Steels for special applications EF420 Lecture 7:
Cast Irons EF420 Lecture 9:
Ferrous Alloys EF420 Lecture 12:
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Alloying
Effects of alloying elements.
Relative effects in combinations
Characteristics of alloying element
Summary table.
Effects of alloying elements.
Effects of Alloying Elements on the Microstructures and Mechanical on ductile cast irons
Carbon. Lead Titanium

Manganese. Hydrogen Cobalt
Nickel. Selenium Tellurium
Chromium. Tantalum
Nickel & Chromium Tin
Molybdenum. Calcium
Vanadium Cerium
Tungsten Nitrogen
Silicon Boron
Copper Aluminium
Phosphorous Zirconium
Sulphur Niobium
Chapter Three:
Articles on alloying elements in steel
Carbon contents, steel classification and alloy steels.

Carbon steels
Stainless steels
Strength in steels.
Alloying and its effects on the critical temperature and tensile strength.
Control of HSLA properties.
Influence of alloying elements on steel microstructures
Martensite in austenitic stainless steel welds.
Alloying effects on martensite, pearlite and bainite formation.
Steel alloys
Carbon steels to austenitic steels.
Selection of age-hardenable superalloys.
Metallurgy of Molybdenum in alloy steel and iron.
Maraging steels.
Periodic table and atomic radii.
17-4PH precipitates hardening martensitic stainless steel.
Thermal Processing of Metal
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Thermal Processing of Metals

More reading.
Steel Making. 冶金视频
Additional reading:
Slag inclusion formation during solidification of Steel alloys and in cast iron.
Clean Steels.
Fundamental steps in thermomechanical processing of steels.
Strengthening of Alloy Steel by High Temperature Thermomechanical Treatment.
Ion-nitriding of Maraging steel.
Microstructures and properties of low-alloy fire resistant steel.
Some fundamental steps in thermomechanical processing of steel.
Strengthening of Alloy Steel by High Temperature Thermomechanical Treatment.
High Performance Copper-Precipitation-Hardened Steel.
Schaeffler diagram.
Comprehensive Characterization of Ageing Behavior in M250 Maraging Steel using Multi-NDE
Techniques.
Effect of Aging on Microstructure and Mechanical Property of 1900 MPa Grade Maraging Stainless
Steel.
Effect of aging conditions on Maraging Steels.
The influence of retained austenite on precipitation hardening of maraging steel.
18Ni 马氏体时效钢时效机理的研究.
1900MPa 级超高强度不锈钢的研制.
固溶处理对新型马氏体时效不锈钢力学性能的影响.
两种马氏体时效不锈钢的相变和力学性能.
马氏体时效不锈钢的发展.
马氏体时效不锈钢时效析出相及位向关系的研究.
无钴马氏体时效钢的研究现状.
无钴马氏体时效钢的研究与应用.
新型 CrCoNiMo 系马氏体时效不锈钢的强韧化机理.
预先冷轧变形对马氏体时效钢强化的影响.
Control of High Strength Low Alloy Steel HSLA Properties by alloying
Brittle fracture 0f A105 flanges – EN10204 3.1B and shortfall
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Introduction to Dislocations, Fourth Edition by Derek Hull, D J Bacon

http://www.arab-eng.org/vb/t93373.html
The Science and Engineering of Materials by Donald R. Askeland
http://university.arabsbook.com/forum23/thread24766.html
Greek Alphabets.
1. Α α alpha
2. Β β beta
3. Γ γ gamma
4. Δ δ delta
5. Ε ε epsilon
6. Ζ ζ zeta
7. Η η eta
8. Θ θ theta
9. Ι ι iota
10. Κ κ kappa
11. Λ λ lamda
12. Μ μ mu
13. Ν ν nu
14. Ξ ξ xi
15. Ο ο omicron
16. Π π pi
17. Ρ ρ rho
18. Σ σ ς sigma
19. Τ τ tau
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Chapter One: The Mechanism of strengthening.
Elastic/Plastic Deformation
When a sufficient load is applied to a metal or other structural material, it will cause the material to change
shape. This change in shape is called deformation. A temporary shape change that is self-reversing after the
force is removed, so that the object returns to its original shape, is called elastic deformation. In other words,
elastic deformation is a change in shape of a material at low stress that is recoverable after the stress is
removed. This type of deformation involves stretching of the bonds, but the atoms do not slip past each other.
When the stress is sufficient to permanently deform

the metal, it is called plastic deformation. As
discussed in the section on crystal defects, plastic
deformation involves the breaking of a limited
number of atomic bonds by the movement of
dislocations. Recall that the force needed to break
the bonds of all the atoms in a crystal plane all at
once is very great. However, the movement of
dislocations allows atoms in crystal planes to slip
past one another at a much lower stress levels.
Since the energy required to move is lowest along
the densest planes of atoms, dislocations have a
preferred direction of travel within a grain of the
material. This results in slip that occurs along
parallel planes within the grain. These parallel slip
planes group together to form slip bands, which can
be seen with an optical microscope. A slip band
appears as a single line under the microscope, but it
is in fact made up of closely spaced parallel slip
planes as shown in the image.
Plastic deformation occurs when large numbers of dislocations move and multiply so as to result in
macroscopic deformation. In other words, it is the movement of dislocations in the material which allows for
deformation. If we want to enhance a material's mechanical properties (i.e. increase the yield and tensile
strength), we simply need to introduce a mechanism which prohibits the mobility of these dislocations.
Whatever the mechanism may be, (work hardening, grain size reduction, etc) they all hinder dislocation motion
and render the material stronger than previously.
The stress required to cause dislocation motion is orders of magnitude lower than the theoretical stress
required to shift an entire plane of atoms, so this mode of stress relief is energetically favorable. Hence, the
hardness and strength (both yield and tensile) critically depend on the ease with which dislocations move.
Pinning points, or locations in the crystal that oppose the motion of dislocations, can be introduced into the
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lattice to reduce dislocation mobility, thereby increasing mechanical strength.
Dislocations may be pinned due to stress field interactions with other dislocations and solute particles, or
physical barriers from grain boundaries and second phase precipitates. There are several strengthening
mechanisms for metals, however the key concept to remember about strengthening of metallic materials is that
it is all about preventing dislocation motion and propagation; you are making it energetically unfavorable for the
dislocation to move or propagate. For a material that has been strengthened, by some processing method, the
amount of force required to start irreversible (plastic) deformation is greater than it was for the original material.
In amorphous materials such as polymers, amorphous ceramics (glass), and amorphous metals, the lack of
long range order leads to yielding via mechanisms such as brittle fracture, crazing, and shear band formation.
In these systems, strengthening mechanisms do not involve dislocations, but rather consist of modifications to
the chemical structure and processing of the constituent material.
Unfortunately, strength of materials cannot infinitely increase. Each of the mechanisms elaborated below
involves some trade off by which other material properties are compromised in the process of strengthening.
Steel can be strengthened by several basic mechanisms, the most important of which are:
1. Work hardening or strain hardening.

2. Solid solution strengthening by interstitial atoms.
3. Solid solution strengthening by substitutional atoms.
4. Refinement of grain size.
5. Effects of heat treatment on microstructures.
6. Precipitation strengthening.
7. Grain boundary strengthening.
8. Dispersion strengthening, including lamellar and random dispersed structures.
The most distinctive aspect of strengthening of iron and steel is the role of the interstitial solutes carbon and
nitrogen. These elements also play a vital part in interacting with dislocations, and in combining preferentially
with some of the metallic alloying elements used in steels.
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Plastic Deformation: Mechanical Testing:
http://www.slideshare.net/charliechong/09-castiron-presentation
http://mmd.sdsmt.edu/stress2.swf
http://mmd.sdsmt.edu/
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Understanding dislocations
Introduction to dislocations
http://www.msm.cam.ac.uk/doitpoms/tlplib/dislocations/printall.php
The Nature of Dislocations
Plastid deformation is a measure of material strength, plastic deformation is irreversible. Therefore, the
configuration of the atoms must be changed during plastic deformation, for otherwise they would return to their
original position on unloading. If we consider shearing a single crystal as an example, it can be deformed
plastically by sliding whole layers of atoms against each other as shown in figure above for this sliding to
happen, the bonds between the atoms have to be stretched elastically until they can switch to the next atom.
The stress required for this process can be estimated and is of the order of one fifth of the shear modulus of
the crystal. The yield strength predicted this way for metallic single crystals is thus between 1GPa and 25GPa.
If we measure the strength of single crystals of pure metals, the values found are several orders of magnitudes
below this theoretical value and even lie below that of engineering alloys. Typical values are in the range of a
few mega Pascal. As single crystals always contain lattice defects, one possible explanation could be that
these are responsible for the reduced strength. If, however, the number of defects is reduced further, for
instance by a heat treatment, the yield strength becomes even smaller. Only an absolutely perfect single
crystal without any defects would possess a yield strength agreeing with the theoretical prediction. This can
only be nearly realized in so-called whiskers, which, however, are extremely small. The reason for this
spectacular failure of the theoretical prediction is that plastic deformation does not occur by sliding of complete
layers of atoms. Instead, it proceeds by a mechanism that is based on a special type of lattice defect, the
dislocations. To understand plastic deformation of metals thus requires an understanding of dislocations.
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Dislocation densities
Dislocation is a lattice imperfection in a crystal structure which exerts a profound effect on a structure sensitive
properties such as strength, hardness, ductility and toughness. There are two types, edge and screw or
combination of both, all of which are characterized by a Burgers vector which represents the amount and
direction of slip when the dislocation moves. Click on the web links provided to read further.
Interaction of Dislocations
Transmission Electron Micrograph of Dislocations Transmission Electron Micrograph of Dislocations
More reading:
http://en.wikipedia.org/wiki/Dislocation
http://www-sgrgroup.materials.ox.ac.uk/lectures/microplasticity.html
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"Atomistics" of edge dislocation motion and Asymmetry of screw and edge dislocation motion in Mo
Origins of Strength from Dislocation Dynamics
http://www.scribd.com/doc/7833526/12142005-Workshop
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Deformation and strengthening mechanisms
http://www.scribd.com/doc/7833689/C7
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Crystal Defects
A perfect crystal, with every atom of the same type in the correct position, does not exist. All crystals have
some defects. Defects contribute to the mechanical properties of metals. In fact, using the term “defect” is sort
of a misnomer since these features are commonly intentionally used to manipulate the mechanical properties
of a material. Adding alloying elements to a metal is one way of introducing a crystal defect. Nevertheless, the
term “defect” will be used, just keep in mind that crystalline defects are not always bad. There are basic
classes of crystal defects:
point defects, which are places where an atom is missing or irregularly placed in the lattice structure.
Point defects include lattice vacancies, self-interstitial atoms, substitution impurity atoms, and interstitial
impurity atoms
linear defects, which are groups of atoms in irregular positions. Linear defects are commonly called
dislocations.
planar defects, which are interfaces between homogeneous regions of the material. Planar defects
include grain boundaries, stacking faults and external surfaces.
It is important to note at this point that plastic deformation in a material occurs due to the movement of
dislocations (linear defects). Millions of dislocations result for plastic forming operations such as rolling and
extruding. It is also important to note that any defect in the regular lattice structure disrupts the motion of
dislocation, which makes slip or plastic deformation more difficult. These defects not only include the point and
planer defects mentioned above, and also other dislocations. Dislocation movement produces additional
dislocations, and when dislocations run into each other it often impedes movement of the dislocations. This
drives up the force needed to move the dislocation or, in other words, strengthens the material. Each of the
crystal defects will be discussed in more detail in the following pages.
Point Defects
Point defects are where an atom is missing or is in an irregular place in the lattice structure. Point defects
include self interstitial atoms, interstitial impurity atoms, substitutional atoms and vacancies. A self interstitial
atom is an extra atom that has crowded its way into an interstitial void in the crystal structure. Self interstitial
atoms occur only in low concentrations in metals because they distort and highly stress the tightly packed
lattice structure.
A substitutional impurity atom is an atom of a different type than the bulk atoms, which has replaced one of the
bulk atoms in the lattice. Substitutional impurity atoms are usually close in size (within approximately 15%) to
the bulk atom. An example of substitutional impurity atoms is the zinc atoms in brass. In brass, zinc atoms with
a radius of 0.133 nm have replaced some of the copper atoms, which have a radius of 0.128 nm.
Interstitial impurity atoms are much smaller than the atoms in the bulk matrix. Interstitial impurity atoms fit into
the open space between the bulk atoms of the lattice structure. An example of interstitial impurity atoms is the
carbon atoms that are added to iron to make steel. Carbon atoms, with a radius of 0.071 nm, fit nicely in the
open spaces between the larger (0.124 nm) iron atoms.
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Vacancies are empty spaces where an atom should be, but is missing. They are common, especially at high
temperatures when atoms are frequently and randomly change their positions leaving behind empty lattice
sites. In most cases diffusion (mass transport by atomic motion) can only occur because of vacancies.
Linear Defects - Dislocations
Dislocations are another type of defect in crystals. Dislocations are areas were the atoms are out of position in
the crystal structure. Dislocations are generated and move when a stress is applied. The motion of dislocations
allows slip – plastic deformation to occur.
Before the discovery of the dislocation by Taylor, Orowan and Polyani in 1934, no one could figure out how the
plastic deformation properties of a metal could be greatly changed by solely by forming (without changing the
chemical composition). This became even bigger mystery when in the early 1900’s scientists estimated that
metals undergo plastic deformation at forces much smaller than the theoretical strength of the forces that are
holding the metal atoms together. Many metallurgists remained skeptical of the dislocation theory until the
development of the transmission electron microscope in the late 1950’s. The TEM allowed experimental
evidence to be collected that showed that the strength and ductility of metals are controlled by dislocations.
There are two basic types of dislocations, the edge dislocation and the screw dislocation. Actually, edge and
screw dislocations are just extreme forms of the possible dislocation structures that can occur. Most
dislocations are probably a hybrid of the edge and screw forms but this discussion will be limited to these two
types.
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Edge Dislocations
The edge defect can be easily visualized as an extra half-plane of atoms in a lattice. The dislocation is called a
line defect because the locus of defective points produced in the lattice by the dislocation lie along a line. This
line runs along the top of the extra half-plane. The inter-atomic bonds are significantly distorted only in the
immediate vicinity of the dislocation line.
Understanding the movement of a dislocation is key to understanding why dislocations allow deformation to
occur at much lower stress than in a perfect crystal. Dislocation motion is analogous to movement of a
caterpillar. The caterpillar would have to exert a large force to move its entire body at once. Instead it moves
the rear portion of its body forward a small amount and creates a hump. The hump then moves forward and
eventual moves all of the body forward by a small amount.
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As shown in the set of images above, the dislocation moves similarly moves a small amount at a time. The
dislocation in the top half of the crystal is slipping one plane at a time as it moves to the right from its position in
image (a) to its position in image (b) and finally image (c). In the process of slipping one plane at a time the
dislocation propagates across the crystal. The movement of the dislocation across the plane eventually causes
the top half of the crystal to move with respect to the bottom half. However, only a small fraction of the bonds
are broken at any given time. Movement in this manner requires a much smaller force than breaking all the
bonds across the middle plane simultaneously.
Screw Dislocations
There is a second basic type of dislocation, called screw

dislocation. The screw dislocation is slightly more
difficult to visualize. The motion of a screw dislocation is
also a result of shear stress, but the defect line
movement is perpendicular to direction of the stress and
the atom displacement, rather than parallel. To visualize
a screw dislocation, imagine a block of metal with a
shear stress applied across one end so that the metal
begins to rip. This is shown in the upper right image.
The lower right image shows the plane of atoms just
above the rip. The atoms represented by the blue
circles have not yet moved from their original position.
The atoms represented by the red circles have moved
to their new position in the lattice and have
reestablished metallic bonds. The atoms represented
by the green circles are in the process of moving. It can
be seen that only a portion of the bonds are broke at
any given time. As was the case with the edge
dislocation, movement in this manner requires a much
smaller force than breaking all the bonds across the
middle plane simultaneously.
If the shear force is increased, the atoms will continue to

slip to the right. A row of the green atoms will find there way back into a proper spot in the lattice (and become
red) and a row of the blue atoms will slip out of position (and become green). In this way, the screw dislocation
will move upward in the image, which is perpendicular to direction of the stress. Recall that the edge
dislocation moves parallel to the direction of stress. As shown in the image below, the net plastic deformation
of both edge and screw dislocations are the same, however.
The dislocations move along the densest planes of atoms in a material, because the stress needed to move
the dislocation increases with the spacing between the planes. FCC and BCC metals have many dense planes,
so dislocations move relatively easy and these materials have high ductility. Metals are strengthened by
making it more difficult for dislocations to move. This may involve the introduction of obstacles, such as
interstitial atoms or grain boundaries, to “pin” the dislocations. Also, as a material plastically deforms, more
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dislocations are produced and they will get into each others way and impede movement. This is why strain or
work hardening occurs.
In ionically bonded materials, the ion must move past an area with a repulsive charge in order to get to the next
location of the same charge. Therefore, slip is difficult and the materials are brittle. Likewise, the low density
packing of covalent materials makes them generally more brittle than metals.
Planar Defects
Stacking Faults and Twin Boundaries

A disruption of the long-range stacking sequence can produce two other common types of crystal defects: 1) a
stacking fault and 2) a twin region. A change in the stacking sequence over a few atomic spacing produces a
stacking fault whereas a change over many atomic spacing produces a twin region.
A stacking fault is a one or two layer interruption in the stacking sequence of atom planes. Stacking faults
occur in a number of crystal structures, but it is easiest to see how they occur in close packed structures. For
example, it is know from a previous discussion that face centered cubic (fcc) structures differ from hexagonal
close packed (hcp) structures only in their stacking order. For hcp and fcc structures, the first two layers
arrange themselves identically, and are said to have an AB arrangement. If the third layer is placed so that its
atoms are directly above those of the first (A) layer, the stacking will be ABA. This is the hcp structure, and it
continues ABABABAB. However it is possible for the third layer atoms to arrange themselves so that they are
in line with the first layer to produce an ABC arrangement which is that of the fcc structure. So, if the hcp
structure is going along as ABABAB and suddenly switches to ABABABCABAB, there is a stacking fault
present.
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Alternately, in the fcc arrangement the pattern is ABCABCABC. A stacking fault in an fcc structure would
appear as one of the C planes missing. In other words the pattern would become ABCABCAB_ABCABC.
If a stacking fault does not corrects itself immediately but continues over some number of atomic spacing, it will
produce a second stacking fault that is the twin of the first one. For example if the stacking pattern is
ABABABAB but switches to ABCABCABC for a period of time before switching back to ABABABAB, a pair of
twin stacking faults is produced. The red region in the stacking sequence that goes
ABCABCACBACBABCABC is the twin plane and the twin boundaries are the A planes on each end of the
highlighted region.
Grain Boundaries in Polycrystals

Another type of planer defect is the grain boundary. Up to this point, the discussion has focused on defects of
single crystals. However, solids generally consist of a number of crystallites or grains. Grains can range in size
from nanometers to millimeters across and their orientations are usually rotated with respect to neighboring
grains. Where one grain stops and another begins is know as a grain boundary. Grain boundaries limit the
lengths and motions of dislocations. Therefore, having smaller grains (more grain boundary surface area)
strengthens a material. The size of the grains can be controlled by the cooling rate when the material cast or
heat treated. Generally, rapid cooling produces smaller grains whereas slow cooling result in larger grains. For
more information, refer to the discussion on solidification.
Bulk Defects
Bulk defects occur on a much bigger scale than the rest of

the crystal defects discussed in this section. However, for
the sake of completeness and since they do affect the
movement of dislocations, a few of the more common bulk
defects will be mentioned. Voids are regions where there
are a large number of atoms missing from the lattice. The
image to the right is a void in a piece of metal The image
was acquired using a Scanning Electron Microscope
(SEM). Voids can occur for a number of reasons. When
voids occur due to air bubbles becoming trapped when a
material solidifies, it is commonly called porosity. When a
void occurs due to the shrinkage of a material as it
solidifies, it is called cavitation.
Another type of bulk defect occurs when impurity atoms cluster together to form small regions of a different
phase. The term ‘phase’ refers to that region of space occupied by a physically homogeneous material. These
regions are often called precipitates. Phases and precipitates will be discussed in more detail latter.
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Pinning points - overview.
In a crystalline material, a dislocation is capable of traveling throughout the lattice when relatively small
stresses are applied. This movement of dislocations results in the material plastically deforming. Pinning points
in the material act to halt a dislocation's movement, requiring a greater amount of force to be applied to
overcome the barrier. This results in an overall strengthening of materials.
Types of pinning points
Point defects
Point defects (as well as stationary dislocations, jogs, and kinks) present in a material create stress fields
within a material that disallow traveling dislocations to come into direct contact. Much like two particles of the
same electric charge feel a repulsion to one another when brought together, the dislocation is pushed away
from the already present stress field.
Alloying elements
The introduction of atom1 into a crystal of atom2 creates a pinning point for multiple reasons. An alloying atom
is by nature a point defect, thus it must create a stress field when placed into a foreign crystallographic position,
which could block the passage of a dislocation. However, it is possible that the allowing material is
approximately the same size as the atom that is replaced, and thus its presence would not stress the lattice (as
occurs in cobalt alloyed nickel). The different atom would, though, have a different elastic modulus, which
would create a different terrain for the moving dislocation. A higher modulus would look like an energy barrier,
and a lower like an energy trough – both of which would stop its movement.
Second phase precipitates
The precipitation of a second phase within the lattice of a material creates physical blockades through
which a dislocation cannot pass. The result is that the dislocation must bend (which requires greater
energy, or a greater stress to be applied) around the precipitates, which inevitably leaves residual
dislocation loops encircling the second phase material and shortens the original dislocation. This is a
schematic shows how a dislocation interacts with solid phase precipitates. The dislocation moves from
left to right in each frame.
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Dislocation slip mechanism
Grain boundaries
Dislocations require proper lattice ordering to move through a material. At grain boundaries, there is a lattice
mismatch, and every atom that lies on the boundary is uncoordinated. This stops dislocations that encounter
the boundary from moving.
Dislocations in motion
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Methods of strengthening
Following are brief description s on the methods of strengthening.
Work or Strain hardening
The reason for strain hardening is that the dislocation density increases with plastic deformation (cold work)
due to multiplication. The average distance between dislocations then decreases and dislocations start
blocking the motion of dislocations.
The primary species responsible for work hardening are dislocations. Dislocations interact with each other by
generating stress fields in the material. The interaction between the stress fields of dislocations can impede
dislocation motion by repulsive or attractive interactions. Additionally, if two dislocations cross, dislocation line
entanglement occurs, causing the formation of a jog which opposes dislocation motion. These entanglements
and jogs act as pinning points, which oppose dislocation motion. As both of these processes are more likely to
occur when more dislocations are present, there is a correlation between dislocation density and yield
strength,
Where G is the shear modulus, b is the Burgers vector, and is the dislocation density.
Increasing the dislocation density increases the yield strength which results in a higher shear stress required to
move the dislocations. This process is easily observed while working a material. Theoretically, the strength of a
material with no dislocations will be extremely high (τ=G/2) because plastic deformation would require the
breaking of many bonds simultaneously. However, at moderate dislocation density values of around 107-109
dislocations/m2, the material will exhibit a significantly lower mechanical strength. Analogously, it is easier to
move a rubber rug across a surface by propagating a small ripple through it than by dragging the whole rug. At
dislocation densities of 1014 dislocations/m2 or higher, the strength of the material becomes high once again.
It should be noted that the dislocation density can't be infinitely high because then the material would lose its
crystalline structure.
Work hardening is an important strengthening process in steel, particularly in obtaining high strength levels in
rod and wire, both in plain carbon and alloy steels. For example, the tensile strength of a 0.05% C steel
subjected to 95% reduction in area by wire drawing, is raised by no less than 550 MPa while higher carbon
steels are strengthened by up to twice this amount. Indeed, without the addition of special alloying elements,
plain carbon steels can be raised to strength levels above 1500 MPa simply by the phenomenon of work
hardening.
Basic work on the deformation of iron has largely concentrated on the other end of the strength spectrum,
namely pure single crystals and polycrystals subjected to small controlled deformations. The diversity of slip
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planes leads to rather irregular wavy slip bands in deformed crystals, as the dislocations can readily move from
one type of plane to another by cross slip, provided they share a common slip direction.
The yield stress of iron single crystals are very sensitive to both temperature and strain rate and a similar
dependence has been found for less pure polycrystalline iron. Therefore, the temperature sensitivity cannot be
attributed to interstitial impurities. It is explained by the effect of temperature on the stress needed to move free
dislocations in the crystal, the Peierls-Nabarro stress.
Case Study 1: The effect of cyclic torsion on the dislocation structure of drawn mild steel
1. Introduction
Cold forming of metals usually causes their work hardening. The magnitude of this hardening depends on the
area reduction, on the temperature and strain rate associated with the processing, and on the way the strain is
imposed on the metal. Keeping all other variables constant, the work hardening of a metal submitted to a
sequential straining under varying directions or of different natures is different from that resulting from
monotonic straining. Changes in the way the material is deformed can alter the hardening rates and even
cause strain softening of the metal1-16.
Recent research results17-19 show that cyclic straining influences in various ways the mechanical behavior of
annealed and drawn metal bars. Annealed Aluminum submitted to cyclic torsion displays higher flow stresses
than the annealed material. On the other hand, cyclic torsion softens previously drawn Aluminum. Cyclic
torsion also softens steel bars previously drawn in one or two passes and hardens the initially annealed
material. Experimental results indicate that the stress-strain curve and the work hardening coefficient (n) of
steel drawn in two passes and submitted to cyclic torsion are similar to those for the material submitted to only
one drawing pass. This is similar to the case of the Aluminum alloy 6063, where the cyclic torsion after two
drawing passes eliminates the hardening associated with the second drawing pass. It is also observed for both
materials that their Ultimate Tensile Strength (UTS) tends to remain unaltered by cyclic torsion, in the case of
initially annealed material, whereas their Yield Strength (YS) is considerably increased by cyclic torsion. The
YS and UTS of both previously drawn materials are decreased by cyclic torsion, with the exception of the YS of
Aluminum drawn in a single pass. The decrease in these properties is more pronounced after two drawing
passes than after a single drawing pass. Finally, cyclic torsion increases the Tensile Elongation to Fracture of
drawn material and decreases this property for initially annealed material.
The present research analyzes the relationship between the mechanical effects described above and the
dislocation structures in Low Carbon steel.
2. Materials and Experimental Methods

The material was an AISI 1010 steel with the following chemical composition: 0.12%C, 0.47%Mn, 0.07%Si,
0.003%Sn, 0.01%Mo, 0.016%P e 0.013%S, received as cylindrical bars 6.4 mm in diameter. The bars were
initially annealed and some of them were drawn in one or two passes. A fraction of these bars were then
submitted to cyclic torsion. The effects of the strain path were analyzed by Transmission Electron Microscopy
(TEM).
Annealing was performed under vacuum, at 850 °C for 2400 seconds, leading to an average hardness of
122.6 HV. Drawing was performed in a hydraulic draw bench, using Tungsten Carbide dies with semi-angle of
8?and abundant lubrication with a Molybdenum Disulfide paste. Different dies were employed, guaranteeing a
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fixed reduction of area of 20% in each pass. Cyclic torsion (11.2% plastic strain per cycle, total of 10 cycles)
was performed in an especially adapted lathe, where the chuck was manually actuated. All experiments were
performed at room temperature, at a strain rate of 0.002 / s5. All deformed samples were stored at
temperatures below 0 °C in order to avoid static strain aging effects.
TEM was performed in a JEOL-JEM microscope, operated at 200 kV. Analyses were performed in 3 mm
samples taken from the cross-section of the bars. Sample preparation involved initial mechanical polishing,
followed by electrolytic thinning with a perchloric acid and ethanol solution at room temperature.
3. Results and Discussion

The dislocation structures of the annealed and of the drawn material (in one or two passes) are shown in
Figures 1 and The effect of cyclic torsion on the dislocation structure of drawn mild steel2 respectively. The
dislocation density is quite low for the annealed material, whereas the deformed material displays a much
higher dislocation density. Drawn material shows an aligned cell structure, with irregular cell sizes and cell wall
thickness. Dense dislocation networks can be observed inside the cells. Higher drawing strains lead to a
smaller cell size, as expected.
Figure 1. Figure 2a.
.
Figure 2b. TEM of annealed and drawn steel
(8% and 20% per pass) a: 1 pass b: 2 passes
The dislocation structure of the material submitted only to cyclic torsion is broadly similar to that resulting from
drawing (see Figure 3), but the cell size is higher and the tendency to cell alignment is less pronounced than in
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drawing. It is important to realize that the total strain caused by cyclic torsion is much higher than in drawing,
but leads to essentially similar dislocation structures.
The analysis of Figure 4 indicates that the dislocation structure of the material after one drawing pass is altered
by subsequent cyclic torsion. There is an increase in the cell size, a decrease in their alignment and in the
dislocation density within the cells, and an overall evolution of alignment in only one direction to a
"checkerboard" appearance, which is typical of the development of two sets of aligned cells, corresponding to
the two directions of twisting. This is also the situation for the material initially annealed, drawn in 2 passes and
cyclically twisted (Figure 5). Under these circumstances, the dislocation cells tend to be larger and the
dislocation density inside the cells lower than for one drawing pass followed by cyclic torsion. Cyclic torsion
promotes dynamic recovery of the material, involving the annihilation of cell walls and the decrease of
dislocation density inside the cells. This is similar to results from the analysis of the Bauschinger effect20.
where such dislocation annihilation stems from dislocation movements in opposing directions.
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Considering the widely established relationship between the material flow stress G, and the corresponding
dislocation density r20:
one should expect higher flow stresses in the drawn or cyclic twisted material than in the annealed material.
On the other hand, the recovery promoted by cyclic torsion of the previously drawn material should lead to their
softening and consequent lower flow stresses.
4. Conclusions
Drawing of low carbon steel leads to the formation of an aligned dislocation structure, displaying irregular cell
sizes and cell wall thickness as well as dense networks of dislocations inside the cells.
Cyclic torsion promotes the softening of material previously strained by drawing. This softening is associated
with a restructuring of the previous dislocation arrangement, involving an increase in cell size, a decrease in
the dislocation density inside the cells and a "checkerboard" dislocation wall structure.
Strain Hardening and Annealing Slide Show: Full download
http://www.slideshare.net/charliechong/askeland-phule-notes-ch12-printable-presentation
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Dislocation and Plastic Deformation:
http://www.slideshare.net/charliechong/chapter05-1-presentation
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Grain Boundary Strengthening
In grain boundary strengthening the grain boundaries act as pinning points impeding further dislocation
propagation. Since the lattice structure of adjacent grains differs in orientation, it requires more energy for a
dislocation to change directions and move into the adjacent grain. The grain boundary is also much more
disordered than inside the grain, which also prevents the dislocations from moving in a continuous slip plane.
Impeding this dislocation movement will hinder the onset of plasticity and hence increase the yield strength of
the material.
Grain boundaries act as an impediment to dislocation motion for the following two reasons:
• Dislocation must change its direction of motion due to the differing orientation of grains.
• Discontinuity of slip planes from grain 1 to grain
Under an applied stress, existing dislocations and dislocations generated by Frank-Read Sources will move
through a crystalline lattice until encountering a grain boundary, where the large atomic mismatch between
different grains creates a repulsive stress field to oppose continued dislocation motion. As more dislocations
propagate to this boundary, dislocation 'pile up' occurs as a cluster of dislocations are unable to move past the
boundary. As dislocations generate repulsive stress fields, each successive dislocation will apply a repulsive
force to the dislocation incident with the grain boundary. These repulsive forces act as a driving force to reduce
the energetic barrier for diffusion across the boundary, such that additional pile up causes dislocation diffusion
across the grain boundary, allowing further deformation in the material.
Decreasing grain boundary size decreases the amount of possible pile up at the boundary, increasing the
amount of applied stress necessary to move a dislocation across a grain boundary. The higher the applied
stress to move the dislocation, the higher the yield strength. Thus, there is then an inverse relationship
between grain boundary size and yield strength, as demonstrated by the Hall-Petch equation. A lower number
of dislocations per grain results in a lower dislocation 'pressure' building up at grain boundaries. This makes it
more difficult for dislocations to move into adjacent grains. This relationship can be mathematically described
as follows:
,
Where k is a constant, d is the average grain diameter and σy,0 is the original yield stress.
However, when there is a large direction change in the orientation of the two adjacent grains, the dislocation
may not necessarily move from one grain to the other but instead create a new source of dislocation in the
adjacent grain. The theory remains the same that more grain boundaries create more opposition to dislocation
movement and in turn strengthens the material.
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Figure 1: Hall-Petch Strengthening is limited by the size of dislocations. Once the grain size reaches
about 10 nm, grain boundaries start to slide.
Obviously, there is a limit to this mode of strengthening, as infinitely strong materials do not exist. Grain
boundary sizes can range from about 100 μm (large grains) to 1 μm (small grains). Lower than this, the size of
dislocations begins to approach the size of the grains. At a grain size of about 10 nm, only one or two
dislocations can fit inside of a grain (see Figure 1 above). This scheme prohibits dislocation pile-up and never
results in grain boundary diffusion. The lattice resolves the applied stress by grain boundary sliding, resulting in
a decrease in the material's yield strength; A phenomenon known as grain-boundary sliding.
To understand the mechanism of grain boundary strengthening one must understand the nature of
dislocation-dislocation interactions. Dislocations create a stress field around them given by:
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Where G is the material's shear modulus, and b is the Burgers vector. If the dislocations are in the right
alignment with respect to each other, the local stress fields they create will repel each other. This helps
dislocation movement along grains and across grain boundaries. Hence, the more dislocations are present in a
grain, the greater the stress field felt by a dislocation near a grain boundary:
This is a schematic roughly illustrating the concept of dislocation pile up and how it effects the strength of
the material. A material with larger grain size is able to have more dislocation to pile up leading to a bigger
driving force for dislocations to move from one grain to another. Thus you will have to apply less force to
move a dislocation from a larger than from a smaller grain, leading materials with smaller grains to exhibit
higher yield stress.
In a polycrystalline metal, grain size has a tremendous influence on the mechanical properties. Because grains
usually have varying crystallographic orientations, grain boundaries arise. While an undergoing deformation,
slip motion will take place.
The refinement of the grain size of ferrite provides one of the most important strengthening routes in the heal
treatment of steels. The grain size effect on the yield stress can therefore be explained by assuming that a
dislocation source operates within a crystal causing dislocations to move and eventually to pile up at the grain
boundary. The pile-up causes a stress to be generated in the adjacent grain, which, when it reaches a critical
value, operates a new source in that grain.
In this way, the yielding process is propagated from grain to grain. The grain size determines the distance
dislocations have to move to form grain boundary pile-ups, and thus the number of dislocations involved. With
large grain sizes, the pile-ups will contain larger numbers of dislocations, which will in turn cause higher stress
concentrations in neighboring grains.
In practical terms, the finer the grain size, the higher the resulting yield stress and, as a result, in modern steel
working much attention is paid to the final ferrite grain size. While a coarse grain size of d-1/2 = 2, i.e. d = 0.25
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mm, gives a yield stress in mild steels of around 100 MPa, grain refinement to d-1/2 = 20. i.e. d = 0.0025 mm,
raises the yield stress to over 500 MPa, so that achieving grain sizes in the range 2-10 μm is extremely
worthwhile.
The effect of grain size on yield strength, 　y, is given by the Hall Petch equation for structural steels:
where 　o is the lattice resistance, i.e. friction stress which opposes dislocation motion
k is a constant, sometimes called the dislocation locking term
d is the ferrite grain size
14 µm
More reading:
Effect of Microstructure on Mechanical Properties of High Strength Steel Weld Metals
Effects of Tempering on the Microstructure and Mechanical Properties of Low Carbon, Low Alloy Martensitic Steel
Effect of Microstructural Variation on Weld Metal Cold Cracking of HSLA-100 Steel
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Effect of Microstructure Refinement on the Strength and Toughness of low alloy martensitic
steel
http://www.scribd.com/doc/7824864/Effect-of-Micro-Structure-Refinement-on-the-Strength-and-Toughness-of-
Low-Alloy-Martensitic-Steel
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Effect of microstructure and notches on the fracture toughness of medium carbon steel
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The influence of austenite grain size on hot ductility of steel
http://www.scribd.com/doc/7825091/The-Influence-of-Austenite-Grain-Size-on-Hot-Ductility-of-Steel
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Dispersion Strengthening
(Mechanical Alloying)
Dispersion strengthening is about the interaction between dislocations and finely dispersed particles in the
metal matrix. Traditionally, dispersion particles are obtained as precipitates from phase transformations during
traditional metallurgical processes (melting, solidification, and heat treating). This is the case of many
high-strength commercial alloys. However, maximum service temperatures are limited by the limited thermal
stability of particles or precipitates obtained from thermal processes.
A: Lattice distortion due to the presence of coherent precipitate:

B: Noncohereny precipitates produce no lattice distortion
Particles, which may not be metallurgical compatible with a given metal, can be introduced in a metal matrix by
violently deforming mixtures of different powders. Such technique is called mechanical alloying . An example is
high-energy ball milling. Using this technique, oxides and other highly stable chemical species can be
introduced uniformly into the metal microstructure. A further refinement of this technique allows oxidation and
other chemical reactions to take place during the mixing process, a technique that allegedly promotes the
formation of ultrafine dispersoids as well as allowing control of particle composition and distribution. After
mixing, the powder mixture can then be consolidated and compacted using a number of powder metallurgy
techniques to produce a solid with a very fine grain structure.
Mechanical alloying methods permit the manufacturing of metallic alloys with a number of interesting
properties. Some examples of materials include nanocrystalline and amorphous materials, metastable phases,
and alloys with extended solubility limits. Mechanical alloying was originally developed as a means of raising
the maximum service temperatures of nickel-based superalloys for aircraft gas-turbine applications. As turbine
operating temperatures rose, so too did the demand for materials with increased high-temperature strength
and oxidation resistance. Mechanical alloying avoids many of the problems associated with conventional
melting and solidification processes, and is now used to make a variety of oxide-dispersion-strengthened
(ODS) Fe-Cr, Ni-Cr, and Ni-Cr-gamma superalloys for turbine-engine industrial applications and aluminum
alloys for aircraft structural components. Mechanical alloying may play a key role in the development of future
aerospace systems by enabling the production of even higher performance materials that are difficult or
impossible to make by other methods.
The effectiveness of dispersion strengthening largely depends on (a) mechanical and geometrical
characteristics of the dispersoids, such as hardness, continuity, size, and shape, and (b) their density and
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distribution (dispersion factor) in the metal matrix. By controlling process parameters, such as characteristics
of the raw powder materials, pressing pressures, atmospheres, cycle time, and temperatures, the
microstructure (e.g., grain size, dispersion size, volume fraction, and distribution) can be tailored for specific
performance requirements. New research initiatives in this field include the synthesis of refractory carbide
nanoparticles and assessment of their use as dispersion strengthening agents, as well as alternative methods
to inoculate the metal matrix.
In all steels there is normally more than one phase present, and indeed it is often the case that several phases
can be recognized in the microstructure. The matrix, which is usually ferrite (bcc structure) or austenite (fcc
structure) strengthened by grain size refinement and by solid solution additions, is further strengthened, often
to a considerable degree, by controlling the dispersions of the other phases in the microstructure. The
commonest other phases are carbides formed as a result of the low solubility of carbon in α-iron. In plain
carbon steels this carbide is normally Fe3C (cementite), which can occur, in a wide range of structures from
coarse lamellar form (pearlite), to fine rod or spheroidal precipitates (tempered steels). In alloy steels, the
same range of structures is encountered, except that in many cases iron carbide is replaced by other carbides,
which are thermodynamically more stable. Other dispersed phases which are encountered include nitrides,
intermetallic compounds, and, in cast irons, graphite.
Most dispersions lead to strengthening, but often they can have adverse effects on ductility and toughness. In
fine dispersions (where ideally small spheres are randomly dispersed in a matrix) are well-defined
relationships between the yield stress, or initial flow stress, and the parameters of the dispersion.
These relationships can be applied to simple dispersions sometimes found in steels, particularly after
tempering, when, in plain carbon steels, the structure consists of spheroidal cementite particles in a ferritic
matrix. However, they can provide approximations in less ideal cases, which are the rule in steels, where the
dispersions vary over the range from fine rods and plates to irregular polyhedral. Perhaps the most familiar
structure in steels is that of the eutectoid pearlite, usually a lamellar mixture of ferrite and cementite. This can
be considered as an extreme form of dispersion of one phase in another, and undoubtedly provides a useful
contribution to strengthening.
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General behaviour of the powder particles during mechanical alloying processing
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http://www.scribd.com/doc/7823923/Mechanical-Alloy
Case Study:
Effect of mechanical alloying and Ti addition on solution and ageing treatment of an AA7050 aluminium alloy
http://www.scielo.br/scielo.php?pid=S1516-14392007000200017&script=sci_arttext
Mechanical Alloys & Milling
http://www.scribd.com/doc/3629131/Mechanical-alloying-and-milling-Suryanarayana
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Solid solution strengthening
This is a schematic illustrating how the lattice is strained by the addition of substitutional and interstitial solute.
Notice the strain in the lattice that the solute atoms cause. The interstitial solute could be carbon in iron for
example. The carbon atoms in the interstitial sites of the lattice create a stress field that impedes dislocation
movement.
http://en.wikipedia.org/wiki/Strengthening_mechanisms_of_materials
A grain boundary in a 2D lattice is the interface between two regions of crystalline order. Each region or 'grain'
has a different orientation with respect to some arbitrary axis perpendicular to the plane of the lattice.
Grain boundaries
A vacancy is a point defect that arises when an atom is 'missing' from the ideal crystal structure.
A vacancy
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A solute atom in a crystal structure is an atomic species that is different from the majority of atoms that form the
structure. Solute atoms of similar size to those in the host lattice may substitute for host atoms - these are
known as substitutional solutes. Solute atoms that are much smaller than the host atoms may exist within
normally empty regions (interstices) in the host lattice, where they are called interstitial solutes.
Substitutional and interstitial solutes.

Note that some distortion of the host lattice occurs around the solutes. A dislocation in a 2D close-packed
plane can be described as an extra 'half-row' of atoms in the structure. Dislocations can be characterised by
the Burgers vector which gives information about the orientation and magnitude of the dislocation.
Dislocation
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Metal Crystal Structure Atomic Radius (nm)

Aluminum FCC 0.1431
Cadmium HCP 0.1490
Chromium BCC 0.1249
Cobalt HCP 0.1253
Copper FCC 0.1278
Gold FCC 0.1442
Iron (Alpha) BCC 0.1241
Lead FCC 0.1750
Magnesium HCP 0.1599
Molybdenum BCC 0.1363
Nickel FCC 0.1246
Platinum FCC 0.1387
Silver FCC 0.1445
Tantalum BCC 0.1430
Titanium (Alpha) HCP 0.1445
Tungsten BCC 0.1371
Zinc HCP 0.1332
A nanometer (nm) equals 10-9 meter or 10 Angstrom units.
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Solid solution strengthening by interstitials
The formation of interstitial atmospheres at dislocations requires diffusion of the solute. As both carbon and
nitrogen diffuse much more rapidly in iron than substitutional solutes, it is not surprising that strain ageing can
take place readily in the range from 20°C to 150°C. Consequently the atmosphere condenses to form rows of
interstitial atoms along the cores of the dislocations. These arise because the temperature is high enough to
allow interstitial atoms to diffuse during deformation, and to form atmospheres around dislocations generated
throughout the stress-strain curve. Steels tested under these conditions also show low ductility, due partly to
the high dislocation density and partly to the nucleation of carbide particles on the dislocations where the
carbon concentration is high. The phenomenon is often referred to as blue brittleness, blue being the
interference color of the steel surface when oxidized in this temperature range.
The break away of dislocations from their carbon atmospheres as a cause of the sharp yield point became a
controversial aspect of the theory because it was found that the provision of free dislocations, for example, by
scratching the surface of a specimen, did not eliminate the sharp yield point. An alternative theory was
developed which assumed that, once condensed carbon atmospheres are formed in iron, the dislocations
remain locked, and the yield phenomena arise from the generation and movement of newly formed
dislocations.
To summarize, the occurrence of a sharp yield point depends on the occurrence of a sudden increase in the
number of mobile dislocations. However, the precise mechanism by which this takes place will depend on the
effectiveness of the locking of the pre-existing dislocations. If the pinning is weak, then the yield point can arise
as a result of unpinning. However, if the dislocations are strongly locked, either by interstitial atmospheres or
precipitates, the yield point will result from the rapid generation of new dislocations.
Under conditions of dynamic strain ageing, where atmospheres of carbon atoms form continuously on
newly-generated dislocations, it would be expected that a higher density of dislocations would be needed to
complete the deformation, if it is assumed that most dislocations which attract carbon atmospheres are
permanently locked in position.
Strengthening at high interstitial concentrations
Austenite can take into solid solution up to 10% carbon, which can be retained in solid solution by rapid
quenching. However, in these circumstances the phase transformation takes place, not to ferrite but to a
tetragonal structure referred to as martensite. This phase forms as a result of diffusion less shear
transformation leading to characteristic laths or plates.
If the quench is sufficiently rapid, the martensite is essentially a supersaturated solid solution of carbon in a
tetragonal iron matrix, and as the carbon concentration can be greatly in excess of the equilibrium
concentration in ferrite, the strength is raised very substantially. High carbon martensites are normally very
hard but brittle, the yield strength reaching as much as 1500 MPa; much of this increase can be directly
attributed to increased interstitial solid solution hardening, but there is also a contribution from the high
dislocation density, which is characteristic of martensitic transformations in iron-carbon alloys.
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Substitutional solid solution strengthening of iron
Many metallic elements form solid solutions in γ- and α-iron. These are invariably substitutional solid solutions,
but for a constant atomic concentration of alloying elements there are large variations in strength. Using single
crystal data for several metals, Fig. 1 shows that an element such as vanadium has a weak strengthening
effect on α-iron at low concentrations (< 2%), while silicon and molybdenum are much more effective
strengthened. Other data indicates that phosphorus; manganese, nickel and copper are also effective
strengtheners. However, it should be noted that the relative strengthening might alter with the temperature of
testing, and with the concentrations of interstitial solutes present in the steels.
Figure 1. Solid solution strengthening of iron crystals by substitutional solutes. Ratio of the critical resolved shear stress τ0
to shear modulus μ as a function of atomic concentration.
The strengthening achieved by substitutional solute atoms is, in general, greater the larger the difference in
atomic size of the solute from that of iron, applying the Hume-Rothery size effect. However, from the work of
Fleischer and Takeuchi it is apparent that differences in the elastic behavior of solute and solvent atoms are
also important in determining the overall strengthening achieved.
In practical terms, the contribution to strength from solid solution effects is superimposed on hardening from
other sources, e.g. grain size and dispersions. Also it is a strengthening increment, like that due to grain size,
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which need not adversely affect ductility. In industrial steels, solid solution strengthening is a far from negligible
factor in the overall strength, where it is achieved by a number of familiar alloying elements, e.g. manganese,
silicon, nickel, molybdenum, several of which are frequently present in a particular steel and are additive in
their effect. These alloying elements arc usually added for other reasons, e.g. Si to achieve deoxidation, Mn to
combine with sulphur or Mo to promote hardenability. Therefore, the solid solution hardening contribution can
be viewed as a useful bonus.
Effect of solid solution strengthening
The graph below shows how different alloying additions affect the yield strength of a ferrite + pearlite structural
steel.
Quiz：
1. C and N are interstitial elements rather than substitutional.

2. C and N are much bigger atoms hence introduce more strain energy.
3. C and N have a much smaller atomic mass number therefore for the same weight % addition you are
adding a higher atomic %.
4. Mn and Mo have much lower diffusivities in steel therefore cannot pin the moving dislocations.
1. and 3. - correct, interstitial elements tend to produce a greater strengthening effect because they cause
more strain in the lattice than substitutional elements in steels. The fact that C and N have a smaller atomic
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mass number does mean that for the same weight % addition there are more C or N atoms introduced into the
steel and hence more lattice strain
Iron and Its Interstitial Solid Solutions
DESCRIPTION
Iron, a silvery white solid metal, appears in Group VIII of the periodic table as a transition element. Its atomic
number is 26, and its atomic weight is 55.847. Iron is notable among the elements in the abundance of its ores
and the vast number of useful alloys that can be formulated with iron as the major constituent. Iron is also
biologically important.
In its pure form, iron is rather soft and is malleable and ductile at room temperature. It melts at 1,535 deg C and
boils at 3,000 deg C. Pure iron can exist in two structural types, or allotropic forms. At room temperature the
iron atoms are arranged in a body-centered cubic lattice called the a-form, which is transformed at 910 deg C
into a cubic close-packed structure called the gamma-form. At 1,390 deg C iron returns to a body-centered
cubic structure, called the delta-form.
APPLICATION
Iron is abundant and easily obtainable from its ores. Its desirable mechanical and magnetic properties, as well
as its resistance to corrosion, may be improved by mixing iron with other elements, frequently metals, to form
alloys.
Perhaps the most important alloy of iron is steel, which contains up to approximately 2% carbon. Steels that
contain about 0.25% carbon are called mild steels; those with about 0.45% carbon are medium steels; and
those with 0.60% to 2% carbon are high-carbon steels. Within this range, the greater the carbon content, the
greater the tensile strength of the steel. The hardness of steel may be substantially increased by heating the
metal until it is red hot and then quickly cooling it, a process known as quench hardening. An important
component of many steels is cementite, a carbon-iron compound. Mild steels are ductile and are fabricated
into sheets, wire, or pipe; the harder medium steels are used to make structural steel. High-carbon steels,
which are extremely hard and brittle, are used in tools and cutting instruments.
The addition of other materials in alloys (for example, manganese or silicon) also increases the hardness of
steel. The inclusion of tungsten permits high-speed drills and cutting tools to remain hard even when used at
high temperatures. The inclusion of chromium and nickel improves the corrosion resistance of the steel and,
within certain limits of composition, is called stainless steel. A common stainless steel contains 0.15% carbon,
18% chromium, and 8% nickel and is used in cooking utensils and food-processing equipment. The inclusion
of silicon, ranging from 1 to 5%, results in an alloy that is hard and highly magnetic. An alloy with cobalt is used
for permanent magnets.
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THE SIMULATION
Computer simulations of defect energies were run for both vacancies in BCC and FCC iron as well as free
surface energy for BCC iron.
Parameters for the simulations included the following facts about iron:
FCC: lattice parameter = 3.515Å, cohesive energy = 4.196eV
BCC: lattice parameter = 2.87Å, cohesive energy = 4.28eV
THE RESULTS
Figure 1 : Vacancy in a BCC crystal lattice.

For visualization purposes, the lattice atoms (arbitrarily designated so) are red and connected while the body
centered atoms are yellow. The vacancy is "located" within the inner red cube.
The BCC iron vacancy simulation resulted in a defect energy of 5.988eV.
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Figure 2 : Vacancy in a FCC crystal lattice.
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The above three figures show the simulation of a defect in FCC iron. Figure 2 is included for the benefit of the
reader. It is not "spiffed up," but rather shows the size and complexity of the simulation. The vacancy is the
irregularity toward the center of the figure. For visualization purposes, both Figure 3 (ortho projection) and
Figure 4 (perspective projection) show diagonals of all lattice faces. These are the "nearest neighbor" bonds.
The lattice face that "contains" the vacancy (a "face" atom) is emphasized by the yellow color of its face's
corners.
The FCC iron vacancy simulation resulted in a defect energy of 5.857eV.
The study of steels is important because steels represent by far the most widely used metallic materials,
primarily due to the fact that they can be manufactured relatively cheaply in large quantities to very precise
specifications. They also provide an extensive range of mechanical properties from moderate strength levels
(200-300MPa) with excellent ductility and toughness, to very high strengths (2000 MPa) with adequate ductility.
It is, therefore, not surprising that irons and steels comprise well over 80% by weight of the alloys in general
industrial use.
Steels form perhaps the most complex group of alloys in common use. Therefore, in studying them it is useful
to consider the behavior of pure iron first, then iron-carbon alloys, and finally examine the many complexities
which arise when further alloying additions are made.
Pure iron is not an easy material to produce. However, it has recently been made with a total impurity content
not exceeding 60 ppm (parts per million), of which 10 ppm is accounted for by non-metallic impurities such as
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carbon, oxygen, sulphur, phosphorus, while 50 ppm represents the metallic impurities. Iron of this purity is
extremely weak: the resolved shear stress of a single crystal at room temperature can be as low as 10 MPa,
while the yield stress of a polycrystalline sample at the same temperature can be well below 150 MPa.
The phase transformation: α- and γ- iron
BCC α-iron
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BCC α- iron
FCC γ- iron
Pure iron exists in two crystal forms, one body-centred cubic (bcc) (α-iron, ferrite) which remains stable from
low temperatures up to 910°C (the A3 point), when it transforms to a face-centred cubic (fcc) form (γ-iron,
austenite). The γ-iron on remains stable until 1390°C, the A4 point, when it reverts to bcc form, (now δ-iron)
which remains stable up to the melting point of 1536°C.
The detailed geometry of unit cells of α- and γ-iron crystals is particularly relevant to, for example, the solubility
in the two phases of non-metallic elements such as carbon and nitrogen, the diffusivity of alloying elements at
elevated temperatures, and the general behavior on plastic deformation.
The bcc structure of α-iron is more loosely packed than that of fcc γ-iron. The largest cavities in the bcc
structure are the tetrahedral holes existing between two edge and two central atoms in the structure, which
together form a tetrahedron.
It is interesting that the fcc structure, although more closely-packed, has larger holes than the bcc-structure.
These holes are at the centers of the cube edges, and are surrounded by six atoms in the form of an octagon,
so they are referred to as octahedral holes.
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Location of octahedral holes (left) and tetrahedral holes (right) relative to lattice spheres in face-centered cubic unit cell.
Note: The holes are gray and the lattice spheres are light blue in the unit cells above.
The α↔γ transformation in pure iron occurs very rapidly, so it is impossible to retain the high-temperature fcc
form at room temperature. Rapid quenching can substantially alter the morphology of the resulting α-iron, but it
still retains its bcc structure.
Carbon and nitrogen in solution in α- and γ- iron

The addition of carbon to iron is sufficient to form a steel. However, steel is a generic term which covers a very
large range of complex compositions. The presence of even a small concentration of carbon, e.g. 0.1-0.2
weight per cent (wt%); approximately 0.5-1.0 atomic per cent, has a great strengthening effect on iron, a fact
known to smiths over 2500 years ago since iron heated in a charcoal fire can readily absorb carbon by solid
state diffusion. However, the detailed processes by which the absorption of carbon into iron converts a
relatively soft metal into a very strong and often tough alloy have only recently been fully explored.
The atomic sizes of carbon and nitrogen are sufficiently small relative to that of iron to allow these elements to
enter the α- iron and &gamma- iron lattices as interstitial solute atoms. In contrast, the metallic alloying
elements such as manganese, nickel and chromium have much larger atoms, i.e. nearer in size to those of iron,
and consequently they enter into substitutional solid solution.
However, comparison of the atomic sizes of C and N with the sizes of the available interstices makes it clear
that some lattice distortion must take place when these atoms enter the iron lattice. Indeed, it is found that C
and N in α-iron occupy not the larger tetrahedral holes, but the octahedral interstices which are more favorably
placed for the relief of strain, which occurs by movement of two nearest neighbor iron atoms. In the case of
tetrahedral interstices, four iron atoms are of nearest-neighbor status and the displacement of these would
require more strain energy. Consequently these interstices are not preferred sites for carbon and nitrogen
atoms.
The solubility of both C and N in austenite should be greater than in ferrite, because of the larger interstices
available. It is, therefore, reasonable to expect that during simple heat treatments, excess carbon and nitrogen
will be precipitated. This could happen in heat treatments involving quenching from the γ state, or even after
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treatments entirely within the α field, where the solubility of C varies by nearly three orders of magnitude
between 720°C and 20°C.
Precipitation of carbon and nitrogen from α-iron. α-iron containing about 0.02 wt % C is substantially
supersaturated with carbon if, after being held at 700°C, it is quenched to room temperature. This
supersaturated solid solution is not stable, even at room temperature, because of the ease with which carbon
can diffuse in α-iron. Consequently, in the range 20-300°C, carbon is precipitated as iron carbide. This process
has been followed by measurement of changes in physical properties such as electrical resistivity, internal
friction, and by direct observation or the structural changes in the electron microscope.
The process of ageing is a two-stage one. The first stage takes place at temperatures up to 200°C and
involves the formation or a transitional iron carbide phase (ε) with a close-packed hexagonal structure which is
often difficult to identify, although its morphology and crystallography have been established. It forms as
platelets on {100}α planes, apparently homogenously in the α-iron matrix, but at higher ageing temperatures
(150-200°C) nucleation occurs preferentially on dislocations. The composition is between Fe2.4C and Fe3C.
Ageing at 200°C and above leads to the second stage of ageing in which orthorhombic cementite Fe3C is
formed as platelets on {110}α. Often the platelets grow on several {110} planes from a common centre giving
rise to structures which appear dendritic in character. The transition from ε-iron carbide to cementite is difficult
to study, but it appears to occur by nucleation of cementite at the ε-carbide/α interlaces, followed by re-solution
of the metastable ε-carbide precipitate.
The maximum solubility of nitrogen in ferrite is 0.10 wt %, so a greater volume fraction of nitride precipitate can
be obtained. The process is again two-stage with a be tetragonal α" phase, Fe16N2, as the intermediate
precipitate, forming as discs on {100}α, matrix planes both homogeneously and on dislocations. Above about
200°C, this transitional nitride is replaced by the ordered fcc γ’, Fe4N.
The ageing of α-iron quenched from a high temperature in the α-range is usually referred to as quench ageing,
and there is substantial evidence to show that the process can cause considerable strengthening, even in
relatively pure iron. In commercial low carbon steels, nitrogen is usually combined with aluminium, or present
in too low concentration to make a substantial contribution to quench ageing, with the result that the major
effect is due to carbon. This behavior should be compared with that of strain ageing.
Some practical aspects. The very rapid diffusivity of carbon and nitrogen in iron compared with that of the
metallic alloying elements is exploited in the processes of carburizing and nitriding.
Carburizing can be carried out by heating a low carbon steel in contact with carbon to the austenitic range, e.g.
1000°C, where the carbon solubility, c1, is substantial. The result is a carbon gradient in the steel, from c1 at
the surface in contact with the carbon, to c at a depth.
The diffusion coefficient D of carbon in iron actually varies with carbon content, so the above relationship is not
rigorously obeyed. Carburizing, whether carried out using carbon, or more efficiently using a carburizing gas
(gas carburizing), provides a high carbon surface on a steel, which, after appropriate heat treatment, is strong
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and wear resistant.
Nitriding is normally carried out in an atmosphere of ammonia, but at a lower temperature (500-550°C) than
carburizing, consequently the reaction occurs in the ferrite phase, in which nitrogen has a substantially higher
solubility than carbon.
Nitriding steels usually contain chromium (≈1%), aluminum (≈1%), vanadium or molybdenum (≈0.2%), which
are nitride-forming elements, and which contribute to the very great hardness of the surface layer produced.
http://www.msm.cam.ac.uk/doitpoms/tlplib/dislocations/dislocations_in_2D.php
http://www.ndt-ed.org/EducationResources/CommunityCollege/Materials/Introduction/introduction.htm
http://www.msm.cam.ac.uk/doitpoms/tlplib/solid-solutions/index.php
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Precipitation Hardening
Theory
The primary species of precipitation strengthening are second phase particles. These particles impede the
movement of dislocations throughout the lattice. You can determine whether or not second phase particles will
precipitate into solution from the solidus line on the phase diagram for the particles. Physically, this
strengthening effect can be attributed both to size and modulus effects, and to interfacial or surface energy.
The presence of second phase particles often causes lattice distortions. These lattice distortions result when
the precipitate particles differ in size from the host atoms. Smaller precipitate particles in a host lattice leads to
a tensile stress, whereas larger precipitate particles leads to a compressive stress. Dislocation defects also
create a stress field. Above the dislocation there is a compressive stress and below there is a tensile stress.
Consequently, there is a negative interaction energy between a dislocation and a precipitate that each
respectively cause a compressive and a tensile stress or vice versa. In other words, the dislocation will be
attracted to the precipitate. In addition, there is a positive interaction energy between a dislocation and a
precipitate that have the same type of stress field. This means that the dislocation will be repulsed by the
precipitate.
Precipitate particles also serve by locally changing the stiffness of a material. Dislocations are repulsed by
regions of higher stiffness. Conversely, if the precipitate causes the material to be locally more compliant, then
the dislocation will be attracted to that region.
Furthermore, a dislocation may cut through a precipitate particle. This interaction causes an increase in the
surface area of the particle. The area created is
where, r is the radius of the particle and b is the magnitude of the burgers vector. The resulting increase in
surface energy is
where is the surface energy. The dislocation can also bow around a precipitate particle.
Governing Equations
There are two equations to describe the two mechanisms for precipitation hardening:
Dislocations cutting through particles:
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where τ is material strength, r is the second phase particle radius, γ is the surface energy, b is the magnitude of
the Burgers vector, and L is the spacing between pinning points. This governing equation shows that the
strength is proportional to r, the radius of the precipitate particles. This means that it is easier for dislocations to
cut through a material with smaller second phase particles (small r). As the size of the second phase particles
increases, the particles impede dislocation movement and it becomes increasingly difficult for the particles to
cut through the material. In other words, the strength of a material increases with increasing r.
Dislocations bowing around particle:
where τ is the material strength, G is the shear modulus, b is the magnitude of the Burgers vector, L is the
distance between pinning points, and r is the second phase particle radius. This governing equation shows that
for dislocation bowing the strength is inversely proportional to the second phase particle radius r. Dislocation
bowing is more likely to occur when there are large particles present in the material.
These governing equations show that the precipitation hardening mechanism depends on the size of the
precipitate particles. At small r, cutting will be the dominant strengthening mechanism, while at large r, bowing
will be the dominant strengthening mechanism.
Looking at the plot of both equations, it is clear that there is a critical radius at which max strengthening occurs.
This critical radius is typically 5-30 nm.
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Some precipitation hardening materials
• 2000-series aluminum alloys (important examples: 2024 and 2019)

• 6000-series aluminum alloys
• 7000-series aluminum alloys (important examples: 7075 and 7475)
• 17-4PH stainless steel (UNS S17400)
• Maraging steel
• Inconel 718
• Alloy X-750
• Rene 41
• Waspaloy
Because precipitation strengthening is generally associated with a reduction in toughness, grain refinement is
often used in conjunction with precipitation strengthening to improve toughness.
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In most binary systems, alloying above a concentration given by the phase diagram will cause the formation of
a second phase. A second phase can also be created by mechanical or thermal treatments. The particles that
compose the second phase precipitates act as pinning points in a similar manner to solutes, though the
particles are not necessarily single atoms.
The dislocations in a material can interact with the precipitate atoms in one of two ways (see Figure 2). If the
precipitate atoms are small, the dislocations would cut through them. As a result, new surfaces (b in Figure 2)
of the particle would get exposed to the matrix and the particle/matrix interfacial energy would increase. For
larger precipitate particles, looping or bowing of the dislocations would occur which results in dislocations
getting longer. Hence, at a critical radius of about 5nm, dislocations will preferably cut across the obstacle
while for a radius of 30nm, the dislocations will readily bow or loop to overcome the obstacle.
Most precipitates in steels are relatively large (compared to GP zones in Al-Cu alloys for example) and strong
so dislocations have to travel between them rather than cut through them. This is called Orowan bowing. The
effectiveness of the precipitates in the steel depend on their composition (as this controls their thermodynamic
stability), size, volume fraction and distribution.
Slowly increase the applied force on the dislocation by holding the button down and see how a dislocation
bows around precipitates of different sizes and spacing. Plot a graph of precipitate bowing stress v average
separation.
Control of the precipitate type, size and distribution can be achieved in plate products using controlled
reheating, rolling and cooling schedules and careful alloying additions. The typical alloying additions that are
used to generate precipitate strengthening are Ti, V, Nb and Al. These additions can be made individually but
more commonly are made in combination depending on the requirements of strength, toughness etc. from the
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customer. The reason that these additions are used is that their precipitates (carbides and nitrides) have high
thermodynamic stability at elevated temperatures which means they also give rise to grain refinement during
processing in addition to strengthening at room temperature.
Alloying additions of fine precipitate forming elements can be used to refine the grain size of a steel. A fine
precipitate distribution in a steel will restrict the growth of austenite grains at high temperature and will retard
recrystallisation of deformed austenite grains. If the combination of precipitates and rolling schedule is used
then a 'pancake' structure of deformed austenite grains is created during rolling. These deformed grains
provide many nucleation sites for subsequent ferrite formation resulting in a fine grained ferritic structure in the
final steel product. The choice of alloying elements is important as the precipitates must be stable at the high
temperatures of processing in order to pin the grain boundaries. The typical alloying additions used in High
Strength Low Alloy steels (HSLA) are Nb, Al, Ti and / or V. They can be added in isolation or in combination
with one another.
Using the diagram above which alloying element gives you the most thermodynamically stable precipitate at
1150°C?
Ans: TiN
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An example of how alloying additions made in combination affect the strength (and toughness) is given below
for Al and V additions to a C-Mn ferrite + pearlite steel. The formation of AlN particles causes grain refinement
on heat treatment and some strengthening and the VC particles provided strengthening. Note that the
toughness decreases as the strength increases except for the strengthening effect of grain refinement which is
also beneficial to toughness.
Nb is used as a microalloying addition to control grain size and provide some precipitation strengthening.
V is used to provide precipitation strengthening. The strengthening that is obtained by V precipitates will
depend upon their size but a guideline is that for every 0.1 wt% V addition an increase of 50 - 60 MPa is
seen in strength
Precipitate hardening of stainless steel grades.

http://www.smihq.org/public/publications/past_articles/jan06_zubek.pdf
17-4PH precipitate hardened martensitic stainless steel.
http://www.sandmeyersteel.com/17-4PH.html
History of precipitate hardening.
http://nvl.nist.gov/pub/nistpubs/sp958-lide/014-015.pdf
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Chapter Two: The Effects of Alloying Elements on Iron-Carbon Alloys
Introduction:
Contributing factors to strength of steel.
The main contributions to the strength of steel come from:
Effect of grain size.

Effect of microstructure.
Effect of solid solution strengthening.
Effect of precipitates.
Effect of dislocations.
These factors are controlled by the chemistry of the steel and the processing route used to produce the final
component. All of these aspects need to be taken into account when selecting or designing steel for a given
application.
The processing routes include:
Alloying.
Thermal heat treatment.
Mechanical straining and deformation.
Thermo-mechanical in combination e.g. TMCP steels.
Age hardening.
Mechanical alloying or dispersion hardening.
Normalizing Heat Treatment Effect on Low Alloy Steel Weld Metals
Effect of High Heat input on CTOD Property of the Thick Steel Plate for Offshore Engineering
Heat treatment of Steels
Steel forming and heat treating handbook
热处理网：http://www.rechuliwang.cn/html/rechulichangshi/
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Ways of improving the strength of alloy steels are:
The solid-solution hardening of carbon has a major effect on the strength of martensite, but ductility can only
be obtained at low carbon levels. Although alloying elements affect hardenability, they have a minor effect on
hardness except to reduce it at high carbon levels by causing austenite to be retained.
1. Grain refinement:
which increases strength and ductility. This can be developed by severely curtailing the time after the
cessation of forging at some low temperature of austenite stability or by rapid heating, coupled with a
short austenitising period. Fine grain is produced in 9% Ni steel by tempering fine lath martensite.
2. Precipitation hardening by carbide, nitride or intermetallic compounds:
By secondary hardening, e.g. 12% Cr steel with additions.

Age hardening a low carbon Fe-Ni lath martensite supersaturated with substitutional elements, e.g.
maraging.
Age hardening of austenite, e.g. stainless steels. Phosphorus and titanium are common additions.
Stacking faults are often associated with fine carbide precipitates, and strength can be raised by
increasing the number of stacking faults (i.e. lower fault energy).
Controlled transformation 18/8 austenite steels in which transformation to martensite is induced by
refrigeration or by strain.
3. Thermomechanical treatments
which may be classified into three main groups:
Deformation of austenite prior to the transformation.
Ausforming consists of steel deforming in a metastable austenitic condition between Ac1 and Ms (e.g.
500 癈 called LT) followed by transformation to martensite and light tempering (Fig. 1). This results in
increased dislocation density in the martensite and a finer carbon precipitation on tempering.
Strengths up to 1800 MPa can be obtained without impairing the ductility (~6 % deformation). Steels
must possess a TTT-curve with a large bay of stable austenite, e.g. 826 M40. Typical application is
for leaf springs.
Figure 1. Methods of thermomechanical treatment

Deformation of stable austenite just above Ac3 before cooling (called HT). The properties are
somewhat inferior to those produced by ausforming.
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Deformation induced transformation originally used in Hadfield 13% Mn steel, but can be adapted to
metastable austenitic stainless steels. The fully austenitic steel is severely warm-worked above the
lowest temperature at which martensite is produced during the straining. The distinctive property is
the high rate of straining hardening, which increases ductility.
Deformation of austenite during the transformation

Isoforming is the deformation of a steel (e.g. 1% Cr) during the isothermal transformation to pearlite,
which refines the structure and improves fracture toughness (Fig. 1). A somewhat similar
thermomechanical process can be used in the bainitic region, producing bainite and martensite.
Zerolling consists in forming martensite by deformation at subzero temperatures to strengthen 18/8
austenitic steels. The amount of martensite is influenced by alloy composition and increased with
deformation and lowering of the temperature.
Deformation after the transformation of austenite

Marforming consists of deforming the maraging steel in the soft martensitic condition, generally cold.
There is a pronounced increase in strength of the subsequent maraged product. With other steels,
considerable increases in strength can be obtained by straining martensite (~3 %) either in the
untempered or tempered condition. A strengthening effect also occurs on re-tempering, probably due
to the resolution and reprecipitation of the carbides in a more finely dispersed form.
Strain tempering and dynamic strain ageing. Both processes involve about 5% deformation at the
room temperature between two stages of tempering -- strain tempering -- while in dynamic strain
ageing deformation is concurrent with tempering.
4. Solid solution Hardening:

For ferrite and pearlite steels relationships between yield and tensile strength and various compositional
and microstructural factors have been developed. These are useful in that they show general
characteristics, although they are unable to incorporate all factors that influence strength in modern steels,
for example precipitation strengthening. Examples of these relationships are given below:
YS (MPa) = 53.9 + 32.3 Mn + 83.2 Si + 354 Nf + 17.4 d-1/2

UTS (MPa) = 294 + 27.7 Mn + 83.2 Si + 3.85 pearlite % + 7.7 d-1/2
Alloying addition in wt%, d is the ferrite grain size in mm, Nf is the free nitrogen content
Minimum Minimum Minimum

ASTM Size Range, Proof Tensile Yield
Material
Designation No. Inclusive, in. Strength, Strength, Strength,
kpsi kpsi kpsi
A307 .25-1.5 33 60 36 Low Carbon
A325, Type 1 0.5-1.0, 1.125-1.4 85, 74 120, 105 92, 81 Medium Carbon, Q&T
Low Carbon Martensite,

A325, Type 2 0.5-1.0, 1.125-1.5 85, 75 120, 106 92, 82
Q&T
A325, Type 3 0.5-1.0, 1.125-1.6 85, 76 120, 107 92, 83 Weathering Steel, Q&T
A354, Alloy Steel, Q&T

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Grade BC
A354, Grade BD 0.25-4.0 120 150 130 Alloy Steel, Q&T
0.25-1.0,
A449 1.125-1.5, 85, 74, 55 120, 105, 90 92, 81, 58 Medium Carbon, Q&T
1.75-3.0
A490, Type 1 0.5-1.5 120 Alloy Steel, Q&T
A490, Type 3 Weathering Steel, Q&T
The microstructure of steel has a significant effect on the strength of steel. For steel with a certain
composition the microstructure can be altered through varying the processing route used. For example
for strip steels the coiling temperature can be controlled to give varying microstructures in the final coil
with varying properties.
In this example, different yield strengths can be achieved for a fixed composition by obtaining different
microstructures.
Changing the amount of second phase in a predominantly ferritic microstructure has a pronounced
effect on the strength of the steel. This microstructural change can be achieved through control of
composition and processing as mentioned earlier. For structural steels produced as plate and sections
with a ferrite + pearlite microstructure relatively small changes in the amount of pearlite and ferrite at
low levels (~5-10%) have a relatively small effect on the strength level, especially the yield strength as
the surrounding ferrite yields first anyway.
The presence of dislocation networks produced through work hardening can result in very high levels of
strength, however, it reduces toughness and ductility so is used only for certain steel products. Work
hardening is not used to any extent in plate and section steel products but is used in some strip and
engineering steel products. For example:
Strip products
Some strip grades that do not require a high level of formability but an increased strength level are
supplied with a degree of work hardening. This work hardening is achieved through controlled cold
rolling passes after any annealing process (annealing removes the dislocation structure by recovery or
recrystallisation). The level of work hardening introduced is determined by the strain during the cold roll
passes (i.e. the thickness reduction per pass) and controlled to give the strength levels required. Work
hardening, and hence strengthening, can also occur during fabrication, for example during press
forming, bending, drawing etc.
High carbon steel products

For example steel wire is often supplied in a work hardened condition as the dislocation networks
provide much of the strengthening. High strength steel wire is used in suspension cables, tyre cords,
pre-stressed wire and wires can have yield strength up to 5000 MPa (lower strength values are usually
seen for the applications mentioned). The wire is cold drawn from hot rolled to 90% reduction which
produces a heavily worked structure
Typical 'mild' steels have a small carbon content, usually under 0.2%. Increasing the carbon content
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hardens the steel and its ability to take and hold an edge but at the expense of toughness. Adding other
alloying elements can alter these properties, though usually at the expense of increased cost and
manufacturability. The main alloying elements and their effects are described in next section. Carbon
steels usually contain less than 1 to 2% carbon and small quantities of manganese, copper, silicon,
sulfur, and phosphorus. Alloy steels are carbon steel with other metals added specifically to improve the
properties of the steel significantly. Stainless steel is considered a separate group. Plain carbon steel
is produced with a wide range of mechanical properties with comparatively low cost. To extend the
range of properties of steel, alloys have been developed.
The benefits of alloying resulting include
• The maximum UTS is increased.

• Thick sections steels are available with high hardness throughout the section.
• More controllable quenching with minimum risk of shape distortion or cracking.
• Improved impact resistance at high temperature range.
• Improved corrosion resistance.
• Improved high temperature performance.
The principle elements that are used in producing alloy steel include nickel, chromium, molydenenum,
manganese, silicon and vanadium. Cobalt, copper and lead are also used as alloying elements.
Steels for special applications EF420 Lecture 7:
http://static.slideshare.net/swf/ssplayer2.swf?doc=07steelap-1226154886327710-9&stripped_title=07steelap-presentation
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Cast Irons EF420 Lecture 9:
http://static.slideshare.net/swf/ssplayer2.swf?doc=09castiron-1226155296468434-9&stripped_title=09-castiron-presentation
Ferrous Alloys EF420 Lecture 12:
http://www.slideshare.net/charliechong/askeland-phule-notes-ch12-printable-presentation
Effects of thermomechanical treatment on microstructure and mechanical properties of T91 steel
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Alloying:
Effect of alloying elements
Elements may encourage formation of graphite from the carbide. Only a small proportion of these
elements can be added to the steel before graphite forms destroying the properties of the steel, unless
elements are added to counteract the effect. Elements which encourage the formation of graphite include
silicon, cobalt, aluminium and nickel.
Alloying elements may go into solid solution in the iron, enhancing the strength. Elements which go into
solid solution include silicon, molybdenum, chromium, nickel and magnesium.
Hard carbides (cementite) associated with iron and carbon may be formed with alloying elements.
Elements which tend to form carbides include chromium, tungsten, titanium, columbium, vanadium,
molybdenum and manganese.
Elements which stabilize austenite include manganese, nickel, cobalt and copper. These increase the
range over which austenite is stable e.g. by lowering the eutectoid temperature, and this retards the
separation or carbides.
Elements which tend to stabilize ferrite include chromium, tungsten, molybdenum, vanadium and
silicon. They reduce the amount of carbon soluble in the austenite and thus increase the volume of free
carbide in the steel at a given carbon content. The effectively reduce the austenite ( γ ) phase by raising
the eutectoid temperature and lowering the peritectic temperature. Intermediate compounds with iron may
be formed e.g. FeCr. Alloying elements may adjust the characteristics such as eutectoid content,
quenching rate which produces bainite or martensite.
Relative effect of alloying elements
The combined effect of alloying elements results from many complex interactions resulting from the processing
history, the number and quantities of constituents, the heat treatments, the section shape etc. Some basic
rules can be identified.
Nickel has reduced carbide forming tendency than iron and dissolves in α ferrite.
Silicon combines with oxygen to form nonmetallic inclusions or dissolves in the ferrite.
Most of the manganese in alloy steels dissolves in the α ferrite. Any manganese that form carbides result
in (Fe,Mn)3C.
Chromium spreads between the ferrite and carbide phases the spread depending on the amount of
carbon and other carbide generating elements present.
Tungsten and molybdenum form carbides if sufficient carbon is present which has not already formed
carbides with other stronger carbide forming elements.
Vanadium, titanium, and Colombian are strong carbide forming elements and are present in steel as
carbides.
Aluminium combines with oxygen and nitrogen to form Al2O an AlN
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Characteristics of alloying
Alloying Additions to Steel
Steels are among the most commonly used alloys. The complexity of steel alloys is fairly significant. Not all
effects of the varying elements are included. The following text gives an overview of some of the effects of
various alloying elements. Additional research should be performed prior to making any design or engineering
conclusions.
Elements
Element Influence Uses
Hardness - Strength - Wear

Most important alloying element. Is essential to
the formation of cementite and other carbides, Added to construction steels to
Carbon bainite and iron-carbon martensite. Within limits increase strength, hardness and
increasing the carbon content increases the hardenability.
strength and hardness of a steel while reducing its
toughness and ductility.
Aluminum Deoxidation - Ease of Nitriding
Boron Hardenability
Copper Corrosion Resistance - Strength
Lead Machinability
Phosphorus Strength
Silicon
Tellurium Machinabilty
Toughness - Strength - Hardenability Used up to help refine grain size. Used

Stabilises gamma phase by raising A4 and in large amounts in stainless and
lowering A3. Refines grains in steels and some heat-resisting steels.
non-ferrous alloys. Strengthens ferrite by solid Nickel based alloys can offer corrosion
Nickel
solution. Unfortunatly is a powerful graphitiser. resistance in more aggressive
Can take into solid solution larger proportions of environments and nickel is used as the
important elements such as chromium, basis of complex superalloys for high
molybdenum and tungsten than can iron. temperature service.
Strength - Hardenability - More Response To Heat

Treatment High manganese (Hadfield) steel
Manganese Deoxidises the melt. Greatly increases the contains 12.5% Mn and is austenitic
hadenability of steels. Stabilises gamma phase. but hardens on abrasion.
Forms stable carbides.
Elements Page 65 of 180

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Elements Carbide former.

Hardenability De-oxidizes melt. Helps casting Up to 0.3% in steels for sand casting,
Silicon
fluidity. Improves oxidation resistance at higher up to 1% in heat resisting steels.
temperatures.
Corrosion Resistance - Strength

Stabilises alpha phase by raising A3 and Small amounts in constructional and
depressing A4. Forms hard stable carbides. tool steels. About 1.5% in ball and
Chromium
Strengthens ferrite by solid solution. In amounts roller bearings. Larger amounts in
above 13% it imparts stainless properties. Stainless and heat-resisting steels.
Unfortunately increases grain growth.
High Temperature Strength - Hardenability

Strong carbide-stabilising influence. Raises high
temperature creep strength of some alloys. Slows
tempering response. Reduces 'temper brittleness' in
When added to stainless steels it greatly improves nickel-chromium steels. Increases
Molybdenum the pitting and crevice corrosion resistance. There red-hardness of tool steels. Now used
are limits to the proportion that can be taken into to replace some tungsten in
an iron based matrix. However up to almost 30% high-speed steels.
can be incorporated into nickel based alloys which
provides excellent corrosion resistance in many
aqueous environments.
Fine Grain - Toughness

Used to retain high temperature
Strong carbide forming tendency. Stabilises
hardness, e.g. in dies for hot-forging
Vanadium martensite and increases hardenability. Restrains
and die casting dies. Increasingly used
grain growth. Improves resistance to softening at
in high speed steels.
elevated temperatures after hardening.
Used in high-speed steels and other

tool and die steels, particularly those
for use at high temperatures.
Stabilises alpha phase and forms stable, very Used in a few stainless steels, in
hard carbides, which improves creep resistance combination with molybdenum. to
Tungsten
and renders transformations very sluggish, hence improve pitting and crevice corrosion
hardened steels resist tempering influences. resistance. It is also used in some high
temperature nickel based alloys and in
some high temperature austenitic
stainless steels.
Hardness - Wear
Has similar corrosion resistance to that of Nickel,
but higher cost means that it is not normally used Used in super high speed steels and
Cobalt for such applications. maraging steels, permanent magnet
Provides matrix - strengthening characteristics to steels and alloys.
stainless and nickel based alloys designed for
high temperature applications.
Elements Page 66 of 180

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Slows the transformation of martensite, hence

increases 'red hardness' which is useful in tool
steels.
Elimination Of Carbide Precipitation

In low alloy steels it acts as a carbide former and
improves creep resistance.
Niobium Used to stabilize stainless steels.
In stainless steels it combines with carbon,
stabilising the steel and reducing the susceptibility
to intergranular corrosion
Elimination Of Carbide Precipitation Used in stabilized stainless steels.

Titanium In stainless steels combines with excess carbon In nickel based alloys it is used with
reducing the risk of intergranular corrosion. aluminium to promote age hardening.
Effect of alloying elements. http://www.scribd.com/doc/7833439/Effects-of-Alloying-Elements
Page 67 of 179
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Page 68 of 180
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Effects of Alloying Elements on the Microstructures and Mechanical on ductile cast irons
http://documents.scribd.com/ScribdViewer.swf?
document_id=7824928&access_key=key-23dv4zbmwge9219ahi5x&page=1&version=1&viewMode=
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Carbon Elements
Carbon has a major effect on steel properties. Carbon is the primary hardening element in steel. Hardness
and tensile strength increases as carbon content increases up to about 0.85% C as shown in the figure
above. Ductility and weldability decrease with increasing carbon.
Carbon is essential in steels which have to be hardened by quenching and for example, in austenitic
manganese steel which is required to have high resistance to wear. The maximum hardness obtainable in any
carbon steel is a function of the carbon content which may vary up to about 2% according to the purpose for
which the steel is to be used. It occurs in varying forms according to the percentage present, and the heat
treatment to which the steel has been submitted. (See allotropy and transformation range). Cast irons usually
contain from about 1.8% to 4.5% carbon, present either as free carbon (graphite) and/or combined carbon
(cementite), the varying distribution of the carbon between these two forms considerably influencing the
strength and hardness.
Carbon is a strong austenite former and strongly promotes an austenitic structure. It also substantially
increases the mechanical strength. Carbon reduces the resistance to intergranular corrosion. In ferritic
stainless steels carbon will strongly reduce both toughness and corrosion resistance. In the martensitic and
martensitic-austenitic steels carbon increases hardness and strength. In the martensitic steels an increase in
hardness and strength is generally accompanied by a decrease in toughness and in this way carbon reduces
the toughness of these steels.
Carbon: Present in all steels, it is the most important hardening element. Also increases the strength of the
steel. We usually want knife-grade steel to have >.5% carbon, which makes it "high-carbon" steel.
it has by far the greatest influence of any of the elements. Steel could not exist without carbon. Martensite,
along with banite gives steel a microstructure of hard, tough carbide. None of the other elements so
dramatically alter the strength and hardness as do small changes in carbon content. Carbon
iron crystalline structures have the widest number and variety known to exist in metallurgy. They also
combine with other elements to furnish steel with an assortment of iron alloy carbide systems.
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Manganese Elements
Manganese fulfils a variety of functions in steel.
It is used as a deoxidizing agent in nearly all steels.

It forms manganese sulphide inclusions which in the ingot are spherical. In the absence of
manganese sulphur forms interdendritic films of iron sulphide causing brittleness at forging
temperature (hot shortness).
It effectively increases harden ability and up to 1.5% is added for this purpose. (d) In larger amounts
it is used to stabilize austenite, as in 14% manganese steel.
MANGANESE (Mn): Is normally present in all steel and functions as a deoxidizer. It also imparts strength
and responsiveness to heat treatment. It is usually present in quantities of 0.5 to 2.0 percent. Range 0.3% to
1.5% always present in steels to reduce the negative effects of impurities carried out forward from the
production process e.g. sulphur embrittlement. It promotes the formation of stable carbides in
quenched-hardened steels. Alloys containing manganese are pearlitic. Up to 1% acts as hardening agent and
from 1% to 2% improves strength and toughness. Alloys containing more than 5% are non-magnetic. Alloys
containing large proportions of up to 12.5% manganese have the property that they spontaneously form hard
skins when subject to abrasion. (Self-hardening)
All commercial steels contain 0.3-0.8% manganese, to reduce oxides and to counteract the harmful influence
of iron sulfide. Any manganese in excess of these requirements partially dissolves in the iron and partly forms
Mn3C which occurs with the Fe3C. There is a tendency nowadays to increase the manganese content and
reduce the carbon content in order to get steel with an equal tensile strength but improved ductility
If the manganese is increased above 1,8% the steel tends to become air hardened, with resultant impairing of
the ductility. Up to this quantity, manganese has a beneficial effect on the mechanical properties of oil
hardened and tempered 0.4% carbon steel. The manganese content is also increased in certain alloy steels,
with a reduction or elimination of expensive nickel, in order to reduce costs. Steels with 0.3-0.4% carbon,
1,3-1,6% manganese and 0.3% molybdenum have replaced 3% nickel steel for some purposes.
Non-shrinking tool steel contains up to 2% manganese, with 0.8-0.9% carbon. Steels with 5 to 12%
manganese are martensitic after slow cooling and have little commercial importance.
Hadfield`s manganese steel a specially steel which is austenitic and usually contains approximately 12%
Manganese. It is used in mining, earth- moving equipment and in railroad track work. . Hadfield`s manganese
steel contains 12 to 14% of manganese and 1,0% of carbon. It is characterized by a great resistance to wear
and is therefore used for railway points, rock drills and stone crushers. Austenite is completely retained by
quenching the steel from 1000°C, in which soft condition it is used, but abrasion raises the hardness of the
surface layer from 200 to 600 VPN (with no magnetic change), while the underlying material remains rough.
Annealing embrittles the steel by the formation of carbides at the grain boundaries. Nickel is added to
electrodes for welding manganese steel and 2% Mo sometimes added, with a prior carbide dispersion
treatment at 600°C, to minimize initial distortion and spreading.
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http://www.arema.org/eseries/scriptcontent/custom/e_arema/library/2005_Conference_Proceeding
s/00040.pdf
Manganese is generally beneficial to surface quality especially in resulfurized steels. Manganese contributes
to strength and hardness, but less than carbon. The increase in strength is dependent upon the carbon
content. Increasing the manganese content decreases ductility and weldability, but less than carbon.
Manganese has a significant effect on the hardenability of steel.
Manganese aids the grain structure, and contributes to hardenability, strength & wear resistance. Improves the
steel (e.g. deoxidizes) during the steel's manufacturing (hot working and rolling). Present in most cutlery steel
except for A-2, L-6 and CPM 420V. Manganese slightly increases the strength of ferrite, and also increases the
hardness penetration of steel in the quench by decreasing the critical quenching speed. This also makes the
steel more stable in the quench. Steels with manganese can be quenched in oil rather than water, and
therefore are less susceptible to cracking because of a reduction in the shock of quenching. Manganese is
present in most commercially made steels.
Manganese is generally used in stainless steels in order to improve hot ductility. Its effect on the
ferrite/austenite balance varies with temperature: at low temperature manganese is a austenite stabiliser but at
high temperatures it will stabilize ferrite. Manganese increases the solubility of nitrogen and is used to obtain
high nitrogen contents in austenitic steels.
Figure 1: Non-metallic inclusion in steel: oxides-dark gray and sulfides-light gray
Manganese is generally used in stainless steels in order to improve hot ductility. Its effect on the
ferrite/austenite balance varies with temperature: at low temperature manganese is a austenite stabiliser but at
high temperatures it will stabilise ferrite. Manganese increases the solubility of nitrogen and is used to obtain
high nitrogen contents in austenitic steels.
In general Manganese increases strength and hardness; forms carbide; increases hardenability; lowers the
transformation temperature range. When in sufficient quantity produces austenitic steel; always present in a
steel to some extent because it is used as a deoxidizer
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Figure 2: Typical duplex oxide–sulfide inclusion (particle A, B and C) and plate-like MnS (particle D) in conventional
continuous casting silicon steel.
SEM of an inclusion.
Effect of Mn and Ni on the Variation of the Microstructure and Mechanical Properties of Low-carbon Weld Metals
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Nickel Elements
Increase Strength.
Improve Toughness.
Unable to increase Hardness
Ferrite Former.
NICKEL (Ni): Increases strength and toughness but is ineffective in increasing hardness. It is generally
added in amounts ranging from 1 percent to 4 percent. In some stainless steels it is sometimes as high as 20
percent. It is used for strength, corrosion resistance, and toughness, nickel increases the strength of ferrite,
therefore increasing the strength of the steel. It is used in low alloy steels to increase toughness and
hardenability. Nickel also tends to help reduce distortion and cracking during the quenching phase of heat
treatment.
Nickel is a ferrite strengthener. Nickel does not form carbides in steel. It remains in solution in
ferrite, strengthening and toughening the ferrite phase. Nickel increases the hardenability and impact strength
of steels. Range 0.2% to 5% Improves strength, toughness, and hardenability without seriously affecting the
ductility. It encourages grain refinement. Nickel and chromium together have opposing properties and are
used together to advantage in nickel-chrome steels. The resulting steels have their advantages combined
and their undesirable features cancel each other At 5% nickel provides high fatigue resistance. When alloyed
at higher proportions significant corrosion resistance results and at 27% a non magnetic stainless steel results.
The addition of nickel, in amounts up to 8% or 10 %, to low carbon steel, increases the tensile strength and
considerably raises the impact resistance. 9% nickel steels are useful at very low temperatures. In
engineering steels it is widely used, often with chromium and molybdenum. High nickel increases resistance
to corrosion, and in combination with chromium, is used in the austenitic corrosion-resisting steels. Certain
iron-nickel alloys have unique properties. 25% nickel steel is practically non-magnetic. Alloys with about 36%
nickel have very low coefficients of expansion, whilst with 50% to 78.5% nickel; alloys are obtained having
very high magnetic permeability in low fields. An alloy containing 29% nickel, 17% cobalt is used for sealing
with certain borosilicate glasses.
For stainless steel, the main reason for the nickel addition is to promote an austenitic structure. Nickel
generally increases ductility and toughness. It also reduces the corrosion rate and is thus advantageous in acid
environments. In precipitation hardening steels nickel is also used to form the intermetallic compounds that are
used to increase the strength.
Nickel and manganese are very similar in behavior and both lower the eutectoid temperature. This change
point on heating is lowered progressively with increase of nickel (approximately 10°C for 1% of nickel), but the
lowering of the change on cooling is greater and irregular. The temperature of this change (Ar1) is plotted for
different nickel contents for 0.2% carbon steels in Fig. 1, It will be seen that the curve takes a sudden plunge
round about 8% nickel. A steel with 12% nickel begins to transform below 300°C on cooling, but on reheating
the reverse change does not occur until about 650°C. Such steels are said to exhibit pronounced lag or
hysteresis and are called irreversible steels. This characteristic is made use of in maraging steels and 9% Ni
cryogenic steel.
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It Increases strength and toughness but is ineffective in increasing hardness. It is generally added in amounts
ranging from 1 percent to 4 percent. In some stainless steels it is sometimes as high as 20 percent.
Maraging steels are a class of high-strength steel with low carbon content and the use of
substitutional (as opposed to interstitial) elements to produce hardening from formation of nickel
martensites. The name maraging has resulted from the combination of
Martensite + Age hardening
Maraging steels contain 18% nickel, along with a amounts of molybdenum, cobalt, and titanium
and aluminium, and almost no carbon. These alloys can be strengthened significantly by a
precipitation reaction at a relatively low temperature. They can be formed and machined in the
solution-annealed condition but not without difficulty. Weldability is excellent. Fracture
toughness of the maraging steels is considerably higher than that of the conventional
high-strength steels. Maraging steels are hardened by a metallurgical reaction that does not
involve carbon. Maraging steels are strengthened by intermetallic compounds such as Ni 3Ti
and Ni 3Mo which precipitate at about 500°C. The carbon content provides no real benefit and is
kept low as possible in order to minimize the formation of titanium carbide which can adversely
affect mechanical properties. Toughness is superior to all low alloy carbon steels of similar
strength, particularly the low temperature toughness. These steels are easy to machine and
heat treat, so some cost savings result in component production to compensate for the high cost
of the steel. A high strength maraging steel (extrusion section MIL-S-46850 grade 300) can have
a 0.2% proof stress of 1930MPa and Ultimate Tensile strength of 2068 MPa with an elongation
of 4%
The addition of nickel acts similarly to increasing the rate of cooling of a carbon steel. Thus with a constant rate
of cooling the 5 to 8% nickel steels become troostitic; at 8 to 10% nickel, where the sudden drop appears, the
structure is martensitic, while above 24% nickel the critical point is depressed below room temperature and
austenite remains. The lines of demarcation are not so sharp as indicated by Fig. 1, but a gradual transition
occurs from one constituent to another.
Nickel
Strengthens steel; lowers its transformation temperature range; increases hardenability, and improves
resistance to fatigue. Strong graphite forming tendency; stabilizes austenite when in sufficient quantity.
Creates fine grains and gives good toughness.
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Figure1. Effect of nickel on change points and mechanical properties of 0.2% carbon steels cooled at a constant rate.
The mechanical properties change accordingly as shown in the lower part of Fig. 1. Steels with 0.5% nickel are
similar to carbon steel, but are stronger, on account of the finer pearlite formed and the presence of nickel in
solution in the ferrite. When 10% nickel is exceeded the steels have a high tensile strength, great hardness,
but are brittle, as shown by the Izod and elongation curves. When the nickel is sufficient to produce austenite
the steels become non-magnetic, ductile, tough and workable, with a drop in strength and elastic limit.
Carbon intensives the action of nickel and the change points shown in Fig. 1 will vary according to the carbon
content. The influences of carbon and nickel on the structure are shown in the small inset (Guillet) diagram in
Fig. 1, for one rate of cooling. Steels containing 2 to 5% nickel and about 0.1% carbon are used for case
hardening; those containing 0.25 to 0.40% carbons are used for crankshafts, axles and connecting rods.
The superior properties of low nickel steels are best brought out by quenching and tempering (550-650°C).
Since the Ac3 point is lowered, a lower hardening temperature than for carbon steels is permissible and also a
wider range of hardening temperatures above Ac3 without excessive grain growth, which is hindered by the
slow rate of diffusion of the nickel. Martensitic nickel steels are not utilized and the austenitic alloys cannot
compete with similar manganese steels owing to the higher cost. Maraging steels have fulfilled a high tensile
requirement in aero and space fields. High nickel alloys are used for special purposes, owing to the marked
influence of nickel on the coefficient of expansion of the metal. With 36% nickel, 0.2% carbon, 0.5%
Page 76 of 180
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manganese, the coefficient is practically zero between 0°C and 100°C. This alloy ages with time, but this can
be minimized by heating at 100°C for several days.
The alloy is called Inver and it is used extensively in clocks, tapes and wire measures, differential expansion
regulators, and in aluminum pistons with a split skirt in order to give an expansion approximating to that of cast
iron. A carbon-free alloy containing 78.5% nickel and 21.5% iron has a high permeability in small magnetic
fields.
Figure 6: Vertical section of Fe-Cr-C diagram for 0.1C wt%.
Figure 7: Schaeffler diagram for weld metals.
Fun reading on Nickel based superalloy:http://www.msm.cam.ac.uk/phase-trans/2003/Superalloys/superalloys.html
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Chromium Elements
Chromium is commonly added to steel to increase corrosion resistance and oxidation resistance, to increase
hardenability, or to improve high-temperature strength. As a hardening element, Chromium is frequently used
with a toughening element such as nickel to produce superior mechanical properties. At higher temperatures,
chromium contributes increased strength. Chromium is strong carbide former. Complex chromium-iron
carbides go into solution in austenite slowly; therefore, sufficient heating time must be allowed for prior to
quenching.
It is added for wear resistance, hardenability, and (most importantly) for corrosion resistance. As with
manganese, chromium has a tendency to increase hardness penetration. When 5 percent chromium or more
is used in conjunction with manganese, the critical quenching speed is reduced to the point that the steel
becomes air hardening. Chromium can also increase the toughness of steel, as well as the wear resistance.
As an alloying element in steel, chromium increases the hardenability and in association with high carbon
gives resistance to abrasion and wear. 4%is present in high speed steel and up to 5% is present in hot die
steels. In Structural steels it may be present in amounts up to about 3 %. Simple chromium-carbon steels are
used for ball bearings having high elastic limit and high uniform hardness due to the uniform distribution of the
hard carbide particles, but for most structural purposes chromium is used in conjunction with up to 4 % nickel
and small amounts of molybdenum or vanadium. In heat-resisting steels, chromium is present in amounts up
to 30%, and it is an important element in many of the highly alloyed heat-resisting materials, whose iron
contents are so low that they cannot be regarded as steel. Chromium is also used as an alloying addition to
high duty cast irons.
This is the most important alloying element in stainless steels. It is this element that gives the stainless steels
their basic corrosion resistance. The corrosion resistance increases with increasing chromium content. It also
increases the resistance to oxidation at high temperatures. Chromium promotes a ferritic structure. Chromium
is unique in its effect on resistance to corrosion and scaling and is an essential constituent in all stainless
steels, e.g., stainless cutlery steels contain 12% to 14% chromium, whilst in steels of the austenitic
corrosion-resisting type, 18% chromium is associated with 8% nickel, and small amounts of other elements.
Steel with at least 13% chromium is deemed "stainless" steel. Despite the name, all steel can rust if not
maintained properly. Chromium can dissolve in either alpha- or gama-iron, but, in the presence of carbon, the
carbides formed are cementite (FeCr)3C in which chromium may rise to more than 15%; chromium carbides
(CrFe)3C2 (CrFe)7C3 (CrFe)4C, in which chromium may be replaced by a few per cent, by a maximum of 55%
and by 25% respectively. Stainless steels contain Cr4C. The pearlitic chromium steels with, say, 2% chromium
are extremely sensitive to rate of cooling and temperature of heating before quenching;
It increases the depth penetration of hardening and also the responsiveness to heat treatment. It is usually
added with nickel (Ni) for use in stainless steels. Most of the chromium (Cr) bearing alloys contain 0.50 to
1.50 percent chromium; some stainless steels contain as much as 20 percent or more. It can affect forging,
causing a tendency in the steel to crack.
For example:
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Critical Hardening Rate

Temperature of Initial Heating, °C
(Min. to cool from 836°C to 546°C)
836 3.5 S
1010 6.5 S
1200 13 S
The reason is that the chromium carbides are not readily dissolved in the austenite, but the amount increases
with increase of temperature. The effect of the dissolved chromium is to raise the critical points on heating (Ac)
and also on cooling (Ar) when the rate is slow. Faster rates of cooling quickly depress the Ar points with
consequent hardening of the steel. Chromium imparts a characteristic form of the upper portion of the
isothermal transformation curve.
The percentage of carbon in the pearlite is lowered. Hence the proportion of free cementite (hardest
constituent) is increased in high carbon steel and, when the steel is properly heat-treated, it occurs in the
spheroidised form which is more suitable when the steel is used for ball bearings. The pearlite is rendered fine.
When the chromium exceeds 1.1% in low-carbon steels an inert passive film is formed on the surface which
resists attack by oxidizing reagents. Still higher chromium contents are found in heat-resisting steel.
Chromium steels are easier to machine than nickel steels of similar tensile strength. The steels of higher
chromium contents are susceptible to temper brittleness if slowly cooled from the tempering temperature
through the range 550/450°C. These steels are also liable to form surface markings, generally referred to as
"chrome lines". The chrome steels are used wherever extreme hardness is required, such as in dies, ball
bearings, plates for safes, rolls, files and tools. High chromium content is also found in certain permanent
magnets.
Figure 2. Effect of alloying with chromium on the critical temperature of steel and austenite (g -iron) phase transformation
zone on the iron-iron carbide diagram.
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Nickel and chromium Elements
Nickel steels are noted for their strength, ductility and toughness, while chromium steels are characterized by
their hardness and resistance to wear. The combination of nickel and chromium produces steels having all
these properties, some intensified, without the disadvantages associated with the simple alloys. The depth of
hardening is increased, and with 4,5% nickel, 1,25% chromium and 0.35% carbon the steel can be hardened
simply by cooling in air.
Low nickel-chromium steels with small carbon content are used for casehardening, while for most
constructional purposes the carbon content is 0.25-0.35%, and the steels are heat-treated to give the desired
properties. Considerable amounts of nickel and chromium are used in steel for resisting corrosion and
oxidation at elevated temperatures.
Embattlement. The effects of tempering a nickel-chromium steel are shown in Fig. 2, from which it will be
noticed that the Izod impact curve No. 1 reaches a dangerous minimum in the range 250-450°C in common
with many other steels. This is known as 350°C embattlement. Phosphorus and nitrogen have a significant
effect while other impurities (As, Sb, Sn) and manganese in larger quantity may also contribute to the
embattlement.
Figure 2. Effect of tempering on the mechanical properties of nickel-chromium steel, C 0.26, Ni 3, Cr 1,2, 29
mm diam, bars hardened in oil from 830°C. Izod (2) for steel with 0.25% molybdenum added
Temper brittleness is usually used to describe the notch impact intergranular brittleness (Grain boundaries are
revealed in temper brittle samples by etching in 1 gm cetyl trimethyl ammonium bromide; 20 gm picric acid;
100 cc distilled water, 100 cc ether. Shake mixture, allow to stand for 24 hrs; use portion of top layer and return
to tube afterwards) induced in some steels by slow cooling after tempering above about 600°C and also from
prolonged soaking of tough material between about 400?and 550°C.
Temper brittleness seems to be due to grain boundary enrichment with alloying elements-Mn, Cr, Mo-during
austenitising which leads to enhanced segregation of embattling elements P, Sn, Sb, As-by chemical
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interaction on slow cooling from 600°C. The return to the tough condition, obtained by rehearing embattled
steel to temperatures above 600°C and rapidly cooling, is due to the redistribution and retention in solution of
the embattling segregation. Antimony (0-001 %), phosphorus (0-008 %), arsenic, tin, manganese increase,
while molybdenum decreases the susceptibility of a steel to embattlement. 0-25 % molybdenum reduces the
brittleness as shown by Izod curve No. 2. Table 1 illustrates the effect rate of cooling after tempering and the
influence of an addition of 0-45 % molybdenum:
Table 1. Steel 0.3% C, 3,5 % Ni, 0.7%, Cr, tempered at 630°C
Cooling TS Izod Izod
Steel Elongation RA
Rate MPa ft lbf J
Ni-Cr Oil 896 18 60 64 87
Ni-Cr Furnance 880 18 60 19 25
Ni-Cr-Mo Furnance 896 18 61 59 80
Nickel And Chromium

Used together for austenitic stainless steels; each element counteracts disadvantages of the other.
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Molybdenum Elements
Molybdenum: A carbide former, prevents brittleness & maintains the steel's strength at high temperatures.
Present in many steels, and air-hardening steels (e.g. A-2, ATS-34) always have 1% or more molybdenum --
molybdenum is what gives those steels the ability to harden in air.
It is Adds greatly to the penetration of hardness and increases toughness of an alloy. It causes steel to resist
softening at high temperatures, which defeats the purpose of forging. If the alloy has below 0.020 percent
molybdenum (Mo), you should be able to forge this alloy with little difficulty.
Molybdenum is used very widely because of its powerful effect in increasing hardenability and also
because in low alloy steels it reduces susceptibility to temper brittleness. It forms stable carbides,
raises the temperature at which softening takes place on tempering and increases resistance to creep.
In high speed steel it can be used to replace approximately twice its weight of tungsten. The corrosion
resistance of stainless steel is improved by molybdenum additions.
Molybdenum increases the hardenability of steel. Molybdenum may produce secondary hardening during the
tempering of quenched steels. It enhances the creep strength of low-alloy steels at elevated temperatures.
Molybdenum substantially increases the resistance to both general and localized corrosion. It increases the
mechanical strength somewhat and strongly promotes a ferritic structure. Molybdenum also promotes the
formation secondary phases in ferritic, ferritic-austenitic and austenitic steels. In martensitic steels it will
increase the hardness at higher tempering temperatures due to its effect on the carbide precipitation.
Molybdenum dissolves in both alpha- and gama-iron and in the presence of carbon forms complex carbides
(FeMo)6C, Fe21Mo2C6, Mo2C. Molybdenum is similar to chromium in its effect on the shape of the TTT-curve
but up to 0.5% appears to be more effective in retarding pearlite and increasing bainite formation. Additions of
0.5% molybdenum have been made to plain carbon steels to give increased strength at boiler temperatures of
400°C, but the element is mainly used in combination with other alloying elements.
Ni-Cr-Mo steels are widely used for ordnance, turbine rotors and other large articles, since molybdenum tends
to minimize temper brittleness and reduces mass effect. Molybdenum is also a constituent in some high-speed
steels, magnet alloys, heat-resisting and corrosion-resisting steels.
Molybdenum
Strong carbide forming element, and also improves high temperature creep resistance; reduces
temper-brittleness in Ni-Cr steels. Improves corrosion resistance and temper brittleness.
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Vanadium Elements
Ferrite Promoter.
Carbide and Nitride Former.
Vanadium acts as a scavenger for oxides, forms vanadium carbide VC, and has a beneficial effect on the
mechanical properties of heat-treated steels, especially in the presence of other elements. It slows up
tempering in the range of 500-600°C and can induce secondary hardening. Chromium-vanadium (0.15%)
steels are used for locomotive forging, automobile axles, coil springs, torsion bars and creep resistance.
Vanadium increases the yield strength and the tensile strength of carbon steel. The addition of small amounts
of Vanadium can significantly increase the strength of steels. Vanadium is one of the primary contributors to
precipitation strengthening in microalloyed steels. When thermomechanical processing TMCP is properly
controlled the ferrite grain size is refined and there is a corresponding increase in toughness. The impact
transition temperature also increases when vanadium is added.
All microalloy steels contain small concentrations of one or more strong carbide and nitride forming
elements. Vanadium, niobium, and titanium combine preferentially with carbon and/or nitrogen to form a fine
dispersion of precipitated particles in the steel matrix.
The presence of vanadium in steel raises the temperature at which grain coarsening sets in and under certain
conditions increases the hardenability. It also lessens softening on tempering and confers secondary hardness
on high speed and other steels. Vanadium carbide is intensely hard and as much as 5% vanadium may be
added to high speed and high chromium tool steel where it improves abrasion resistance. Vanadium is an
important constituent in many types of steel, for widely varying applications, e.g., nitriding, heat-resistance,
tools, wearing plates and other fully hardened parts. In conjunction with molybdenum, vanadium has a marked
effect in enhancing creep resistance.
Vanadium increases the hardness of martensitic steels due to its effect on the type of carbide present. It also
increases tempering resistance. Vanadium stabilises ferrite and will, at high contents, promote ferrite in the
structure. It is only used in hardenable stainless steels.
It retards grain growth within steel even after long exposures at high temperatures, and helps to control grain
structures while heat treating. It is usually present in small quantities of 0.15 to 0.20 percent. Most tool steels
which contain this element seem to absorb shock better that those that do not contain vanadium (V).
Vanadium contributes to wear resistance and hardenability. A carbide former that helps produce fine-grained
steel. A number of steels have vanadium, but M-2, Vascowear, and CPM T440V and 420V (in order of
increasing amounts) have high amounts
Vanadium
Strong carbide forming element; has a scavenging action and produces clean, inclusion free steels. Can cause
re-heat cracking when added to chrome molly steels.
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Tungsten Elements
TUNGSTEN (W): Also known as wolfram, is used as an alloying element in tool steels, as it tends to impart a
tight, small, and dense grain pattern and keen cutting edges when used in relatively small amounts. It will also
cause steel to retain its hardness at higher temperatures and hence will have a detrimental effect upon the
steel's forgeability (otherwise known as "red hard")
Tungsten dissolves in gama-iron and in alpha-iron. With carbon it forms WC and W2C, but in the presence of
iron it forms Fe3W3C or Fe4W2C. A compound with iron, Fe3W2 provides an age-hardening system. Tungsten
raises the critical points in steel and the carbides dissolve slowly over a range of temperature. When
completely dissolved, the tungsten renders transformation sluggish, especially to tempering, and use is made
of this in most hot-working tool ("high speed") and die steels. It Increases wear resistance. When combined
properly with chromium or molybdenum, tungsten will make the steel to be a high-speed steel. The high-speed
steel M-2 has a high amount of tungsten. Tungsten refines the grain size and produces less tendency to
decarburisation during working. Tungsten is also used in magnet, corrosion- and heat-resisting steels.
The effect of the addition of this metal to steel is to increase the strength at normal and elevated
temperatures. Owing to the hardness of tungsten carbide and its influence on secondary hardening,
tungsten is used as the main alloy addition in high speed tool steels, molybdenum being its only
substitute. In addition, tungsten finds considerable application in general tool steels, die and
precipitation hardening steels. It has found a useful application in valves and other steels required for
use at high temperatures. Tungsten is an essential constituent in the sintered hard metals.
Tungsten
Forms hard and stable carbides; raises the transformation temperature range, and tempering temperatures.
Hardened tungsten steels resist tempering up to 6000C
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Silicon Elements
Ferrite Former.
Encourage Brittleness.
Silicon Si, is one of the principal deoxidizers used in steelmaking. Silicon is less effective than manganese in
increasing as-rolled strength and hardness. In low-carbon steels, silicon is generally detrimental to surface
quality. Silicon increases the resistance to oxidation, both at high temperatures and in strongly oxidising
solutions at lower temperatures. It promotes a ferritic structure.
It has a beneficial effect upon tensile strength and improves hardenability of an alloy. It has a toughening
effect when used in combination with certain other elements. Silicon (Si) is usually added to improve
electrical
conductivity of an alloy. Its average concentration is between 1.5 and 2.5 percent.
Silicon is used as a deoxidizer in the manufacture of steel. It slightly increases the strength of ferrite, and when
used in conjunction with other alloys can help increase the toughness and hardness penetration of steel.
Silicon is a powerful deoxidizer, and as such is used in steel making processes in amounts up to about
0·8%. When used as an alloying element, silicon in small percentages will increase the tensile strength
and yield point of structural steels. It is used in amounts of 1·5% to 2% in silicon-manganese spring
steels and ultra-high tensile steels due to its effect in raising the limit of proportionality and resistance
to tempering. Up to 4% in heat resisting steels improves scale resistance owing to the formation of a
protective layer (see also Ihrigizing). The higher the silicon, the higher the temperature at which
protection against further atmospheric oxidation is given. Water vapour and carbon dioxide, however,
attack the layer. Alloys of iron and silicon, containing 15% of the element, are used as acid-resisting
materials, but have the properties of cast irons rather than of steels. Carbon-free alloys with up to 4%
silicon have a high electrical resistance and low hysteresis loss, and are used as transformer steels. In
cast iron, silicon not only serves as a deoxidizer but also has a marked graphitizing effect, thus
improving machinability.
Silicon dissolves in the ferrite, of which it is a fairly effective hardener, and raises the Ac change points
and the Ar points when slowly cooled and also reduces the gama-alpha volume change. Only three types
of silicon steel are in common use-one in conjunction with manganese for springs; the second for
electrical purposes, used in sheet form for the construction of transformer cores, and poles of dynamos
and motors, that demand high magnetic permeability and electrical resistance; and the third is used for
automobile valves.
C Si Mn
1. Silico-manganese 0.5 1,5 0.8
2. Silicon steel 0.07 4,3 0.09
3. Silichrome 0.4 3,5 8
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It contributes oxidation resistance in heat-resisting steels and is a general purpose deoxidizes.

In general Silicon strengthens ferrite and raises the transformation temperature temperatures; has a strong graphitizing
tendency. Always present to some extent, because it is used with manganese as a deoxidizer
Copper Elements
Austenite Former.
Impair Forging.
Use as precipitation hardening alloy e.g17-4PH
Copper dissolves in the ferrite to a limited extent; not more than 3.5% is soluble in steels at normalizing
temperatures, while at room temperature the ferrite is saturated at 0.35%. It lowers the critical points, but
insufficiently to produce martensite by air cooling. The resistance to atmospheric corrosion is improved and
copper steels can be temper hardened.
Copper Cu, in significant amounts is detrimental to hot-working steels. Copper negatively affects forge
welding, but does not seriously affect arc or oxyacetylene welding. Copper can be detrimental to surface
quality. Copper is beneficial to atmospheric corrosion resistance when present in amounts exceeding 0.20%.
Weathering steels are sold having greater than 0.20% Copper.
The addition of about 0.20% copper to low carbon steel may increase its resistance to atmospheric
corrosion by as much as 20% to 30%. In amounts of about 0·50% copper appreciably increases the
tensile and yield strengths. The addition of increasing amounts of copper leads to defects in rolling.
High yield point structural steels containing copper, in association with chromium and appreciable
percentages of silicon and phosphorus have been developed. Copper is also added to some stainless
steels to improve corrosion resistance.
Copper enhances the corrosion resistance in certain acids and promotes an austenitic structure. In
precipitation hardening steels copper is used to form the intermetallic compounds that are used to increase the
strength.
Phosphorous Elements
Embrittlement Effects
Increase Machinability.
Undesirable Element.
Phosphorus P, increases strength and hardness and decreases ductility and notch impact toughness of
steel. The adverse effects on ductility and toughness are greater in quenched and tempered higher-carbon
steels. Phosphorous levels are normally controlled to low levels. Higher phosphorus is specified in
low-carbon free-machining steels to improve machinability.
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Although it has been used to increase the tensile strength of steel and to improve resistance to
atmospheric corrosion, phosphorus is usually regarded as an undesirable impurity because of its
embrittling effect. In most British specifications the maximum permitted is 0.05 %, but in steel for
nitriding it may be restricted to a maximum of 0·02 % since during the nitriding treatment phosphorus
has a temper embrittling effect.
Sulphur Elements
Increase Machinability.
Undesirable element.
Embrittlement Effects.
Impair Ductility.
Impair Weldability.
SULFUR S, Is usually regarded as an impurity in most alloys and its addition to steel is held to a minimum as it
is damaging to the hot forming characteristics of steel. It is, however added to increase machinability. A
word of caution, some alloys are offered in different forms, an example is E52100. This particular steel
can be had in either a "Bearing Quality" or "Machining Quality" the latter having sulfur added to increase
machinability.
Sulfur decreases ductility and notch impact toughness especially in the transverse direction. Weldability
decreases with increasing sulfur content. Sulfur is found primarily in the form of sulfide inclusions. Sulfur
levels are normally controlled to low levels. The only exception is free-machining steels, where sulfur is added
to improve machinability.
A non-metal, which combines with iron to form iron sulphides, in which form its effect is to make the
steel red short but combined with manganese its influence is less injurious. In steel the sulphur content
is usually specified as less than 0.05 % but it may be added deliberately to improve machinability.
Sulphur is added to certain stainless steels, the free-machining grades, in order to increase the machinability.
At the levels present in these grades sulphur will substantially reduce corrosion resistance, ductility and
fabrication properties, such as weldability and formability.
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Lead Elements
Improve Machinability.
Undesirable Element.
Impair Ductility.
Impair Toughness.
Impair Creep Strength.
Lead Pb, increase the machinability of steel and has no effect upon the other properties of the metal. Lead is
virtually insoluble in liquid or solid steel. However, lead is sometimes added to carbon and alloy steels by
means of mechanical dispersion during pouring to improve the machinability.
The addition of about 025% lead improves machinability. It also causes a reduction in fatigue strength,
ductility and toughness but this only becomes serious in the transverse direction and at high tensile
levels. In creep resisting alloys very small amounts of lead may be harmful.
Hydrogen Elements
Hydrogen H, in steel is an undesirable impurity which is introduced from moisture in the atmosphere or
the charge during melting. If a large amount of hydrogen is present in the liquid steel, some may be
liberated on freezing giving an unsound ingot, evolution of hydrogen subsequently when the solid steel
cools may cause hair line cracks. Hydrogen can be reduced to safe proportions by casting in vacuum
or by prolonged annealing. It may also be introduced into steel by electrolytic action or by pickling and
may then cause brittleness.
Selenium Elements
Selenium Se, A metalloid closely resembling sulphur in its properties. It is sometimes added to steels
to the extent of 0·2 % to 0·3 % to improve machinability.
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Tantalum Elements
Tantalum Ta, This metal is associated with niobium and is very similar to it chemically. As an alloying
addition to steel, niobium is preferred.
Tellurium is added to steel either alone or together with selenium to promote machinability. It is a
powerful carbide stabilizer and has been also added to cast iron where it is said to increase the depth
of chill and to prevent shrinkage. It may be added in small amounts to the molten iron or by the use of
cores dipped or painted with washes containing tellurium in suspension.
Tin Elements
Tin Sn, Owing to its good resistance to corrosion in many conditions, the major use of tin is in the form
of coatings for steel and copper alloys. It is an undesirable impurity in steel giving rise to temper
brittleness, but is less harmful than phosphorus.
Calcium Elements
Calcium Ca, This metal in the form of calcium silicide is sometimes added to steel as a deoxidizer and
degasefier.
Cerium Elements
Cerium Ce, a metal of the rare earth class which in many respects resemble the alkali metals. The hot
working properties of high alloy corrosion- and heat-resistant steels maybe improved by the addition of
cerium, whilst in cast iron, cerium acts as a deoxidizer and desulphurizer but when the sulphur content
has been reduced to a value of about 0·015%, the cerium enters into solution in the cast iron and
functions as a powerful carbide stabilizer. In amounts above 0·02%, cerium is the operative factor in
the production of nodular graphite structures in cast iron.
Cerium is one of the rare earth metals (REM) and is added in small amounts to certain heat resistant
temperature steels and alloys in order to increase the resistance to oxidation and high temperature corrosion.
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Nitrogen Elements
Nitrogen N, Nitrogen can combine with many metals to form nitrides and is thus applied to the case
hardening of steel, the usual source for this purpose being ammonia. The incorporation of nitrogen in
austenitic chromium-nickel steels stabilizes the austenite and increases the strength. In carbon steels it
has an influence on creep. (See Abnormal Steels)
Nitrogen is a very strong austenite former and strongly promotes an austenitic structure. It also substantially
increases the mechanical strength. Nitrogen increases the resistance to localised corrosion, especially in
combination with molybdenum. In ferritic stainless steels nitrogen will strongly reduce toughness and corrosion
resistance. In the martensitic and martensitic-austenitic steels nitrogen increases both hardness and strength
but reduces the toughness.
Boron Elements
Boron B, is added to fully killed steel to improve hardenability. Boron-treated steels are produced to a range of
0.0005 to 0.003%. Whenever boron is substituted in part for other alloys, it should be done only with
hardenability in mind because the lowered alloy content may be harmful for some applications.
The addition of about 0.003 % of boron confers increased harden ability to steels in the quenched and
tempered condition. Further, it has been found that the addition of 0·003% boron to low carbon, 0·50%
molybdenum steel in the normalized condition doubles the yield strength and gives a 30% increase in
tensile strength, but the advantage due to boron is very slight when molybdenum is less than 0.35%
causes difficulty in forging. As much as 2% may be added to steels used in nuclear engineering.
Boron is a potent alloying element in steel. A very small amount of boron (about 0.001%) has a strong effect
on hardenability. Boron steels are generally produced within a range of 0.0005 to 0.003%. Boron is most
effective in lower carbon steels.
Boron. In recent years, especially in USA, 0.003-0.005% boron has been added to previously fully killed,
fine-grain steel to increase the hardenability of the steel. The yield ratio and impact are definitely improved,
provided advantage is taken of the increased hardenability obtained and the steel is fully hardened before
tempering. In conjunction with molybdenum boron forms a useful group of high tensile bainitic steels. Boron is
used in some hard facing alloys and for nuclear control rods.
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Aluminium Elements
Aluminum Al, is widely used as a deoxidizer. Aluminum can control austenite grain growth in reheated steels
and is therefore added to control grain size. Aluminum is the most effective alloy in controlling grain growth
prior to quenching. Titanium, zirconium, and vanadium are also valuable grain growth inhibitors, but there
carbides are difficult to dissolve into solution in austenite.
As a deoxidizer, up to 0.05% aluminum may be added to steel. For increasing fine grain characteristics
or sub-zero impact properties, up to 0·10% may be added. Nitriding steels contain about 1% aluminum
for promoting a high surface hardness when heated in ammonia. Still larger additions made to heat
resisting steels promote resistance to scaling. Approximately 5% added to chromium steel increases
electrical resistivity.
Aluminium improves oxidation resistance, if added in substantial amounts. It is used in certain heat resistant
alloys for this purpose. In precipitation hardening steels aluminium is used to form the intermetallic compounds
that increase the strength in the aged condition.
Zirconium Elements
Zirconium Zr, can be added to killed high-strength low-alloy steels to achieve improvements in inclusion
characteristics. Zirconium causes sulfide inclusions to be globular rather than elongated thus improving
toughness and ductility in transverse bending.
Zirconium acts as a deoxidizing element in steel and combines with the sulphur.
Niobium Elements
Niobium Nb (Columbium) increases the yield strength and, to a lesser degree, the tensile strength of carbon
steel. The addition of small amounts of Niobium can significantly increase the yield strength of
steels. Niobium can also have a moderate precipitation strengthening effect. Its main contributions are to form
precipitates above the transformation temperature, and to retard the recrystallization of austenite, thus
promoting a fine-grain microstructure having improved strength and toughness.
The metal is also known as columbium. It occurs in association with tantalum, to which it is closely
related. Niobium is a strong carbide-forming element and as such is added to certain austenitic
corrosion-resistant steels of the 18/8 chromium-nickel type for the prevention of intercrystalline
corrosion. Where niobium is used as the stabilizer, it is usually specified that it should be present in an
amount at least 8 times that of the carbon content. Further, niobium is often used as a constituent of
the electrodes used in the welding of such steels. Niobium is added to heat-resisting steels and
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enhances creep strength. In small amounts, of the order of 0·05%, it increases the yield strength of
mild steel.
Niobium is both a strong ferrite and carbide former. As titanium it promotes a ferritic structure. In austenitic
steels it is added to improve the resistance to intergranular corrosion but it also enhances mechanical
properties at high temperatures. In martensitic steels niobium lowers the hardness and increases the
tempering resistance. In U.S. it is also referred to as Columbium (Cb).
Titanium Elements
Titanium Ti, is used to retard grain growth and thus improve toughness. Titanium is also used to achieve
improvements in inclusion characteristics. Titanium causes sulfide inclusions to be globular rather than
elongated thus improving toughness and ductility in transverse bending.
Titanium is a strong ferrite former and a strong carbide former, thus lowering the effective carbon content and
promoting a ferritic structure in two ways. In austenitic steels it is added to increase the resistance to
intergranular corrosion but it also increases the mechanical properties at high temperatures. In ferritic stainless
steels titanium is added to improve toughness and corrosion resistance by lowering the amount of interstitials
in solid solution. In martensitic steels titanium lowers the martensite hardness and increases the tempering
resistance. In precipitation hardening steels titanium is used to form the intermetallic compounds that are used
to increase the strength.
The principal use of titanium is to stabilize carbon by forming titanium carbide. In austenitic stainless
steels it is used in this way to prevent inter crystalline corrosion, the titanium addition being at least four
times the carbon content. It is also added to low carbon steels to prevent blistering during vitreous
enameling. Titanium carbide is used with tungsten carbide in the manufacture of hard metal tools.
Strong carbide forming element. Not used on its own, but added as a carbide stabiliser to some austenitic stainless steels.
Cobalt Elements
Cobalt Co, Increases strength and hardness, permits quenching at higher temperatures. In some
steels used for nuclear engineering cobalt is an undesirable impurity, even in amounts as small as
0·02%. Unlike most other alloying elements cobalt reduces hardenability. It raises the red hardness of
steel and this is the reason for adding 5% to 10% cobalt to certain types of high speed steels,
developed for the specific purpose of cutting exceptionally hard materials. Heat resisting alloys with
high cobalt contents have been developed for use in gas turbines. Cobalt is added to the extent of up
to 40 % to magnet steels requiring high coercive force and it is used in electrical- resistance alloys. In
the sintered hard metals Cobalt acts as the binding metal.
Cobalt only used as an alloying element in martensitic steels where it increases the hardness and tempering
resistance, especially at higher temperatures.
Cobalt has a high solubility in alpha- and gama-iron but a weak carbide-forming tendency. It decreases
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hardenability but sustains hardness during tempering. It is used in "Stellite" type alloys, gas turbine steel,
magnets and as a bond in hard metal.
Tellurium Elements
Tellurium (Te)
Tellurium is added to steel either alone or together with selenium to promote machinability. It is a powerful
carbide stabilizer and has been also added to cast iron where it is said to increase the depth of chill and to
prevent shrinkage. It may be added in small amounts to the molten iron or by the use of cores dipped or
painted with washes containing tellurium in suspension.
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Chapter Three: Articles on alloying elements in steel
Carbon content, steel classifications, and alloy steels
Generally, carbon is the most important commercial steel alloy. Increasing carbon content increases hardness
and strength and improves hardenability. But carbon also increases brittleness and reduces weldability
because of its tendency to form martensite. This means carbon content can be both a blessing and a curse
when it comes to commercial steel.
And while there are steels that have up to 2 percent carbon content, they are the exception. Most steel
contains less than 0.35 percent carbon. To put this in perspective, keep in mind that’s 35/100 of 1 percent.
Now, any steel in the 0.35 to 1.86 percent carbon content range can be hardened using a heat-quench-temper
cycle. Most commercial steels are classified into one of three groups:
1. Plain carbon steels
2. Low-alloy steels
3. High-alloy steels
Plain Carbon Steels
These steels usually are iron with less than 1 percent carbon, plus small amounts of manganese, phosphorus,
sulfur, and silicon. The weldability and other characteristics of these steels are primarily a product of carbon
content, although the alloying and residual elements do have a minor influence.
Plain carbon steels are further subdivided into four groups:

1. Low
2. Medium
3. High
4. Very high
Low. Often called mild steels, low-carbon steels have less than 0.30 percent carbon and are the most
commonly used grades. They machine and weld nicely and are more ductile than higher-carbon steels.
Medium. Medium-carbon steels have from 0.30 to 0.45 percent carbon. Increased carbon means increased
hardness and tensile strength, decreased ductility, and more difficult machining.
High. With 0.45 to 0.75 percent carbon, these steels can be challenging to weld. Preheating, postheating (to
control cooling rate), and sometimes even heating during welding become necessary to produce acceptable
welds and to control the mechanical properties of the steel after welding.
Very High. With up to 1.50 percent carbon content, very high-carbon steels are used for hard steel products
such as metal cutting tools and truck springs. Like high-carbon steels, they require heat treating before, during,
and after welding to maintain their mechanical properties.
Low-alloy Steels
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When these steels are designed for welded applications, their carbon content is usually below 0.25 percent
and often below 0.15 percent. Typical alloys include nickel, chromium, molybdenum, manganese, and silicon,
which add strength at room temperatures and increase low-temperature notch toughness.
These alloys can, in the right combination, improve corrosion resistance and influence the steel’s response to
heat treatment. But the alloys added can also negatively influence crack susceptibility, so it’s a good idea to
use low-hydrogen welding processes with them. Preheating might also prove necessary. This can be
determined by using the carbon equivalent formula, which we’ll cover in a later issue.
High-alloy Steels
For the most part, we’re talking about stainless steel here, the most important commercial high-alloy steel.
Stainless steels are at least 12 percent chromium and many have high nickel contents. The three basic types
of stainless are:
1. Austenitic
2. Ferritic
3. Martensitic
Martensitic stainless steels make up the cutlery grades. They have the least amount of chromium, offer high
hardenability, and require both pre- and postheating when welding to prevent cracking in the heat-affected
zone (HAZ).
Ferritic stainless steels have 12 to 27 percent chromium with small amounts of austenite-forming alloys.
Austenitic stainless steels offer excellent weldability, but austenite isn’t stable at room temperature.
Consequently, specific alloys must be added to stabilize austenite. The most important austenite stabilizer is
nickel, and others include carbon, manganese, and nitrogen. Special properties, including corrosion resistance,
oxidation resistance, and strength at high temperatures, can be incorporated into austenitic stainless steels by
adding certain alloys like chromium, nickel, molybdenum, nitrogen, titanium, and columbium. And while carbon
can add strength at high temperatures, it can also reduce corrosion resistance by forming a compound with
chromium. It’s important to note that austenitic alloys can’t be hardened by heat treatment. That means they
don’t harden in the welding HAZ.
http://www.matter.org.uk/steelmatter/raw_materials/default.htm
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* Stainless steels always have a high chromium content, often considerable amounts of nickel, and sometimes contain
molybdenum and other elements. Stainless steels are identified by a three-digit number beginning with 2, 3, 4, or 5.
Figure 1
Be sure to check the appropriate AISI and SAE publications for the latest revisions.
Steel Classification Systems
Before we look at a couple of common steel classification systems, let’s consider one more high-carbon metal,
cast iron. The carbon content of cast iron is 2.1 percent or more. There are four basic types of cast iron:
1. Gray cast iron, which is relatively soft. It’s easily machined and welded, and you’ll find it used for
engine cylinder blocks, pipe, and machine tool structures.
2. White cast iron, which is hard, brittle, and not weldable. It has a compressive strength of more than
200.000 pounds per square inch (PSI), and when it’s annealed, it becomes malleable cast iron.
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3. Malleable cast iron, which is annealed white cast iron. It can be welded, machined, is ductile, and
offers good strength and shock resistance.
4. Ductile cast iron, which is sometimes called nodular or spheroidal graphite cast iron. It gets this name
because its carbon is in the shape of small spheres, not flakes. This makes it both ductile and
malleable. It’s also weldable.
Now let’s take a look at a typical steel classification system (see Figure 1). Both the Society of Automotive
Engineers (SAE) and the American Iron and Steel Institute (AISI) use virtually identical systems. Both are
based on a four-digit system with the first number usually indicating the basic type of steel and the first two
numbers together indicating the series within the basic alloy group.
Keep in mind there may be a number of series within a basic alloy group, depending on the amount of the
principal alloying elements. The last two or three numbers refer to the approximate permissible range of
carbon content in points (hundredths of a percent).
These classification systems can become fairly complex, and Figure 1 is just a basic representation. Be sure to
reference the most recent AISI and SAE publications for the latest revisions.
That’s a look at some basics concerning the iron-carbon-steel relationship and its influences on welding and
metal alloys. Next time we’ll look at hardening and ways to make metals stronger. We’ll also consider the
influences of some key alloying elements and the effects of welding on metallurgy.
Carbon Steel
Carbon steels and alloy steels are designated by a four digit number, where the first two digits indicate
the alloying elements and the last two digits indicate the amount of carbon, in hundredths of a percent by
weight. For example, a 1060 steel is a plain carbon steel containing 0.60 wt% C.
designation Type
Carbon steels
10xx Plain carbon (Mn 1.00% max)
11xx Resulfurized
12xx Resulfurized and rephosphorized
15xx Plain carbon (Mn 1.00% to 1.65%)
Manganese steels
13xx Mn 1.75%
Nickel steels
23xx Ni 3.50%
25xx Ni 5.00%
Nickel-chromium steels
31xx Ni 1.25%, Cr 0.65% or 0.80%

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32xx Ni 1.25%, Cr 1.07%
33xx Ni 3.50%, Cr 1.50% or 1.57%
34xx Ni 3.00%, Cr 0.77%
Molybdenum steels
40xx Mo 0.20% or 0.25% or 0.25% Mo & 0.042 S
44xx Mo 0.40% or 0.52%
Chromium-molybdenum (Chromoly) steels
41xx Cr 0.50% or 0.80% or 0.95%, Mo 0.12% or 0.20% or 0.25% or 0.30%
Nickel-chromium-molybdenum steels
43xx Ni 1.82%, Cr 0.50% to 0.80%, Mo 0.25%
43BVxx Ni 1.82%, Cr 0.50%, Mo 0.12% or 0.35%, V 0.03% min
47xx Ni 1.05%, Cr 0.45%, Mo 0.20% or 0.35%
81xx Ni 0.30%, Cr 0.40%, Mo 0.12%
81Bxx Ni 0.30%, Cr 0.45%, Mo 0.12%
86xx Ni 0.55%, Cr 0.50%, Mo 0.20%
87xx Ni 0.55%, Cr 0.50%, Mo 0.25%
88xx Ni 0.55%, Cr 0.50%, Mo 0.35%
93xx Ni 3.25%, Cr 1.20%, Mo 0.12%
94xx Ni 0.45%, Cr 0.40%, Mo 0.12%
97xx Ni 0.55%, Cr 0.20%, Mo 0.20%
98xx Ni 1.00%, Cr 0.80%, Mo 0.25%
Nickel-molybdenum steels
46xx Ni 0.85% or 1.82%, Mo 0.20% or 0.25%
48xx Ni 3.50%, Mo 0.25%
Chromium steels
50xx Cr 0.27% or 0.40% or 0.50% or 0.65%
50xxx Cr 0.50%, C 1.00% min
50Bxx Cr 0.28% or 0.50%
51xx Cr 0.80% or 0.87% or 0.92% or 1.00% or 1.05%
51xxx Cr 1.02%, C 1.00% min
51Bxx Cr 0.80%
52xxx Cr 1.45%, C 1.00% min
Chromium-vanadium steels
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61xx Cr 0.60% or 0.80% or 0.95%, V 0.10% or 0.15% min
Tungsten-chromium steels
72xx W 1.75%, Cr 0.75%
Silicon-manganese steels
92xx Si 1.40% or 2.00%, Mn 0.65% or 0.82% or 0.85%, Cr 0.00% or 0.65%
High-strength low-alloy steels
9xx Various SAE grades
xxBxx Boron steels
xxLxx Leaded steels
Stainless steel
200 Series: austenitic chromium-nickel-manganese alloys

300 Series: austenitic chromium-nickel alloys
Type 301: highly ductile, for formed products. Also hardens rapidly during mechanical working.
Type 303: free machining version of 304 via addition of sulfur
Type 304: the most common; the classic 18/8 stainless steel.
Type 316: the next most common; for food and surgical stainless steel uses; alloy addition of
molybdenum prevents specific forms of corrosion. 316 steel is more resistant to corrosion than
18-8 stainless steels. 316 steel is used in the handling of certain food and pharmaceutical
products where it is often required in order to minimize metallic contamination. 316 steel is also
known as "marine grade" stainless steel due to its increased ability to resist saltwater corrosion
compared to type 304. SS316 is often used for building nuclear reprocessing plants.
400 Series: ferritic and martensitic chromium alloys
Type 408: heat-resistant; poor corrosion resistance; 11% chromium, 8% nickel.
Type 409: cheapest type; used for automobile exhausts; ferritic (iron/chromium only).
Type 410: martensitic (high-strength iron/chromium).
Type 416: the most machinable stainless steel; achieved by the addition of extra sulfur which
reduces corrosion resistance. Often used for "stainless" rifle barrels
Type 420: "Cutlery grade" martensitic; similar to the Brearley's original "rustless steel". Also
known as "surgical steel".
Type 430: decorative, e.g., for automotive trim; ferritic.
Type 440: a higher grade of cutlery steel, with more carbon in it, which allows for much better
edge retention when the steel is heat treated properly.
500 Series: heat resisting chromium alloys
600 Series: martensitic precipitation hardening alloys
Type 630: most common PH stainless, better known as 17-4; 17% chromium, 4% nickel
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Stainless steel designations
SAE UNS
% Cr % Ni %C % Mn % Si %P %S %N Other
designation designation
Austenitic
201 S20100 16–18 3.5–5.5 0.15 5.5–7.5 0.75 0.06 0.03 0.25 -
202 S20200 17–19 4–6 0.15 7.5–10.0 0.75 0.06 0.03 0.25 -
205 S20500 16.5–18 1–1.75 0.12–0.25 14–15.5 0.75 0.06 0.03 0.32–0.40 -
301 S30100 16–18 6–8 0.15 2 0.75 0.045 0.03 - -
302 S30200 17–19 8–10 0.15 2 0.75 0.045 0.03 0.1 -
302B S30215 17–19 8–10 0.15 2 2.0–3.0 0.045 0.03 - -
0.15 Mo 0.60
303 S30300 17–19 8–10 0.15 2 1 0.2 -
min (optional)
303Se S30323 17–19 8–10 0.15 2 1 0.2 0.06 - 0.15 Se min
304 S30400 18–20 8–10.50 0.08 2 0.75 0.045 0.03 0.1 -
304L S30403 18–20 8–12 0.03 2 0.75 0.045 0.03 0.1 -
304Cu S30430 17–19 8–10 0.08 2 0.75 0.045 0.03 - 3–4 Cu
304N S30451 18–20 8–10.50 0.08 2 0.75 0.045 0.03 0.10–0.16 -
305 S30500 17–19 10.50–13 0.12 2 0.75 0.045 0.03 - -
308 S30800 19–21 10–12 0.08 2 1 0.045 0.03 - -
309 S30900 22–24 12–15 0.2 2 1 0.045 0.03 - -
309S S30908 22–24 12–15 0.08 2 1 0.045 0.03 - -
310 S31000 24–26 19–22 0.25 2 1.5 0.045 0.03 - -
310S S31008 24–26 19–22 0.08 2 1.5 0.045 0.03 - -
314 S31400 23–26 19–22 0.25 2 1.5–3.0 0.045 0.03 - -
316 S31600 16–18 10–14 0.08 2 0.75 0.045 0.03 0.10 2.0–3.0 Mo
316L S31603 16–18 10–14 0.03 2 0.75 0.045 0.03 0.10 2.0–3.0 Mo
0.10
316F S31620 16–18 10–14 0.08 2 1 0.2 - 1.75–2.50 Mo
min
316N S31651 16–18 10–14 0.08 2 0.75 0.045 0.03 0.10–0.16 2.0–3.0 Mo
317 S31700 18–20 11–15 0.08 2 0.75 0.045 0.03 0.10 max 3.0–4.0 Mo
317L S31703 18–20 11–15 0.03 2 0.75 0.045 0.03 0.10 max 3.0–4.0 Mo
Ti 5(C+N)
321 S32100 17–19 9–12 0.08 2 0.75 0.045 0.03 0.10 max
min, 0.70 max
329 S32900 23–28 2.5–5 0.08 2 0.75 0.04 0.03 - 1–2 Mo
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330 N08330 17–20 34–37 0.08 2 0.75–1.50 0.04 0.03 - -
Nb + Ta, 10 x
347 S34700 17–19 9–13 0.08 2 0.75 0.045 0.030 -
C min, 1 max
Nb + Ta, 10 x
C min, 1 max,
348 S34800 17–19 9–13 0.08 2 0.75 0.045 0.030 -
but 0.10 Ta
max; 0.20 Ca
384 S38400 15–17 17–19 0.08 2 1 0.045 0.03 - -
Ferritic
0.1–0.3 Al,
405 S40500 11.5–14.5 - 0.08 1 1 0.04 0.03 -
0.60 max
Ti 6 x C, but
409 S40900 10.5–11.75 0.05 0.08 1 1 0.045 0.03 -
0.75 max
429 S42900 14–16 0.75 0.12 1 1 0.04 0.03 - -
430 S43000 16–18 0.75 0.12 1 1 0.04 0.03 - -
0.15 0.60 Mo
430F S43020 16–18 - 0.12 1.25 1 0.06 -
min (optional)
430FSe S43023 16–18 - 0.12 1.25 1 0.06 0.06 - 0.15 Se min
434 S43400 16–18 - 0.12 1 1 0.04 0.03 - 0.75–1.25 Mo
0.75–1.25
Mo; Nb+Ta 5
436 S43600 16–18 - 0.12 1 1 0.04 0.03 -
x C min, 0.70
max
442 S44200 18–23 - 0.2 1 1 0.04 0.03 - -
446 S44600 23–27 0.25 0.2 1.5 1 0.04 0.03 - -
Martensitic
403 S40300 11.5–13.0 0.60 0.15 1 0.5 0.04 0.03 - -
410 S41000 11.5–13.5 0.75 0.15 1 1 0.04 0.03 - -
414 S41400 11.5–13.5 1.25–2.50 0.15 1 1 0.04 0.03 - -
0.15 0.060 Mo
416 S41600 12–14 - 0.15 1.25 1 0.06 -
min (optional)
416Se S41623 12–14 - 0.15 1.25 1 0.06 0.06 - 0.15 Se min
420 S42000 12–14 - 0.15 min 1 1 0.04 0.03 - -
0.15 0.60 Mo max

420F S42020 12–14 - 0.15 min 1.25 1 0.06 -
min (optional)
0.90–1.25
422 S42200 11.0–12.5 0.50–1.0 0.20–0.25 0.5–1.0 0.5 0.025 0.025 -
Mo;
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0.20–0.30 V;
0.90–1.25 W
431 S41623 15–17 1.25–2.50 0.2 1 1 0.04 0.03 - -
440A S44002 16–18 - 0.60–0.75 1 1 0.04 0.03 - 0.75 Mo
440B S44003 16–18 - 0.75–0.95 1 1 0.04 0.03 - 0.75 Mo
440C S44004 16–18 - 0.95–1.20 1 1 0.04 0.03 - 0.75 Mo
Heat resisting
501 S50100 4–6 - 0.10 min 1 1 0.04 0.03 - 0.40–0.65 Mo
502 S50200 4–6 - 0.1 1 1 0.04 0.03 - 0.40–0.65 Mo
Unified numbering system
Introduction to the Unified Numbering System of Ferrous Metals and Alloys

http://www.key-to-steel.com/Articles/Art111.htm
http://en.wikipedia.org/wiki/Unified_numbering_system
Introduction to steels and cast irons
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Strength in Steel
Strength in steels arises from several phenomena, which usually contribute collectively to the observed
mechanical properties. The heat treatment of steels is aimed at adjusting these contributions so that the
required balance of mechanical properties is achieved. Fortunately the γ/α phase change allows great
variations in microstructure to be produced, so that a wide range of mechanical properties can be obtained
even in plain carbon steels. The additional use of metallic alloying elements, primarily as a result of their
influence on the transformation, provides an even greater control over microstructure, with consequent
benefits in the mechanical properties
The simplest version of analyzes the effects of alloying elements on iron-carbon alloys would require analysis of
a large number of ternary alloy diagrams over a wide temperature range. However, Wever pointed out that iron
binary equilibrium systems fall into four main categories (Fig. 1): open and closed γ-field systems, and expanded
and contracted γ-field systems. This approach indicates that alloying elements can influence the equilibrium
diagram in two ways:
by expanding the γ-field, and encouraging the formation of austenite over wider compositional limits. These
elements are called γ-stabilizers.
by contracting the γ-field, and encouraging the formation of ferrite over wider compositional limits. These
elements are called α-stabilizers.
The form of the diagram depends to some degree on the electronic structure of the alloying elements which is
reflected in their relative positions in the periodic classification.
Class 1: open γ-field. To this group belong the important steel alloying elements nickel and manganese, as well
as cobalt and the inert metals ruthenium, rhodium, palladium, osmium, iridium and platinum. Both nickel and
manganese, if added in sufficiently high concentration, completely eliminate the bcc α-iron phase and replace it,
down to room temperature, with the γ-phase. So nickel and manganese depress the phase transformation from γ
to α to lower temperatures (Fig. 1a), i.e. both Ac1 and Ac3 are lowered. It is also easier to obtain metastable
austenite by quenching from the γ-region to room temperature, consequently nickel and manganese are useful
elements in the formulation of austenitic steels.
Class 2: expanded γ-field. Carbon and nitrogen are the most important elements in this group. The γ-phase field
is expanded, but its range of existence is cut short by compound formation (Fig.1b). Copper, zinc and gold have
a similar influence. The expansion of the γ-field by carbon, and nitrogen, underlies the whole of the heat
treatment of steels, by allowing formation of a homogeneous solid solution (austenite) containing up to 2.0 wt %
of carbon or 2.8 wt % of nitrogen.
Class 3: closed γ-field. Many elements restrict the formation of γ-iron, causing the γ-area of the diagram to
contract to a small area referred to as the gamma loop (Fig. 1c). This means that the relevant elements are
encouraging the formation of bcc iron (ferrite), and one result is that the δ- and γ-phase fields become
continuous. Alloys in which this has taken place are, therefore, not amenable to the normal heat treatments
involving cooling through the γ/α-phase transformation. Silicon, aluminium, beryllium and phosphorus fall into
this category, together with the strong carbide forming elements, titanium, vanadium, molybdenum and
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chromium.
Figure 1. Classification of iron alloy phase diagrams: a. open γ-field; b. expanded γ-field; c. closed γ-field
Class 4: contracted y-field. Boron is the most significant element of this group, together with the carbide forming
elements tantalum, niobium and zirconium. The γ-loop is strongly contracted, but is accompanied by compound
formation (Fig. 1d).
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The distribution of alloying elements in steels. Although only binary systems have been considered so far, when
carbon is included to make ternary systems the same general principles usually apply. For a fixed carbon content,
as the alloying clement is added the y-field is either expanded or contracted depending on the particular solute.
With an element such as silicon the γ-field is restricted and there is a corresponding enlargement of the α-field. If
vanadium is added, the γ-field is contracted and there will be vanadium carbide in equilibrium with ferrite over
much of the ferrite field. Nickel does not form a carbide and expands the γ-field. Normally elements with
opposing tendencies will cancel each other out at the appropriate combinations, but in some cases anomalies
occur. For example, chromium added to nickel in a steel in concentrations around 18% helps to stabilize the
γ-phase, as shown by 18Cr8Ni austenitic steels.
One convenient way of illustrating quantitatively the effect of an alloying element on the γ-phase field of the Fe-C
system is to project on to the Fe-C plane of the ternary system the γ-phase field boundaries for increasing
concentration of a particular alloying element. For more precise and extensive information, it is necessary to
consider series of isothermal sections in true ternary systems Fe-C-X, but even in some of the more familiar
systems the full information is not available, partly because the acquisition of accurate data can be a difficult and
very time-consuming process.
Recently the introduction of computer-based methods has permitted the synthesis of extensive thermochemical
and phase equilibria data, and its presentation in the form, for example, of isothermal sections over a wide range
of temperatures.
If only steels in which the austenite transforms to ferrite and carbide on slow cooling are considered, the alloying
elements can be divided into three categories:
elements which enter only the ferrite phase
elements which form stable carbides and also enter the ferrite phase
elements which enter only the carbide phase.
In the first category there are elements such as nickel, copper, phosphorus and silicon which, in transformable
steels, are normally found in solid solution in the ferrite phase, their solubility in cementite or in alloy carbides
being quite low.
The majority of alloying elements used in steels fall into the second category, in so far as they are carbide
formers and as such, at low concentrations, go into solid solution in cementite, but will also form solid solutions in
ferrite. At higher concentrations most will form alloy carbides, which are thermodynamically more stable than
cementite.
Typical examples are manganese, chromium, molybdenum, vanadium, titanium, tungsten and niobium.
Manganese carbide is not found in steels, but instead manganese enters readily into solid solution in Fe3C. The
carbide-forming elements are usually present greatly in excess of the amounts needed in the carbide phase,
which are determined primarily by the carbon content of the steel. The remainder enters into solid solution in the
ferrite with the non-carbide forming elements nickel and silicon. Some of these elements, notably titanium,
tungsten, and molybdenum, produce substantial solid solution hardening of ferrite.
In the third category there are a few elements which enter predominantly the carbide phase. Nitrogen is the most
important element and it forms carbo-nitrides with iron and many alloying elements. However, in the presence of
certain very strong nitride forming elements, e.g. titanium and aluminum, separate alloy nitride phases can occur.
While ternary phase diagrams, Fe-C-X, can be particularly helpful in understanding the phases which can exist in
simple steels, isothermal sections for a number of temperatures are needed before an adequate picture of the
equilibrium phases can be built up. For more complex steels the task is formidable and equilibrium diagrams can
only give a rough guide to the structures likely to be encountered. It is, however, possible to construct
pseudobinary diagrams for groups of steels, which give an overall view of the equilibrium phases likely to be
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encountered at a particular temperature.

Structural changes resulting from alloying additions. The addition to iron-carbon alloys of elements such as nickel,
silicon, manganese, which do not form carbides in competition with cementite, does not basically alter the
microstructures formed after transformation. However, in the case of strong carbide-forming elements such as
molybdenum, chromium and tungsten, cementite will be replaced by the appropriate alloy carbides, often at
relatively low alloying element concentrations. Still stronger carbide forming elements such as niobium, titanium
and vanadium are capable of forming alloy carbides, preferentially at alloying concentrations less than 0.1 wt%.
It would, therefore, be expected that the microstructures of steels containing these elements would be radically
altered. It has been shown how the difference in solubility of carbon in austenite and ferrite leads to the familiar
ferrite/cementite aggregates in plain carbon steels. This means that, because the solubility of cementite in
austenite is much greater than in ferrite, it is possible to redistribute the cementite by holding the steel in the
austenite region to take it into solution, and then allowing transformation to take place to ferrite and cementite.
Examining the possible alloy carbides, and nitrides, in the same way, shows that all the familiar ones are much
less soluble in austenite than is cementite.
Chromium and molybdenum carbides are not included, but they are substantially more soluble in austenite than
the other carbides. Detailed consideration of such data, together with practical knowledge of alloy steel behavior,
indicates that, for niobium and titanium, concentrations of greater than about 0.25 wt % will form excess alloy
carbides which cannot be dissolved in austenite at the highest solution temperatures. With vanadium the limit is
higher at 1-2%, and with molybdenum up to about 5%. Chromium has a much higher limit before complete
solution of chromium carbide in austenite becomes difficult. This argument assumes that sufficient carbon is
present in the steel to combine with the alloying element. If not, the excess metallic element will go into solid
solution both in the austenite and the ferrite.
In general, the fibrous morphology represents a closer approach to an equilibrium structure so it is more
predominant in steels which have transformed slowly. In contrast, the interphase precipitation and dislocation
nucleated structures occur more readily in rapidly transforming steels, where there is a high driving force, for
example, in microalloyed steels.
The clearest analogy with pearlite is found when the alloy carbide in lath morphology forms nodules in
association with ferrite. These pearlitic nodules are often encountered at temperatures just below Ac1, in steels
which transform relatively slowly.
For example, these structures are obtained in chromium steels with between 4% and 12% chromium and the
crystallography is analogous to that of cementitic pearlite. It is, however, different in detail because of the
different crystal structures of the possible carbides. The structures observed are relatively coarse, but finer than
pearlite formed under equivalent conditions, because of the need for the partition of the alloying element, e.g.
chromium between the carbide and the ferrite. To achieve this, the interlamellar spacing must be substantially
finer than in the equivalent iron-carbon case.
Interphase precipitation. Interphase precipitation has been shown to nucleate periodically at the γ/α interface
during the transformation. The precipitate particles form in bands which are closely parallel to the interface, and
which follow the general direction of the interface even when it changes direction sharply. A further characteristic
is the frequent development of only one of the possible Widmanstätten variants, for example VC plates in a
particular region are all only of one variant of the habit, i.e. that in which the plates are most nearly parallel to the
interface.
The extremely fine scale of this phenomenon in vanadium steels, which also occurs in Ti and Nb steels, is due to
the rapid rate at which the γ/α transformation takes place. At the higher transformation temperatures, the slower
rate of reaction leads to coarser structures. Similarly, if the reaction is slowed down by addition of further alloying
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elements, e.g. Ni and Mn, the precipitate dispersion coarsens.

The scale of the dispersion also varies from steel to steel, being coarsest in chromium, tungsten and
molybdenum steels where the reaction is relatively slow, and much finer in steels in which vanadium, niobium
and titanium are the dominant alloying elements and the transformation is rapid.
Transformation diagrams for alloy steels. The transformation of austenite below the eutectoid temperature can
best be presented in an isothermal transformation diagram, in which the beginning and end of transformation is
plotted as a function of temperature and time. Such curves are known as time-temperature-transformation, or
TTT curves, and form one of the important sources of quantitative information for the heat treatment of steels.
In the simple case of a eutectoid plain carbon steel, the curve is roughly C-shaped with the pearlite reaction
occurring down to the nose of the curve and a little beyond. At lower temperatures bainite and martensite are
formed. The diagrams become more complex for hypo- and hyper-eutectoid alloys as the ferrite or cementite
reactions have also to be represented by additional lines
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Alloying and Its Effects on the Critical Temperature, Hardness

and Tensile Strength
Alloying elements have significant effect on the iron-iron carbide equilibrium diagram. The addition of some of
these alloying elements will widen the temperature range through which austenite (gamma -iron) is stable while
other elements will constrict the temperature range. What this means is that some elements will raise and some
elements will lower the critical temperature of steel.
Manganese, cobalt, and nickel increase the temperature range through which austenite is stable. This also
means that the lower critical temperature of steel will be lowered by these alloying elements. Other alloying
elements that lower the critical temperature of steel are carbon, copper and zinc. The alloying elements that are
used to reduce the critical temperature are highly soluble in the gamma iron (austenite). Figure 1 shows the
effect of manganese on the critical temperature of steel.
Figure 1. The effect of alloying with manganese on the critical temperature of steel and austenite (γ-iron) phase
transformation zone on the iron-iron carbide diagram..
Alloys such as aluminum, chromium, molybdenum, phosphorus, silicon, tungsten tend to form solid solutions
with alpha iron (ferrite). This constricts the temperature region through which gamma iron (austenite) is stable.
As shown in Figure 2, chromium at different percentages constricts the critical temperature range which results
in a marked reduction of the region where austenite is stable.
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Figure 2. Effect of alloying with chromium on the critical temperature of steel and austenite (g -iron) phase
transformation zone on the iron-iron carbide diagram.
The elements shown in Figure 3 have the greatest solubility in ferrite and also influence the hardenability of iron
when in the presence of carbon. With a slight increase in the carbon content, they respond markedly to heat
treating, because carbon acts as a ferrite strengthener. As indicated in Figure 3, Phosphorus will improve the
hardness of the ferrite significantly by adding only a very small percentage of Phosphorus, while Chromium will
not strengthen the ferrite that well even at very high percentage of Chromium addition to the steel
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Figure 3. The effect of various alloying elements on the hardness of steel.
Figure 4 shows the effect of furnace cooling vs. air cooling on the tensile strength of steel for three different
percentages of carbon in the presence of chromium. As this figure indicates, furnace cooling has very little effect
on the tensile strength of the material. The addition of chromium does not change the tensile strength properties
when the steel is cooled in the furnace. If the same steels are air cooled at the same rate, the slope of the curves
increases significantly which means that a slight increase in the chromium content increases the strength
drastically when air cooling is applied.
Figure 4. Effect of different percentages of carbon on the tensile strength of steel in the presence of chromium.
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Control of High Strength Low Alloy (HSLA) Steel Properties
Most HSLA steels are furnished in the as-hot-rolled condition with ferritic-pearlitic microstructure. The exceptions
are the controlled-rolled steels with an acicular ferrite microstructure and the dual-phase steels with martensite
dispersed in a matrix of polygonal ferrite. These two types of HSLA steels use the formation of eutectoid
structures for strengthening, while the ferritic-pearlitic HSLA steels generally require strengthening of the ferrite.
Pearlite is generally an undesirable strengthening agent in structural steels because it reduces impact toughness
and requires higher carbon contents. Moreover, yield strength is largely unaffected by a higher pearlite content.
Strengthening Mechanisms in Ferrite
The ferrite in HSLA steels is typically strengthened by grain refinement, precipitation hardening, and, to a lesser
extent, solid-solution strengthening. Grain refinement is the most desirable strengthening mechanism because it
improves not only strength but also toughness.
Grain refinement is influenced by the complex effects of alloy design and processing methods. For example, the
various methods of grain refinement used in the three different stages of hot rolling (that is, reheating, hot rolling,
and cooling) include:
The addition of titanium or aluminum to retard austenite grain growth when the steel is reheated for hot
deformation or subsequent heat treatment
The controlled rolling of microalloyed steels to condition the austenite so that it transforms into fine-grain ferrite
The use of alloy additions and/or faster cooling rates to lower the austenite-to-ferrite transformation temperature.
The use of higher cooling rates for grain refinement may require consideration of its effect on precipitation
strengthening and the possibility of undesirable transformation products.
Precipitation strengthening occurs from the formation of finely dispersed carbonitrides developed during heating
and cooling. Because precipitation strengthening is generally associated with a reduction in toughness, grain
refinement is often used in conjunction with precipitation strengthening to improve toughness.
Precipitation strengthening is influenced by the type of carbonitride, its grain size, and, of course, the number of
carbonitrides precipitated. The formation of MC is the most effective metal carbide in the precipitation
strengthening of microalloyed niobium, vanadium, and/or titanium steels. The number of fine MC particles
formed during heating and cooling depends on the solubility of the carbides in austenite and on cooling rates.
Steelmaking
Precise steelmaking operations are also essential in controlling the properties and chemistry of HSLA steels.
Optimum property levels depend on such factors as the control of significant alloying elements and the reduction
of impurities and nonmetallic inclusions.
Developments in secondary steelmaking such as desulphurization, vacuum degassing, and argon shrouding
have enabled better control of steel chemistry and the effective use of microalloyed elements. Compositional
limits for HSLA steel grades described in ASTM specifications the use of vacuum degassing equipment allows
the production of interstitial-free (IF) steels. The IF steels exhibit excellent formability, high elongation, and good
deep draw/ability.
Compositions and Alloying Elements
Chemical compositions for the HSLA steels are specified by ASTM standards. The principal function of alloying
elements in these ferrite-pearlite HSLA steels, other than corrosion resistance, is strengthening of the ferrite by
grain refinement, precipitation strengthening, and solid-solution strengthening. Solid-solution strengthening is
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closely related to alloy contents, while grain refinement and precipitation strengthening depend on the complex
effects of alloy design and thermo-mechanical treatment.
Alloying elements are also selected to influence transformation temperatures so that the transformation of
austenite to ferrite and pearlite occurs at a lower temperature during air cooling. This lowering of the
transformation temperature produces a finer-grain transformation product, which is a major source of
strengthening. At the low carbon levels typical of HSLA steels, elements such as silicon, copper, nickel, and
phosphorus are particularly effective for producing fine pearlite. Element such as, manganese and chromium,
which are present in both the cementite and ferrite, also strengthen the ferrite by solid-solution strengthening in
proportion to the amount, dissolved in the ferrite.
In the presence of alloying elements, the practical maximum carbon content at which HSLA steels can be used in
the as-cooled condition is approximately 0.20%. Higher levels of carbon tend to form martensite or bainite in the
microstructure of as-rolled steels, although some of the higher-strength low-alloy steels have carbon contents
that approach 0.30%.
The required strength is developed by the combined effect of:
Fine grain size developed during controlled hot roiling and enhanced by microalloyed elements (especially
niobium)
Precipitation strengthening caused by the presence of vanadium, niobium, and titanium in the composition.
Nitrogen additions to high-strength steels containing vanadium are limited to 0.005% and have become
commercially important because such additions enhance precipitation hardening. The precipitation of vanadium
nitride in vanadium-nitrogen steels also improves grain refinement because it has a lower solubility in austenite
than vanadium carbide.
Manganese is the principal strengthening element in plain carbon high-strength structural steels. It functions
mainly as a mild solid-solution strengthener in ferrite, but it also provides a marked decrease in the
austenite-to-ferrite transformation temperature. In addition, manganese can enhance the precipitation
strengthening of vanadium steels and. to a lesser extent, niobium steels.
One of the most important applications of silicon is its use as a deoxidizer in molten steel. Silicon has a
strengthening effect in low-alloy structural steels. In larger amounts, it increases resistance to scaling at elevated
temperatures. Silicon has a significant effect on yield strength enhancement by solid-solution strengthening and
is widely used in HSLA steels for riveted or bolted structures.
Copper in levels in excess of 0.50% also increases the strength of both low- and medium-carbon steels by virtue
of ferrite strengthening, which is accompanied by only slight decreases in ductility. Copper can be retained in
solid solution even at the slow rate of cooling obtained when large sections are normalized, but it is precipitated
out when the steel is reheated to about 510 to 605°C (950 to 1125°F). At about 1% copper, the yield strength is
increased by about 70 to 140 MPa regardless of the effects of other alloying elements. Copper in amounts up to
0.75% is considered to have only minor adverse effects on notch toughness or weldability. Copper precipitation
hardening gives the steel the ability to be formed extensively and then precipitation hardened as a complex
shape or welded assembly.
The atmospheric-corrosion resistance of steel is increased appreciably by the addition of phosphorus, and when
small amounts of copper are present in the steel, the effect of the phosphorus is greatly enhanced. When both
phosphorus and copper are present, there is a greater beneficial effect on corrosion resistance than the sum of
the effects of the individual elements.
Chromium is often, added with copper to obtain improved atmospheric-corrosion resistance.
Nickel is often added to copper-bearing steels to minimize hot shortness.
Molybdenum in hot-rolled HSLA steels is used primarily to improve hardenability when transformation products
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other than ferrite-pearlite are desired. Molybdenum (0.15 to 0.30%) in microalloyed steels also increases the
solubility of niobium in austenite, thereby enhancing the precipitation of NbC(N) in the ferrite. This increases the
precipitation-strengthening effect of NbC(N).
Aluminum is widely used as a deoxidizer and was the first element used to control austenite grain growth during
reheating. During controlled rolling, niobium and titanium are more effective grain refiners than aluminum.
Vanadium strengthens HSLA steels by both precipitation hardening the ferrite and refining the ferrite grain size.
The precipitation of vanadium carbonitride in ferrite can develop a significant increase in strength that depends
not only on the rolling process used, but also on the base composition. Carbon contents above 0.13 to 0.15%
and manganese content of 1% or more enhances the precipitation hardening, particularly when the nitrogen
content is at least 0.01%.
Titanium is unique among common alloying elements in that it provides both precipitation strengthening and
sulfide shape control. Small amounts of titanium (<0.025%) are also useful in limiting austenite grain growth.
However, it is useful only in fully killed (aluminum deoxidized) steels because of its strong deoxidizing effects, the
versatility of titanium is limited because variations in oxygen, nitrogen, and sulfur affect the contribution of
titanium as carbide strengthened.
Zirconium can also be added to killed high-strength low-alloy steels to improve inclusion characteristics,
particularly in the case of sulfide inclusions, for which changes in inclusion shape improve ductility in transverse
bending.
Boron has no effect on the strength of normal hot-rolled steel but can considerably improve hardenability when
transformation products such as acicular ferrite are desired in low-carbon hot-rolled plate.
Treatment with calcium is preferred for sulfide inclusion shape control.
Controlled Rolling
The hot-rolling process has gradually become a much more closely controlled operation, and controlled rolling is
now being increasingly applied to microalloyed steels with compositions carefully chosen to provide optimum
mechanical properties at room temperature.
Controlled rolling is a procedure whereby the various stages of rolling are temperature controlled, with the
amount of reduction in each pass predetermined and the finishing temperature precisely defined. This
processing is widely used to obtain reliable mechanical properties in steels for pipelines, bridges, offshore
platforms, and many other engineering applications. The use of controlled rolling has resulted in improved
combinations of strength and toughness and further reductions in the carbon content of microalloyed HSLA
steels
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Influence of Alloying Elements on Steel Microstructure
It is a long-standing tradition to discuss the various alloying elements in terms of the properties they confer on
steel. For example, the rule was that Chromium (Cr) makes steel hard whereas Nickel (Ni) and Manganese (Mn)
make it tough. In saying this, one had certain types of steel in mind and transferred the properties of particular
steel to the alloying element that was thought to have the greatest influence on the steel under consideration.
This method of reasoning can give false impressions and the following examples will illustrate this point.
When we say that Cr makes steel hard and wear-resisting we probably associate this with the 2% C, 12% Cr tool
steel grade, which on hardening does in fact become very hard and hard-wearing. But if, on the other hand, we
choose a steel containing 0.10% C and 12% Cr, the hardness obtained on hardening is very modest.
It is quite true that Mn increases steel toughness if we have in mind the 13% manganese steel, so-called
Hadfield steel. In concentrations between l% and 5%, however, Mn can produce a variable effect on the
properties of the steel it is alloyed with. The toughness may either increase or decrease.
A property of great importance is the ability of alloying elements to promote the formation of a certain phase or to
stabilize it. These elements are grouped as austenite-forming, ferrite-forming, carbide-forming and
nitride-forming elements.
Austenite-forming elements
The elements C, Ni and Mn are the most important ones in this group. Sufficiently large amounts of Ni or Mn
render a steel austenitic even at room temperature. An example of this is the so-called Hadfield steel which
contains 13% Mn, 1,2% Cr and l% C. In this steel both the Mn and C take part in stabilizing the austenite.
Another example is austenitic stainless steel containing 18% Cr and 8% Ni.
The equilibrium diagram for iron-nickel, Figure 1, shows how the range of stability of austenite increases with
increasing Ni-content.
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Figure 1. Fe-Ni equilibrium diagram

More diagrams: http://www.calphad.com/phase_diagrams.html
An alloy containing 10% Ni becomes wholly austenitic if heated to 700°C. On cooling, transformation from g to a
takes place in the temperature range 700-300°C.
Ferrite-forming elements
The most important elements in this group are Cr, Si, Mo, W and Al. The range of stability of ferrite in
iron-chromium alloys is shown in Figure 2. Fe-Cr alloys in the solid state containing more than 13% Cr are ferritic
at all temperatures up to incipient melting. Another instance of ferritic steel is one that is used as transformer
sheet material. This is a low-carbon steel containing about 3% Si.
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Figure 2. Cr-Fe equilibrium diagram
Multi-alloyed steels
The great majority of steels contain at least three components. The constitution of such steels can be deduced
from ternary phase diagrams (3 components). The interpretation of these diagrams is relatively difficult and they
are of limited value to people dealing with practical heat treatment since they represent equilibrium conditions
only. Furthermore, since most alloys contain more than three components it is necessary to look for other ways
of assessing the effect produced by the alloying elements on the structural transformations occurring during heat
treatment.
One approach that is quite good is the use of Schaeffler diagrams (see Figure 3). Here the austenite formers are
set out along the ordinate and the ferrite formers along the abscissa. The original diagram contained only Ni and
Cr but the modified diagram includes other elements and gives them coefficients that reduce them to the
equivalents of Ni or Cr respectively. The diagram holds good for the rates of cooling which result from welding.
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Figure 3. Modified Schaeffler diagram

A 12% Cr steel containing 0.3% C is martensitic, the 0.3% C gives the steel a nickel equivalent of 9. An 18/8 steel
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(18% Cr, 8% Ni) is austenitic if it contains 0-0.5% C and 2% Mn. The Ni content of such steels is usually kept
between 9% and 10%.
Hadfield steel with 13% Mn (mentioned above) is austenitic due to its high carbon content. Should this be
reduced to about 0.20% the steel becomes martensitic.
Carbide-forming elements
Several ferrite formers also function as carbide formers. The majority of carbide formers are also ferrite formers
with respect to Fe. The affinity of the elements in the line below for carbon increases from left to right.
Cr, W, Mo, V, Ti, Nb, Ta, Zr.
Some carbides may be referred to as special carbides, i.e. non-iron-containing carbides, such as Cr7C3 W2C,
VC, Mo2C. Double or complex carbides contain both Fe and a carbide-forming element, for example Fe4W2C.
High-speed and hot-work tool steels normally contain three types of carbides, which are usually designated M6C,
M23C6 and MC. The letter M represents collectively all the metal atoms. Thus M6C represents Fe4W2C or
Fe4Mo2C; M23C6 represents Cr23C6 and MC represents VC or V4C3.
Carbide stabilizers
The stability of the carbides is dependent on the presence of other elements in the steel. How stable the carbides
are depends on how the element is partitioned between the cementite and the matrix. The ratio of the
percentage, by weight, of the element contained in each of the two phases is called the partition coefficient K.
The following values are given for K:
Al Cu P Si Co Ni W Mo Mn Cr Ti Nb Ta
0 0 0 0 0.2 0.3 2 8 11,4 28 Increasing
Note that Mn, which by itself is a very weak carbide former, is a relatively potent carbide stabilizer. In practice, Cr
is the alloying element most commonly used as a carbide stabilizer.
Malleable cast iron (i.e. white cast iron that is rendered soft by a graphitizing heat treatment called malleablizing)
must not contain any Cr. Steel containing only Si or Ni is susceptible to graphitization, but this is most simply
prevented by alloying with Cr.
Nitride-forming elements
All carbide formers are also nitride formers. Nitrogen may be introduced into the surface of the steel by nitriding.
By measuring the hardness of various nitrided alloy steels it is possible to investigate the tendency of the
different alloying elements to form hard nitrides or to increase the hardness of the steel by a mechanism known
as precipitation hardening.
The results obtained by such investigations are shown in Figure 4, from which it can be seen that very high
hardnesses result from alloying a steel with Al or Ti in amounts of about 1,5%.
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Figure 4. Effect of alloying element additions on hardness after nitriding Base composition: 0.25% C, 0.30% Si,
0.70% Mn
On nitriding the base material in Figure 4, hardness of about 400 HV is obtained and according to the diagram
the hardness is unchanged if the steel is alloyed with Ni since this element is not a nitride former and hence does
not contribute to any hardness increase
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Martensite in Austenitic Stainless Steel Welds
Background
Martensite is a crystal structure that forms in steels during rapid cooling. Cooling rates are dependent on the
particular chemistry of the steel. Certain conditions can be met that will cause martensite formation in austenitic
stainless steels.
Long, needle-like clusters of crystals in the metal characterize martensite. The martensite crystals have a highly
stressed body centered tetragonal structure. In austenitic stainless steels and the austenite phase of a magnetic
(austenitic/ferritic) stainless, when martensite is present in a weld, don't expect it to pass the bend test. The weld
will not have the toughness and ductility that we normally expect from a stainless steel, and in some
circumstances there may be unanticipated corrosion.
Fillet Composition
With only one exception, adding alloying elements to steel allows martensite to form at a slower cooling rate.
That exception is cobalt, which works the other way. With cobalt, martensite will form at a faster cooling rate.
We recognize that the actual composition of the weld fillet will vary along a line running across or bisecting the
weld fillet. On the centerline, we expect the fillet composition to be closer to the wire composition. Approaching
each base metal, the composition shifts from the filler metal composition towards each base metal. In welding
metallurgy, we mark on the phase diagram the chemistry of one base metal and the chemistry of the filler wire.
We find that the actual fillet compositions lie on the line drawn on the phase diagram. When the base metals are
different, it takes different lines on the phase diagram to represent the compositions approaching each base
metal.
Predicting Martensite
The results and microstructural consequences of this sort of exercise in physical metallurgy appeared in 1949 as
the "Schaeffler Diagram". Our technology did not stand still and the Diagram iterated through several updates.
The 1994 Winter Addendum to the ASME Code brought us the Welding Research Council's "WRC-1992
Diagram" which continues to be extensively used. Still, there has been a problem associated with manganese,
which brought yet another modification into use. The analysis behind the modification appears, for example, in
D.J. Kotecki's, "A martensite boundary on the WRC-1992 diagram" (Welding Journal , Vol. 78, No. 5, pp
180-192).
In lots of cases the 1% manganese line satisfactorily predicts martensite or not martensite. However, we
sometimes encounter steels having higher manganese and quite often encounter much lower. High side
examples include 1.0-1.5% manganese in a 309L filler wire, 4% in a 307, and 6% in the European 18 8 Mn filler
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wire. On the low side, if you are joining stainless to a modern carbon steel, the manganese can be quite low,
perhaps even 0.3%.
(The 1949 Schaeffler diagram - click image to enlarge)
To enter the modified Diagram, we need to calculate two numbers roughly based on chromium and nickel
content. We also have to apply a lot of welding "know-how" as to the mixing of the metals.
Calculate the
Nickel Ni Equivalent = %Ni + 35%C + 20%Mn + 0.25%Cu

Chrome Cr Equivalent = %Cr + Mo + 1.5%Si + 0.7%Nb
The Amount of Nitrogen
One of the problems we have to also confront is the amount of nitrogen. The best shielding practice with a wire
electrode might not introduce nitrogen. Flux cored electrodes tend to add nitrogen. For example, the metal in a
flux cored electrode might analyze to 0.05% nitrogen while it deposits as 0.075% nitrogen. Most of us deal with
the nitrogen by first plotting the points with only the known nitrogen and then we plot the nearby point based on
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our estimate of the actual nitrogen. The compositions at risk are those on the Diagram and below the indicated
manganese brands. Within the bands the diagram is known to be imprecise.
In practice, you have to cope with the range of compositions between one base metal and the filler metal, and
between the other base metal and the filler metal. You could put all of your predicted nickel and chromium
equivalent compositions on the graph. However, examining the diagram we see that the compositions more at
risk for forming martensite are those with low nickel and chromium equivalent numbers, coupled with low
manganese. After a little practice with the diagram we know pretty well which compositions are likely to be at risk
and we tend to plot only those numbers.
A warning: Notice that all of the alloying elements in the calculation contribute to hardenability. Should either
base metal or the filler metal contain any unlisted elements which are known to contribute to hardenability then
the Diagram doesn't apply. After decades of absence, tungsten is showing up mostly as a substitute for
molybdenum and mostly in Russian and Chinese metals. In doing the calculation the practice is to lump the
tungsten with the moly on a 1:1 basis. When forced to do it, welding metallurgists may tweak the calculations a
little to reflect other unlisted elements, however, there isn't much of a research foundation on which to base such
adjustments.
Ferrite Number
The 300 series of stainless steels is austenitic (non-magnetic) while the duplex stainless steels are mixed
austenite and ferrite. In the field, the amount of ferrite is measured through its magnetic response. The portable
meter is calibrated for % ferrite and it is called the "ferrite number". Martensite gives a magnetic response, but
not as strongly as ferrite, so when it is present it contributes to the "ferrite number".
Recognize also that perfectly good austenitic stainless steel that has been heavily cold worked can become
slightly magnetic and give a ferrite number even though ferrite nor martensite are present.
In the upper right side of the diagram there is a cluster of lines of constant ferrite number. The upper left line is
1% ferrite number which is nominally 99% austenite and 1% ferrite. The last line along the lower right side of the
cluster is nominally 98% ferrite and 2% austenite.
Learning by Doing (and "cya")
Good record keeping means photocopying a bunch of diagrams and every time you confront the martensite
issue you make a record of how you calculated the nickel and chromium equivalents. You plot these on the
graph, draw the lines between and estimate an adjustment for nitrogen. You note the ferrite number and whether
the bend test is pass or fail.
You don't just do the exercise for samples that fail the bend test. Otherwise you won't learn the limits for welds
that pass every time! If testing the weld for its ferrite number is worthwhile then making the record is also
worthwhile. The day will come when you note the manganese is low and you make yourself into a hero when you
predict the need for a little preheat.
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(The WRC-1992 Diagram modified to reflect experience with manganese. Martensite is predicted to form with
composition equivalents below and to the left of the manganese bands. Reprinted from Advanced
Materials&Process, June 1000, p. 75 - click image to enlarge)
There will be discrepancies. When it happens it most likely means that you misjudged the effect of cooling rate,
or you didn't get the chemistry right, or the basic diagram is imperfect!
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Effects on the martensite, pearlite and bainite formation
Effect on the temperature of martensite formation
All alloying elements with the possible exception of Co, lower Ms the temperature of the start of the martensite
formation, as well as Mf, the finish of the martensite formation, i.e. at 100% martensite. For the majority of steels
containing more than 0.50% C, Mf lies below room temperature.
This implies that after hardening these steels practically always contain some residual austenite. Ms may be
calculated from the equation given below, by inserting the percentage concentration of each alloying element in
the appropriate term. The equation is valid only if all the alloying elements are completely dissolved in the
austenite.
Ms = 561 - 474C - 33Mn - 17Ni - 17Cr - 21Mo
For high-alloy and medium-alloy steels Stuhlmann has suggested the following equation:
Ms(°C) = 550 - 350C - 40Mn - 20Cr - 10Mo - 17Ni - 8W - 35V - 10Cu + 15Co + 30Al
It can be noted that carbon has the strongest influence on the Ms temperature. Figures 1 and 2 show diagrams
with an example of experimental results of the effect of Mn and Ni on the Ms temperature of various types of
steel.
Figure 1. Effect of Mn on the Ms - temperature (after Russel and McGuire,

Payson and Savage, Zyuzin, Grange and Stewart)
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Figure 2. Effect of Ni on the Ms - temperature (after Russel and McGuire,

Payson and Savage, Zyuzin, Grange and Stewart)
Effect on the formation of pearlite and bainite during the isothermal transformation
All alloying elements except Co delay the formation of ferrite and cementite. It is very difficult to formulate any
general rules regarding the influence exerted by the various alloying elements. However, it has definitely been
found that some elements affect the bainite transformation more than the pearlite transformation, while other
elements act in the opposite manner.
Certain elements will, paradoxically, accelerate the transformations if their concentration increases beyond a
certain limiting value, this limit been affected by other alloying elements present. For case-hardening and tool
steels the time taken to initiate the pearlite-bainite transformation is reduced as the carbon content exceeds
about 1%. For tool steels and constructional steels Si-concentrations of 1,5% and above have been found to
promote pearlite formation.
As a general principle it may be stated that by increasing the concentration of one alloying element by some few
percent and the basic carbon content being kept about 0.50%, only a relatively small retardation of the
transformation rates is noticed. For plain carbon steels a successive increase in C from 0.30% to 1% produces
but a negligible effect. It is only in conjunction with several alloying elements that a more noticeable effect is
produced.
The diagram in Figure 3, applicable to steel W 1 (l% C) will serve as a basis for this discussion. The shortest
transformation time for this steel is less than 1/8th second. Note that the time scale is logarithmic; hence there is
no zero time. As has been mentioned previously, both pearlite and bainite form simultaneously in this steel at
about 550°C. Since the curves overlap it is customary to draw only one curve. With increasing contents of certain
alloying elements, however, the noses of the pearlite and bainite curves will separate.
The structures shown in Figure 3 are obtained by austenitizing samples of steel W 1 at 780°C for 10 min and
quenching in a salt bath at various temperatures. After holding them for predetermined times at various
temperatures they are finally quenched in water. Before the salt-bath quenching the steel contains undissolved
carbides but in view of the composition of the austenite the steel may be regarded as an eutectoid one. The
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diagram should be studied with the aid of the explanatory text below.
Figure 3. TTT diagram for isothermal transformation of steel W 1 (1% C)

A = austenite, B = bainite,
Ms = start of martensite transformation,
M50 = 50% M, P = pearlite
1. Quenching in a liquid bath at 700°C; holding time 4 min. During this interval the C has separated out,
partly as pearlite lamellae and partly as spheroidized cementite. Hardness 225 HV.
2. Quenching to 575°C, holding time 4 s. A very fine, closely spaced pearlite as well as some bainite has
formed. Note that the amount of spheroidized cementite is much less than in the preceding case.
Hardness 380 HV.
3. Quenching to 450°C, holding time 60 s. The structure consists mainly of bainite. Hardness 410 HV.
4. Quenching to 20°C (room temperature). The matrix consists of, roughly, 93% martensite and 7%
retained austenite. There is some 5% cementite as well which has not been included in the matrix figure.
Hardness 850 HV.
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Steel Alloys
Below is a list of some SAE-AISI designations for Steel (the xx in the last two digits indicate the carbon
content in hundredths of a percent)
Carbon Steels
10xx Plain Carbon
11xx Resulfurized
12xx Resulfurized and rephosphorized
Manganese steels
13xx Mn 1.75
Nickel steels
23xx Ni 3.5
25xx Ni 5.0
Nickel Chromium Steels
31xx Ni 1.25 Cr 0.65-0.80
32xx Ni 1.75 Cr 1.07
33xx Ni 3.50 Cr 1.50-1.57
34xx Ni 3.00 Cr 0.77
Chromium Molybdenum
steels
41xx Cr 0.50-0.95 Mo 0.12-0.30
Nickel Chromium
Molybdenum steels
43xx Ni 1.82 Cr 0.50-0.80 Mo 0.25
47xx Ni 1.05 Cr 0.45 Mo 0.20 – 0.35
86xx Ni 0.55 Cr 0.50 Mo 0.20
Nickel Molybdenum
steels
46xx Ni 0.85-1.82 Mo 0.20
48xx Ni 3.50 Mo 0.25
Chromium steels
50xx Cr 0.27- 0.65 Illustration of effect of Carbon content on
51xx Cr 0.80 – 1.05 Steel Hardness
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Carbon Steel to Austenitic Steel
When a weld is made using a filler wire or consumable, there is a mixture in the weld consisting of approximately
20% parent metal and 80% filler metal alloy ( percentage depends on welding process, type of joint and welding
parameters).
Any reduction in alloy content of 304 / 316 type austenitic is likely to cause the formation of martensite on
cooling. This could lead to cracking problems and poor ductility. To avoid this problem an over alloyed filler
metal is used, such as a 309, which should still form austenite on cooling providing dilution is not excessive.
The Shaeffler diagram can be used to determine the type of microstructure that can be expected when a filler
metal and parent metal of differing compositions are mixed together in a weld.
The Shaeffler Diagram
The Nickel and other elements that form Austenite, are plotted against Chrome and other elements that form
ferrite, using the following formula:-
Nickel Equivalent = %Ni + 30%C + 0.5%Mn
Chrome Equivalent = %Cr + Mo + 1.5%Si + 0.5%Nb
Example, a typical 304L = 18.2%Cr, 10.1%Ni, 1.2%Mn, 0.4%Si, 0.02%C
Ni Equiv = 10.1 + 30 x 0.02 + 0.5 x 1.2 = 11.3
Cr Equiv = 18.2 + 0 + 1.5 x 0.4 + 0 = 18.8
A typical 309L welding consumable Ni Equiv = 14.35, Cr Equiv = 24.9
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The main disadvantage with this diagram is that it does not represent Nitrogen, which is a very strong Austenite
former.
Ferrite Number
The ferrite number uses magnetic attraction as a means of measuring the proportion of delta ferrite
present. The ferrite number is plotted on a modified Shaeffler diagram, the Delong Diagram. The Chrome and
Nickel equivalent is the same as that used for the Shaeffler diagram, except that the Nickel equivalent includes
the addition of 30 times the Nitrogen content.
Examples
The Shaeffler diagram above illustrates a carbon steel C.S , welded with 304L filler. Point A represents the
anticipated composition of the weld metal, if it consists of a mixture of filler metal and 25% parent metal. This
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diluted weld, according to the diagram, will contain martensite. This problem can be overcome if a higher
alloyed filler is used, such as a 309L, which has a higher nickel and chrome equivalent that will tend to pull point
A into the austenite region.
If the welds molten pool spans two different metals the process becomes more complicated. First plot both
parent metals on the shaeffler diagram and connect them with a line. If both parent metals are diluted by the
same amount, plot a false point B on the diagram midway between them. (Point B represents the microstructure
of the weld if no filler metal was applied.)
Next, plot the consumable on the diagram, which for this example is a 309L. Draw a line from this point to false
point B and mark a point A along its length equivalent to the total weld dilution. This point will give the
approximate microstructure of the weld metal. The diagram below illustrates 25% total weld dilution at point A,
which predicts a good microstructure of Austenite with a little ferrite.
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The presence of martensite can be detected by subjecting a macro section to a hardness survey, high hardness
levels indicate martensite. Alternatively the weld can be subjected to a bend test ( a side bend is required by the
ASME code for corrosion resistant overlays), any martensite present will tend to cause the test piece to break
rather than bend.
However the presence of martensite is unlikely to cause hydrogen cracking, as any hydrogen evolved during the
welding process will be absorbed by the austenitic filler metal.
More reading:
http://nhml.com/search.cfm?zoom_query=stainless+steel&zoom_per_page=10&zoom_and=0&zoom_sort=0
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Selection of Age-Hardenable Superalloys
By Richard B. Frank
High-Temperature R&D
Carpenter Technology Corp., Reading, PA, USA
Superalloys are high-performance materials designed to provide high mechanical strength and resistance to
surface degradation at high temperatures of 1200°F (650°C) or above. They combine high tensile, creep-rupture,
and fatigue strength; good ductility and toughness, with excellent resistance to oxidation and hot corrosion.
Furthermore, superalloys are designed to retain these properties during long-term exposures at the elevated
temperatures.
This article focuses on the wrought age-hardenable alloys, which are the most commonly used superalloys.
Wrought materials can be formed using hot and cold working operations. Not discussed here are the cast,
powder (P/M), and oxide dispersion strengthened (ODS) superalloys that can also offer enhanced properties.
The first age-hardenable, high-temperature alloy dates back to about 1929 when various developers added
titanium and aluminum to the standard 80% nickel/20% chromium resistance wire alloy. This was a precursor to
the 80A nickel-base superalloy, developed in 1940-1944, but still in use today.
Little was done to advance the original age-hardenable alloys until the time period of 1935-1944 when World
War II spurred demand for improved alloys that could be used in the early aircraft gas turbine engines. Alloy
development activity exploded in the 1950’s and 1960’s to keep pace with the demands of the gas turbine engine
industry. Progress in superalloy development not only made the jet engine possible, but allowed for constantly
increasing thrust-to-weight ratios over the last 60 years.
Applications
The primary application for superalloys is still in hot sections of aircraft gas turbine engines, accounting for over
50% of the weight of advanced engines. However, the excellent performance of these materials at elevated
temperatures has expanded their application far beyond one industry.
In addition to the aerospace industry, these alloys are used in turbine engines for marine, industrial, land-based
power generation, and vehicular applications. Specific engine parts using superalloys include turbine discs,
blades, compressor wheels, shafts, combustor cans, afterburner parts and engine bolts.
Beyond the gas turbine engine industries, superalloys are commonly used for applications in rocket engines,
space, petrochemical/energy production, internal combustion engines, metal forming (hot-working tools and
dies), heat-treating equipment, nuclear power reactors, and coal conversion.
While these alloys are primarily used for service at elevated temperatures above 1000°F (540°C), the
characteristics of high strength and excellent environmental resistance have made some superalloys an
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excellent choice for lower-temperature applications. Examples are prosthetic devices in the medical industry and
components for deep sour gas wells in the oil/gas exploration industry.
Chemical Composition
Table 1 contains the nominal compositions of the most common wrought age-hardenable superalloys. These
alloys contain various combinations of nickel, iron, cobalt, and chromium with lesser amounts of other elements
including molybdenum, niobium, titanium, and aluminum. With minor additions of beneficial elements such as
boron and zirconium, these alloys may contain up to 12 intentional additions. All these additions help to impart
and maintain the desired properties at elevated temperatures.
Many other elements such as silicon, phosphorus, sulfur, oxygen, nitrogen and a larger number of tramp
elements (like lead, bismuth, selenium) must be tightly controlled in superalloys to avoid detrimental effects on
high-temperature properties. These minor and tramp elements are controlled during raw material selection prior
to melting, as well as during the melting/remelting processes.
Superalloys can be classified into nickel-base, iron-base, and cobalt-based groups. Nickel-based superalloys
(>50% Ni) are the most common group. About half of the alloys in Table 1 are considered nickel-base alloys and
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the others contain large additions of nickel. The nickel base has a high tolerance for alloy additions that might
otherwise cause phase instability leading to loss of strength, ductility, and/or environmental resistance.
Iron-based superalloys are less costly, but are less tolerant of alloying additions and typically have lower
mechanical properties and maximum temperature limitations. Examples are Pyromet® Alloy A-286 and NCF
3015 (Ni-30) alloy. These alloys contain an austenitic stainless steel base with additions of nickel, titanium, and
aluminum to promote age hardening. Pyromet Alloy 706 and Pyromet Alloy 901 have similar amounts of nickel
and iron and can be considered nickel-iron-base superalloys. The higher nickel levels of 901 and 706 alloys
allow for larger additions of strengthening elements without undesirable effects.
Although there are some cobalt-base superalloys, they are significantly higher in cost and typically cannot be
age hardened to high strength levels. However, cobalt is an important alloying addition to nickel-based alloys
because it extends the maximum temperature for usage by reducing the solubility of the age-hardening phase.
Waspaloy and Pyromet Alloy 41 and Pyromet Alloy 720 are nickel-base alloys with 10-15% cobalt additions.
These alloys have the highest temperature capability of the common wrought age-hardenable superalloys.
Chromium, usually in the range of 14 to 23 weight percent, is a critical alloying addition to nearly all superalloys.
As in stainless steels, chromium forms a tightly-adherent, protective oxide film (Cr2O3) on the alloy surface to
resist oxidation and corrosion at high temperatures as well as corrosion at lower temperatures. This surface layer
protects the alloy from the harmful effects of the elements oxygen, nitrogen, and sulfur.
Although most superalloys contain at least 14% chromium, in some applications, it is critical to minimize thermal
expansion. Pyromet CTX-909 and Thermo-Span® alloys are considered low-expansion superalloys that have
low chromium contents to minimize expansion of the nickel-cobalt-iron base. Resistance to oxidation and hot
corrosion are reduced so high-temperature coatings are often applied prior to service. Of the two alloys, 909
alloy provides the lowest expansion coefficient while Thermo-Span alloy (5.5% chromium) provides improved
environmental resistance.
Refractory elements like molybdenum, tungsten, and niobium, with their large atomic diameters, increase high
temperature strength and stiffness by straining the nickel/iron base matrix. Alloys 901 and 41 contain larger
additions of molybdenum to increase this solid solution strengthening effect. Other alloying additions such as
chromium and aluminum also contribute to solid solution strengthening but to a lesser extent.
The elements titanium, aluminum, and niobium are added to the nickel or nickel-iron matrix to form an
intermetallic Ni3 (Al, Ti, Nb) phase during age-hardening heat treatments. The resultant gamma prime or gamma
double prime phases are the primary strengthening agents in superalloys. This will be discussed in more detail in
the next section on age-hardening.
Although elements such as boron, zirconium, and magnesium may be added at levels less than 0.1 weight
percent, the beneficial effects can be very potent. These elements segregate to and stabilize grain boundaries,
which significantly improves hot workability, high temperature strength and ductility. Small additions of carbon
also may be added to form carbides that restrict grain growth and grain boundary sliding during high temperature
exposure.
Age-Hardening
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The major strengthening method in superalloys is age-hardening. Yield strength of nickel alloys is typically
increased by a factor of two or three by precipitation of the gamma prime and/or gamma double prime, Ni3 (Al, Ti,
Nb) hardening phase. Although the phase is based on the nickel aluminide (Ni3Al) intermetallic, up to 60% of the
aluminum can be replaced by titanium or niobium, which actually increases strength of the alloy.
The gamma prime phase is rather unique in that its strength actually increases with temperature up to 1200°F
(650°C) and it is relatively ductile and resistant to oxidation. Gamma prime precipitates as very fine spheroidal or
cuboidal particles in the nickel-iron matrix during aging.
While most of the superalloys employ the titanium-rich gamma prime phase for age hardening, a niobium-rich
variant called gamma double prime is the primary strengthening phase in some superalloys such as Pyromet
Alloy 706 and Pyromet Alloy 718. The niobium-rich phase provides higher strength up to 1200°F (650°C) but is
unstable above 1200°F. Thus, 706 and 718 alloys have a lower temperature limit than the alloys strengthened
with the titanium-rich gamma prime phase. Since the gamma double prime reaction is more sluggish, these
alloys also tend to have better hot workability and weldability.
Heat Treatment
Proper heat treatment is critical to achieving the desired level of properties in age-hardenable superalloys.
Typical heat treatments for these alloys are listed in the mechanical property Tables 2 and 3. The initial solution
heat treatment typically dissolves all precipitated phases except for some primary carbide and nitride phases.
The typical range for the wrought age-hardenable superalloys is 1650-2100°F (900-1150°C) for 1 to 4 hours
followed by a rapid air cool or a quench in water, polymer or oil.
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The selection of solution treatment time and temperature varies with the alloy and its phase solvus temperatures,
and also depends on the specific properties that are most important for the intended application. Alloys with
higher hardener contents (Ti, Al, Nb) require higher temperatures to solution any hardener phase that may have
precipitated during hot working or cooling. Best tensile and fatigue properties are typically obtained with lower
solution temperatures that result in a finer grain size. In contrast, better long-term stress-rupture and creep
properties are generally obtained with higher-temperature solution treatments that result in coarser grain size
and lower tensile yield strength. For these reasons, it is common to specify two or more preferred heat
treatments for superalloys.
In some cases, another objective of the solution treatment is to form a desirable distribution of a second phase
such as carbide in Pyromet 41 alloy and delta phase (Ni3Nb) in Pyromet 718 alloy. After solution treatment, one
or more aging treatments are applied to precipitate the hardening phase and possibly other phases in the
desired amount and distribution. As with solution treatment, the selection of aging temperatures is dependent on
the alloy and the combination of properties desired.
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The aging range for age-hardenable superalloys is 1150-1600°F (620-870°C). Aging times range from 4 hours to
24 hours. Double-aging treatments are quite common to maximize strength and to develop the best combination
of short-term tensile and long-term creep-rupture properties. The primary aging treatment precipitates a coarser
distribution of the hardener phase and may also improve the type and distribution of carbides on grain
boundaries.
The secondary age is typically about 200°F below the primary aging temperature, precipitating a finer dispersion
of the gamma prime phase. For some higher-strength applications, the alloy is direct aged after hot, warm, or
cold working without an intermediate solution treatment. The strain from working is used to further enhance
tensile and fatigue properties with some sacrifice in creep-rupture properties.
Mechanical Properties
For the design engineer or materials specifier, a review of terms defining applicable mechanical properties may
be helpful:
Tensile Properties – The design of load-bearing structures is often based on yield strength or, in some cases,
the ultimate tensile strength of the material. Yield strength is a measure of the maximum stress a material can
withstand before it permanently deforms. Tensile strength is a measure of the maximum stress a material can
withstand before it fractures. Elevated temperature tensile properties are most applicable to short-time
exposures at higher temperatures. Creep and stress-rupture properties are more applicable for longer
exposures.
Creep and Rupture Properties – Creep and rupture strengths become important when the material must
withstand the combined effects of high temperature and stress for long periods of time. At elevated temperatures,
metals will stretch or "creep" at stresses well below the yield strength. Superalloys are more resistant to creep
than low-alloy or stainless steels, but creep will still occur above about 1000°F (540°C). Creep properties are a
measure of the alloy’s resistance to stretching under a constant load. Stress-rupture or creep-rupture properties
are a measure of resistance to fracture under a constant load (creep test taken to fracture). Both properties are
expressed as stress or strength values that will cause a given amount of creep (0.1%-1%) or rupture in a given
amount of time (100 to 100,000 hours).
Tables 2 and 3 list typical tensile (yield) and stress-rupture strength properties of the age-hardenable superalloys
at temperatures of 1200-1600°F (650-870°C). Yield strengths at room temperature are also listed in Table 2.
These properties are shown graphically in Figures 1 and 2. It should be noted that the data represents
approximate nominal strength values for specific heat treatments. Actual values can vary by up to 35% due to
differences in composition, hot/cold working practices, and heat treatment.
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For example, superalloys like Pyromet 718 and Waspaloy may contain several different aim compositions within
the broader industry ranges to optimize properties for specific applications. Higher levels of the age-hardening
elements titanium, aluminum, and niobium result in higher strength. Hot or cold working an alloy to obtain a finer
grain size typically increases tensile yield strength but decreases stress-rupture strength.
As discussed previously, properties of all age-hardenable superalloys are dependent on heat treatment. Alloys
like Pyromet Alloy X-750 and Waspaloy have two or more preferred heat treatments (see Table 2) depending on
whether the application requires better short-time tensile and fatigue properties or long-time creep and
stress-rupture properties. Examples of alternative heat treatments have been shown for Waspaloy and X-750
alloys but the reader should refer to manufacturers’ datasheets for a more complete listing of alternative heat
treatments for the other superalloys.
Other Properties – While tensile and creep-rupture are the most basic mechanical properties considered for
high-temperature applications, design criteria may also consider resistance to fatigue (low- and high-cycle),
crack growth, and wear/erosion. Hardness and hot hardness tests are sometimes used as a rough measure of
yield strength and wear/erosion.
Alloy Selection
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A simplified method known as the Carpenter Selectaloy® system can help designers and engineers select the
most suitable superalloy based on strength and maximum temperature requirements. Figures 3 and 4 contain
Selectaloy diagrams for the 15 superalloys discussed in this article. Yield strength (Figure 3) or stress-rupture
strength (Figure 4) increases vertically on the Selectaloy diagram, and temperature increases from left to right.
The alloys are shown multiple times on the diagrams since the alloys are useful over a range of temperatures.
The diagram can be used to estimate how the strength of an alloy decreases with temperature, but also how the
strength of different alloys compare at different temperatures.
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It should be noted that the alloys were positioned on the Selectaloy diagrams based on average strength values
representative of compositions and heat treatments commonly used for each alloy. An alloy’s relative position
could move up or down, left or right, with relatively minor modifications of composition, processing and heat
treatment. Temperature limits should be considered approximate. Therefore, while the Selectaloy diagrams are
useful tools to screen candidate alloys, they are not a substitute for a more detailed evaluation of the critical
properties required for an intended application.
Pyromet A-286 alloy is the most basic age-hardenable superalloy in terms of properties and cost. A-286 provides
the lowest strength levels, but still higher by a factor of two than other non-age-hardenable stainless alloys.
When increased strength or temperature resistance is required, higher nickel alloys are typically preferred. Alloys
with the highest levels of strength and temperature resistance typically contain the highest alloy contents and
significant levels of cobalt. Relative cost of these alloys will be discussed in the next section.
The Selectaloy diagrams presented in this article provide a method to compare basic strength properties and
temperature limitations of common wrought age-hardenable superalloys. However, alloy selection will
undoubtedly depend on many other considerations, including other physical and mechanical properties as well
as environmental resistance and cost. For example, Thermo-Span and Pyromet CTX-909 alloys provide a
benefit of much lower expansion during heating but at the expense of oxidation and corrosion resistance in the
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uncoated condition. Pyromet 31V and Pyromet 751 alloys provide similar strength and temperature resistance,
but the higher chromium content of 31V alloy results in much improved resistance to sulfidation and other forms
of hot corrosion.
Alloy Cost
From the user’s standpoint, alloy selection must be based on expected cost effectiveness.
In today’s competitive global environment, overdesign is less common. The trend is to select the lowest-cost
material to meet design requirements for the application. However, a higher-cost alloy may be justified to
minimize overall life cycle cost or for longer service of certain components in a system that is critical or too
expensive to be shut down for maintenance. Surely, knowledge of alloy capabilities is critical in making the best
decision.
As temperature and strength requirements increase, so does the necessary alloy content. Figure 5 compares the
relative alloying costs of the 14 alloys using Pyromet A-286 alloy as a base (cost factor of 1.0). The cost factors
are based on 10-year averages of the intrinsic alloying element costs at market prices. Higher temperature
strength and resistance typically require higher nickel and cobalt contents. Nickel and cobalt prices have
historically been volatile, with high and low prices varying by a factor of 4 to 5. More recently, the price of
molybdenum, a potent solid solution strengthener, has increased in price by a factor of nearly ten over the last
two years.
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As discussed above, the cost factors in Figure 5 are based only on raw material elemental costs (10-year
averages) that fluctuate significantly with time. Differences in melting, working, and other processing costs,
which can be substantial, are not included in these factors. Processing yields and specific end user requirements
(grain size, ultrasonic testing, etc.) significantly impact product cost. However, the cost comparisons are useful
because alloying costs typically represent a large portion of superalloy product cost. Since superalloys are
designed for high temperature strength and resistance to deformation, processing difficulty and cost also
increase with hot strength and maximum temperature capability.
Figure 6 shows the relationships of stress-rupture strength at 1200-1500°F (650-815°C) with raw material cost
factor. It is apparent that the alloys that provide higher levels of strength, temperature resistance, and/or
specialized properties also cost more, which reinforces the importance of the alloy selection process.
More Technical Article:

http://crswnew.cartech.com/wnew/techarticles/TechLibrarySelector.html
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Metallurgy of Mo in Alloy Steel & Iron
Spherical Agglomerates of Mo powder (lacy appearance), with solid spheres of the Ni-Cr alloy binder for the Mo powder
Molybdenum metal is usually produced by powder metallurgy techniques in which Mo powder is hydrostratically
compacted and sintered at about 2100°C. Hot working is done in the 870-1260°C range. Moly forms a volatile
oxide when heated in air above about 600°C and therefore high temperature applications are limited to
non-oxidizing or vacuum environments.
Moly alloys have excellent strength and mechanical stability at high temperatures (up to 1900°C). Their high
ductility and toughness provide a greater tolerance for imperfections and brittle fracture than ceramics.
High temperature furnace with molybdenum hot zone (Courtesy of PLANSEE AG, Austria)
The unique properties of molybdenum alloys are utilised in many applications:
• High temperature heating elements, radiation shields, extrusions, forging dies, etc;
• Rotating X-ray anodes used in clinical diagnostics;
• Glass melting furnace electrodes and components that are resistant to molten glass;
• Heat sinks with thermal expansivity matching silicon for semiconductor chip mounts;
• Sputtered layers, only Ångstroms (10-7 mm) thick, for gates and interconnects on integrated circuit
chips;
• Sprayed coatings on automotive piston rings and machine components to reduce friction and
improve wear.
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For specialised applications, Mo is alloyed with many other metals:
• Mo-tungsten alloys are noted for exceptional resistance to molten zinc;

• Mo is clad with copper to provide low expansion and high conductivity electronic circuit boards;
• Mo-25% rhenium alloys are used for rocket engine components and liquid metal heat exchangers
which must be ductile at room temperature.
Hardening
The purpose of quenching steel after heating is hardening, i.e. to produce a hardened microstructure over the
full cross section of the workpiece.
A round steel bar quenched in water from a temperature up to 900°C will cool faster near the surface than in the
center (Fig 2 below).
Fig 2: Quenching round bar
Fig 3: Simulating cooling of steel sections
On a laboratory scale this is simulated by the Jominy end quench test (Fig 3 above).
The standard sample is heated and then water quenched on one end. The cooling rate in the sample decreases
from the water sprayed end where it is highest to the opposite end where it is lowest. When the sample is cool,
the surface is ground and the hardness profile is taken. The change of hardness along the sample reflect
variations of the microstructure brought about by the different cooling rates.
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The curves in Fig 4 compare the hardness profile of steels with different alloy contents. The carbon manganese
steel without molybdenum has only been hardened near the quenched end of the sample and the hardness
drops quickly when moving away from the quenched end. With increasing molybdenum content the hard
microstructure is maintained at increasing distances from the quenched end. That means that it is possible to
harden a steel with higher molybdenum content with slower cooling rates: the hardenability is improved.
Fig 4: Jominy hardenability curves: Hardenability improves with increasing Mo content (after W.W. Cias1)
The hardenability indicates the depth, to which a steel grade can be hardened.
In standard Quenched and Tempered Steels a combination of alloying elements is usually used, including
manganese, chromium, molybdenum, nickel and silicon.
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Fig 5: The Hardenability Multiplying Factor shows the rate at which the hardening depth is increased with the percentage of
2
the alloying element (after Honeycombe )
The basis of steel hardening lies in the fact, that iron exists in two crystal structures:
Below 912°C and from 1394°C to its melting point iron is body centered cubic – bcc – called ferrite. In the lower
temperature range ferrite is also referred to as alpha iron, in the higher temperature range as delta iron.
At a temperatures from 912°C to 1394°C iron is in the face centered cubic crystal structure – fcc – called gamma
iron or austenite. Heating pure iron above 912°C transforms the structure from Ferrite into Austenite. Cooling
the iron from the austenitizing area below 912°C results in the original bcc iron structure, no matter what cooling
rate is applied.
Pure iron can not be hardened.
The addition of carbon converts iron into hardenable steel. (Alloying elements such as manganese, molybdenum
and chromium enhance the hardenability).
Carbon is present in iron both in solid solution and in the form of carbides. It is significant that the sides of the
face centered cubes of the austenite are about 25% larger than the sides of the body centered cube of the ferrite.
The solubility for carbon is therefore much greater in austenite than in ferrite.
When a steel with say 0.4% carbon is heated above the ferrite.austenite (alpha-gamma) transformation point,
carbon and the other alloying elements can go into solid solution in the spacious austenitic fcc
structure. Subsequent cooling through the gamma – alpha transformation point leads into the narrow ferrite
structure. There is not enough space in this structure to keep carbon in solid solution.
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So, if the cooling rate is low, carbide is formed in connection with the transformation process. As a result the
microstructure at room temperature consists of ferrite and carbide. (The fine lamellar structure of ferrite and iron
carbide is called pearlite - see Fig 6).
Fig 6: Ferrite – Pearlite microstructure – soft and ductile
Fig 7: Martensite microstructure –hard and brittle
The critical factor is, that there is enough time available for the carbon atoms to move through the lattices to form
carbides, which results in the soft microstructure of ferrite and pearlite.
Increasing the cooling rate progressively reduces the carbide formation. A very high cooling rate is achieved
with water quenching, which completely supresses the carbide formation. In that case carbon is uncomfortably
forced into narrow spaces in the ferrite structure. The microstructure which is generated that way is called
martensite. This is the hardest and most brittle form of steel. (See Fig 7)
In plain carbon steels the high cooling rates required for the formation of martensite are only achieved near the
quenched surface. Inside the work piece the structure remains soft. Water quenching larger sections also
involves the risk of quench cracking.
This is where molybdenum and the other alloying elements enter the scene. Alloying elements slow down the
diffusion of carbon atoms through the iron lattice., which delays the transformation from austenite into
ferrite. The hardenability of the steel is thus improved since martensite can be produced at slower cooling
rates. As shown in Fig 5, molybdenum is very effective in that respect.
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Also, in larger cross sections at intermediate cooling rates a structure called Bainite is formed particularly in Mo
alloyed steel. In that case, some nucleation of carbides has taken place during cooling before the austenite-
ferrite transformation.
In practice, the microstructure of quenched and tempered steel components consists of a combination of
martensite and bainite.
Tempering
Hardened steel must be tempered, i.e. reheated for two reasons:
• Different cooling rates between edge and core of components result in internal stresses, which
must be relieved.
• High hardness martensite and bainite must be softened to avoid brittle cracking.
The improvement of ductility is inevitably accompanied by softening, i.e. a loss of strength. This is very
pronounced with carbon steel. An important function of alloying elements is to delay temper softening.
Through its capability of forming carbides, molybdenum, carefully combined with chromium and vanadium, is
very efficient in delaying the loss of strength during tempering while improving fracture toughness. The resulting
structure, tempered martensite, is very strong with an acceptable level of toughness.
Fig 8 shows the effect of molybdenum on the hardness after tempering of a 0.35% carbon steel. It significantly
delays softening of the steel. At sufficiently high Mo contents the hardness curve may even increase with
increasing tempering temperature. This is known as secondary hardening.
The effect of secondary hardening on tempering is an important function of molybdenum in high speed steels
and in some tool- and die steels.
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Fig 8: Influence of Mo content on temper softening (after E.C. Bain3)
Temper brittleness
Temper embrittlement may occur when steels are slowly cooled after tempering through the temperature range
between 450 and 550°C. This is due to the segregation of impurities such as phosphorus, arsenic, antimony
and tin on the grain boundaries. The molybdenum atom is very large relative to other alloying elements and
impurities. It effectively impedes the migration of those elements and thereby provides resistance to temper
embrittlement.
Fig 9 shows the ductile-to-brittle transition temperature for two steels. This temperature is an indication for the
lower limit of the service temperature without the risk of brittle failure.
If the steels are water quenched after tempering, both steels one without molybdenum and one with 0.15%
molybdenum, have essentially the same ductile to brittle behaviour (transition at approx. -50°C). However, if the
steels are slowly cooled in the furnace after tempering the picture changes. The transition to brittle fracture has
shifted to +25°C for the Cr-steel, while it remained at -50°C for the Cr-Mo steel. The slow cooling rate has not
embrittled the molybdenum containing steel, it is, therefore, less susceptible to temper embrittlement.
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Fig 9: Ductile to brittle transition for two tempered steels, as a function of cooling rate after tempering (after Dunn et al4)
Hydrogen embrittlement and sulphide stress cracking
As outlined above, the strength levels obtained in quenched and tempered steels are based mainly on the high
strength of martensite, a microstructure characterized by a high density of dislocations and high internal
stresses.
Unfortunately, exactly these conditions enhance the diffusion of hydrogen into steel and cause hydrogen
embrittlement. Tempering reduces the internal stresses and the dislocation density of martensite, hence
reduces hydrogen diffusion. However, the strength can be lowered to insufficient levels. Molybdenum is efficient
in mittigating this effect in two ways: through solid solution strengthening and the formation of complex carbides
together with other elements such as chromium and niobium.
In cases, where hydrogen sulphide is the source of the hydrogen the phenomenon is called sulphide stress
cracking (SCC). The capability of molybdenum to provide resistance to sulphide stress cracking has been the
key to the development of a broad range of steel grades used for Oil Country Tubular Goods and in chemical and
petrochemical plants.
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High temperature hydrogen attack
Carbon steel has severe limitations at conditions of hydrogen attack above about 200 C as are common in
processes such as petroleum distilling and catalytic reforming. The hydrogen diffusing into the steel
combines with carbon present to form methane and other products. The result is first decarburization and
subsequently fissuring due to high gas pressure at localized sites.
Fig. 10 below compares the loss of rupture strength of various steels exposed to pressurized hydrogen at 540 C:
• the unalloyed carbon steel has obviously suffered the damage described above, loosing more tha
50 % of it’s original strength after less tha 50 hours exposure,
• additions of 0.5% Mo or 1%Cr-0.5%Mo show a slight improvement, but are not adequate under the
given conditions, whereas
• the alloy content of 2.25%Cr plus 1% Mo provide protection to the extent, that after 500 hours
exposure the original rupture strength of the steel has not deteriorated at all.
Fig. 10: Effect of composition and exposure time on the strength of steels exposed to hydrogen at 63 bar at 540 C. The
5
strength of samples exposed in argon is taken as 100%. (After Nelson )
The positive effect of Cr plus Mo in this context used to be described as carbide forming and is now referred to as
elements lowering grain boundary energy. In any event with suitable selection of Mo and Cr contents the steel
will be resistant to hydrogen attack in respect to decarburization, fissuring and loss of strength (4; page 65ff).
http://www.imoa.info/moly_uses/moly_grade_alloy_steels_irons/hardening.html
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Maraging Steels 马氏体时效钢
Maraging steel Al/maraging steel fibre composite prepared via vacuum diffusion bonding of
plasma sprayed monolayers
Maraging steels are carbon free iron-nickel alloys with additions of cobalt, molybdenum, titanium and
aluminium. The term maraging is derived from the strengthening mechanism, which is transforming the alloy to
martensite with subsequent age hardening. Air cooling the alloy to room temperature from 820°C creates a soft
iron nickel martensite, which contains molybdenum and cobalt in supersaturated solid solution. Tempering at
480°C to 500°C results in strong hardening due to the precipitation of a number of intermetallic phases, including,
nickel-molybdenum, iron-molybdenum and iron-nickel varieties.
Age harden carbon free martensitic steel

Principle alloying element Nickel.
Precipitates hardening
Secondary alloying elements: Mo, Al, Cu, Ti, Ni and Co
Intermetallic precipitates such as Ni3Ti and Ni3Mo on age hardening at about 500°C.
Introduction:
The 18% Ni-maraging steels, which belong to the family of iron-base alloys, are strengthened by a process of
martensitic transformation, followed by age or precipitation hardening. Precipitation hardenable stainless steels
are also in this group. Maraging steels work well in electro-mechanical components where ultra-high strength is
required, along with good dimensional stability during heat treatment. Several desirable properties of maraging
steels are:
The result is steel which:
• Possesses high strength and toughness.

• Allows for easy machining with minimal distortion.
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• Has uniform, predictable shrinkage during heat treatment which results in minimum distortion
• Can be easily nitrided.
• Resists corrosion and crack propagation.
• Superior fracture toughness compared to quenched and tempered steel of similar strength level
• Low carbon content, which precludes decarburization problems
• Section size is an important factor in the hardening process
• Easily fabricated
• Can be finely polished.
• Good weldability.
These factors indicate that maraging steels could be used in applications such as shafts, and substitute for long,
thin, carburized or nitrided parts, and components subject to impact fatigue, such as print hammers or clutches.
Maraging steels (from Martensitic Aging) are iron alloys which are known for possessing superior strength
without losing malleability. The iron base is alloyed principally with a large percentage of nickel to produce a very
specific heat-treatment product. Other alloying elements include molybdenum, aluminum, copper and titanium
and are added to produce intermetallic precipitates. Cobalt is added in percentages up to 12% to accelerate the
precipitation reactions and ensure profuse and uniform precipitates. Maraging steel is essentially free of carbon,
which distinguishes it from most other types of steel. These steels are a special class of low carbon ultra-high
strength steels which derive their strength not from carbon, but from precipitation of inter-metallic compounds.
The principal alloying element is 15 to 25% nickel. Secondary alloying elements are added to produce
intermetallic precipitates, which include cobalt, molybdenum, and titanium. Original development was carried out
on 20 and 25% Ni Nickel steels to which small additions of aluminium Al, titanium Ti, and niobium Nb were made.
The common, non-stainless grades contain 17~19% nickel, 8~12% cobalt, 3~5% molybdenum and 0.2~1.6%
titanium. Stainless grades rely on chromium not only to prevent their rusting, but to augment the hardenability of
the alloy as their nickel content is substantially reduced. This is to ensure they can transform to martensite when
heat-treated, as high chromium, high nickel steels are generally austenitic, and unable to undergo such a
transition.
Maraging steels are hardened by a metallurgical reaction that does not involve carbon. These steels are
strengthened by intermetallic compounds such as Ni3Ti and Ni3Mo that precipitate at about 500°C. These steels
typically have very high nickel, cobalt and molybdenum contents while carbon is essentially an impurity and its
concentration is kept as low as possible in order to minimize the formation of titanium carbide which can
adversely affect mechanical properties.
Ultra-high strengths may be obtained with these steels, and weldability is good. Toughness is superior to all low
alloy carbon steels of similar strength, particularly the low temperature toughness. Although they are expensive,
they are easy to machine and heat treat, so that some economies result in component production.
The common, non-stainless grades contain 17~19% nickel, 8~12% cobalt, 3~5% molybdenum, and 0.2~1.6%
titanium. Stainless grades rely on chromium not only to prevent their rusting, but to augment the hardenability of
the alloy as their nickel content is substantially reduced. This is to ensure they can transform to martensite when
heat treated, as high-chromium, high-nickel steels are generally austenitic, and unable to undergo such a
transition.
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Properties:
Due to the low carbon content maraging steels have good machinability. Prior to aging, they may also be cold
rolled to as much as 80~90% without cracking. Maraging steels offer good weldability, but must be aged
afterward to restore the properties of heat affected zone.
When heat treated the alloy has very little dimensional change, so it is often machined to its final dimensions.
Due to the high alloy content the alloys have a high hardenability. Since ductile FeNi martensites are formed
upon cooling, cracks are non-existent or negligible. They can also be nitrided to increase case hardness. They
can be polished to a fine surface finish. Non-stainless varieties of maraging steels are moderately corrosion
resistant and resist stress corrosion and hydrogen embrittlement. More corrosion protection can be gained by
cadmium plating or phosphating.
Surface markings due to the formation of martensite plates in Fe-Ni single crystals.
The width of the figure corresponds to 4mm of the sample.
• Offer the best available combination of ultra-high yield and tensile strength, ductility and fracture
toughness of any ferrous materials.
• Can retain strength at least up to 350 °C.
• Being a very low-carbon martensite, the structure is soft. Readily machinable. May be cold rolled to as
much as 80 - 90% without cracking before aging treatment. Hot deformation is also possible.
• Possible to finish-machine before aging. Very little dimensional change after aging treatment.
• Parts uniformly harden throughout the entire section because they have high hardenability.
• Exhibit good weldability. Properties of heat affected zone (HAZ) can be restored by a post-weld aging
treatment.
• Since ductile FeNi martensites are formed upon cooling, cracks are non-existent or negligible.
• Can be surface hardened by nitriding.
• Good corrosion, stress corrosion and hydrogen embrittlement characteristics.
• Protection can be provided by cadmium plating or phosphating.
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Heat Treatment:
Annealing.
The steel is first annealed, at approximately 820 °C for 15 to 30 minutes for thin sections and for 1 hour per 25
mm thickness for heavy sections, to ensure formation of a fully austenitized structure. This is followed by air
cooling to room temperature to form a soft, heavily dislocated iron-nickel lath (untwinned) martensite (hence the
"mar-" in mar-aging). Subsequent aging (precipitation hardening) of the more common commercially used alloys
for ~3 hours in 480-500 °C range produces a fine dispersion of Ni3(X,Y) intermetallic phases along dislocations
left by martensitic transformation, where X and Y are solute elements added for such precipitation, eg; Mo, Ti, Al,
Cu, Si. Newer compositions of maraging steels have revealed other intermetallic stoichiometries and
crystallographic relationships with the parent martensite, including rhombohedral and massive complex
Ni50(X,Y,Z)50 - usually simplified to Ni50M50. Overaging leads to a reduction in stability of the primary, metastable,
coherent precipitates, leading to their dissolution and replacement with semi-coherent Laves phases such as
Fe2Ni/Fe2Mo. Further excessive heat-treatment brings about the decomposition of the martensite and reversion
to austenite.
Tempering:
Maraging steels are carbonless Fe-Ni alloys additionally alloyed with cobalt, molybdenum, titanium and some
other elements. A typical example is an iron alloy with 17-19% Ni, 7-9% Co, 4.5-5% Mo and 0.6-0.9% Ti. Alloys
of this type are hardened to martensite and then tempered at 480°C~500°C. The tempering results in strong
precipitation hardening owing to the precipitation of intermetallic from the martensite, which is supersaturated
with the alloying elements. By analogy with the precipitation hardening in aluminum, copper and other
non-ferrous alloys, this process has been termed ageing, and since the initial structure is martensite, the steels
have been called maraging.
The structure of commercial maraging steels at the stage of maximum hardening can contain partially coherent
precipitates of intermediate metastable phases Ni3Mo and Ni3Ti. Of special practical value is the fact that
particles of intermediate intermetallic in maraging steels are extremely disperse, which is mainly due to their
precipitation at dislocations.
The structure of maraging steels has a high density of dislocations, which appear on martensitic rearrangement
of the lattice. In lath (untwined) martensite, the density of dislocations is of an order of 1011-1012 cm-2, i.e. the
same as in a strongly strain-hardened metal. In that respect the substructure of maraging steel (as hardened)
differs appreciably from that of aluminum, copper and other alloys which can be quenched without polymorphic
change. (Polymorphism (materials science), the ability of a solid material to exist in more than one form or crystal structure)
It is assumed that the precipitation of intermediate phases on tempering of maraging steels is preceded with
segregation of atoms of alloying elements at dislocations. The atmospheres formed at dislocations serve as
centers for the subsequent concentration stratification of the martensite, which is supersaturated with alloying
elements.
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In maraging steels the dislocation structure that forms in the course of martensitic transformation, is very stable
during the subsequent heating and practically remains unchanged at the optimum temperatures of tempering
(480°C -500°C). Such a high density of dislocations during the whole course of tempering may be due to an
appreciable extent, to dislocation pinning by disperse precipitates.
A long holding in tempering at a higher temperature (550°C or more) may coarsen the precipitates and increase
the inter particle spacing, with the dislocation density being simultaneously reduced. With a long holding time,
semi coherent precipitates of intermediate intermetallic are replaced with coarser incoherent precipitates of
stable phases such as Fe2Ni or Fe2Mo.
At increased temperatures of tempering (above 500°C), maraging steels may undergo the reverse martensitic
transformation, since the as point is very close to the optimum temperatures of tempering. The formation of
austenite is then accompanied with the dissolution of the intermetallic that has precipitated from the
gamma-phase.
Application:
Maraging steel's strength and malleability in the pre-aged stage allows it to be formed into thinner rocket and
missile skins, allowing more room for payload while still possessing sufficient strength for the application.
Maraging steels have very stable microstructural properties, and even after overaging due to excessive
temperature only soften very sluggishly. These alloys retain their properties at mildly elevated operating
temperatures and have maximum service temperatures of over 400 °C. They are suited to engine component
applications such as crankshafts and gears, that work at 'warm' temperatures, and the firing pins of automatic
weapons that cycle from hot to cool repeatedly while under substantial loads and impacts. Their uniform
expansion and easy machinability, carried out before aging makes maraging steel useful in high wear portions of
assembly lines, as well as in the manufacture of dies. Other ultra-high strength steels, such as the secondary
hardening 'Aermet©' family are not so amenable to processing because of their ever-present carbide particle
dispersion.
In the sport of fencing, testing has shown that the blade breakage patterns in carbon steel and maraging steel
blades are identical. Maraging blades are required in foil and épée (there is no such requirement for sabre
blades) because the crack propagation in maraging steel is 10 times slower than in carbon steel. This results in
less blade breakage and fewer injuries.
Stainless maraging steels have been used in golf club heads and in surgical components and hypodermic
syringes. They are not suitable for scalpel blades, as their virtually zero carbon content prevents holding a good
cutting edge.
Maraging steel is also an item of great interest to those responsible for national security. Maraging steel is used
in creating gas centrifuges for uranium enrichment due to its extremely high strength and balance. Very few other
materials will work for this task, and maraging steel’s other uses are very specialized. Nations importing
maraging steel often find themselves receiving a great deal of attention.
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Physical Properties:
• Density: 8.1 g/cm³ (0.29 lb/in³)

• Specific heat, mean for 0–100 °C (32–212 °F): 813 J/(kg·K) (0.108 Btu/(lb·°F))
• Melting point: 2575 °F, 1413 °C, 1686 K
• Thermal conductivity: 25.5 W/(m·K)
• Mean Coefficient of Thermal Expansion: 11.3×10-6
• Yield tensile strength: typically 1400-2100 MPa (200,000-300,000 PSI)
• Ultimate strength: typically 1600-2500 MPa (230,000-360,000 PSI). Grades exist up to 3.5 GPa
(500,000 PSI)
• Elongation at break: up to 15%
• KIC fracture toughness: up to 175MPam½
• Young's modulus: 195 GPa
• Shear modulus: 77 GPa
• Bulk modulus: 140 GPa
Variation of Properties:
The dependence of mechanical properties of maraging steels on the temperature of tempering is of the same
pattern as that for all precipitation-hardenable alloys, i.e. the strength properties increase to a maximum, after
which softening takes place. By analogy with ageing, the stages of hardening and softening tempering may be
separated in the process.
The hardening effect is caused by the formation of segregates at dislocations and, what is most important, by the
formation of partially coherent precipitates of intermediate phases of the type Ni3Ti or Ni3Mo. The softening is
due, in the first place, to replacement of disperse precipitates having greater inter particle spacing and, in the
second place, to the reverse martensitic transformation which is accompanied by the dissolution of intermetallic
in the austenite.
The ultimate strength of maraging steels increases on tempering roughly by 80% and the yield limit, by 140%, i.e.
the relative gain in strength properties is not greater than in typical age-hardening alloys, such as beryllium
bronze or aluminum alloy Grade 1915, but the absolute values of ultimate and yield strength on tempering of
maraging steels reach record figures among all precipitation hardening alloys. This is mainly due to the fact that
maraging steels have a very high strength (Rm = 1100 MPa) in the initial (as-hardened) state.
The high strength of maraging steels on tempering at 480-500 ‹C for 1-3 hours may be explained by the
precipitation of very disperse semi coherent particles of the size and inter particle spacing of an order of 103 nm
in the strong matrix, these intermetallic precipitates also possessing a high strength. Thus, with the same
disparity of precipitates as that of G. P. zones in precipitation, hardening non-ferrous alloys, maraging steels
possess an appreciably higher ultimate strength (Rm = 1800-2000 MPa).
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As compared with martensite-hardenable carbon-containing steels, carbonless maraging steels show, for the
same strength, a substantially greater resistance to brittle fracture, which is their most remarkable merit. On
tempering to the maximum strength, the ductility indices and impact toughness, though diminish somewhat, still
remain rather high. The high ductility of the carbonless matrix and the high disparity of uniformly distributed
intermetallic precipitates are responsible for a very high resistance to cracking, which is the most valuable
property of modern high-strength structural materials.
The properties of maraging steels clearly indicate that these steels have many potential applications in
mechanical components of electro-mechanical data processing machines. Use of these steels in shafts that
require good dimensional control following heat treatment should be pursued for two reasons. First, maintaining
dimensions should be easier because quenching and tempering are not necessary. Second, wear data indicate
that equivalent or better wear resistance is obtained from the maraging steel than from the more commonly used
shaft materials.
Impact-fatigue strength of 18% Ni-maraging steels indicates that these steels could be used in repeated impact
loading situations. The good fracture toughness, compared to that of quenched and tempered alloy steels at the
same strength level, indicates possible use in high-impact low-cycle load applications.
Finally, due to the relatively low temperature of aging, the use of the maraging steels for long, thin parts should
be considered. Here, their use as a replacement for some case hardened or nitrided components is indicated
that the potential application should be carefully studied.
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Table 1 summarizes the alloy content of the 18% nickel – cobalt - molybdenum family as developed by Inco in
the late 1950s.
Maraging Steels
Yield Strength % Alloy content
Type (0,2% proof stress)
Ni Co Mo Ti Al
(MPa)
18Ni1400 1400 18 8.5 3 0.2 0.1
18Ni1700 1700 18 8 5 0.4 0.1
18Ni1900 1900 18 9 5 0.6 0.1
18Ni2400 2400 17.5 12.5 3.75 1.8 0.15
17Ni1600 (cast) 1600 17 10 4.6 0.3 0.05
Table 1: Summary of the alloy content of the 18% nickel – cobalt - molybdenum family
With yield strength between 1400 and 2400 MPa maraging steels belong to the category of ultra-high-strength
materials. The high strength is combined with excellent toughness properties and weldability.
Typical applications areas include:
• aerospace, e.g. undercarriage parts and wing fittings,

• tooling & machinery , e.g. extrusion press rams and mandrels in tube production, gears
• Ordnance components and fasteners.
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Maraging 250
Maraging 250 is an 18 percent nickel steel that has been strengthened with cobalt. Maraging 250, like all
maraging steels, goes through an aging process that forces the metal to cool from its molten state to its
solid state over an artificially long time. This process results in a tempered steel that has both high levels of
strength and hardness. It will also resist certain stresses and maintain its structure in environments that
would cause irreparable changes to many other steels.
The properties that make Maraging 250 particularly appealing to many industries is its workability. This
allows Maraging 250 to be more versatile than many other alloys in its class. However, it is still the alloy's
strength and resistance to extreme temperatures that make it a truly effective material in a wide range of
atmospheres. After Maraging 250 has undergone heat treatment, it demonstrates excellent mechanical
properties. It will reach a yield strength of 240 ksi and a fracture toughness of 75 kic. These properties have
made Maraging 250 effective in the construction of missile and rocket motor cases, landing and takeoff gear,
and high-performance shafting.
Alloy Steels Maraging 250

Related Metals: VascoMax 250(tm)
Specifications: DIN 1.6358
Chemistry Data
Aluminum
Boron
Carbon 0.03 max
Cobalt
Iron Balance
Manganese 0.1 max
Molybdenum
Nickel
Phosphorus 0.01 max
Silicon 0.1 max
Sulphur 0.01 max
Titanium
Zirconium
Physical Data
Density (lb / cu. in.) 0.289
Maraging Alloy 250 - Age Hardenable (Maraging) Iron-Nickel Steel from Super Alloys
http://www.azom.com/Details.asp?ArticleID=4368
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Maraging 300
Maraging 300 is an iron-nickel steel alloy that, as with all maraging steels, exhibits high levels of strength
and hardness. However, Maraging 300 also possesses an extreme resistance to crack propagation, even in
the most extreme environments. Maraging 300 is often used in applications where high fracture toughness
is required or where dimensional changes have to remain at a minimal level.
The unique properties of Maraging 300 have made it a integral part of the aircraft and aerospace industries.
It is often used in rocket motor casings and the landing gear for certain planes. Maraging 300 is also
effective in the design of power shafts and low-temperature cooling systems.
Alloy Steels Maraging 300

Specifications
The following specifications cover Alloy Steels Maraging 300: DIN 1.6354
Property Results Related Metals: VascoMax 300 (tm)
Chemistry Data
Carbon : 0.03 max
Iron : Balance
Manganese : 0.1 max
Phosphorus : 0.01 max
Silicon : 0.1 max
Sulphur : 0.01 max
Principal Design Features：

Maraging 300 alloy is a very high strength iron base, nickel , molybdenum, cobalt alloy. It may be age hardened to a strength
level of 300 ksi ultimate with a hardness on the order of Rockwell C 53.
Applications：
Used for very high strength structural applications such as aircraft land gear components.
Machinability：
Machinability is good, similar to that for 304 stainless steel.
Forming：
Maraging 300 steel has good ductility and is readily formed by conventional methods.
Welding：
The alloy is weldable by conventional methods, much the same as for 304 stainless steel.
Heat Treatment：
Maraging steel is not heat treatable for hardening except by aging. See "Aging".
Forging：
The alloy may be forged as for stainless 304 alloy.
Hot Working：
Hot working of maraging steel may be done at temperatures in the 500 to 200 F range. Prolonged exposure at these
temperatures may result in some age hardening. However a full aging treatment should be given.
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Cold Working：
The alloy is readily cold worked by conventional methods.
Annealing：
Annealing, if required after cold working, can be done at 1900 F followed by rapid air cooling.
Aging：
The high strength and hardness properties are a result of an aging heat treatment at 900 F
Tempering：
Not applicable to this alloy.
Hardening：
Maraging 300 hardens by cold working and by aging - see "Aging".
Physical Data
Density (lb / cu. in.) 0.289
Specific Gravity 8
Specific Heat (Btu/lb/Deg F - [32-212 Deg F]) 0.108
Melting Point (Deg F) 2575
Thermal Conductivity 136
Mean Coeff Thermal Expansion 5.6
Modulus of Elasticity Tension 27.5
More technical information:

http://www.suppliersonline.com/buy/exchange/post/ChooseGradeTokens.asp?Tokens=maraging
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Maraging 350
Maraging refers to a crystalline tempered steel, Martensite, that is created through an aging process. When
aging is used, steel is forced to cool from its molten state to its solid state over a prolonged period of time.
The result is a metal that is harder and stronger than it would be had the steel been allowed to cool at a
natural rate.
Maraging 350 is an alloy that has become an integral material in the airplane and aerospace industries.
Due to its strength and its ability to withstand extreme conditions including frequent and sudden changes in
speed and temperature, Maraging 350 is used in the production of rocket motor cases, takeoff and landing
gear, and certain munitions created by defense companies. Maraging 350 also has uses in less drastic
applications such as die casting and high-performance shafting.
Maraging 362
Maraging materials are known for their exceptional strength and hardness. Their ability to resist various
forms of stress in extreme environments has made maraging steels commonplace in the aerospace and
aircraft industries. Each maraging alloy has its own unique qualities, but many of them are used in similar
applications.
Maraging 362, like other maraging steels, undergoes an artificial aging process. This process leads to the
material's added strength and hardness. The results of the aging procedure has recently caught the eye of
golf club designers and manufacturers who have begun to use maraging alloys on the faces of their clubs in
the hope that players will see increased power and that clubs will not corrode over time.
Maraging Steel
Maraging steel gives you an elevated level of strength, hardness, and ductility. These steels are created
through an aging process that results in the development of a hard, brittle crystalline called martensite. The
term "maraging" is, in fact, a simple combination of martensite and aging.
The construction of maraging steel allows it to withstand atmospheres that would quite simply destroy most
standard steel. The aging process instills maraging steel with the ability to withstand sudden changes in
speed and temperature, even at extreme levels. This quality has made maraging steel alloys an important
component of many of the air and spacecraft used today.
Its specific use in military programs and space programs has made maraging steel a rather unique material.
It is not generally carried by small-scale metals companies. Instead, it can be found through distributors
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who regularly work with organizations in the aerospace and aeronautical industries. A metals company that
has the capacity to supply maraging steel will usually distribute a wide range of hard-to-find alloys.
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The Periodic Table:
The Atomic Radii:
In specifying values for the radius of an atom, one must keep in mind the fact that atoms are not hard spheres,
and the electron distribution in the outer part of the atom does not have a sharp cutoff radius. You could
characterize the radius of the atom as a limiting radius where a certain percentage of the electron charge will be
found. The illustration above is a plot of "covalent radii" (from Ebbing) which are determined by measuring the
bond lengths in the molecules of chemical compounds. Another way to determine characteristic radii is to
measure ionic radii in crystals using x-ray diffraction. If the crystalline composition is such that the ions can be
considered to be in contact with each other, and you can determine the lattice spacing from x-ray diffraction, then
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you can imply the ionic radius. As might be expected, the ionic radius of negative ions is slightly larger than the
covalent radius since they have extra electronic charge, and that of positive ions is slightly smaller.
Atoms and Nuclei

http://www.practicalphysics.org/go/Topic_40.html?topic_id=40
Schaeffler diagram.
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Precipitation hardening stainless steels
Precipitation hardening stainless steels like the martensitic types, can be strengthened by heat treatment.
The mechanism is metallurgically different to the process in the martensitic types. This means that either
martensitic or austenitic precipitation hardening structures can be produced. This family of stainless alloys
utilizes a thermal treatment to intentionally precipitate phases, which cause a strengthening of the alloy. The
principle of precipitation hardening is that a supercooled solid solution changes its metallurgical structure on
aging. The advantage is that products can be fabricated in the annealed condition and then strengthened by
a relatively low temperature treatment, minimizing the problems associated with high temperature treatment.
Precipitation hardening stainless steel has high strength and relatively good ductility and corrosion
resistance at high temperature. They reach these high strengths by precipitation of intermetallic compounds
Alloy 17-4PH
Sandmeyer Steel Company stocks a large inventory of 17-4PH stainless steel plate in the annealed
condition in thicknesses from 3/16" through 3", ready to be processed and shipped to your specific
requirements.
Alloy 17-4PH is a precipitation hardening martensitic stainless steel with Cu and Nb/Cb additions. The grade
combines high strength, hardness (up to 572°F /300°C), and corrosion resistance. Mechanical properties
can be optimized with heat treatment. Very high yield strength up to 1100-1300 MPa (160-190 ksi) can be
achieved.
17-4PH (UNS S17400)

A 17Cr-4Ni-3Cu Precipitation Hardening Martensitic Stainless Steel
General Properties
Applications
Standards
Corrosion Resistance
Chemical Analysis
Physical Properties
Heat Treatment
Processing
Welding
Machining
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General Properties
Alloy 17-4 PH is a precipitation hardening martensitic stainless steel with Cu and Nb/Cb additions. The grade
combines high strength, hardness (up to 572°F / 300°C), and corrosion resistance.
Mechanical properties can be optimized with heat treatment. Very high yield strength up to 1100-1300 MPa
(160-190 ksi) can be achieved.
The grade should not be used at temperatures above 572°F (300°C) or at very low temperatures. It has
adequate resistance to atmospheric corrosion or in diluted acids or salts where its corrosion resistance is
equivalent to Alloy 304 or 430.
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Applications
• Offshore (foils, helicopter deck platforms, etc.)

• Food industry
• Pulp and paper industry
• Aerospace (turbine blades, etc.)
• Mechanical components
• Nuclear waste casks
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Standards
ASTM.....................A693 grade 630 (AMS 5604B) UNS S17400
EURONORM...........1.4542 X5CrNiCuNb 16-4
AFNOR...................Z5 CNU 17-4PH
DIN.........................1.4542
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Corrosion Resistance
Alloy 17-4 PH withstands corrosive attacks better than any of the standard hardenable stainless steels and is
comparable to Alloy 304 in most media.
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If there are potential risks of stress corrosion cracking, the higher aging temperatures then must be selected
over 1022°F (550°C), preferably 1094°F (590°C). 1022°F (550°C) is the optimum tempering temperature in
chloride media.
1094°F (590°C) is the optimum tempering temperature in H2S media.
The alloy is subject to crevice or pitting attack if exposed to stagnant seawater for any length of time.
It is corrosion resistant in some chemical, petroleum, paper, dairy and food processing industries (equivalent
to 304L grade).
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Chemical Analysis
Typical values (Weight %)
C Cr Ni Cu Nb/Cb Mn
0.04 16.5 4.5 3.3 0.3 0.7
PREN (%Cr+3.3%Mo+16%N) ≥17
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Room temperature properties (longitudinal direction)
Guaranteed values (ASTM A693 hot rolled plates); thickness from 3/16" up to 3".
YS 0.2% UTS YS 0.2% UTS

Heat El%
N/mm N/mm ksi ksi
treatment
Min. Typ. Min. Typ. Min. Typ. Min. Typ. Min. Typ.
A 1070 1207 1170 1310 155 175 170 190 8 14
B 790 931 965 1034 115 135 140 150 10 17
A: hardening 925°F (496°C) - 4 hours - air cooling

B: hardening 1100°F (593°C) - 4 hours - air cooling
2 examples of heat treatments that may be applied.
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Elevated temperature properties

Minimum guaranteed values following EN 10088 hot rolled plates. The EN guaranteed values are valid for a
thickness from 3/16" up to 3".
Temperature °F 212 302 392 482 572

Temperature °C 100 150 200 250 300
YS N/mm_ 730 710 690 670 650

0.2%
ksi 106 103 100 97 95
Heat treatment : hardening 1094°F (590°C) - 4 hours - air cooling. 1 example of heat treatments that may be
applied.
Minimum guaranteed room temperature impact values
Minimum guaranteed values following ASTM A693 hot rolled plates. The ASTM guaranteed values are valid
for a thickness from 3/16" up to 3".
KV transverse
Heat treatment
J ft.lbf
Hardening 1100°F (593°C) - 4

20 15
hours - air cooling
Minimum guaranteed room temperature hardness values
Minimum guaranteed values following ASTM A693 hot rolled plates. The ASTM guaranteed values are valid
for a thickness from 3/16" up to 3".
Hardness
Heat treatment
Rockwell Brinell
Hardening 925°F (496°C) - 4

C38 375
hours - air cooling
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Physical Properties
Density: 7800 kg/m3 (.28 lbs/in3)
Following physical properties have been obtained after hardening 896°F (480°C) – 1 hour - air cooling.
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Interval Thermal Thermal Young

Temperature expansion °C °F conductivity modulus
-6 -1 -1 -1
°C 　x10 °C (w.m .K ) (GPa)
0-100 10.8 20 68 14 197
0-200 11 100 212 16 193
0-300 11.3 200 392 18.5 186
0-400 11.6 300 572 20 180
0-500 12 400 752 22 175
500 932 23 170
Room temperature properties:

Resistivity : 80 µ*.cm
Specific heat : 460 J.kg-1.K-1
Tension modulus : 77 GPa
The alloy is magnetic.
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Heat Treatment
Martensitic transformation
Indicative values
Ms : 266°F (130°C)
Mf : 86°F (30°C)
Solution annealing
1925°F+ /-50°F (1050°C +/-25°C) – 30 min up to 1 hour.
air cooling / oil quenching below 76°F (25°C)
Aging / Tempering
The highest mechanical properties are obtained with the following heat treatment : 896°F (480°C) – 1 hour –
air cooling. Higher ductilities are obtained when using higher aging temperatures up to 1148°F (620°C).
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Hardness/Temperature tempered for 4 hours after austenitizing at 1904°F (1040°C) for 30 min quenched
212°F/sec (100°C/sec).
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Processing
Hot Forming
Hot forming should be carried out in a temperature range of 1742-2192°F (950-1200°C). A full heat
treatment including solution annealing, cooling lower than 76°F (25°C) and aging at the required temperature
must be made after hot forming (function of the requested mechanical properties).
Cold Forming
Cold forming can be performed only to a limited extent and only on plates in the fully softened condition.
Stress corrosion resistance is improved by re-aging at the precipitation hardening temperature after cold
working.
The following processes may be performed: rolling, bending, hydroforming, etc. (fully softened conditions).
Cutting
Thermal cutting (plasma, thermal sawing, etc.). Due to the HAZ, the grade requires a suited cutting process.
After cutting, grinding is necessary to eliminate the oxide formed layer.
Mechanical cutting (shearing, stamping, cold sawing, etc).
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Welding
Alloy 17-4 PH can be welded by the following welding processes: SMAW, GTAW, PAW and GMAW. SAW
should not be used without preliminary testing (to check freedom of cracks and toughness of the weld metal).
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Due to a ferrite delta primary type of solidification, the hot cracking risk of the weld metal or the HAZ is
reduced.
Generally, no preheating must be done and interpass temperature must be limited to 248°F (120°C). The
better toughness is obtained in the weld after a complete heat treatment (solution annealing + precipitation
hardening).
Due to the martensitic microstructure, a low oxygen content in the weld metal is preferable to increase
ductility and toughness. To avoid cold cracking, the introduction of hydrogen in the weld must be limited.
Alloy 17-4 PH can be welded with homogeneous filler metals such as E 630 (AWS A5.4) electrodes and ER
630 (AWS A5.9) wires.
Austenitic filler material can be used when the mechanical properties of 17-4 PH steel are not required in the
weld and, in this case, no post-weld heat treatment must be applied.
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Machining
Alloy 17-4 PH can be machined in both solution treated and precipitation hardened conditions. Machining
condition may vary according to the hardness of the material. High speed steel tools or preferably carbide tools
with standard lubrification are normally used. If very stringent tolerances are required, it is necessary to take into
account the dimensional changes during heat treatment.
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Thermal Processing of Metal:
http://www.tntech.edu/me/courses/Zhang/ME30103110/Chap11pt3.ppt
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Online reading materials:
Ductile Iron Tutorial

http://www.ductile.org/didata/Section2/2intro.htm
Alloys and Stainless Steels
http://www.roymech.co.uk/Useful_Tables/Matter/Alloy_Steels.html
Metallurgical Engineering
http://www.sut.ac.th/Engineering/Metal/course.html
Matters
http://www.matter.org.uk/steelmatter/metallurgy/default.htm
Microplasticity: dislocations and strengthening mechanisms
http://www-sgrgroup.materials.ox.ac.uk/lectures/microplasticity.html
Steel Heat Treatment: Metallurgy and Technologies
http://www.ebookee.com.cn/Steel-Heat-Treatment-Metallurgy-and-Technologies_148046.html
Metallurgy fundamentals.
http://rapidshare.com/files/9027049/Metallurgy_Fundamentals_Warner_Brandt.djvu.html
Solid-State Phase Transformations in Steels
http://upload.sms.csx.cam.ac.uk/collection/19
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Stainless Steel Data.

http://www.sandmeyersteel.com/precipitation-hardening.html
Stainless Steel grades data.
http://www.bssa.org.uk/topics.php?article=59
Materials and Processes in Manufacturing
http://www.tntech.edu/me/courses/Zhang/ME30103110/
Engineering Materials and physical metallurgy.
DEFORMATION-MECHANISM MAPS The Plasticity and Creep of Metals and Ceramics
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Additional Reading
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More reading:
Applied Metallurgy
http://www.esdep.org/members/master/wg02/toc.htm
Steels
http://www.key-to-steel.com/default.aspx?ID=Articles&LN=EN
Material Property Search
http://www.matweb.com/search/QuickText.aspx?SearchText=4140
http://www.matter.org.uk/default.htm
The Alloying Elements in Steel, by Edgar C. Bain
http://www.msm.cam.ac.uk/phase-trans/2004/Bain.Alloying/ecbain.html
Material Science Course

http://info.lu.farmingdale.edu/depts/met/met205/index.html
http://www.cs.slcc.edu/engr/moore/mse/mse2010.html
Now you can perform virtual tensile testing.

http://www.uow.edu.au/cedir/progservs/samples/anim_ENGG153/intro.swf
Articles on steel making and inclusions:

Steel making: http://www.sigi.ca/engineering/documents/steel_making.pdf
Effects of deoxidation practice on the inclusion formation:
http://www.ferroforsk.com/ekstern/publications/mikron/PaperStockholm2000.pdf
Slag inclusion formation during solidification:
http://www.diva-portal.org/diva/getDocument?urn_nbn_se_kth_diva-4371-2__fulltext.pdf
Introduction to materials and processes:
http://www.ndt-ed.org/EducationResources/CommunityCollege/Materials/cc_mat_index.htm
Appendix A.
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Chapter1: http://www.cs.slcc.edu/engr/moore/mse/lectures/chapter1_files/frame.htm
All Chapters: http://www.cs.slcc.edu/engr/moore/mse/lectures/
http://mc-mjnde.ornl.gov/Babu/Teaching/Brazil/PTFolder/SolidFol/sld001.htm
Appendix A.
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Ahindra Ghosh, "Secondary Steelmaking: Principles and Applications"

CRC; 1 edition (December 13, 2000) | ISBN: 0849302641 | 344 pages | PDF | 17 Mb
well as modify harmful nonmetallic inclusions and achieve the optimum casting temperature,
content of alloying elements, and homogeneity. These improvements can come only through
the diverse refinement processes that together comprise "secondary steelmaking."
Secondary Steelmaking: Principles and Applications reviews the scientific fundamentals and
explores the various unit processes associated with secondary steelmaking. Synthesizing the science and its
technology, the author examines the relevant reactions and phenomena, presents an integrated picture of "clean
steel" manufacture, and provides an overview of the mathematical modeling important to process research.
Solved examples, ample references, and summaries of recent technological advances mean that the
steelmaking industry finally has a comprehensive reference, in English, for the all-important secondary
steelmaking processes. Students and instructors, steelmakers and R & D engineers will welcome the author's
readable style, his knowledge, and his expertise, all gleaned from decades of experience in research, academic,
and industrial settings.
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A wealth of data on metals and their extraction is revealed in this

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description of how a particular metal is extracted industrially from different
raw materials, and on what its important compounds are. The present
work is a collection of 58 articles written by over 280 specialists. It supplies
thousands of top-quality illustrations, diagrams and charts, and provides
hand-picked references ensuring the most up-to-date coverage. A unique
feature of this reference work is its structure. The system used here is
according to an economic classification, which reflects mainly the uses,
occurrence and economic value of metals. First, the ferrous metals, i.e.,
those used in the production of iron and steel, are outlined. Then,
nonferrous metals are subdivided into primary, secondary, light, precious,
refractory, scattered, radioactive, rare earth, ferroalloy metals, and, finally,
the alkali and the alkaline earth metals are described.
The handbook is an essential aid for the practising metallurgist. Mining
engineers, mineralogists, chemical engineers, chemists and geologists will find it a comprehensive desk
reference. It is of interest to engineers and scientists in industry seeking an exhaustive sourcebook, and it should
be present in every library.
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Appendix A.
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Steel Heat Treatment: Metallurgy and Technologies

(Steel Heat Treatment Handbook)
CRC | 848 pages | 2006-09-28 | ISBN: 0849384559 | PDF | 33.3MB
One of two self-contained volumes belonging to the newly revised Steel

Heat Treatment Handbook, Second Edition, this book examines the
behavior and processes involved in modern steel heat treatment
applications. Steel Heat Treatment: Metallurgy and Technologies
presents the principles that form the basis of heat treatment processes
while incorporating detailed descriptions of advances emerging since
the 1997 publication of the first edition. Revised, updated, and
expanded, this book ensures up-to-date and thorough discussions of
how specific heat treatment processes and different alloy elements
affect the structure and the classification and mechanisms of steel
transformation, distortion of properties of steel alloys. The book includes
entirely new chapters on heat-treated components, and the treatment of
tool steels, stainless steels, and powder metallurgy steel components. Steel Heat Treatment: Metallurgy and
Technologies provides a focused resource for everyday use by advanced students and practitioners in
metallurgy, process design, heat treatment, and mechanical and materials engineering.
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Madeleine Durand-Charre , «Microstructure of Steels and Cast

Irons»
Publisher: Springer | Number Of Pages: 404 | Publication Date: 2004-04-15 |
ISBN / ASIN: 3540209638 | PDF | 24 MB
The book comprises three parts. Part 1 gives a historical description of the
development of ironworking techniques since the earliest times. Part 2 is the
core of the book and deals with the metallurgical basis of microstructures, with
four main themes: phase diagrams, solidification processes, diffusion, and solid
state phase transformations. Part 3 begins by an introduction to steel design
principles. It then goes on to consider the different categories of steels, placing
emphasis on their specific microstructural features. Finally, a comprehensive
reference list includes several hundred pertinent articles and books. The book is
the work of a single author, thus ensuring uniformity and concision. It is
intended for scientists, metallurgical engineers and senior technicians in research and development laboratories,
design offices and quality departments, as well as for teachers and students in universities, technical colleges
and other higher education establishments.
http://rapidshare.com/files/44188131/Microstructure.of.Steels.and.Cast.Irons_muya.rar
Appendix A.
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Metallurgy Fundamentals
By Daniel A. Brandt,&nbspJ. C. Warner,
* Publisher: Goodheart-Wilcox Publisher
* Number Of Pages: 301
* Publication Date: 2004-02
* ISBN / ASIN: 1590703456
An excellent introduction to metal making
I found Metallurgy Fundamentals to be an
excellent resource for myself. While not
overly technical it covers the basic principles
and theory of metal making in clear and
straightforward language. I recommend it for
persons in drafting, quality, design, or
purchasing
114 MB ~ Pdf. Good Quality.
Scanned copy-poor quality, however it is simple,

informative, lots of photos and educational
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Appendix A.
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Slag inclusion formation during solidification of Steel

alloys and in cast iron
Sofia Adolfi
Licentiate Thesis
Materials Processing
Department of Material Science and Engineering
School of Industrial Engineering and Management
Royal Institute of Technology
SE-10044 Stockholm, Sweden
Akademisk avhandling som med tillstånd av Kungliga Tekniska Högskolan i Stockholm framlägges till offentlig
granskning för avläggande av teknologie Licentiatexamen, fredagen den 11 maj 2007, kl. 10:00, Sal B1, Brinellvägen 23,
KTH, Stockholm.
ISSNKTH/MSE-07/10-SE+CER/AVH, ISBN 978-91-7178-624-1

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Sofia Adolfi, Slag inclusion formation during solidification of Steel alloys and in
cast iron
School of Industrial Engineering and Management

Department of Materials Science and Technology, Materials Processing
Royal Institute of Technology
SE-100 44 Stockholm, Sweden
ISSN KTH/MSE-07/10-SE+CER/AVH
ISBN 978-91-7178-624-1
© Sofia Adolfi March 2007
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Slag inclusion formation during Solidification of Steel alloys and in cast iron
Sofia Adolfi 2007
Department of Materials Science, Royal Institute of Technology
S-100 44 Stockholm, Sweden
Abstract
This thesis explores the formation of segregation and inclusions during solidification
of steel and cast iron. A better understanding of the formation mechanism should result
in decreasing fraction of defects during solidification of ingot and strand material.
Density driven macrosegregation was studied both experimentally and theoretically to
see the effect of channel segregation on the total segregation. Formation of these pencil-
like segregations is due to natural convection in the solidifying metal caused by liquid
enrichment of elements with lower density compared to the bulk. It is suggested to
change the composition to compensate for this density difference.
Inclusion precipitation can be finite by limitations in segregation. Saturated liquid is
found in the last solidified areas, often between dendrites. Here the enrichment of the
liquid is possible due to microsegregation. Meanwhile crystals form and solidify the
elements with low solubility in the solid is pushed out in the remaining liquid. Soon the
liquid is saturated to the level where spontaneous formation of inclusions occurs.
Microstructure studies by aid of SEM and micro-probe measurements are analysed to
find at what point during solidification process the inclusions start to form. In steel
making this formation has a detrimental effect on the mechanical properties in contrary
to the production of nodular cast iron where the inclusions have a beneficial effect on
the graphite formation.
Inoculation of cast iron aims at reaching higher number density of graphite nodules,
nodule morphology modification and control of nodule distribution during solidification.
Late precipitation of nucleation sites has shown to have a positive impact on preventing
chill. To find the most potent inoculation agent different additives were tested. Special
effort has been made to analyse the effect of oxides and sulphides as nucleation sites.
Descriptors: solidification, segregation, precipitation, inclusions, inoculation, EPMA
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Supplements
The thesis includes the following supplements
Supplement 1
Crack formation during continuous casting of tool steel
A. Lagerstedt, S. Adolfi and H. Fredriksson
Trans. Indian Inst. Met. Vol. 58, No. 4, August 2005, pp. 671 – 678
I performed the hot-tensile tests, evaluation and part of report writing
Supplement 2
Macrosegregation in ingot cast tool steel
A. Lagerstedt, J. Sarnet, S. Adolfi and H. Fredriksson
ISRN KTH-MG-INR-04:09 SE
TRITA-MG 2004:09
I took part in all experiments and part of final evaluation and report writing. In particular
I performed the temperature measurements and EPMA analysis
Supplement 3
A thermodynamic analysis of the inoculation process
L. Magnusson, S. Adolfi and H. Fredriksson
ISRN KTH-MG-INR-06:03 SE
TRITA-MG 2006:03
I performed the experimental part and together with Lena Magnusson the theoretical
evaluation
Supplement 4
MnS precipitation during solidification in presence of oxide nuclei
S. Adolfi, K. Mori and H. Fredriksson
Accepted to the 5th Decennial International Conference on Solidification Processing
I performed the experiments and report writing
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Contents
1. Introduction 1
2. Experimental methods 3
2.1 Material preparation 3
2.2 Thermal properties 3
2.2.1Differential Thermal Analysis 3
2.2.2 “In-situ” solidified hot tensile tests 4
2.3 Macrosegregation study 5
2.4 Inclusion study 6
2.4.1 Inclusion characteristics 6
2.4.2 Electron Probe Micro-Analysis 6
2.5 Inoculation in nodular cast iron 7
3. Results 8
3.1 Macrosegregation 10
3.2 Inclusion characteristics 10
3.3 Inoculation in nodular cast iron 10
4. Discussion 13
5. Conclusions 15
6. Future work 17
7. References 21
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1 Introduction
The aim of this study was to analyse the solidification process in steel alloys and cast
iron. Focus has been on segregation and defects and their formation mechanism. Both
experimental and theoretical method to analyse this has been used. A great part of the
work has been to design the proper experiment. The experimental outcomes are used for
further theoretical work.
During solidification of steel ingots and strand compositional variations referred to as
macrosegregation range in scale from several millimetres to centimetres or even metres.
The in-homogenous distribution of alloy elements have a detrimental impact on the
following processing behaviour and the material properties and can lead to rejection of
cast components or processed products. The formation of these variations is driven by
natural convection where hot metal will flow upward inside the centre of the ingot and
cooler solidifying liquid will grow heavier in density and flow downward the mould wall.
At this stage some crystal with lower liquidus temperature can remelt while in contact
with the high-temperature melt leading to channel formation where highly segregated
liquid will flow upwards due to its lower density. During solidification crystals will freeze
at the solidus temperature and gradually form a solid. This solid will continue to grow
meanwhile the remaining liquid will be enriched by elements with lower solubility in solid
phase compared to the liquid. This enrichment or commonly referred to as
microsegregation will open up for precipitation of other phases, inclusions which benefit
from the saturation of alloying elements.
Hot cracks are often the result from the solidification process. The material will go
through a brittle to ductile transformation during solidification. The brittle region causes
this crack formation. This brittleness is caused by the presence of thin liquid films in the
interdendritic region at the crystal boundaries.1 These are often type II MnS inclusions.
By means of hot-tensile-tests, DTA and Electron Probe Micro-analysis the proper
material data can be found for further theoretical analysis on crack- and inclusion
formation. Inclusions in steel are categorized according to type (chemical composition)
and morphology (shape). They origin either from before casting or they spontaneously
precipitate during solidification. The first case is often a result from secondary metallurgy
and can be an effect of slag or mould material being dragged into the liquid steel. This
type is often referred to as macro slag. Precipitation of inclusion during solidification is
possible when the supersaturation needed to form a certain compound is reached in the
liquid and the formation facilitates by presence of small nuclei, mainly of oxide type. One
of the most common inclusions is the MnS. Early it was discovered by Sims and Dahle,2
they are of different morphology due to formation process. They classified the globular
shaped as type I, enveloped thin sheeted as type II and the faceted ones as type III. Later
work made by Fredriksson and Hillert,3 revise this classification by adding the type IV
morphology, a lamellar eutectic structured MnS. They suggest that the formation of
types I and II are by a monotectic reaction where MnS forms as a liquid phase. Types III
and IV are a eutectic reaction where MnS forms a crystalline phase. A monotectic
reaction is a process in which a melt gives a solid phase and another liquid phase,
L1→α+L2. A eutectic reaction is a solidification process in which a liquid solidifies to
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two solid phases, L→α+β. The type of MnS inclusion depends on many variables. The
main factors are: cooling rate, concentrations of Mn and S in the melt, the solubilities of
the alloying elements in molten MnS + Fe and the deoxidation process of the melt.
Common deoxidants are Al and Si. Another method to reduce O concentration is
vacuum degassing.
During solidification inclusions are pushed in front, entrapped or engulfed by the
solidifying front. Stefanescu et al.,4 explain there exist a critical velocity of the planar
solid – liquid interface below which particles are pushed ahead of the advancing front
and above which particle engulfment occurs. Engulfment is used to describe
incorporation of a particle (i.e. inclusion) by a planar interface and entrapment is used to
explain how particles incorporate between cells and dendrites. Engulfment will normally
lead to a uniform particle distribution, while pushing will result in particle segregation.
Later studies by Stefanescu et al.5 show that particle interaction with dendritic solid –
liquid fronts can be explained with similar controlling parameters as for planar fronts.
Based on dendrite tip radius, particle radius, natural convection induced liquid velocity,
VL, and the solidification velocity, VSL, engulfment or entrapment occurs. Engulfment
can occur if convection is low and surface velocity is high. Slow interface velocity result
in particle being entrapped between dendrite arms. However if VL is high but VSL is
small the particle will be pushed in front of the interface. These types of defects in steel
production should be possible to decrease by better understanding on the formation
mechanism.
Precipitation of oxides and sulphides has a beneficial effect on the graphite formation
in production of nodular cast iron. The inclusions act as nucleation sites for graphite. By
addition of different inoculation agents we can promote nodularity, refine the graphite
structure and suppress carbide formation. In earlier work by Skaland,6 it is suggested that
different oxides and sulphides may increase the inoculation effect. Oxide and sulphide
inclusions which are formed after addition of the inoculants act as nucleation sites for
graphite nodules. To find the most potent inoculants we studied the nucleation process
of graphite in presence of different inoculation agents. In contrary to inclusions formed
during steel making precipitation of oxides and sulphides is most wanted.
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2 Experimental methods
2.1 Material preparation

The material used in this thesis work is presented in table 1, supplement 4. Steel A is
represented by one octagonal 12 ton ingot and one rectangular 10 ton ingot produced by
uphill casting at Scana Steel Björneborg AB. Steel B comes from a continuous casting
experiment carried out in slab caster 2 at SSAB Oxelösund AB. Steel C is a aluminium-
killed 6 ton ingot produced by uphill casting at Ovako AB. Ingots were cold sawed to
pieces in order to allow for sulphur printing and drilling for chemical composition to
obtain the segregation pattern of C and S. The old but well known Sulphur printing
technique was re-discovered and prints were made on sawed surfaces in order to obtain
macrographs of the ingot structure. To get as detailed information as possible from the
prints some surfaces was milled to give good sharpness. Photo paper was soaked in 5%
sulphuric acid and rolled on to the metal surface in good contact. The prints are taken at
the vertical cross section. Sample drilling was performed over the vertical cross section
to obtain the segregation pattern of C and S.
Test with different inoculation additives are made on a base alloy of white nodular
vast iron, presented in table 1, supplement 3.
2.2 Thermal properties
2.2.1 Differential Thermal Analysis

Differential Thermal Analysis, DTA was used to study the solidification process. The
result is used as in-data for further theoretical calculations. During heating and cooling
the sample temperature was measured and any transformation will be shown as a change
in temperature compared to a known reference state. The technique is to measure the
difference in temperature between the specimen and a known reference which are
exposed to the same heating schedule. The reference could be any material with about
the same thermal mass as the sample, which undergoes no transformations in the
temperature range of interest. When the sample undergoes a transformation it will either
absorb or release heat. The thermocouple will detect and indicate if the transformation is
“exothermic” on a plot of temperature versus time. Heating rate is an important
consideration in this investigation. Slower heating rate will more accurately depict the
onset temperature of a transformation. Furthermore two transformations which are very
close in temperature range may be mistaken for a single transformation under rapid
heating rate. Measurements were performed using a resistant heated tube furnace. A
graphite cylinder was place around the alumina crucible both to be used as reference but
also to prevent convection in the melt. A constant heating and cooling rate of 10°C/min
was used. Argon is used as shield gas. Temperature was measured by PtRh10%-Pt
thermocouples. Calibration was performed with pure silver resulting in corrections of
about +3°C and the measuring device work with an accuracy of ± 1°C. Sample
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dimension was 7 mm in diameter, 14 mm in height with a 3 mm wide and 9 mm deep

centre hole drilled to fit the thermocouple. Data were sampled 20 times every second.
reference
1500 sample
1450
Temperature [°C]
exothermal process
1400
1350
1300
5000 5200 5400 5600 5800 6000 6200 6400 6600 6800 7000
Time [s]
Figure 1: Temperature vs. time curve (DTA)
2.2.2 “In-situ” solidified hot tensile tests

The high temperature parameter known as the transition temperature from ductile- to
brittle fracture, TDB can be used as indicator if a metal is crack sensitive. In the study on
crack formation during solidification of liquid metal this is a technique to find proper
material data for further mathematical modelling. This temperature is measured during
solidification and cooling of the metal and correspond to the point when the metal start
to have a brittle mechanical behaviour. At temperatures below the transition we find
plastic behaviour with necking and ability to high elongation and strains leading to
ductile fractures. Low transition temperatures, below the metal solidus temperature
indicate crack sensitivity.
This specific temperature can be measured by high temperature tensile testing of in-
situ solidified samples. The technique is from the beginning used in the work of Rogberg
and Fredriksson, and additionally developed by Karin Hansson.7 The concept is to have
a mirror furnace, which can be inserted into a tensile testing machine. The mirror
furnace gives a limited heating zone by its focus, which makes it possible to melt a small
part of the sample and let it solidify and cool to the tensile test temperature. This
technique has the advantage that one can melt the sample and let it solidify with a
controlled cooling rate which can simulate the real conditions in the casting process with
regards to cooling rate, microsegregation etc.. The mirror furnace consists of three gold
plated ellipsoidal reflectors with a halogen lamp inserted at the focal point. Using a
maximum power of 1020 W and the centre of the test specimen placed in focal point a
5mm long melting zone was formed and held in place by the surface tension. The
temperature was measured with thermocouples of type S made of Pt-Pt10%Rh placed in
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the centre of the melting zone. A quartz tube with argon atmosphere is placed around
the specimen to protect it from oxidation. The reflectors and tensile rods were water-
cooled. Elongation is measured by an extensometer. Force is measured with a load cell
of 5kN in a range of ± 2.5kN. Force, position of the piston, elongation and temperature
is sampled by the computer controlling the tensile test machine. Tensile specimens of 40
mm length and 4 mm diameter were heated up to TL+5° and then cooled down with a
constant rate of 2°C/s. When reaching the tensile test temperature the tensile test is
performed during isothermal conditions with a constant pulling rate of 0.5mm/s which
corresponds to a strain rate of 0.1/s if we assume the deformation zone to be of the
same length as the heated zone i.e. 5mm.
Results from tensile tests are analyzed by the reduction of area (RA), ultimate tensile
stress (σb), elongation (lvdt) and strain to fracture (ε). The fracture surface with zero
ductility is used as indication of transition between ductile and brittle fracture. The
corresponding temperature is the transition temperature, TDB.
A0 − A1
RA = ⋅ 100% (A1 is a mean value over three measurements)
A0
Fmax
σb =
A0
⎛ l 0 + ∆l ⎞
ε = ln⎜⎜ ⎟⎟
⎝ l0 ⎠
2.3 Macrosegregation study

Macrosegregation occurs during solidification due to relative movement or flow of
segregated liquid and solid. There are numerous causes of fluid flow and solid movement
in casting processes. One reason for this movement of segregated liquid may be density
differences of the metal due to temperature or variations in composition. The hot liquid
metal becomes cooler close to the chill surfaces and its density increase causing
downward movement. Liquid being enriched by rejected solutes with higher density
compared to the bulk composition will flow downward and the opposite will happen
when low mass elements enrich the liquid. During ingot casting, the most common
macrosegregations are the positive, negative and channel segregations8,9. Positive segregation
means that the concentration of alloying element exceeds the average bulk concentration.
Negative segregation is instead a local lack of alloying element. The positive segregation is
often found at the top and is the result of segregated liquid flow toward the top,10,11 and
the negative zone with more pure material at the bottom of the ingot is explained by
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sedimentation of equiaxed crystals formed in the bulk liquid.12 Approximate at one third
from the surface the so-called A-segregates are found. They have the shape of pencil-like
channels, filled with alloy which contains high concentrations of the alloying elements.
Liquid jet streams melt the dendrite network allowing for channels to form and be filled
by enriched liquid flowing upward due to its lower density.
Drilling for chemical composition was made on ingots along the central axis and at
several cross sections at different heights. The results are plotted to obtain the
segregation pattern over C and S. Sulphur prints which reveal the S as dark marks are
used to analyse segregation channel placement and number density. These results are
used as in-data for numerical analysis.
2.4 Inclusion study
2.4.1 Inclusion characteristics

Inclusions studied in this present work were analysed with emphasis on its
precipitation process and morphology. Our goal was trying to present a model on
inclusion formation based on measurements on liquid supersaturation, inclusion
characteristics and solidification process. Comparisons were made between different
crystal morphologies such as the columnar and equiaxed crystals and metallurgical
processing prior casting. Inclusions were characterized by use of scanning electron
microscopy (SEM) and element concentrations are measured by electron probe micro-
analysis (EPMA). From SEM images we determine type, shape and size distribution. By
use of energy dispersive scanning (EDS) we analyse inclusion chemistry. EPMA results
on concentration levels are used to study the precipitation process.
2.4.2 Electron Probe Micro-Analysis

Inclusions were investigated by Electron Probe Micro-Analysis, EPMA. This
technique has been known since late 1950. The first instrument was in place at The
Swedish Institute of Metals Research in the beginning of the 60’s. An electron beam is
focused to a 1 µm point by aid of electromagnetic lenses. The beam is used to penetrate
the surface (2 µm deep in steel materials) influencing the atoms to enable emitted x-ray
to analyse element specific wavelengths. Intensity is proportional to element amount. To
enable this type of measurement some modification must be made to the original SEM
equipment. Much higher, 500 – 1000 times, currents are used compared to conventional
SEM and sliding sample holder render possible surface scan. Calibration for each
element is made by mapping reference materials with known spectrums. One sample
with low element concentration and one sample with high element concentration are
used. One can choose to scan step wise in the range from 1×1 µm to 50×50 µm. The
micro distribution of selected elements are traced and transformed into a two
dimensional colour picture, each colour representing a certain amount. Each point
represents a mean value of the element concentration. All data about references,
coordinates and analyses are saved to be used for further investigation such as line-scan,
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mean values of certain structure areas or to better bring out low content of interesting
elements.
2.5 Inoculation in nodular cast iron

The same model on precipitation process used in the study on inclusions in steel
alloys can be used when evaluating the graphite formation during solidification of cast
iron. Precipitation of graphite nodules during solidification in nodular cast iron was
studied to better understand inoculation efficiency. Three different additives were used,
FeSi – Ca, FeSi – (Ca, Ce) and FeSi – (Ca, Ce, S, O). The same mirror furnace used for
hot tensile test was used to melt samples which solidify with a controlled cooling rate.
The samples melt by heat conduction while heating the graphite holder to about 1400
°C. All samples were cast in Zr2O-crucibles. A 250 mm long and 30 mm wide quartz
tube is placed around the specimen set-up and was continuously filled with argon gas to
protect it from oxidation. Quenching was made in water. Inoculation seeds were placed
at the bottom of the crucible before melting. A total of six tests from each alloy have
been studied. One from each alloy representing the total solidification interval. Five were
quenched within the solidification interval (1150 – 1010 °C). Maximum heating- and
cooling rate was set to 300°C and 60 °C/min respectively. Samples were kept for about
one minute at the maximum temperature. Temperature was sampled every 0.4 s and
measured in the centre of each sample. The time from completely liquid to start of
cooling is about 100 s for all tests. A maximum temperature of about 1375 – 1360 °C has
been recorded in the melt and is regarded as the inoculation temperature.
Samples were polished to a 3 um diamond paste finish and etched in 2-5% Nital, 2%
Pikrin or 5%Br – 95%Methanol solution. Studies were concentrated towards
microstructure, nodule count, nodule size distribution, inoculants efficiency and
inclusion characteristics. Nodule count and structure fractions were made by means of
point counting in 5×-magnifications. The inclusions are analysed by EDS in SEM.
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3 Results
3.1 Macrosegregation
Figure 3 shows a plot over the segregation ratio, C/C0 of carbon and sulphur in the
rectangular ingot. As to be expected the macrosegregations follow the well known
behaviour. In the figure, the concentration along three horizontal lines, representing
three height levels, from surface to centre are shown to the left, the centreline
segregation is shown in the middle and the position of each drill sample are shown to the
right. A sulphur print of the corresponding surface is shown in figure 4. In this ingot, an
increase of the segregation ratio is seen toward the top. The horizontal lines show that
the composition are even toward the surface at the mid to lower levels but has clearly
unstable segregation ratio towards the centre at the higher level, which is close to the
hot-top region. This instability coincides with the A-segregates seen in the sulphur print
in figure 4. At the bottom of the ingot a somewhat increasing negative segregation is
found.
3 1800
Top Centreline
2
1600
0
C/C
1
1400
0
-300 -200 -100 0
1200
1.5
Ingot heigth [mm]

Middle
1000
0
C/C
1
800
0.5
-300 -200 -100 0 600
1.5
Bottom
400
0
C/C
1
C 200
S
0.5 0
-300 -200 -100 0 0.5 1 1.5 2 2.5 -500 0 500
C/C Ingot width [mm]
0
Figure 3: Segregation ratio of S and C. Sample location is shown in the right figure.
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Figure 4: Sulphur print of vertical cross-section of rectangular ingot.
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3.2 Inclusions characteristics

Three types of inclusions were found. To the left in figure 5 we see a duplex oxy-
sulphide inclusion where MnS has grown on Al2O3-nucleis, the centre picture is a MnS
inclusion and to the right in the figure we see the Al2O3. The inclusions are found in all
three materials but are different in type, shape and size. MnS found in the ingots are
classified as type III and I since they are sharp edged to spherical. Continuous cast
material contains type II MnS which are smooth and stringy. The oxides are all faceted.
Inclusion size and number density are found to be a function of crystal morphology.
Columnar structure favour precipitation of MnS and duplex oxy-sulphides. Equiaxed
crystal zone contains these inclusions too but to less extend together with pure Al2O3,
most of which are very small in size.
Figure 5: Duplex oxy-sulphide, pure MnS and pure Al2O3 in high-sulphur tool steel ingot
3.3 Inoculation in nodular cast iron

Nodule size measurements are presented in figure 6. The un-inoculated base iron
samples show a low number of large nodules. The number of nodules then increase at a
size of 20 – 25µm, and an additional increase is seen at a size of 5 – 10µm. Addition of
Ca and S – O treated inoculants lead to a more even distribution in comparison to
addition of FeSi – (Ca, Ce). FeSi – (Ca, Ce, S, O) which show a peak at 5 – 20µm is the
additive with most small sized nodules.
This is explained by formation of nodules at the beginning and at the end of
solidification. A support for this is found in the thermodynamic calculations [Fig 13a and
14a, supplement 3]. These show that MgO and MgS inclusions are formed at the
addition of Mg and nodules are nucleated on those. MgO and MgS inclusions are also
formed at the end of solidification acting as nucleation sites for graphite nodules.
Addition of inoculants containing Ce or other elements with high affinity to oxygen
shows a quite different nodule distribution. There is hardly any favourite size and the
distribution is more even [Fig. 6, supplement 3]. This might be explained by sulphides
and oxides are repeatedly formed during solidification process.
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60
(Ca)
(Ca, Ce)
50 (Ca, Ce, S, O)
Number of nodules
(pure base iron)

40
30
20
10
0
m
m
m
5µ
0µ
5µ
0µ
5µ
0µ
5µ
0µ
0µ
-1
-2
-2
-3
-3
-4
-4
-5
1
5-
10
15
20
25
30
35
40
45
Figure 6: Nodule size distribution
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4 Discussion
Results from supplement 1, 2 and 4 are to be considered as one investigation. We
made different types of experiments and analyses in order to investigate the origin of
defects such as segregation, crack formation and inclusions in cast ingots and continuous
cast slabs. The experiments are made on the same steel quality through out the work of
this thesis. Experiments were designed and tried out in order to achieve the correct
material data for further mathematical modelling.
The segregation pattern in the work made in supplement 2 follows the general view
on segregation behaviour. It is clear that the areas at which segregation channels are
found are prone to house high number density of inclusions. This is supported by
EPMA analysis over the area. The channel formation with remelting of the dendrite
network causing liquid enrichment with alloy elements being pushed from the solid into
the liquid with higher solubility enables the needed supersaturation to form these
inclusions. Results on macrosegregation and type of inclusions has been further analysed
in supplement 4 with emphasis on the inclusion formation process. The investigation
shows two different types of inclusions, (1) duplex inclusion where the core constitute an
oxide inclusion with a MnS outer shell and (2) pure MnS and Al2O3 inclusions in
different morphologies. It also shows that inclusion precipitation has crystal structure
dependence which is a function of solidification process. At higher solidification rates
the oxides incorporate into the solid and no small nuclei are available for MnS
precipitation.
The theoretical model used in supplement 3 and 4, based on well known segregation
models, analyses the precipitation behaviour of inclusions during solidification process.
The method to find at what point in the solidification process inclusions are expected to
precipitate are based on calculations with the Scheil and Lever rule in combination with
calculations on solubility products for nucleation. The theoretical results are compared
with experimental observations from EPMA and microstructure investigations. The
experimental result supports the calculations that Al2O3 inclusions precipitate before
MnS and thus acting nucleation sites for MnS. Results from the structure investigation of
Steel C also support this since this material contains less MnS and no oxides. This could
be an effect of the metallurgical treatment prior to casting.
In the same way as for the duplex inclusions found in the steel ingots the graphite
nodules precipitates on oxide nuclei. Pure base iron show uneven graphite nodule size
distribution compared to the iron inoculated with S and O treated additives. When
adding inoculants with Ce or elements with high affinity to oxygen the nodule size
distribution change from being uneven with a low number of large nodules to a more flat
distribution with hardly any favourite size. This is explained by repeatedly formed
sulphides and oxides during solidification process.
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5 Conclusions
Ingot casting, continuous casting and inoculation experiments has been performed
with the intention to study crack formation, macrosegregation, inclusion characteristics
and the effect of metallurgy and solidification process. A crack prediction model used to
calculate temperature and elastic stresses was presented together with a model to
calculate the influence of the A-segregates in large ingots. The formation of inclusions in
steel alloys has been analysed by use of a new way to calculate the precipitation as
function of supersaturation and solidification process. The same model can also be
applied in the case with inoculation of cast iron.
Macrosegregation in the steel experiment in this study is similar to the general view of
segregation pattern, a negative segregation zone in the lower parts of the ingot and an
increasing composition toward the top. The primary source of the macrosegregation in
the ingot cast material is the transport of segregated liquid in the A-segregates. These
areas of saturated metal contain inclusions, mainly oxides and sulphides.
Inclusions are formed in the interdendritic areas where the liquid is highly enriched.
Sulphides and oxides are the most common types together with a duplex oxy-sulphide
where the MnS grow on oxide nuclei. Inclusion characteristics depend on crystal
morphology which can be related to casting process. Probably this is an effect of the
solidification rate, both in ingot and continuous cast processing. Calculations by aid of
homogeneous nucleation theory together with segregation calculations show that
precipitation of oxides start at a solid fraction of about 0.7 and the MnS not until a solid
fraction of 95% is reached. Results from structure analysis support the idea that oxides
act as nucleation sites for MnS precipitation. In the study on nodular cast iron it shows
that oxides present in the liquid promote nodule precipitation. During solidification re-
nucleation of oxides and graphite nodules result in a flat nodule size distribution with the
beneficial effect of less chill i.e. less problem with micro porosity.
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Clean Steel: Part One
Abstract:
Steel cleanliness is an important factor of steel quality and the demand for cleaner steels increases every
year. The so-called clean steel generally is the steel in which the content of impurity elements, such as
phosphorus, sulphur, total oxygen, nitrogen, hydrogen (including carbon sometimes) and inclusions are
very low. The improvement of steel cleanliness has therefore become a more and more important subject in
the development of ferrous metallurgical technology, and also an important task for the iron and steel
producers.
Steel cleanliness is an important factor of steel quality and the demand for cleaner steels increases every year.
The so-called clean steel generally is the steel in which the content of impurity elements, such as phosphorus,
sulphur, total oxygen, nitrogen, hydrogen (including carbon sometimes) and inclusions are very low. The
improvement of steel cleanliness has therefore become a more and more important subject in the
development of ferrous metallurgical technology, and also an important task for the iron and steel producers.
The demand for better mechanical properties of steels was urging steel producers to improve cleanliness of
their final products. In order to obtain the satisfactory cleanliness of steel it is necessary to control and improve
a wide range of operating practices throughout the steelmaking processes like deoxidant- and alloy additions,
secondary metallurgy treatments, shrouding systems and casting practice.
Due to the vague nature of the term "clean steel", some authors imply that it is more precise to refer to:
• steels with low levels of solutes as "high purity steels"

• steels with low levels of impurities that originate from the re-melting scrap as "low residual steels"
steels with a low frequency of product defects that can be related to the presence oxides as "clean steels".
It has been well known that the individual or combined effect of carbon [C], phosphorus [P], sulphur [S],
nitrogen [N], hydrogen [H] and total oxygen (T.O.) in steel can have a remarkable influence on steel properties,
such as tensile strength, formability, toughness, weldability, cracking-resistance, corrosion-resistance,
fatigue-resistance, etc. Also, clean steel requires control of non-metallic oxide inclusions and controlling their
size distribution, morphology and composition.
The control of the elements mentioned above is different for different performance demands. Those impurity
elements also vary with different grades of steel. Table 1 lists the influence of common steel impurities on steel
mechanical properties which means that some element is harmful to certain steel grades, but may be less
harmful or even useful to another steel grades.
For examples for IF steels, the content of carbon, nitrogen, total oxygen and inclusions should be as low as
possible in order to get good flexibility, high "r" value, perfect surface quality etc. In other hands the high quality
pipeline steel requires ultra low sulphure, low phosphorus, low nitrogen, low total oxygen content and a certain
ratio of Ca/S.
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Element Form Mechanical Properties Affected

　 Ductility, Charpy impact value, anisotropy
　 Formability (elongation, reduction of area and bendability)
S, O Sulfide and oxide inclusions 　 Cold forgeability, drawability
　 Low temperature toughness
　 Fatigue strength
Solid solution 　 Solid solubility (enhanced), hardenability
Settled dislocation Strain aging (enhanced), ductility and toughness (lowered)
Pearlite and cementite 　 Dispersion (enhanced), ductility and toughness (lowered)
C, N
　 Precipitation, grain refining (enhanced), toughness
Carbide and nitride
(enhanced)
precipitates
　 Embrittlement by intergranular precipitation
　 Solid solubility (enhanced), hardenability (enhanced)
P Solid solution 　 Temper brittleness
　 Separation, secondary work embrittlement
Table 1: Influence of typical impurities on mechanical properties
As we mentioned before, steel cleanliness depends on the amount, morphology and size distribution of
non-metallic inclusions. The inclusions generate many defects and many applications restrict the maximum
size of inclusions so the size distribution of inclusions in steel products is also important. For certain
applications where stringent mechanical properties are required the internal cleanliness of steel is very
important. Table 2 shows the cleanliness requirements for various steel grades.
Maximum allowed impurity Maximum allowed inclusion

Steel product
fraction size
[C]≤30 ppm, [N]≤40 ppm, T.O.≤40
IF steels ppm
[C]≤10 ppm, [N]≤50 ppm
Automotive and deep-drawing
[C]≤30 ppm, [N]≤30 ppm 100 µm
Sheets
[C]≤30 ppm, [N]≤40 ppm, T.O.≤20
Drawn and Ironed cans 20 µm
ppm
Alloy steel for Pressure vessels [P]≤70 ppm
[H]≤2 ppm, [N]≤20 ppm, T.O.≤10
Alloy steel bars
ppm
HIC resistant steel sour gas tubes [P]≤50 ppm, [S] ≤10 ppm
[S]≤30 ppm, [N]≤50 ppm, T.O.≤30
Line pipes 100 µm
ppm
Sheets for continuous annealing [N]≤20 ppm
Plates for welding [H]≤1.5 ppm
Bearings T.O.≤10 ppm 15 µm
Tire cord [H]≤2 ppm, [N]≤40 ppm, T.O.≤15 10 µm
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ppm
Non-grain-orientated Magnetic
[N]≤30 ppm
Sheets
[H]≤2 ppm, [N]=30-40 ppm, T.O.≤20 Single inclusion 13 µm
Heavy plate steels
ppm Cluster 200 µm
Wires [N]≤60 ppm, T.O.≤30 ppm 20 µm
Table 2: Cleanliness requirements for various steel grades
As Table 2 shows for sheets used for car body, carbon [C], nitrogen [N], and total oxygen (T.O.) are each
required to be very low. For sheets for tin plate application, total oxygen is not only needed below 20 ppm, but
the size of the non-metallic inclusions in steel has to be less than 20 µm.
For steel cord used in tires, the size of non-metallic inclusions in steel has to be less than 10 μm and even
smaller (5 µm) for TV shadow masks. For ball bearings, in order to improve their fatigue-resistance properties,
T.O. in steel has to be below 10 ppm and the size of non-metallic inclusions has to be less than 15 µm. For
meeting the specification of increasingly improved toughness for petroleum pipeline and of Hydrogen Induced
Cracking (HIC) resistance for the transport of sour natural gas, the sulphur [S] content in steel has to be
extremely low, less than 10 ppm.
Steel cleanliness is controlled by a wide range operating practices throughout the steelmaking processes.
These include the time and location of deoxidant and alloy additions, the extent and sequence of secondary
metallurgy treatments, stirring and transfer operations, shrouding systems, tundish geometry and practices,
the absorption capacity of the various metallurgical fluxes, and casting practices.
A one of the steelmaking process routes for the production of clean steels is outlined in Figure 1.
Figure 1: The process route for the production of clean steels

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Clean Steel: Part Two
Abstract:
Non-metallic inclusions, which are undesirable components of all steels, play an important role with respect
to their effect on the steel properties. Controlling inclusions in steel is closely connected with the concept of
"clean steel". The improvement in steel properties by control of non-metallic inclusions plays an important
part in defending the applications of steel against newer competitive materials.
Non-metallic inclusions, which are undesirable components of all steels, play an important role with respect to
their effect on the steel properties. Controlling inclusions in steel is closely connected with the concept of
“clean steel”. The improvement in steel properties by control of non-metallic inclusions plays an important part
in defending the applications of steel against newer competitive materials. The aims of the metallurgist are to
eliminate undesirable inclusions and control the nature and distribution of the remainder to optimize the
properties of the final product.
Generally, non-metallic inclusions in steel normally have a negative contribution to the mechanical properties
of steel, since they can initiate ductile and brittle facture. Among various types of nonmetallic inclusions, oxide
and sulphide inclusions have been thought harmful for common steels.
All steels contain non-metallic inclusions to a greater or less extent. The type and appearance of these
non-metallic inclusions depends on factors such as grade of steel, melting process, secondary metallurgy
treatments and casting of steel. Because of this, it is of particular significance to determine how pure the steel
is. The term steel cleanness is relative one, since even steel with only 1 ppm each of oxygen and sulfide will
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still contains 10 -10 non-metallic inclusions per ton. From the viewpoint of “cleanness” all steels are “dirty”.
Non metallic inclusions in steel are the cause for dangerous and serious material defects such as brittleness
and a vide variety of crack formations. However, some of these inclusions can also have a beneficial effect on
steels properties by nucleating acicular ferrite during the austenite to ferrite phase transformation especially in
low carbon steels. According to definition, the non-metallic inclusions are chemical compounds of metal with
nonmetal which are present in steel and alloys like separated parts.
Classification of non-metallic inclusions
Non-metallic inclusions are divided by chemical and mineralogical content, by stableness/stability and origin.
By chemical content non-metallic inclusions are divided into the following groups:
• Oxides (simple: FeO, MnO, Cr2O3, TiO2, SiO2, Al2O3 etc.; compound: FeOFe2O3, FeOAl2O3,
MgOAl2O3, FeOCr2O3 etc.)
• Sulphides (FeS, MnS, CaS, MgS, Al2S3 etc.; compound: FeSFeO, MnSMnO etc.)
• Nitrides (simple: TiN, AlN, ZrN, CeN etc.; compound: Nb(C,N), V(C,N) etc, which can be found in
alloyed steels and has strong nitride-generative elements in its content: titanium, aluminum, vanadium,
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cerium etc.)
• Phosphides (Fe3P, Fe2P etc.)
The majority of inclusions in steels are oxides and sulphides. Among various types of nonmetallic inclusions,
oxide and sulphide inclusions have been thought harmful for common steels. Usually, nitrides are present in
special steels (stainless steels, tool steels) which have elements with a strong affinity for nitrogen (e.g.
chrome, vanadium), which create nitrides.
Figure 1 shows sulfides and oxides of non metallic inclusion in steel.
Figure 1: Non-metallic inclusion in steel: oxides-dark gray and sulfides-light gray
By mineralogical content oxygen inclusions are divided into the following groups:
• Free oxides – FeO, MnO, Cr2O3, SiO2 (quartz), Al2O3 (corundum) etc.
• Spinels-compound oxides which are formed by bi- and tri-valent elements as a ferrites, chromites and
aluminates.
• Silicates which are presented in steel like a glass formed with pure SiO2 or SiO2 with admixture of
iron, manganese, chromium, aluminum and tungsten oxides and also crystalline silicates.
Depending on the melting temperature, in liquid steel non-metallic inclusions are in solid or liquid condition.
As mentioned above the majority of inclusions in steels are oxides and sulfides. Sulfides in steel have been
paid much attention because their treatment is an important problem in the steelmaking process. They affect
on the properties of the final products by their deformation during the steel working process; especially their
morphology has a significant effect on the steel properties.
According to analysis based on the steel ingots containing 0.01-0.15% S, the morphology of MnS can be
classified into three types:
1) Type I is a globular .MnS with a wide range of sizes, and is often duplex with oxides.
2) Type II has a dendritic structure and is often called grain-boundary sulfide because it is distributed as
chain-like formation or thin precipitates in primary ingot grain boundaries.
3) Type III is angular sulfide and always forms as monophase inclusion.
Most of the above mentioned sulfides are formed both during the process of secondary metallurgy or the
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solidification process. Recently, with the development of steelmaking technology, the sulfur concentration in
steel was lowered drastically. Also, the continuous casting technology of steels with higher cooling rate than
the ingot casting almost replaced the ingot casting.
So, the sulfides in the modern commercial steel are usually formed on solidification process or in solid steel
during the subsequent cooling process. For example, the Widmanstätten plate-like MnS2, is formed in solid
steel and Figure 2 shows the common morphology of MnS in conventional continuously casting steel,
including the globular duplex oxide–sulfide (particle A, B and C) and the Widmanstätten plate-like MnS
(particle D).
Figure 2: Typical duplex oxide–sulfide inclusion (particle A, B and C) and plate-like MnS (particle D) in
conventional continuous casting silicon steel.
Numerous examples of the effect of non-metallic inclusions on steel properties show the importance of the
behavior of the inclusions as well as of surrounding metal matrix during plastic working of steels. The aims of
the metallurgist are to eliminate undesirable inclusions and control the nature and distribution of the remainder
to optimize the properties of the final product.
An attempt by using program ABACUS was performed to model the behavior of slag inclusions and their
surrounding matrix material during hot rolling and hot forging of hardenable steels. It is shown that it can be
helpful for studying the behavior of inclusions, which is difficult or even impossible to obtain from a
conventional experiment.
Figure 3 shows the effective strain contour during plastic deformation. Three regions of strain concentration
(red) can be seen and a trihedral void (white region) close to the round inclusion is formed. The strain
concentrations arise at the inner surface of the matrix. Another interested thing is that two edges of the pore
tend to emerge and a bonding is formed. The difference in mechanical properties between the matrix and the
inclusion is found to be the primary reason to create a void. The weak bonding at the interface between the
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matrix and the inclusion seems to facilitate to open the void.
Figure 4 shows the effect of rolling temperature on the relative plasticity index during hot rolling of steels. The
relative plasticity index of inclusion increases while the rolling temperature rises. There exists a transition
region, where the relative plasticity index changes rapidly. This trend agrees with the existing experimental
results.
Figure 3: Void formation close to the inclusion.

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Figure 4: Effects of rolling temperature on the relative plasticity index.

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Clean Steel: Part Three
Abstract:
The presence of non-metallic oxide inclusions is a major cause of incompatibility between the attainable and
desirable level of cleanliness in many grades of commercial steel. Generally, inclusions degrade the
mechanical properties of the steel and thereby reduce the ductility of the cast metal and increase the risk for
mechanical and/or corrosion failure of the final product.
The increasing demand in recent years for high-quality steel products has led to the continuous improvement
of steelmaking practices. There is a special interest in the control of non-metallic inclusions due to their
harmful effect on the subsequent stages and their great influence on the properties of the final product.
Through the control of the amount, size and chemical composition of the inclusions it is possible to obtain a
final product of good quality. The control of the formation of non-metallic inclusions and the identification of
their constituent phases are of extreme importance for the obtaining of clean steels.
The presence of non-metallic oxide inclusions is a major cause of incompatibility between the attainable and
desirable level of cleanliness in many grades of commercial steel. Generally, inclusions degrade the
mechanical properties of the steel and thereby reduce the ductility of the cast metal and increase the risk for
mechanical and/or corrosion failure of the final product.
Oxide inclusions originate from two sources:
• residual products resulting from intentionally added alloying elements to deoxidize the molten steel
after oxygen treatment (endogenous or micro inclusions);
• products resulting from reactions between the melt and atmosphere, slag, or refractory (exogenous or
macro inclusions).
Among various types of nonmetallic inclusions, oxide and sulphide inclusions have been thought harmful for
common steels.
Alumina inclusions occur as deoxidation products in the aluminum-based deoxidation of steel. Pure alumina
has a melting point above 2000°C, i.e., these alumina inclusions are present in a solid state in liquid steel. The
addition of calcium to steel which contains such inclusions changes the composition of these inclusions from
pure alumina to CaO-containing calcium aluminates.
As it can be see from Figure 1, the, melting point of the calcium aluminates will decrease as the CaO content
increases, until liquid oxide phases occur at about 22% of CaO, i.e., when the CaO.2Al2O3 compound is first
exceeded at 1600°C. The liquid phase content continues to increase as CaO content rises further and is 100%
at 35% of CaO. The minimum melting temperature for the liquid calcium aluminates is around 1400°C, i.e.,
such liquid calcium aluminates may be present in liquid form until, or even after, the steel solidifies.
Most grades of steel are treated with calcium using either a Ca-Si alloy or a Ca-Fe(Ni) mixture, depending on
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the silicon specification. This treatment is made after trim additions and argon rinsing.
In most melt shops the cored wire containing Ca-Si or Ca-Fe(Ni) injection system is used in the calcium
treatment of steel. The melting and boiling points of calcium are 839°C and 1500°C respectively. During
calcium treatment, the alumina and silica inclusions are converted to molten calcium aluminates and silicate
which are globular in shape because of the surface tension effect. The change in inclusion composition and
shape is known as the inclusion morphology control.
Figure 1: Binary system CaO-Al2O3
The calcium aluminates inclusions retained in liquid steel suppress the formation of MnS stringers during
solidification of steel. This change in the composition and mode of precipitation of sulphide inclusion during
solidification of steel is known as sulphide morphology or sulphide shape control.
Several metallurgical advantages are brought about with the modification of composition and morphology of
oxide and sulphide inclusions by calcium treatment of steel, as for instance:
• To improve steel castability in continuous casting, i.e. minimize nozzle blockage

• To minimize inclusion related surface defects in billet, bloom and slab castings
• To improve steel machinability at high cutting speeds and prolong the carbide tool life
• To minimize the susceptibility of steel to re-heat cracking, as in the heat-affected zones (HAZ) of
welds
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• To prevent lamellar tearing in large restrained welded structures

• To minimize the susceptibility of high-strength low alloy (HSLA) linepipe steels to hydrogen-induced
cracking (HIC) in sour gas or sour oil environments. The Ca content in the final product can be controlled
within the range of 15 to 20 ppm
• To increase both tensile ductility and impact energy in the transverse and through-thickness
directions in steels with tensile strengths below 1400 MPa
When calcium is injected deep into the melt, the following series of reactions are expected to occur to varying
extents in Al-killed steels containing alumina inclusions:
Ca + O = CaO (1)
Ca + S = CaS (2)
Ca + (x+1/3)Al2O3 = CaO·x Al2O3 + 2/3[Al] (3)
Depending on the steel composition, the manner of calcium adding in steel bath and other process variables,
there will be variations in the conversion of alumina inclusions to aluminates inclusions, the smaller inclusions
will be converted to molten calcium aluminates more readily than the larger inclusions.
Thermodynamically, if sulfur or oxygen is dissolved in the steel at moderate levels, or if Al2O3 inclusions are
present in steel, calcium will react with oxygen or sulfur until the contents of reactants are very low (< 2ppm).
One of the critical questions is whether or not calcium added to steel will react with sulfur by reaction (2) and
form CaS or modify Al2O3 to liquid calcium aluminates by reaction (3).
The formation of calcium sulfide can occur if calcium and sulfur contents are sufficiently high. Since calcium
has higher affinity for oxygen than for sulfur, the addition of calcium initially results in a more or less
pronounced conversion of the alumina into calcium aluminates until the formation of calcium sulfides starts as
the addition of calcium continues.
Calcium sulfides are solid at steelmaking temperatures and result in nozzle clogging similar to that caused by
alumina. As can be observed from the Figure 2, the conversion of alumina into calcium aluminates occurs until
all the inclusions in the steel are present only in liquid form.
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Figure 2: Change of inclusions composition during calcium additions
To prevent nozzle clogging in continuous casting by solid inclusions, calcium is added to steel to modify
inclusions and desulfurize the steel. Calcium will convert solid alumina (Al2O3) inclusions into lower melting
point calcium aluminates, which will help prevent the clogging of the casting nozzles. However, when calcium
is added to steel, it will also react with oxygen and sulfur and modify the sulfide inclusions. If the sulfur content
of the steel is high, calcium will react with sulfur forming solid CaS, which could clog up the continuous casting
nozzle.
The Figure 3 shows influence of calcium treatment on the type of inclusions formed and its relationship with
nozzle clogging.
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Figure 3: Influence of calcium treatment on the type of inclusions formed and its relationship with
nozzle clogging
Calcium treatment cannot be applied to all kinds of steel. For those with high requirement on formability, such
as automobile sheet, calcium treatment is not suitable, because this treatment causes the formation of calcium
aluminates inclusion which is hard. Therefore, for those kinds of steel, the method of improving molten steel´s
purity is usually taken to optimize castability. Through controlling carry-over slag from melting furnace,
deformation treatment of ladle slag, metallurgy in tundish, protective casting and other measures, purity of
steel is guaranteed and total oxygen content in molten steel decrease
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Control of Sulfur in Melts
Abstract:
Sulfur has a strong surface activity both in binary (Fe-S) and ternary (Fe-C-S, Fe-Si-S) alloys. It has been
concluded from the results of numerous studies that sulfur can exist in two forms in molten iron: in one case
it forms an interstitial solutions, and in other partially substitutional solutions. It has been found that the
activity of sulfur increase substantially when carbon and silicon are present in the melt. This explains why
pig iron can be desulfurized more readily than steel.
Sulfur (S) is a typical metalloid. The radius of sulfur atom is 1.05 Å. It easily acquires two electrons to form an
2- -4 -4
ion S . The coefficient of diffusion of sulfur in liquid iron is 0.74x10 , 13x10 , 1.9x10-5 cm/s, according to
various experimental data. Sulfur has a strong surface activity both in binary (Fe-S) and ternary (Fe-C-S,
Fe-Si-S) alloys. It has been concluded from the results of numerous studies that sulfur can exist in two forms in
molten iron: in one case it forms an interstitial solution, and in other partially substitutional solutions. It has
been found that the activity of sulfur increase substantially when carbon and silicon are present in the melt.
This explains why pig iron can be desulfurized more readily than steel.
A good understanding of the desulphurization of hot metal and liquid steel has been developed in terms of
slag-metal reactions, based on a number of studies of the partition of sulfur between liquid slag and liquid iron.
These results show that a highly basic slag, high temperature and reducing conditions enhance
desulphurization via slag-metal reactions.
Sulfur Equilibrium between Liquid Iron and Slag
The desulphurization of liquid iron with slag may be examined on the basis of the following reaction (1), in
which the equilibrium constant can be expressed by equation (2).
[S] + (O2-) = (S2-) + [O] .......... (1)
2- 2-
log K1 = as . ao / as. ao .......... (2)
where,
• ao, as: the activities of oxygen and sulfur in liquid iron, respectively
•
2- 2-
ao , as : the activities of oxygen and sulfur ions in slag, respectively.
The sulfur partition ratio between metal and slag is given by equation (3) according to reaction (1).
2- 2-
LS = (wt%S) / [wt%S] = K1 • ao • fs / ao • fs .......... (3)
where,
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•
2-
fs, fs : the activity coefficients of sulfur in liquid iron and slag, respectively.
2- 2-
Since the values of K1, ao and fs cannot be determined experimentally, the sulfide capacity is defined as
equation (5) on the basis of reaction (4) and is utilized for the examination of desulphurization in iron and steel
making processes.
2-
½ S2 + (O2-) = (S ) + ½ O2 .......... (4)
2-
CS = (wt%S) • (PO2 / Ps)½ = K4 ao2- / fs .......... (5)
where,
• PO2 and Ps are the oxygen and sulfur partial pressure in atm;
• K4 the equilibrium constant of reaction (4).
In order to calculate the value of CS, the equilibrium constants of reactions (6) and (7) are substituted into
equation (5), and equation (8) is obtained.
½ O2 = [O] .......... (6)
½ S2 = [S] .......... (7)
log Cs = log (wt % S) ao / as + 936 / T-1.375 .......... (8)
By the use of the interaction coefficients of sulfur and oxygen in liquid iron, the values of CS can be calculated
from equation (8).
As an illustration, the calculation of sulfide capacity (CS) has been given for CaO-MgO-Al2O3-SiO2 ladle slags.
In order to examine the relationship between CS and composition of slag, the following relationship is assumed
to hold at certain temperatures.
log CS = α (NCaO + KMgO • NMgO + KAl2O3• NAl2O3 + KSiO2 • NSiO2)+ β .......... (9)
where:
• α, β: the constants
• Ni, Ki: the mole fraction and the lime equivalent coefficient of i-component in the slag phase,
respectively.
At 1600°C, the values of KMgO, KAl2O3 and KSiO2 determined by trial and error are 0.1, -0.8 and -1.0,
respectively. As shown in Figure 1, there are linear relations between log Cs and (NCaO + 0.1 NMgO – 0.8 NAl2O3
– NSiO2) at 1575, 1600 and 1650°C.
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Figure 1: Plot of the log Cs against NCaO + 0.1NMgO – 0.8NAl2O3 – NSiO2 at 1575, 1600 and 1650°C
The three lines obtained by the method of least squares are shown in the figure. The intercepts of the lines
were determined by the use of the slope at 1600°C because the most runs were done at this temperature. The
following equation was obtained as a function of temperature.
log CS = 3.44 (NCaO +0.1NMgO – 0.8NAl2O3 – NSiO2) - 9894 / T+2.05 .......... (10)
The observed values of log CS with the correlation coefficient (R) of 0.99 and the standard deviation (σ) of
0.044 can well be expressed by the above equation.
On the other hand, log LS may be expressed by the following general equation derived from equations. (3), (8)
and (10).
log LS = α ∑ Ki•Ni - log [wt%O] - β .......... (11)
where,
• ∑ Ki•Ni = NCaO +0.1NMgO – 0.8NAl2O3 – NSiO2.
The experimental data were arranged by the method of least squares according to equation (11) and the
following relationship was obtained.
log LS = 3.44 ∑ Ki•Ni - log [wt% O] - 10 980 / T+3.50 .......... (12)
Relationship Between Sulfide Capacity and Theoretical Optical Basicity
Duffy and Ingram defined the theoretical optical basicity (Λ) as follows:
Λ = ∑ (xi / fi) .......... (13)
where, xi, fi : the equivalent cationic fraction and the basicity moderating parameter for the constituent cation i,
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respectively.
It was verified by them that fi can be expressed by the Pauling's electronegativity xi as follows:
fi =1.36 (xi -0.26) .......... (14)
It was also found by Duffy and Ingram that log CS are linearly correlated to the theoretical optical basicity.
As an illustration of the above mentioned the experimental results performed on ladle CaO-MgO-Al2O3-SiO2
slags has been given. The values of log CS are plotted against the optical basicities at 1575, 1600 and 1650°C,
as shown in Figure 2.
Figure 2: Plot of log CS against theoretical optical basicity Λ
The slopes and intercepts of the lines were determined by the method of least squares, and the following
linear relationship was obtained as a function of temperature.
log CS = 14.20Λ - 9 894 / T -7.55 .......... (15)
As described above, it can be seen that both the sum of lime equivalent and the optical basicity are able to be
used as parameters for the representation of sulfide capacity. From the relationship between these two
parameters, the linear equation (16) from regression was obtained.
Λ = 0.24(NCaO + 0.1NMgO – 0.8NAl2O3 – NSiO2) + 0.67 .......... (16)
The correlation coefficient (R) is larger than 0.99, and the standard deviation (σ) is smaller than 0.01. This
shows that the two parameters have almost the same character for the representation of sulfide capacity of
slag.
Equilibrium of Oxygen Partition between Metal and Slag
It is well known that the oxygen potential exerts a large influence on the sulfur partition between metal and
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slag. The equilibrium of reaction (17) was determined by the use of the value of the equilibrium constant (18)
reported in literature.
(FeO) = [Fe] + [O] .......... (17)
log K17 = log ao / aFeO = -6 150 / T + 2.604 .......... (18)
Equation (18) may be modified to the following equation.
log [wt%O] = log NFeO + log γFeO - log fo - 6 150 / T + 2.604 .......... (19)
where γFeO is the activity coefficient of FeO on the basis of mole fraction.
Since log γFeO is a function of temperature and slag composition, log [wt%O] can be expressed by an equation
including the term of log NFeO, then the following relationship was obtained.
log [wt%O] = 0.905 log NFeO -0.15 ∑ Ki•Ni - 6 340 / T + 3.115 .......... (20)
where, ∑ Ki•Ni = NCaO + 0.1NMgO – 0.8NAl2O3 – NSiO2.
As shown in Figure 3, the observed values of log [wt% O] agree well with the values calculated from the
equation (20). By substituting equation (20) into equation (12), equation (21) is derived:
log LS = 3.59 ∑ Ki•Ni -0.905 log NFeO – 4 640 / T + 0.385 .......... (21)
The above equation can conveniently be used for the estimation of the sulfur partition between liquid iron and
slag in which the oxygen content in liquid iron is not analyzed. Next, the values of γFeO calculated from the
equation (19) were arranged by the way similar to that described previously, and the following relationship was
obtained.
Figure 3: Comparison of the observed log [wt%O] with calculated log [wt%O] from the equation (20)
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Some Fundamental Steps in Thermomechanical Processing

of Steels* .
By Imao TAMURA**
Key words: ~hermomechanicalprocetsing;steel; deformation o f austenite; essing of steels, we can point out that:
restoration process; phase transformation; microalloying; ferrite grain re-
1) The deformation and restoration processes of y
Jinement. during and after hot rolling.
2) The kinetics of y to a transformation and grain
I. Introduction size of a.
Thermomechanical processing is a treatment of 3) The effect of cooling rate on transformation of
which plastic deformation is introduced into the heat work-hardened y to a , and grain size of a.
treatment of steel. We can find many treatments in 4) Structure of martensite in ferrous alloys.
such processes. But controlled rolling and acceler- 5) Structure and properties of martensite formed
ated cooling, and the ausforming or deformation- from work-hardened y.
quenching are representative and are used in practical 6) Hardenability of work-hardened y and recrystal-
production. lized y.
I n controlled rolling, the austenite (y) is work- I will explain on these processes based on our re-
hardened with plastic deformation (rolling) in high search results.
strain rate a t elevated temperatures, and then air
cooled to transform to ferrite (a). Sometimes, work-
hardened austenite is cooled acceleratedly to take fine II. Deformation Behaviors of Austenite during
-
ferrite grains in steel plate. and after Hot Working
I n the ausforming, work-hardened austenite is
quenched to room temperature. We can take the I. Restoration Process during Hot Deformation of Auste-
ausformed martensite which increases its strength and
not decrease its toughness. The ausforming is not so I t is well known that the deformation behavior of
popular in practice but the deformation-quenching is austenite a t elevated temperatures is a dynamic re-
getting to be popular. The martensite in the defor- crystallization type. Figure 1 shows schematically
mation-quenching looks like as usual martensite. But, both types of dynamic recovery type and dynamic
this martensite has a little bit of fine facet size be- recrystallization type.
cause it is formed from smaller austenite grains than I n the case of a dynamic recrystallization type,
usual austenite. This process can abridge to ration- since the rate of softening due to recovery is slow, the
alize the heat treatment process of steel. work-hardening can not be balanced only by dynamic
As fundamental steps in thermomechanical proc- recovery even at high temperatures, and the disloca-
tion density is still gradually increased with strain,
and finally the recrystallization starts to occur during
(a) deformation. The true stress is lowered beyond the
tn dynamic recovery peak stress by the occurrence of dynamic recrystal-
3 lization and reaches a certain steady state stress
level at which the work-hardening and softening due
to recrystallization occurring repeatedly are balanced.
The dynamic recrystallization starts at the strain of
(b) dynamic recrystallization around 0.78, (E,: the strain showing the peak stress).
I n Fig. l(b), the strain range up to about 0 . 7 ~is ~
the work-hardening region, the strain range between
about 0.78, and 8, (the strain at which the steady
state deformation starts) is the range of partially
dynamic recrystallization, and the strain range after
E , ~ is the range of steady dynamic recrystallization.
Austenite in steels belongs to this type. I n a-Fe (fer-

True strain rite), since the recovery occurs very fast, the restora-
Fig. 1. Schematic illustration of two types of true stress- tion is performed mainly by dynamic recovery. The
true strain curves accompanying the steady state peak stress (a,) and the steady state stress (a,) in the
deformation at elevated temperatures. dynamic recrystallization type change with the Zener-
* Based on the Special Lecture delivered by Prof. Tamura in commemoration of his receiving Nishiyama Medal in the 113th ISIJ
Meeting, April 2, 1987, a t The University of Tokyo in Tokyo. Manuscript received on May 18, 1987. 0 1987 ISIJ
** Professor Emeritus, Kyoto University; Technical Advisor, Sumitomo Metal Industries, Ltd., Nishinagasu-hondori, Amagasaki 660.
Special Lecture ( 763 )

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[ 764 ) Transactions ISIJ, Vol. 27, 1987
Hollomon parameter (2). Z is expressed by them when Z is high.

I n the same way as the static recry~tallization,~)it
has been observed that there are two main mech-
where, i: the strain rate (s-l) anisms for dynamic recrystallization, i.e., the bulging
I? : a gas constant (J/mol) mechanism and the nucleation-growth mechanism.
Dynamic recrystallization becomes easier to take
Q: the activation energy for deformation (J/
mol) place when the initial grain size (do) of austenite is
7: temperature (K). smaller. Therefore, in the case of fine initial grain
a?,, ep, g s and E , are increased with increase in Z (i.e., size, c p and E, become small even at the deformation
with increase in i or decrease in 7). under the same Z condition. However, a,, and a , are
Figure 2 shows the change in optical microstructure independent of do. The average size (d) of dynam-
with strain in Fe-31%Ni-0.3%C austenitic alloy ically recrystallized grains is the only function of Z
which was tensile deformed at 1 273 K (1 000°C) at a and is expressed by the following equation,')
strain rate of 1.7 x 10-2/s. Figure 2(a) is the austenite
structure before deformation. Austenite grains are
equiaxed and their boundaries are smooth and planer. where, A, : material's constant.
Many annealing twins exist in austenite grains. When A is larger for C-steel than for alloy steels, especially
deformed slightly (E=0.08), as shown in Fig. 2 (b), the small for Nb-containing steel and high alloy steel. p
grain boundaries become finely serrated and the bulg- is about 0.3-0.4 for all steels. I t should be noted
i n g ~of grain boundary are observed as indicated by that d is independent of do.
the arrows. At the strain slightly after E,, many small
grains are newly formed along the austenite bound- 2. Static Restoration Process during Holding Right after
aries as shown in Fig. 2(c). I t is characteristic that Hot Deformation
these newly formed grains hardly contain annealing When the hot deformation is finished a t the work-
twins. Furthermore, some of the initial austenite hardening stage, the work-hardened austenite is sof-
grains becomes larger by the strain-enhanced coarsen- tened by the usual static recrystallization during iso-
ing. Figure 2(d) shows the structure in the range of thermal holding after deformation. However, if the
steady state deformation at which the work-hardening strain is too small, the recrystallization can not occur
and the dynamic recrystallization softening are bal- and only the recovery takes place. O n the other
anced. This structure consists of several grains cor- hand, when specimens are isothermally held after de-
responding to various stages of recrystallization, i.e., formation to the range of the steady state deformation,
from small grains which have just started to recrys- in which the dynamic recrystallization has occurred,
tallize to fairly large grains which have been subjected the recrystallization and the grain growth can succeed
to deformation after the finishing of recrystallization to occur continuously during holding after hot defor-
and are the work-hardened state just before the next mation. Such a recrystallization is called a meta-
recrystallization. I n the stage of steady state defor- dynamic or postdynamic recrystallization. Namely,
mation, the recrystallization occurs repeatedly during the dynamically recrystallized structure is further
deformation. Dynamic recrystallized grains contain softened by the metadynamic recrystallization. When
a few annealing twins a t low Z but scarcely contain specimens are deformed to the range of (11) in Fig.
(a) Before testing (E=O)

(b) €=0.08
(c) e=0.24
(d) &=0.40
Pig. 2. Optical micrographs showing tlie formation process of dynamically recrystallized austenite in Fc-31Ni-0.3C
austenitic alloy deformed a t 1 OOO°C, 1.7 x 10-2/s.
Special Lecture
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Transactions ISIJ, Vol. 27, 1987 ( 765 )
l ( b ) in which the work-hardened austenite and dy- tenite grain size with At is also plotted in Fig. 3.
namically recrystallized austenite have coexisted, the Microstructural changes during isothermal holding a t
static recrystallization occurs in work-hardened aus- 1 373 K (1 100°C) are shown in Fig. 4 and Fig. 5.
tenite and the metadynamic recrystallization occurs As shown in Fig. 4 ( ~ = 0 . 1 8 )work-hardened
, austenites
in dynamically recrystallized austenite at the same are slightly elongated along the tensile direction (Fig.
time. 4(a)). The austenite hardly changes by holding for
I n case of rolling by hot strip mill in which slabs 1 s (Fig. 4(b)), although the softening occurs to some
are rolled by several passes, the static restoration proc- extent by the static recovery as can be seen in Fig. 3.
ess occurring during interval between rolling passes However, when specimens were isothermally held for
has great influence on the deformation behavior of 4 s (Fig. 4(c)), fine austenite grains which are form-
next rolling pass. If the softening due to the static ed by static recrystallization are partially formed
restoration is not completed during interval between mainly along the deformed austenite grain boundaries
rolling passes, the work-hardening is successively ac- and the static recrystallization is completed by the
cumulated by the subsequent rolling passes. holding of 15 s (Fig. 4(d)). Annealing twins in static
Fraction of softening (X) occurring during iso- recrystallized austenites are gradually developed with
thermal holding right after hot deformation can be increase in holding time. By holding for 40 s, recrys-
evaluated by the two-step deformation test from the tallized austenite grains are coarsened (Fig. 3). When
following e q ~ a t i o n , ~ ) the austenite was much more heavily deformed under
higher Z condition (work-hardened), the static re-
crystallized austenite grains become much finer as
shown in Fig. 6. As shown in Fig. 5 (a=1.0), dy-
where, cr,,,: the flow stress immediately before un- namically recrystallized austenites are characterized
loading by irregular grain boundaries, a low density of an-
c ~ , , ~ : the yield stress on reloading after hold- nealing twins and the mixed grain size. With in-
ing the specimen for various periods of crease in holding time, austenite grain boundaries
time (At) become fairly straight and austenite structure becomes
u,,,: the initial yield stress. almost equiaxed grains, and furthermore, the density
As an example, the change in the fractional softening of annealing twins is increased. This is the typical
(X) with the holding time (At) in Fe-31 %Ni-O.S%C microstructural change occurring during metadynam-
austenitic alloy is shown in Fig. 3. Specimens were ic recrystallization process. Metadynamic recrystal-
tensile deformed a t 1 373 K (1 100°C) a t a strain rate lization is completed by the holding for about 30 s in
of 4 x 10-2/s to E = 0.18 (work-hardened austenite) and the case of Fig. 5, and the usual grain coarsening oc-
e = 1.0 (completely dynamically recrystallized auste- curs by further holding. The grain size right after
nite), respectively, and then isothermally hild for the completion of metadynamic recrystallization is
various periods of time. The change in average aus- smaller, as the grain size of dynamically recrystallized
Hdding time. A t ( s )
Fig. 3.
Change in fraction of softening (a) and austenite As-deformed ( A t = 0 S) (b) At = 1 s (c) At = 4 s (d) ~t = 15 s
grain size (b) with the isothermal holding time of Fig. 4. Change in optical microstructure of work-hardened austenite (de-
work-hardened austenite and dynamically recrystal- formed at 1 100°C, t = 4.0 x 10-2/s, c ~ 0 . 1 8 during
) isothermal holding
lized austcnite in Fe-31Ni-0.3C austenitic alloy. at 1 100°C for At in Fe-31Ni-0.3C austcnitic alloy.
Special Lecture
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[ 7 6 6 ) Transactions ISIJ, Vol. 27, 1987
(a) AS-deformed ( ~= Ot s) (b) At = 1 s (c) At=2 s (d) At=30 s (a) Work-hardened austenite (detormed a t 900°C,
Fig. 5. Change in optical microstructure of dynamically recrystallized austenite e=3/s, ~ z 1 . 0 )
(deformed a t 1 100°C, d = 4.0 x 10-Z/s, E = 1.O) during isothermal (h) Static recrystallized austenite (isothermally
holding a t 1 100°C for At in Fe-31Ni-0.3C austenitic alloy. held a t 900°C for 50 s of structure (a)
Fig. 6.
Optical micrographs showing the static recrystal-
austenite is smaller. lization occurring during isothermal holding after
heavily work-hardened austenite in Fe-31Ni-0.3C
3. Efect of Alloying Elements on the lietardation of Re- austenitic alloy.
crystallization5)
Table 1. The values of n and m in Eq. (4) for varlous
The effect of alloying elements on the restoration transformation conditions.
process during or after hot deformation is very im-
portant. Micro-addition of N b or T i acts as a re- Mechanism Site saturation
Nucleation and
markable retardation effect on recrystallization due to growth
-- - -- -- --
the suppression of grain boundary migration. The Site n m n m
suppression of grain boundary migration due to micro- Grain surface 1 1 4 1
alloying is caused from (1) the solute dragging effect Grain edge 2 2 4 2
due to segregation of alloying elements to the bound- Grain corner 3 3 4 3
aries, or (2) the pinning effect due to precipitates of
carbonitride of alloying elements at grain boundaries.
For example, Mo segregates to the austenite grain x = l - exp [ - k ( ~ ) $ ] ...............(4)
boundaries, resulting in the suppression of grain
boundary migration. Even N b micro-addition, at where, X: the transfbrmed fraction
high 1, it can retard the recrystallization by dragging t: the isothermal holding time
effect. But, usually, N b and T i are precipitated as d: the austenite grain size
fine carbonitride particles and these precipitates sup- k(7): the rate constant which depends only
press the grain boundary migration by the pinning on transformation temperature and di-
effect. rectly corresponds to the C-curve of
T T T diagram (isothermal transforma-
III. Transformation Kinetics and Grain Size of tion diagram).
Ferrite Transformed from Austenite The values oS the exponent m and n are listed in Table
1.6) These values depend on both the transformation
I. Isothermal Transformation Kinetics of Austenite mechanism and type of nucleation site. Here the
When the ferrite or pearlite Sorms from austenite transformation which progresses with nucleation and
by isothermal holding below the transformation tem- growth over almost entire range of transformation is
perature, these nuclei form preferentially a t the prior called " nucleation and growth ". The transforma-
austenite grain boundaries. We expressed as Eq. (4)'3 tion where all the nuclei are nucleated a t the early
that their transformation kinetics include the effect of stage in the reaction and the progress of transforma-
austenite grain size, by modification of Johnson-Mehl tion is controlled mostly by their growth is called
equation. " site saturation ". An austenite grain is assumed to
Special Lecture
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Transactions ISIJ, Vol. 27, 1987 ( 767)
be a tetrakaidecahedra, and the nucleation sites a t Now extend this Scheil's additivity rule to the
austenite grain boundary can be classified into sur- entire range of transformation. I n this case the incu-
faces, edges and corners as are shown in Fig. 7.697) bation time ( ~ ( 7 )is) replaced with the time required
Of course the actual nucleation sites are not limited to for the reaction to reach a certain fractional comple-
any one of such types, and the value of m would be tion X by isothermal holding at temperature T. If
the weighted average of the various nucleation sites we combine Eq. (5) with Eq. (4)
and not always be an integer.
According to Umemoto and Tamura,e) the values
of n and m, and transformation modes were experi-
mentally shown as in Table 2. I t is mentioned in
Table 2 that the mode of y + a transformation is site
where, Q ( T ) = -dT/dt: a cooling rate.
saturation, but it means the large number of nuclea-
This equation expresses the transformed fraction at
tion o f a would occur at the beginning of transforma-
temperature T during cooling from austenite condi-
tion, which would not be real "site saturation ".
tion with a cooling rate Q(T).6t9) Furthermore, from
Sometimes the nucleation site is varied by supercool-
Eqs. (4) and (6) we obtain
ing (accelerated cooling). I t seems that the nuclea-
tion site of a is moved gradually from edge to surhce 1
by decrease in transformation temperature with cool- t ( 7 )= - J
K T )
-TTe K(T1)1/7~
- -
Q(T')
dT' = t., ...... (7)
ing rate, as described later.
This equation tells that the fraction transformed by
2. Continuous Cooling Transformation Kinetics of Austenite cooling from 7, to T with cooling rate Q ( T ) is equal
Scheils) considered the case where the austenite is to that obtained by the isothermal holding at tem-
cooled continuously through its transformation temperature T for time t ( 7 ) . Thus we call t ( T ) as an
perature. He assumed that austenite consumes its equivalent cooling time, t,,. t,, means the isothermal
fractional nucleation time and when the sum of a holding time which gives the equivalent transformed
number of such fractions equals unity, the transfor- fraction with continuous cooling. The curve pro-
mation starts, i.e., duced by the successive plot oS such t,, at each tem-
perature during cooling with cooling rate Q ( T ) will
be called an equivalent cooling curve.'O) The trans-
formation behavior for a given cooling curve can be
predicted from the T T T diagram by plotting such
curve on a T T T diagram.
3. Ferrite Grain Size Transformed from Austenite

1. Expression for Ferrite Grain Size (Isothermal)
I n general, ferrites nucleate at austenite grain
boundaries and grow into austenite grains. The
grain size of ferrite formed from austenite is directly
related with the process of transformation.") The
nominal ferrite grain diameter D, can be expressed
with the total number of ferrite grains uncleated
throughout transfbrmation per unit volume of auste-
nite, n,, as12)
Fig. 7. Schematic diagram of austenite grain as a tetra-

kaidecahedra and showing 3 types of nucleation
sites offerritc.
where, I : nucleation rate per unit volume oS aus-
tenite
'Table 2. The values of r2 and m for various trans- X: volume Sraction transformed
formation modes. Thus the problem of obtaining the exprcssion for fer-
rite grain size is the problem of how to express n,>.
Transformation n m Nucleation When ferrites nucleate a t the austenite grain bound-
-
Pearlite 4 2 Edge nucleation ary surfaces, they grow as ellipsoid with the aspect
Nucleation and growth ratio of 3 : 1 1 3 ) as shown in Fig. 8. The total number
1:errite 1 1 Surface nucleation near
of rerrite grains nucleated per unit area of austenite
Site saturation grain boundary surface is
)dt = -
4 0.6 9
Bainite Grain boundary,
Inside grain
n, = I,J; exp (-Tzaz~stz 3:2-(':')
-
Nuclcation and growth
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[ 768) Transactions ISIJ, Vol. 27, 1987
ferrite g r a i n grain boundary nucleation a small austenite grain

leads to a small ferrite grain. The effect of austenite
grain size on ferrite grain size depends on the type of
g r a i n boundory nucleation site, and it becomes large in the following
r=3Cl(t- 2) ascending order: homogeneous, grain surSaces, and
grain edges.
Fig. 8. Schematic drawing of a ferrite grain nucleated at
I t should be noted that the grain refinement on
austenite grain boundary surface.
austenite turns out to be less effective in ferrite grain
refinement. For instance in the case of grain surface
where, I , : the nucleation rate per unit area oL aus- nucleation D, is proportional to D',I3 in Eq. (13).
tenite grain surface This means that when D, is reduced to 118 of the ini-
a : parabolic rate constant for thickness. tial, D, would be reduced only into 112.
The ferrite grain size D, is given as Figure 914)shows experimental results of isothermal
transformation in a steel (0.2 % C, 0.0016 0/, B). The
steel was austenitized between 1 000 and 1200°C to
change its austenitic grain size from about 53 to 88
where, Sg.b: the austenite grain surface area per pm, and then transformed a t 700, 680 and 660°C into
unit volume Ferrite. The results are recognized as the dependent
and can be expressed by austenite grain diameter, D,, of y-grain diameter that a nucleates mainly at grain
as edges a t 700°C, at grain edges and surfaces a t 680°C
and at the surfaces a t 660°C.
2. Estimation of Ferrite Grain Size Formed by Continu-
ous Cooling Transformation
Substituting Eqs. (10) and (12) into Eq. ( l l ) , the It can be assumed ferrite nucleates preferentially at
ferrite grain size and the y / a transfbrmation ratio can austenite grain surfaces by supercooling. A continu-
be expressed as ous cooling transformation can be considered as the
sum of short time isothermal holdings a t successive
temperatures as is schematically shown in Fig. 10.
During cooling, ferrite grains are nucleated and
and grow at each temperature with the corresponding
nucleation and growth rates, as is schematically shown
in the Fig. 10 (bottom). During ferrite transforma-
tion carbon enriches in retained austenite, however,
since ferrite nucleation occurs mostly in the early stage
of transformation, it can be assumed that both the
In the above derivation it was assumed that the
nucleation and growth rates of ferrite are a function of
nucleation rate and the parabolic rate constant of
a n instantaneous temperature only and not a function
growth are time independent and one nuclei grows
of thermal history.
and forms one grain.
Based on this assumption, the number of ferrite
Similarly the D, and y / a transformation ratio in the
nuclei (N,) nucleated at temperature I, during cool-
case of homogeneous and grain edge nucleation has
ing, N, is given as Eq. (16).
been obtained asl1)
where, Q ( T ) (= -dT/dt) : a cooling rate.

Ferrite grains once nucleated grow thereafter with a
corresponding growth rate at each temperature during
cooling. Thus, at temperature T, the radius of a fer-
rite grain on an austenite grain surface nucleated a t
temperaturc T,, is given as Eq. (1 7).
where, I h : the homogeneous nucleation rate per unit

volume The austenite grain boundary area occupied at tcm-
pcrature 7 by a ferrite grain nucleated a t temperature
I,: nucleation rate per unit length of auste-
nite grain edge. T, is given as Eq. (18).
I t should be noted that the equations introduced
above indicate that ferrite grain size and y/a trans-
formation ratio depend on the ratio of square root of
the nucleation rate to the parabolic rate constant in I t will be convenient to use the concept of extended
all three types of nucleation sites. Furthermore Sor area which is the sum of the areas of austenite grain
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Transactions ISIJ, Vol. 27, 1987 ( 769 ]
Austenite G r a i n Size
o ~ *
TI
d(h)
T2
d(T2)
T3
d(T3)
Tl,
~ ( T L )
Is(T ) Is(T2) Is(T3) Is(TL )
Fig. 10. Diagrams to explain the relation between iso-
thermal and continuous cooling transformation
and schematic drawing showing the formation
process of ferrite during continuous cooling.
Fig. 9. An example of D,- or D,/D,,-D, rclationsllip for

S15C steel.
surface occupied by ferrite grains, assuming that fcr-

rite grain never stop growing and that ferrite grains
keep nucleating a t the same rate during transforma-
tion as well as on untransformed austenite grain sur-
faces. The extended grain boundary area occupied
by all the ferrite grains nucleated a t T , during cool-
ing is given as Eq. (1 9).
Thus the grain boundary arca fraction occupied by

the ferrite grains nucleated during cooling horn A 3 ( T , )
to T is givcn by Eq. (20).
673 773 873 973 1073 1173
{J:$?&; dl-' 1d T , 1............(2 0) TEMPERATURE, K

Fig. 11. Calculated parabolic rate constant and nucleation
rate I, as a function of' temperature for the steel
The total number of ferrite grains nucleated per unit studied. (S15C)
area of austenite grain boundary surfacc is given by
Eq. (21).
where, Sg.,,(=4/(dn D,)): the austenite grain surface
area pcr unit volume.
From these equations, ferrite grain s i ~ ecan be cal-
culated.
I t is fairly difficult to estimate of I , ( T ) and tt(T)
by some kinds of calculation, but it is not impossible.
By using several assumptions and h y p o t h e s i ~ , ~ ~ ' ~ - ~ ~ )
Ferrite grain size is given as Eq. (22). I , ( T ) and a ( T ) are roughly calculated as shown in
Fig. 1 lZ4)as a function of transformation tempera-
ture. I n this figure, I , shows a maximum value a t
913 K (640°C) and n shows a maximum value a t
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( 770 ) Transactions ISIJ, Vol. 27, 1987
873 K (600°C) fbr S15C steel (0.15 % C, 0.4 % Mn). IV. Ferrite Grain Refinement by Work-harden-
Figure l2Z4) shows a comparison of calculated ing of Austenite
values and experimental values for C15C steel. Wc
can get a roughly agreement, that is, a-grain size is I. Ferrite Nucleation in Deformed Austenite (Isothermal)
getting smaller with cooling rate increases. The Sor- Figure 14 is typical micrographs showing the effect
mulations are : of austenite defhrmation on the progress of ferrite
transformation.Z5) Specimens of an Fe-0.12C-0.04-
Dtv= Q-0.17(D,)1'~cal~ulat~d) ..................(23) Nb-0.04V steel were austenitized at 1 200°C for 30
(experimental) ... ......(24)
Do = 5.7Q-0.2'3(D,)0.46 min, rolled 30 or 50 % in reduction by a single pass
a t 840°C (in the unrecrystallized temperature range)
Figure 1324)shows experimental results. and held at 680°C for 15, 30 and 180 s. The ferrite
transformation is clearly accelerated by deformation
COOLING IRATE , K is
Fig. 1 l'erritc grain s i ~ eas a function of cooling rate lor

the specimens of D, = 151 pm. (S 15C) Fig. 13. Ferrite grain size as a function of Q-0.2'3Dt4G.
Not Rolled Rolled(30%) Rolled(50%)
(a) Non-deformed, 15 s (b) 30 % rolled, 15 s (c) 50 % rolled, 15 s

(d) Non-deformed, 30 s (e) 30 % rolled, 30 s (f) 50 % rolled, 30 s
(g) Non-defbrmed, 3 min (h) 30 % rolled, 3 min (i) 50 0/6 rolled, 3 min
Fig. 14. Optical micrograph showing the efrect of austenite deformation on the proccss of' ferrite transfbrma-
tion a t 680°C in a Fe-O.12C-0.04Nb-0.04V steel.
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ofaustenite. I n the non-deformed specimen austenite

grain boundaries are the predominant nucleation sites S,.,,(p) = St''-* [(q x J:
-1'1-*
J 1-(2p-pvsiFzB do.
of ferrite, but in the deformed specimens nucleation
occurs not only on austenite grain boundaries but also
within grains. Moreover, the nucleation rate on
grain boundaries is substantially accelerated. l h c ratio of the surface area before to after rolling,
Figure 15 shows various types of nucleation sites of q(=S,.b/SO,.,,), is plotted in Fig. 17 as a function of
ferrite observed in deformed specimens.25) Figure rolling reduction p. Since the volume of the sphere
15(a) shows ferrite grains nucleated a t austenite grain shown in Fig. 16(a) is equal to that of the ellipsoid
boundaries. The ferrite grains grow into both sidcs shown in Fig. 16(b), the ratio q in Fig. 17 is equal to
of austenite grains, and the prior austenite grain that obtaining to grain surface areas per unit volume
boundaries disappear once ferritcs are nucleated. Fig- before and after rolling. I t is seen that the increase
ure 15(b) shows the ferrite grains nucleated a t the in the grain surface area per unit volume with the in-
annealing twin boundaries. I n contrast to the non- crease in p is quite small when p is smaller than 0.5.
deformed specimens, the annealing twin boundaries For instance 50 % reduction by rolling increases the
in the deformed specimens are the preferential nuclc- surface area by 25 %. This increase is equivalent to
ation site of ferrite. The ferrite grains nucleated at that obtained by only 20 0/, reduction in austenite
annealing twin boundaries grow mostly into one side, grain size.
and the traces of prior annealing twin boundaries The number of ferrite grains nucleated on austenite
remain after transformation. Figure 15(c) shows fer- grain boundaries is substantially increased by defor-
rite grains nucleated intragranularly. These ferrites mation. Figure 1825) shows the ferrite grains nu-
were considered to be nucleated on the dislocations at cleated on the austenite grain boundaries: (a) non-
the cell wall distributed almost uniformly inside the deformed, (b) 30 % rolled, and (c) 50 % rolled,
grains. Figure 15(d) shows the ferrite grains nucle- respectively. From these pictures the acceleration of
ated at decormation bands. ferrite nucleation rate on austenite grain boundaries
The increase in the ferrite nucleation rate per unit by deformation can be estimated. The number of
volume of austenite by deformation is attributed (1) ferrite grains intersect per 1 mm of austenite grain
to the increase in the austenite grain surface by elon-
gation of grains, (2) to the increase in the nucleation
rate per se per unit area of grain surface, and (3) to
the formation of additional nucleation site such as
annealing twin boundaries, deformation bands, etc.
The grain boundary surface area of austenite per
unit volume of a specimen increases by deformation.
A spherical austenite grain (Fig. 16(a)) becomes an
ellipsoid as shown in Fig. 16(b) by applying the roll-
ing with reduction p. The surface area of a grain (a) (b)
with an unit radius before rolling is given as
(a) Kcfore rolling (sphere)
(b) After rolling (ellipsoid)
The surface area of the grain after rolling with reduc- l i g . 16. Tlic shapc change ol' a n austcnite grain by the
tion p is given as rolling with reduction p.
Rolled (30V0)30s Rolled(30%) 15s
(a) W ~ ~ c . l t , ~;it
~ tgr~ii11
i o ~ ~ I>o~~n(laric~s
(I,) Nuc.l(.atiun on ;i~ni~.nli~ig t \ \ . i r ~ I)ou~~cl;iric~~
(c.) S~iclcntioni n d c gr;iinr
((1) Suclc:~tionon clt.IL1.1nntion bantls
Fig. 15.
~ i 01'
Opticxl n>ic.rogl.nplis showi~lglllr \ . ; ~ r i o ~types
~iucleatiun bites 01' IC3rrite obier\,ccl i l l drll1.111rd
specimens. Rolled(50%) 15s Rolled(30%) 15s
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strain & (=-ln(1-p))

0 -0.5 - 1.0
Not Rolled
680 'C
3min
1 7 --
1.6 --
1. 5 --
1.4 --
1.3 --
Rolled (5O0Io)
o 0.1 0.2 0.3 0.4 0.5 0.6 0.7 680 O C
Rolling Reduction p
30s
Fig. 17. The ratio of austenitc grain surfacc arca bcforc
rolling to that of after rolling as a f~~nction
of roll-
ing rcduction $. (a) Non-deformed, 3 min at G80°C
(b) 30 0/, rolled, 3 s at 680°C
(c) 30 % rolled, 3 s at 680°C
boundaries werc counted as 4 1, 214 and 330 for 1 18. Optical micrographs showing the efycct of defor-
0, 30 and 50 rolled specimens, respectively. The mation on the number of ferrite formed on auste-
numbers of ferrite grains nucleated per unit area nite grain boundaries.
of austenite grain boundary surface are proportional
to the square of these numbers. Furthermore the
number of ferrite grains nucleated per unit area of
austenite grain surface, n,, is proportional to the
square root of I, as is shown in Eq. (10). Since a is
not much changed by deformation, the ferrite nuclea- $.,,.,j-
rcrrite
tion rate per unit area of austenite grain boundary ,A-F

surface is estimated to be increased by 740 ((214/41)4)
and 4 200 ((330/41)4) times faster by 30 and 50 %
rolling, respectively. (a) A ledgc on grain boundary
(b) Ferrite nuclcation at a lcdgc
As is shown above, the nucleation of ferrite on
austenite grain boundaries is substantially accelerated Fig. 19. Scllematic drawing showing ferrite nucleation at
by deformation. The mechanism of enhanced nu- a ledge on deformed austcnite grain boundaries.
cleation is considered to be as follows. The deformed
austenite grain boundaries may have many ledges (or the similar structure with that of austenite grain
steps) shown schematically in Fig. 19(a). If ferrite boundary surfaces and act as the preferential nu-
nucleates a t the corner or such a ledge, as is shown cleation site of ferrite.
in Fig. 19(b), the activation energy for nucleation be- Similar mechanisms have bcen proposed for the
comes B/n times less than that fbr nucleation on a enhanced nucleation on deformed austenitc grain
planar grain boundary (if the surface energy is as- boundaries by several researchcrs. Sandberg and
sumed to be equal for all kinds of interfaces). Thus Robertsz7)have suggested that deformation leads to
if a large number of ledges are produced on grain the formation of grain boundary serrations or bulges,
boundaries by deformation, considerable increase in and these act as nucleation sites. Amin and Pic-
the nucleation rate can be expected. As is shown keringZ8) proposcd that deformed austenitc grain
in Fig. 15(b) the annealing twin boundaries in boundaries appear to exhibit greater lattice mismatch,
work-hardened austenite also act as the preferential possibly because of greater lattice distortion and a
nucleation site of ferrite. The reason of this can be higher dislocation density near deformed grain bound-
considered to be as follows. At the coherent twin aries. These would be the predominant nucleation
boundaries before deformation a large number of sites of ferrite and hence accelerate the nucleation.
ledges are produced on the twin boundaries by Deformation structures within austenite grains have
deformation. Thus deformed twin boundarics have bern known to act as the effective nucleation sites of
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ferrite and play an important role in the ferrite grain ary surface, annealing twin boundary and deforma-
refinement. The deformation structure is generally tion bands ( S , ( P ) = S g . b ( p ) + S d . ~ ( P ) + S t . h ( P ) ) . Fur-
called as deformation bands. These regions are char- thermore, if both the nucleation and the growth rates
acterized by a high density of cells consisting of tangled are a function of strain, the ferrite grain size in the
dislocations. Dislocations are favor nucleation sites deformed specimen is considered to be expressed as
through its stress field. Consequently ferrite nuclea-
tion appears to occur frequently at the deformation
structures.
Thus if d I o / w o and the coefficients A and B are de-
2. Growth of Ferrite in Deformed Austenite (Isothermal) termined from an experiment, the ferrite grain size
When ferrite grains grow into deformed austenite, formed from deformed austenite can be calculated.
their growth rate would be accelerated by the follow- Figure 20 shows an example of such calculation.
ing two factors. One is due to the enhancement of Here the calculated ferrite grain size using the com-
diffusivity by dislocations and supersaturated vacan- monly observed values of JIi/cuo, A and B is plotted
cies. Another is due to the additional driving force as a function of the rolling reduction, P. From this
associated with stored energy. Since carbon, whose figure it is seen that the ferrite grain size formed from
diffusivity controlls the growth rate of ferrite in HSLA work-hardened austenite decreases drastically with the
steels, is an interstitial element, the former effect is increase in a rolling reduction for a small rolling re-
considered to be small. The latter [actor is also not duction and decreases gradually for a large rolling
so large estimation by some kinds of calculation (ac- reduction.
celeration is less than 10 %).z4) We can find that the
ferrite growth rate is slightly enhanced by the defor- 4 . Ferrite Grain Refinement by Accelerated Cooling
mation of austenite. The acceleration of growth rate Accelerated cooling after hot rolling is currently
by deformation is much less than enhancement of nu- being realized as a further advanced thermomechani-
cleation rate for the transformation kinetics. cal treatment in hot rolling proce~s.29>3~) This cooling
process is characterized by accelerated cooling in a
3. Ferrite Grain Size firmed ,from Dfirmed Austenite 7-+a transformation range just after controlled rolling.
(I~othermal)2~) I t has been shown that the accelerated cooling refines
the ferrite grain size and thus further improves both
For simplicity we assume;
the strength and toughness.
(i) that austenite grain boundary surfaces are the The effect of accelerated cooling on ferrite grain
nucleation site and the additional nucleation sites
refinement can be seen in a non-deformed specimen.
produced by deformation are the deformation bands
Figure 13 and Eq. (24) show the effect of cooling rate
and annealing twin boundaries,
on ferrite grain size in an Fe-0.15C
(ii) that the nucleation rates per unit area of de- This dependence of ferrite grain size by cooling
formation bands and annealing twin boundaries are
rate means that when a cooling rate becomes 10 times
equal to that of the grain boundary surface,
faster ferrite grain diameter becomes almost half
(iii) that the total area of deformation bands and (0.55).
annealing twin boundaries per unit volume of auste-
The principle of grain size refinement by accel-
nite is quadratic with respect to
erated cooling can be understood by considering the
the strain E(= -In (1 -P)), i.e., effect of transformation temperature on ferrite grain
size in an isothermal transformation. As mentioned
S,.,i(p)+Sl.l,(p)= A(- In (1 -p))2 .........(27)
in the previous section the grain size of isothermally
where, A is a constant, and formed ferrite depends on the ratio of the square root
(iv) that the ratio JI,(p)/a(p) can be expressed
as a function of strain e as, Da(prn)lnDa True Strain & = -ln(l-p)
1.0 2.0
40
30.-
where, I o , a,: the nucleation rate and parabolic rate 20-3 0 Austenite Grain Size
constant of growth in the non-de-
formed specimen, respectively 10..
B : a constant. 2.o
An exponent of 1.3 came from an experiment for Fig.
5-
18.
As discussed above the ferrite grain size formed
1.0
from non-deformed austenite in the case of grain sur- 0 .I .2 .3 .4 .5 .6 .7 .8
face nucleation can be expressed by Eq. (1 1). From Rolling Reduction, p
the assumptions made for deformed specimen Sg.bin Fig. 20. Calculated ferrite grain size formed from work-
Eq. (1 1) should be replaced by the effective interfacial hardened austenite as a function of rolling reduc-
area, S,, which is the sum of the areas ofgrain bound- tion for various austenite grain sizes.
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[ 774) Transactions ISIJ, Vol. 27, 1 9 8 7
of nucleation rate to the parabolic rate constant for to room temperature to produce lath martensite. It
various types of nucleation sites. Thus when the appears from Fig. 2233)that the number of packets in
ratio d n a increases with the decrease in the transfor- an austenite grain markedly decreases and hence the
mation temperature, the grain size of an isothermally packet size becomes large with an increase in the
formed ferrite decreases with the decrease in the amount of deformation of austenite. The block be-
transformation temperature. comes narrower and finely segmented, and the block
The continuous cooling transformation can be con- boundaries become heavily waved with an increase in
sidered as the sum of short time isothermal holdings the amount of ausforming. Figure 23 shows the
at successive temperatures, as described in previous change in the mean packet size and block width of
section and derived two equations of (21) and (22) lath martensite in 18 Ni maraging steel with the
which show n, and D,, respectively. amount of ausforming. These results indicate that
As a whole, austenite deformation results in a large the morphology of ausformed lath martensite is char-
increase in the ratio of the nucleation rate to the acterized by large packet size and less-developed
parabolic rate constant and leads to ferrite grain re- blocks. And also it is characteristic that the block
finement. The accelerated cooling further refines a boundaries are waved in the case of ausformed mar-
ferrite grain size. tensite. Similar tendency was observed in low carbon
N b steel (HSLA steel) as shown in Fig. 24, in which
the specimen was rolled at 1 123 K by 50 % after
V . Structures and Properties of Martensite austenitizing a t 1 573 K for 1.8 ks and then water
Formed f r o m Work-hardened Austenite quenched to produce lath martensite. These micro-
structural characteristics might arise from the pre-
I. Morfhology of Microstructure Composed of Lath Mar- ferential formation of lath martensites with the same
tensite Formed from Work-hardened Austenite habit plane along the most active slip plane (one of
Among various types of ferrous martensite (such as four (11 11, planes) which is macroscopically bent by
lath, lenticular, etc.) the lath martensite is the most heavy deformation.
important one because most of the commercial heat- As shown above, the packet size of ausformed mar-
treatable steels produce lath martensite. Lath martensite is large compared with that of conventionally
tensite structure is characterized by packets and blocks quenched lath martensite. I t was observed that the
within a original austenite grains as shown schemati- ausformed lath martensites form along the curved
cally in Fig. Zl.31) I t is known that the basic micro- {111}, planes as shown in Fig. 22(f)35)and Fig. 24
structural unit for controlling mechanical properties (b).") This indicates that the crystal planes of aus-
especially, toughness of lath martensitic steel is size of tenite (and hence, of martensite) are bent. I n such
packets or blo~ks,~2-3~) and thus the refinement of a situation, there would be a possibility that the
packets or blocks improves the mechanical properties propagation of cleavage crack is suppressed since the
of lath martensitic structure. Therefore, we examined plane of cleavage fracture ({001],,) is heavily waved.
the change in lath martensite morphology with the This might be one reason for some improvements in
amount of deformation of austenite using an 18 Ni toughness by ausforming in spite of the coarsening of
maraging steel (18.3 % Ni, 9.0 % Co, 5.0 % Mo, 0.7 packet size.
% Ti, 0.015 % C) and N b bearing low carbon steel
(0.12 % C, 0.038 % Nb, 0.039 % V). 2. Mechanical Proferties of Ausformed Martensite
An example of results in 18 Ni maraging steel is I n order to account for the good ductility of aus-
shown in Fig. 22.35) I n this case, specimens were formed steels, the relation between the ductility of de-
austenitized at 1 523 K for 120 s in Ar gas atmosphere formed austenite and the ductility of ausformed mar-
(austenite grain size of 200 pm was obtained by this tensite was studied using an Fe-25.4XNi-0.38XC
treatment) and cooled to 773 K (above M d tempera- alloy (Ms=236 K).37) I n this experiment, specimens
ture) and deformed in tension to various strains at were solution treated at 1 423 K for 10.8 ks. Since
773 K at strain rate of 3 x 10-2/s and then air cooled the M s temperature of this alloy is below room tem-
Fig. 2 1. Schematic illustration showing the morpholog-

I I ical characteristics of lath martensite structure
0.2% Carbon Steel l8Ni Maraging Steel in 0.2 0/, C steel and 18 % Ni maraging steel.
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( a ) ( c ) : Packed structure (electrirally etched with CrO, 10 g + H , O 90 cc)

( d ) ) : Block structure (chemically etched with FeCI, 10 g + H C l 30 cc+H,O 120 cc)
Fig. 22. Optical micrographs showing the change in packed or block structure of lath martensite with
amount of deformation oT austenite (ausformed by tennion at 773 K) in 18Ni maraging steel.
1 1 573 K for 1.8 ks -+ W.Q.

(a)
0 0.1 0.2 0.3 0.4 0.5 0.6 1 573 K for 1.8 ks --t 50 % rolled at 1 123 K
(b)
True Strain -t w.9_.
Fig. 23. Change in the packet size and block width of lath Fig. 24. Optical micrographs of non-ausformed (a) and
martensite with the amount of deformation of ausformed (b) lath martensite in Nb steel.
austenite (ausformed at 773 K ) in 18Ni maraging Etchant: 2 % nital.
steel. D, = 200 pm.
which is above Md temperature.
perature, the solution treated specimen was austenite Figure 25 shows the results of tensile strength of the
single phase at room temperature. These specimens deformed austenite and the ausformed martensite.
were deformed at 473 K by rolling to various amounts Both of tensile strengths of austenite and martensite
of reduction. The rolling temperature of 473 K was are increased with an increase in the amount of
applied in order to avoid the formation or strain- prior-deformation of austenite. Figure 26 shows the
induced martensite during deformation. Some of relation between the elongation and the amount of
specimens of deformed austenite were subzero cooled prior-deformation of austenite. I n the case of de-
into liquid nitrogen to produce the ausformed mar- formed austenite, the elongation is markedly decreased
tensite. Tensile properties were measured in both (from 60 to 3 %) with an increase in the amount of
specimens of deformed austenite and ausformed mar- prior-derormation. O n the other hand, it is charac-
tensite with an Instron-type tensile machine a t 353 K teristic that the elongation of ausformed martensite is
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( 7 7 6 ) Transactions ISIJ, Vol. 27, 1987
0 15 30 L5 60
Pre-deformation ( %)
Test temperature: 353 K

Fig. 26. Relation between elongation and the amount of
prior-deformation of austenite at 473 K in Fe-
25Ni-0.38C alloy.

P, T : Parallel and transverse specimens against formed martensite has been studied mainly by func-
rolling direction, respectively tions of the amount of deformation and the defor-
S: Subzero cooling to 77 K, namely speci-
mation temperature below Al. And it is generally
mens are of martensite
believed that the increase in the strength of ausformed
Fig. 25. Relation between tensile strength and the amount
martensite is closely related to the amount of work-
of prior-deformation of austenite at 473 K in
hardening of austenite. However, few attempts have
Fe-25Ni-0.38C alloy.
been made to relate the strength of ausformed mar-
tensite to the flow stress of austenite during ausform-
hardly effected by the amount of ausforming and is ing at elevated temperatures.
almost same as the elongation of non-ausformed mar- I n order to make clear this point, the experiment
tensite. The ausformed martensite exhibits almost was carried out using austenitic steels (a high M n
constant elongation of about 8- 10 %, irrespective of steel : 13.9 % Mn, 0.68 % C) and Fe-high Ni alloy
the amount of ausforming. Therefore, the elongation (32.4 % Ni 0.005 % C), and martensitic steels (SNC
of deformed austenite becomes smaller than that of 815: 3.0 % Ni, 0.8 % Cr, 0.16 % C).38) Ausforming
ausformed martensite, when the amount of deforma- was performed with a tensile machine a t various tem-
tion (ausforming) is more than about 30 % in the peratures between 773 and 1 173 K a t strain rate
case of the present alloy. I t must be emphasized that of 1 . 7 10-21s.
~ After deformation, specimens were
the heavily deformed austenite is rather enhanced in rapidly quenched by water spray. These ausformed
both strength and ductility by martensitic transforma- specimens were tensile tested at room temperature at
tion. strain rate of 1 . 7 10-3/s
~ to measure the yield stress of
These results indicates that the dislocations in deformed austenite (austenitic steels) and ausformed
austenite produced by deformation are inherited and martensite (martensitic steels) a t room temperature.
that the stress concentrated region a t the obstacles in Figure 27 shows the relation between the increase
austenite produced by heavy deformation are healed in 0.2 % proof stress at room temperature (Aa;.,) of
by the martensitic transformation itself. As a reason ausformed austenite and the amount of work-harden-
for the healing effect, it can be considered that the ing (Aar) of austenite by ausforming at elevated tem-
stress concentration in austenite may be released by peratures in austenitic steels. I t appears that the
the formation of preferential variants of martensite at yield stress increase of austenite (Aa;.,) at room tem-
the stress-concentrated areas. perature is linearly proportional to the amount of
work-hardening of austenite (Aur) by ausforming in
3. Effect of Ausforming Temperatures on the Increase of both steels, and all data lie on the same straight line,
Strength ff Ausformed Martensite irrespective of ausforming conditions such as defor-
I n the most published papers, the strength of aus- mation temperature and the amount of strain. This
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Transactions ISIJ, Vol. 27, 1987 (777)
result indicates that the strength of ausformed austen- formation temperature, i.e., do;:, is increased with an
ite at room temperature is uniquely determined only increase in deformation temperature. Furthermore,
by the amount of work-hardening by ausforming. when the ausforming temperature is fixed, the con-
This probably suggests that the strengths of austenite tribution of A 0 7 on the An;:, is small at smaller Aur
at both of high and room temperatures are mainly range and becomes large at larger Aar range. Same
determined by the dislocation density. tendency was also observed in SKD 61 steel. These
Figure 28 shows the relation between the increase results strongly suggest that, in addition to the dislo-
of 0.2 % proof stress of ausformed martensite (Au;:~) cation density in austenite, the dislocation configu-
(i.e., the difference of 0.2 % proof stress at room tem- ration in austenite is also an important factor for
perature between ausformed martensite and conven- increase in strength of ausformed martensite.
tionally quenched martensite) and the amount of Figure 29 shows the examples of transmission elec-
work-hardening (Aar) in austenite at elevated tem- tron micrographs of austenite in a high M n austenitic
perature in SNC 815 steel. I t is characteristic that steel deformed to the same amount of work-hardening
the obtained data lie on the different curves by the (Aor= I0 kg/mm2) at different temperatures. As can
ausforming temperature. I t should be emphasized be seen, the total dislocation density seems to be
that the d a f , is not determined only by the Aar, but almost same, but the dislocation configuration is dif-
functions of both Aar and ausforming temperature. ferent from each other. With increase in the defor-
Even at the same Aar, the effect of ausforming on the mation temperature, the dislocation configuration is
strengthening of martensite is different with the de- changed from uniformly distributed pile-up to disloca-
tion cells. I n this austenitic steel, despite the dif-
ference of dislocation configuration the 0.2 % proof
Deformat ion temperature:

30 - A -993K
-1023K
L1
25. o -1073K
E
E 0
b20-
Y 0
erT 15-
C
a t H.T. -0N
0
Q 0
5.
E
0 5 10 15 20
bar at H.T. kg.rnrn-=
Fig. 27. Relation between the increase in 0.2 O//o proof Fig. 28. Relation between the increase in 0.2 % proof
stress a t room temperature of ausformed austenite stress of ausformed martensite (dot,;) and the
(do:,) and the amount of work-hardening of amount of work-hardening of austenite (do?) by
austenite (Aor) by ausforming in austenitic steels. ausforming in SNC 813 steel (3Ni-0.8Cr-0.16C).
Fig. 29. Transmission electron micrographs of austenite deformed to the same amount of work-hardening of
austenite ( A u ~ =10 kg/mm2)a t strain rate of 1.7 x 10-2/s a t (a) 1 073 K, (b) 1 023 K and (c) 873 K,
respectively, in Fe-14Mn-0.7C austenitic steel.
Special Lecture
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stress of austenite at room temperature is the same as VII. Conclusion

shown in Fig. 27, because the Aar is the same. How- I have explained the abstract of kinetics, structure
ever, as shown in Fig. 28, in the case of ausformed and mechanical properties of transformation products
martensite, Aa$, is increased as the ausforming tem- of ferrite and martensite formed from work-hardened
perature is raised even at the same Aor. Therefore, austenite. Because of too much contents, I am afraid
it can be considered that the dislocation cell structure that it would be difficult to understand.
in prior austenite is very effective in strengthening of Thank you very much for your kind attention.
ausformed martensite through the martensitic trans-
formation, and pile-up or uniformly distributed dis-
locations in prior austenite have little effect on REFERENCES
strengthening of ausformed martensite.
T. Maki, K. Akasaka and I. Tamura: Proc. Int. Conf.
Thermomechanical Process. Microalloyed Austenite, ed.
VI. Hardenability of Work-hardened Austenite
by A. J. DeArdo et al., TMS-AIME, Pittsburgh, (1981),
and Recrystallized Austenite 217.
As described in the former section, the work-hard- T. Maki, S. Okaguchi and I. Tamura: Strength of Metals
ened austenite can transform easily by diffusional and Alloys (ICSMA-6), ed. by R. G. Gifkins, Pergamon
process, because the rate of nucleation of ferrite is Press, Melbourne, (1982), 529.
high. It means that the hardenability of steel is de- P. A. Beck and P. R. Sperry: J. Appl. Phy~.,21 (1950),
creased with work-hardening of the austenite. 150.
A bearing steel (SUJ2: 1.33 % Cr, 0.9 % C) with H. J. McQueen and J. .J. Jonas: Plastic Deformation of
Materials, ed. by R. T. Arsenault, Academic Press, N.Y.,
spheroidized carbide particles was austenitized at
(1975), 393.
850°C a t which the steel was in two phase region of
J.J. Jonas and I. Weiss: Metal Sci., 13 (1979), 238.
y and carbide, and deformed by compression of 60 %
M. G. Akben, I. Weiss and J . J. Jonas: Acta Metall., 29
(s=3x 10°/s), and then immediately or after holding (1981), 111.
in some intervals of time (At) at the same temperature M. Umemoto, N. Komatsubara and I. Tamura: J. Hent
as the deformation quenched into water. The hard- Treating (ASM), 1 (1980), No. 3, 57.
ness at the center portion of SUJ2 specimen at room J. W. Cahn: Acta Metall., 4 (1956), 449.
temperature after quenching changed with holding E. Scheil: Arch. Eisenhiittenwes., 12 (1935), 565.
time (At) as shown in Fig. 30. M. Umemoto, N. Nishioka and I. Tamura: J. Heat Treat-
The austenite of SUJ2 with spheroidized carbide ing (ASM), 2 (1981), 130; Trans. Iron Steel Inst. Jpn., 22
particles can dynamically recrystallized easier than (1982), 629.
without carbide particles. The work-hardened aus- M. Umemoto, N. Komatsubara and I. Tamura: Proc.
Int. Conf. Solid-Solid Phase Transf., ed. by H. I. Aaronson
tenite of SUJ2 has poor hardenability and becomes its
el al., TMS-AIME, Pittsburgh, (1981), 1111.
hardenability recover to usual SUJ2 with holding
M. Umemoto, H. Ohtsuka and I. Tamura: Proc. Int.
time (At) during the static recrystallization is progress- Conf. High Strength Low Alloy Steels, ed. by D. P. Dunn
ing as shown in Fig. 30. and T. Chandra, Univ. Wollongong, Wollongong, (1984), 96.
Ausforming is quenching method of work-hardened G . H . Gulliver: J. Inst. Met.,19 (1981), 145.
austenite. Such a n austenite has poor hardenability. J. R. Bradley, J. M. Risbee and H. I. Aaronson: Metall.
The steel for ausforming should have high harden- Trans. A., 8A (1977), 323.
ability by including several alloying elements of Ni, M. Umemoto, Z. H. Guo and I. Tamura: Proc. Int. Conf.
Cr, Mo, etc. HSLA Steels (HSLA Steels, Metallurgy and application^,
For direct quenching it seems that the austenite is HSLA Steel '85), ed. by J. M. Gray et al., ASM-INTER-
deformed and recrystallized and then quenched. I n NATIONAL, Beijing, (1985), 97.
this case, we can not expect to increase strength and C. Zener: J. Appl. Phys., 20 (1949), 950.
M. Hillert and L. I. Staffanson: Acta Chem. Scand., 24
toughness of martensite as ausforming does.
(1970), 3618.
H. I. Aaronson and H. A. Domian: Trans. AIME, 236
(1966), 781.
C. Wells, W. Batz and R. F. Mehl: Trans. AIME, 188
(1950), 553.
L. Kaufman, S. V. Radcliffe and M. Cohen: Decomposi-
tion of Austenite by Diffusional Process, ed. by V. E.
Zackay and H. I. Aaronson, Interscience Publisher, a divi-
sion of John Wiley & Sons, N. Y., (1962), 313.
C. Wagner: Trans. AIME, 194 (1952), 91.
W. F. Lange and H . I. Aarowon: Metall. Tranc., in press
I I I I W.Q. (Private communication).
M. Hillert: Lecture on the Theory of Phase Transforma-
6001 100 1 tion, ed. by H. I. Aaronson, TMS-AIME, Pittsburgh
200 300 400 (1975), 1-50.
~t Hold~ng Time (5)
C. A. Dube: PhD Thesis, to Carnegie Institute of Tech-
Fig. 30. Change in hardness of water-quenched specimen nology, (1948).
with holding time after deformation at 850°C in M. Umemoto, Z. H. Guo and I. Tamura: Muter. Sci.
SU.J2. Technol., 3 (1987), 249.
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25) M. Umemoto, H. Ohtsuka, H. Kato and I. Tamura: 31) T. Maki, K. Tsuzaki and I. Tamura: Trans. Iron Steel Znst.
Proc. Int. Conf. High Strength Low Alloy Steels, ed. by Jpn., 20 (1980), 207.
D. P. Dunn and T. Chandra, Univ. Wollongong, Wol- 32) S. Matsuda, T. Inoue, H. Miura and Y. Okamoto:
longong, (1984), 107. Proc. of Int. Symp. on Toward Improved Ductility and
26) M. Umemoto, H. Ohtsuka and I. Tamura: Trans. Iron Toughness, ISIJ and JIM, Tokyo, Sendai, (1971), 47.
Steel Inst. Jpn., 23 (1983), 775. 33) Y. Ohmori, H. Ohtani and T. Kunitake: Met. Sci., 8
27) A. Sandberg and W. Roberts: Proc. Int. Conf. Thermo- (1974), 357.
mechanical Processing of Microalloyed Austenite, ed. by 34) A. R. Marder and G. Krauss: Proc. of Int. Conf. Strength
A. J. DeArdo et al., TMS-AIME, Pittsburgh, (1981), 405. of Metals and Alloys (Znd), 111, ASM, Asilomar, (1970),
28) R. K. Amin and F. B. Pickering: Proc. Int. Conf. Thermo- 822.
mechanical Processing of Microalloyed Austenite, ed. by 3.5) I. Tamura, K. Tsuzaki and T. Maki: Proc. of Int.
A. J. DeArdo et al., TMS-AIME, Pittsburgh, (1981), 377. Conf. Martensitic Transformation (ICOMAT-82), ed. by
29) C. Ouchi, J. Tanaka, I. Kozasu and K. Tsukada: " Op- L. Delaey et al., Les Edition de Physique, Paris, Leuven,
timization of Processing, Properties and Service Performance (1982), c4-551.
through Microstructural Control ", ASTM Spec. Tech. 36) I. Tamura, T. Maki and H. T. Yui: to be published.
Publ. No. 672, (1979), 105. 37) Y. Tomota, K . Tanabe, K. Kuroki and I. Tamura: J .
30) H . Sekine, T. Maruyama, H. Kageyama and Y. Kawa- J p n Inst. Met., 41 (1977), 313.
shima: Proc. Int. Conf. Thermomechanical Processing of 38) C. K. Yao, S. Y. Gao, T. Maki and I. Tamura: Proc.
Microalloyed Austenite, ed. by A. J. DeArdo et al., TMS- 3rd Int. Cong. Heat Treatment of Materials, ed. by T.
AIME, Pittsburgh, (1981), 141. Bell, Metals Soc., London, Shanghai, (1983), 5-80.
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Journal of Applied Sciences Research, 2(8): 484-485, 2006

© 2006, INSInet Publication
Strengthening of Alloy Steel by High Temperature Thermomechanical Treatment

1
J.A. Omotoyinbo, 2 O.E. Olorunniwo, 2O. Ogundare and 2O.O. Oluwole
1
Federal University of Technology, Akure. Nigeria.
2
Obafemi Awolowo University, Ile-Ife. Nigeria.
Abstract: Micro-alloyed steels produced by controlled rolling are of the most attractive propositions in many
engineering applications because of their relative low cost, moderate strength and very good toughness when
compared with as-castalloy steel.. This research work has shownthe possible substitution of cheaper, low-alloy
steel for the high alloy steel for the same application. The effect of HTMT on the mechanical properties of low
alloy steel was investigated.
Key words: Strengthening. High Temperature Themomechanical Treatment (HTMT), micro alloyed,
controlled rolling.
INTRODUCTION MATERIALS AND METHODS
Steels are weaker than they should be theoretically Tensile test samples: To prepare the tensile test
because of dislocations and the ease with which these specimen, the hot-rolled samples which were initially of
dislocations moveunder applied shear stress[4]. Therefore, round shape were prepared as follows. The 10mm
the primary aim of strengthening is to retard the diameter rod was held tightly in position on the bench
dislocationmovements. However, complete barrier can be vice where it was cut into lengths of 5mm ach with he aid
dangerous because pile-up of dislocations can lead to a of hack saw. Each of the samples was then mounted and
catastrophic crack[2]. turned consecutively on the lathe machine into cylindrical
Strength in steels arises from several phenomenon shape. The vernier caliper was used to take the accurate
including solid solution strengthening, dispersion measurement. For reproducibility of results, four samples
strengthening and ferrite grain refinement which usually were prepared for the 10mm diameter rod. This process
contribute collectively to the observed mechanical was repeated for the 12mm and 16mm diameter rod, one
properties such as ductility, strength,etc. Alloying after the other.
elements’ presence provides greater control over
microstructure and consequent benefit in mechanical The impact test samples: They were prepared by
properties. notching to 4mm depth at 450 with the aid of the lathe
Therefore, to produce steels with improved machine. Four samples were prepared each for 10mm,
strength-to-ductility ratio, a combined use of mechanical 12mm and 16mm diameter rod as well as for the as-cast
working and heat treatment is employed as sample to be used in izod impact test.
strengthening mechanism [8], resulting in structural steels The hardness test sample-This sample is obtained by
with improved weldability, cleannessand inclusion shape grinding the surface with emery paper. Then, with the aid
control[9]. of hacksaw and lathe machine, cut into 25mm x 25mm x
This paper seeks to investigate and establish the 25mm square cube for Rockwell test. Four samples were
possible benefits derived from strengthening of alloy prepared for 12mm and 16m diameter samples.
steels by HTMT. This includes improved mechanical
properties, substant ial energy savings (through Microstructural test: The specimens were ground in
elimination of subsequent normalizing treatment) and succession with 220,320, 400, 600 frit emery paper. Then,
possible substitution of cheaper, low alloy steel for high they were polished until mirror-like surfaces was
alloyed steel for the same application under the same obtained. The surface was etched with Nital solution and
conditions. examined under the microscope. For reproducibility of
results, four samples were prepared for 10mm, 12mm and
Experimental procedure: The chemical composition of 16mm samples.
low alloy steel as-cast specimens (AISI-SAE 1037 ),
presented in table 1, was obtained from the Universal RESULTS AND DISCUSSIONS
Steels Limited, Lagos, Nigeria. All mechanical tests
(tensile, hardness, impact) were carried out according to From the result, it has been shown that the rolled
the A 296 ASTM requirement. (HTMT) samples possess both the yield strength and the
Corresponding Author: O.E. Olorunniwo, Department of Material Sciences and Engineering,

2
Obafemi Awolowo University, Ile-ife. Osun state, nigeria
484
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J. Appl. Sci. Res., 2(8): 484-485, 2006
`% red. Fracture UTS Yield strength Hardness Impact

Sample % Elongation in area strength N/mm2 N/mm2 N/mm2 HRC (J)
10mm diam as- rolled 1.80 51.41 668.11 688.78 255.10 47.58 48.15
-----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
12mm diam. As –rolled 4.63 56.55 367.36 377.55 239.8 41.4 45.57
----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
16mm diam as-rolled 7.81 61.26 213.64 221.94 147.96 37.45 41.40
--------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
As-cast 0.80 3.60 171.94 - - 55.78 11.25
Table 1: The low alloy steel specimens used have the following Also, the as rolled (HTMT) samples are much more
composition in weight percent as below.
ductile than the as cast samples for the same reason cited
C 0.368 Sn 0.014
Si 0.226 Al 0.003 above[6]. Conversely, the as-cast samples are harder than
S 0.33 Zn 0.003 the as rolled due to the presence of inclusions, residual
P 0.039 Mo 0.021 internal stress, residual coring and non-uniformity during
Mn 0/688 Cu 0.227
solidification, which are virtually elimination by
Ni 0.177 As 0.014
Cr 0.119 Co 0.013 HTMT[1,8].
V 0.002 Pb 0.001
W 0.003 Fe 98.055 Conclusion: The application of HTMT on low alloy steel
has led to the reduction in hardness while the strength and
60 AS.CAST toughness increase considerably, compared to the as-cast
92.22% samples. Hence, for applications that require adequate
50 98.87% Deformation me c h a n i c a l p r o p er ties, high temp er atur e
Brinell hardness valu es
97.99% Deformation
Deformation themomechanically treated low alloy steel should be
40 employed
30
REFERENCES
20
1. Adeyeye Oluseyi, 1996. Influence of thermo
10 mechanical working on the strengthening of
Aluminum alloys, Unpublished B.Sc. Thesis,
0 Metallurgical and Material Engineering department,
1 2 3 4
Federal University of Technology Akure, Nigeria,
Fig. 1: Average hardness values. 1998
60 2. Benjamin, W.N., B.D. Alan, and A.W. Richard,
98.87% 99.22% 1989. Modern manufacturing process Engineering
50 McGrawHill, New York, pp: .32-33, 61-62 , 77-114.
Deformation Deformation
Im pact values (joules)
97.99%
Deformation 3. Bolton, 1988. Production Technology-Processes,
40
Materials and planning Heinemann London pp:
30 174-185.
4. Dieter, G.E. 1988 Mechanical metallurgy McGraw
20 Hill, London, pp: 309-312.
AS.CAST 5. Degarmo, E.P., J.T. Black and A.K. Ronald, 1993.
10 Materials and processes in manufacturing, 7th Edn.
Macmillan, London, pp: 222-223.
0
1 2 3 4 6. Higgins, R.A., 1993. Engineering Metallurgy part 1:
Applied Physical Metallurgy’ 6th Ed. 124: 219-233,
Fig. 2: Impact values
285-330.
Ultimate Tensile Strength while the as-cast samples do 7. Llewellyn, D.T., 1992. Steels: metallurgy and
application’ 1st Edn., Butterworth Heinemann,
not. Reasons that could be adduced to these are that,
during the HTMT, the as-cast sample has its defective oxford, pp: 64-77.
structure homogenized, blowholes and gas pores welded 8. Rajan, T.V, C.P. Sharma and A. Sharma, 1988. Heat
shut and atomic segregation reduced and internal stresses treatment-principle and techniques, McGraw Hill,
relieved[3]. These, coupled with hot plastic deformation India, pp: 175-181.
as well as the presence of alloying elements (carbide 9. Novikov, L., 1978. Theory of Heat treatment of
formers such as nickel, titanium, etc), inhibiting metals,’ 1st Edn. Moscow, pp: 105-106, 418-425.
dislocation movement, to effect strengthening with 10. Honeycombe, RWK, 1981. Microstructure and
respect to Ultimate Tensile Strength (UTS) and yield properties’ 1st Ed., Edward Arnold, London, pp:
stress[2,9]. 167-185.
485
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IVC-17/ICSS-13 and ICN+T2007 IOP Publishing

Journal of Physics: Conference Series 100 (2008) 062013 doi:10.1088/1742-6596/100/6/062013
Ion-nitriding of Maraging steel (250 Grade) for

Aeronautical application
Kishora Shetty1,2, Subodh Kumar3 and P. Raghothama Rao2

2
Regional Centre for Military Airworthiness (Foundry and Forge), CEMILAC, DRDO,
Bangalore-560 037, India.
3
Department of Materials Engineering, Indian Institute of Science, Bangalore-560 012, India.
E-mail: kishora_shetty@yahoo.com
Abstract. Ion nitriding is one of the surface modification processes to obtain better wear
resistance of the component. Maraging steel (250 Grade) is used to manufacture a critical
component in the control surface of a combat aircraft. This part requires high strength and
good wear resistance. Maraging steels belong to a new class of high strength steels with the
combination of strength and toughness that are among the highest attainable in general
engineering alloys. Good wear resistance is achieved by ion-nitriding (also called as plasma
nitriding or glow discharge nitriding) process of case nitriding. Ion-nitriding is a method of
surface hardening using glow discharge technology to introduce nascent (elemental) nitrogen
to the surface of a metal part for subsequent diffusion into the material. In the present
investigation, ion-nitriding of Maraging steel (250 grade) is carried out at 450 0C and its effect
on microstructure and various properties is discussed.
1. Introduction
Surface Engineering means ‘engineering the surface’ of a material or components to impart
surface properties, which are different from the bulk of base material [1]. The purpose may be to
reduce wear, minimize corrosion, increase fatigue resistance, reduce frictional energy losses,
provide a diffusion barrier, provide thermal or electrical insulation, exclude certain wave lengths
of radiation, promote radiation, electronic interactions, or simply improve the aesthetic
appearance of the surface. Surface engineering processes, which give required properties at
surfaces include flame hardening, induction hardening, laser hardening, carburizing, nitriding,
cyaniding, plasma nitriding, ion implantation, weld overlay, roll cladding, thermal spraying,
plasma spraying, ion plating, CVD, PVD etc. Nitriding is a process for case hardening of alloy
steel in an atmosphere consisting of a mixture of ammonia gas and dissociated ammonia [2]. In
ion-nitriding (also called as Plasma nitriding or Glow discharge nitriding) method glow discharge
technology is used to introduce nascent (elemental) nitrogen to the surface of a metal part for
subsequent diffusion into the material [3-5].
1
To whom any correspondence should be addressed

c 2008 IOP Publishing Ltd 1
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The plasma assisted surface modification techniques offer a great flexibility and are capable
of tailoring desirable chemical and structural surface properties independent of the bulk properties
[3]. It has other advantages like nil or very thin white layer after nitriding and there is no
machining or grinding involved for complex parts after the process. The hardened surface layers
become an integral part of the base material without any significant reduction in properties of
base material. It is also known to provide the modified surface without dimensional change or
distortion of the component. Ion-nitriding provides better control of case chemistry and
uniformity [3,6,7]. This method is one of the most effective techniques for increasing wear
resistance, fatigue strength, surface hardness and corrosion resistance of industrial components
[8]. In this process, vacuum environment and high voltage electrical energy is used to form
plasma through which nitrogen ions are accelerated to impinge on work piece. The ion
bombardment heats the work piece and cleans the surface as the active nitrogen diffuses through
it [3,9].
Maraging steels belong to a new class of high strength steels with the combination of strength
and toughness that are among the highest attainable in general engineering alloys [10]. These
steels differ from conventional steels in that they are hardened by a metallurgical reaction that
does not involve carbon. These steels contain very low carbon (<0.03%) and are strengthened by
the precipitation of intermetallic compounds at temperature about 480 0C [11-13]. The term
maraging is derived from martensite age hardening and denotes the age hardening of a low
carbon, iron – nickel lath martensite matrix [12,14]. Different maraging steels are designed to
provide specific levels of yield strength from 1030 to 2420 MPa (150 to 350 ksi). These steels
typically have very high nickel, cobalt and molybdenum and very low carbon content. Carbon is
treated as an impurity in these steels and is kept as low as commercially feasible (<0.03%) in
order to minimize the formation of Titanium carbide (TiC), which can adversely affect strength,
ductility and toughness [11,12]. Nominal composition of 250 Grade is Fe-18Ni-8.5Co-5Mo-
0.4Ti-0.1Al [10].
Good wear resistance of Maraging steel can be achieved by ion-nitriding process of case
nitriding. In conventional gas nitriding process, the nitriding temperature is 500 0C – 550 0C
[2,15], which is above the ageing temperature of maraging steel. Hence ion-nitriding of Maraging
steel (250 grade) at a temperature lower than the aging temperature has been carried out in the
present investigation. Microstructure of the ion-nitrided specimens was examined and properties
like tensile, low cycle fatigue, hardness, case depth and corrosion by salt spray test were
evaluated. These tests were also carried out on un-nitrided specimens for comparison.
2. Experimental
Figure 1 shows a simplified schematic and figure 2 shows the actual ion-nitriding installation.
The work load is supported on a hearth plate inside a double walled, water cooled vacuum
chamber, connected to vacuum pumps and gas supply. The chamber is evacuated to a pressure of
about 2.5 X 10-2 mbar, a pressure low enough for the background level of oxygen to be within
acceptable limits (less than 50 ppm), then filled with a low pressure mixture of nitrogen and
hydrogen. The use of auxiliary A.C. heaters to heat the cathode to 250 °C is desirable to minimize
cycle time. It can also help provide better temperature uniformity of the part in ion-nitriding
treatment. The discharge is ignited using a D.C. power supply, and pressure and temperature are
raised to the desired operating values by controlling gas flow and pressure, applied voltage and
current. The discharge can be monitored by meters and viewed through inspection windows. The
work is cathode and the vessel is anode. The furnace is electrically grounded, cool to the touch,
and quiet in operation. Maraging steel (250 grade) specimens were prepared from solutionised
material and then aged at 450 0C for 3 hrs. These aged specimens were ion-nitrided in the
nitriding furnace under the vacuum. Plasma is obtained by passing the gas mixture of H2 and N2
gases in the ratio 3:1 into the chamber and maintaining the pressure of 5 mbar. Ion-nitriding is
carried out at 450 0C for 10 h.
2
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Figure. 1. Schematic arrangement of an ion- Figure. 2. Ion-nitriding installation.

nitriding system [7].
3. Results
3.1 Chemical Composition
The chemical analysis of the Maraging steel (250 grade) was carried out using Optical emission
spectroscopy to confirm the material specification. The values obtained are given in Table 1.
Table 1. Chemical composition of the alloy (wt.%).
Element C Ni Mo Co Ti Al S P Fe
Composition 0.01 17.29 4.89 7.90 0.41 0.14 0.005 0.006 Balance
3.2 Visual Check

Ion-nitrided samples were checked for any visible defects and discoloration and no defects were
observed.
3.3 Microstuctural studies

The samples for Metallography were prepared from both ion-nitrided and un-nitrided samples.
Microstructural studies were carried out using both optical microscope and scanning electron
microscope (SEM). Optical micrographs of un-nitrided specimen is shown in figure 3 and that of
ion-nitrided specimen is shown in figure 4. Etchant used here is Ferric Chloride. SEM studies
were carried out by etching the specimens using Ferric Chloride. The microphotographs obtained
from un-nitrided and ion-nitrided samples are shown in figures 5 and 6 respectively.
Figure 3. Optical micrograph of un- Figure 4. Optical micrograph of ion-nitrided

nitrided sample showing martensite sample showing martensite structure at the
structure. core and nitrided layer at the case.
3
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Figure 5. SEM micrograph of un-nitrided Figure 6. SEM micrograph of ion-nitrided

sample. sample.
3.4 Hardness and Case depth measurement

Hardness was measured for both un-nitrided and ion-nitrided samples using Vickers Hardness
Tester. The hardness values obtained on un nitrided specimen is 616 VPN where as for ion-
nitrided specimen it is 900 VPN.
Case depth was determined by hardness measurements. Hardness values are listed in Table
2. Figure 7 shows the variation of hardness with depth from the surface. Case depth here is taken
as distance from the surface to which hardness is 100 VPN more than the core hardness. From the
graph the case depth estimated is 93 µm.
Table 2. Hardness and corresponding distance from the surface.
Distance from the edge (µm) Hardness (VPN)

50 797
75 761
100 702
125 626
150 623
175 623
200 623
Core 616
850
800
750
Hardness (VPN)
700
650
600
550
500
0 25 50 75 100 125 150 175 200 225
Depth from the surface (micrometer)
Figure 7. Graph of case depth vs hardness
3.5 Salt spray test

Salt spray test was carried out on both un-nitrided and ion-nitrided specimens for 144 hrs at 5 %
NaCl solution in a Salt Spray Test chamber. Figure 8 shows the photograph of samples
4
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before and after the salt spray test. Corrosion started in un-nitrided specimen after 48 h of
exposure, whereas no corrosion was noticed in ion-nitrided specimen.
1
1 1
2 2
2 (a) (b)
1 - Ion nitrided 2 - Un nitrided
1
Figure 8. (a). Photograph of the samples (a) before the salt spray test and (b) after the salt
spray test.
2
3.6 Tensile Properties
Tensile properties – Ultimate tensile strength (UTS), 0.2 % Proof stress (0.2 % PS), %
Elongation (% El.) and % Reduction in Area (% RA) were measured using TIRA Test 2820S
Universal Testing Machine (UTM). The results obtained are presented in Table 3.
Table 3. Tensile properties.

Property UTS (MPa) 0.2% PS (MPa) % El. % RA
Sample 1 1694 1606 9.32 60
Un nitrided Sample 2 1696 1619 8.84 56
Sample 3 1702 1622 9.23 55
Sample 1 1847 1757 5.66 25
Ion nitrided Sample 2 1864 1810 6.24 28
Sample 3 1877 1813 6.70 30
3.7 Impact Strength

Impact strength was measured on Charpy ‘U’ notch specimens using FIE make Charpy Impact
Testing machine. The values obtained are given in Table 4.
Table 4. Impact strength (Joules).

Sample 1 Sample 2 Sample 3
Un nitrided 21 22 22
Ion nitrided 17 19 19
3.8 Low Cycle Fatigue

Low cycle fatigue testing was carried out on smooth specimens in Zwick Roell UTM with
applied stress of 1172 MPa and with stress ratio (R) of -1. The values obtained are presented in
Table 5.
Table 5. Low cycle fatigue properties (No. of cycles to failure)
Sample 1 Sample 2 Sample 3

Un nitrided 3755 3287 5220
Ion nitrided 5500 14400 11200
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4. Discussion
Chemical composition analysed conforms to the Maraging steel 250 grade.
Both Optical microscopy and SEM examination confirm that no change in core
microstructure of the material after ion-nitriding occurs.
The ion-nitrided specimens exhibit higher surface hardness and good case depth than the un-
nitrided specimens. The introduction of nitrogen to the surface of Maraging steel by ion nitriding
process improves the wear properties by increasing the hardness.
Salt spray test results show that there is an improvement in corrosion resistance after
nitriding. This is due to the formation of an anodic layer after nitriding.
The ion-nitrided samples show higher UTS and 0.2 % PS values than the un-nitrided ones,
whereas % El and % RA are less for ion-nitrided samples compared to the un nitrided samples.
This can be attributed to the surface layer getting hardened because of ion-nitriding. Impact
strength of ion-nitrided samples is lower compared to un-nitrided samples. This is again due to
the surface layer getting hardened because of ion nitriding.
The number of cycles to failure in low cycle fatigue test also increase on ion-nitriding. The
introduction of nitrogen to surface layers increases the fatigue properties of the maraging steel by
introducing the residual compressive stresses.
5. Conclusions
From this ion nitriding study of Maraging steel (250 grade), the following conclusions can be
drawn.
Case depth obtained is sufficient for the design requirement.
Ion-nitriding improves the surface hardness of Maraging steel 250 grade.
An improvement in UTS, 0.2 % PS and LCF properties is observed on ion-nitriding. The %
El, % RA and impact strength decrease but they satisfy the design requirements.
No change in microstructure observed after ion-nitriding.
Ion-nitriding of 250 Grade appears to be suitable for parts which are subjected to constant
wear.
Acknowledgements
The authors thank Mr. B. S Vedaprakash, Group Director (Propulsion), and Mr. K. Tamilmani,
Chief Executive (Airworthiness), CEMILAC for their support.
References
[1] Kumar B, Upadhyay N C 2005 IIM Metal News 8 5
[2] Sidney Avner H 1997 Introduction to Physical Metallurgy 2nd Edition 383
[3] Spalvins T Ion Nitriding Conference proceedings ASM International 1
[4] Moller W, Parascandola S, Telbizova T, Gunzel R and Richter E 2001 Surface & Coatings
Technology 136 73
[5] ASM Handbook 1996 Vol. 5 411
[6] Bernd Edenhofer 1976 Metal Progress 181
[7] EPRI Centre for Materials Fabrication Ohio 1994 Ion nitriding 2
[8] Ahangarani Sh., Mahboubi F and Sabour A. R 2006 Vacuum 80 – Surface Engineering, Surface
Instrumentation & Vacuum Technology 1032
[9] Pavel Novak, Dalibor Vojtech and Jan Serak 2006 Surface & Coatings Technology 200 5229
[10] Gupta B, 1996 Aerospace Materials II 695
[11] ASM Handbook 1991Vol. 4 219
[12] ASM Handbook 1990 Vol. 1 793
[13] INCO Databook, 1976 351
[14] Morito S, X-Huang, Furuhara T, Maki T and Hansen N 2006 Acta Materialia 54 5323
[15] David Pye 2005 Practical Nitriding and Ferritic Nitrocarbourizing ASM International 71
6
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Bull. Mater. Sci., Vol. 29, No. 1, February 2006, pp. 59–66. © Indian Academy of Sciences.
Microstructures and properties of low-alloy fire resistant steel
BIMAL KUMAR PANIGRAHI

R&D Centre for Iron and Steel, Steel Authority of India Limited, Ranchi 834 002, India
MS received 10 June 2004; revised 2 November 2005
Abstract. Microstructures and properties of weldable quality low-alloy fire resistant structural steels (YS:
287–415 MPa) and TMT rebar (YS: 624 MPa) have been investigated. The study showed that it is possible to obtain
two-thirds of room temperature yield stress at 600°°C with 0⋅⋅20–0⋅⋅25% Mo and 0⋅⋅30–0⋅⋅55% Cr in low carbon
hot rolled structural steel. Microalloying the Cr–Mo steel by niobium or vanadium singly or in combination
resulted in higher guaranteed elevated temperature yield stress (250–280 MPa). The final rolling temperature
should be maintained above austenite recrystallization stop temperature (~ 900°°C) to minimize dislocation
hardening. In a quenched and self-tempered 600 MPa class TMT reinforcement bar steel (YS: 624 MPa), low
chromium (0⋅⋅55%) addition produced the requisite yield stress at 600°°C. The low-alloy fire resistant steel will
have superior thermal conductivity up to 600°°C (> 30 W/m⋅⋅k) compared to more concentrated alloys.
Keywords. Fire resistant steel; thermomechanical processing; microstructure; strength; thermal conductivity.
1. Introduction any information on alloying required to obtain two-thirds

of room temperature yield stress at 600°C for thermome-
Steel structures using mild steel in fire sensitive areas are chanically treated (TMT) rebar particularly, the high strength
protected from fire by providing fire resistant coating or variety with yield strength above 600 MPa. The present
insulation. This adds to the constructional cost. The problem work was carried out to ascertain minimum requirement of
with unprotected carbon–manganese mild steel is its poor molybdenum/chromium in steels with and without micro-
strength at temperatures above ~ 350°C, which can make alloying elements in order to achieve the guaranteed
a structure unsafe after a major fire. In case of short duration strength at 600°C in plate, structurals and TMT rebar and
fire, it is rather difficult to assess the damage to structures their effects on structure and properties.
caused by fire and may call for demolition/renovation of the
structures. Most of the research efforts relating to construction
2. Experimental
in fire sensitive areas were directed towards development
of steels that can retain adequate strength after prolonged
Six experimental laboratory heats (steels A–F) and one
exposure in fire. The building codes of some specifications
industrial heat (steel G) were melted in 0⋅1 T air induction
require the steel to have a minimum of one-half (ASTM
(IF) and 6 T electric arc furnace (EAF), respectively for proce-
1996) to two-thirds (Fushioni et al 1995; BIS 2002) of room
ssing to plate and beam. The ingots from IF heats were
temperature yield strength at 500–600°C compared to the
soaked at 1250°C for 2 h and thermomechanically processed
mild steel which retains about one-third of room temperature
(TMP) in an experimental rolling mill to 12–14 mm thick
yield strength at 600°C. In order to achieve this strength
plates in nine passes. The ingot from EAF heat was soaked
level, the steel chemistry and manufacturing process are
at 1320°C for 4 h and rolled to blooms of size 230 ×
closely controlled. Previous studies on microstructure and
160 mm. These blooms were soaked at 1250°C and sub-
mechanical properties of fire resistant steels carried out
sequently thermomechanically processed to 200 × 100 mm
by Chijiwa et al (1993) and Assefpour-Dezfully et al (1990)
beam section. The finishing rolling temperatures (FRT)
focussed on processing, structure and properties of fire
for plates and beam were measured with an infrared pyrome-
resistant steels with different combinations of alloying
ter up to an accuracy of ± 5°C and were between 800 and
elements. In the present investigation, the effect of lower
925°C. The finishing pass reduction was 20–30% for plates
alloying addition, particularly molybdenum, on the elevated
and about 10% for beam. The plates and beam were allowed
temperature properties will be discussed which is important
to cool in natural air after rolling. Another heat (steel H)
due to increasing alloy cost. Over and above, there is hardly
was made in 250 T twin hearth furnace and cast as 9 T
ingots for processing to TMT rebar. The ingots were rolled
to billets of size 100 × 100 mm after soaking at 1300°C
(panigrahi@sail-rdcis.com) for 4 h. These billets were subsequently reheated at 1250°C
59
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60 Bimal Kumar Panigrahi
and processed to TMT rebar of 32 mm diameter through a and the open roof top for mounting the beam specimen.
Thermex cooling system. The flue gas for heating passed through a duct surrounding
Round tensile specimens (dia. 6⋅25 mm) were machined the sides of the walls and then was disposed off through a
from the quarter width position of the plates (width of chimney. There were ten long flame burners. The capacity
plate: 135 mm) in the longitudinal direction as per ASTM A of each burner was 35–40 l/h. The furnace was run on positive
370 standard and tested at room temperature (30°C) and pressure. The heating of the specimen was done as specified
at elevated temperatures up to 600°C at cross head speed of in ASTM E119 standard. The thermocouples were fixed
2 mm/min in a servohydraulic test machine as per ASTM at four different sections of the beam to measure the rise
E 8 and E 21 standards, respectively. Tensile testing of of temperature at different intervals. While plotting the tem-
plates was also carried out selectively at room tempera- perature vs time curves, average temperature measured by
ture after exposure at 600°C for 3 h under applied stress concerned thermocouples in a section was used.
of 140 MPa. The specimens after exposure were allowed to Tensile testing of rebar was done using unmachined
cool to room temperature inside the furnace. In the elevated rebar (gauge length: 5 dia.) at ambient temperature in a
temperature test of plates the specimens were heated from 60 T servo hydraulic tensile testing machine at a cross
room temperature to the test temperature and soaked at head speed of 10 mm/min. For the elevated temperature
the desired temperature for 15 min before tensile stress test at 600°C, round specimens were used from the core
was applied. The accuracy of the test temperature was con- region of rebar and tested as described for plate material.
trolled within ± 1°C. Charpy V-notch impact test specimens Charpy V-notch impact specimens were also prepared
of size 10 × 10 × 55 mm from steels A–F were machined from the location described previously (Panigrahi and
across the plate width in the longitudinal direction and Jain 2002) and tested similar to plate. The optical micro-
tested at RT to – 30°C as per ASTM E 23 standard. The structure was examined in the transverse section after
optical microstructure was examined in the longitudinal polishing and etching by 3% nital. TEM specimens were
through thickness direction after polishing and etching by prepared from the rim and core regions of the rebar as
2% nital. The average grain size was measured by linear described for plate and observed at 200 keV.
intercept method. Transmission electron microscopic (TEM)
investigation was carried out using thin foils prepared
from mechanically thinned strip of thickness below 0⋅1 mm. 3. Results and discussion
The electropolishing was done in a twin jet polisher using
a solution of 5% perchloric acid and 95% glacial acetic 3.1 Chemical composition
acid at 20°C and 60V operating voltage. The foils were
observed at 200 keV. In a structural steel, the composition will be determined
Flat tensile specimens (gauge length: 5⋅65 √area) were by the requirement of strength, toughness and weldabi-
prepared in the longitudinal direction from the web of the lity. The chemical composition of steels is given in table 1.
beam as per IS 2062 standard (BIS 1998). The ambient The carbon was 0⋅11–0⋅13% in plate, 0⋅17% in structural
and elevated temperature tensile testing was conducted as beam and 0⋅25% in TMT rebar. The conventional way to
described for plates. Tensile testing was also done after improve moderately the strength at elevated temperature
an aging treatment at 600°C for 3 h under applied tensile (up to ~ 350°C) is by increasing the carbon content (Houdre-
stress of 140 MPa. Charpy V-notch specimens (size mont 1953). Lower carbon in hot-rolled steel improves
7⋅5 × 10 × 55 mm) were prepared from the flange region notch toughness and weldability. In TMT rebar carbon
as described in IS 2062 standard and tested as described increases the hardenability. Manganese increases the strength
for plate in the longitudinal direction. The optical micro- by solid solution hardening (Baird and Jamieson 1972) in
structure was examined in the longitudinal through thickness hot rolled steel. Manganese tends to lower the eutectoid
direction after polishing and etching by 2% nital. The carbon content in steel and promotes segregation particu-
average grain size was measured by linear intercept method. larly in hot rolled structural steel with carbon > 0⋅10%.
TEM specimens were prepared from the flange region as This can adversely affect the mechanical properties. Manga-
described for plate and observed at 200 keV. Full scale nese was restricted to 1% in fire resistant hot rolled plate
fire resistance test was carried out on beam section (size and structural with carbon 0⋅10–0⋅20% and 1⋅5% in TMT
200 × 100 × 3900 mm) as per ASTM E 119 standard (ASTM rebar where manganese is a potential hardenability en-
1996) at Fire Research Laboratory, CSIR, Roorkee, India. hancing element. Silicon content in steels A–G varied
The bare beam was mounted on the specimen frame from 0⋅29–0⋅35%. Silicon is a solid solution strengthener
holder of a gas fired furnace. The furnace was rectangular in and a deoxidizer. Silicon retards softening at high tem-
shape. The casing was made up of steel reinforced sec- peratures (Irvine 1962) and also increases the hardenability.
tions. The refractory lining of the furnace consisted of However, in steel H, its content was low due to tech-
front layer of kyanite insulation bricks backed by hot face noeconomic reasons. The aluminium (0⋅01–0⋅02%) is
insulation. The burner casing was made up of fire bricks. required to tie-up free nitrogen to improve toughness. In
The complete furnace assembly consisted of four walls the steels A, D, E and F, the content of aluminium was
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Fire resistant steel 61
Table 1. Chemical composition of steels (wt.%).

Steel A B C D E F G H
C 0⋅11 0⋅12 0⋅12 0⋅13 0⋅13 0⋅12 0⋅17 0⋅25

Mn 1⋅02 1⋅02 1⋅08 0⋅99 1⋅00 0⋅96 0⋅74 1⋅42
Si 0⋅35 0⋅35 0⋅29 0⋅31 0⋅31 0⋅30 0⋅31 0⋅056
S 0⋅022 0⋅032 0⋅029 0⋅025 0⋅026 0⋅025 0⋅034 0⋅024
P 0⋅019 0⋅025 0⋅027 0⋅021 0⋅022 0⋅021 0⋅027 0⋅024
Cr 0⋅31 0⋅29 0⋅40 0⋅38 0⋅39 0⋅38 0⋅54 0⋅55
Mo 0⋅26 0⋅20 0⋅14 0⋅26 0⋅26 0⋅26 0⋅22 –
Nb – – – 0⋅02 – 0⋅02 – –
V – – – – 0⋅07 0⋅12 – –
Al 0⋅0033 0⋅099 0⋅097 0⋅0034 0⋅0039 0⋅0039 0⋅052 0⋅004
N 0⋅0042 0⋅0063 0⋅0067 0⋅0047 0⋅0047 0⋅0070 0⋅0124 0⋅0075
lower than the prescribed range. The rebar steel was As the finish rolling temperatures (FRT) of all steels ex-
semi-killed. Chromium in small percent forms (FeCr)3C cept steel F and a few structurals of steel G were above tnr,
(Houdremont 1953) in the cementite of pearlite. It is a an equiaxed ferrite microstructure could be obtained with
ferrite stabilizer and increases the hardenability. However, low dislocation density. Steel F was finish rolled at 800°C,
its potential as a solid solution strengthening element is quite below tnr (884⋅1°C) but above Ar3 temperature (771°C)
small due to its high affinity to carbon. The amount of chro- (Ouchi et al 1982). Deformation in this region strain
mium was 0⋅29–0⋅40% in plate and 0⋅55% in structural hardened the austenite, increasing its dislocation density.
beam and TMT rebar. Molybdenum increases elevated Deformation bands are also formed (Tanaka 1981). Since
temperature yield strength (Argent et al 1970; Honey- ferrite nucleates both on austenite grain boundaries and
combe 1981) even when present in small percent (~ 0⋅25%) deformation bands, the grains are finest (7⋅7 µm). How-
in solid solution in low carbon steel. It also forms carbide ever, the cellular structure retained by rolling below tnr,
(Fe, Mo)3C in the cementite of pearlite resisting softening lowered the yield strength at elevated temperatures.
on prolonged exposure in a fire (Houdremont 1953). Molyb- In the processing of TMT rebar (figure 1), initially at
denum tends to hinder self-diffusion of iron (Houdremont higher temperatures (1200–1100°C) the material recrys-
1953), thus increasing the recrystallization temperature of tallizes statically. At the intermediate and finishing stages
steel. Microalloying elements, vanadium and niobium, of processing (1000–1050°C), static, dynamic as well as
increase the elevated temperature strength (Pickering 1978; metadynamic recrystallization of austenite can occur (Poliak
Sage 1983). They also increase the recrystallization tempera- and Jonas 2003) depending upon strain at different passes
ture of steel (Borato et al 1988). Their carbides also offer producing an equiaxed austenite structure. On leaving the
resistance to softening when the steel is exposed to fire. finishing stand at 1000–1050°C, the bar enters a Thermex
The chemistry of the present investigation differs from cooling chamber where the surface of the bar is cooled by
the previous studies (Assefpour-Dezfully et al 1990; Chi- pressurized water at ~ 200°C/s forming a thin rim of lath
jiwa et al 1993; Fushioni et al 1995) in the following martensite while the core is still austenite. On emergence
ways: (a) the content of molybdenum and chromium is from the cooling chamber, the martensite rim gets self-
low, (b) low niobium and vanadium are used in micro- tempered by the heat of the core and the core finally
alloyed steels and (c) chromium without molybdenum has transforms to bainite.
been used in TMT rebar.
3.3 Microstructure
3.2 Thermomechanical processing (TMP)
Typical optical microstructures of some steels in as-rolled
Processing plays an important role since it determines the condition are shown in figure 2. The Cr–Mo (steel A) and
final microstructure and mechanical properties of hot Cr–Mo–Nb (steel D) alloyed plates (figures 2a and b) and
rolled steel (Panigrahi 2004). The TMP schedule for plate beam (figure 2c) showed a predominantly polygonal fer-
and beam is shown in figure 1. TMP of plate and beam rite–pearlite microstructure. At higher magnification, steel
involves controlled deformation of austenite at higher A (figure 2d) also showed upper bainite (arrow mark). The
temperatures above the recrystallization stop temperature bainite in steel A resembles pearlitic bainite (Bhadeshia
(tnr) (Borato et al 1988) during which static and dynamic 1992) as the colonies tend to have crystallographic facets
restoration processes occur (Tanaka 1981). Table 2 shows rather than nicely rounded colonies of conventional pear-
data on total reduction, approximate recrystallization stop lite. The vanadium (steel E) and niobium plus vanadium
temperature, finishing temperature and grain size of steels. (steel F) microalloyed steels also showed similar micro-
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Figure 1. Schematic of TMP schedule for plate, beam and TMT rebar (M, martensite; γ, austenite).
Figure 2. As hot rolled microstructures of a. Cr–Mo plate (steel A), b. Cr–Mo–Nb plate
(steel D), c. Cr–Mo beam (steel G) and d. pearlitic bainite of Cr–Mo plate (steel A).
Table 2. Process parameters and microstructural data.

Thickness Total FRT Grain size
Steels (mm) reduction (%) tnr (°C) (°C) Structure (µm) Product
A 14 86 814⋅0 900 F+P+B 10⋅4 Plate

B 12 88 853⋅5 900 F+P 13⋅5 Plate
C 12 88 874⋅3 900 F+P 12⋅5 Plate
D 12 88 876⋅9 900 F+P+B 11⋅0 Plate
E 12 88 828⋅5 875 F+P+B 12⋅5 Plate
F 12 88 884⋅1 800 F+P+B 7⋅7 Plate
G – 94* 874 850–925 F+P+B 10⋅3 Beam
H – 92 984⋅4 1000 M+B – Rebar
F, Ferrite; P, pearlite; B, bainite; M, tempered martensite; *flange region; tnr = 887 +
464%C + (6645%Nb−664√%Nb) + (732%V−230√%V) + 890% Ti + 363%Al−357%Si.
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Figure 3. Bright field TEM of a. Cr–Mo–Nb–V plate (steel F), b. and c. Cr–Mo beam (steel G) and d. TMT rebar.
structures. The bainite ‘colonies’ in steel G were coarser 3.4 Elevated temperature yield stress
than steels A, D, E and F and were more numerous possi-
bly due to presence of somewhat higher carbon and The dependence of yield stress and UTS with temperature
chromium in this steel, lower reduction per pass and for steels A–G is shown in figure 4. Steel F showed a
coarser austenite grains prior to transformation. The bainite faster drop of yield stress after 500°C. However, except
was not observed in steels B and C. The finishing rolling steel C (0⋅14%Mo) whose yield stress was marginally
in the austenite region above recrystallization stop tempera- below the desired level at 600°C, all other steels retained
ture helped to form polygonal ferrite grain structure in two-thirds of their room temperature yield strength at
Cr–Mo, Cr–Mo–Nb and Cr–Mo–V plate steels. In this 600°C (table 3). The elevated temperature yield stress de-
case ferrite nucleates on austenite grain boundaries (Tanaka pends mainly on the stability of microstructure at higher
1981). Cr–Mo–Nb–V plate (steel F) was finish rolled in temperatures. Chromium and molybdenum have a stabi-
the unrecrystallized austenite region producing grain size lizing effect on cementite of pearlite (Houdremont 1953).
finer than other steels (table 2) due to nucleation of ferrite A higher amount of chromium in steel C prevented exce-
on austenite grain boundaries, transgranular twins and ssive drop of yield stress at 600°C despite low molybdenum
deformation bands (DeArdo 1995; Panigrahi 2001) after (0⋅14%) in it. Steels D and E that are microalloyed with
transformation. The partial cellular structure of steel F Nb and V, respectively have highest level of yield stress
with dislocations retained is shown in figure 3a. The beam at 600°C viz. 82% and 85%, respectively. Nb and V have
steel also showed upper bainite (figure 3b) with cementite added advantages due to their precipitation hardening
particles distributed between ferrite platelets (figure 3c). potential and the loss of strength at higher temperature is
An exposure treatment up to 3 h at 600°C did not show minimal. The rapid drop of yield stress of steel F above
changes in the appearance of microstructure. Unlike 500°C was due to lowering of dislocation density on
martensite in which dissolved carbon in solid solution is soaking above 500°C. The UTS of all steels fell sharply
high, bainite has little carbon in solid solution and is above 400°C (figure 4). The elongation of all steels at
much less sensitive to tempering at low temperatures 600°C was higher than elongation at the ambient tem-
(~ 600°C). However, cementite particles can coarsen and perature. Exposure at 600°C for 3 h increased the yield
a general recovery of dislocation substructure occurs stress by about 50 MPa without significant change in
(Bhadeshia 1992). The TMT rebar steel showed a tempered elongation in steels A, D, E, F and G. The core of rebar steel
martensite rim. The core structure was bainitic (figure 3d) H with bainitic structure also showed two-thirds of room
due to high hardenability of this steel. temperature yield stress at 600°C (table 3). Due to presence of
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Temperature (°C) Temperature (°C)
Figure 4. Dependence of (a) yield stress and (b) UTS on temperatures of fire resistant steels and mild steel (MS).
Table 3. Tensile properties of the investigated steels.

Steel A B C D E F G H
Ambient temperature (RT)

YS (MPa) 287 293 298 338 293 415 320 624
UTS (MPa) 505 486 539 582 530 622 541 819
El. (%) 38⋅0 36⋅2 32⋅0 30⋅0 37⋅8 26⋅8 27⋅3 12⋅5
Elevated temperature (600°C)
YS (MPa) 219 191 188 279 250 280 214 419
UTS (MPa) 326 259 247 332 327 338 292 426
El. (%) 42⋅2 41⋅7 49⋅0 40⋅4 36⋅2 46⋅0 33⋅0 30⋅5
% of room temperature YS 76⋅3 65⋅1 63⋅0 82⋅5 85⋅3 67⋅4 66⋅8 67⋅1
After thermal exposure at 600°C under applied stress
YS (MPa) 360 – – 408 348 469 369 –
UTS (MPa) 432 – – 523 475 584 492 –
El. (%) 22⋅5 – – 30⋅8 34⋅0 22⋅8 27⋅0 –
tempered martensite rim, the overall strength of TMT 3.5 Impact toughness
rebar at 600°C should be higher than two-thirds of its
room temperature yield strength. In a composite micro- The ambient temperature impact toughness, 50% energy
structure comprising tempered martensite rim and bainitic ductile brittle transition temperature (DBTT) (Dahl 1992)
core, the overall yield stress is given by area fraction of and fracture characteristics are given in table 4. The upper
rim multiplied by yield stress of rim plus area fraction of shelf energy of as-rolled plate and beam varied from 65–
core multiplied by yield stress of core. The area fraction 118 J (figure 5). The steels A, D, E and F showed DBTT
of bainite core was 0⋅766 and that of tempered martensite at – 4°C to –12°C. The DBTT of steel B was below –30°C
rim was 0⋅234. Previous investigation (Panigrahi 2002) and that of steel C was –28°C. Presence of upper bainite
showed that low-alloyed tempered martensite structure in all steels except steels B and C, low aluminium content
had more than two-thirds of room temperature yield (steels A, D, E and F) and cellular structure (steel F)
stress at 600°C. were responsible for increase in DBTT. Notwithstanding
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higher carbon content, steel H showed a DBTT of –14°C carbon). On exposure at 600°C, the improved toughness
due to presence of tempered martensite and some acicular (DBTT: –34°C) of steel G could be due to lowering of
ferrite in it. Steel G showed a DBTT of –5°C in as rolled dislocation density of bainite and diffusion of embrittling
condition and –34°C in aged condition. The DBTT of atoms present on the grain boundaries to the dislocations.
steel G in as rolled condition was higher than steel A possibly Improvement of impact transition temperature by diffusion
due to presence of relatively coarser ‘colonies’ of pearlitic of phosphorus from prior austenite grain boundaries to
bainite in its microstructure and a higher carbon content lattice defects was reported earlier for spring steel (Wettlaufer
(0⋅17%) (Pickering 1978) compared to steel A (0⋅11% and Kasper 2000). However, upper shelf energy of aged
steel was lower than the as-rolled beam possibly due to
microstructural heterogeneity leading to formation of local-
ized carbide rich areas that aided lowering of the absorbed
energy.
3.6 Fire resistance
The average temperature rise of fire resistant steel (FRS)

beam and mild steel (MS) beam (0⋅17C, 0⋅69Mn, 0⋅04Si,
0⋅048S, 0⋅028P, 0⋅007Al) is shown in figure 6 for section
Table 4. Charpy toughness data.

Toughness at RT DBTT Fracture
Steel (Joule) (°C) surface at RT
A 118 − 12 Dimple
B 116 <− 30 Dimple
C 100 − 28 Dimple
D 94 −9 Dimple
E 82 −8 Dimple
Temperature (°C) F 73 −4 Dimple
G (as rolled) 87 −5 Dimple
G (after thermal exposure 50 − 34 Dimple
Figure 5. Charpy energy vs temperature curves of plates and at 600°C)
beam. H 88 − 14 Quasi cleavage
Note: All values of toughness are for full size specimens.
Temperature ( °C)
Temperature (°C)
Figure 6. Typical time–temperature curves for Cr–Mo beam
(steel G) and mild steel (T1, T2 and T3 are locations of thermo- Figure 7. Dependence of thermal conductivity of dilute steel
couples at section 1). alloys on temperatures.
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1 (inset). The rise of temperatures up to 600°C for other References

sections was similar to section 1. It was observed that the
temperature of the fire resistant steel was at a lower level American Society of Testing Materials 1996 Standard test
compared to mild steel. The data points for these curves methods for fire tests of building construction and materials,
remain below the ASTM E 119 standard time–temperature Philadelphia, E119
curve in a fire test (ASTM 1996). The time to reach the Argent B B, Niekenk M N and Redfern G A 1970 J. Iron &
Steel Inst. 208 830
critical temperature (538°C) was 32 min and 21 min for
Assefpour-Dezfully M, Hugas B A and Brownrigg A 1990 Mater.
fire resistant steel and mild steel, respectively. The rate of
Sci. & Technol. 6 1210
heating is dependent on the thermal conductivity which is Baird J D and Jamieson A 1972 J. Iron & Steel Inst. 210 847
a material property governing the flow of heat through a Bhadeshia H K D H 1992 Bainite in steels (London: Institute of
material at steady state. Figure 7 shows the dependence Materials)
of thermal conductivity with temperature for pure iron Borato F, Barbosa R, Yue S and Jonas J J 1988 Proc. Thermec’88
and some constructional steels (Riemann 1953; McGannon (ed.) I Tamura (Tokyo: Iron and Steel Inst. Japan) p. 388
1966). The thermal conductivity of pure iron and dilute Bureau of Indian Standards 1998 Indian Standards IS 2062,
alloys decreases with rising temperature. The likely be- New Delhi
haviour of 0⋅5Cr–0⋅22Mo fire resistant steel which is a Bureau of Indian Standards 2002 Indian Standards IS 15103,
dilute alloy is also shown in this figure. Its conductivity New Delhi
Chijiwa R, Tamehiro H, Yoshida Y, Funato K, Uemori R and
should be higher than 30 W/m⋅k at 600°C. The dominant
Horii Y 1993 Nippon Steel Tech. Report 58 47
carrier of the thermal conduction in pure metals and dilute
Dahl W 1992 Steel (Dusseldorf: Springer Verlag and Verlag
alloys is electrons (Ho et al 1975; Isachenko et al 1980; Stahl Eisen) 1
Touloukian and Ho 1981; Landolt 1991). When small DeArdo A J 1995 Microalloying’95 (Warrendale: Iron and Steel
amount of alloying elements (impurities) are introduced Society) p. 15
in iron, it causes discontinuities in the crystal lattice struc- Fushioni M, Chikaraishi H and Keira K 1995 Nippon Steel Tech
ture and promotes scattering of free electrons decreasing Report 66 29
the room temperature thermal conductivity (Riemann 1953; Ho C Y, Powell R W and Liley P E 1975 Thermal conductivity
McGannon 1966). With rising temperature, the scattering of the elements: A comprehensive review (NewYork: AIP)
of free electrons is intensified (Isachenko et al 1980). This Honeycombe R W K 1981 Steel microstructure and properties
causes a net reduction of thermal conductivity at higher (London: Edward Arnold; Ohio : ASM)
Houdremont E 1953 Handbook of special steels (Berlin:
temperature. Even then the thermal conductivity of dilute
Springer Verlag) 1
steel alloy is still high (> 30 W/m⋅k) at 600°C. Since in a
Irvine K J 1962 J. Iron & Steel Inst. 200 820
fire, temperature gradients are encountered, a high ther- Isachenko V P, Osipova V A and Sukomel A S 1980 Heat
mal conductivity material is desired to avoid degradation transfer (Moscow: Mir Publisher)
by local necking. Landolt B 1991 Thermal conductivity of pure metals and alloys
(eds) O Madelun and G K White (Berlin: Springer Verlag)
4. Conclusions 15C
McGannon H E (ed.) 1966 Making, shaping and treating of
steels (Pittsburgh : USS)
Small additions of Mo (0⋅20–0⋅25%) and Cr (0⋅30–0⋅55%)
Ouchi C, Sampei T and Kozasu I 1982 Iron & Steel Inst., Japan
in low carbon steel produced hot rolled fire resistant steel 22 214
with a minimum of two-thirds of room temperature yield Panigrahi B K 2001 Bull. Mater. Sci. 24 361
stress at 600°C. Microalloying by niobium and vanadium Panigrahi B K 2002 Unpublished result
improved the ratio of YS600°C/YSRT. However, final rolling Panigrahi B K 2004 Seminar on Structural steel for construction
temperature should be maintained in the recrystallized industry (NIT, Rourkela: The Institution of Engineers)
austenite region to ensure a microstructure free from high Panigrahi B K and Jain S K 2002 Bull. Mater. Sci. 25 319
dislocation density. The steels should be adequately treated Pickering F B 1978 Physical metallurgy and design of steels
by aluminium to tie-up free nitrogen in order to realize (London: Applied Science Pub.)
lower DBTT. In the quenched and self-tempered TMT Poliak E I and Jonas J J 2003 Iron & Steel Inst. Japan Int. 43
692
rebar steel, addition of ~ 0⋅55% chromium was adequate
Riemann W 1953 Stahl und Eisen 73 721
to ensure the guaranteed strength at 600°C due to transforma-
Sage A M 1983 Proc. int. conf. steels for line pipe and pipe line
tion to tempered martensite rim and bainitic core. Despite fittings (London: Metals Soc.) p. 39
decreasing trend of thermal conductivity with the rise of Tanaka T 1981 Int. Metal. Rev. 26 185
temperature in dilute alloys, the low alloy fire resistant Touloukian Y S and Ho C Y 1981 Properties of selected fer-
steel will have higher thermal conductivity up to 600°C rous alloying elements (New York: McGraw Hill Book Co.)
(> 30 W/m⋅k) compared to more concentrated alloys and III.1
is less expensive. Wettlaufer M and Kasper R 2000 Steel Res. 71 357
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Some Fundamental Steps in Thermomechanical Processing

of Steels* .
By Imao TAMURA**
Key words: ~hermomechanicalprocetsing;steel; deformation o f austenite; essing of steels, we can point out that:
restoration process; phase transformation; microalloying; ferrite grain re-
1) The deformation and restoration processes of y
Jinement. during and after hot rolling.
2) The kinetics of y to a transformation and grain
I. Introduction size of a.
Thermomechanical processing is a treatment of 3) The effect of cooling rate on transformation of
which plastic deformation is introduced into the heat work-hardened y to a , and grain size of a.
treatment of steel. We can find many treatments in 4) Structure of martensite in ferrous alloys.
such processes. But controlled rolling and acceler- 5) Structure and properties of martensite formed
ated cooling, and the ausforming or deformation- from work-hardened y.
quenching are representative and are used in practical 6) Hardenability of work-hardened y and recrystal-
production. lized y.
I n controlled rolling, the austenite (y) is work- I will explain on these processes based on our re-
hardened with plastic deformation (rolling) in high search results.
strain rate a t elevated temperatures, and then air
cooled to transform to ferrite (a). Sometimes, work-
hardened austenite is cooled acceleratedly to take fine II. Deformation Behaviors of Austenite during
-
ferrite grains in steel plate. and after Hot Working
I n the ausforming, work-hardened austenite is
quenched to room temperature. We can take the I. Restoration Process during Hot Deformation of Auste-
ausformed martensite which increases its strength and
not decrease its toughness. The ausforming is not so I t is well known that the deformation behavior of
popular in practice but the deformation-quenching is austenite a t elevated temperatures is a dynamic re-
getting to be popular. The martensite in the defor- crystallization type. Figure 1 shows schematically
mation-quenching looks like as usual martensite. But, both types of dynamic recovery type and dynamic
this martensite has a little bit of fine facet size be- recrystallization type.
cause it is formed from smaller austenite grains than I n the case of a dynamic recrystallization type,
usual austenite. This process can abridge to ration- since the rate of softening due to recovery is slow, the
alize the heat treatment process of steel. work-hardening can not be balanced only by dynamic
As fundamental steps in thermomechanical proc- recovery even at high temperatures, and the disloca-
tion density is still gradually increased with strain,
and finally the recrystallization starts to occur during
(a) deformation. The true stress is lowered beyond the
tn dynamic recovery peak stress by the occurrence of dynamic recrystal-
3 lization and reaches a certain steady state stress
level at which the work-hardening and softening due
to recrystallization occurring repeatedly are balanced.
The dynamic recrystallization starts at the strain of
(b) dynamic recrystallization around 0.78, (E,: the strain showing the peak stress).
I n Fig. l(b), the strain range up to about 0 . 7 ~is ~
the work-hardening region, the strain range between
about 0.78, and 8, (the strain at which the steady
state deformation starts) is the range of partially
dynamic recrystallization, and the strain range after
E , ~ is the range of steady dynamic recrystallization.
Austenite in steels belongs to this type. I n a-Fe (fer-

True strain rite), since the recovery occurs very fast, the restora-
Fig. 1. Schematic illustration of two types of true stress- tion is performed mainly by dynamic recovery. The
true strain curves accompanying the steady state peak stress (a,) and the steady state stress (a,) in the
deformation at elevated temperatures. dynamic recrystallization type change with the Zener-
* Based on the Special Lecture delivered by Prof. Tamura in commemoration of his receiving Nishiyama Medal in the 113th ISIJ
Meeting, April 2, 1987, a t The University of Tokyo in Tokyo. Manuscript received on May 18, 1987. 0 1987 ISIJ
** Professor Emeritus, Kyoto University; Technical Advisor, Sumitomo Metal Industries, Ltd., Nishinagasu-hondori, Amagasaki 660.
Special Lecture ( 763 )

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Hollomon parameter (2). Z is expressed by them when Z is high.

I n the same way as the static recry~tallization,~)it
has been observed that there are two main mech-
where, i: the strain rate (s-l) anisms for dynamic recrystallization, i.e., the bulging
I? : a gas constant (J/mol) mechanism and the nucleation-growth mechanism.
Dynamic recrystallization becomes easier to take
Q: the activation energy for deformation (J/
mol) place when the initial grain size (do) of austenite is
7: temperature (K). smaller. Therefore, in the case of fine initial grain
a?,, ep, g s and E , are increased with increase in Z (i.e., size, c p and E, become small even at the deformation
with increase in i or decrease in 7). under the same Z condition. However, a,, and a , are
Figure 2 shows the change in optical microstructure independent of do. The average size (d) of dynam-
with strain in Fe-31%Ni-0.3%C austenitic alloy ically recrystallized grains is the only function of Z
which was tensile deformed at 1 273 K (1 000°C) at a and is expressed by the following equation,')
strain rate of 1.7 x 10-2/s. Figure 2(a) is the austenite
structure before deformation. Austenite grains are
equiaxed and their boundaries are smooth and planer. where, A, : material's constant.
Many annealing twins exist in austenite grains. When A is larger for C-steel than for alloy steels, especially
deformed slightly (E=0.08), as shown in Fig. 2 (b), the small for Nb-containing steel and high alloy steel. p
grain boundaries become finely serrated and the bulg- is about 0.3-0.4 for all steels. I t should be noted
i n g ~of grain boundary are observed as indicated by that d is independent of do.
the arrows. At the strain slightly after E,, many small
grains are newly formed along the austenite bound- 2. Static Restoration Process during Holding Right after
aries as shown in Fig. 2(c). I t is characteristic that Hot Deformation
these newly formed grains hardly contain annealing When the hot deformation is finished a t the work-
twins. Furthermore, some of the initial austenite hardening stage, the work-hardened austenite is sof-
grains becomes larger by the strain-enhanced coarsen- tened by the usual static recrystallization during iso-
ing. Figure 2(d) shows the structure in the range of thermal holding after deformation. However, if the
steady state deformation at which the work-hardening strain is too small, the recrystallization can not occur
and the dynamic recrystallization softening are bal- and only the recovery takes place. O n the other
anced. This structure consists of several grains cor- hand, when specimens are isothermally held after de-
responding to various stages of recrystallization, i.e., formation to the range of the steady state deformation,
from small grains which have just started to recrys- in which the dynamic recrystallization has occurred,
tallize to fairly large grains which have been subjected the recrystallization and the grain growth can succeed
to deformation after the finishing of recrystallization to occur continuously during holding after hot defor-
and are the work-hardened state just before the next mation. Such a recrystallization is called a meta-
recrystallization. I n the stage of steady state defor- dynamic or postdynamic recrystallization. Namely,
mation, the recrystallization occurs repeatedly during the dynamically recrystallized structure is further
deformation. Dynamic recrystallized grains contain softened by the metadynamic recrystallization. When
a few annealing twins a t low Z but scarcely contain specimens are deformed to the range of (11) in Fig.
(a) Before testing (E=O)

(b) €=0.08
(c) e=0.24
(d) &=0.40
Pig. 2. Optical micrographs showing tlie formation process of dynamically recrystallized austenite in Fc-31Ni-0.3C
austenitic alloy deformed a t 1 OOO°C, 1.7 x 10-2/s.
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l ( b ) in which the work-hardened austenite and dy- tenite grain size with At is also plotted in Fig. 3.
namically recrystallized austenite have coexisted, the Microstructural changes during isothermal holding a t
static recrystallization occurs in work-hardened aus- 1 373 K (1 100°C) are shown in Fig. 4 and Fig. 5.
tenite and the metadynamic recrystallization occurs As shown in Fig. 4 ( ~ = 0 . 1 8 )work-hardened
, austenites
in dynamically recrystallized austenite at the same are slightly elongated along the tensile direction (Fig.
time. 4(a)). The austenite hardly changes by holding for
I n case of rolling by hot strip mill in which slabs 1 s (Fig. 4(b)), although the softening occurs to some
are rolled by several passes, the static restoration proc- extent by the static recovery as can be seen in Fig. 3.
ess occurring during interval between rolling passes However, when specimens were isothermally held for
has great influence on the deformation behavior of 4 s (Fig. 4(c)), fine austenite grains which are form-
next rolling pass. If the softening due to the static ed by static recrystallization are partially formed
restoration is not completed during interval between mainly along the deformed austenite grain boundaries
rolling passes, the work-hardening is successively ac- and the static recrystallization is completed by the
cumulated by the subsequent rolling passes. holding of 15 s (Fig. 4(d)). Annealing twins in static
Fraction of softening (X) occurring during iso- recrystallized austenites are gradually developed with
thermal holding right after hot deformation can be increase in holding time. By holding for 40 s, recrys-
evaluated by the two-step deformation test from the tallized austenite grains are coarsened (Fig. 3). When
following e q ~ a t i o n , ~ ) the austenite was much more heavily deformed under
higher Z condition (work-hardened), the static re-
crystallized austenite grains become much finer as
shown in Fig. 6. As shown in Fig. 5 (a=1.0), dy-
where, cr,,,: the flow stress immediately before un- namically recrystallized austenites are characterized
loading by irregular grain boundaries, a low density of an-
c ~ , , ~ : the yield stress on reloading after hold- nealing twins and the mixed grain size. With in-
ing the specimen for various periods of crease in holding time, austenite grain boundaries
time (At) become fairly straight and austenite structure becomes
u,,,: the initial yield stress. almost equiaxed grains, and furthermore, the density
As an example, the change in the fractional softening of annealing twins is increased. This is the typical
(X) with the holding time (At) in Fe-31 %Ni-O.S%C microstructural change occurring during metadynam-
austenitic alloy is shown in Fig. 3. Specimens were ic recrystallization process. Metadynamic recrystal-
tensile deformed a t 1 373 K (1 100°C) a t a strain rate lization is completed by the holding for about 30 s in
of 4 x 10-2/s to E = 0.18 (work-hardened austenite) and the case of Fig. 5, and the usual grain coarsening oc-
e = 1.0 (completely dynamically recrystallized auste- curs by further holding. The grain size right after
nite), respectively, and then isothermally hild for the completion of metadynamic recrystallization is
various periods of time. The change in average aus- smaller, as the grain size of dynamically recrystallized
Hdding time. A t ( s )
Fig. 3.
Change in fraction of softening (a) and austenite As-deformed ( A t = 0 S) (b) At = 1 s (c) At = 4 s (d) ~t = 15 s
grain size (b) with the isothermal holding time of Fig. 4. Change in optical microstructure of work-hardened austenite (de-
work-hardened austenite and dynamically recrystal- formed at 1 100°C, t = 4.0 x 10-2/s, c ~ 0 . 1 8 during
) isothermal holding
lized austcnite in Fe-31Ni-0.3C austenitic alloy. at 1 100°C for At in Fe-31Ni-0.3C austcnitic alloy.
Special Lecture
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[ 7 6 6 ) Transactions ISIJ, Vol. 27, 1987
(a) AS-deformed ( ~= Ot s) (b) At = 1 s (c) At=2 s (d) At=30 s (a) Work-hardened austenite (detormed a t 900°C,
Fig. 5. Change in optical microstructure of dynamically recrystallized austenite e=3/s, ~ z 1 . 0 )
(deformed a t 1 100°C, d = 4.0 x 10-Z/s, E = 1.O) during isothermal (h) Static recrystallized austenite (isothermally
holding a t 1 100°C for At in Fe-31Ni-0.3C austenitic alloy. held a t 900°C for 50 s of structure (a)
Fig. 6.
Optical micrographs showing the static recrystal-
austenite is smaller. lization occurring during isothermal holding after
heavily work-hardened austenite in Fe-31Ni-0.3C
3. Efect of Alloying Elements on the lietardation of Re- austenitic alloy.
crystallization5)
Table 1. The values of n and m in Eq. (4) for varlous
The effect of alloying elements on the restoration transformation conditions.
process during or after hot deformation is very im-
portant. Micro-addition of N b or T i acts as a re- Mechanism Site saturation
Nucleation and
markable retardation effect on recrystallization due to growth
-- - -- -- --
the suppression of grain boundary migration. The Site n m n m
suppression of grain boundary migration due to micro- Grain surface 1 1 4 1
alloying is caused from (1) the solute dragging effect Grain edge 2 2 4 2
due to segregation of alloying elements to the bound- Grain corner 3 3 4 3
aries, or (2) the pinning effect due to precipitates of
carbonitride of alloying elements at grain boundaries.
For example, Mo segregates to the austenite grain x = l - exp [ - k ( ~ ) $ ] ...............(4)
boundaries, resulting in the suppression of grain
boundary migration. Even N b micro-addition, at where, X: the transfbrmed fraction
high 1, it can retard the recrystallization by dragging t: the isothermal holding time
effect. But, usually, N b and T i are precipitated as d: the austenite grain size
fine carbonitride particles and these precipitates sup- k(7): the rate constant which depends only
press the grain boundary migration by the pinning on transformation temperature and di-
effect. rectly corresponds to the C-curve of
T T T diagram (isothermal transforma-
III. Transformation Kinetics and Grain Size of tion diagram).
Ferrite Transformed from Austenite The values oS the exponent m and n are listed in Table
1.6) These values depend on both the transformation
I. Isothermal Transformation Kinetics of Austenite mechanism and type of nucleation site. Here the
When the ferrite or pearlite Sorms from austenite transformation which progresses with nucleation and
by isothermal holding below the transformation tem- growth over almost entire range of transformation is
perature, these nuclei form preferentially a t the prior called " nucleation and growth ". The transforma-
austenite grain boundaries. We expressed as Eq. (4)'3 tion where all the nuclei are nucleated a t the early
that their transformation kinetics include the effect of stage in the reaction and the progress of transforma-
austenite grain size, by modification of Johnson-Mehl tion is controlled mostly by their growth is called
equation. " site saturation ". An austenite grain is assumed to
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Transactions ISIJ, Vol. 27, 1987 ( 767)
be a tetrakaidecahedra, and the nucleation sites a t Now extend this Scheil's additivity rule to the
austenite grain boundary can be classified into sur- entire range of transformation. I n this case the incu-
faces, edges and corners as are shown in Fig. 7.697) bation time ( ~ ( 7 )is) replaced with the time required
Of course the actual nucleation sites are not limited to for the reaction to reach a certain fractional comple-
any one of such types, and the value of m would be tion X by isothermal holding at temperature T. If
the weighted average of the various nucleation sites we combine Eq. (5) with Eq. (4)
and not always be an integer.
According to Umemoto and Tamura,e) the values
of n and m, and transformation modes were experi-
mentally shown as in Table 2. I t is mentioned in
Table 2 that the mode of y + a transformation is site
where, Q ( T ) = -dT/dt: a cooling rate.
saturation, but it means the large number of nuclea-
This equation expresses the transformed fraction at
tion o f a would occur at the beginning of transforma-
temperature T during cooling from austenite condi-
tion, which would not be real "site saturation ".
tion with a cooling rate Q(T).6t9) Furthermore, from
Sometimes the nucleation site is varied by supercool-
Eqs. (4) and (6) we obtain
ing (accelerated cooling). I t seems that the nuclea-
tion site of a is moved gradually from edge to surhce 1
by decrease in transformation temperature with cool- t ( 7 )= - J
K T )
-TTe K(T1)1/7~
- -
Q(T')
dT' = t., ...... (7)
ing rate, as described later.
This equation tells that the fraction transformed by
2. Continuous Cooling Transformation Kinetics of Austenite cooling from 7, to T with cooling rate Q ( T ) is equal
Scheils) considered the case where the austenite is to that obtained by the isothermal holding at tem-
cooled continuously through its transformation temperature T for time t ( 7 ) . Thus we call t ( T ) as an
perature. He assumed that austenite consumes its equivalent cooling time, t,,. t,, means the isothermal
fractional nucleation time and when the sum of a holding time which gives the equivalent transformed
number of such fractions equals unity, the transfor- fraction with continuous cooling. The curve pro-
mation starts, i.e., duced by the successive plot oS such t,, at each tem-
perature during cooling with cooling rate Q ( T ) will
be called an equivalent cooling curve.'O) The trans-
formation behavior for a given cooling curve can be
predicted from the T T T diagram by plotting such
curve on a T T T diagram.
3. Ferrite Grain Size Transformed from Austenite

1. Expression for Ferrite Grain Size (Isothermal)
I n general, ferrites nucleate at austenite grain
boundaries and grow into austenite grains. The
grain size of ferrite formed from austenite is directly
related with the process of transformation.") The
nominal ferrite grain diameter D, can be expressed
with the total number of ferrite grains uncleated
throughout transfbrmation per unit volume of auste-
nite, n,, as12)
Fig. 7. Schematic diagram of austenite grain as a tetra-

kaidecahedra and showing 3 types of nucleation
sites offerritc.
where, I : nucleation rate per unit volume oS aus-
tenite
'Table 2. The values of r2 and m for various trans- X: volume Sraction transformed
formation modes. Thus the problem of obtaining the exprcssion for fer-
rite grain size is the problem of how to express n,>.
Transformation n m Nucleation When ferrites nucleate a t the austenite grain bound-
-
Pearlite 4 2 Edge nucleation ary surfaces, they grow as ellipsoid with the aspect
Nucleation and growth ratio of 3 : 1 1 3 ) as shown in Fig. 8. The total number
1:errite 1 1 Surface nucleation near
of rerrite grains nucleated per unit area of austenite
Site saturation grain boundary surface is
)dt = -
4 0.6 9
Bainite Grain boundary,
Inside grain
n, = I,J; exp (-Tzaz~stz 3:2-(':')
-
Nuclcation and growth
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[ 768) Transactions ISIJ, Vol. 27, 1987
ferrite g r a i n grain boundary nucleation a small austenite grain

leads to a small ferrite grain. The effect of austenite
grain size on ferrite grain size depends on the type of
g r a i n boundory nucleation site, and it becomes large in the following
r=3Cl(t- 2) ascending order: homogeneous, grain surSaces, and
grain edges.
Fig. 8. Schematic drawing of a ferrite grain nucleated at
I t should be noted that the grain refinement on
austenite grain boundary surface.
austenite turns out to be less effective in ferrite grain
refinement. For instance in the case of grain surface
where, I , : the nucleation rate per unit area oL aus- nucleation D, is proportional to D',I3 in Eq. (13).
tenite grain surface This means that when D, is reduced to 118 of the ini-
a : parabolic rate constant for thickness. tial, D, would be reduced only into 112.
The ferrite grain size D, is given as Figure 914)shows experimental results of isothermal
transformation in a steel (0.2 % C, 0.0016 0/, B). The
steel was austenitized between 1 000 and 1200°C to
change its austenitic grain size from about 53 to 88
where, Sg.b: the austenite grain surface area per pm, and then transformed a t 700, 680 and 660°C into
unit volume Ferrite. The results are recognized as the dependent
and can be expressed by austenite grain diameter, D,, of y-grain diameter that a nucleates mainly at grain
as edges a t 700°C, at grain edges and surfaces a t 680°C
and at the surfaces a t 660°C.
2. Estimation of Ferrite Grain Size Formed by Continu-
ous Cooling Transformation
Substituting Eqs. (10) and (12) into Eq. ( l l ) , the It can be assumed ferrite nucleates preferentially at
ferrite grain size and the y / a transfbrmation ratio can austenite grain surfaces by supercooling. A continu-
be expressed as ous cooling transformation can be considered as the
sum of short time isothermal holdings a t successive
temperatures as is schematically shown in Fig. 10.
During cooling, ferrite grains are nucleated and
and grow at each temperature with the corresponding
nucleation and growth rates, as is schematically shown
in the Fig. 10 (bottom). During ferrite transforma-
tion carbon enriches in retained austenite, however,
since ferrite nucleation occurs mostly in the early stage
of transformation, it can be assumed that both the
In the above derivation it was assumed that the
nucleation and growth rates of ferrite are a function of
nucleation rate and the parabolic rate constant of
a n instantaneous temperature only and not a function
growth are time independent and one nuclei grows
of thermal history.
and forms one grain.
Based on this assumption, the number of ferrite
Similarly the D, and y / a transformation ratio in the
nuclei (N,) nucleated at temperature I, during cool-
case of homogeneous and grain edge nucleation has
ing, N, is given as Eq. (16).
been obtained asl1)
where, Q ( T ) (= -dT/dt) : a cooling rate.

Ferrite grains once nucleated grow thereafter with a
corresponding growth rate at each temperature during
cooling. Thus, at temperature T, the radius of a fer-
rite grain on an austenite grain surface nucleated a t
temperaturc T,, is given as Eq. (1 7).
where, I h : the homogeneous nucleation rate per unit

volume The austenite grain boundary area occupied at tcm-
pcrature 7 by a ferrite grain nucleated a t temperature
I,: nucleation rate per unit length of auste-
nite grain edge. T, is given as Eq. (18).
I t should be noted that the equations introduced
above indicate that ferrite grain size and y/a trans-
formation ratio depend on the ratio of square root of
the nucleation rate to the parabolic rate constant in I t will be convenient to use the concept of extended
all three types of nucleation sites. Furthermore Sor area which is the sum of the areas of austenite grain
Special Lecture
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Transactions ISIJ, Vol. 27, 1987 ( 769 ]
Austenite G r a i n Size
o ~ *
TI
d(h)
T2
d(T2)
T3
d(T3)
Tl,
~ ( T L )
Is(T ) Is(T2) Is(T3) Is(TL )
Fig. 10. Diagrams to explain the relation between iso-
thermal and continuous cooling transformation
and schematic drawing showing the formation
process of ferrite during continuous cooling.
Fig. 9. An example of D,- or D,/D,,-D, rclationsllip for

S15C steel.
surface occupied by ferrite grains, assuming that fcr-

rite grain never stop growing and that ferrite grains
keep nucleating a t the same rate during transforma-
tion as well as on untransformed austenite grain sur-
faces. The extended grain boundary area occupied
by all the ferrite grains nucleated a t T , during cool-
ing is given as Eq. (1 9).
Thus the grain boundary arca fraction occupied by

the ferrite grains nucleated during cooling horn A 3 ( T , )
to T is givcn by Eq. (20).
673 773 873 973 1073 1173
{J:$?&; dl-' 1d T , 1............(2 0) TEMPERATURE, K

Fig. 11. Calculated parabolic rate constant and nucleation
rate I, as a function of' temperature for the steel
The total number of ferrite grains nucleated per unit studied. (S15C)
area of austenite grain boundary surfacc is given by
Eq. (21).
where, Sg.,,(=4/(dn D,)): the austenite grain surface
area pcr unit volume.
From these equations, ferrite grain s i ~ ecan be cal-
culated.
I t is fairly difficult to estimate of I , ( T ) and tt(T)
by some kinds of calculation, but it is not impossible.
By using several assumptions and h y p o t h e s i ~ , ~ ~ ' ~ - ~ ~ )
Ferrite grain size is given as Eq. (22). I , ( T ) and a ( T ) are roughly calculated as shown in
Fig. 1 lZ4)as a function of transformation tempera-
ture. I n this figure, I , shows a maximum value a t
913 K (640°C) and n shows a maximum value a t
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873 K (600°C) fbr S15C steel (0.15 % C, 0.4 % Mn). IV. Ferrite Grain Refinement by Work-harden-
Figure l2Z4) shows a comparison of calculated ing of Austenite
values and experimental values for C15C steel. Wc
can get a roughly agreement, that is, a-grain size is I. Ferrite Nucleation in Deformed Austenite (Isothermal)
getting smaller with cooling rate increases. The Sor- Figure 14 is typical micrographs showing the effect
mulations are : of austenite defhrmation on the progress of ferrite
transformation.Z5) Specimens of an Fe-0.12C-0.04-
Dtv= Q-0.17(D,)1'~cal~ulat~d) ..................(23) Nb-0.04V steel were austenitized at 1 200°C for 30
(experimental) ... ......(24)
Do = 5.7Q-0.2'3(D,)0.46 min, rolled 30 or 50 % in reduction by a single pass
a t 840°C (in the unrecrystallized temperature range)
Figure 1324)shows experimental results. and held at 680°C for 15, 30 and 180 s. The ferrite
transformation is clearly accelerated by deformation
COOLING IRATE , K is
Fig. 1 l'erritc grain s i ~ eas a function of cooling rate lor

the specimens of D, = 151 pm. (S 15C) Fig. 13. Ferrite grain size as a function of Q-0.2'3Dt4G.
Not Rolled Rolled(30%) Rolled(50%)
(a) Non-deformed, 15 s (b) 30 % rolled, 15 s (c) 50 % rolled, 15 s

(d) Non-deformed, 30 s (e) 30 % rolled, 30 s (f) 50 % rolled, 30 s
(g) Non-defbrmed, 3 min (h) 30 % rolled, 3 min (i) 50 0/6 rolled, 3 min
Fig. 14. Optical micrograph showing the efrect of austenite deformation on the proccss of' ferrite transfbrma-
tion a t 680°C in a Fe-O.12C-0.04Nb-0.04V steel.
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ofaustenite. I n the non-deformed specimen austenite

grain boundaries are the predominant nucleation sites S,.,,(p) = St''-* [(q x J:
-1'1-*
J 1-(2p-pvsiFzB do.
of ferrite, but in the deformed specimens nucleation
occurs not only on austenite grain boundaries but also
within grains. Moreover, the nucleation rate on
grain boundaries is substantially accelerated. l h c ratio of the surface area before to after rolling,
Figure 15 shows various types of nucleation sites of q(=S,.b/SO,.,,), is plotted in Fig. 17 as a function of
ferrite observed in deformed specimens.25) Figure rolling reduction p. Since the volume of the sphere
15(a) shows ferrite grains nucleated a t austenite grain shown in Fig. 16(a) is equal to that of the ellipsoid
boundaries. The ferrite grains grow into both sidcs shown in Fig. 16(b), the ratio q in Fig. 17 is equal to
of austenite grains, and the prior austenite grain that obtaining to grain surface areas per unit volume
boundaries disappear once ferritcs are nucleated. Fig- before and after rolling. I t is seen that the increase
ure 15(b) shows the ferrite grains nucleated a t the in the grain surface area per unit volume with the in-
annealing twin boundaries. I n contrast to the non- crease in p is quite small when p is smaller than 0.5.
deformed specimens, the annealing twin boundaries For instance 50 % reduction by rolling increases the
in the deformed specimens are the preferential nuclc- surface area by 25 %. This increase is equivalent to
ation site of ferrite. The ferrite grains nucleated at that obtained by only 20 0/, reduction in austenite
annealing twin boundaries grow mostly into one side, grain size.
and the traces of prior annealing twin boundaries The number of ferrite grains nucleated on austenite
remain after transformation. Figure 15(c) shows fer- grain boundaries is substantially increased by defor-
rite grains nucleated intragranularly. These ferrites mation. Figure 1825) shows the ferrite grains nu-
were considered to be nucleated on the dislocations at cleated on the austenite grain boundaries: (a) non-
the cell wall distributed almost uniformly inside the deformed, (b) 30 % rolled, and (c) 50 % rolled,
grains. Figure 15(d) shows the ferrite grains nucle- respectively. From these pictures the acceleration of
ated at decormation bands. ferrite nucleation rate on austenite grain boundaries
The increase in the ferrite nucleation rate per unit by deformation can be estimated. The number of
volume of austenite by deformation is attributed (1) ferrite grains intersect per 1 mm of austenite grain
to the increase in the austenite grain surface by elon-
gation of grains, (2) to the increase in the nucleation
rate per se per unit area of grain surface, and (3) to
the formation of additional nucleation site such as
annealing twin boundaries, deformation bands, etc.
The grain boundary surface area of austenite per
unit volume of a specimen increases by deformation.
A spherical austenite grain (Fig. 16(a)) becomes an
ellipsoid as shown in Fig. 16(b) by applying the roll-
ing with reduction p. The surface area of a grain (a) (b)
with an unit radius before rolling is given as
(a) Kcfore rolling (sphere)
(b) After rolling (ellipsoid)
The surface area of the grain after rolling with reduc- l i g . 16. Tlic shapc change ol' a n austcnite grain by the
tion p is given as rolling with reduction p.
Rolled (30V0)30s Rolled(30%) 15s
(a) W ~ ~ c . l t , ~;it
~ tgr~ii11
i o ~ ~ I>o~~n(laric~s
(I,) Nuc.l(.atiun on ;i~ni~.nli~ig t \ \ . i r ~ I)ou~~cl;iric~~
(c.) S~iclcntioni n d c gr;iinr
((1) Suclc:~tionon clt.IL1.1nntion bantls
Fig. 15.
~ i 01'
Opticxl n>ic.rogl.nplis showi~lglllr \ . ; ~ r i o ~types
~iucleatiun bites 01' IC3rrite obier\,ccl i l l drll1.111rd
specimens. Rolled(50%) 15s Rolled(30%) 15s
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strain & (=-ln(1-p))

0 -0.5 - 1.0
Not Rolled
680 'C
3min
1 7 --
1.6 --
1. 5 --
1.4 --
1.3 --
Rolled (5O0Io)
o 0.1 0.2 0.3 0.4 0.5 0.6 0.7 680 O C
Rolling Reduction p
30s
Fig. 17. The ratio of austenitc grain surfacc arca bcforc
rolling to that of after rolling as a f~~nction
of roll-
ing rcduction $. (a) Non-deformed, 3 min at G80°C
(b) 30 0/, rolled, 3 s at 680°C
(c) 30 % rolled, 3 s at 680°C
boundaries werc counted as 4 1, 214 and 330 for 1 18. Optical micrographs showing the efycct of defor-
0, 30 and 50 rolled specimens, respectively. The mation on the number of ferrite formed on auste-
numbers of ferrite grains nucleated per unit area nite grain boundaries.
of austenite grain boundary surface are proportional
to the square of these numbers. Furthermore the
number of ferrite grains nucleated per unit area of
austenite grain surface, n,, is proportional to the
square root of I, as is shown in Eq. (10). Since a is
not much changed by deformation, the ferrite nuclea- $.,,.,j-
rcrrite
tion rate per unit area of austenite grain boundary ,A-F

surface is estimated to be increased by 740 ((214/41)4)
and 4 200 ((330/41)4) times faster by 30 and 50 %
rolling, respectively. (a) A ledgc on grain boundary
(b) Ferrite nuclcation at a lcdgc
As is shown above, the nucleation of ferrite on
austenite grain boundaries is substantially accelerated Fig. 19. Scllematic drawing showing ferrite nucleation at
by deformation. The mechanism of enhanced nu- a ledge on deformed austcnite grain boundaries.
cleation is considered to be as follows. The deformed
austenite grain boundaries may have many ledges (or the similar structure with that of austenite grain
steps) shown schematically in Fig. 19(a). If ferrite boundary surfaces and act as the preferential nu-
nucleates a t the corner or such a ledge, as is shown cleation site of ferrite.
in Fig. 19(b), the activation energy for nucleation be- Similar mechanisms have bcen proposed for the
comes B/n times less than that fbr nucleation on a enhanced nucleation on deformed austenitc grain
planar grain boundary (if the surface energy is as- boundaries by several researchcrs. Sandberg and
sumed to be equal for all kinds of interfaces). Thus Robertsz7)have suggested that deformation leads to
if a large number of ledges are produced on grain the formation of grain boundary serrations or bulges,
boundaries by deformation, considerable increase in and these act as nucleation sites. Amin and Pic-
the nucleation rate can be expected. As is shown keringZ8) proposcd that deformed austenitc grain
in Fig. 15(b) the annealing twin boundaries in boundaries appear to exhibit greater lattice mismatch,
work-hardened austenite also act as the preferential possibly because of greater lattice distortion and a
nucleation site of ferrite. The reason of this can be higher dislocation density near deformed grain bound-
considered to be as follows. At the coherent twin aries. These would be the predominant nucleation
boundaries before deformation a large number of sites of ferrite and hence accelerate the nucleation.
ledges are produced on the twin boundaries by Deformation structures within austenite grains have
deformation. Thus deformed twin boundarics have bern known to act as the effective nucleation sites of
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ferrite and play an important role in the ferrite grain ary surface, annealing twin boundary and deforma-
refinement. The deformation structure is generally tion bands ( S , ( P ) = S g . b ( p ) + S d . ~ ( P ) + S t . h ( P ) ) . Fur-
called as deformation bands. These regions are char- thermore, if both the nucleation and the growth rates
acterized by a high density of cells consisting of tangled are a function of strain, the ferrite grain size in the
dislocations. Dislocations are favor nucleation sites deformed specimen is considered to be expressed as
through its stress field. Consequently ferrite nuclea-
tion appears to occur frequently at the deformation
structures.
Thus if d I o / w o and the coefficients A and B are de-
2. Growth of Ferrite in Deformed Austenite (Isothermal) termined from an experiment, the ferrite grain size
When ferrite grains grow into deformed austenite, formed from deformed austenite can be calculated.
their growth rate would be accelerated by the follow- Figure 20 shows an example of such calculation.
ing two factors. One is due to the enhancement of Here the calculated ferrite grain size using the com-
diffusivity by dislocations and supersaturated vacan- monly observed values of JIi/cuo, A and B is plotted
cies. Another is due to the additional driving force as a function of the rolling reduction, P. From this
associated with stored energy. Since carbon, whose figure it is seen that the ferrite grain size formed from
diffusivity controlls the growth rate of ferrite in HSLA work-hardened austenite decreases drastically with the
steels, is an interstitial element, the former effect is increase in a rolling reduction for a small rolling re-
considered to be small. The latter [actor is also not duction and decreases gradually for a large rolling
so large estimation by some kinds of calculation (ac- reduction.
celeration is less than 10 %).z4) We can find that the
ferrite growth rate is slightly enhanced by the defor- 4 . Ferrite Grain Refinement by Accelerated Cooling
mation of austenite. The acceleration of growth rate Accelerated cooling after hot rolling is currently
by deformation is much less than enhancement of nu- being realized as a further advanced thermomechani-
cleation rate for the transformation kinetics. cal treatment in hot rolling proce~s.29>3~) This cooling
process is characterized by accelerated cooling in a
3. Ferrite Grain Size firmed ,from Dfirmed Austenite 7-+a transformation range just after controlled rolling.
(I~othermal)2~) I t has been shown that the accelerated cooling refines
the ferrite grain size and thus further improves both
For simplicity we assume;
the strength and toughness.
(i) that austenite grain boundary surfaces are the The effect of accelerated cooling on ferrite grain
nucleation site and the additional nucleation sites
refinement can be seen in a non-deformed specimen.
produced by deformation are the deformation bands
Figure 13 and Eq. (24) show the effect of cooling rate
and annealing twin boundaries,
on ferrite grain size in an Fe-0.15C
(ii) that the nucleation rates per unit area of de- This dependence of ferrite grain size by cooling
formation bands and annealing twin boundaries are
rate means that when a cooling rate becomes 10 times
equal to that of the grain boundary surface,
faster ferrite grain diameter becomes almost half
(iii) that the total area of deformation bands and (0.55).
annealing twin boundaries per unit volume of auste-
The principle of grain size refinement by accel-
nite is quadratic with respect to
erated cooling can be understood by considering the
the strain E(= -In (1 -P)), i.e., effect of transformation temperature on ferrite grain
size in an isothermal transformation. As mentioned
S,.,i(p)+Sl.l,(p)= A(- In (1 -p))2 .........(27)
in the previous section the grain size of isothermally
where, A is a constant, and formed ferrite depends on the ratio of the square root
(iv) that the ratio JI,(p)/a(p) can be expressed
as a function of strain e as, Da(prn)lnDa True Strain & = -ln(l-p)
1.0 2.0
40
30.-
where, I o , a,: the nucleation rate and parabolic rate 20-3 0 Austenite Grain Size
constant of growth in the non-de-
formed specimen, respectively 10..
B : a constant. 2.o
An exponent of 1.3 came from an experiment for Fig.
5-
18.
As discussed above the ferrite grain size formed
1.0
from non-deformed austenite in the case of grain sur- 0 .I .2 .3 .4 .5 .6 .7 .8
face nucleation can be expressed by Eq. (1 1). From Rolling Reduction, p
the assumptions made for deformed specimen Sg.bin Fig. 20. Calculated ferrite grain size formed from work-
Eq. (1 1) should be replaced by the effective interfacial hardened austenite as a function of rolling reduc-
area, S,, which is the sum of the areas ofgrain bound- tion for various austenite grain sizes.
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[ 774) Transactions ISIJ, Vol. 27, 1 9 8 7
of nucleation rate to the parabolic rate constant for to room temperature to produce lath martensite. It
various types of nucleation sites. Thus when the appears from Fig. 2233)that the number of packets in
ratio d n a increases with the decrease in the transfor- an austenite grain markedly decreases and hence the
mation temperature, the grain size of an isothermally packet size becomes large with an increase in the
formed ferrite decreases with the decrease in the amount of deformation of austenite. The block be-
transformation temperature. comes narrower and finely segmented, and the block
The continuous cooling transformation can be con- boundaries become heavily waved with an increase in
sidered as the sum of short time isothermal holdings the amount of ausforming. Figure 23 shows the
at successive temperatures, as described in previous change in the mean packet size and block width of
section and derived two equations of (21) and (22) lath martensite in 18 Ni maraging steel with the
which show n, and D,, respectively. amount of ausforming. These results indicate that
As a whole, austenite deformation results in a large the morphology of ausformed lath martensite is char-
increase in the ratio of the nucleation rate to the acterized by large packet size and less-developed
parabolic rate constant and leads to ferrite grain re- blocks. And also it is characteristic that the block
finement. The accelerated cooling further refines a boundaries are waved in the case of ausformed mar-
ferrite grain size. tensite. Similar tendency was observed in low carbon
N b steel (HSLA steel) as shown in Fig. 24, in which
the specimen was rolled at 1 123 K by 50 % after
V . Structures and Properties of Martensite austenitizing a t 1 573 K for 1.8 ks and then water
Formed f r o m Work-hardened Austenite quenched to produce lath martensite. These micro-
structural characteristics might arise from the pre-
I. Morfhology of Microstructure Composed of Lath Mar- ferential formation of lath martensites with the same
tensite Formed from Work-hardened Austenite habit plane along the most active slip plane (one of
Among various types of ferrous martensite (such as four (11 11, planes) which is macroscopically bent by
lath, lenticular, etc.) the lath martensite is the most heavy deformation.
important one because most of the commercial heat- As shown above, the packet size of ausformed mar-
treatable steels produce lath martensite. Lath martensite is large compared with that of conventionally
tensite structure is characterized by packets and blocks quenched lath martensite. I t was observed that the
within a original austenite grains as shown schemati- ausformed lath martensites form along the curved
cally in Fig. Zl.31) I t is known that the basic micro- {111}, planes as shown in Fig. 22(f)35)and Fig. 24
structural unit for controlling mechanical properties (b).") This indicates that the crystal planes of aus-
especially, toughness of lath martensitic steel is size of tenite (and hence, of martensite) are bent. I n such
packets or blo~ks,~2-3~) and thus the refinement of a situation, there would be a possibility that the
packets or blocks improves the mechanical properties propagation of cleavage crack is suppressed since the
of lath martensitic structure. Therefore, we examined plane of cleavage fracture ({001],,) is heavily waved.
the change in lath martensite morphology with the This might be one reason for some improvements in
amount of deformation of austenite using an 18 Ni toughness by ausforming in spite of the coarsening of
maraging steel (18.3 % Ni, 9.0 % Co, 5.0 % Mo, 0.7 packet size.
% Ti, 0.015 % C) and N b bearing low carbon steel
(0.12 % C, 0.038 % Nb, 0.039 % V). 2. Mechanical Proferties of Ausformed Martensite
An example of results in 18 Ni maraging steel is I n order to account for the good ductility of aus-
shown in Fig. 22.35) I n this case, specimens were formed steels, the relation between the ductility of de-
austenitized at 1 523 K for 120 s in Ar gas atmosphere formed austenite and the ductility of ausformed mar-
(austenite grain size of 200 pm was obtained by this tensite was studied using an Fe-25.4XNi-0.38XC
treatment) and cooled to 773 K (above M d tempera- alloy (Ms=236 K).37) I n this experiment, specimens
ture) and deformed in tension to various strains at were solution treated at 1 423 K for 10.8 ks. Since
773 K at strain rate of 3 x 10-2/s and then air cooled the M s temperature of this alloy is below room tem-
Fig. 2 1. Schematic illustration showing the morpholog-

I I ical characteristics of lath martensite structure
0.2% Carbon Steel l8Ni Maraging Steel in 0.2 0/, C steel and 18 % Ni maraging steel.
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( a ) ( c ) : Packed structure (electrirally etched with CrO, 10 g + H , O 90 cc)

( d ) ) : Block structure (chemically etched with FeCI, 10 g + H C l 30 cc+H,O 120 cc)
Fig. 22. Optical micrographs showing the change in packed or block structure of lath martensite with
amount of deformation oT austenite (ausformed by tennion at 773 K) in 18Ni maraging steel.
1 1 573 K for 1.8 ks -+ W.Q.

(a)
0 0.1 0.2 0.3 0.4 0.5 0.6 1 573 K for 1.8 ks --t 50 % rolled at 1 123 K
(b)
True Strain -t w.9_.
Fig. 23. Change in the packet size and block width of lath Fig. 24. Optical micrographs of non-ausformed (a) and
martensite with the amount of deformation of ausformed (b) lath martensite in Nb steel.
austenite (ausformed at 773 K ) in 18Ni maraging Etchant: 2 % nital.
steel. D, = 200 pm.
which is above Md temperature.
perature, the solution treated specimen was austenite Figure 25 shows the results of tensile strength of the
single phase at room temperature. These specimens deformed austenite and the ausformed martensite.
were deformed at 473 K by rolling to various amounts Both of tensile strengths of austenite and martensite
of reduction. The rolling temperature of 473 K was are increased with an increase in the amount of
applied in order to avoid the formation or strain- prior-deformation of austenite. Figure 26 shows the
induced martensite during deformation. Some of relation between the elongation and the amount of
specimens of deformed austenite were subzero cooled prior-deformation of austenite. I n the case of de-
into liquid nitrogen to produce the ausformed mar- formed austenite, the elongation is markedly decreased
tensite. Tensile properties were measured in both (from 60 to 3 %) with an increase in the amount of
specimens of deformed austenite and ausformed mar- prior-derormation. O n the other hand, it is charac-
tensite with an Instron-type tensile machine a t 353 K teristic that the elongation of ausformed martensite is
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( 7 7 6 ) Transactions ISIJ, Vol. 27, 1987
0 15 30 L5 60
Pre-deformation ( %)

Fig. 26. Relation between elongation and the amount of
prior-deformation of austenite at 473 K in Fe-
25Ni-0.38C alloy.

P, T : Parallel and transverse specimens against formed martensite has been studied mainly by func-
rolling direction, respectively tions of the amount of deformation and the defor-
S: Subzero cooling to 77 K, namely speci-
mation temperature below Al. And it is generally
mens are of martensite
believed that the increase in the strength of ausformed
Fig. 25. Relation between tensile strength and the amount
martensite is closely related to the amount of work-
of prior-deformation of austenite at 473 K in
hardening of austenite. However, few attempts have
Fe-25Ni-0.38C alloy.
been made to relate the strength of ausformed mar-
tensite to the flow stress of austenite during ausform-
hardly effected by the amount of ausforming and is ing at elevated temperatures.
almost same as the elongation of non-ausformed mar- I n order to make clear this point, the experiment
tensite. The ausformed martensite exhibits almost was carried out using austenitic steels (a high M n
constant elongation of about 8- 10 %, irrespective of steel : 13.9 % Mn, 0.68 % C) and Fe-high Ni alloy
the amount of ausforming. Therefore, the elongation (32.4 % Ni 0.005 % C), and martensitic steels (SNC
of deformed austenite becomes smaller than that of 815: 3.0 % Ni, 0.8 % Cr, 0.16 % C).38) Ausforming
ausformed martensite, when the amount of deforma- was performed with a tensile machine a t various tem-
tion (ausforming) is more than about 30 % in the peratures between 773 and 1 173 K a t strain rate
case of the present alloy. I t must be emphasized that of 1 . 7 10-21s.
~ After deformation, specimens were
the heavily deformed austenite is rather enhanced in rapidly quenched by water spray. These ausformed
both strength and ductility by martensitic transforma- specimens were tensile tested at room temperature at
tion. strain rate of 1 . 7 10-3/s
~ to measure the yield stress of
These results indicates that the dislocations in deformed austenite (austenitic steels) and ausformed
austenite produced by deformation are inherited and martensite (martensitic steels) a t room temperature.
that the stress concentrated region a t the obstacles in Figure 27 shows the relation between the increase
austenite produced by heavy deformation are healed in 0.2 % proof stress at room temperature (Aa;.,) of
by the martensitic transformation itself. As a reason ausformed austenite and the amount of work-harden-
for the healing effect, it can be considered that the ing (Aar) of austenite by ausforming at elevated tem-
stress concentration in austenite may be released by peratures in austenitic steels. I t appears that the
the formation of preferential variants of martensite at yield stress increase of austenite (Aa;.,) at room tem-
the stress-concentrated areas. perature is linearly proportional to the amount of
work-hardening of austenite (Aur) by ausforming in
3. Effect of Ausforming Temperatures on the Increase of both steels, and all data lie on the same straight line,
Strength ff Ausformed Martensite irrespective of ausforming conditions such as defor-
I n the most published papers, the strength of aus- mation temperature and the amount of strain. This
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Transactions ISIJ, Vol. 27, 1987 (777)
result indicates that the strength of ausformed austen- formation temperature, i.e., do;:, is increased with an
ite at room temperature is uniquely determined only increase in deformation temperature. Furthermore,
by the amount of work-hardening by ausforming. when the ausforming temperature is fixed, the con-
This probably suggests that the strengths of austenite tribution of A 0 7 on the An;:, is small at smaller Aur
at both of high and room temperatures are mainly range and becomes large at larger Aar range. Same
determined by the dislocation density. tendency was also observed in SKD 61 steel. These
Figure 28 shows the relation between the increase results strongly suggest that, in addition to the dislo-
of 0.2 % proof stress of ausformed martensite (Au;:~) cation density in austenite, the dislocation configu-
(i.e., the difference of 0.2 % proof stress at room tem- ration in austenite is also an important factor for
perature between ausformed martensite and conven- increase in strength of ausformed martensite.
tionally quenched martensite) and the amount of Figure 29 shows the examples of transmission elec-
work-hardening (Aar) in austenite at elevated tem- tron micrographs of austenite in a high M n austenitic
perature in SNC 815 steel. I t is characteristic that steel deformed to the same amount of work-hardening
the obtained data lie on the different curves by the (Aor= I0 kg/mm2) at different temperatures. As can
ausforming temperature. I t should be emphasized be seen, the total dislocation density seems to be
that the d a f , is not determined only by the Aar, but almost same, but the dislocation configuration is dif-
functions of both Aar and ausforming temperature. ferent from each other. With increase in the defor-
Even at the same Aar, the effect of ausforming on the mation temperature, the dislocation configuration is
strengthening of martensite is different with the de- changed from uniformly distributed pile-up to disloca-
tion cells. I n this austenitic steel, despite the dif-
ference of dislocation configuration the 0.2 % proof
Deformat ion temperature:

30 - A -993K
-1023K
L1
25. o -1073K
E
E 0
b20-
Y 0
erT 15-
C
a t H.T. -0N
0
Q 0
5.
E
0 5 10 15 20
bar at H.T. kg.rnrn-=
Fig. 27. Relation between the increase in 0.2 O//o proof Fig. 28. Relation between the increase in 0.2 % proof
stress a t room temperature of ausformed austenite stress of ausformed martensite (dot,;) and the
(do:,) and the amount of work-hardening of amount of work-hardening of austenite (do?) by
austenite (Aor) by ausforming in austenitic steels. ausforming in SNC 813 steel (3Ni-0.8Cr-0.16C).
Fig. 29. Transmission electron micrographs of austenite deformed to the same amount of work-hardening of
austenite ( A u ~ =10 kg/mm2)a t strain rate of 1.7 x 10-2/s a t (a) 1 073 K, (b) 1 023 K and (c) 873 K,
respectively, in Fe-14Mn-0.7C austenitic steel.
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stress of austenite at room temperature is the same as VII. Conclusion

shown in Fig. 27, because the Aar is the same. How- I have explained the abstract of kinetics, structure
ever, as shown in Fig. 28, in the case of ausformed and mechanical properties of transformation products
martensite, Aa$, is increased as the ausforming tem- of ferrite and martensite formed from work-hardened
perature is raised even at the same Aor. Therefore, austenite. Because of too much contents, I am afraid
it can be considered that the dislocation cell structure that it would be difficult to understand.
in prior austenite is very effective in strengthening of Thank you very much for your kind attention.
ausformed martensite through the martensitic trans-
formation, and pile-up or uniformly distributed dis-
locations in prior austenite have little effect on REFERENCES
strengthening of ausformed martensite.
T. Maki, K. Akasaka and I. Tamura: Proc. Int. Conf.
Thermomechanical Process. Microalloyed Austenite, ed.
VI. Hardenability of Work-hardened Austenite
by A. J. DeArdo et al., TMS-AIME, Pittsburgh, (1981),
and Recrystallized Austenite 217.
As described in the former section, the work-hard- T. Maki, S. Okaguchi and I. Tamura: Strength of Metals
ened austenite can transform easily by diffusional and Alloys (ICSMA-6), ed. by R. G. Gifkins, Pergamon
process, because the rate of nucleation of ferrite is Press, Melbourne, (1982), 529.
high. It means that the hardenability of steel is de- P. A. Beck and P. R. Sperry: J. Appl. Phy~.,21 (1950),
creased with work-hardening of the austenite. 150.
A bearing steel (SUJ2: 1.33 % Cr, 0.9 % C) with H. J. McQueen and J. .J. Jonas: Plastic Deformation of
Materials, ed. by R. T. Arsenault, Academic Press, N.Y.,
spheroidized carbide particles was austenitized at
(1975), 393.
850°C a t which the steel was in two phase region of
J.J. Jonas and I. Weiss: Metal Sci., 13 (1979), 238.
y and carbide, and deformed by compression of 60 %
M. G. Akben, I. Weiss and J . J. Jonas: Acta Metall., 29
(s=3x 10°/s), and then immediately or after holding (1981), 111.
in some intervals of time (At) at the same temperature M. Umemoto, N. Komatsubara and I. Tamura: J. Hent
as the deformation quenched into water. The hard- Treating (ASM), 1 (1980), No. 3, 57.
ness at the center portion of SUJ2 specimen at room J. W. Cahn: Acta Metall., 4 (1956), 449.
temperature after quenching changed with holding E. Scheil: Arch. Eisenhiittenwes., 12 (1935), 565.
time (At) as shown in Fig. 30. M. Umemoto, N. Nishioka and I. Tamura: J. Heat Treat-
The austenite of SUJ2 with spheroidized carbide ing (ASM), 2 (1981), 130; Trans. Iron Steel Inst. Jpn., 22
particles can dynamically recrystallized easier than (1982), 629.
without carbide particles. The work-hardened aus- M. Umemoto, N. Komatsubara and I. Tamura: Proc.
Int. Conf. Solid-Solid Phase Transf., ed. by H. I. Aaronson
tenite of SUJ2 has poor hardenability and becomes its
el al., TMS-AIME, Pittsburgh, (1981), 1111.
hardenability recover to usual SUJ2 with holding
M. Umemoto, H. Ohtsuka and I. Tamura: Proc. Int.
time (At) during the static recrystallization is progress- Conf. High Strength Low Alloy Steels, ed. by D. P. Dunn
ing as shown in Fig. 30. and T. Chandra, Univ. Wollongong, Wollongong, (1984), 96.
Ausforming is quenching method of work-hardened G . H . Gulliver: J. Inst. Met.,19 (1981), 145.
austenite. Such a n austenite has poor hardenability. J. R. Bradley, J. M. Risbee and H. I. Aaronson: Metall.
The steel for ausforming should have high harden- Trans. A., 8A (1977), 323.
ability by including several alloying elements of Ni, M. Umemoto, Z. H. Guo and I. Tamura: Proc. Int. Conf.
Cr, Mo, etc. HSLA Steels (HSLA Steels, Metallurgy and application^,
For direct quenching it seems that the austenite is HSLA Steel '85), ed. by J. M. Gray et al., ASM-INTER-
deformed and recrystallized and then quenched. I n NATIONAL, Beijing, (1985), 97.
this case, we can not expect to increase strength and C. Zener: J. Appl. Phys., 20 (1949), 950.
M. Hillert and L. I. Staffanson: Acta Chem. Scand., 24
toughness of martensite as ausforming does.
(1970), 3618.
H. I. Aaronson and H. A. Domian: Trans. AIME, 236
(1966), 781.
C. Wells, W. Batz and R. F. Mehl: Trans. AIME, 188
(1950), 553.
L. Kaufman, S. V. Radcliffe and M. Cohen: Decomposi-
tion of Austenite by Diffusional Process, ed. by V. E.
Zackay and H. I. Aaronson, Interscience Publisher, a divi-
sion of John Wiley & Sons, N. Y., (1962), 313.
C. Wagner: Trans. AIME, 194 (1952), 91.
W. F. Lange and H . I. Aarowon: Metall. Tranc., in press
I I I I W.Q. (Private communication).
M. Hillert: Lecture on the Theory of Phase Transforma-
6001 100 1 tion, ed. by H. I. Aaronson, TMS-AIME, Pittsburgh
200 300 400 (1975), 1-50.
~t Hold~ng Time (5)
C. A. Dube: PhD Thesis, to Carnegie Institute of Tech-
Fig. 30. Change in hardness of water-quenched specimen nology, (1948).
with holding time after deformation at 850°C in M. Umemoto, Z. H. Guo and I. Tamura: Muter. Sci.
SU.J2. Technol., 3 (1987), 249.
Special Lecture
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25) M. Umemoto, H. Ohtsuka, H. Kato and I. Tamura: 31) T. Maki, K. Tsuzaki and I. Tamura: Trans. Iron Steel Znst.
Proc. Int. Conf. High Strength Low Alloy Steels, ed. by Jpn., 20 (1980), 207.
D. P. Dunn and T. Chandra, Univ. Wollongong, Wol- 32) S. Matsuda, T. Inoue, H. Miura and Y. Okamoto:
longong, (1984), 107. Proc. of Int. Symp. on Toward Improved Ductility and
26) M. Umemoto, H. Ohtsuka and I. Tamura: Trans. Iron Toughness, ISIJ and JIM, Tokyo, Sendai, (1971), 47.
Steel Inst. Jpn., 23 (1983), 775. 33) Y. Ohmori, H. Ohtani and T. Kunitake: Met. Sci., 8
27) A. Sandberg and W. Roberts: Proc. Int. Conf. Thermo- (1974), 357.
mechanical Processing of Microalloyed Austenite, ed. by 34) A. R. Marder and G. Krauss: Proc. of Int. Conf. Strength
A. J. DeArdo et al., TMS-AIME, Pittsburgh, (1981), 405. of Metals and Alloys (Znd), 111, ASM, Asilomar, (1970),
28) R. K. Amin and F. B. Pickering: Proc. Int. Conf. Thermo- 822.
mechanical Processing of Microalloyed Austenite, ed. by 3.5) I. Tamura, K. Tsuzaki and T. Maki: Proc. of Int.
A. J. DeArdo et al., TMS-AIME, Pittsburgh, (1981), 377. Conf. Martensitic Transformation (ICOMAT-82), ed. by
29) C. Ouchi, J. Tanaka, I. Kozasu and K. Tsukada: " Op- L. Delaey et al., Les Edition de Physique, Paris, Leuven,
timization of Processing, Properties and Service Performance (1982), c4-551.
through Microstructural Control ", ASTM Spec. Tech. 36) I. Tamura, T. Maki and H. T. Yui: to be published.
Publ. No. 672, (1979), 105. 37) Y. Tomota, K . Tanabe, K. Kuroki and I. Tamura: J .
30) H . Sekine, T. Maruyama, H. Kageyama and Y. Kawa- J p n Inst. Met., 41 (1977), 313.
shima: Proc. Int. Conf. Thermomechanical Processing of 38) C. K. Yao, S. Y. Gao, T. Maki and I. Tamura: Proc.
Microalloyed Austenite, ed. by A. J. DeArdo et al., TMS- 3rd Int. Cong. Heat Treatment of Materials, ed. by T.
AIME, Pittsburgh, (1981), 141. Bell, Metals Soc., London, Shanghai, (1983), 5-80.
Special Lecture
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Journal of Applied Sciences Research, 2(8): 484-485, 2006

© 2006, INSInet Publication
Strengthening of Alloy Steel by High Temperature Thermomechanical Treatment

1
J.A. Omotoyinbo, 2 O.E. Olorunniwo, 2O. Ogundare and 2O.O. Oluwole
1
Federal University of Technology, Akure. Nigeria.
2
Obafemi Awolowo University, Ile-Ife. Nigeria.
Abstract: Micro-alloyed steels produced by controlled rolling are of the most attractive propositions in many
engineering applications because of their relative low cost, moderate strength and very good toughness when
compared with as-castalloy steel.. This research work has shownthe possible substitution of cheaper, low-alloy
steel for the high alloy steel for the same application. The effect of HTMT on the mechanical properties of low
alloy steel was investigated.
Key words: Strengthening. High Temperature Themomechanical Treatment (HTMT), micro alloyed,
controlled rolling.
INTRODUCTION MATERIALS AND METHODS
Steels are weaker than they should be theoretically Tensile test samples: To prepare the tensile test
because of dislocations and the ease with which these specimen, the hot-rolled samples which were initially of
dislocations moveunder applied shear stress[4]. Therefore, round shape were prepared as follows. The 10mm
the primary aim of strengthening is to retard the diameter rod was held tightly in position on the bench
dislocationmovements. However, complete barrier can be vice where it was cut into lengths of 5mm ach with he aid
dangerous because pile-up of dislocations can lead to a of hack saw. Each of the samples was then mounted and
catastrophic crack[2]. turned consecutively on the lathe machine into cylindrical
Strength in steels arises from several phenomenon shape. The vernier caliper was used to take the accurate
including solid solution strengthening, dispersion measurement. For reproducibility of results, four samples
strengthening and ferrite grain refinement which usually were prepared for the 10mm diameter rod. This process
contribute collectively to the observed mechanical was repeated for the 12mm and 16mm diameter rod, one
properties such as ductility, strength,etc. Alloying after the other.
elements’ presence provides greater control over
microstructure and consequent benefit in mechanical The impact test samples: They were prepared by
properties. notching to 4mm depth at 450 with the aid of the lathe
Therefore, to produce steels with improved machine. Four samples were prepared each for 10mm,
strength-to-ductility ratio, a combined use of mechanical 12mm and 16mm diameter rod as well as for the as-cast
working and heat treatment is employed as sample to be used in izod impact test.
strengthening mechanism [8], resulting in structural steels The hardness test sample-This sample is obtained by
with improved weldability, cleannessand inclusion shape grinding the surface with emery paper. Then, with the aid
control[9]. of hacksaw and lathe machine, cut into 25mm x 25mm x
This paper seeks to investigate and establish the 25mm square cube for Rockwell test. Four samples were
possible benefits derived from strengthening of alloy prepared for 12mm and 16m diameter samples.
steels by HTMT. This includes improved mechanical
properties, substant ial energy savings (through Microstructural test: The specimens were ground in
elimination of subsequent normalizing treatment) and succession with 220,320, 400, 600 frit emery paper. Then,
possible substitution of cheaper, low alloy steel for high they were polished until mirror-like surfaces was
alloyed steel for the same application under the same obtained. The surface was etched with Nital solution and
conditions. examined under the microscope. For reproducibility of
results, four samples were prepared for 10mm, 12mm and
Experimental procedure: The chemical composition of 16mm samples.
low alloy steel as-cast specimens (AISI-SAE 1037 ),
presented in table 1, was obtained from the Universal RESULTS AND DISCUSSIONS
Steels Limited, Lagos, Nigeria. All mechanical tests
(tensile, hardness, impact) were carried out according to From the result, it has been shown that the rolled
the A 296 ASTM requirement. (HTMT) samples possess both the yield strength and the
Corresponding Author: O.E. Olorunniwo, Department of Material Sciences and Engineering,

2
Obafemi Awolowo University, Ile-ife. Osun state, nigeria
484
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J. Appl. Sci. Res., 2(8): 484-485, 2006
`% red. Fracture UTS Yield strength Hardness Impact

Sample % Elongation in area strength N/mm2 N/mm2 N/mm2 HRC (J)
10mm diam as- rolled 1.80 51.41 668.11 688.78 255.10 47.58 48.15
-----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
12mm diam. As –rolled 4.63 56.55 367.36 377.55 239.8 41.4 45.57
----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
16mm diam as-rolled 7.81 61.26 213.64 221.94 147.96 37.45 41.40
--------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
As-cast 0.80 3.60 171.94 - - 55.78 11.25
Table 1: The low alloy steel specimens used have the following Also, the as rolled (HTMT) samples are much more
composition in weight percent as below.
ductile than the as cast samples for the same reason cited
C 0.368 Sn 0.014
Si 0.226 Al 0.003 above[6]. Conversely, the as-cast samples are harder than
S 0.33 Zn 0.003 the as rolled due to the presence of inclusions, residual
P 0.039 Mo 0.021 internal stress, residual coring and non-uniformity during
Mn 0/688 Cu 0.227
solidification, which are virtually elimination by
Ni 0.177 As 0.014
Cr 0.119 Co 0.013 HTMT[1,8].
V 0.002 Pb 0.001
W 0.003 Fe 98.055 Conclusion: The application of HTMT on low alloy steel
has led to the reduction in hardness while the strength and
60 AS.CAST toughness increase considerably, compared to the as-cast
92.22% samples. Hence, for applications that require adequate
50 98.87% Deformation me c h a n i c a l p r o p er ties, high temp er atur e
Brinell hardness valu es
97.99% Deformation
Deformation themomechanically treated low alloy steel should be
40 employed
30
REFERENCES
20
1. Adeyeye Oluseyi, 1996. Influence of thermo
10 mechanical working on the strengthening of
Aluminum alloys, Unpublished B.Sc. Thesis,
0 Metallurgical and Material Engineering department,
1 2 3 4
Federal University of Technology Akure, Nigeria,
Fig. 1: Average hardness values. 1998
60 2. Benjamin, W.N., B.D. Alan, and A.W. Richard,
98.87% 99.22% 1989. Modern manufacturing process Engineering
50 McGrawHill, New York, pp: .32-33, 61-62 , 77-114.
Deformation Deformation
Im pact values (joules)
97.99%
Deformation 3. Bolton, 1988. Production Technology-Processes,
40
Materials and planning Heinemann London pp:
30 174-185.
4. Dieter, G.E. 1988 Mechanical metallurgy McGraw
20 Hill, London, pp: 309-312.
AS.CAST 5. Degarmo, E.P., J.T. Black and A.K. Ronald, 1993.
10 Materials and processes in manufacturing, 7th Edn.
Macmillan, London, pp: 222-223.
0
1 2 3 4 6. Higgins, R.A., 1993. Engineering Metallurgy part 1:
Applied Physical Metallurgy’ 6th Ed. 124: 219-233,
Fig. 2: Impact values
285-330.
Ultimate Tensile Strength while the as-cast samples do 7. Llewellyn, D.T., 1992. Steels: metallurgy and
application’ 1st Edn., Butterworth Heinemann,
not. Reasons that could be adduced to these are that,
during the HTMT, the as-cast sample has its defective oxford, pp: 64-77.
structure homogenized, blowholes and gas pores welded 8. Rajan, T.V, C.P. Sharma and A. Sharma, 1988. Heat
shut and atomic segregation reduced and internal stresses treatment-principle and techniques, McGraw Hill,
relieved[3]. These, coupled with hot plastic deformation India, pp: 175-181.
as well as the presence of alloying elements (carbide 9. Novikov, L., 1978. Theory of Heat treatment of
formers such as nickel, titanium, etc), inhibiting metals,’ 1st Edn. Moscow, pp: 105-106, 418-425.
dislocation movement, to effect strengthening with 10. Honeycombe, RWK, 1981. Microstructure and
respect to Ultimate Tensile Strength (UTS) and yield properties’ 1st Ed., Edward Arnold, London, pp:
stress[2,9]. 167-185.
485
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High Performance Copper-Precipitation-Hardened Steel

Semyon Vaynman, Morris E. Fine
Department of Materials Science and Engineering and Infrastructure Technology Institute
Northwestern University
Evanston, IL 60208
Riad I. Asfahani
U.S. Steel Research and Technology Center
4000 Tech Center Drive
Monroeville, PA 15146
David M. Bormet
U.S. Steel Plate Products
Gary Works
One North Broadway
Gary, IN 46402
Christopher Hahin
Illinois Department of Transportation
Bureau of Materials and Physical Research
126 E. Ash Street
Springfield, IL 62704
Introduction Experiments
This paper presents data for a high performance hot-rolled The cast steel slab, 178-mm (7-inch-) thick, received from
and air-cooled low-carbon, copper-precipitation-hardened steel OSM was cut in two and hot-rolled into plates of 25.4-mm (1
developed at Northwestern University (NUCu steel). The inch) and 19.1 mm (0.75-inch) thickness. The cast slabs were
approach taken for developing a tough, strong, improved reheated to 1066o C (1950o F) and then rolled. The first pass for
1-4
weldability and weatherability steel was to derive additional the 25.4-mm-(1-inch-) thick plate was done after the slab was
strength by copper precipitation hardening which occurs during cooled down to 973o C (1783o F). The finishing hot-rolling
air cooling. Further increase in strength is achieved by aging temperature for this plate was 937o C (1719o F). The second slab
after air cooling or normalizing. Nickel is present to prevent hot- was first rolled down to 96.3 mm (3.79-inches) and then it was
shortness during hot rolling but also gives solid solution reheated to 1277o C(2300o F). Before rolling was continued the
strengthening. Niobium was added to reduce grain size. The slab was cooled to 1039o C (1902o F) and then rolled down to
steel has very low carbon equivalent weldability index. 19.1 mm (0.75 inches). The finishing rolling temperature for this
The initial development was done with laboratory heats of plate was 937o C (1719o F), the same as for the 25.4-mm- (1-inch)
steel that were produced at Inland Steel Company and US Steel thick plate. The plates were air cooled after hot rolling. Portions
Research and Technology Center. Two commercial 80,000-kg of the plates were cut for specimen preparation. Some of these
heats were produced at Oregon Steel Mills (OSM) to investigate were austenitized at 900o C(1650o F) and air-cooled or quenched.
the steel production under industrial conditions and for bridge The time at temperature for austenitizing and/or aging was 40
repair. These heats were cast into slabs by a bottom pour minutes per inch thickness.
1-4
process. Results of the previous work were published earlier . Round tensile specimens with a gauge section of 50.8 mm
Recently a slab previously cast at OSM was hot-rolled at (2 inches) (ASTM E8 Standard) and Charpy specimens (ASTM
U.S.Steel Gary Works. The production and properties of plates E23 Standard) were machined in longitudinal direction from the
made from this slab are presented and discussed in this paper. quarter thickness of the plates and tested. For each plate multiple
specimens were tested with very little variation observed. A
metallographic study was also made.
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Results and Discussion absorbed impact energy at -40°C (-40°F). Microstructural

examination did not find any Widmanstatten ferrite present in
Chemical Composition. Chemical composition of the steel the steel.
heat is shown in the Table 1. Aging of as-rolled 19.1-mm- (0.75-inch)-thick plate
Mechanical Properties. Results of the mechanical testing increased the strength of the steel by about 35-45 MPa (5-7 Ksi)
are summarized in the Tables 2-5. Tables 2 and 3 demonstrate with only a very slight reduction in the Charpy absorbed impact
the effects of different treatments on mechanical and fracture energy. Normalizing reduced the strength, but significantly
properties respectively of the 19.1-mm- (0.75-inch)-thick plate. increased the Charpy absorbed impact energy. Aging of the
As-rolled the yield stress is 503 MPa (73 Ksi) and 567 MPa (82 normalized steel significantly increased the strength with some
Ksi) ultimate tensile strength. The elongation exceeds 30%. The reduction of the Charpy absorbed impact energy. Quenching and
Charpy absorbed impact energy is remarkably high down to then aging of the steel had a significant effect on the properties.
–40°C (-40°F), the lowest temperature used. Previously we The yield strength increased dramatically when the steel was
-4
found2 that the Charpy absorbed impact energy is reduced quenched from 900°C (1650°F) and then aged at 524°C (975°F)
significantly if the rolling temperature exceeded 1150°C but the Charpy impact energy was reduced to 64 J (47 ft-lb) at
(2100°F). This was attributed to the formation of Widmanstatten -40°C (-40°F), still a high value for a structural steel at this low
ferrite at high temperatures. Despite the fact that the second temperature. Increasing the aging temperature reduced the yield
reheat temperature for the slab used to roll this plate was strength to about 650 Mpa (95 Ksi) but increased the Charpy
1277o C(2300o F) cooling the slab down to 1039o C (1902o F) impact energy.
before continuing the rolling gave 161J (118 ft-lb) Charpy
Table 1. Composition of the steel (wt.%)
C Mn P S Si Cu Cr Mo Nb Al Ca
0.06 0.78 0.006 0.005 0.38 1.37 0.06 0.03 0.038 0.029 0.0037
Table 2. Mechanical properties of 19.1 mm (0.75 inch)-thick plate
Yield Strength* Tensile Strength Elongation (%) Reduction in

Plate Condition MPa (Ksi) (Ksi) Area (%)
As-Rolled and air cooled 503 (73) 567 (82) 32.2 68.7
As-Rolled & Aged 524o C (975o F) 539 (78) 610 (89) 33.0 64.6
Normalized 900o C (1650o F) 461 (67) 546 (79) 36.2 63.1
Normalized & Aged 524o C (975o F) 557(81) 638 (93) 35.2 66.5
RhQ& Aged 524o C (975o F) 712 (103) 780 (113) 26.3 62.5
RhQ& Aged 552o C (1025o F) 658 (96) 733 (107) 29.8 65.2
RhQ& Aged 579o C (1075o F) 642(93) 716 (104) 29.5 68.0
* 0.2% offset.
Table 3. Charpy absorbed impact energy of 19.1-mm (0.75-inch)-thick plate
Charpy - V- Notch Impact

Plate Condition Energy, J (ft –lbs) at temperatures:
-40°C (-40°F) -23°C (-10°F) -12°C (+10°F) 0°C ( +32°F)

As-Rolled and air cooled 161 (118) 192 (141) 202 (148) 206 (151)
As-Rolled & Aged 524o C (975o F) 149 (109) 164 (120) 173 (127) 179 (131)
Normalized 900o C (1650o F) 233 (171) 242 (177) 255 (187) 257 (188)
Normalized & Aged 524o C (975o F) 126 (92) 153 (112) 165 (121) 176 (129)
RhQ& T 524o C (975o F) 64 (47) 89 (65) 115 (84) 132 (97)
RhQ& T 552o C (1025o F) 124 (91) 143 (105) 152 (111) 169 (124)
RhQ& T 579o C (1075o F) 168 (123) 175 (128) 183 (134) 214 (157)
Results for the 25.4-mm (1-inch)-thick plate, Tables 4 is slightly lower. Since copper precipitation is the main
and 5, are similar to those for the 19.1-mm- (0.75-inch)-thick strengthening mechanism, slower cooling in a thicker plate leads
plate. As expected, the strength of 25.4-mm (1-inch)-thick plate to larger copper precipitates.
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The microstructures are very similar in both steel plates and as-rolled steel, the grains in quenched and aged steel are
are functions of heat-treatment. The microstructures of the 25.4- significantly smaller, on the order of a few microns. Reduction
mm (1-inch)-thick plate are shown in Figure 1. The steel has an in grain size contributes to the strength of the steel in addition to
equaxed ferritic microstructure. In as-rolled, as-rolled and aged, strengthening from copper precipitate aging. Copper precipitates
normalized, and normalized and aged conditions pearlite regions could not be observed in optical microscope, they are
are observed. They form bands parallel to the surface of the approximately 3 nm in diameter as determined in the three
plates. Pearlite is not present in the quenched and aged steel. dimensional atom probe5 .
While the average grain size is approximately 12-15µm in the
Table 4. Mechanical properties of 25.4-mm (1-inch)-thick plate
Yield Strength* Tensile Strength Elongation (%) Reduction in

Plate Condition MPa (Ksi) (Ksi) Area (%)
As-Rolled and air cooled 465 (68) 547 (80) 32 70
As-Rolled & Aged 524o C (975o F) 625 (91) 665 (97) 26 61
Normalized 900o C (1650o F) 466 (68) 542 (79) 36 72
Normalized & Aged 524o C (975o F) 559 (81) 636 (92) 31 72
RhQ& T 524o C (975o F) 678 (99) 756 (110) 29 68
RhQ& T 552o C (1025o F) 661(96) 737 (107) 28 67
RhQ& T 579o C (1075o F) 615 (89) 682 (99) 29 73
* 0.2% offset.
Table 5. Charpy absorbed impact energy of 25.4-mm (1-inch)-thick plate
Charpy - V- Notch Impact

Plate Condition Energy, J (ft –lb) at temperatures:
-40°C (-40°F) -23°C (-10°F) -12°C (+10°F) 0°C ( +32°F)

As-Rolled and air cooled 161 (118) 187 (137) 221 (162) 228 (167)
As-Rolled & Aged 524o C (975o F) 64 (47) 117 (86) 132 (97) 150 (110)
Normalized 900o C (1650o F) 205 (150) 266 (195) 258 (189) 270 (198)
Normalized & Aged 524o C (975o F) 137 (100) 164 (120) 173 (127) 195 (143)
RhQ& T 524o C (975o F) 96 (70) 124 (91) 167 (122) 202 (148)
RhQ& T 552o C (1025o F) 98 (72) 106 (78) 160 (117) 173 (127)
RhQ& T 579o C (1075o F) 195 (143) 238 (174) 235 (172) 238 (174)
Welding. Due to the very low carbon level and the absence KJ/inch). In fracture tests; at -30°C(-22°F) the average Charpy
of chromium and molybdenum NUCu steel has a very low absorbed impact energy was 124 J (91 ft-lb). The requirement by
carbon equivalent welding criterion. The steel was designed to American Welding Society Standard is 34 J (25 ft-lb) at this
be welded without pre-heat or post-heat. Previously welding was temperature.
evaluated without pre-heat or post-heat by a submerged arc Corrosion Performance. Copper imparts weathering
(SAW) process and also by a manual process in a construction resistance in inland and marine environments and the high
shop environment (Trinity Bridge and Arlington Construction copper content in NUCu steel is effective in substantially
Companies). Matching consumables were used. No brittle heat- reducing the weight loss in accelerated weathering tests.
affected zone was formed. These results were confirmed in a In SAE J2334 standard accelerated tests performed at
welding laboratory at Northwestern University using very high- Bethlehem Steel Corporation by Townsend7 , the weight loss of
2-4
energy input . NUCu steel was compared to that for A36 steel and other
Duplicate G-BOP tests conducted earlier at the U.S. Steel weathering steels. Townsend’s results are summarized in Figure
Research and Technology Center using a heat input of 1.4 2. The thickness loss of A36 steel was133% greater than that of
KJ/mm (53 KJ/inch) and low hydrogen AWS E7018 and E9018 NUCu steel. The thickness losses of A588 weathering steels and
electrodes without pre-heat or post-heat did not show weld metal HPS70W A709 steel were 69% larger than that of NUCu steel.
cracks in the welds or base plates. Using existing data bases corrosion indexes have been
Stupp Bridge Company, Bowling Green, Kentucky, recently established and the index for NUCu steel is far lower than that
performed a Procedure Qualification (PQR) SAW Test without for any other structural steel6,7,8 .
pre-heat and post-heat using Lincoln LA85 electrodes and At the present time NUCu steel together with a number of
Mil800-HPNi flux. The heat input was 2.36 KJ/mm (60 plain carbon and weathering steels are being exposed at different
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As-Rolled As-Rolled & Aged 524o C (975o F)
Normalized 900o C (1650o F) Normalized & Aged 524o C (975o F)
RhQ & T 524o C (975o F) RhQ & T 552o C (1025o F)
RhQ & T 579o C (1075o F)

Figure 1. Microstructure of 25.4 mm- (1-inch-) thick plate
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corrosion sites around the USA to establish the long time

weathering resistance but not enough time has elapsed to reach 4
Rusted Scratch, mm
any firm conclusions7 . A36
3
Width of the
The same steel grades were coated with epoxy -based A709 HPS70
Carboguard 890 paint from Carboline Company, scratched and A588
2
then tested in a salt-fog chamber (ASTM B-117 Standard, 49.97 NUCu
g/liter salt solution). The extent of corrosion was measured after 1

exposure at 35o C for 3 weeks. Results of the tests are shown in
the Figure 3. The widths of the corroded regions adjacent to the 0
scratches are compared to the weight loss reported by Townsend 0 200 400 600
in Fig. 4. Again NUCu steel showed the best corrosion
Thickness Loss, microns
resistance; the corroded surfaces at the scratches of A36, A588
and HPS 70W A709 steels were 93%, 52% and 54%
Figure 4. Comparison of the width of the rusted region on the
respectively wider than that of NUCu steel.
salt sprayed scratched painted steel panels with the thickness
loss of the bare steel panels in SAE J2334 tests.
600
500 Summary
Corrosion Loss, microns
400
Copper precipitation strengthening is an alternate route to
300
quench and tempering or thermomechanical processing to a high
200 performance low-carbon 70-grade structural steel. Cast slabs of
100 a NUCu steel 200 mm thick were hot-rolled to 25 and 19 mm
thickness and air-cooled. Tensile and Charpy impact tests were
0
done on samples as cooled, aged, normalized, and normalized
A36 A588B HPS 70W NUCu
and aged. With the 25.4-mm- (1-inch-) thick plate aging after air
Figure 2. Results of the accelerated corrosion test (automotive cooling from hot rolling or normalizing was required to reach
SAE J2334 Standard) performed at Bethlehem Steel Company7 the desired yield strength level. Particularly noteworthy are the
very high Charpy impact energies at cryogenic temperatures.
The 19-mm- (0.75-inch-) thick plate successfully passed a PQR
welding test without pre-heat or post-heat and with matched
welding rods. Corrosion tests on bare and painted panels are
reported. The corrosion for NUCu steel was significantly less
than that for ordinary weathering steels including the high
performance A709W steel.
References
1. M.E. Fine, R. Ramanathan, S. Vaynman, S.P. Bhat,

International Symposium on Low Carbon Steels for 90's,
p. 511, ASM International , Cincinnati, OH (1993)
2. S. Vaynman, M.E. Fine, G. Ghosh, S.P. Bhat, Materials for
the New Millennium, Proceedings of the Fourth Materials
Engineering Conference, p. 1551, ASCE, New York, New
York (1996)
3. S. Vaynman, I. Uslander, M.E. Fine, Proceedings of 39th
Figure 3. Painted steel panels after 3 weeks, 35o c exposure in Mechanical Working and Steel Processing Conference, p.
salt-fog chamber (A36; A588; ASTM HPS70W; NUCu (ASTM 1183, ISS, Indianapolis, Indiana (1997)
A710 Grade B) steels) 4. S. Vaynman, M.E. Fine, International Symposium on Steel
for Fabricated Structures, p. 59, ASM International ,
Cincinnati, OH (1999)
Acknowledgments 5. M. Gagliano, D. Isheim, unpublished research
6. S. Vaynman, R.S. Guico, M.E. Fine, S.J. Manganello, Metall.
Support of Northwestern University’s Infrastructure Trans., 28A, 1274-1276 (1997)
Technology Institute is appreciated. 7. H. Townsend, retired from Bethlehem Steel Company,
private communications
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ECNDT 2006 - Fr.1.7.1
Comprehensive Characterization of Ageing

Behaviour in M250 Maraging Steel using
Multi-NDE Techniques
K.V. RAJKUMAR, ANISH KUMAR, T. JAYAKUMAR, S. VAIDYANATHAN,
S. MAHADEVAN, B. SASI, G. AMARENDRA,
Metallurgy and Materials Group,
Indira Gandhi Centre for Atomic Research, Kalpakkam, India,
BALDEV RAJ AND K. K. RAY
Indian Institute of Technology, Kharagpur, India
Abstract: Nondestructive measurements have been carried out in M250 grade

maraging steel specimens subjected to solution annealing at 1093 K for 1 h followed
by ageing at 755 K for various durations in the range of 0.25 to 100 h. Different NDE
techniques such as ultrasonic velocity, magnetic barkhausen emission (MBE), positron
annihilation spectroscopy (PAS), eddy current and X-ray diffraction (XRD) have been
employed for comprehensive characterization of microstructural features evolved
consequent to aging treatment.
1.0 Introduction
M250 grade maraging steel, by virtue of its excellent mechanical properties i.e. ultra-high
yield strength combined with good fracture toughness [1], is the preferred structural material
for critical applications in advanced technologies. In addition to the above mentioned
properties, its high strength to weight ratio, good weldability and easy machinability in the
solution annealed condition and dimensional stability during aging make this material as an
ideal choice for critical rocket motor casing applications in aerospace industries. The ageing
behaviour of the maraging steels has been extensively studied [2-12]. The strength in aged
condition is derived from the fine and coherent intermetallic precipitates, whereas low carbon
martensitic structure provides the high fracture toughness. Over-aging results in coarsening of
the intermetallic precipitates in addition to the reversion of martensite to austenite. These two
processes that occur due to overaging affects both tensile and fracture properties of these
steels. Hence, characterization of microstructure plays an important role in qualification of
fabricated components for service. Particularly, non destructive evaluation (NDE) techniques
are most sought as they provide fast and reliable means of characterizing microstructures of
actual components.
Various NDE techniques such as ultrasonic, magnetic Barkhausen emission (MBE),
positron annihilation spectroscopy, X-ray diffraction and eddy current testing have shown
good promise in characterizing the microstructure in various alloy systems. Though
considerable work has been done on other alloy systems, so far no systematic study has been
carried out for characterization of aging behaviour in maraging steels, which leads to
complex microstructure consequent to aging. In view of this, in the present study, an attempt
has been made to unfold the effects of various microstructural features of maraging steel that
evolve during aging treatment, on different NDE parameters and in-turn to develop
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nondestructive methodology for comprehensive assessment of ageing behavior of M250

grade maraging steel.
2.0 Experimental
The chemical composition (wt %) of the maraging (M250) steel used in this study is as
follows: 17.89 Ni, 8.16 Co, 4.88 Mo, 0.43 Ti, 0.05 Mn, 0.05 Cr, 0.05 Si, 0.05 Cu, 0.096 Al,
0.003 C, Bal. Fe. A plate of maraging steel (M250) was solution annealed at 1093 K for 1 h
followed by air cooling. The specimens of approximate dimensions 30x25x7 mm extracted
from the solution annealed plates, were encapsulated in quartz tubes under vacuum and aged
at 755 K for different durations of 0.25, 1, 3, 10, 30, 40, 70 and 100 h followed by water
quenching. The same sets of specimens were used for all the NDE studies using multiple
techniques. The Vicker’s hardness measurements were carried out on the specimens at 10 kg
load. The average value of five hardness measurements has been reported for each specimen.
The maximum scatter in the hardness measurements was found to be less than ± 5 VHN.
For ultrasonic measurements, surface grinding of the heat treated specimens was
carried out to obtain a constant thickness of 7 mm and plane parallelism to an accuracy of
better than ± 2 μm. Ultrasonic velocity was measured at room temperature using 15 MHz
longitudinal wave and 5 MHz shear wave transducers. A 100 MHz broad band pulser-
receiver (M/s. Accutron, USA) and 500 MHz digitizing oscilloscope (M/s. Lecroy, USA)
were used for carrying out the ultrasonic measurements. Cross correlation technique has been
used for precise velocity measurements [13]. For the velocity measurements, the ultrasonic
signals were digitized at 500 MHz and the gated backwall echoes from the oscilloscope were
transferred to a personal computer with the help of GPIB interface and specific software
developed in LabVIEW. The accuracy in time of flight measurements was better than 1 ns
and the maximum scatter in the ultrasonic velocity was found to be less than ± 2.5 m/s.
Magnetic Barkhausen emission measurements were performed using encircling pick
up coil (5000 turns) and magnetizing the sample at a frequency of 66 mHz. A U-shaped
electromagnet assembly was used to magnetize the maraging steel specimen
(30mmx25mmx7mm) fixed between two conical pole pieces of an electromagnet. The
maximum field was set to 1500 Oes for complete magnetic saturation of the specimen. This
corresponds to a magnetization field strength (H) of 80 0000 A m-1. The MBE signal was
amplified using a low noise preamplifier and a post amplifier (80 dB). The detailed
experimental setup for MBE measurements has been reported elsewhere [14].
XRD measurements were carried out using MAC Science MXP18 X-ray
diffractometer with Cr Kα radiation and the samples were analyzed in the complete angular
range of 60-130°. The volume percent of austenite formed by reversion of martensite during
ageing, was determined by direct comparison of the integrated intensities of the (111) and
(200) planes of the γ phase with the intensities of the (110) and (200) planes of α phase.
Positron Doppler broadening measurements were carried out using a high purity
germanium detector having an energy resolution of 1.4 keV at annihilation gamma ray energy
of 511 keV. A defect sensitive line shape S-parameter viz. the ratio of central peak counts to
total counts around 511 keV γ-ray is deduced from these measurements. The S-parameter
signifies the positron annihilation events with low momentum electrons of the medium.
Various defects such as vacancies, vacancy clusters, dislocations and precipitate–matrix
interfaces act as trapping sites for positrons, leading to an increase in the S-parameter value
[15].
The eddy current (EC) testing was carried out using MIZ-20A ZETEC system with
optimized testing parameters such as frequency (10 kHz) and phase (5°). Specially designed
probe consisting of transmit-receive (T/R) coil was used, which was relatively insensitive to
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permeability variations. The EC response is measured in terms of signal amplitude i.e.

magnitude of real and imaginary components.
3.0 Results and Discussion
Figure 1 shows the variations in hardness, ultrasonic longitudinal wave velocity and positron
annihilation parameter (S parameter) with aging duration. The variation in the ultrasonic
velocity with aging time exhibits similar trends as that of the hardness. The velocity initially
increases with aging time, peaked at intermediate ageing duration followed by continuous
decrease at longer durations of ageing. In contrast, the S parameter decreased drastically from
the solution annealed conditioned up to 1 h of aging and then increases with further aging.
Figure 2 show the variations in hardness, MBE rms voltage, volume % of austenite
and EC amplitude value with aging duration. The variation in the EC amplitude with aging
time exhibits similar trends as that of the volume of austenite determined from XRD. They
were initially constant and increased drastically at longer aging time. In contrast, the MBE
rms value remained constant initially and drastically dropped at longer aging durations.
Hardness 650 0.552

5700 Ultrasonic Long. Vel.
S Parameter
Ultrasonic Long. Velocity, m/s
600
S-Parametre, arb units

5650
Hardness, VHN
550
0.544
5600 500
450
5550
400
0.536
5500 350
0.1 1 10 100
Aging Time,h
Fig. 1. Variation in hardness, ultrasonic wave velocity and
Positron Annihilation (S Parameter) with aging at 755 K.
The initial increase in the hardness up to 3 h is attributed to the precipitation of Ni3Ti

intermetallic precipitates from the martensite matrix. The detailed transmission electron
microscopy (TEM) results substantiating this have been reported elsewhere [16]. The
continuous increase in the hardness at intermediate durations (10-40 h) is attributed to
additional precipitation of fine Fe2Mo precipitates from the solid solution. The decrease in the
hardness upon ageing for longer durations is attributed to the formation of soft reverted
austenite phase. The variation in ultrasonic velocity with aging exhibited similar behaviour
as that of hardness. The initial increase in the ultrasonic velocity is attributed to the
precipitation of mainly Ni3Ti intermetallic phase, which increases the hardness up to 616
VHN. The subsequent steep rise in velocity reaching a maximum is attributed to the
precipitation of Fe2Mo along with Ni3Ti. The variation in ultrasonic longitudinal wave
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velocity and hardness with ageing time could reveal various stages of precipitation and
reversion of austenite; however the initiation of the reversion of austenite at 30 h of ageing
could not be identified by ultrasonic velocity measurements. Though TEM studies revealed
the initiation of reversion of austenite occurring below 30 h itself [16], decrease in hardness
and ultrasonic longitudinal wave velocity is observed only after 40 h of ageing. This is
attributed to the fact that the precipitation of Fe2Mo, which tends to increase the hardness and
velocities, continues to take place in parallel with the austenite reversion. Hence, decrease in
the hardness and ultrasonic longitudinal wave velocity due to formation of austenite can be
felt only when this decrease is more than the increase in these parameters due to continued
Fe2Mo precipitation. Drastic drop in velocity at longer aging duration is attributed to the
formation of reverted austenite. Austenite has been reported to be a soft phase having lowest
modulus among all the phases present in ferritic steels [17].
Unlike hardness and ultrasonic velocity, S parameter drastically decreases upon
ageing up to 1 h duration and increases continuously beyond this up to 100 h of ageing
(Figure 1). The initial decrease in S parameter up to 1 h of ageing is attributed to annihilation
of defects and reduction in defect density associated with precipitation. The main defects
observed in these steels are vacancies and dislocations. Reduction in the defect density with
aging occurs especially during the initial aging time, when defect density is the highest.
Hence, the decrease in the S-parameter in the initial regime (up to 1h) of aging is attributed to
two simultaneous mechanism i.e. the reduction in defect density due to martensitic recovery
and predominantly the precipitation of intermetallics preferentially on defects, which results
in decrease in trapping sites. On the other hand, coarsening of precipitates acts as trapping
sites due to the strain field associated with them, leading to the increase in the S parameter.
Since the two processes affect the S parameter in opposite ways, net effect is manifested as
continuous decrease up to 1 h showing the reduction in defect structure as the dominant
feature beyond this the precipitation is found to be the dominant factor. Though at longer
ageing durations (30-100 h), reversal of austenitic also take place, the S parameter seems to
have subtle affect as it results in only structural change with less effect on defect
concentration. The continuous increase in S parameter up to 100 h is the result of continuous
precipitation of intermetallics, which acts as trapping sites for positrons.
Figure 2 shows the variation in EC amplitude with aging time for M250 maraging
steel. EC amplitude remained almost constant up to 10 h of aging. Aging for 30 h resulted in
drastic increase in EC response compared to 10 h. The EC amplitude continued to increase
with further aging for longer durations reaching a value of 2.0 V at 100 h. Because of the
specially designed probe, the effect of permeability is nullified and the change in EC
response can be explained in terms of change in conductivity only. Though the EC amplitude
remained constant with aging time up to 10 h, the hardness increases continuously in this
regime due to precipitation of intermetallics. From this it can be inferred that the change in
resistivity is negligible with precipitation of Ni3Ti initially and Fe2Mo at later stage. Upon
ageing for 30 h, the EC amplitude increased drastically due to the presence of austenite in the
microstructure. From the TEM investigations [16], it was also evident that austenite is
observed earliest in the specimen aged for 30 h. Habiby et al. [18] have also reported similar
observations in similar steel upon ageing. Even a very low volume fraction of austenite (less
than 1% in specimen aged for 30 h) could be easily revealed because of the substantial
difference in the resistivity values for martensite and austenite. The resistivity values for pure
iron and stainless steel differ widely i.e. 2463x10-7 ohm-m and 7.496x10-7 ohm-m
respectively. The eddy current parameter could be correlated with the amount of reverted
austenite and hence has potential for in-situ detection and assessment for austenitic reversal
on actual components.
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650 Hardness
Vol% austenite from XRD 30
EC Amplitude
600 MBE RMS Voltage
2 2
Vol.% of austenite from XRD

Hardness, VHN
550 20
MBE,RMS Volatge
EC Amplitude, Volts
500
10
450
400
0
350 0 0
0.1 1 10 100
Aging time, h
Fig. 2. Variation in hardness, magnetic barkhausen emission RMS,

Eddy current RMS value and Volume % of austenite
determined by XRD with aging at 755 K.
Figure 2 also shows the variation in MBE peak height and volume % of reverted
austenite (measured by XRD) with ageing duration for the isothermally aged specimens at
753 K. The MBE peak height remains almost constant up to 10 h of aging. Beyond this,
substantial drop in MBE rms voltage was observed on aging up to 100 h.
MBE rms voltage remains almost constant up to 10 h regime showing that the
increase in MBE rms voltage due to dislocation annihilation is compensated by decrease in
MBE rms due to precipitation of intermetallic phases. Hence, a net manifestation of constant
voltage is obtained. Beyond 10 h of ageing, the substantial decrease in MBE rms is attributed
to the formation of reverted austenite due to dissolution of Ni rich precipitates. An interesting
observation is that the onset of austenitic reversion is picked up sensitively by MBE whereas
it requires appreciable amount to be detected by XRD (~2% at 40 h). Otherwise early
detection of this austenite reversion requires support of TEM. The increase in austenite from
30 h to 100 h is evident from XRD. From Fig. 2, it is also evident that upon 40 h, 70 h and
100 h of ageing, the volume of austenite increases continuously as 2, 6 and 30 %
respectively. The substantial decrease in MBE with reversal of austenite is attributed to the
fact that the paramagnetic austenite impedes domain wall movement in addition to reducing
the total domains taking part in magnetization. This clearly indicates that the MBE technique
is very sensitive to characterize the initiation of austenitic reversion.
Ultrasonic velocity showed good promise in characterizing the intermetallic
precipitation process and was able to pick up the austenite information only when high
amount of austenite is precipitated. Its drawback is with respect to obtaining any information
about the defect structure and early detection of initiation of austenite reversion. Hence, this
technique is found to be very sensitive to monitor the intermetallic precipitation behaviour.
Positron annihilation studies were found to be very sensitive to defect structure and
precipitation to some extent. The austenite reversion has almost no effect on positron
annihilation parameter. Hence this technique can be used for high sensitive characterization
of defects such as vacancies or dislocations. Magnetic Barkhausen emission study showed
good promise in identifying the non-magnetic austenite phase compared to intermetallic
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precipitation and defect structure. Hence, MBE technique can be used selectively for very
sensitive determination of early initiation of reversion of austenitic phase. Eddy current
technique is also found to have good promise in early detection of initiation and
characterization of the austenitic reversion ahead of ultrasonic and almost on par with MBE.
As this technique is more amenable to shop floor, it can be used for determination of volume
% of austenite in actual components with ease. XRD technique was found to be good in
characterizing austenite but was unable to determine the austenitic initiation early due to low
sensitiveness of the technique for austenite volume fraction (less than 2 %). Hence XRD
technique can not be used for recognition of austenite initiation and moreover its portability
to shop floor and to component site is difficult. However, XRD technique can be used as a
benchmark for establishing correlations for quantitative estimation of volume fraction of
reverted austenite using MBE and ECT techniques.
4.0 Conclusion
Various NDE techniques have been used in the present study for comprehensive
characterization of microstructural features generated by ageing the solution annealed M250
maraging steel at 755 K for different durations in range of 0.25-100 h. Each technique
provided complimentary information with regard to complex microstructural features that
evolve during the aging treatment of maraging steel. Ultrasonic velocity was found to be
more sensitive to the precipitation of intermetallics, whereas magnetic Barkhausen emission
could clearly identify the onset of austenitic reversion. Positron annihilation spectroscopy
could clearly identify the reduction in defect structure during initial aging periods, in addition
to the characterization of continued precipitation of intermetallics at longer aging periods.
XRD studies were used for quantitative determination of amount of reverted austenite. Eddy
current parameters could be correlated with the amount of reverted austenite and has potential
for in-situ assessment for austenitic reversion on actual components. The present study has
clearly brought out the complementary nature of various NDE techniques for comprehensive
characterization of ageing behaviour in maraging steels
ACKNOWLEDGEMENTS
We are thankful to Dr. S. L Mannan, Former Director, Metallurgy and Materials Group and
Mr. P. Kalyanasundaram, Associate Director, Inspection and Technology Group, Indira
Gandhi Centre for Atomic Research (IGCAR), Kalpakkam for their cooperation and support.
We are also thankful to Dr. B.P.C. Rao and Dr. C. Babu Rao of IGCAR, Kalpakkam for
useful discussions. We are also thankful to Dr. R. Rajaraman and Mrs. Padma Gopalan of
IGCAR, Kalpakkam for their support in carrying out positron annihilation studies.
5.0 References
1) G.P. Miller and W.I.Mitchell, J. Iron Steel Inst., 203, (1965) 899.
2) D.T. Peters and C.R. Cupp, Trans. Met. Soc. AIME, 236, (1966) 1420.
3) V.K. Vasudevan, S.J. Kim And C.M. Wayman, 1990, Metall. Trans. A 21, 2655.
4) W. Sha, A. Cerezo and G.D.W. Smith, Metall. Trans. A 24 (1993) 1221.
5) S. Floreen, R.F. Decker, in: R.F. Decker (Ed.), Source Book on Maraging Steels, ASM,
Metals Park, OH, 1979, pp. 20–32.
6) R.F. Decker, S. Floreen, IN: R.K. Wilson (Ed.), Maraging Steels: Recent Developments
and Applications, TMS-AIME, Warrendale, PA, (1988) pp. 1–38.
7) U.K. Viswanathan, G.K. Dey and M.K. Asundi, Metall. Trans. A 21 (1990) 2429.
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12) Z. Guo, W. Sha and D. Vaumousse, Acta Mater. 51 (2003) 101.
13) Anish Kumar, T. Jayakumar, Baldev Raj and K. K. Ray, Mat. Sci. & Engg. A, 360
(2003) 58.
14) V. Moorthy, S. Vaidyanathan, T. Jayakumar and Baldev Raj, Mater. Sci. Tech. 13 (7)
(1997) 614.
15) B. Somieski, R. Krause-Rehberg, H. Salz and Meyendorf, Journal DE Physique III, 5 ,
Janvier (1995).
16) K.V. Rajkumar, Anish Kumar, T. Jayakumar, Baldev Raj and K. K. Ray, “Characterization
of Aging Behaviour in M250 Grade Maraging Steel using Ultrasonic Measurements”,
Metall.& Mater.Trans A, Communicated (2006)
17) H.M.Ledbetter and M.W. Austin, Materials Science and Engineering, 72 (1985) 65.
18) F.Habiby,T.N Siddique, S.H.Khan, A Ul Haq and A.Q.Khan, NDT&E International
25, No.3, (1992) 145.
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Effect of Aging on Microstructure and Mechanical Property

of 1900 MPa Grade Maraging Stainless Steel
Yiyin SH/I,VI, Zhi.yonp YAN@), ~ianxiongLIANG'), Lun Lv)and Ke YANG1)q
Kai L111'~*~,
3.1 Institute of Metal Eewarch, .Chinme Academy d Sciences, S h c n p g 110016, China
2) Graduate %ml or Chinwe A t d e m y d Sciencw, B~ijing100039,China
3) Gmerab Resewrh Institnke h r Iron m d Steel, Beijing ID0081, China
Sp~cialStcd Croup Co,, Ashun lI3001, Chinh
41 Technical C ~ r r t ~D~ngbci
r,
[h.lanuaeript r m i d March 2, 20176, i n revised form Ortoher 16,
The 1S%Ni alfoy st& provide high strength and toughness, while agehardenable or PH stainfess s t e i s also
have good corrosion resisance. This paper f o c u on ~ an investigation o f the heat treatment, mechanical
propeeis and microstructural development of a new mayaging stainless; s t e l , It is reported that the heat
treatment process should consist of solution treatment and cryogenic cooling to attain a fufly rnartensitic
structure, f o l l d by aghg a t 813 K. This heat treatment resulted in an ultimate tensile strength of owr
1900 MPa cornbind with good impact toughnes. Transmission electron microscopy is used t o show that.
for the peak-aged condition (813 K/4 h), nano-sized precipitates, e.g. Ni3Mo and/or R-phase, and a high
density of dislocations wete uniformly dispersed in the lath martensite matrix. The calculatd yiclrl strength,
bawd an a revixd Orowan mechanism, is in good agreement with the test data. The steel studied has an
ultimate tensile stwngth aver 1900 MPa, mcellent fracture toughness, and good mistance against over-aging
and relatively good cario5ion resishnct as well.
WORDS: Maraging stainless steals; Precipitati~n;High strength s t e l a ; Aging kmtment
the optimal adng t r ~ ~ t m e n t .PTe d a1.M dcwl-

o p d a new type of high stmgth maraging steel
Precipitation hardrning (PHI maraqing stainless by modification of the alloy campcwition, hut the
stwl is a spmial dam of ultrahigh atrrngth and steel r c q u i r d CT at 200 K in o d c r t o obtain a
gmd tmaghnms r n a r t ~ n s i tstccl, ~ which is also stain- frlLly martensite matrix hared on dilatomttry ms~rlL5.
less, i.r, co~ttdnsm o w tl~rtn11% [all in wt pct) Viswmathan e l al.lal] studied the rnmhaniml prop-
~ r [ ' - ~ lA. p p m t l y , time, stwls are suitable f i r r n w y erties, microstructure and precipitate typcs obtain4
r n a i a ~and p c t m h m n i c a l applications, particnlnrly in C350 maraging steel duriq aging and mraging.
where ch8orirEm are present. In general, PH stain- After aging at 783 K fm 3 h, t.he yield strcngth (a,)
less steel is solution treated at whole mstenitic r e xnb ultimatc tmsila stmgth. In,) mhi& t h ~ i r r n m -
@on for r proper time to homogar~i7~: chemical cam- imurn r;alue of 2195 5 d 2227 MPa, mpectiv~l)r,but
position, and then qucnchml t o r r w m t a n p r a t u w to the impact encrgy (12 .I) and elongation (5.3%) wcm
ol>t;ljn a whole rnartc~~sitic microstructure '-4. S o m e quite low. I t is often difficult t o o p t i r n i 7 ~the heat
times, subzero temperature treatment, i . ~ cryogwiic . twatmcnt paramPtmb, espwidly those for aging, so
treatment (CT),is a1.w applird after solution t r ~ a b as to ensure the highest stre~igthw l ~ i l emaintaining
men1 (ST)b e c a u ~d : the 9tlh~erornartmsitic finish- relatidy good duct iliby.
ing hmperatuw ( ~ f ~ ' r ] [ ~ - ' l .Finally, PR steel is & at Up t a now, several PH stainbss steels are mmmer-
673-873 Ti fnr suitable time t o hrnl fins prptlipitates, cially available, inc[uding UKS SI77130,LPJS S155WO
rcuch as Nig31~,Fr2Mcl, and R ph~se,in a martcn- and X N S 545500. The age t~ardeningof thew allays i s
site matrix, which cnabh PH stmf to reach its high- the: result, of alloyin# witti one or more of the! dements
est strength level and dm k e q good tolqhn%dln Is]- Cu, Ti, Ma, Nb and A]. Generally speaking, the max-
Obviously, besidcs the important m l a of ST,&& imum tensile strength d~ve10pe.din any d f h m dloys
nf aging t r m t m ~ n t[AT]dm pla.m a very irnprtant is on the nrdar of lGDO m a . Hmevcr, mcept for t h e
role an the m i ~ r o s t . r u ~ tand new wire alloy, Bidine IRKSI,reported by Nilsson
u l ~machxnical p r n p ~ r t i r ~ ,
which have bml i n m t i g a d by many reewclms. So et ~ d . 1 ~ultrahigh
~1 strength maraging stainlee4 sml
fa, diffewnt conciusion,ns have heen drawn for diflcrent has not yet b e n reported.
maraging steels, and mur-h mfarch has also brrn d ~ - hn thc prmcnt study, the Qarmtwistics d x new
voted t o deternuning t h seructurm,
~ precipitate t y p ~ type o f ultrahigh strength maraging stainlm &el are
a d rnechanicd propmties of BII s m l s or marag- examined. The composition of this s t ~ Ewas hasod
i n g sttxls [IG-'!, such as the 18Ni ma rag in^ stwls on p m i p i t a t i o n s of Mo phases in an F e C r - C e N i
and UITS315500 maragingst;tinless steel;1'*L8.L9.24~251. marmsitr matrix. As a new typc d steel, the m-
Hsiacs rt id,['"discussd the aging reactions in UNS dmmding of the miwtmctlmral feature¶ t h a t en-
517400 BH sldnlesrr s t e l at F2U-753 K for t.irnes aurc thc mmllcnt combinations of pprp~rtiesfor this
ranging froin 0.5 to R 11. T h ~ yanaiped the pre- steel are nut p t d ~ ~ Therefore,
r . the purpme of the
cipitate types m d confirmed that 775 3 f~lr1 h wafi p r m n t work W;L~ tT) wtimize the .aging pwmetprs
of Lhe stml, miifinn the p r w . i p i t a t ~&Tcc,t and under-
rmf,,Ph.D-, l o whom carnfiporrdmreshor~lrlhe Rddmsd, stand the nature of the dislocation-precipita~inter-
Fh-tail: kyangP%mr.Ar,ch. action at rliffcrcnt stages of tile aging process. I t is
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belicwd that the infnrmatim drwlnpd in this pa- prment t.t%s, whir,^ pm?.poncdthc p~r.ipitatjon r e
per will b wry m~~ningflrla d useful Em the further action; and due to thc addition or Mo, b c x a u ~MO
dewioprnmt of a co~n~n~lrciaIl
y uwf~ilmat~rial. mntaining precipitatm am IikeTy tta farm al higlicr
t.mperatum and Iongm q i n g limes thm Ti con-
taining or Cu i,rt.r.ipitatn~[".L".191. A,, thc allstmite
da~t.ingtpmperdure, 835 X, and Af, the auetenik?
The experimental &el waq pw@ by wc- finishing tmpcraturr, 1123 K,are dm d ~ s i g m t din
uum inrluctian meltin# and vacuum arc remelting Fig. 1 biiwd on deviations f m linearity in khc heating
[VIM/VAR), and the rrr~minalc h m i c d mrnpn~ir~ion t:onrp. T h ~ s c % i c d l1,hc y ~ t m t d stwl shr~uldbc W ~ U -
rangc is as follows I%): C [0.01-4.fl3), Cr (15.0-16.5), tion treated at a rrlativ~lplow w~npcratilrethat is
Si (6.&7.5), Slo (6.6-7.51, Co (9.5-ll.@, S (<O.Ol), abme Af, in order to avoitl the rapid grmtth of p,rdn
P (<0.01), O [<O.Nl2), I4 [SD.OM),Fe @a].). A 50 kg sixa that will rwtllt in the deceme in both s t r m e h and
ingot was forgedl rolled bb~twwna stclrting tmnpcrii- tonghnmsk41.H o w m r , the ST tcmpwaturc, 1323 K,
turn o€1425 K and n finishing wmpcrature of 1123 K, was det.~rmindrrcmrding to rr ~ p t ~ m H.11dy i c d ST
and the rmulting 20 mm rods wcw air cfir~!cd. Sam- prior a i ~ s t ~ i i i tgca i n [PAG]siw and mechanical
p!m nf the mrl WTY? dutioil treated at 1323 K Em.1 h, pmpcrg of tesccd alloy, which was discused in a sw
and rapid!y air coded to rrmm tmperarure. T h q ;irate paper. The main eonclraion drawn is that PAG
w r e t h ~ ncryogmimlly treatmi at 2211 0 for 8 h to s i 7 ~ a, f t ~ r57' for 1 h at 1323 K or l o w r t ~ m p e r a t u t ~ s
attain a Fully mwknaitic; matrix. Finall>*,t.hc ssm- RW almmt the s m o , w d i i n g in minor jnfl~aencpon
plcs ~ m taged l at 713, 763, $13 a ~ l d873 K for a% long mwhanicJ property, Rut high ST tempmnt.llre is fa-
as 20 h to mdym the qq+l~arrleni~lg c~lrve. Then, vurahlc to diasolvc alloying chmmts, e.g. Cr and h h ,
Vichs h~lrdn~ s wrc carricrl out in all condi-
twts i n lliE matrix and benrficial to harnn@nou~ldistribu-
t-ions. Staidarc1 tcnsih tests (samp!c dimctcr 5 mm) tion af yr~cipitatesi n m the matrix in the foilawing
were cxrriwl a ~on t a tlG-;EDDIlA >ITS rnwliine at Q i s aging p~acms. )ME, the M f i n s i t . ~ starting t~rnpcr-
placement rate of 0.2 mJenin. Impact toughness was a t - u r ~clhtaincd
, from the cooling c u m , was 353 K.
t m t d r~singstmdardGharpy U notch spcrjm~nson a TEie martenbitre transformation m-as incornplelt~aAm
REP 450 impact test, niashine. TI), spwi111rn3wrr! amling to room Wmp~xatnrr-,~n,in,-if, thc martmensite
mted for each mndiLion anrl the data were a ~ ~ r a g w i . finishing fxmperatnnre, of the steel -4 shown to he
All tmts wcrc conducted at i m m txmperatur~. bdour room ternpel-atrlrrt. According tn t h I;M,-Mf] ~
DiIatomctric t i was pcrfomd otl. a i.cl.rnpPlt.atrlmof other similar high alloy ~ t w l ~ ; ~the ~~'],
Fomzlrter-F diJatamed~rfrom Fuji Industry, lnc. For
Ms to ttmperat.ore rangc is about 140 150K. Con-
this tcsling, s p ~ l m m scut, from tlw cqopnirrally
wqumt.ly it W M predict4 ?hat thc ,WE of the! t s t d
treated mrls wrc n ~ w h i n dto 3 rnm diameter by
alhy shntlld ho appnximately 213 #, and -as also
10 mtn long cylindrical mds wit11 a 2 mm r l i a m a r
dftermined by X3r;n.Dphase analysis and TEM mmi-
and 2 rnm d e p hole in crnc side. During tire t ~ t ,
nation of specimen CT, a4 will be disctlsserl latter.
R wcurlrn of IU-' Pa w ~ maintain49 l o yrot.ect the
sprimens Frnrn oxidation, and the length, time and
t c m p a t u r e were fiimulL~ncouslyrcsor(l~1. 3.2 3 f d i ~ i ~ Pproperty
J
For t.rmmission ~lcctronrr~icrmctyq,t-hin foils Figrm 2 shows the prccipitaiim hIvdming clirvcs
Wprr made from aged material, 0.3 ntm thick discs, of t h t~ ~ t steel d a@ a t 713, 763, 815 arrd 87.7 K,
wcre mwhairidly p6Iish~dto 0.05 rnm thickn~ss wsp~tively.OiVi0~4y,abt testid aginpimpwaturcs,
and t h n twin-jct c!lec?.rn-polished a t 44 V i n a 92:R t h bardn~ss
~ incr~merate wag quitr high mithin &Ire
[vol. p d ) ethmnl: pcrchloric acid ~ 1 1 1 t i oat n 243 5. 'beginning 30 rnin of aging. Ewn aged at 713 K for
'She solution rrcatd qxcirnms uere spmidly twatml 30 nlin, the hxrdnms d s p w i r r ~ ~rn~ ~ w h 425 r d Hhr.
where lheY wr.r ion mil[Pd in order to keep the K+ Frorn thrn on, the inmasc In h;udnss was r~'lati.vdg
taincd nusknire. All t h thin ~ bils sarnpl~swew ex- slow at 1nw a g i n ~t.~~ruperaturw, . md 763 K,
i . ~713
amin~din a JEM 2011)transmission elclctron m i c m as long as 211 1). l5%ilr?t ~ w d n mwaq i n ~ ~ ~ k sharply scd
s c o p ~(Tl3hi) at mlarating wltag~nf 2.00kV. Frrcc- and c.f~nt,inuoiisly w h ~ naged at 813 K, mc1 wachrd its
tographic examinxt~onof the iinpact-trrtml samples p ~ a kY ~ I U C , i.e. 540 HV, after aged for 4 h, a t 1 then
wm rrwdrlctrd in a J3J3-58[XILY scanning cIcct,ron mi- dccr~amdsIi~htlywith Increaqing aging time, corre
crawopo (SEM) b mduata the failure mode. X-ray s~iflndingto a relatively good ivsistarrce agd1~4t OW-
diffraction (XR.D) andysis was pwfnrmd in s ~ l m t ~ d aging. For o v w - ~ mrondifioa, l r.c. R73 K, tlw hacd-
pond ition$. ncss increaqd quickly a t i.hc beginning, But began
ta drop a f m aging for mow thrm1 11. Thr cflrcts
3. Results of t11e various heat. treatments, wgecidly t h aging ~
trentrnpnts, on a, by, dongation (d), d u c t i ~ n in
3,J Plme t~msfoma2ion
area id), and irnj~acttoughnrs arc!ah- in TdJe J
P11asetrmdtrmatinn tempwiltures during lthc rn- and Fig.3. 'LbhcST m d CT samples m e quite low
Circ h ~ a tI r m t m ~ r ~pmcws
t nvre estimat~d using
in gtr~ilgth.nnd high in toughness. Drlrinig the w-
dilatometry. Figr~wI sttows t h rlilaton~~try
~ cirrvc
ing trmtmeot, t h my ~ and q, nf t . h ~steel incwwd
with thc various ttmsformation tempmiturn irldt-
mntineacrs1.y with increkqing the aging tmpcratrue
catt.6. During hratjng, the Lwrw a n bc c o n $ i d ~ r ~ rod
w d rparhrd their maui~mmvalacs on l*ng at 813 K.
be n ~ m l ylinear rlp to 839 K. The point at wfiieh thc
Above XI3 K, the strength droppd signiticantly, i.e.
CURT deviatd Dom Iin~arityiq identifier1 as t.11~ pw-
ovrl--&ng; arid thc unpact toz~ghnesq;slmmascd con-
cipiLtirw starihg brnpcratzire, P,.I I ~ m e r P , , was
much 11ighcr than that report4 in lit,~ratnm[7,19], tin~iorrq[y. Eqwially, tS and cl~~ncr~asPcI slightly on
aging at 873 Tr' cotrtpad with that nf at 613 K.
~ q i b l yrlnc to tile 1 1 s of
~ a faqter heating race in the
Menu
Fig.8 Mw.t d aging temperature (for 4 h) on mmachmkd p r o p h i e s d the expwirnentd stel: {a) ulkimate
Itcnqik strength, nh; D,2% p m l yield strength, my and impact toughas, [b] reduction in area, d~ and
dmg~kion,d
Pipl.4 TEM i m p xnd mult~ of the mic+ast+u&un?a & z a p d ST and CT specicimms: (a) bright field
[BF)irnry;~of thc strriet~mafter S T and oa6ling to room t m p ~ a t m with , arrows i n d i t i n g wtaincd.
austenite films, and markmite laths with a high dwsity d <lislmtioia, [h) mrrqondinp, SAD pattern
from the 101 117 and [fl01]C?zone m,[c} BF i m ; with ~ cmmsponding SAD pattern from r h il~ll]e m n e
=is, showing a fi~llymartensitie r n i m t r u d t u r ~a f k r CT,[d) XRD pattmn of s w i m e n s
Menu
Table 1 Ifeth~uicalpropartie at ltstrvl atwl iu different h~rcttrmtm~ntconditions

Conditions ub/MPa rrY/MPa 6/% dl% lmpacttot~gh:ha~/J
s.l.l> 1095 :I); 20.0 73.8 2;n
CT*) 1297 773 18.5 654,R 234
AT=)at
713 K 1675 1426 19.5 57.8 1 fl0
763 K 1790 9 600 17-F~ 57.0 71
813 K 1940 1774 16,3 56,3 50
873 K 3645 3 220 19,O 5g.5 47
Nates: 11 S7-%1111tion twatmmt at 1323 K for I h+air cnaling; 2) C'l'
ST+cryopnical!y trestmmt st 2tIt1 K for R h; 3) AT-SrJ'+CT+nging tmtmmt
f t r 4 l a aL rligcrcnt Lrmprrrtlrrm
3.3 M i m t n ~ c r ~ l r c ~aturatrrlmrten~it~ir: n~atrix,rn mentioned by , v t l ~ e ~

rwarcl~~rd"-"~. The formation of such clustm was
Tlie p r d o r n i n a ~ ~phwct irr the ST spm:im~nuraq
r , In x s i s t d hy pipe difi~sinnt'timugh h e
t l ~ o u ~ hto
lath r n a r t ~ n a i tw~ i l h a high dlrloca~iondcn6ir.y. In ,;_, lnr.rr;wmr .I:rlnnnC:n.rr :- +C,n enl,rF trnq+nA
D'CllL 411C p l l l l l r l j J l C 1 1 t I 1 , U l ~ C W C U 'LUDLULQI.IVJI U l U W U U

lath martensite rnkmtruct,r~re,a4 shim in Fig.4[~].
under this rnechanjsrn~~~~~~]. the 813 K peak-aged
XIEiD a~~dp*;rti
in Fig-4[d)a1w proved t h w TEM re spwci~ncns,homogcnmus, fine precipitatm, primarily
s111ts<
containine manensite laths, RTFE fonnd, as shown
Figure 5 shorn TEM imag~sof t h e~x p ~ r i m m - in Vig.5tl.r). T11c size rlisfribution d prmipitatm i s
td g k w l altw agjrrg at Y ~ ~ O I tprnperatures
I R for 4 h. sho~'11 in Fic.B{c] and thc me,m prccipitat~loi7e mm-
When a g d at 763 K far 4 h, it is significmt. that w a w r r d WRS a1101118-in nm*awuming a spl~r~isal par-
m a r M by t.hc n m w u jn Fig.S[a), clrrly n smdl r.01- r.icle morphnlogy. Thc awragp inwr-partide spacing
ume fraction of plate-slrapfl p w c i p i t a l ~m e fc11111d war;lcm than 25 nm. A t the Piigh~slaging tempera-
in a sira~1~ l a t h d m a r t m x i t e , but Lhis had a l r ~ d y
rr- t u r ~nf 873 K , n slightly i n m ~ ~ wvrnl l i i m ~fr,act,irm of
soltecl in thr: sharp inmease i t i hmclnes and gtwngth lha precipitate, f u n l r r r ~o:rra~ningor t h prwipitatcs
~
compared w i t h that of S T or CT conditions as slloivn and even rn~rgingwith thrir nrigl~hom(Mack arrtnvs)
in TaI~lp1 and Fig.3. Similarly. TVF can p r ~ d i c tt11m H~PTCRWII and dcmonsit~~nled irr Fig.S(d); rnorcarrer,
x b r aging at. 713 K for 4 h, t.hc F+R"i-Mo atnm or nlthwgii austrnitc was noi foiind in TEM image, a
nthcr type 01 clnstcm nia~slbe formed in the super- fraction or s~istcnitc xras rletcrmincd by XRll
Menu
Fig.6 SEM Frmture m f i m af impact toughrrm speimenr: dhr CT and AT at 813 K: [a]CT,(b) AT at 813 K
substructure] harbming, respectively. Tbc sum of

[ ~ ~ + u ~ , - t - t i~s ~
equal
- t rto
~~the] d u e OF ay in the
3.4 Fkactography CT condition, it. 773 MPa, which neglects tbcir in-
Figure 6 wbows Erclcture surfam of the impact t& ter& on strength. In our prcviou~study, the influ-
specinlens &r CT anrl AT at 815 K for 4 h. It is of ST on prior austeniM grain [PAG) size and
evid~ntthat aher CT,thn kacture siarface consisted mechanical property hxs been it~vcstigated,%.c. P A 6
mainly of fine dilnplm as shown in Fig,6(a), which ex- siz~,and nr obey the Hall-Petch h
hibited m entirely transgram tar r u p t ~ mode
~ ~ c known addition, it was found that pr~cipitationhardening
as microvoid c o a l c s m c ~ .Also, there wee some: large plays the most. impcsrtmt role in strengthming of this
dimplm in sOmp regions, in agnxnlent with the high steel. As a mult., several i n ~ e s t i ~ ; r t o r s [ "haw?
~~~~~~]
fracture taughas~saftfir this treatment. However, the proposed that stmgthening can bc amounted for by
rupture mad^ of the specimen hcga.n to change from an Orowan tncchxni~rn1~~*"-~~{ S.e. Eq.(2],
ductile to a I~rittleappvzuanw when a g d at 813 K.
It cwr bc wen tirat ffnilur~had ocrtirrcd wia a m i x ~ d
mode of ductile and clcawgelikc Iracture, shown
in Fig.G(b).
whew u, i.4 the total yidd strength, ut~thc matrix
4. Discussion yield strength, T the line tension, b thc Bur ers r w -
tor, and b the interparticle spacing Det~rt[~~~uztiIimd
Aa a PH maraging stainlrss stccl, mow than the cxpre~lsionput hrth by Ansell and ~ ~ ~ n e l l to ~~*."~!
Bl%Cr waq added in ardm towsure its goad mmsion argue that a ~igflific~fktcontribution b t h strength
~
mistmce. Also, a quantity of Xi nra5u m l to halance corncs from the hidl shew strength of' the precipi-
Cr and obtain a wholly martensite matrix m r d i n g tates. H m w r , it seems that if t h matrix
~ strength
to thc Schafllefs diaRram123].However, Mf temper- was tdwn into acwunt, a yield s t r ~ n g t hconsiderably
t K, and the s t e l
ature of tt~stedstml is a b u ~ ~213 higher than the o b w d me, which would have hen
has to be cryoppidly treated t o obtain a maitensite predicted. Thc following is xn attempt tu predict thc
structure b~Tow@ng. Espceially, Co was < a d r l ~in I strengthening mehanism. The uy of the 18Ni[250)
ordm tn ml~micethr hd formability of the steel and steel predicted by 3 modified m o d ~ lof the Orowan
l o w the solubility of Mo in the martensite matrix, rplationghip, i.e. F4.[3), was in g o d agreement with
so that there would be more M o taking part in the a#- the experimental d u e of 1640 ~ ~ a l The ~ ~ 1d t. h e
ing react-ion to stmgthm tlre steel. This inberution peak-aged ($13 K, 4 h) and over-aged (873 K, 4 h)
was called the synergistic effect of Co and h ~ [ ~ * ~ 7
conditions were cstirnatd in the prewnt study, us-
~ ~ 1 .
Fufihwrnolc, prwipitaka wntaining Mo iwe likely to ing the mean particle sizes and interparticle spacings,
form at higher ternpcratum and longer sging t i m e which were remlily measurable. The s p h w i d p m i p
than Ithose containing Ti w C U [ ~ ~ ' which
~ ~ ' ~W.W
~ , &O itates in the pcak-aged and arm-aged conditions were
p r d by the optirnum aging pararnetws, i.e. 813 K approximately 10 nm and 30 nrn in diameter Id), r e
for 4 h. Theti, preripitah msrltaining Ma, e.g. FezMo spectivcly. Taking the vnlumc fraction of precipitates,
and F e 7 M ~arc, likcIy to form in thc dlql2'34, and j,a?5% fnr the pak-aged c~ndition,Rf~~] and 7.5% for
R phase i s drw,the msible pmipitaw based on other the wer-BglLd condition, interparticle ~pacings,A, of
rarar&ersf resultlP"2~1h9 ~ 1 1 .But the SAD patr 16.7 nm and 58.3 nm were obtaind by using the a-
kern corresponding to p d - a & TEM image WBS not pression ~ ' ~ ~ = [ ) . 8 2 6 /Then
~ [ ~uy
~ *was ~ ~estimakdl
].
enough, which was not illustrntcd in the p r m n t by the following equation:
paper, So the exact precipitnatct y p nwd
~ tc, LM! con-
firmed in hture study.
For PI1 s m l , the stren thening mechanism c a n
be assumed ai Eq2(I)*.m73fl, where 0,. as,on, o,,
and udqc are the uy contribution from the match, where G is the stlcar modul~~s d the matrix, 4
d i d ml~it.ionstrcngthcni~~g, grain boundary h a d - is related t
a the Poisson's ratio of the matrix by
ening, prrrcipitatimr hardening and [dislocation m d $=I1 + 1/(1 - v)]/2, v is the Pi~.c:on'sratio of
Menu
t11~ ~mttiY,taken as 0.3["1~~1: the o t h ~ rtcmis, haw zhc dongatinn m d rduction d area w ~ r e16% and
the same ~ne~lning~ as a b m . Thing G=71 GPa, ,56?4% mpect-ively*and the Charpy U notch toughl~cr~s
k 0 . 2 4 9 nm1291,and fl0=T7S MPa, tllc calculatrd fly of was a w r 50 J. This mmbination of prnpM8icrr~ x c m l s
1G0 and 1260 ?dPx here ~btaincdfor the p d - q e d the highwt Iewla prcvio~~sly r~portedfor a ~naraging
and m-agerl conditi~ns,in g m d agrmmwt nit11r he staipjl1lPSs stwl.
ex?xperirnen~ddata. (2) Aftaimaging at 873 K for 4 11, the prccipitnt,k%
Tn w m m q , the whde strengthening pmrm nf in the cxpctimmltal s t m l rrhnw a high volume Frmim
the prsent stect can b~ c o n s i d ~ r dto b~ as follows. and critical sizr, and a.~~rliform dispersion.
(1) After CT, the st-1 matrix consisted of martrnrtite (3) After the snlntian treatment, relain~dallsten-
with R high dpngity of di~locations,which myurerl the itc filnis r~nminedalong the rr~artcnsitclath bound-
basic hall strength of tllp steel. Ttw incwrnei~tof aries in the matrix I.11~stwl duc tcr t h r~d ~ i v d low
y
~ rmditiorr was dale to fhp dirni-
s t r ~ n g l hr m r t h ST :14r tmperaiure. Thp ~ c t a i n a11stmib
~~i ws taran$
nation of r e h i n d austmrite. (2) Then, in thp initial formed to m r m s i l c by a crppnic trcatmmt at
&'I~PS of aging, the sf.rmgt.hmingwm attriht.ab\c t r ~ 200 K that wxs b l o w the ,'idr ternpcraturc and an-
t.hr-~tres ;srr~ddfor disiocrcations b crlt fhrnugh the tributfcl to the stwl atmilling high stm~gth.
mhm~tt:elertaents c1ust~rsand/or the prwipilates.
lI.rawcvm, thr strcngtli did ml reach its peak value
at t 1 1 i stage,
~ bccau~,even thalgh t h e e r l u ~ l ~ rand
rt~ Arknowf~dprnentrr
pmipitatrs were rff~ctiwfor pinning thp dislocations, This wurk was p ~ l fitrppmd
y by khc h d of Na-
t-llcir wlnrnc f r m i o n was too anal1 and t h i r i n t ~ r - tional Hjg11-Tda De\~Bapm~nt Projmt or China ["8&3"
pasticle spacing wm hug^$^^. (3)11s thc prt!r:ipitatw Pr%~rsm,Yo. ?UR?AASOfrIO5]1. Aslrl thc author, K.Liri,
c m ~ s e nw ~ d thpir wlumr fraction inrrcasm, ~ h stress
c dm, expr- t Dr. Wi1li;am lN;lrkr!
~ e c k n m r l c d ~ a ntr,
n m f d for dislocations to cut thmugh them incmaqd fmm Rp Aarocn for mpnding the paper and t o &. Yi
We fmzn hharatory of Mat~riaisScic~~cc, b l f t Uaivvrsity
which 1 4 to an incr~ascin 0,. Finally, thc prwipi- of Twhncrlou, €or cnlightraing &wus~ir>ns.
tat* v w tn a eriticd s i ~ d ' ~and ] their r~lurnefrac-
tion alsn reached an optimum d r r c , mrmponding
whirh Id to A c-ritird interparticle spacing arid t l ~ c

djsloc;ltiona werr forcd lo bow wl bfinqrn +,hPm in- [I ] W.J.Chen, Y.Y.itru md S.X.Shen: 3. Mater. Sci,
s t ~ of d t~rtt~ingthrough thmni"]. (4) Aging at higher 'Ikhnol., M W , 20[2], 217.
, example 875 K f i i 4 11, hcsider re
m p e r a t u r ~for 12 1 X.Lir and W.M.Zhou:
r,.D.\I'ang, I..ZH.Jiang. 31.i.n~u,
.F. Afatrr. Sci. Twf!noJ,, 2005, 21(5), 710.
t ~ t l ~ a u ~ t c n i ~ m d ~ ~ e t ~ a n d ~ m [ ~ ' ~~ i ' In ~ Dd b .~ R . ~ ~ M ~ ~ ~ , ~ ,
~ t h m s ~ ~ - ~the
~ lfurther
"l, i i n m c 8 ~in partirl~si7e and onr~ and Engmwrinrf 'I'singh~iaLniwrsity Prm, %-
spacing dm rcmlultrd in t i rlecwaw in s l ~ n @ l iin , ac- jing, 2005.
cordante with thc Omwan ~nechani..m. [4 ] Y.IIe, X.Yang, W.S.Qn, I'.Y,Kolrg and G.Y.Su:
Inkresting h - t t a m of the ttenuile Wts 01the mu- Matep. Sci. T d n d . , 2003, 29, 717-
plm a& at 873 K m e thr d c r r ~ m oin the ratio nf [ j1 Yi HE, IIr TATG, bknva KOKG, Wenqhcng QX and
uy t o rrb and a slightly increase in d ant1 dl as well, Gnoyue SU: Acta MrfaJ!. Sin.. 2002, 30{3), 278. (in
a~ shmn in 'F~blcI and Fig.S(a). AR prgdit:Wd by Cbinrsc)
[ 6 ] Y.HP, K.Ymg, W.Sha and D.J.CIelmd: McesrM.
Sinha et a6.1331,it appeam that kherc is a change in M~ltrr.Tram. A, 2W136, 1.
t tie hilhavim ofthis type of ~ t r ca hl: the yield point l71 H,,, K.l-mg, l Y . S . ~ u , F.Y.KonF: G.Y.~~~:
k c a ~ i wof the pmmce OF R m f t ~ rphm, srlrh as Marfir. LP~L.,2002, Sfl, 763.
auut~lrite. ID other nards, n'hen the strcss excccds
, - 3 ., , . . 3 % . . r I . r
[R ] J-J iycbtpr:nmP. A.SM, IBN, gl+ 816.
or IQhgm aging Irlmeb. 30, it can b e dM11wrl r.t~sstthe - ----

7
[13] G,?V,TuCTncll and RL,Cairns: Tkms. ASM, 1968, 8E,

dchritcittiort indi~mltransformatian of ausltmiltc to
7%.
martmsitc abow the yield p i n t c m ~ l dhc responsible [I41 Y.Kambr, K.Knh7awa m d S.Muaeki: ?Mswtn-
for thit highcr tPnsile slrcngth, which would 1~mdto a N n p n e (J. Iron SIW! Inst. Jpn], 1976, 62, 1229.
lower raiio d a y myr u b . [I51 H . J . h t , k : Aafarrr. Sci. Eng., 1978, 34, 2M.
[IG] Ifr.Sha, A.C~mzosnil G.D.W.Smith: d1I~t.d. B ~ R A .
A, 1993, 24, 1221.
117
M . A l ~ ~ n m l .H.Ayub, I.Na5in1, F.H.Hashmi and
A.Q.Iihan: Maker. Sri. Thnd.,7995, f 1, Y2Rl.
{I] Thc optimum heat t.rentmpnl For mxxirniirn
!IS] K.3 ill=, F.Dmrrix and M.liithmtrand: ~ M a t ~ r9 . ;.
s t ~ m g t h in the new ultrahigh strength rnnragi~ig r n ~ . ,
1998, A2511, 22.
stainlrss steel was rletermira~dto h~ aging for 4 11 [I91 C.N.Hsiao, U.S.L'hinrl snd d.RYmg: Ma&. CI?rm.
at 813 K, following mlutiorl and cryogenir t r ~ a t ~ Ph-p., 2 M 2 , 74, 1.74.
mmts. 1Fritlli this tmatm~nn.,the 6, and b,, of t h [2D] M-Watt~nstrand, J.O.Kilma, K.S#llw, P.Liu and
s t e l remhd 1773. StPn and 1940 MPa, r ~ p r c t i w l p ; ?d,~lndm?on: Acre 5IctaJJ., 2004, 62, 1023.
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318 J . Mvlater, Sci. Techno!., Vo1.23 Nn.3, 2007

1211 U.K.Vimmathan, G.K.Dey an8 M.K.As~\ndi:Metdl. [30]A.S'h~khta,H,I.karofison, M.K.Miller, S.Ib.Rinwr
lhmg. A, 1993, 24, 2429. and E.V.Pcreloma: Metall. ;Water. Ttans. A, 20~14,
[22] P-Lir, A.H.Stigenbmg and J.O.Kilmn: Acta Metafl. 33, 973.
Maker., 1994, 43, 28R1. [31] K.Liu, Y.Y.SLan, X,Y.Yang,J.X.Liang, L.Lu and
[23]Ij.K,MndaL and R.R,aj: Hig& Nitmgen 5-Lr: and K.Yang: J. Mater. S L ~ TecJ~ad,
. 2006, 22(G), 769.
SLainlw SteeLqzNxosa Publishing Horw, NPWDell~i, [321 M.Mart~yama, K . H m , M . S w and M.Kiky&i:
20U4. 1Mat~1.%J. Eng A, 1998, 230, 127.
[24] W.Sha, A.Cmwa and G.D.W.Smith: McMJ. Trans. [33] P.P.Sinha,K.T.T'hzvian,K.Srcekumar,K.V.Nagamjan
A, 1993, 24, 1233. md D.S.Sma: Mater. Sti. M ~ n o l .1998,
, 14, 1.
[251 W.Sha, A.Cerezo and G.D.W.Smith: Met&. Tkans. [MIV,K.Vasud~van,S.J.Kim and C.M.?Vayman: -4fetd-
A, 1993,24, 1241. n a o s . A, 1990, 21, 2655.
[MI H.RH.Baj~isimi: Mater. Sci. Eng. A, 2002, 333, [%I K.Debrt: Trans. 9. AS-If, 1968, 53, 262.
147. [XjG.S.Anw11 mil F.Xr h r l : A d a Metar! a Z!360a R, 612.
[27] J . O , W i l m , A.R.Stigenberg and P.T,iu: MeM. [37] G.S.Ans~ll:A c t a Metall., 1961,9, 518.
134ater. T km- A, 1994, 26, 2225. [ 3 ~ ]Z.Guo and W.Sha: M~tall,Tkans., 20012, 43, 1275.
p3] K.P.aalan, A.Vmugapal R d d y and D.S.Sarma. [39j I3.L.C- mrl A . R ? V i w J. Imn S t d J d . , 1963,
S r . p t a kfetdl., 1999, Sg, 902. 21)8, 600.
1291 E.V.Pmlama, A . S h e k b ~ ~ r , M.K.Miller and 1401 V.F . Z x h y l E.RParLr, D . W m and R.Bnsh: Tkans,
S.P.Ringcr:A e t a M~tdf.,2004, 52, 55R9. ASM, 1%7, 80, 252.
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Effect of Aging Condition of Tensile Properties

of Iron-Nickel-Titanium Maraging Steels*
By Kii SOENO** and Masatoshi TSUCHIYA**
Synopsis ty.9,17)
Resirtivi@ change during isothermal aging and the associated tensile Fe-Ni-Ti ternary maraging steels have not yet
properties have been investigated on Fe-IONi-1.8Ti, Fe-I5Ni-1.8Ti been throughly investigated on the effect of aging
and Fe-20Ni-1.8Ti maraging steels. I n order to investigate the effect of condition on the strain rate sensitivity in ductility.
strain rate on ductility, a crosshead speed was varied from 0.005 to I 0 ~ h present
, paper is concerned with the tensile prop-
mmlmin.
erties and their strain rate sensitivity of the ternary
Embrittlement caused by the decrease in strain rate i s found in'the
maraging steels containing Jine and coherent precipitates, formed i n the
maraging steels.
jrst precipitation process. Brittleness independent of strain rate is also
II. Experimental Procedure
found i n the Fe-IONi-1.8Ti and Fe-I5Ni-1.8Ti maraging steels
Raw materials for alloy preparation were electro-
strengthened.fully by the Jirst process at lower temperatures. Both cases
lytic iron deoxidized by adding 0.1 % A1 in vacuum-
result from the slip character that intense slip bands tend to be formed
melting, electrolytic nickel, electrolytic manganese,
during deforming. Tensile properties which are ductile and insensitive to
and titanium melted in a consumable electrode arc
strain rate are obtained after subjecting to the second process. Aging
structures in which intense slip bands are dzficult to be formed during
furnace. For the elimination of carbon and nitrogen
deforming are concluded to be suitable for the improvement of ductility.
contained in the vaccum-melted iron, the iron cold
rolled to 1 mm in thickness was subjected to annealing
I. Introduction for 24 hr at 650 "C in wet hydrogen, and cooled at
I t has been known that Fe-Ni-Ti ternary marag- pressures around low5torr. The purities of the alloy-
ing steels are possible to be precipitation-hardened. ing elements were more than about 99.9 %.
Fe-ZO%Ni-l.G%Ti and Fe-25%Ni-1.6%Ti steels Ternary maraging steels with the nominal com-
have been developed for practical use. Many inves- positions listed in Table 1 were prepared by arc-melt-
tigations have also been carried out on the precipitates ing in an argon atmosphere, using a nonconsumable
in the ternary maraging stee1s.l) tungsten electrode and water cooled copper crucible.
The ternary maraging steels containing relatively The ingots were turned and remelted triply to achieve
high titanium contents have been considered to be homogeneity. As the weight loss during melting was
less ductile than 18 % Ni type maraging steels con- very little,2J0)the nominal compositions were accepted
taining cobalt, molybdenum and small amounts of for the alloys. All the ingots were homogenized for
titanium. This fact was considered to be attributable 8 hr at 1 050 "C in a vacuum of torr, hot-forged
to the preferential growth of precipitates a t prior and homogenized finally for 1 hr at 1 100 O C in a
austenitic grain boundaries or lath b o ~ n d a r i e s . ~ ~ ~vacuum
) of torr. Plates cold rolled to 1 mm in
Mishima et aL4) reported that the ductilities of Fe- thickness and wires cold drawn to 1.5 mm in diameter
8XNi-Ti ternary maraging steels were closely related were prepared for tensile tests and for resistivity mea-
to precipitated phase: The decrease in ductility was surements, respectively.
much more evident in the precipitation of CsC1-type All the alloys were solution-treated for 1 hr a t 900
NiTi than in that of DO,,-type Ni,Ti. "C, and quenched in water. Prior austenite grain size
Soeno et aL5-s) have reported investigations carried numbers were in the range 6.5 to 7.5. Aging for 300
out on the strain rate sensitivity in ductility by using min and less was performed in a salt bath. I n case
nickel maraging steels containing cobalt, molybdenum of aging more than 300 min, specimens aged for 300
and titanium. Embrittlement caused by decreasing min in the salt bath were quenched in water, washed
strain rate has been observed in the maraging steels and then reaged at the same temperature in a high
containing coherent precipitates which are possible to purity argon atmosphere sealed in a furnace. The
be cut by the movement of dislocations. Ductility in-
sensitive to strain rate is possible to be obtained, when
Table 1. Chemical compositions of Fe-Ni-Ti ternary
the precipitates contained are relatively difficult to be
maraging steels used. (wt%)
cut by the movement of dislocations and intense slip - -- - - - - - -- - -
bands decrease to occur. Stress concentration built Ni Ti Mn A1

up at grain boundaries during the course of plastic
10 1.a 0.1 less than 0 . 1
deformation is possible to be decreased by the refine-
15 1.8 0.1 less than 0.1
ment of austenitic grains. Accordingly, the refine-
20 1.8 0.1 less than 0.1
ment is also needed for the improvement of ductili- -- - - - -- - - - -
-
-- ------ ---- - -- - - - --
a 1982 ISIJ
- - - - - - - - - - - - - - - - - - -
* Originally published in Tetsu-to-Hagant!, 68 (1982), 309, in Japanese. English version received September 3, 1981.
** Hitachi Research Laboratory, Hitachi Ltd., Saiwai-cho, Hitachi 317.
[ 848 ) Research Article

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Transactions ISIJ,Vol. 22, 1982 1849 ]
form of the specimens used for tensile tests is shown in of the precipitation in Fe-Ni-Ti maraging steels simi-
Fig. 1. After aging, the thickness of the specimens lar to those used in the present investigation.10) Ar-
was ground off from 1 to 0.3 mm by using a centerless rows in Fig. 2 express that the resistivity decrease due
grinder. Crosshead speeds used in the present inves- to the second precipitation process becomes evident.
tigation were 0.005 (strain rate, i = 0 . 7 6 ~ sec-l), The precipitate phase in the first process and that in
1.0 ( i k 1 . 5 2 ~ sec-I), I0 mm/min (i= 1.52x lowZ the second process are, for a while, referred to PI-
sec-l). In order to investigate the precipitation be- phase and P,-phase, respectively. From the com-
havior in the alloys, resistivity change with aging time parison between Fig. 2 and Fig. 3, the strain rate
was also measured at liquid nitrogen temperature by sensitivity in total elongation is found to be evident
the four-probe potentiometric technique. in case of being not fully strengthened by the first
precipitation process. Total elongation decreases with
III. Results the progress of the first process, and increases with
the decrease in strength due to the progress of the
I. Fe-IONi-I. 8Ti Maraging Steel
Figure 2 shows resistivity changes, and tensile prop-
erties are given in Figs. 3 and 4. Each point of
tensile strength or total elongation in the figures rep-
resents the average of three to five tensile test results.
A uniform elongation can be measured from a load-
elongation curve with a local elongation. No sys-
tematic influence of strain rate on uniform elongation
was found in the maraging steel investigated by using
the cross head speeds.* Each point of uniform elon-
gation in the figures represents the average of values
measured a t the cross head speeds. When fracture
with local elongation was not observed a t the cross
head speeds used, uniform elongation was not shown.
The existence of two precipitation processes has
already been shown in our resistometric investigation
Aging time(min)
Fig. 3. Tensile properties of the Fe-1ONi-1.8Ti maraging
Thickness: 0.3mm steel aged a t 500 "C (a) and 525 OC (b).
Fig. 1. Tensile test specimen.
I I 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1
500'~- Aging
II
8 -12 -
h
A
.
.-
'--•
2
.-
-14 -
Ln
L1: -16 ' I 1 1 , 1 1 1 1 1 I I

10 Io2 1o3 1o4
Aging time ( min
p,: Specific resistivity after solution-treatment
pt : Specific resistivity after aging
Arrows express that the resistivity decrease due to
the second precipitation process becomes evident.
Fig. 2. Resistivity change at liquid nitrogen temperature Aging time (min )
during isothermal aging of the Fe-1ONi-1.8Ti mar- Fig. 4. Tensile properties of the Fe-1ONi-1.8Ti maraging
aging steel. steel aged at 550 "C (a) and 575 "C (b).
- .-
-. - - - - - -. - - - - - - - - - - - - - - - - - .
. - - - .-- .- - .. .- -
* This fact was also found in the Fe-15Ni-1.8Ti and Fe-20Ni-1.8Ti maraging steels.
Research Article
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( 8 5 0 ) Transactions ISIJ, Vol. 22, 1 9 8 2
second process. For the maraging steel containing less for aging at 550 "C. I n case of aging at 575 "C,
the P,-phase precipitates, the decrease in total elonga- the resistivity curve measured shows that the second
tion is not found even in tensile tests at a cross head process starts after short times of aging. Thus, ductile
speed of 0.005 mm/min. tensile properties are obtainable after short times of
Figure 4(a) shows that the decrease in total elonga- aging at this temperature.
tion with the progress of the first process is evident,
as seen in the specimens aged for times in the range 10 2. Fe-15Ni-I. 8Ti Mayaging Steel
to 100 min. The strain rate sensitivity in total elon- Resistivity curves and tensile properties are shown
gation is also found in the specimens aged for relain Figs. 6, 7 and 8. The existance of two precipita-
tively short times. Uniform elongation increases with tion processes is also seen in the resistivity curve at
aging time in the range of the second process. An 525 "C or less. As seen in Fig. 7, the variation in
increase in total elongation by the progress of the elongation with aging time at 475 or 500 "C is similar
second process can be attributed mainly to the in- to that found in the Fe-1ONi-1.8Ti maraging steel
crease in uniform elongation. This fact is also seen
in Fig. 3. When an aging temperature is raised to I I ' ' " " " I ' " " " ' I " I
575 "C, total elongation becomes insensitive to strain
rate after relatively short times of aging (see Fig.
4(b)).
Figure 5 shows the relation between tensile strength
and resistivity decrease, constructed by comparing
Figs. 3 and 4 with Fig. 2. Aging up to the time when
the resistivity decrease measured during aging a t 500
"C, or 550 "C reaches -8 to -9 pQ-cm is regarded
as the first process, as seen in Fig. 2. Figure 5 shows
that tensile strength a t a given resistivity decrease in
the range of the first process is evidently less for aging
at 550 "C than for aging at 500 or 525 "C. I t is con-
sidered that the P,-phase precipitates are mixed during
the course of the first process at 550 "C and result in
the decrease in strengthening. The decrease in total
elongation with the progress of the first process is also
1 0 500"~-~gikg
I " "
Aging time (min)

Fig. 7. Tensile properties of the Fe-l5Ni-1.8Ti maraging
steel aged at 475 OC (a) and 500 OC (b).
Fig. 5. Tensile strength us. resistivity decrease of the Fe- -0- 1.0 mmlmin
10Ni-1.8Ti maraging steel.
10
II I I , , , , , , I I I I 1 1 1 1 1 1
to lo2 lo3 1 o4 I I
01' ' ' """I
Aging time (rnin) 10 1 02 1 o3
Fig. 6. Resistivity change at liquid nitrogen temperature Aging time (min )
during isothermal aging of the Fe-15Ni-1.8Ti mar- Fig. 8. Tensile properties of the Fe-15Ni-1.8Ti maraging
aging steel. steel aged at 525 OC (a) and 550 "C (b).
Research Article
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Transactions ISIJ, Vol. 22, 1982 [851)
aged at 500 or 525 "C; total elongation is sensitive to

strain rate at an early stage of the first precipitation
process and decreases rapidly with the increase in
aging time. When a n aging time is lengthened in
the second process, total elongation increases with the
decrease in strength and becomes insensitive to strain
rate.
I n case of aging a t 525 "C, the strain rate sensitivity
in total elongation is found in the specimens aged for I I
times in the range of the first process (see Figs. 6 and -8 L1
10 1 02 1 o3 lo4
8(a)). I t is also noted that total elongation decreases Aging time ( min
less rapidly with aging time in the first process. The Fig. 9. Resistivity change at liquid nitrogea temperature
P,-phase precipitates are considered to be mixed dur- during isothermal aging of the Fe-2ONi-1.8Ti mar-
ing the course of the first process. Tensile properties aging steel.
of the specimens aged at 550 "C are ductile and in-
sensitive to strain rate, as seen in Fig. 8(b). The
resistivity curve measured during aging at 550 "C does
not show the existance of the first process.
3. Fe-2ONi-1.8Ti Maraging Steel

Resistivity curves and tensile properties are shown
in Figs. 9, 10 and 11. Soenolo) has shown that the
resistivity of this maraging steel increases during the
very early stage of precipitation and then decreases.
Because of this initial process, resistivities after short
period of aging at 450 or 475 "C are larger than those
immediately after the solution-treatment (Fig. 9). I t
can be also seen in Fig. 9 that two processes appear
in the resistivity curves measured during isothermal
agings at 450 and 475 "C. As the initial process as-
sociated with the increase in resistivity ceases after
very short period of agings at both temperatures,
aging process till the beginning of the latter resistivity
Aging time ( m i n )
decrease is referred to the first process for convenience.
As seen in Fig. 10, the strain rate sensitivity in total Fig. 10. Tensile properties of the Fe-20Ni-1.8Ti maraging
steel aged at 450 O C (a) and 475 OC (b).
elongation is found in the specimens aged for times in
the range of the first process. Specimens aged a t 500
"C for relatively short times show also the strain rate
sensitivity (Fig. 11(a)), although the first process is
not clearly shown in the resistivity curve at this tem-
perature (Fig. 9). Tensile properties which are duc-
- 47
[ -0- 0.005 m m l rnin 1
tile and insensitive to strain rate are obtained, when
the P,-phase precipitates are increased by lengthening
aging time or by raising aging temperature. The
fact that the rapid decrease in total elongation with
the progress of the first process is not found in the
maraging steel will be discussed in the following chap-
ter.
I V . Discussion
Extensive investigationsl1) carried out on the de-
formation of precipitates and on slip line observation
in deformed alloys have shown that dislocations are
possible to pass through small coherent precipitates
and intense slip bands tend to be produced in alloys
Aging time ( min
containing coherent precipitates. I t has also been
known that cross-slipping is relatively difficult to oc- Fig. 11. Tensile properties of the Fe-20Ni-1.8Ti maraging
cur in maraging steels containing coherent precipi- steel aged at 500 "C (a) and 525 OC (b).
tates.12-16)
I t is natural to conclude that the PI-phase is co- duced across grains during deforming the maraging
herent with the matrix. Therefore, it is considered steels containing the PI-phase precipitates. Intense
that intense and straight slip bands tend to be pro- stress concentration may be produced in regions where
Research Article
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[ 852 ] Transactions ISIJ, Vol. 22, 1982
intense and straight slip bands are blocked by grain where, otr, etr: true stress and true strain, respec-
boundaries or intersected by other intense slip bands. tively
Steps produced at the surfaces of a tensile test speci- K : constant.
men by intense slip bands may also provide the sources We can obtain n=c, at the beginning of necking.
for intense stress concentration. The increase in n is attributed to the fact that disloca-
The strain rate sensitivity found in the ductilities tions moving through the matrix leave many loops
of the maraging steels containing PI-phase precipi- around the DO2,-type Ni3Ti precipitates, and, in
tates can be interpreted in terms of the hydrogen em- addition, the operation of a large number of slip sys-
brittlement usually observed in steel^.^-^) The de- tems leads to many dislocation intersections. I t is
crease in ductility with the decrease in strain rate reasonable to consider that the DO2,-type Ni3Ti pre-
results from the diffusion of hydrogen, contained and/ cipitates are difficult to be cut by the movement of
or absorbed at the steps from the atmosphere, to the dislocations.
regions with intense stress concentrations. For the
Fe-1 ONi-1.8Ti and Fe-15Ni-1.8Ti maraging steels, V . Summary
the brittleness independent of strain rate is also ob- (1) The existence of two precipitation processes
served after full strengthening by the first process. is seen in the curves of resistivity decreases measured
The brittleness seems to be attributed mainly to the during isothermal agings of the Fe-1ONi-1.8Ti and
very intense and straight slip bands blocked strongly Fe-15Ni-1.8Ti maraging steels. The resistivity of the
by obstacles. We regard the grain boundary as a Fe-2ONi-1.8Ti maraging steel initially increases and
main obstacle, as the ductilities of maraging steels then decreases with aging time. Two precipitation
containing nickel, cobalt, molybdenum and titanium processes also appear during the course of resistivity
have been known to be considerably increased by the decrease. The upper temperature limit of the first
refinement of g r a i n ~ . ~ J Under
~) such circumstances, process for resistivity decrease lowers with the increase
the stress concentration exceeding the theoretical in nickel content.
strength of the solid may form a crack within the grain ( 2 ) The embrittlement caused by decreasing strain
containing the blocked slip band, in the grain bound- rate, i.e., the hydrogen embrittlement is found in the
ary, or in the adjoining grain.ls) When an aging maraging steels aged for times in the range of the first
temperature is raised to 550 "C for the Fe-1ONi-1.8Ti process. The brittleness independent of strain rate is
maraging steel, or to 525 "C for the Fe-15Ni-1.8Ti also found in the Fe-1ONi-1.8Ti and Fe-15Ni-1.8Ti
one, the P,-phase precipitates partially formed during maraging steels strengthened fully by the first process
the first process lead to lowering the level of the very at lower temperatures. Both cases result from the
strong blocking of slip bands, and crack formation in distribution of slip bands, or slip character that in-
regions with stress concentrations is enhanced after tense slip bands tend to be formed during deforming.
diffusing of hydrogen. I t is considered that the precipitates formed in the
The decrease in ductility with the progress of the first process are coherent with the matrix and are
first process is less in the Fe-20Ni-1.8Ti maraging possible to be cut by the movement of dislocations.
steel. Brittleness independent of strain rate is not (3) During the second process, the DO2,-type
found even in the first process a t 450 "C. As de- Ni3Ti precipitates are formed with the decrease in the
scribed for the Fe-1ONi-1.8Ti and Fe-15Ni-1.8Ti precipitates formed in the first process. As the DOz4-
maraging steels, slip bands become less intense when type Ni3Ti precipitates are difficult to be cut by the
the partial formation of the P,-phase takes place dur- movement of dislocations, the formation of intense
ing the first process. I t may be expected that the slip bands decreases. Thus, tensile properties which
P,-phase precipitates formed partially during the first are ductile and insensitive to strain rate are obtained
process is enhanced in the Fe-20Ni-1.8Ti maraging after subjecting to the second process. I t is reason-
steel. able to conclude that the aging structures in which
From investigations carried out on the precipitates intense slip bands are difficult to be formed during
in the Fe-Ni-Ti ternary maraging steels,lJO) the deforming are suitable for the improvement of duc-
PI-phase in the Fe-15Ni-1.8Ti and Fe-20Ni-1.8Ti tility.
maraging steels is believed to be DO3-type Ni3Ti.
However, CsC1-type NiTi has also been considered to Acknowledgements
be the PI-phase for the Fe-1ONi-1.8Ti maraging The authors wish to express their sincere thanks to
steel.4j10) DO,,-type Ni3Ti is believed to be the P,- Mr. K. Taguchi for his help in the experimental
phase in the ternary maraging steels from previous work.
investigation^.^^^^^^)
When the maraging steels contain the DO2,-type REFERENCES
Ni3Ti precipitates, less intense slip bands are formed
1) T. Suzuki: Trans. ISIJ, 14 (1974), 67.
during deformation. The increase in uniform elon- 2) K. Soeno and T. Kuroda: Tetsu-to-Hagani, 58 (1972),
gation with the progress of the second process can be 1663.
attributed to the increase in strain hardening exponent 3) H. Hosomi, Y. Ashida, H. Namito and K. Ishihara: Tetsu-
n in the form to-Hagane', 61 (1975), 1012.
4) Y. Mishima, T. Suzuki and M. Tanaka: Tetsu-to-Hagani,
63 (1977), 496.
Research Article
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Transactions ISIJ,Vol. 22, 1982 ( 853 )
K. Soeno, T. Kuroda and K. Taguchi: Trans. ZSZJ, 19 13) T. Yasunaka and T. Araki: J. Japan Znst. Metals, 38 (1974),
(1979), 484. 877.
K. Soeno, K. Taguchi and M. Tsuchiya: Tetsu-to-Hagant!, 14) Y. Kawabe, M. Kanao and M. Muneki: Tetsu-to-Hagant!,
65 (1979), 665. 59 (1973), 1388.
K. Soeno: Trans. ZSZJ, 21 (1981), 469. 15) Y. Kawabe, M. Kanao, K. Nakazawa and M. Muneki:
K. Soeno and K. Taguchi: Trans. ZSZJ, 21 (1981), 618. Tetsu-to-Hagant!, 60 (1974), 269.
T. Kuroda and K. Soeno: Tetsu-to-Hagant!, 66 (1980), 16) Y. Kawabe, K. Nakazawa, M. Kanao and M. Muneki:
1361. Tetsu-to-Hagant!, 60 (1974), 1613.
K. Soeno: J. Japan Znst. Metals, 39 (1975), 1059. 17) K. Soeno, T. Kuroda, M. Tsuchiya and K. Taguchi:
A. Kelly and R. B. Nicholson: Precipitation Hardening, Tetsu-to-HaganL, 62 (1976), 220.
Progress in Material Sci., X, Pergamon Press Ltd., New 18) N. S. Stolofi Effects of Alloying on Fracture Character-
York, (1963). istics, Fracture, VI, ed. by H. Liebowitz, Academic Press
T. Yasunaka and T. Araki: J. Japan Znst. Metals, 36 (1972), Inc., New York and London, (1969).
1202.
Research Article
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I.
I. Kladarić,
KladarićD.etKrumes, I. Vitez
al.: THE INFLUENCE OF RETAINED AUSTENITE ON precipitation hardening ISSN 0543-5846
OF ...
METABK 46 (2) 97-99 (2007)
UDC - UDK 669.15´x´24´25´28–194:669–153–157.8:669.112.227.343=111
THE INFLUENCE OF
RETAINED AUSTENITE ON precipitation hardening OF MARAGING STEEL
Received - Primljeno: 2006-06-02

Accepted - Prihvaćeno: 2006-09-02
Original Scientific Paper - Izvorni znanstveni rad
The investigation of the influence of multiple solution-annealing on kinetics of structural transformation of ma-
raging steels has shown that procedures of solution annealing are not totally reversible. Recurrent solution
annealing results in the increase of the retained austenite share in maraging steel structure. In this paper the
influence of retained austenite on precipitation hardening of maraging steels X2NiCoMo18-9-5 was determined.
The laboratory experimental tests have shown that the growth of retained austenite share in the maraging steel
structure decreases the hardness after aging.
Key words: maraging steel, solution annealing, aging, retained austenite
Utjecaj zaostalog austenita na precipitacijsko čvršćavanje maraging čelika. Istražujući utjecaj višestrukog
rastvornog žarenja na kinetiku strukturnih pretvorbi maraging čelika uočeno je da postupci rastvornog žarenja
nisu u potpunosti reverzibilni. Ponavljanje postupka rastvornog žarenja uzrokuje povećanje udjela zaostalog
austenita u strukturi maraging čelika. U radu je istraživan utjecaj zaostalog austenita na precipitacijsko očvrsnuće
maraging čelika X2NiCoMo18-9-5. Laboratorijska eksperimentalna ispitivanja su pokazala da prirast udjela
zaostalog austenita u strukturi maraging čelika rezultira padom tvrdoće nakon starenja.
Ključne riječi: maraging čelik, rastvorno žarenje, starenje, zaostali austenit
INTRODUCTION fore aging, no danger of decarburizing (C < 0,05 %) and

oxidation [1, 2].
The increased demand for high tensile strength of ma- The investigation of the kinetics of structural trans-
terials used in mechanical engineering was the reason for formation of maraging steel during heat treatment has the
the vigorous development of ultra strong steels resulting purpose to determine the conditions for development of
in production of maraging steel in the sixties of the XX microstructures with good impact on properties. Current
century [1, 2]. dilatometric studies of solution annealing have shown
Superior properties, such as: high ductility, high yield that the maraging of steel does not fulfill the rule of Ms
stress, good hardenability, good weldability, simple heat interdependence on temperature and length of austenitizing
treatment without deformations, have led to a widespread as in the case of carbon and alloyed steels. Procedures of
application of maraging steels, not only in the manufactur- solution annealing of maraging steel are not totally revers-
ing of diverse construction components, but also in the ible, i.e. they do not result in the same structural condition
manufacturing of molds (i.e. for processing of polymers, of material, but lead to visible phase changes that is the
for pressure casting, etc.). increase of the content of retained austenite [3].
Maraging steels are delivered in solution annealed and, The main intention of this paper was to investigate the
for this reason, the low hardness and ductility make them influence of retained austenite on precipitation hardening
suitable for work treatment. They steel are strengthened of maraging the steel X2NiCoMo18-9-5.
with a simple annealing procedure (ageing), which almost
doubles their hardness and tensile strength compared to EXPERIMENTAL WORK
solution annealed state. Their heat treatment yields some
advantages also that is; machining to final measure be- The experiments were carried out on four samples φ
6 × 18 mm. The samples were multiple solution annealed
I. Kladarić, D. Krumes, I. Vitez, Faculty of Mechanical Engineering and aged in Netzsch electronic dilatometer 402 EP (Table
University of Osijek, Slavonski Brod, Croatia 1.). The use of dilatometer enabled to observe dilatometric
METALURGIJA 46 (2007) 2, 97-99 97

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I. Kladarić et al.: THE INFLUENCE OF RETAINED AUSTENITE ON precipitation hardening OF ...
changes by controlled an- tions (As and Ms), measured values of contractions (∆lRŽ)
nealing parameters (tem- for each sample and the calculated average coefficients of
perature and time). dilatation during heating (between ϑ1 = 20 °C and ϑ2 = 525
Experiments were °C) and contraction during quenching (between ϑ3 = 300
planned and performed °C and ϑ4 = 700 °C) are shown.
in two directions:
I. Solution annealing
with determination of
the temperatures of
martensite-austenite
transformation (As), of
austenite-martensite
transformation (M s)
and values of total di-
latation ∆lRŽ from di-
latogram, and calculation of the average coefficients of
dilatation (α) for the range of heating (ϑ1 = 20 °C … ϑ2 =
525 °C) and quenching (ϑ3 = 700 °C … ϑ4 = 300 °C).
The content of retained austenite based on average dilata-
tion coefficients was also calculated. After heat treatment
the samples were tested for Vickers hardness HV1.
II. Heat treatment experiment of aging after multiple solu-
tion annealing.
After ageing the Vickers hardness HV1 was measured. The growth of the average dilatation coefficient (during
heating) with every repeated solution annealing indicates
Multiple solution annealing the increment of the content of retained austenite. Based
on the calculated dilatation coefficients at heating and
In Figure 1. the aggregate of dilatograms of multiple quenching a mathematical relation for the determination
solution annealing with the points of structural transforma- of increment of retained austenite content after every
repeated solution annealings was estab-
lished [3, 4].
αZ − α M
%A = ⋅100
α A − αM
αZ −10,30 ⋅10−6
= ⋅100 / %,
8,66 ⋅10−6 (1)
where:
%A - content of residual austenite / %,

αM - average dilatation coefficient of

martensite (sample A) / K–1 (10,30
× 10–6 K–1),
α A - average dilatation coefficient of
austenite (sample A) / K–1 (18,96 ×
10–6 K–1),
αZ - average dilatation coefficient during
heating (samples B, C and D) (20 °C
to 525 °C) / K–1.
Figure 2. shows the increment of

retained austenite content after every re-
peated solution annealing.
98 METALURGIJA 46 (2007) 2, 97-99

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I. Kladarić et al.: THE INFLUENCE OF RETAINED AUSTENITE ON precipitation hardening OF ...
Before and after the CONCLUSION

multiple solution anneal-
ing each sample was test- In the investigation of the influence of retained austen-
ed for the hardness value ite on precipitation hardening of the maraging steel X2Ni-
Vickers HV1 with load of CoMo18-9-5 the following was observed:
9,81 N, and the average - after every repeated solution annealing results the con-
value was determined tent of retained austenite was increased;
from five measurements - the retained austenite has no influence on hardness in
(Table 2.). solution annealed state. The explanation could be a high
hardness of austenite in the high alloyed steel;
Aging of multiple - the increase of retained austenite content results in
solution annealed decrease of hardness value after aging.
maraging steel
Based on knowledge of the mechanism of maraging steel
The heat treatment precipitation hardening (increase of hardness value after
of aging (ϑa = 500 °C, aging is result of precipitation very hard intermetalic com-
ta = 240 min) has been pounds from martensite matrix) and considering the above
carried out on each sam- mentioned, it can be concluded that the retained austenite
ple after multiple solu- retards the precipitation process or that there is no precipita-
tion annealings. After tion of intermetalic compounds from retained austenite.
aging of maraging steel
X2NiCoMo18-9-5 each REFERENCES
sample was tested for
[1] G. Roberts, G. Krauss, R. Kennedy, Tool Steels, ASM International,
hardness value by Vick-
USA 1998, p. 1 - 97.
ers HV1 method (Table [2] M. Novosel, D. Krumes, Posebni čelici, Strojarski fakultet, Slavon-
3.). ski Brod 1998, str. 375 - 393.
Figure 3. shows cha- [3] I. Kladarić: Doprinos proučavanju kinetike strukturnih pretvorbi
čelika maraging, Doktorska disertacija, Strojarski fakultet, Slavon-
nges in hardness values
ski Brod 2002, str. 6 - 17 i 39 - 57.
after solution annealing and after aging in dependence of [4] I. Kladarić, D. Krumes, R. Marković, Proceedings, 1st International
the content of retained austenite. conference on heat treatment and surface engineering of tools and
dies, Pula, B. Smoljan, H. Jäger, V. Leskovšek (Editors), Croatian
Society for Heat Treatment and Surface Engineering (CSHTSE),
Zagreb 2005, p. 107 - 112.
List of symbols and abbreviation
JSA - solution annealing temperature / °C

JA - aging temperature / °C
tSA - solution annealing time / min
tA - aging time / min
As - temperature of martensite-austenite transformation
/ °C
Ms - temperature of austenite-martensite transformation
/ °C
HV1 - hardness value by Vickers method with load of 9,81
N
DlRŽ - contraction after solution annealing / mm
α - average coefficients of dilatation / K–1
αM - average dilatation coefficient of martensite / K–1

α A - average dilatation coefficient of austenite / K–1
αZ - average dilatation coefficient during heating / K–1
%A - content of residual austenite / %
%M - content of martensite / %
l0 - original sample length / mm
METALURGIJA 46 (2007) 2, 97-99 99

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第 32 卷第 3 期机　械　工　程　材　料 Vol. 32 　No . 3
2008 年 3 月 Material s 　for 　Mechanical 　Engineering Mar. 2008
1 900 MPa 级超高强度不锈钢的研制

刘振宝1 , 杨志勇1 , 雍歧龙1 , 梁剑雄1 , 孙永庆1 , 李文辉1 , 卢伦2
( 1. 钢铁研究总院结构研究所 ,北京 100081 ; 2. 东北特殊钢集团技术中心 ,辽宁抚顺 113001)
摘　要 : 研制出一种 Rm ≥1 900 M Pa 的铬2镍2钴2钼系大规格棒材 ( < 200 mm ) 超高强度马氏体

时效不锈钢 ,通过研究热处理工艺对八种不同成分的铬2镍2钴2钼系马氏体时效不锈钢力学性能的
影响 ,进一步优化了合金成分。结果表明 : 优化成分后得到一种高强 ( Rm = 1 940 M Pa ) 、
高韧 ( A KU2
= 55 J , KIC = 104 M Pa ・ m ) 的马氏体时效不锈钢。
关键词 : 马氏体时效不锈钢 ; 析出相 ; 超高强度
中图分类号 : T G142. 1 　　　文献标识码 : A 　　　文章编号 : 100023738 ( 2008) 0320048204
A 1 900 MPa Grade Ultra2high Strength Sta inless Steel

L IU Zhen2bao1 , YANG Zhi2yong1 , YONG Qi2long1 , L IANG Jian2xiong1 ,
SUN Yong2qing1 , L I Wen2hui1 , L U lun2
( 1. Cent ral Iro n and Steel Research Instit ute , Beijing 100081 , China ;
2. Do ngbei Special Steel Gro up , Fushun 113001 , China)
Abstract : A large size of super2high2st rengt h maraging stainless steel Cr2Ni2Co2Mo bar has been developed.
Effect s of heat t reat ment on mechanical p roperties of Cr2Ni2Co2Mo maraging stainless steel wit h eight different
co mponent s were shudied. Thro ugh f urt her optimization of t he alloy co mpo sitio n : a high2st rengt h ( Rm = 1 940
M Pa) , high2ductile ( A KU2 = 55 J and KIC = 104 M Pa ・ m ) maraging steel has been o btained. Good technological
p roperties of t his kind of steel make it suitable to be used as critical component s wit h high st rengt h and toughness
and sea water corro sio n2resistantce. It also reveals broad applicatio n p ro spect s in aero space , aviation and ot her
fields.
Key words : maraging stainless steel ; p recipitatio n ; ult ra2high st rongt h
向更高的水平 ,目前 ,各国正在开展更高强度并具有

0 　引　言
足够韧性的马氏体时效不锈钢的研制。
马氏体时效不锈钢的发展距今已近 40 a 的历作者结合马氏体时效不锈钢合金化原理以及典
史 ,该钢种采用低碳马氏体相变强化和时效强化效型工程需要合理设计了八种合金成分 , 通过优化最
应叠加的手段使钢具有超高的强度和优异的综合性终得到一种新型的 < 200 mm ( 棒材 ) 、Rm ≥1 900
能 [ 1 - 4 ] ,并迅速成为航空、
航天、
海洋等高科技领域 M Pa 的超高强度马氏体时效不锈钢 , 提高了国内马
如机翼大梁、
舰载飞机起落架、
潜艇动力装置等承力氏体时效不锈钢的强度级别。
耐蚀或高温部件的首选材料 [ 5 - 7 ] 。马氏体时效不
( ) 1 　试样制备及试验方法
锈钢所具有高强、
高韧、
良好的耐蚀性能是其它钢种
首先采用 50 kg 真空感应炉 ( ZG2005) 熔炼八种
不可替代的。1997 年 Martin 等获得了马氏体时效
成分试验钢 ,其化学成分见表 1 ,经对这八种成分试
不锈钢 Custo m465 专利 ,其强度达到 1 800 M Pa ,则
验钢热处理工艺优化 ,选定最佳性能的合金成分及优
将马氏体时效不锈钢的强度级别从 1 700 M Pa 推
化的热处理工艺 (表 2) ,同时对该合金的个别元素含
量优化调整后 ,采用 3 000 kg 真空感应炉 + 真空自耗
收稿日期 :2007204225 ; 修订日期 :2007209213
基金项目 : 国家高技术研究发展计划资助项目 ( 863 - 炉熔炼 ,最后得到高纯洁度的合金成分见表 3 。
2002AA305105) 50 kg 炉熔炼的钢锭经 1 150 ℃加热和均匀化
作者简介 : 刘振宝 (1977 - ) ,男 ,黑龙江鸡西人 ,博士。处理后锻成 < 15 mm 和 < 50 mm 、
长度为 50 mm 的
・4 8 ・
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刘振宝 ,等 :1 900 M Pa 级超高强度不锈钢的研制
表 1 　50 kg 真空感应炉熔炼八种试验钢化学成分( 质量分数/ %)

Tab. 1 　Chemical composion of eight different test steel( mass/ %)
炉号 C Si Mn S P Ni Cr Mo Co Ti V Fe
011 # 0. 030 0. 040 0. 028 0. 004 < 0. 005 4. 29 12. 46 5. 52 12. 95 - - 余
012 # 0. 031 0. 054 0. 028 0. 004 < 0. 005 4. 29 12. 56 5. 04 12. 90 0. 11 - 余
013 # 0. 039 0. 037 0. 022 0. 003 < 0. 005 4. 00 12. 02 3. 96 14. 60 0. 17 - 余
014 # 0. 096 0. 046 0. 022 0. 004 < 0. 005 4. 79 13. 86 4. 96 14. 40 - 0. 30 余
015 # 0. 140 0. 041 0. 027 0. 005 < 0. 005 4. 84 13. 93 4. 91 14. 34 - 0. 32 余
016 # 0. 097 0. 033 0. 027 0. 007 < 0. 005 4. 77 11. 93 4. 94 14. 36 - 0. 32 余
017 # 0. 180 1. 26 0. 041 0. 008 < 0. 005 3. 46 13. 10 2. 60 3. 82 - - 余
018 # 0. 220 1. 48 0. 044 0. 010 < 0. 005 3. 38 12. 86 2. 58 3. 45 - - 余
表 2 　热处理工艺对试验钢力学性能的影响
Tab. 2 　Effect of heat treatment on the mechanical properties of the steel
011 # 012 # 013 # 017 # 018 #
工艺
Rm / MPa Rp0. 2 / MPa A KU2 / J Rm / MPa Rp0. 2 / MPa A KU2 / J Rm / MPa Rp0. 2 / MPa A KU2 / J Rm / MPa Rp0. 2 / MPa A KU2 / J Rm / MPa Rp0. 2 / MPa A KU2 / J
1 1 690 1 440 67 1 540 1 300 106 1 560 1 360 16 1 680 1 460 17 1 750 1 390 20
2 1 780 1 510 70 1 630 1 340 95 1 770 1 650 37 1 570 1 370 23 1 540 1 400 18
3 1 650 1 350 76 1 640 1 400 82 1 540 1 320 30 1 820 1 360 40 1 850 1 410 18
4 1 710 1 390 60 1 730 1 460 70 1 730 1 600 23 1 650 1 350 20 1 670 1 400 26
5 1 640 1 440 72 1 600 1 420 80 1 580 1 410 18 1 870 1 240 46 1 930 1 210 42
6 1 820 1 440 60 1 850 1 560 64 1 740 1 610 24 1 670 1 290 37 1 690 1 300 29
表 3 　3 000 kg 真空感应炉 + 真空自耗炉冶炼的 < 200 mm 时 018 # 的硬度最高 ( 47. 9 HRC) ;011 # 、
013 # 钢的硬
棒材的化学成分( 质量分数/ %) 度随固溶温度升高先上升然后再下降 , 在 1 000 ℃
Tab. 3 　Chemical composition of the optimizated 到达最大值 ;012 # 钢的硬度随固溶温度的升高而增
steel( mass/ %)
加 ,在 1 050 ℃时硬度最高 ( 27. 9 HRC) ; 固溶处理后
炉号 C Mn Si Ni Cr Mo Al Ti Co Fe 014 # 钢的硬度均低于其它钢。由图 1b 可见 , 经过
0. 02～ ≤ ≤ 4. 0～ 11. 0～ 5. 0～ ≤ 0. 4～ 14. 0～
031 # 余 550 ℃时效处理后 , 钢的硬度均有不同程度的提高 ,
0. 05 0. 1 0. 1 5. 0 14. 0 6. 0 0. 2 0. 5 16. 0
但 014 # 、 015 # 、
016 # 钢的硬度值与时效前的硬度相
棒材然后进行固溶处理 , 固溶温度为 950 , 1 000 , 比提高幅度很小 ,即硬度值仍很低 ,虽然 017 # 、 018 #
1 050 ℃,固溶时间为 60 min , 固溶处理后空冷 , 为钢的硬度提高幅度也不大 , 但能够保持很高的硬度
使马氏体相变完成 ,再进行 - 73 ℃保温 480 min ( 采值 ;值得一提的是 012 # 钢经 550 ℃时效后硬度到达
用的介质为干冰 + 酒精的饱和溶液) 的负温处理 ,时 50. 3 HRC ,由此可见对于 012 # 钢在此温度时效处理
效温度为 500 ,550 ℃,保温 240 min 空冷 ;3 000 kg 效果最佳。经上述分析可以认为 , 研究的 011 # 、

熔炼的钢锭经过 1 180 ℃加热和均匀化处理后再经 012 # 、 013 # 、
017 # 、018 # 这五种成分的试验钢有可
3 500 t 快锻机两镦两拔锻成 < 20 mm 、

< 200 mm 和能会得到超高强度的马氏体时效不锈钢。
本试验采用六种热处理工艺对以上五种成分钢
90 mm ×90 mm 的棒材 , 经 1 050 ℃固溶处理 + 负
进行处理 : ( 1) 950 ℃×1 h + 负温处理 + 500 ℃×4
温处理后 ,在 440～600 ℃内时效 240 min ,空冷。
h ; ( 2 ) 950 ℃×1 h + 负温处理 + 550 ℃×4 h ; ( 3 )
冲击试验和拉伸试验分别参照 GB/ T 229 -
1 000 ℃×1 h + 负温处理 + 500 ℃×4 h ; ( 4 ) 1 000
1994 和 GB/ T 228 - 2002 标准进行。用 H2800 型
℃×1 h + 负温处理 + 550 ℃×4 h ; ( 5 ) 1 050 ℃×
透射电镜 ( TEM ) 观察和分析钢的显微组织 ; 用
1 h + 负温处理 + 500 ℃×4 h ; ( 6) 1 050 ℃×1 h +
TIM E T H300 型试验机测量钢的洛氏硬度。
负温处理 + 550 ℃×4 h 。由表 2 可见 ,017 # 、 018 #
2 　试验结果与分析钢经工艺 5 处理后抗拉强度分别为 1 870 , 1 930
2. 1 　热处理工艺对八种成分试验钢力学性能的影响 M Pa ,屈服强度分别为 1 240 ,1 210 M Pa , 此时的冲
由图 1a 可见 ,014 # 、
015 # 、
016 # 、
017 # 、
018 # 钢的击吸收功分别为 46 ,42 J 。因为这两种钢的屈强比
硬度值均随固溶温度的升高而逐渐降低 , 在 950 ℃ 较低 ,且冲击吸收功较低 , 通常在工程上会受到限
・4 9 ・
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图 2 　1 050 ℃固溶及负温处理后时效温度
　　　　　　( a) 　固溶　　　( b) 　固溶 + 负温 + 550 ℃时效对 031 # 钢力学性能的影响
图 1 　热处理对试验钢硬度( HRC) 的影响 Fig. 2 　Effects of aging temperature after 1 050 ℃ solution and
Fig. 1 　Effect of heat treatment on the hardness of the steel subzero treatment on the mechanical propertiesof 031 # steel
( a) 　the hardness of the steel after solution treatment at different
2. 3 　时效温度对钢显微组织的影响及其强化机理
temperatures for 60 min 　( b) 　the hardness of the steel after solution
由图 3 可见 ,031 # 钢固溶后的显微组织为高密
treatment and subzero treatment and aging at 550 ℃for 240 min
度位错的板条马氏体组织 , 板条的平均宽度为 0. 2
制 , 而该钢的性能属典型的抗震、防震用超高强度不
μm 左右 , 细小的板条及高密度的位错分布是使钢
锈钢 ,因此具有潜在的用途。
具有良好韧性和较高强度的前提 , 同时高密度的位
013 # 钢经工艺 2 处理后抗拉强度 Rm 为 1 770
错为时效析出相形核提供了更多的场所。而 440 ℃
M Pa , R P0. 2 为 1 650 M Pa ,但此时的冲击吸收功为 37
时效后钢的显微组织中基本观察不到析出相 , 此时
J ,强韧性匹配较差。011 # 、
012 # 钢经工艺 6 处理后
钢的强度较低。对在 535 ,600 ℃时效显微组织比较
强度均达到最大值 , 抗拉强度分别为 1 820 ,1 850
可知 ,随着时效温度的升高 , 析出相的尺寸逐渐长
M Pa ,冲击吸收功分别为 60 ,64 J , 此时钢的强韧性
大 ,这是钢的强度达到峰值后又随着时效温度升高
匹配良好。结果表明 , 对 011 # 、 012 # 钢的合金成分
而下降的原因。分析认为随着时效温度的升高析出
微量调整 ,例如增加强化元素钛含量 ,并采用高纯洁
相聚集、长大 , 破坏了与基体间的共格或半共格关
度的双真空熔炼 , 可以使钢的强度和韧性进一步
系 ,从而使钢的强度下降。图 3c 中在高密度位错的
提高。
板条马氏体上弥散分布着大量的纳米级析出相。根
2. 2 　时效温度对 < 200 mm 棒材力学性能的影响
据文献介绍 [ 8 - 11 ] ,在高合金超高强度马氏体时效不
结合 011 # 、 012 # 钢化学成分特点 , 增加钛等强
锈钢中常见的析出相有椭球状 Fe2 Mo 型的 Laves
化元素含量后得到表 3 成分的 < 200 mm 棒材 ,经测
相 ( hcp 点阵结构 ) Ni3 Ti , R 相 ,μ 相和针状的 M2 C
定钢中氢、氧、氮、硫、磷的总含量低于 80 mg/ kg 。
等 ,这些细小的强化相大大地提高了钢的强度。
通过对 011 、 #
012 钢最佳热处理工艺及其与 031 #
#
钢成分特点的研究 ,对 031 # 钢采用 1 050 ℃固溶处 3 　结　论

理 ( 保温 60 min) 。图 2 为 1 050 ℃固溶处理 + 负温研制成功的 031 # 钢 < 200 mm 棒材的抗拉强度
处理后时效温度对 031 # 钢力学性能的影响 , 可见 ,
高达 1 940 M Pa ,断裂韧度 KIC 为 104 M Pa ・ m 。
Rm 、 R0. 2 随时效温度的增加 , 钢的强度随之增加 , 至
参考文献 :
535 ℃时效后钢的强度达到峰值 ( Rm = 1 940
M Pa) ,之后强度开始随着时效温度的升高而降低。 [ 1 ] 　Crawfird W M , Cont ractor G P. The effect s of st rengt hening
Be and Ti in maraging stainless steel [J ] . J IPI ,1969 ,207 (12) :
冲击功值随着时效温度的升高逐渐下降到最低点
1642 - 1645.
( 535 ℃) 然后再上升 ,此时冲击功 A KU2 为 55 J ,断面
[ 2 ] 　魏振宇. 马氏体时效不锈钢[J ] . 新金属材料 ,1972 (4) :22 - 24.
收缩率 Z 和伸长率 A 变化规律与冲击吸收功相似 , [ 3 ] 　Imrie W H. Maraging steel in t he British aero space indust ry
在 535 ℃时效时降到最低值 ,之后随着时效温度的 [J ] . Metal Forming ,1970 (1/ 2) :41 - 45.
升高而缓慢上升 ,另测得该时效温度下钢的室温断 [ 4 ] 　姜越 ,尹钟大 , 朱景川 , 等 . 马氏体时效不锈钢的发展现状
[J ] . 特殊钢 ,2003 ,24 (3) :1 - 5.
裂韧度 KIC 为 104 M Pa ・ m 。
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( a) 　1 050 ℃固溶 ( b) 　440 ℃时效 ( c) 　535 ℃时效 ( d) 　600 ℃时效

图 3 　031 # 钢经不同热处理后的 TEM 形貌
Fig. 3 　TEM images of 031 # steel after heat treatment
( a) 　solution treatment at 1 050 ℃　( b) 　aging at 440 ℃　( c) 　aging at 535 ℃　( d) 　aging at 600 ℃
[ 5 ] 　Decker R F , Loreen S. Maraging Steel s2t he First 30 Years (54) :115 - 118.
[ C]/ / Wilson R K. Maraging Steels2Recent Develop ment and [ 9 ] 　Versnyder F L , Beattlejr H J . The Laves and chip hases in a
Applications. Warrendale : TMSA IM E ,PA ,1988. modified 12Cr stainless alloy [ J ] . Trans of t he ASM , 1955
[ 6 ] 　赵先存 ,黄桂煌 . 国外不锈钢现状及动向 [J ] . 国外金属材料 , (47) :211 - 230.
1980 (5) :1 - 6. [ 10 ] 　Irvine K J . The develop ment of high st rengt h steel [ J ] . J
[ 7 ] 　刘振宝 ,宋为顺 ,杨志勇 , 等. 时效对超高强马氏体时效不锈钢 Iron and Steel Inst ,1962 ,200 (10) :820 - 828.
组织与性能的影响 [J ] . 材料热处理学报 ,2005 ,26 (4) :52 - 55. [ 11 ] 　Kasak A , Chandho k C K , Dulis E J . Develop ment of p recipi2
[ 8 ] 　Honeyco mbe R W K. Metallurgical develop ment s in high alloy tation hardening Cr2Mo2Co stainless stells [J ] . Trans ASM ,
steels[ J ] . Special Rep rot 8b , The Iron and steel Inst , 1964 1963 (56) :455 - 467.
( 上接第 47 页) 收缩区、烧结收缩区、烧结完成区。

( 2) 最佳烧结参数为 1 600 ℃、 50 M Pa 、
5 min ,
烧结体密度达 3. 27 g ・cm ,致密度达 99. 09 % 。
- 3
( 3) 烧结得到的 SiC 陶瓷晶粒大小为 1 ～ 2
μm ,说明 SPS 快速烧结较好地控制了晶粒的长大 ,
而且晶粒大小均匀 ,无个别晶粒的异常长大。
参考文献 :
[ 1 ] 　Izhevskyi V A , Genova L A. Review article : silicon carbide.

( a) 　表面 st ruct ure , properties and p rocessing[J ] . Ceramica ,2000 ,46 :4
- 14.
[ 2 ] 　J ensen R J , L uecke W E , Padt ure N P. High temperat ure
p roperties of liquid p hase sintered α2SiC[J ] . Materials Science
and Engineering A ,2000 ,282 (12) :109 - 114.
[ 3 ] 　Magnani G , Minoccari G L , PilottiL . Flexural st rengt h and
toughness of liquid p hase sintered silicon carbide[J ] . Ceramics
International ,2000 ,26 (5) :495 - 500.
[ 4 ] 　She J H , Ueno K. Effect of additive content on liquid2p hase
sintering on silicon carbide ceramics[J ] . Mater Res Bull ,1999 ,
( b) 　断面 34 (10/ 11) :1629 - 1636.
图 6 　烧结后 SiC 陶瓷 SEM 形貌 [ 5 ] 　Tamari N , Tanaka T , Tanaka K , et al . Effect of spark plasma
Fig. 6 　SEM images of the SiC ceramics sintering on densification and mechanical p roperties of silicon
carbide [J ] . Journal of Ceramic Societ y of J apan ,1995 ,103 (7) :
3 　结　论 740 - 742.
[ 6 ] 　Francois G , Alexandre A . Densification of SiC by SPS2effect s
( 1) SiC 的 SPS 致密化过程可以根据时间2温
of time , temperat ure and p ressure[J ] . Journal of t he Europe2
度、
位移曲线分为 4 个区间即放气膨胀区、
气体溢出 an Ceramic Societ y ,2007 ,27 (7) :2725 - 2728.
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　第 42 卷　第 3 期钢铁　Vol. 42 , No . 3
　2 0 0 7 年 3 月 Iron and Steel March 　2007
固溶处理对新型马氏体时效不锈钢力学性能的影响
刘振宝1 , 　杨志勇1 , 　雍歧龙1 , 　梁剑雄1 , 　卢　伦2
(1. 钢铁研究总院结构材料研究所 , 北京 100081 ; 　2. 东北特殊钢集团技术中心 , 辽宁抚顺 113001)
摘　要 : 研究了固溶处理对新型 Cr2Ni2Co2Mo 马氏体时效不锈钢力学性能的影响。结果表明 ,在低于1 050 ℃固溶

处理时钢中存在一些以χ 相为主的金属间相 ,它们不仅严重破坏了钢的韧性 , 而且使钢在时效处理后的最终强度
降低了 100 M Pa ; 经1 050 ℃固溶处理后钢的基体组织为高密度位错的板条马氏体 ,此固溶态组织经适当时效处理
可以使钢的强度达到1 940 MPa ,且得到与其高韧性匹配良好的综合力学性能。
关键词 : 固溶处理 ; χ 相 ; 力学性能
中图分类号 : T G142. 7 　　文献标识码 : A 　　文章编号 : 04492749X(2007) 0320047205
Effect of Solution Treatment on Mechanical Properties

of a Ne w Maraging Stainless Steel
L IU Zhen2bao 1 , 　YAN G Zhi2yo ng1 , 　YON G Qi2lo ng1 , 　L IAN G J ian2xio ng1 , 　L U2lun2
(1. Instit ute for St ruct ural Materials , Cent ral Iron and Steel Research Instit ute , Beijing 100081 , China ;
2. Technical Center , Do ngbei Special Steel Group , Fushun 113001 , Liaoning , China)
Abstract : The effect of solution t reat ment on mechanical p roperties of a new stainless steel , Cr2Ni2Co2Mo maraging
stainless steel was st udied. The result shows t hat t here are intermetallics in t he steel solution t reated at a tempera2
t ure lower t han 1 050 ℃ wit h χ p hase as t he major p hase. The intermetallics deterio rate toughness of t he steel ,and
t he st rengt h of t he steel is reduced by 100 MPa. There is lat hy martensite of high density dislocatio n in t he steel af 2
ter 1 050 ℃ solid solution t reat ment fo r o ne hour. By p roper aging t reat ment , t he st rengt h of t he steel may reach up
to 1 940 M Pa ,wit h a good co mbinatio n of st rengt h and to ughness.
Key words : solutio n temperat ure ; χ p hase ; mechanical p roperties
　　马氏体时效不锈钢的强韧化机制主要包括马氏钢锭经过 1 150 ℃加热和均匀化处理后锻成

体相变强化、
固溶强化、
时效强化以及“有效晶粒”
细 <20 mm 、90 mm ×90 mm 和 55 mm ×55 mm 的试
化强化等 ,其固溶处理工艺在很大程度上决定了晶料 ,并加工成试样 ,然后进行固溶处理。固溶温度为
粒的有效尺寸及后期可能产生的时效强化效果 , 从 830～1 100 ℃,固溶时间为 60 min 。固溶处理后空
而明显影响钢的最终力学性能 , 因此研究固溶处理冷。为了完成马氏体相变 ,进行负温处理 ,处理工艺
工艺对固溶态微观组织及力学性能的影响就显得十为 - 73 ℃保温 480 min ( 采用的介质为干冰 + 酒精
分重要。笔者研究了一种自行研制开发的强度级别的饱和溶液) 。时效态试样则在上述固溶处理的基
在1 900 M Pa 的 Cr2Ni2Co2Mo 马氏体时效不锈钢的础上 ,在 490～ 600 ℃范围内等温时效 240 min , 空
固溶处理工艺对钢的固溶态、
时效态的力学性能的冷。采用 A PD210 X 射线衍射仪对低温固溶处理后
影响规律 ,从而为这种新型马氏体时效不锈钢的工钢中的析出相进行了鉴定。
业化生产及应用提供了热处理数据。
2 　试验结果
1 　试验材料和方法 2. 1 　固溶温度对固溶态钢力学性能的影响
试验用料采用真空感应炉熔炼 ( 200 kg V IM ) 图 1 为固溶温度对试验钢固溶态力学性能的影
+ 真空自耗炉重熔的双真空熔炼 , 试验钢的化学成响 ,可以看出 ,试验钢的强度随着固溶温度的升高基
分 ( 质量分数 , %) 为 :Cr 13. 0 ～ 16. 5 、
Ni 4. 0 ～ 7. 5 、本呈连续下降趋势 , 抗拉强度由 1 145 M Pa 降至
Co 9. 5～15. 0 、
Mo 5. 0～7. 5 , 是一种自行研制开发 1 060 M Pa ,而屈服强度下降的幅度比抗拉强度更
的新型超低碳马氏体时效不锈钢。大 ,由 790 M Pa 降至 520 M Pa ; 塑性指标 ( Z 、A ) 则
基金项目 : 国家高技术研究发展计划资助项目 (2002AA305105)
作者简介 : 刘振宝 (19772) , 男 , 博士生 ; 　　E2mail : liuzhenbao1977 @yahoo . co m. cn ; 　　修订日期 : 2006205222
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・4 8 ・钢　铁第 42 卷
随着固溶温度的升高先小幅下降然后持续增大 , 大　　由图 2 ( a ) 可以发现 ,经 880 ℃固溶处理后钢中

约在 950 ℃出现塑性值的最低点 ,韧性指标 ( 冲击功存在大量的析出相。经 1 040 ℃固溶处理后钢中也
A KU2 ) 也随着固溶温度的升高先下降然后持续增大 , 存在析出相 ( 图 2 ( b ) ) , 但其数量已十分稀少。在
韧性值的最低点出现在 880 ℃左右。 1 050 ℃以上的温度固溶处理的试样中已看不到析
2. 2 　固溶温度对钢固溶态组织的影响及强韧化机出相。说明析出相随着固溶温度的升高而不断溶解
理分析消失也是钢的强度持续下降的重要原因。
为了较详细地解释固溶温度对钢的固溶态力学经分析 , 这种析出相是以 χ 相为主的金属间
性能的影响规律 ,用扫描电镜观察了不同温度固溶相。图 3 为经 880 ℃固溶处理后试验钢中析出相经
处理后钢的组织 ( 图 2 ) 。可以看出 , 经过固溶处理 X 射线衍射分析的结果。电解条件 : 3. 6 % ZnCl 2 ,
后基体组织主要是板条马氏体。随着固溶温度的升 5 %盐酸 ,1 %柠檬酸甲醇溶液 ,电流密度为 0. 05 A/
高钢的晶粒增大 , 固溶温度由 880 ℃升至 1 100 ℃, cm2 ,温度为 5～ - 10 ℃。经过分析图 3 可知 , 析出
晶粒平均尺寸由 12 μm 增至 60 μm 以上 ,而强度由相是以χ 相为主的金属间相 ,χ 相的晶面间距和强
1 140 M Pa 降至1 060 M Pa , 根据 Hall2Petch 经验公度见表 1 。
式 ,晶粒尺寸增大是钢的强度随着固溶温度升高而图 4 为观察到的沿晶界析出的χ 相及其衍射斑
下降的一个原因。点。从图中可看出 ,χ 相的平均尺寸较大 ,且向晶内
生长 ,严重破坏了基体的连续性 , 导致钢的韧性下
降 ,这也恰好说明了 880 ℃固溶后钢的冲击功较低
的原因 ( 图 1) 。
图 5 为观察到的另一种形貌的χ 相 ,暗场像中的
χ 相上有放射状的条纹 ,这种条纹的成因有待探索。
通过上述的方法确定了 880 ℃固溶处理后钢中
的金属间相为χ 相 ,有文献报道了这类高合金钢中
两种χ 相的典型组成式分别为 Fe35 Ni3 Cr 13 Ti7 [ 1 ] 和
Fe27 Ni8 Cr 13 Ti4. 5 Mo 0. 55 [ 2 ] , 并说 χ 相的生成不仅会
图 1 　固溶温度对力学性能的影响严重降低钢的韧性而且还会降低时效后钢的强度。
Fig. 1 　 Effect of solution temperature on mechanical 根据本试验结果可知钢在 880 ℃固溶处理后生成χ
properties 相是此钢韧性降低的主要原因。
(a) 880 ℃; 　( b) 1 040 ℃; 　(c) 1 050 ℃; 　(d) 1 100 ℃

图 2 　试验钢经不同温度固溶处理 60 min 后的组织( SEM)
Fig. 2 Microstructure of steel after solution treatment at different temperatures for 60 min ,SEM
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第3期刘振宝等 : 固溶处理对新型马氏体时效不锈钢力学性能的影响・4 9 ・
表 1 　钢中χ 相的晶面指数
Table 1 　Interplaner spacings of χ phase in test steel
I
试样号 ( hkl) d/ nm
I0
1 321 15 0. 237 8
2 330 100 0. 209 8
3 332 24 0. 189 7
4 552 22 0. 121 1
　　注 :χ 相为体心立方结构 , a0 = 0. 890 nm 。
2. 3 　固溶温度对钢时效态的力学性能的影响
研究了两种不同的固溶处理工艺 ( 880 ℃固溶
图 3 　880 ℃×60 min 固溶处理后钢中χ相的 X 射线
处理 + 负温处理 , 以下简称工艺 1 ; 1 050 ℃固溶处
衍射分析
理 + 负温处理 ,以下简称工艺 2) 对经时效处理的钢
Fig. 3 　X2ray phase analysis of χ phase in steel after 880
的力学性能的影响。从图 6 可以看出钢的强度随着
℃ solution treatment for 60 min
(a) χ相的 B F ; 　( b) χ相的 DF ; 　(c) 选区电子衍射谱 ; 　(d) 衍射斑点的标定

图 4 　880 ℃×60 min 固溶处理后钢中的χ相( TEM)
χ phase in steel after 880 ℃ solution treatment for 60 min , TEM
Fig. 4 　
(a) χ相的 DF 及选区电子衍射谱 ; 　( b) 衍射斑点的标定

图 5 　880 ℃×60 min 固溶处理后钢中的χ相( TEM)
χ phase in steel after 880 ℃ solution treatment for 60 min , TEM
Fig. 5 　
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・5 0 ・钢　铁第 42 卷
2. 4 　固溶温度对钢时效态组织的影响及强韧化机
理分析
图 7 ( a ) 、( b ) 分别为经工艺 2 + 530 ℃ ×240
min 、
工艺 1 + 550 ℃×240 min 处理后 ,钢的微观组
织的 T EM 像。从图 7 ( a ) 可以看出 , 经工艺 2 + 时
效处理后 ,高密度位错的板条马氏体上弥散分布着
大量的纳米级析出相。根据大量文献的介绍 [ 3～7 ] ,
在高合金高强度马氏体时效不锈钢中常见的析出相
有椭球状 Fe2 Mo 型的 Laves 相 ( hcp 点阵结构) 和针
状的 M2 C 等 ,这些细小的强化相大大地提高了钢的
图 6 　时效温度对力学性能的影响
强度。
Fig. 6 　Effect of aging temperature on mechanical prop2
从图 7 ( b) 可以看出 ,虽然同样在基体上生成了
erties of steel
大量细小的析出相 ,但由于以χ 相为主的金属间相
时效温度的升高先上升然后再逐渐下降。由于固溶
的存在 ,使钢中细小强化相的体积分数减少 ,由此可
温度不同 ,达到强度峰值的温度也不同。经工艺 1
见 ,以χ 相为主的金属间相夺走了大量的强化元素
处理后钢的强度在 550 ℃×240 min 达到峰值1 840 ( 如 Mo 、
Co ) , 占据了钢中纳米级强化相的体积分
M Pa ,而经工艺 2 处理后钢的强度在 530 ℃×240
数 ,从而影响了钢的时效强化效果 , 又因为 χ 相的
min 达到峰值 1 940 M Pa 。韧性指标冲击功随着时
存在 ,使钢的韧、塑性均下降 ( 图 6 ) , 因而在所研究
效温度的升高先缓慢下降然后逐渐上升 , 且均在
的试验钢的成分范围内 , 在低温固溶处理时存在的
530 ℃时效后降到最低。经工艺 2 + 时效处理后钢
以χ 相为主的金属间相不但会降低钢的强度 , 而且
的冲击功均高于工艺 1 + 时效处理 , 经工艺 1 + 550
还会降低钢的韧、
塑性。
℃×240 min 处理后虽强度较高但冲击功仅为 24
J ,而经工艺 2 + 530 ℃×240 min 处理后的冲击功 3 　讨论
达到 59 J 。塑性指标 ( A 、Z) 与冲击功的变化规律相
近。值得一提的是 , 工艺 1 + 时效处理后钢的断面在温度低于1 050 ℃、60 min 的固溶处理后 , 钢
收缩率和伸长率均低于工艺 2 + 时效处理。由此可中存在以χ 相为主的金属间相 , 尤其是在 880 ℃×

60 min 的固溶处理后 , 金属间相的数量最多 , 此时
见 ,经1 050 ℃×60 min + - 73 ℃×480 min + 530
℃×240 min 工艺处理后 , 试验钢具有高强度和高钢的韧、塑性指标均很低 ,特别是冲击值。这些金属
韧性 ,综合力学性能匹配良好。间相在晶界上生长 ,尺寸较大 ,且无规律地向晶内延
伸长大 ,会显著降低钢的韧性 ,它们的存在导致钢中
(a) 工艺 2 + 530 ℃×240 min 处理后基体的 BF ; 　( b) 工艺 1 + 550 ℃×240 min 处理后基体的 BF

图 7 　经固溶处理后在峰时效时钢的组织的 TEM 像
Fig. 7 　Microstructure of steel at aging peak after solution treatment , TEM
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第3期刘振宝等 : 固溶处理对新型马氏体时效不锈钢力学性能的影响・5 1 ・
强化元素的含量下降 , 使时效时生成的纳米级强化 min + 550 ℃×240 min 处理后 , 虽然钢的强度较高

相的体积分数下降 , 从而降低了钢的最终强度 ; 经 ( 1 840 M Pa) ,但是韧、
塑性指标很低 ,很难应用在工
1 050 ℃×60 min 固溶后 , 钢的基体组织均为高位程上。
错密度的板条马氏体 , 没有金属间相 , 此时钢的韧、
参考文献 :
塑性最好 ,经过负温处理 + 时效处理后钢中析出大
量弥散的纳米级强化相 , 析出相大大提高了钢的强 [ 1 ] 　Hughes H , Llewelyn D T. χ Phase in t he Fe2Cr2Ni2 Ti System
[J ] . J Iron Steel Inst , 1959 ,192 (6) :170.
度。经上述分析可知 ,1 050 ℃×60 min + - 73 ℃
[ 2 ] 　Beette J r H J . Int ragranular Precipitation of Intermetallic
×480 min + 530 ℃×240 min 是试验钢最好的热
Compounds in Co mplex Austenitic Alloys [ J ] . Trans A IME ,
处理工艺。 1961 ,221 (1) :28235.
[ 3 ] 　Irvine K J . The Develop ment of High St rengt h Steel [J ] . J I2
4 　结论 ron and Steel Inst ,1962 ,200 (10) :8202828.
[ 4 ] 　Kasak A , Chandho k C K , Dulis E J . Develop ment of Precipi2
( 1) 经1 050 ℃×60 min 固溶处理后 ,钢的微观
tation Hardening Cr2Mo2Co Stainless Steels [J ] . Trans ASM ,
组织结构为高密度位错的板条马氏体 , 此时合金元
1963 ,56 :4552467.
素充分地固溶在钢中 , 为时效强化提供了必要的准 [ 5 ] 　赵振业 ,李春志 ,李　志 ,等 . 一种超高强度不锈齿轮钢强化相
备。研究 [J ] . 航空材料学报 ,2003 ,23 (1) :126. ( ZHAO Zhen2ye ,
( 2) 经 880 ℃×60 min 固溶处理后 , 钢中存在 L I Chun2zhi , L I2Zhi ,et al . St udy on t he St rengt hening Phase
in a Ult ra2 High St rengt h Stainless Gear Steel [J ] . Journal of
大量的以χ 相为主的金属间相 ,它们在晶界上的尺
Aeronautical Material s ,2003 ,23 (1) : 126. )
寸较大、形状不规则 ,严重降低了钢的韧、塑性。
[ 6 ] 　Honeyco mbe R W K. Metallurgical Develop ment s in High Al2
( 3) 经1 050 ℃×60 min + - 73 ℃×480 min + loy Steels[J ] . The Iron and Steel Inst ,1964 ,Special Report 8b.
530 ℃×240 min 处理后 ,钢中生成大量弥散的纳米 [ 7 ] 　Versnyder F L , Beattle J r H J . The Laves and Chip hases in a
级强化相 ,此时钢的强度达到了 1 940 M Pa , 且保持 Modified 12Cr Stainless Alloy [ J ] . Trans of t he ASM , 1955 ,
良好的韧性 ; 而经 880 ℃×60 min + - 73 ℃×480 47 :2112230.

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%15% % 4 # ! ! &E#F% Vol. 15, No.4

1 9 7 9 q 12 A ACTA METALLURGICA SINICA December 1 9 7 9
? O 1994-2008 China Academic Journal Electronic Publishing House. All rights reserved. http://www.cnki.net
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PHASE TRANSFORMATION AND MECHANICAL PROPERTIES

OF MARAGING STAINLESS STEELS
Li Jianchun, Gao Anjuan and Wang Zhanyi
(Central South Institute of Mining and Metallurgy)
Abstract
The volume fractions of ~lustenite have been determined on two maraging

stainless steels with respect to tempering temperature and time or quenching tem-
perature. When the specimens were quenched from 850°C and tempered under dif-
ferent temperatures for 4h, the reverted austenite began to appear L; a tempering
temperature of about 550°C, reached its peak value of ?C% vc-kil~e fraction at
about 610°C and disappeared over 700°C. Unc'er reriain detnitc tercpering temper-
ature their volume fractions were increa~ct! ss prolon~e:r,r, the tempering time.
And the process seems to be of dif:usian cor.tro1lir.k. The minimum volume frac-
tion of austenite, being rlecr ;:ero, r ~ s r ; ~esulted by being quenched at 1000 or
950°C under SGrrce tr91~1peri;~g i:mperature of 580°C for 4h.
T::r efl'cc'. 0,' dizerent heat treatment on the microstrain Aa/a of the steels,
closely rcidtol to phase transformation process of M S A , has also been investigated
by means of X-ray diffraction. The presence of austenite at a n y 10% would cause
loss of strength of both steels about 10 kg/mm2, however, their toughness might
be actually improved by these softer austenites formed along the boundaries of
lath martensite. In view of combining both strength and toughness of the steels
the proper heat treatment process to form 5-10% stable reverted austenite would
perhaps be desirable.
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第 29 卷　第 4 期材　料　热　处　理　学　报 Vol . 2 9 　No . 4
2 0 0 8 年　8 月 TRANSACTIONS OF MATERIALS AND HEAT TREATMENT August 2008
马氏体时效不锈钢的发展
杨志勇 , 　刘振宝 , 　梁剑雄 , 　孙永庆 , 　李文辉
( 钢铁研究总院 ,北京　100081)
摘　要 : 叙述了马氏体时效不锈钢的发展历史与现状 ,并总结了该钢种的成分、
性能和强韧化机理等方面的特
点。马氏体时效不锈钢的发展趋势是采用超高洁净度 ( [ H] + [O ] + [N ] + [ S] + [ P] ≤40 ×10 - 6 (ppm) ) 的真空
熔炼及全流程组织细化及成分均匀化控制等技术 ,研制高强、
高韧、
具有优良综合性能的马氏体时效不锈钢。
关键词 : 马氏体时效不锈钢 ; 　合金元素 ; 　力学性能
中图分类号 : TG14211 　　　文献标识码 : A 　　　文章编号 : 100926264 (2008) 0420001207
Development of maraging stainless steel

YANG Zhi2yong , 　LIU Zhen2bao , 　LIANGJian2xiong , 　SUN Yong2qing , 　LI Wen2hui
( Institute for Structural Materials Central Iron and Steel Research Institute , Beijing 100081 ,China)
Abstract :The development and state2of2the2art of maraging stainless steel , including its chemical composition , properties and the mechanism of
strengthening and toughening is reviewed. The developing trend of application of super pure vacuum melting technology( [ H] + [O ] + [N ] + [ S]
+ [ P] ≤40 ×10
-6
(ppm) ) and the controlling of extra2fine grain homogenization structure in whole fabricating process is emphasized.
Key words :maraging stainless steel ; alloy element ; mechanical property
[8 ,9 ]
　　20 世纪 60 年代后期问世的马氏体时效不锈钢后 ,为发展高强度马氏体不锈钢引入了马氏体时效
是一类新型的高强度不锈钢 ,它的发展一方面是由于强化这一新概念 , 促进了马氏体时效不锈钢的发展。
沉淀硬化不锈钢的某些性能较差或热处理工艺复杂 1961 年美国 Carpenter Technology 公司研制了第一个含
而亟待改进 ,另一方面是受到了马氏体时效钢合金化 Co 的 Pyromet X212 马氏体时效不锈钢 ,后又发表了不
的原理以及良好的综合性能的启发。马氏体时效不含 Co 的 Custom450 、455 ; 1967 、1973 年先后发表了
锈钢不仅具有马氏体时效钢优良的强、韧性能 , 还具 Pyromet X215 、
Pyromet X22 ,此间美国一些公司先后发表
有不锈钢较好的耐腐蚀性能 , 同时 , 它的加工性能和了 AM363 、Almar362 、In736 、PH1328Mo 、Unimar CR 等 ;
焊接性能好、弹性优异、
热稳定性良好 ,热处理工艺简 Martin 等人分别于 1997 年和 2003 年获得了
单 ,因而在国内外得到了广泛的应用和发展 , 已成为 [10 ]
和 Custom475 的发明专利。法国有高强
Custom465
[11 ]
[1 ,2 ]
高强度不锈钢系列中最有发展前途的钢类。我国度不锈钢标准 (7 个钢号) , 此外还研究了
从上个世纪 70 年代开始研究 , 并且已经研制出了强 Cr12Ni7Mo2TiAl 、
0Cr14Ni4Cu3Mo 、
0Cr14Ni4Cu3 等钢号。
度级别为 1200 、1400 、
1600MPa 的马氏体时效不锈钢 , 英国研发的钢种有 FV448 、
520 、
520 (B ) 、
520 ( S) 、
535 、
它以最高的强度 ,满意的不锈性和良好的综合性能迅 566 、 SΠSJ2 ,12Cr28Ni2Be 等
D70 以及 SΠSAV 、
[12 ]
。德国于
速成为飞机、火箭、导弹壳体等关键设备的主承力耐 [13 ]
[327 ]
1967 、
1971 年研制发表了 Ultrafort401 、
402 等钢种。
蚀 ( 或中温) 部件的首选材料。
前苏联除仿制、
改进美国钢号外 ,还独立研究了一系列
新钢号 , 常见的钢有 0 Х15 Н8 Ю、0 Х17 Н5 М3 、
1 　马氏体时效不锈钢的发展历史 1 Х15 Н4 АМ3 、
07 Х16 Н6 等以及大量含钴钢号 , 如
20 世纪 60 年代初 ,国际镍公司发表马氏体时效钢 00 Х12 К14 Н5 М5 Т、
00 Х14 К14 Н4 М3 Т等。2002 年美国
QuesTek 新技术有限责任公司承担美国防部战略环境
收稿日期 : 　2007207209 ; 　修订日期 : 　2008206210 研究与发展计划 ( SERDP) 污染防止项目 , 该项目要求
基金项目 : 　国家高技术研究发展计划 (86322002AA305105)
设计新型飞机起落架材料 , 即马氏体时效不锈钢
作者简介 : 　杨志勇 (1959 —) ,男 ,钢铁研究总院结构所教授 , 主要从
事超高强度不锈钢领域研发工作 , 电话 : 010262183324 , E2mail :
FerriumS53 ,该材料于 2006 年底研制成功 ,FerriumS53 强
[14 ]
yangzhiyong @nercast . com 。度约 1980MPa , KIC 达到 80MPa m以上。
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2 材　料　热　处　理　学　报第 29 卷
我国从 20 世纪 70 年代开始马氏体时效不锈钢性 ,高的屈强比 ,有较高的断裂韧性。

[5 ]
的研制工作 , 研制的典型钢种有表 2 　典型马氏体时效不锈钢的力学性能
, 00Cr12Ni8Cu2AlNb , 00Cr10Ni102
[7 ]
00Cr13Ni8Mo2NbTi Table 2 　Mechanical properties of typical maraging stainless steels
[15 ]
Mo2Ti1 等 10 余种。2002 至 2005 年钢铁研究总院 Rm Rp012 α/ KIC/
Steel designation A% Z%
成功设计并研制出新型的超高韧性与超高强度马氏 ΠMPa / MPa (JΠcm ) 2
m1Π2 )
(MPa・
体时效不锈钢 ,该钢是我国自主研发并具有自主知识 Pyromet X215 1550 1350 17 — — —
产权的 Cr2Ni2Co2Mo 系马氏体时效不锈钢 , 其强度为 Custom455 1724 1689 10 45 12J (V) 48
[16 ,17 ]
1940MPa , KIC 达到 141MPa m 。 Custom465 1779 1703 14 51 — 71
Custom475 1979 1827 6 — — —
Pyromet X223 — 96～104

2 　马氏体时效不锈钢典型钢号与性能 1779 1634 15 58
0Kh16AN4B 1490 1140 16 67 — —

表 1、
表 2 分别列出了典型马氏体时效不锈钢的
[14 ,18235 ] PH1328Mo 1620 1600 918 5017 68 —
化学成分和力学性能。
VNS65 1800 1600 12 — 125 —
表 1 　国外典型马氏体时效不锈钢的化学成分( wt %)
VNS49 1200 1170 14 68 180 —
Table 1 　Chemical composition of overseas
VNS59 1400 1300 13 67 180 —
typical maraging stainless steels( wt %)
D70 1656 1617 915 — 17 —
Steel designation C Cr Ni Mo Co Ti Al Else element
000 KH14N4 K14M3T 1620 1470 20 62 76 —
PH1328Mo ≤0105 1212Π1312 715Π815 210Π215 — — 112 01005N
03Kh11N10M2T2 1720 — — — ≥14 —
Custom450 01035 1419 615 018 — — — 115Cu , 0175Nb
03 Kh12N8 K5M3TYu 1780 1620 — 55 — —
Custom455 ≤0105 1110Π1215 715Π915 — — 018 — 2125Cu , 013Nb
0Kh12N8MTYu 2097 1568 713 2615 — —
Custom465 ≤0102 1110Π1215 11Π1112 0175Π112 — 115 — —
Pyromet X223 ≤0102 915Π1015 615Π715 510Π610 915Π1110 — — —
Pyromet X215 ≤0103 1510 — 219 2010 — — — 3 　合金元素的影响及成分设计
Custom475 ≤0103 910 610 610 1410 — — — 马氏体时效不锈钢中的合金元素按其作用主要
D70 ≤0103 1115Π1215 410Π510 410Π510 1210Π1410 — — — 有三类 ,一类是使钢具有不锈性和耐腐蚀性能的元
03Kh11N10M2T 0103 10145 9177 2124 — 113 — — 素 ,如 Cr ; 一类是形成金属间强化相的强化元素 , 如
VNS25 ≤0103 1115Π1215 910Π1015 015Π018 — — — — Ni ,Mo ,Cu ,Ti ,Al 等 ; 另一类是平衡组织以保证钢中
VNS65 ≤0102 1314Π1316 212Π216 319Π410 1611Π1613 — — — 尽量少的残余奥氏体或δ2铁素体的元素 , 如 Ni ,Mn ,
VNS59 ≤0103 915Π1015 818Π918 312Π316 615Π715 — — — Co 等 ,值得一提的是近些年来对该钢种合金设计时
Almar362 ≤0103 1415 615 — — 018 — — 常加入少量的 V ,B ,Nb 等元素 ,它们起到了细化晶粒
AM367 01025 1410 315 210 1515 014 — — 尺寸、
净化晶界的作用。
000KH14N4K14M3T 0102 1415 410 219 1416 0126 — — 311 　合金元素的作用
03Kh11N10M2T2 0103 1015 917 210 — — — — 铬是使钢钝化并赋予其良好耐蚀性和不锈性的
03Kh12N8K5M3TYu 01028 1115 718 213 513 0195 0133 — 元素 , 钢的耐蚀性按 nΠ8 规律作跃进式的突变 , 随着
0Kh12N8MTYu 0103 1212 718 0188 — — 018 — 铬含量的提高其不锈性、
抗氧化能力明显提高 , 铬可
11Cr9Ni2MoTi 01015 1110 910 210 — 115 — B < 01005 以提高钢的淬透性 ,使 C 曲线明显向右移 , 从而降低
FerriumS53 0121 10 515 210 1410 — — 110W ,013V 了淬火的临界冷却速度 , 使钢的淬透性提高 , 并在室
温就可以得到马氏体组织 ,铬与钼配合能提高钢的耐
[15 ,36 ]
　　由表 1 、表 2 可以看出 , 马氏体时效不锈钢以超海水腐蚀性 ,降低钢对点蚀的敏感性。在马氏体
低碳 Fe2Cr ( ≥12 %) 为基体 ,为了提高其强韧性、
耐蚀时效不锈钢中 Cr 含量约 12 % ,不低于 10 % 。Cr 是铁
性 ,又加入 Mo 和 Al 、
Ti 、
Cu 等元素 , 通过时效在板条素体形成元素和缩小奥氏体区元素 ,Cr 含量过高 ,固
马氏体基体析出大量的细小、
高度弥散分布的强化溶处理后钢中会有少量的铁素体组织 ,而铁素体的存
相 ,获得高强度、
高韧性 , 该钢种具有良好的可焊接在会影响钢的热塑性 ,降低钢的强度并恶化钢的横向
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第4期杨志勇等 : 马氏体时效不锈钢的发展 3
[5 ,15 ,37 ,38 ]

韧性 ,Cr 也是降低 M s 点的元素之一。的耐孔蚀性 ,但铜的加入将使热加工性能变得困难。
镍是马氏体时效不锈钢中的重要元素 ,它可以提铜在马氏体时效不锈钢中 , 以富铜ε 相使钢强化 , 并
高不锈钢的电位和钝化倾向 ,还可以改善马氏体不锈且 Cu 能起到固溶强化的作用。
钢的耐气蚀和耐土壤腐蚀性。Ni 的含量不能太高 , 钛对马氏体时效不锈钢的影响类似于铝 ,Ti 在马
当大于 10 %后镍将扩大γ 相区和降低马氏体转变温氏体时效不锈钢中是最有效的强化元素 ,Ti 作为强化
度 M s ,1 %的 Ni 就可使其降低 50 ℃,使钢丧失淬火能元素加入 Ni > 3 % 的钢中 , 时效时形成金属间相η2
力 ,导致室温组织中的残留奥氏体过多 , 使钢的强度 Ni3 Ti 。Ti < 014 %时在某种程度上可以提高马氏体转
[51 ]
降低
[5 ,15 ]
。镍可以提高钢的塑性和韧性 , 特别是超低变温度 ,钛的含量过高将导致钢的裂纹敏感性增
[52 ]
温下的韧性 ,这与它降低位错与间隙原子的交互作用加 ,提高钢的脆性破断倾向。
能量的性质有关 ,Ni 还会形成强化作用的金属间
[39 ] Mn 是扩大 γ 区的元素 , 在钢中 Mn 稳定奥氏体
相 ,特别是形成η2Ni3 Ti 、
[40 ]
β2NiAl 相 [41 ,42 ] 。组织的能力仅次于 Ni , 是强烈提高钢的淬透性元
[53 ]
钼主要是增加回火稳定性和二次硬化效应 ,提高素 ,在马氏体时效不锈钢中 Mn 可以代替 Ni ,但 Mn
钢的强度及裂纹抗力 ,Mo 改善回火稳定性的机理是的加入会降低 Cr 含量较低的不锈钢的耐蚀性。
钼的加入形成了细小的密排立方 M2 X 相 , 增加了二 312 　马氏体时效不锈钢的成分设计
[43 ] 在马氏体时效不锈钢的设计时要保证钢的强韧
次硬化效应。2 %左右的钼可使钢在不同固溶处
性、最少的 δ2Fe 含量和适量的残余奥氏
耐腐蚀性、
理条件下经冷处理均保持较高的硬度 ,但钼增加到一
体 ,在成分设计时要求 : C ≤0103 % , 使钢的基体组织
定值 ( > 5 %) 后 ,δ2铁素体的量增加 , 硬度开始下
[44 ] 为板条马氏体 ,它可以使钢的强韧性有好的配合 , 特
降。在时效初期析出的富钼析出相 , 在强化的同
[45 ,46 ] 别是使其具有好的韧性 , 还可以改进耐蚀性、可焊性
时使钢保持良好的韧性 ,Mo 含量相对于 Fe 而
及冷热加工性 ; 铬含量最好大于 12 % , 尽量不低于
言 ,是一种表面活性元素 , 将 Ti 或 Cu 从界面区域置
10 % ,以保证钢有足够的不锈性与耐蚀性 ; 钢要具有
换出来 ,因此降低了过剩相在晶界析出的可能性。钼
[15 ] 很高洁净度 , 其中的杂质 S 、
P、Si 、
Mn 、
H、O 含量要尽
提高不锈钢耐海水腐蚀性能 , 有资料表明 , 当不锈
量低 ,以提高钢的耐蚀性、
韧塑性和可焊性 ,特别是提
钢中的 Mo ≤215 %时 , 即使 Cr > 25 % , 不锈钢在海水
高疲劳性能 ; 足够含量的奥氏体稳定化元素 ( 如 Ni ) ,
中的耐蚀性也不再提高。
既要避免形成δ2铁素体 ,又要使其不产生过量的残留
钴的加入并不形成金属间化合物 ,Co 对基体的
奥氏体 ; 适当含量的时效强化元素 , 例如 Ni 、
Mo 、
Al 、
强化作用主要是降低基体的堆垛层错能 ( stacking2
[47 ]
Ti 、
Cu 等 , 以便形成金属间化合物而使钢强化 ; 为保
fault energy ,缩写为 SFE) , 钴还可以抑制马氏体中
证得到室温的组织是板条马氏体 , 除了控制碳含量 ,
位错亚结构的回复 ,为随后的析出相形成提供更多的
还要控制 M s 在 150 ℃左右 , 并精确控制镍当量与铬
形核位置 ; 研究表明 ,Co 有降低 Mo 在α2Fe
[48 ] [49 ,50 ]
中
当量的配合及其他合金元素影响等。
的溶解度而间接影响强化 ; Co 会大大降低δ2铁素体
人们在设计一种新钢种时常通过一些经验公式
和χ 相在组织中存在的可能性 ,Co 还可以提高 C 的和相图来初步判定该设计成分是否合理 , Schaeffler
活度 ,促进碳化物的析出 ; Co 是合金中唯一能提高 [54 ]
图已被广泛用于判定化学成分对不锈钢的类型和
M s 温度或者对 M s 点降低较小的元素 ,Co 可以有效组织结构影响的初步依据。但该图存在着很多缺陷 ,
地调控 M s 温度 , 但是当 Co 含量太高会促进孪晶的如合金元素 Co 、
Cu 、
Ti 、
Al 等对组织的影响没有考虑 ,
形成 ,这对钢的韧性不利。对于 12 %Cr 马氏体钢的奥氏体型和马氏体型钢在δ2铁素体相区分界线应是
研究结果表明 ,钴增加了马氏体本身的硬度 , 主要是 [55 ]
曲线等 ,Potak 和 Sagalevich 根据 110 种成分不同的
固溶强化的效果。不锈钢及大量文献数据 ,计算并绘出了合金元素相对
铝是铁素体形成元素 ,铝在马氏体时效不锈钢中于 Cr 对铁素体和马氏体形成量的影响示意图 ( 如图
的主要作用起时效强化的作用。 1) 。通过对已设计的合金成分对应的元素所计算得
铜是一种奥氏体形成元素 , 其能力远低于镍 , 约到当量 ,对照该图后可以初步判定该合金成分的室温
是镍的 30 % , Cu 提高钢的耐海水腐蚀性 , 因为铜离组织 ,这大大地减少了科研工作量。如图 1 所示 , X
子有毒而减少海生物附着造成的缺氧 ,从而提高了钢轴表示所有合金元素相对于 Cr 对铁素体形成量的影
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F
响 ,即 Crequ ( 公式 1) ; Y 轴表示所有合金元素相对于晶格中 ,由于原子尺寸效应、弹性模量效应和固溶有
Cr 对马氏体形成量的影响 ,即 Creqv ( 公式 2) 。
M
序化的作用而使钢强化 ,其强化效应随着元素含量增
加而明显 ,如 ,溶剂原子与溶质原子的尺寸差异 ,造成
的固溶体点阵畸变 ,形成以溶质原子为中心的弹性应
变场 ,阻碍位错运动而强化 , 原子大小差别愈大强化
效应也愈大 ; 固溶强化的程度 ,也取决于基体组织 ,间
隙元素 C 、 N 对马氏体组织强化效果最大。
41113 　析出强化
马氏体时效不锈钢经时效处理在板条马氏体基
体上析出大量细小、弥散分布的金属间化合物是使钢
获得超高强度的关键。在马氏体时效不锈钢中常见
的析出相有圆球状 Fe2 Mo 型 Laves 相、
R 相 ,细长棒状
Ni3 Mo ,不规则形状χ 相等。表 3 为马氏体
的η2Ni3 T、
[15 ,18 ,34 ,41 ,56 ,57 ]
时效不锈钢钢中常见的析出相。
表 3 　马氏体时效不锈钢的析出相
Table 3 　Precipitate phases in maraging stainless steel
Aging
Steel designation Precipitate
temperatureΠ℃
[55 ]
图 1 　铬当量对不锈钢室温组织的影响
PH1328Mo 450～500 NiTi ,NiAl
[55 ]
Fig.1 　Effect of Creqv and Creqv on microstructure of stainless steel
F M
χ2Phase , Laves2Phase ,
AM367 427～510
Mo2Compounds , Ti2Compounds
Creqv = %Cr2115 ×%Ni + 2 ×% Si20175 ×%Mn2KF ×
F
500～550 χ2Phase ,Fe2Mo ,Ni 3 Ti

( %C + %N) + %Mo + 4 ×%Al + 4 ×%Ti + 115
Ultrofort401
Ni 3 ( Ti ,Al) ,R2Phase ,
×%V + 015 ×%W + 019 ×%Nb2016 ×% Co2 1RK91 475～550
Laves2Phase , R’
2Phase
015 ×%Cu ( 1)
00Cr12Ni5Mo5Co5Ti015 500～700 χ2Phase ,Ni 3 Ti ,R2Phase
= 20[ %Cr + 115 ×%Ni + 017 ×%Si + 0175 ×%Mn
M
Creqv
00Cr12Co12Mo5Ni415～610 500～525 R2Phase σ
, 2Phase
+ KM ×( %C + %N) + 016 ×%Mo + 115 ×%V
03Kh11N10M2T 500～550 Ni 3 Ti
+ 111 ×%W + 012 ×%Co + 012 ×%Cu + 119
03 Kh11N10T 600～650 Ni 3 Ti ,Fe 2 Ti
×%Ti2011 ×%Al ] ( 2)
412 　韧化机理
4 　马氏体时效不锈钢的强韧化机理 41211 　残留奥氏体的韧化
411 　强化机理残留奥氏体沿板条马氏体束之间或片状马氏体
41111 　板条马氏体相变强化周围呈薄片状分布 , 对改善材料的韧性十分有利 , 不
马氏体时效不锈钢经固溶处理后基体组织为高仅可阻止裂纹在马氏体板条间的扩展 ,还可以减缓板
密度位错的板条马氏体组织 ,相邻的马氏体板条位向条间密集排列时位错前端引起的应力集中 ,Thomas
[58 ]
相同 ,相互之间以小倾角晶界接触 , 板条的宽度为曾研究过 Fe2Cr2C 系马氏体钢 , 也观察到了断裂韧性

0102～311μm ,晶粒大小对板条的宽度和分布没有影与残留奥氏体膜有关 ,认为稳定的残留奥氏体薄膜存
响 ; 亚结构主要是位错、极少量的孪晶 ,位错密度可达在板条马氏体之间对韧性有利。
41212 　形变热处理提高韧性
11 12 - 2
10 ～10 cm ; 体心立方结构的马氏体可以变温或
等温过程中形成 ,马氏体的屈服强度约为 686MPa ,具形变热处理可有效改变马氏体时效不锈钢的组
有良好的塑性和韧性。织 ,细化钢的“有效晶粒尺寸”,碎化板条马氏体 ,提高
41112 　固溶强化位错密度并改变位错组态 ,对时效强化相的析出更为
合金元素以置换或间隙的形式溶入基体金属的有利 ,在提高强度的同时改善钢的韧性。
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5 　马氏体时效不锈钢的进展
[14 ]
1980MPa , KIC 达到 80MPa m 。
目前 ,马氏体时效不锈钢的生产采用了精料、
超 “十一五”
期间国家大力支持发展高性能、
高品质
高洁净度、超高均匀化以及全流程的细组织控制等先的超高强度不锈钢 , 进一步推动了该钢种的发展 , 例
进的生产工艺技术 , 使得该钢的性能有了较大的提如 ,高强不锈钢结构功能一体化材料高强度导磁不锈
高 ,并以很高强度、韧性、
不锈耐蚀性和经济可行的加钢的开发 ,大规格锻件 Φ400mm 超高强度不锈钢的研
工制造性能的完美配合而迅速成为高科技领域关键制等 ,都显示由于该钢种的发展在许多方面有了更广
设备的承力耐蚀 ( 或高温) 部件的首选材料。泛的用途。
近几年 ,钢铁研究总院和东北特殊钢公司采用 3t
真空感应炉 + 真空自耗炉冶炼获得一种新型的 6 　展望
Φ200mm ( 棒材 ) 、Rm ≥1900MPa 、KIC 达到 141MPa m 随着马氏体时效不锈钢的强度级别及综合性能
的耐海洋环境腐蚀的马氏体时效不锈钢 ,该钢是我国的提高 ,该钢在航空航天、海洋等领域的应用的前景
自主研制具有国际先进水平的高韧性超高强度不锈十分广阔 ,就目前该领域的发展状况提出几点展望 :
钢 ,其在航空航天技术、海洋技术、先进能源技术等方 1) 马氏体时效不锈钢的发展将采用精确控制与
面也有潜在的用途。与此同时 , 还开发了 R P012 ≥ 超高洁净度 ( [ H] + [O ] + [N ] + [ S] + [ P ] ≤40 ×10
- 6
1200MPa 耐海水腐蚀马氏体时效不锈钢 , 该钢具有良 (ppm) ) 的熔炼技术 , 全流程特细晶控制及成分均匀

好的耐海水环境腐蚀性及良好的工艺性能等。化控制技术 ,在大幅提高现有钢种性能的同时 , 研制
PH1328Mo 是一种具有高强度、
高硬度以及优良更高强度、高韧、
综合性能优良的马氏体时效不锈钢 ;
的抗腐蚀性能的马氏体时效不锈钢 ,所有沉淀硬化不 2) 以高效和循环利用资源为核心 ,以市场需求为
锈钢中强韧性配合最好的 , 可用于航天、核反应堆以向导 ,以新能源技术、航空航天和海洋技术为战略重
及石油化工等行业 ; 由于 PH1328Mo 是高级宇航优质点 ,发展资源节省型、环保型马氏体时效不锈钢 , 例
材料 ,主要用于制造第四代飞机、舰载飞机中温耐蚀如 ,以 Mn ,N 部分代替 Ni ,用 Ti 部分代 Co ,用 W 和 Ti
的重要承力构件 ,以及制作航天、航空飞机、火箭发动部分代 Mo 以及多元复合微合金化及低合金化等 ;
机框架、发射结构架 ,并在现有飞机机种 A380 客机上 3) 发展具有特殊性能的马氏体时效不锈钢 , 例
[59261 ]
使用。Martin 等人分别于 1997 年和 2003 年获得如 ,良好加工性、可塑性的钢种 , 超低温与耐中温钢
[10 ] [11 ]
了 Custom465 和 Custom475 的发明专利 , 其中种 ,耐较苛刻介质腐蚀与耐磨蚀钢种 , 以及高抗疲劳
Custom465 钢主要应用于导弹壳体等关键设备的主承性钢种等 ;
力耐蚀 ( 或中温) 部件的首选材料。 4) 高强不锈钢结构功能一体化材料是高强度不
近年来国外开发的 HSL180 钢是 Cr2Mo2Co2Fe 系锈钢发展的重要趋势之一 ,例如 ,高强度无磁不锈钢 ,
的马氏体不锈钢 , 其含有较高的 Co 和添加 Mo 试图沉淀硬化软磁不锈钢 ,低膨胀不锈钢 ,减振不锈钢等 ;
得到高强度和高韧性 , 与 4340 钢等低合金钢的具有 5) 在不断深化高强度不锈钢强韧化机理理论的
相同的抗拉强度 ( 大约为 1800MPa) ,HSL180 已被列为基础上 ,借助现代计算机技术与材料科学结合而出现
[61 ]
AMS5933 标准。的“材料微观结构设计”新型科研成果 , 精确设计 , 反
美国 QuesTek 新技术有限责任公司于 2002 年运复实践 ,逐步实现按制定性能设计高强度不锈钢的战
用计算机技术设计一种新型的二次硬化超高强度马略目标。
氏体不锈钢来代替现服役的 Aermet100 钢 , 经历了 4 致谢 : 感谢钢铁研究总院赵先存教授和宋为顺教授对本文提
年多的时间成功研制出 FerriumS53 , 该钢的强度可达出的宝贵意见。
参考文献
[ 1 ] 　于维乐 ,宋为顺 . 国外马氏体时效钢与高强度不锈钢 [J ] . 新金属材料 ,1974 , (10) :173 - 1751

　　　YU Wei2le ,SONG Wei2shun. Foreign maraging steel and high strength maraging stainless steel [J ] . New Metal Material ,1974 , (10) :173 - 1751
[ 2 ] 　Sadoski E P. Development of a stainless maraging steel [J ] . Metals Engineering Quarterly , 1972 ,2 (12) :47 - 55.
[ 3 ] 　魏振宇 . 马氏体时效不锈钢 [J ] . 新金属材料 ,1972 , (4) :22 - 301
　　　WEI Zhen2yu. Maraging stainless steel [J ] . New Metal Material ,1972 , (4) :22 - 301
[ 4 ] 　赵振业 ,李　志 ,刘天琦 ,等 . 探索新强韧化机制开拓超高强度钢新领域 [J ] . 中国工程科学 ,2003 ,5 (9) :39 - 42 .
Menu
　　　ZHAO Zhen2ye , LI Zhi , LIU Tian2qi ,et al . Study of existing problems and solution in vehicle monitoring system[J ] . Engineering Science ,2003 ,5 (9) :39 - 421
[ 5 ] 　宋为顺 ,赵先存 . 高强度不锈钢的进展和展望 [ G] . 北京 : 冶金部钢铁研究总院合金部 ,1992 :209 - 2151
[ 6 ] 　Crawfird W M ,Contractro G P. The effects of strengthening Be and Ti in maraging stainless[J ] . J IPI ,1969 ,207 (12) :1642 - 1645.
[ 7 ] 　陆世英 . 我国不锈钢研究与应用的回顾和进步发展的展望 [J ] . 钢铁研究学报 ,1966 ,8 (2) :64 - 68.
　　　LU Shi2ying. Expectation of develop and retrospect of research and application stainless steel in china[J ] . J Rron & Steel Research ,1966 ,8 (2) :64 - 681
[ 8 ] 　Floreen S. Hardening behavior of ternary alloys based on iron218 %nickel [J ] . Trans ASM ,1964 ,57 (1) :3 - 10.
[ 9 ] 　Contractor G P , Schempp E G, et al . A study of carbide composition and microstructure during the quenching and tempering of 5 % Cr2Mo2V steel [J ] . Trans
ASM ,1961 ,54 :208 - 219.
[ 10 ] 　Martin Jame W , et al . High2strength ,notch2ductile precipitation2hardening stainless steel alloy :US ,5681528[ P] . 1997 - 10 - 28.
[ 11 ] 　Martin Jame W , et al . Ultra2high strength precipitation2hardenable stainless steel and strip made thereform :US , 6630103[ P] . 2003 - 10 - 07.
耐热材料和高强度钢的研究动向 [J ] . 钢铁 ,1981 ,16 (4) ,66 - 711
[ 12 ] 　魏振宇 . 国外不锈钢、
　　　Wei Zhen2yu . Trends in research works on stainless sreels ,heat resistant materials and ultrahigh strength steels abroad[J ] . Iron and Steel ,1981 ,16 (4) ,66 - 711
[ 13 ] 　王正樵 ,吴幼林 . 不锈钢 [M] . 北京 : 化学工业出版社 ,1991 :268 - 275.
[ 14 ] 　Kuehmann Charles J . Computational Design of High2Strength , High2Toughness Stainless Steel for Carrier2Based Aircraft [ C] . United States : Airan Perez ,
Navy & Industry R&D Partnership Conference , 2004.
[ 15 ] 　陆世英 ,张廷凯 ,等 . 不锈钢 [M] . 北京 : 原子能出版社 ,1995 :19 - 59.
[ 16 ] 　刘振宝 ,宋为顺 ,杨志勇 ,等 . 时效对一种超高强马氏体时效不锈钢微观组织与力学性能的影响 [J ] . 材料热处理学报 ,2005 ,26 (4) :52 - 55.
　　　LIU Zhen2bao ,SONG Wei2shun , YANG Zhi2yong ,et al . Effect of aging on microstructure and mechanical properties of a ultra2high strength maraging stainless
steel [J ] . Trans Mater Heat Treat , 2005 ,26 (4) :52 - 551
[ 17 ] 　刘振宝 ,杨志勇 ,等 . 固溶处理对新型马氏体时效不锈钢力学性能影响研究 [J ] . 钢铁 ,2007 ,42 (3) :47 - 51.
　　　LIU Zhen2bao , YANG Zhi2yong ,et al . The effect of solution treatment on mechanical properties of a new type maraging stainless steel [J ] . Iron and Steel ,2007 ,
42 (3) :47 - 511
[ 18 ] 　Robert Brown. New Stainless Steel for Instruments Combines High Strength and Toughness[ C] . PA :Carpenter Technology Corporation Reading , 2000.
[ 19 ] 　Jepson K S , Stubbington C A. Recent advances in metallic aerospace materials[J ] . Metals and Materials , 1969 , (3) :115 - 126.
[ 20 ] 　Spiridonov V B ,Fridman V S , Yu L Rodionov ,et al . Structural changes during aging of maraging steel 03 Kh11N10M2T[J ] . Metallovedenie i Termicheskaya
Obrabotka Metallov , 1974 , (10) :28 - 321
[ 21 ] 　Bratuhin A G. Ways to increase the reliability of welded joints of high2strength steels in a new generation of aircraft [J ] . Metal Science and Heat Treatment ,
1997 ,39 (3 - 4) :123 - 1251
[ 22 ] 　Voznesenskaya N M , Kablov E N , Petrakov A F ,et al . High2strength corrosion2resistant steels of the austenitic2martensitic class[J ] . Metal Science and Heat
Treatment ,2002 ,44 (7 - 8) :300 - 3031
[ 23 ] 　Kostina M V ,et al . Effect of plastic deformation and hest treatment on the structure and hardening of nitrogen2bearing steel 0 Kh16AN4B[J ] . Metal Science
and Heat Treatment ,2001 ,43 (7 - 8) :259 - 2621
[ 24 ] 　Tsukrov E V ,Bannykh O A. Structure and properties of welded joints with steel EP767VD[J ] . Metallovedenie i Termicheskaya Obrabotka Metallov ,1973 ,
(6) :23 - 261
ina1 V P. Effect of heat treatment mode on the microstructure and fracture behavior of maraging steels 03 Kh11N10M2T2VD and 03 Kh11N10M2T22VD[J ] .
[ 25 ] 　Il ’
Metal Science and Heat Treatment , 2002 , 44 (3 - 4) :116 - 123.
[ 26 ] 　Rundkvist N A , Grschev S V. Effect of alloying and of the austenizing temperature on the phase composition and properties of corrosion2resistant maraging
steels[J ] . Metallovedenie i Termicheskaya Obrabotka Metallov ,1989 , (4) :8 - 14.
[ 27 ] 　Asaysma Yuiteru , Kazuaki Higuchi . High strength cobalt2free maraging steel :US ,4579590[ P] . 1986204201.
[ 28 ] 　Korchemkin A E , Kondratov A M , Yu I Lyapin. Use of maraging steels for hot2work dies[J ] . Metallovedenie i Termicheskaya Obrabotka Metallov , 1976 , (9) :
44 - 471
[ 29 ] 　Shlyamnev A P ,Sorokina N A. Phase composition and properties of maraging steels alloyed with molybdenum[J ] . Metallovedenie i Termicheskaya Obrabotka
Metallov , 1975 , (11) :63 - 651
[ 30 ] 　Beltyukov A A ,Stepanov V P , Shein A S. Effect of carbon on the properties of corrosion2resistant maraging steels without titanium[J ] . Metallovedenie i
Termicheskaya Obrabotka Metallov , 1989 , (11) :24 - 261
[ 31 ] 　Liu Ping ,Stigenberg A H ,Nilsson J O. Quasicrystalline and crystalline precipitation during isothermal tempering in a 12Cr29Ni24Mo maraging stainless steel
[J ] . Acta Mater ,1995 ,43 (7) :2881.
[ 32 ] 　Hiroyuki Ezawa. Golf culb head :US ,6334817[ P] . 2002.
[ 33 ] 　Young G Kim ,Soon H Hong ,Jin I Suk. Maraging stainless steel having high strength ,high toughness and high corrosion resistance and it ’s manufacturing
process :US ,5116570[ P] . 1992205226.
[ 34 ] 　王　为 ,陈复民 ,李国俊 ,等 . 新型超高强度马氏体时休不锈钢组织及性能 [J ] . 钢铁 ,1989 ,24 (2) :53 - 57.
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[ 35 ] 　姜　越 ,尹钟大 ,朱景川 ,等 . 马氏体时效不锈钢的发展现状 [J ] . 特殊钢 ,2003 ,24 (3) :1 - 5.

[ 36 ] 　° g g g g g g ≤ g 、g g g g g g . 耐蚀性 gg g2 g g g 合金 [ N] . 日本公开特许公报 ,特开平 92143626 ,1997.
[ 37 ] 　Bendel Lee P (Lebanon NJ) , Sardel A ,Timothy(Somerset NJ) . Nickl titanium martensitic steel for surgical needles : US , 5000912[ P] . 1991203219.
[ 38 ] 　Bendel Lee P , Sardelis Timothy ,Trozzo Lawrence P ,et al . Means for predicting performance of stainless steel alloy for use with surgical needles :US , 5651843
[ P] . 1997207229.
[ 39 ] 　Zykova R A , Ya I Spektor , Yu M Politaev. Effect of titanium on the structure and properties of maraging tool steel 05 Kh12N6D2SGTMF[J ] . Metallovedenie i
Termicheskaya Obrabotka Metallov , 1986 , (9) :48 - 511
[ 40 ] 　Apiridonov V B ,Fridman V S ,Rodionov Yu L , et al . Structural changes during aging of maraging steel 03 Kh11N10M2T[J ] . Metallovedenie i Termicheskaya
[ 41 ] 　Seetharman V ,Sundararaman M , Krishnan R. Precipitation hardening in a PH 1328 Mo stainless steel [J ] . Materials Science and Engineering ,1981 ,47 :1 - 11.
[ 42 ] 　Garrison W M ,Brooks J A. The thermal and mechanical stability of aystenite in low carbon martensitic steel PH1328[J ] . Materials Scinece and Engineering A ,
1991 ,149 :65 - 721
[ 43 ] 　Voznesenskaya N M , Kablov E N ,Petrakov A F ,et al . High2strength corrosion2resistant steels of the austenitic2martensitic class[J ] . Metal Science and Heat
Treatment ,2002 , 44 (7 - 8) : 300 - 3041
[ 44 ] 　梁剑雄 ,宋为顺 ,赵先存 . σ012 ≥880MPa 耐海水腐蚀铁素体时效不锈钢的研究 [J ] . 钢铁 ,2001 ,36 (Suppl) :149 - 153.
[ 45 ] 　Peters D T ,Cupp R. The kinetics of aging reactions in 18 Pct Ni maraging steel [J ] . Trans AIME ,1966 ,236 (10) :1420 - 1428.
[ 46 ] 　Miner R E ,Janckson J K, Gibbons D F. Internal friction in 18 pct Ni maraging steel [J ] . Trans AIME ,1966 ,236 (11) :1561 - 1565.
[ 47 ] 　Banerjee B R ,et al . Role of cobalt in the marage2type alloy matix[J ] . Metal Science Journal , 1968 , (2) :76 - 801
[ 48 ] 　Abson L E ,Whiteman J A. Precipitation from iron2base alloys containing cobalt [J ] . Journal of the Iron and Steel Institute , 1970 , 208 :594 - 6001
[ 49 ] 　Alekseeva L E , Koritskaya G I ,Talalakina E I. Stabilization of small deformations of maraging steels by steels relaxation[J ] . Metallovedenie i Termicheskaya
[ 50 ] 　Grachev S V ,Sheyn A S ,Pavlova S V ,et al . Infl2uence of quenching programmes on phase compostistion and effectiveness of subsequent aging of maraging
steels[J ] . Phys Met Metall , 1988 , 66 (1) :151 - 1571
[ 51 ] 　Lapin P G, Gulyaev A P , Ul ’yanin E A. The influence of the alloying elements on the properties of stainless maraging steels at low temperature [ J ] .
Metallovednie i Termicheskaya Obrabotka Metallov , 1972 , (2) :47 - 521
[ 52 ] 　　浸浩一郎 . 钢铁技术の流れ g ƒ g g g 钢 [ R] . 东京 : 日本钢铁协会 ,2002.
[ 53 ] 　崔　　 . 钢铁材料及有色金属材料 [M] . 北京 : 机械工业出版社 ,1992 :639 - 641.
[ 54 ] 　Schaeffler Anton L. Constitution diagram for stainless steel weld metal [J ] . Metal Progress , 1949 ,56 :680 - 685.
[ 55 ] 　Potak Ya M ,Sagalevich E A. Phase diagram of wrought stainless steels[J ] . Metallovedenie i Termicheskaya Obrabotka Metallov , 1971 , (9) :12 - 161
[ 56 ] 　Bityukov S M , Grachev S V ,Rundkvist N A. Peculiarities of formation and decomposition of ferrite in stainless maraging steels[J ] . Phys Met Metall ,1984 ,58 :
151 - 156.
[ 57 ] 　Vzvigintse N ,Mogutnov B M , Khadyyev M S ,et al . Features of microstructure formation in stainless Fe2Cr2Ni2Ti maraging steels[J ] . Phys Met Metall ,1985 ,
59 :116 - 123.
[ 58 ] 　Thomas P M , Gruzleski J E. Communication threshold hydrogen for pore formation during the solidfication of aluminum alloy[J ] . Metall Trans B ,1978 ,9 (1) :
139 - 141.
[ 59 ] 　ASTM. Standard Specification for Age2Hardening Stainless Steel Forgings[ S] . A705ΠA705295.
[ 60 ] 　中　真一 . 降著装置用材料 [J ] . 特殊钢 ,2006 , 55 (6) :18 - 19.
[ 61 ] 　二宫崇 . 航空飞机和材料 [J ] . 特殊钢 ,2006 ,55 (6) :9 - 13.
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　第 43 卷　第 3 期钢铁　Vol. 43 , No . 3
　2 0 0 8 年 3 月 Iron and Steel March 　2008
马氏体时效不锈钢时效析出相及位向关系的研究
陈嘉砚1 , 　刘　江2 , 　杨卓越1 , 　张永权1
( 1. 中国钢研科技集团公司结构材料研究所 , 北京 100081 ; 　2. 中国钢研科技集团公司科技信息室 , 北京 100081)
摘　要 : 系统研究了 Custo m 465 钢 510 ℃时效析出相及相关的位向关系 , 结果表明 : Ni3 Ti 是钢的主要时效析出

相 ,析出相为杆状 ,杆的长度方向与马氏体基体的 [ 111 ] M 方向一致 ; (011) M / / (0001) Ni3 Ti 、
[ 111 ] M / / [ 1120 ] Ni3 Ti 是马
氏体和 Ni3 Ti 金属间化合物确切的位向关系 ,这种位向关系使 Ni3 Ti 在马氏体基体内出现 12 种可能的亚型。
关键词 : 析出相 ; Ni 3 Ti ; 时效 ; 马氏体时效不锈钢
Research on Precipitates and Relationship With

Martensite of Maraging Stainless Steel
C H EN J ia2yan1 , 　L IU J iang2 , 　YAN G Zhuo2yue1 , 　ZHAN G Yo ng2quan1
( 1. Instit ute of St ruct ure Materials , Steel Research Technology Gro up Corporation of China ,
Beijing 100081 , China ; 　2. Depart ment of Science and Technology Information , Steel
Research Technology Gro up Corporation of China , Beijing 100081 , China)
Abstract : The aging p recipitates and t he relationship s wit h martensite of Custom 465 were researched. The result s
show t hat Ni 3 Ti is t he major p recipitate in t he steel. The p recipitates take t he fo rm of poles wit h t he lo ngit udinal ax2
is parallel to [ 111 ] M . The relatio nship s between t he p recipitates and t he martensite are ( 011 ) M / / ( 0001 ) Ni3 Ti
[ 111 ] M / / [ 1120 ] Ni3 Ti . These relationship s make Ni3 Ti p recipitate in 12 kinds of po ssible variant s.
Key words : p recipitates ; Ni3 Ti ; aging ; maraging stainless steel
　　众所周知 , 通过时效析出可以使 Co 、 Mo 和 Ti 统的 P H 不锈钢强度高出 20 %以上 ,并具有优良的缺

合金化的低碳马氏体钢最终获得超高的强度 , 同时口拉伸强度和断裂韧性。过时效条件下 ( 540 ℃时
保持良好的韧性和塑性。如 20 世纪 60 年代初开发效) ,与传统的 P H 不锈钢 ( 如 Custom 455 和 1328 不
的 18 %Ni 马氏体时效钢 ,通过时效在韧性的马氏体锈钢) 相比 ,仍具有优良的强度、韧性和 SCC 抗力组
基体内析出 Ni3 Mo 、 Ni3 Ti 和 Fe2 Mo 等金属间化合合。
物 ,最终可以使强度达到 2 000 M Pa 以上。目前已 Custo m 465 钢的化学成分与传统高强不锈钢
经开发含 Co 的 C250 、C300 级和无 Co 的 T2250 、存在极大的差异 ,其强化析出相及相应的强化机制
T2300级马氏体时效钢已获得广泛的应用 , 尤其是必然有较大的差异 ,因此研究时效析出相的类型、相
在航天、航空、军事和核工业领域。但传统的 18 % 应的晶体结构以及与基体的位向和匹配关系 , 对探
Ni 马氏体时效钢的抗蚀性很差 ,限制了该类型钢在索 Custo m 465 钢析出强化机制是十分重要的。为
某些领域的应用。另一方面 , 传统沉淀硬化不锈钢此笔者借助透射电子显微镜 ( T EM ) 对双真空冶炼
虽然具有足够的腐蚀抗力 , 但主要依靠 Cu 、碳化物的 Custo m 465 钢的时效析出相进行了分析 ,得到了
或有序相强化 ,因此强度无法与传统的马氏体时效析出相的特性、晶体学特征等重要结果。
钢相比 ,如 P H1328Mo 沉淀硬化不锈钢 ,通过 B2 结
构β2NiAl 有序相和 M2 C 碳化物强化 [ 1 ] , 强度仅能
1 　实验材料与实验方法
达到 1 300 ～ 1 600 M Pa , 而依靠 Cu 沉淀析出的用 350 kg 真空感应炉冶炼后浇注成 2 支电极
P H1525 、
Custom 455 等的强度则更低。虽然也有添棒 ,电极棒经真空自耗重熔。钢锭的化学成分 ( 质量
加 Ti 、Nb 等强化的不锈钢 , 但强度仍偏低。美国分数 , %) 为 : C 0. 004 , Si 0. 026 , Mn 0. 013 , S
Carpenter 公司开发的 Custom 465 马氏体时效不锈 01 004 4 , P 0. 004 , Cr 11. 72 , Ni 10. 83 , Mo 1. 05 ,
钢 ,510 ℃时效条件下抗拉强度达到1 724 MPa ,比传 Ti 1. 68 , Al 0. 083 。重熔的钢锭经过1 200 ℃×8 h
作者简介 : 陈嘉砚 (19692) , 男 , 博士 , 高级工程师 ; 　　E2mail : chenjiayan @nercast . co m ; 　　修订日期 : 2007207205

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・8 2 ・钢　铁第 43 卷
均质化处理后 , 锻造成 40 mm ×90 mm ×200 mm 980 ℃×1 h 固溶、

冷轧变形 70 % ,随后在 510 ℃保
的板坯。板坯经过热轧 , 并经 980 ℃×1 h 固溶处温 24 h 后得到的 T EM 照片。从图 1 ( a ) 的明场像
理后冷轧成 0. 3 mm 和 1. 0 mm 厚的板材 , 冷轧变 (B F) 可以看出马氏体基体内存在极细小的弥散析
形量分别控制在约 30 %和 70 % 。在重新固溶和冷出相 ,在电子束入射方向接近平行于马氏体的晶带
轧的板材上切取 12 mm ×16 mm 的薄片试样。根轴 [ 100 ] M 时 ,可观察到漫射条纹 ( 图 1 ( d) ) , 说明析
据李楠研究得出的“510 ℃×4 h 时效后综合力学性出相的存在 ,适当倾转试样后得到对称的析出相衍
能最佳” 的结果 [ 2 ] ,并考虑到透射电镜电子衍射要求射花样 ( 图 1 ( b) ) , 经分析确认析出相为 Ni 3 Ti 。随
析出相衍射具有足够的强度 ,笔者采用 510 ℃×24 后不同低指数马氏体晶带轴的电子衍射也证实析出
h 过时效以便使析出物充分长大。时效后的 12 mm 相为 Ni 3 Ti 。
×16 mm 的薄片试样用手工减薄至 0. 05 mm 后 ,用 2. 2 　Ni3 Ti 析出相亚型及其与基体的位向关系
电解双喷在 - 20 ℃以下减薄 ,电解液为 5 %的高氯 Ni3 Ti 金属间化合物是 Ti 强化的时效合金中
酸 + 95 %乙醇溶液 ,制成的薄膜样品用 H2800 透射主要强化析出相之一 [ 3～5 ] , 在 Fe2Ni2Mn2 Ti 、Fe2Cr2
电镜观察 ,操作电压为 200 kV 。 Ni2W2 Ti 和 Fe2Mo2 Ti ( T2200 、T2250 、T2300) 钢中均
发现 Ni 3 Ti 金属间化合物是主要时效析出强化相 ,
2 　实验结果与分析 Ni3 Ti 与马氏体基体之间的位向关系遵从密排面/
2. 1 　时效析出相的确认密排面、密排方向之间分别平行 , 即 : { 110 } M / /
图 1 是具有上述化学成分的 Custo m 465 钢经 {0001} Ni3 Ti 、< 111 > M / / < 1120 > Ni3 Ti 。
(a) 明场像 ; 　(b) (a) 的选区电子衍射花样 ; 　(c) 用 (2022) Ni3 Ti 得到的中心暗场像 ; 　(d) (c) 的选区电子衍射花样 ; 　(e) 衍射花样指数化
图 1 　经冷轧变形 70 %、
510 ℃保温 24 h 试样的 TEM 照片
Fig. 1 　Diagrams of the specimen cold rolled with 70 % reduction rate ,and aged at 510 ℃ for 24 h , TEM
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第3期陈嘉砚等 : 马氏体时效不锈钢时效析出相及位向关系的研究・8 3 ・
　　上述取向关系被称为 Ⅰ类取向关系 , 这类取向 [ 1 11 ] M 晶向 , 从而证明图 2 ( b ) 符合实际情况。因

关系的密排面相互平行已在图 1 中得到证实。按照此马氏体与 Ni3 Ti 析出相之间确切的位向关系为第
密排面、
密排方向分别平行的取向关系 ,根据体心立 Ⅰ类位向关系。
方马氏体晶体的对称性 , 马氏体基体内存在 Ni3 Ti 用与 [ 111 ] M 和 [ 1 11 ] M 平行的 Ni3 Ti (2240) 衍射
析出相的 12 种可能的亚型。但从图 1 ( b) 所示的马斑 ( 图 3 ( b ) 中箭头所指处 ) 得到 Ni3 Ti 亚型 1 和亚
氏体与 Ni3 Ti 析出相复合电子衍射谱可以看出 : 马型 2 的中心暗场像 ( 图 3 ( c ) 和 ( d ) ) , 可以得到一些
氏体与 Ni3 Ti 析出相之间存在另一种位向关系 ,即 : 重要的信息 : 首先 , Ni3 Ti 金属间化合物均为杆状 ;
{110} M / / {0001} Ni3 Ti 、< 001 > M / / < 1210 > Ni3 Ti 。这其次 ,杆的长度方向分别与马氏体基体的 [ 111 ] M 和
与 Suk 在 Fe210Cr210Ni22W 钢中得到的结果吻 [ 1 11 ] M 方向对中 ( 图 3 ( c ) 、( d) 中箭头所指方向 ) 。
合 [ 5 ] ,这类取向关系称为 Ⅱ类取向关系 ,但大多数文与图 1 ( c ) 的暗场像相比 , 图 3 ( c ) 、( d ) 所示的杆状
献 ,如 Vasudevan 报导的结果均为第 Ⅰ类位向关 Ni3 Ti 的长度较长 ,而且从所有低指数晶带轴观察 ,
系 [ 3 ] ,由于 Ⅰ、Ⅱ两类取向关系中 ,密排面均平行 ,即 Ni3 Ti 杆的长度最长 , 说明 Ni3 Ti 沿着马氏体基体
{110} M / / {0001} Ni3 Ti , 但密排方向不同。为了判定的{111} M 方向长大。
上述马氏体基体/ Ni3 Ti 析出相之间密排方向的真为进一步证实 Ni3 Ti 析出相与马氏体基体的位
伪 , 最好的办法是观察既含有 { 100 } M , 又含有向关系 ,选取入射电子束与 [ 011 ] M 晶带轴相垂直的
{111} M 的电子衍射花样 ,即只有入射电子束平行于 [ 211 ] M 进行观察 ( 图 4 ) ,可以看出 : 因 Ni3 Ti 亚型 2
[ 011 ] M 晶带轴情况下能满足所观察的条件。若仅不满足 Bragg 衍射条件 ,复合衍射谱 ( 图 4 ( b) ) 中仅
考虑 Ni3 Ti 析出相的一个亚型 , 按照上述两种位向存在 Ni 3 Ti 亚型 1 的衍射斑 , 再次证明 Ni3 Ti 与马
关系显然应得到图 2 所示的两种不同的衍射花样。氏体基体之间存在第 Ⅰ类位向关系。
从仿真的衍射花样可以看出 : Ⅰ、Ⅱ两类取向关系的上述从 [ 011 ] M 和 [ 211 ] M 两个晶带轴观察到马
位相差约 5° 15′。氏体与 Ni3 Ti 析出相之间确切的位向关系为第 Ⅰ类
图 3 是与图 1 同一试样得到的 T EM 照片 ,图 3 位向关系 ,图 3 ( b) 的衍射分析证实第 Ⅱ类取向关系
( b) 所示的衍射谱证实电子束接近平行于马氏体的并不存在 , 根据图 2 的仿真分析 , [ 100 ] M 与
[ 011 ] M 晶带轴 ,滤除掉以马氏体基体衍射束作为入 [ 1210 ] Ni3 Ti 之间相差 5°
15′, 因此 , 图 1 ( b ) 得到对称
射束进行的二次衍射 , 一次衍射为 Ni3 Ti 金属间化 Ni3 Ti 析出相衍射情况下 , 马氏体基体斑点不对称 ;
合物 2 个亚型的复合衍射 ,衍射花样 ( 图 3 ( b) ) 及相而马氏体基体斑点对称情况下 , 观察不到 Ni3 Ti 析
应的指数化 ( 图 3 ( e) ) 证实 Ni3 Ti 亚型 1 的 [ 1120 ] 方出相的斑点 ,仅能观察到漫散线 ,这些证据充分说明
向平行于 [ 1 1 1 ]M ; 亚型 2 的 [ 1 1 2 0 ] 方向平行于 [ 1210 ] Ni3 Ti 晶带轴与 [ 100 ] M 晶带轴互不平行 ,因马
(a) < 111 > M / / < 1120 > Ni3 Ti ; 　( b) < 001 > M / / < 1210 > Ni3 Ti
图 2 　根据不同的取向关系模拟的[ 011] M 电子衍射谱

Fig. 2 　Simulated electronic diffraction diagrams of [ 011] M according to different relationships
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・8 4 ・钢　铁第 43 卷
(a) 明场像 ; 　( b) (a) 的选区电子衍射花样 ; 　(c) 用 (2240) Ni3 Ti 得到的 Ni 3 Ti 亚型 1 的中心暗场像 ;
(d) 用 (2240) Ni3 Ti 得到的 Ni 3 Ti 亚型 2 的中心暗场像 ; 　(e) 衍射花样指数化
图 3 　经冷轧变形 70 %、
Fig. 3 　Diagrams of the specimen cold rolled with 30 % reduction rate aged at 510 ℃ for 24 h , TEM
氏体的杆状倒易阵与薄膜垂直 ( 倒易杆平行于
[ 100 ] M 晶带轴 ) , 容易与 Ewald 球相截 , 因此在
3 　结论
[ 1210 ] Ni3 Ti 晶带轴与入射电子束基本平行、得到 ( 1) Custo m 465 钢经过 510 ℃时效后 , Ni3 Ti
Ni3 Ti 析出相对称衍射谱的情况下 , 仍有马氏体的是主要的时效析出相。
倒易杆与 Ewald 球相截 ,最终得到图 1 ( b) 所示的不 ( 2) 从 [ 011 ] M 和 [ 211 ] M 晶带轴电子衍射花样
对称 [ 100 ] M 晶带轴衍射花样 ; 相反 , 杆状 Ni3 Ti 析证明 : ( 011 ) M / / ( 0001 ) Ni3 Ti 、[ 111 ] M / / [ 1120 ] Ni3 Ti 及
出相倒易点阵形状是饼状的 [6 ]
, 在入射电子束与相关的位向关系是马氏体和 Ni 3 Ti 金属间化合物确
[ 100 ] M 晶带轴基本平行时 , 饼形的 Ni 3 Ti 与 Ewald 切的位向关系 , 这种位向关系使 Ni3 Ti 在马氏体基
球相截得到漫散条纹 ( 图 1 ( d) ) 。体内出现 12 种可能的亚型。
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第3期陈嘉砚等 : 马氏体时效不锈钢时效析出相及位向关系的研究・8 5 ・
(a) 明场像 ; 　( b) (a) 的选区电子衍射花样 ; 　(c) 用 (2240) Ni3 Ti 得到的 Ni 3 Ti 亚型 1 的中心暗场像 ; 　(d) 衍射花样指数化
图 4 　经冷轧变形 30 %、
Fig. 4 　Diagrams of the specimen cold rolled with 30 %reduction rate aged at 510 ℃ for 24 h , TEM
　　( 3) 电子衍射和暗场分析表明 ,Ni3 Ti 析出相为 Steels [ J ] . Metallurgical and Materials Transactions , 1990 ,
21A (10) : 2655.
杆状 ,杆的长度方向与马氏体基体的 [ 111 ] M 方向一
[ 4 ] 　H E Y , YAN G K , SHA W. Micro st ruct ure and Mechanical
致。 Properties of a 2 000 MPa Grade Co2Free Maraging Steel [J ] .
Metallurgical and Materials Transactions , 2005 , 36A ( 9 ) :
参考文献 :
2273.
[ 1 ] 　Ping D H , Ohnuma M , Hirakawa Y ,et al . Micro st ruct ural E2 [ 5 ] 　Suk J I , Hong S H , Nam S W. Crystallograp hic Orientation
volution in 13Cr28Ni221 5Mo22Al Martensitic Precipitation2 Relationship s Among Η2Ni 3 Ti Precipitate , Reverted Austen2
Hardened Stainless Steel [J ] . Materials Science and Engineer2 ite , and Martensitic Mat rix in Fe210Cr210Ni22W Maraging
ing ,2005 , 394A :285. Steel [ J ] . Metallurgical and Materials Transactions , 2005 ,
[ 2 ] 　李　楠 ,陈嘉砚 ,龙晋明 . Custom 465 马氏体时效不锈钢的强 24A (12) : 2643.
韧化特征及工艺优化 [J ] . 物理测试 ,2005 ,23 (6) :4. [ 6 ] 　刘文西 ,黄孝瑛 ,陈玉如 . 材料结构电子显微分析 [ M ] . 天津 : 天
[ 3 ] 　Vasudevan V K , Kim S J , Wayman C M. Precipitation Reac2 津大学出版社 ,1989.
tions and St rengt hing Behavior in 18 Wt Pct Nickel Maraging
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第 12 卷　第 1 期材　料　科　学　与　工　艺 Vol112 No 11
　　
2 0 0 4年2月 MA TER IAL S SCIENCE & TECHNOLO GY Feb. , 2004
　　　　　　
无钴马氏体时效钢的研究现状
姜　越 , 尹钟大
( 哈尔滨工业大学材料科学与工程学院 ,黑龙江哈尔滨 150001 , E2mail : jiangyue @hit . edu. cn)
摘　要 : 综述了无钴马氏体时效钢的发展和研究现状 ,阐述了无钴马氏体时效钢的时效组织结构及强化机
制 ,分析了合金元素在马氏体时效钢中的作用 ,并提出了无钴马氏体时效钢未来的发展趋势 .
关键词 : 无钴马氏体时效钢 ; 力学性能 ; 析出物 ; 强化机制
中图分类号 : T G142 文献标识码 : A 文章编号 : 1005 - 0299 ( 2004) 01 - 0108 - 05
Present status of cobalt2free maraging steel
J IAN G Yue , YIN Zhong2da
( School of Materials Science and Engineering ,Harbin Institute of Technology , Harbin 150001 ,China ,E2mail : jiangyue @hit. edu. cn)
Abstract : The develop ment and research stat us of cobalt2f ree maraging steel was reviewed wit h illumination
of aging microst ruct ure and st rengt hening mechanism. The effect of t he alloy element s on t he maraging
steel were analyzed. And t he develop ment tendency of cobalt2f ree maraging steel is forecast as well.
Key words : cobalt2f ree maraging steel ; mechanical property ; precipitation ; st rengt hening mechanism
　　马氏体时效钢是 60 年代由国际镍公司 ( IN2 塑性和韧性是一个重要的研究方向 . 本文将从无

CO) 开发的新型超高强度钢[ 1 ] , 其在具有高强度钴马氏体时效钢的成分、
组织结构、
性能、强化机
和高韧性的同时 ,亦具有良好的冷、
热加工性能和制等多方面反映无钴马氏体时效钢目前的研究状
良好的可焊性 ,因此广泛应用于航空、
航天等尖端况.
领域 [ 2 ] . 目前广泛应用的是 18Ni 型马氏体时效
钢 ,其强度为 1 400～2 500 M Pa [ 2 ,3 ] ,主要的合金 1 　无钴马氏体时效钢的开发、
成分
元素为 Ni 、
Co 、
Mo 、Ti 等 . 随着强度级别的提高 , 与力学性能
马氏体时效钢中合金元素总量超过 40 % , 其中
　　无钴马氏体时效钢的研制始于美国 , 国际镍
Co 、
Ni 含量之和在 26 %～ 30 %. 这使得马氏体时
公司 ( INCO) 与 Teledyne Vasco 公司合作 ,开发了
效钢的价格昂贵 . 尤其近 20 年来 , 作为战略元素
T - 250 无钴马氏体时效钢 [ 4 ] . 与 18Ni 马氏体时
Co 的资源短缺 ,这使马氏体时效钢的生产成本大
效钢相比较 , T - 250 成分中完全去掉了 Co ,降低
幅度增加 ,其应用和发展受到了极大的限制 . 因此
了 Mo 的含量 ,增加了 Ti 的含量 . 通过调整 Ti 含
马氏体时效钢研究的一个重要方向就是发展无钴
量 ,进一步开发了 T - 200 和 T - 300 无钴马氏体
马氏体时效钢 . 目前国外已研究和开发出多种无
时效钢 ,其性能相当于相应级别的含钴 18Ni 马氏
钴马氏体时效钢 , 并成功应用于关键部件[ 4 ] . 研
体时效钢 . 与此同时 ,日本、韩国、
印度等国也相继
究较多的是 T - 200 、T - 250 、T - 300 型 ( 前缀 T
开发了无钴含铬、无钴钼含钨、低镍无钴马氏体时
表示 Ti 强化钢) 无钴马氏体时效钢 , 但钛强化的 [ 5～7 ]
效钢 . 我国在无钴马氏体时效钢方面也进行
无钴马氏体时效钢在强度达到较高水平时 ,塑性、了一些研究 [ 8～11 ] .
韧性急剧下降 [ 2 ] . 如何提高无钴马氏体时效钢的上述无钴马氏体时效钢的强度与含钴马氏体
收稿日期 : 2002 - 05 - 13. 时效钢相当 ,有的甚至超过含钴马氏体时效钢 ,而
作者简介 : 姜　越 (1963 - ) ,男 ,高级工程师 ,博士生 ; 塑、韧性各异 . 表 1 、表 2 分别给出了一些典型无
尹中大 (1937 - ) ,男 ,教授 ,博士生导师 . 钴马氏体时效钢的化学成分和力学性能 .
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第1期姜　越 ,等 : 无钴马氏体时效钢的研究现状・1 0 9 ・
表 1 　无钴马氏体时效钢的成分( 质量分数/ %) [ 4～12]

材　料 Ni Mo Ti Al Cr 其他产地
T - 250 18150 3100 1140 0110 - - 美国
T - 300 18150 4100 1185 0110 - - 美国
W - 250 19100 - 1120 0110 - 415W 韩国
14Ni - 3Cr - 3Mo - 115 Ti 14131 3124 1152 - 2188 - 日本

12Ni - 312Cr - 511Mo - 1 Ti 12100 5110 1100 0110 3120 - 印度
Fe - 15Ni - 6Mo - 4Cu - 1 Ti 15100 6100 1100 410 中国
Fe - 8Ni - 3Mn - 5Mo 7180 4180 0150 0120 01005Ce 中国
Fe - 18Ni - 4Mo - 1 17 Ti 18100 4100 1170 中国
表 2 　无钴马氏体时效钢的力学性能 [ 4～12]
材　料 σ/b MPa σ/s MPa δ/ % ψ/ % HRC K /Ⅰ(CMPa・m1/ 2)
T - 250 1817 1775 1015 5611 5018 106
T - 300 2100 2050 10 54 5316 76
W - 250 1800 1780 9 45
14Ni - 3Cr - 3Mo - 115 Ti 1820 1750 1315 6510 5110 130
12Ni - 312Cr - 511Mo - 1 Ti 1700 1660 10 102
Fe - 15Ni - 6Mo - 4Cu - Ti 1893 1785 915 46 5215
Fe - 8Ni - 3Mn - 5Mo 1545 1485 14 4012
Fe - 18Ni - 4Mo - 117 Ti 2000 9 70
18Ni250 ( 含钴钢) 1830 1710 1216 7018 5110 137
的存在降低 Ms 点 . 镍是马氏体时效钢中主要的析
2 　无钴马氏体时效钢中合金元素的出相形成元素 . 在马氏体时效钢中 ,镍与强化元素
作用结合形成强化相 ,加入强化元素要消耗镍 ,如基体
中镍含量低于 10 % ,则会引起韧性下降 . 对于无钴
　　与含钴马氏体时效钢相比 , 无钴钢的化学成
钢 ,为保证钢的强韧性 ,镍、
钼、钛 3 元素含量应控
分中除了 Ni 、
Co 、
Mo 、Ti 合金元素的含量变化外 ,
制在一定含量范围之内 [ 15 ] . 虽然镍是提高韧性的
不同的钢种增加了另外一些强化元素 , 如 Cr 、 W、
有效元素 ,但没有必要加入过多的镍 ,如镍含量过
Mn 、
Cu 等合金元素 .
多 ,Ms 点降低 ,冷却时会导致残余奥氏体的形成 ,
在含钴马氏体时效钢中 , 钴虽固溶于基体但
从而使时效后的强度降低 [ 16 ] .
并不形成金属间化合物[ 12 ,13 ] , 而与钼产生协作效
在马氏体时效钢中对强韧性都有利的合金元
应 ( synergistic effect ) [ 1 ] . 其作用在于减少钼在马
素是钼 . 时效初期析出的富钼析出物 ,在强化的同
氏体中的固溶度 , 从而促进含钼金属间化合物的
时保持钢的韧性中起着重要作用[ 17 ] . 同时钼也可
析出 [ 14 ] ; 另外 , 钴可以抑制马氏体中位错亚结构
的回复 ,为随后的析出相形成提供更多的形核位以阻止析出相沿原奥氏体晶界析出[ 18 ] , 从而避免
置 ,使析出相粒子更为细小而又分布均匀 . 然而这了沿晶断裂、
提高了断裂韧性 . 但过量添加钼也
并不说明钴钼的交互作用对韧性有贡献 , 至今还会生成残余奥氏体 . 在 18Ni 系马氏体时效钢中钼
没有实验数据证明钴在提高强度的同时具有改善的质量分数应控制在 8 %以下[ 19 ] . 对于无钴马氏
韧性的作用 . 因此 , 马氏体时效钢中即使不含钴 , 体时效钢 ,由于失去了钴、
钼的交互作用 , 富钼析
也不一定会导致塑韧性恶化 . 出物的析出量相对降低 ,使强化效果减弱 . 但如果
马氏体时效钢具有良好韧性是由于基体中含为加强钼的强化作用而增加钼含量 , 则在钢中易
有较多镍的缘故 . 镍是奥氏体形成元素 ,镍的存在形成高温固溶时都不易溶解的富钼金属间化合
扩大了奥氏体区 ,钢在加热时获得单相奥氏体 ,以物 ,同时也可能导致残余奥氏体的形成 ,从而使钢
备在冷却时获得具有良好范性的马氏体 . 同时 ,镍的塑、
韧性下降 ,因此不能通过增加钼含量保持强
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・110 ・材　料　科　学　与　工　艺　　　　　　　　　　　　　　　第 12 卷　
化作用 . 文献 [ 10 ] 指出 ,在含铜无钴马氏体时效钢取代 Ni 的量不能超过 6 % , 最佳的 Ni - Mn 配合

中 ,钼的质量分数大于 7 % ,冲击韧性显著降低 . 大约为 1215 %Ni - 2 %Mn.
无论在含钴还是无钴马氏体时效钢中 , 钛都铝通常是作为脱氧剂加入到钢中的 . 关于铝
是最有效的强化元素 [ 17 ] . 在无钴钢中 , 每添加的作用 ,本质上说 ,在马氏体时效钢中也可以产生
011 % 的钛 , 强度增加 54 M Pa [ 7 ] . 但钛强化的硬化 ,故在无钴马氏体时效钢中也有用铝作为强
Fe - Ni合金在强度达到较高水平时 , 韧性严重恶化元素的 [ 9 ,22 ] , 并且已有无钛含铝 ( 质量分数为
化 . 因此 ,钛加入量要有一定限制 . Tharian 认为在 1 %～315 %) 马氏体时效钢问世 [ 23 ] .
无钴马氏体时效钢中钛含量 ( 质量分数 ) 最大为稀土元素可提高马氏体时效钢的塑韧性[ 24 ] .
110 %[ 7 ] . T - 250 钢中钛的质量分数为 114 % , 已但关于稀土元素对无钴马氏体时效钢性能方面的
与 C - 350 含钴马氏体时效钢中钛含量相当 ; 影响 ,所进行的研究还比较少 ,需要进一步研究 .
T - 300钢中钛的质量分数高达 1185 % ,这说明再
通过增加钛含量发展更高级别的无钴马氏体时效
3 　无钴马氏体时效钢的时效组织
钢 ,必将引起塑、
韧性的严重下降 . 因此应寻求利无钴马氏体时效钢与含钴马氏体时效钢一
用其他合金元素来发展超高强度的无钴马氏体时样 ,其高强度来源于时效强化 ,通过 400～500 ℃时
效钢 . 效 ,在马氏体基体内产生了大量的金属间化合物
在 Fe - Cr - Ni 三元合金系中 , Cr 能促进奥析出物 . 析出物的类型、结构决定于成分、时效温
氏体相的形成 [ 18 ] . 因此 ,在无钴马氏体时效钢中 , 度和时效时间 .
铬可以替代部分镍 [ 5 ,7 ] . 有研究表明要得到良好韧目前 ,研究者对常规使用的 Fe - Ni - ( Co ) -
性 ,至少需要 17 % ( Ni + Cr) ( 质量分数) ,要保证得 Mo - Ti 马氏体时效钢已进行了大量的研究 , 但关
到最大强度 ,17 %～ 21 % ( Ni + Cr ) 是最大值[ 20 ] . 于析出相的种类和其析出过程尚有很大争议 . 不
浅山行昭等指出 :在 14Ni - 3Cr - 3Mo - 115Ti 钢中 , 同的研究者在同一钢中所得到的结果也不尽相
为获得良好韧性 ,至少需要 ( 12 %～14 %) Ni + 3 % 同 [ 4 ] . Decker 等在文献 [ 4 ] 中作了概括 , 在马氏体
Cr ( 质量分数 ) 以减少 Ni Ti 析出引起基体中贫镍时效钢中主要沉淀物为 : Ni3 M ( M = V , Mo , Nb ,
而造成的韧性损失 [ 5 ] . 在这种低镍无钴马氏体时 W) 、 η - Ni3 Ti 、Fe2 Mo Laves 相、不同类型的σ 相
效钢中 ,镍含量降低 ,Ms 点升高 ,固溶处理冷却过 ( FeMo 、 μ χ
Fe Ti 、 - Fe7 Mo 6 和相 . 三角晶系的 R
)
程中有可能产生析出相 ,这对韧性不利 ,因此加入相也有发现但不常见 .η - Ni3 Ti 在含钴和无钴钢
Cr 以降低 Ms 点 . 铬还可能通过控制钛的析出反中都是重要的析出物[ 7 ] . Fe2 Mo 相在含低钴合金
应来提高韧性 . 在 Fe - 14Ni - 115 Ti - 3Mo 钢中 , μ - Fe7 Mo 6 相在含钴和无钴钢中都有发现 .
中 [ 12 ] 、
伴随添加 3 %Cr 可以有效地防止 Ti 低温相析出此外 , 在含 Cr 马氏体时效钢还观察到 ω 相和
引起的脆化 ,但添加铬防止脆化 ,只有镍的质量分 Ti6 Si7 Ni16 硅化物 [ 25 ,26 ] .
[ 21 ]
数高于 12 %时才有效果 . 事实上 , 高的 Cr/ Ni 对 W - 250 钢时效过程的电子衍射研究表
比对 Fe2 ( Mo , Ti ) 的析出比 Ni3 Ti 更为有利 , 从而 [6 ]
明 ,主要强化析出相是正交结构的 Ni3 W 相和
使更多的镍保留在基体中 , 但这要求在固溶处理六方结构的η - Ni3 Ti 相 . Ni3 W 相的取向关系为
和时效过程中很好地控制 ,以保证生成细小的 Fe2 {011 } M / / ( 010 ) Ni3 W , < 111 > M / / [ 100 ] Ni3 W . η -
( Mo , Ti) 质点 [ 20 ] . Ni3 Ti 的取向关系为 { 011 } M / / ( 0001 ) Ni3 Ti , <
在传统的马氏体时效钢中 ,Mn 一直是作为杂
111 > M / / [ 1120 ] Ni3 Ti .
质元素而存在的 , 其含量 ( 质量分数 ) 受到了严格
Vanderwaiker [ 27 ] 研究了 T - 250 钢的时效析
的控制 ( ≤011 %) . 不过 , 由于在 Fe - Mn 系合金
出过程 ,发现析出过程中首先产生镍偏析 ,由于镍
中 ,可以在较宽的冷却速度范围内形成板条或块
偏析 ,导致富镍区出现逆转变奥氏体 , 最后 Ni3 Ti
状马氏体组织 , 所以 Fe - Mn 合金也为时效强化
在逆转奥氏体上成核长大 ,Ni Ti 析出的形状和取
提供了良好的基础 . Mn 是扩大γ 区的元素 , 在钢
向由逆转变奥氏体决定 ,Ni3 Ti 析出后 , 部分逆转
中 Mn 的稳定奥氏体组织的能力仅次于 Ni [ 18 ] . 因
变奥氏体可能重新转变成马氏体 . 在位错和晶界
此 ,在 18Ni 马氏体时效钢中 , Mn 可以部分取代
上也发生同样的非均匀析出过程 . 在长大的最终
Ni 和 Co [ 9 ] . 文献 [ 22 ] 指出 , 1 % 的 Mn 可以取代
阶段 ,Ni3 Ti 析出相中又溶入了一部分钼 , 因此实
3 %的 Ni ; 但 Mn 取代 Ni 将使合金韧性下降 , Mn
际上析出相是 Ni3 ( Ti ,Mo ) .
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第1期姜　越 ,等 : 无钴马氏体时效钢的研究现状・1 1 1 ・
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・112 ・材　料　科　学　与　工　艺　　　　　　　　　　　　　　　第 12 卷　
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无钴马氏体时效钢的研究与应用
1 1 1 2 2
刘福广 ,席守谋 ,张建国 ,施延龄 ,郑淑丽
( 11西北工业大学材料科学与工程学院 ,陕西西安　710072; 21航天二院 210 所 ,陕西西安　710065 )
摘要 : 从无钴马氏体时效钢的种类、合金化、热处理对该材料力学性能的影响及强化机理等方面综述了无钴马氏
体时效钢的研究和应用概况。无钴马氏体时效钢中不含昂贵的钴元素 , 利用板条马氏体基体上析出的 N i3 ( Ti,
Mo )等沉淀相来实现强化 ,在低于 2100M Pa 的强度范围内 ,与同级别的含钴的 18N i马氏体时效钢相比 ,有相近的
强韧性。
关键词 : 无钴马氏体时效钢 ; 固溶处理 ; 时效处理 ; 强化机制 ; 力学性能
中图分类号 : TG142124 　　文献标识码 : A 　　文章编号 : 0254 26051( 2007) 02 20007 205
Research and Applica tion s of Coba lt2Free M arag in g Steels
L IU Fu 2guang , X I Shou 2mou , ZHANG J ian 2guo , SH I Yan 2ling , ZHENG Shu 2li
1 1 1 2 2
( 11 School of M aterials Science and Engineering, Northwestern Polytechnical University, Xi′

an Shaanxi 710072, China;
21 The 210 Research Institute of CASIC, Xi′
an Shaanxi 710065, China )
Abstract: Research and app lications of Co 2free m araging steels were introduced in m any respects, including their kinds,
alloying, influence of solution and aging treatm ents on mechanical p roperties and the strengthening mechanism of the al2
loys. Co 2free maraging steels have a good combination of ultra 2high strength and moderate toughness, close to that of the
18N i m araging steel containing Co w ith the same strength level below 2100 M Pa. The superior performance is achieved by
aging p recip itations such as N i3 ( Ti,Mo ) in lath martensite matrix.
Key words: cobalt2free maraging steels; solution treatm ent; aging treatm ent; strengthening mechanism; m echanical p roper2
ties
　　马氏体时效钢以其超高强度、
高韧性、
优异的加工时效钢相比 ,它们的力学性能相近 , 而 T250 无钴马氏
[1]
和焊接性能而广泛应用在航空、
航天等尖端领域。体时效钢的成分中不含钴元素 ,降低了钼含量 ,增加了
目前应用较多的是含钴的 18N i 型马氏体时效钢 , 其钛含量。通过调整钛含量 ,又研制出了 T200 及 σ012接
Co 含量高达 8% ～12% , 过高的成本限制其进一步发近 2000 M Pa的 T300 无钴马氏体时效钢。与此同时 ,
[6]
展和应用。因此发展高性能无钴马氏体时效钢 , 降低韩国研制出了用 W 代替 Mo 的 W 250 无钴马氏体时
成本是超高强度钢研究中的一个重要方向。目前国外效钢 , 其 σ012 与 T250 相当 , 而塑韧性则较低。日
已开发出多种无钴马氏体时效钢 , 并已有部分无钴钢本、
[ 7, 12 ] [8]
印度也开发了用部分铬代替镍的无钴马氏
成功应用于关键部件 , 例如 , 美国已将 T250 无钴马氏体时效钢。日本的无钴马氏体时效钢强度与 T250 相
体时效钢成功应用于 TOW 、Stinger、
AMRAAM 导弹 ,军当 ,而塑韧性要优于 T250。印度的无钴钢强韧性与
[2]
用轻型攻击桥、
压铸模、注塑模、风洞设备等。我国对 T250 相比强韧性偏低。从表 1 可以看出 , 无钴钢的力
无钴马氏体时效钢的研究和应用还很少 ,本文通过概述学性能可以与相同级别的含钴钢相相当 , 而成本却降
分析现有无钴马氏体时效钢的研究成果 ,希望能够推动低了 20% ～30% 。
无钴马氏体时效钢在我国高技术领域的应用。我国在无钴马氏体时效钢方面也曾开展过研究工
1 　无钴马氏体时效钢的种类
[9]
作 ,曾有含铜无钴马氏体时效合金的报道 , 但塑性、
[ 13 ] [ 10 ]
表 1 列出了一些典型马氏体时效钢的成分及其力韧性太低。最近何毅等人称开发出了强度高达
学性能
[ 1 ～11 ]
。开发成功最早的无钴马氏体时效钢是 2078 M Pa 的新型 18N i 无钴马氏体时效钢
含 18%N i的 T250 型无钴马氏体时效钢 , 由国际镍
[4] ( 00N i18Mo4Ti) ,其力学性能与 T300 接近 , 但到目前
公司 ( INCO )与 Teledyne Vasco 公司合作研制 , 其中 T 为止 ,还只是处于试验阶段。近几年来 , T250 无钴马
表示增强元素为 Ti。与 C 型含钴的 18N i ( 250 )马氏体氏体时效钢也已经在国内研制成功并已逐步投入生产
[ 14 ]
和使用 ,但现在的热处理工艺还很不成熟。例如 ,
作者简介 : 刘福广 ( 1981. 04 —) , 男 , 河北献县人 , 硕士研究生 , 多道次大变形量旋压状态 T250 型无钴马氏体时效钢
主要从事马氏体时效钢强韧化机理研究。联系电话 : 029 2
经过常规热处理后 ,其强度和塑性不能满足技术要求 ,
88488023 　E2mail: lfuguang@163. com
其工艺和机理都有待研究。
收稿日期 : 2006 210 228
《金属热处理》2007 年第 32 卷第 2 期 7
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表 1 　国内外一些典型马氏体时效钢的化学成分和力学性能 [ 1～11]
Table 1 　Chem ica l com position and m echan ica l properties of som e typ ica l marag in g steels a t hom e and abroad
化学成分 (wt% ) 力学性能
国家材料牌号
Ni Co Mo Ti Al 其他 σ012 /MPa δ( % ) ψ( % ) K IC /MPa ・m 1 /2
美国 18N i (250) 1815 715 418 014 011 - 1760 11 58 135
美国 18N i (300) 1815 910 418 016 011 - 2000 11 57 100
美国 18N i (350) 1815 1210 418 114 011 - 2340 713 52 61
美国 T250 1815 - 310 114 011 - 1750 1015 5611 100 2123
美国 T300 1815 - 410 1185 011 - 1940 818 45 74
韩国 W 250 1819 - - 112 011 412W 1780 910 - 100
日本 14N i23Cr23Mo 2115Ti 1413 - 312 1152 - 219Cr 1750 1315 6510 130
印度 12N i2312Cr2511Mo 21Ti 1210 - 511 110 011 312Cr 1660 1010 - 102
中国 Fe215N i26Mo 24Cu 21Ti 1510 - 610 110 - 410Cu 1785 915 4610 -
中国 Fe218N i24Mo 2117Ti 1810 - 410 117 - - 2078 910 - 70
注 : 其中 W250 的 K IC是通过文献 [ 11 ]将原文献中的冲击功近似换算而来
2 　无钴马氏体时效钢的合金化钼作为析出相的强化作用减弱 , 但可以阻止析出相沿

在含钴马氏体时效钢中 , 钴虽固溶于基体但并不晶界分布 ,得到细小均匀且弥散分布的析出相 ,从而起
[ 21 ]
形成金属间化合物
[ 15 216 ]
, 而与钼产生协同效应
[ 17 ] 到保持钢强韧性的作用。钼含量过高会形成在高
( synergistic effect ) , 促进含钼金属间化合物的析温固溶处理时都不易溶解的富钼金属间化合物 (如
[9]
出
[ 18 ]
,达到强化效果。另外 , 钴还可以影响位错亚结 Fe2 Mo ) ,引起韧性下降。任怀亮认为 , 在含铜无钴
构 ,为析出相提供均匀的形核位置 ,促进析出相粒子细马氏体时效钢中 ,钼的含量大于 7%时 ,冲击韧性显著
小均匀分布。至今没有试验表明钴有阻止韧性下降的下降。
[ 6 27 ]
作用 ,因此马氏体时效钢中不含钴并不一定导致塑韧对于用铬替代镍的无钴钢 ,镍和铬的含量范围
性下降。要严格控制。要得到良好的强韧性 , ( N i + Cr) 的含量
[ 22 ] [7]
无钴马氏体时效钢中主要的合金元素包括 : N i、应控制在 17% ～2 l% 。A sayama 认为 , 无钴马氏
Mo、Ti、A l 等 , 也有用 W 代替 Mo
[6]
, 用 Cr 代替部分体时效钢中至少需要 ( 12 ～14 ) % N i + 3% Cr, 以减少
Ni
[ 7 28 ]
,以及无钴含铜的合金报道 , 该报道认为铜可以由于 N i3 Ti析出引起基体贫镍而造成的韧性损失 , 日
加宽时效强化峰值的温度范围
[9]
。本的 14N i23C r23Mo 2l15Ti钢就是基于此设计的。
镍可以提高马氏体时效钢基体的韧性 , 这是因为铝通常是作为脱氧剂加入钢中的 , 也可以在马氏
它既可以促进位错的交滑移 , 又有利于获得完全的板体时效钢中产生硬化 , 已有用铝作为无钴钢强化元素
[ 23 224 ]
条状马氏体。马氏体时效钢中镍元素要与强化元素形和无钛含铝 ( 1% ～315% )马氏体时效钢的报道。
成强化相析出 , 使基体中的 N i含量降低 , 所以钢中镍关于稀土元素对无钴马氏体时效钢性能的影响的
含量不能太低 ,如果低于 10%就会引起韧性下降
[ 19 ]
。研究还比较少。已有资料报道 , 稀土元素能提高马氏
[ 25 ]
镍含量过多 ,提高了过冷奥氏体的稳定性 ,固溶后冷却体时效钢的塑韧性。我国稀土资源丰富 ,应在这方
时会保留较多的残留奥氏体 , 使时效后的强度降面进行广泛而深入地研究。
[ 20 ]
低。因此 , 要保证钢良好的强韧性 , 镍、钼、钛三元 3 　热处理对无钴马氏体时效钢力学性
能的影响
[ 12 ]
素含量要控制在一定范围内。
钛是无钴马氏体时效钢中最有效的强化元素 , 它马氏体时效钢的热处理主要是固溶和时效 , 固溶
可以与 N i形成 N i3 ( Ti, Mo ) , 是无钴马氏体时效钢的温度的高低既影响晶粒的大小 , 又影响合金元素的固
主要强化相。 Tharian 等认为 ,每添加 011% (质量分
[7]
溶程度 ,在很大程度上决定了时效后的性能。目前关
数 ,下同 )的钛 ,σ012增加 54 M Pa。钛含量也不能过高 , 于固溶温度对无钴马氏体时效钢力学性能影响的研究
因为 Ti容易与有害元素形成各种形态的夹杂物 ,例如还很少 ,也存在一些分歧。
[ 26 ]
与 C 形成 ( Ti, Mo ) C 颗粒 , 和 S、O、N 等形成 Ti2 S、Ti 何毅等人对国内新型无钴马氏体时效钢的研
( C, N ) 、TiO2等夹杂物 ,这些夹杂物会在材料内部形成究认为 ,尽管固溶温度 ( 800 ～1200 ℃) 和保温时间 ( 0
微孔及裂纹源而严重危害钢的韧性。～5 h ) 的变化范围都比较大 , 平均晶粒尺寸从 20 μm
与含钴马氏体时效钢相比 , 无钴马氏体时效钢中长大到 800 μm , 固溶态材料的硬度变化范围仍在
8 《金属热处理》2007 年第 32 卷第 2 期
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[ 14 ]
2 HRC之间。张强对固溶态 T250 无钴钢的性能研
究表明 ,随着固溶温度 ( 800 ～950 ℃)和保温时间 ( 1 ～
6 h )的变化 ,硬度几乎没有变化 ( 280 ～292 HB ) , 对屈
服强度 σ012的影响也不大 ( 61 M Pa 之内 ) 。
[8]
Tharian 对印度无钴马氏体时效钢进行了研究 ,
随固溶温度 ( 750 ～950 ℃)的提高 ,时效态无钴马氏体
时效钢的强度从 1660 M Pa 缓慢降低到 1570 M Pa, 而
[ 26 ]
延伸率从 6%上升到 12% 。何毅等人认为时效态
无钴马氏体时效钢的屈服强度和晶粒尺寸之间很好地图 2 　不同的时效温度下 ,时效时间对 T250 无钴马氏体
时效钢硬度的影响 [ 29 ]
符合 Hall2Petch关系 ,如图 1, 塑性随晶粒性尺寸的长
Fig. 2 　Effect of aging tim e on hardness of T250 Co 2free
大没有明显变化 ,当强度高于 1900 M Pa 时 , 晶粒进一 [ 29 ]
maraging steels at different temperatures
步长大塑性会严重恶化。由此可见 , 二者的研究结果
为了提高无钴马氏体时效钢强韧性 , 还可以采用
中强度与晶粒大小的关系是一致的 , 而塑性的变化规
其他的热处理工艺。例如 , 在含钴钢中采用循环相变
律却有很大不同 ,这是值得深入研究的课题。
工艺 ,可以有效地细化晶粒 ,极大地提高了材料的强韧
[ 29 230 ]
性。国内外在无钴钢中应用此工艺的报道还很
[ 31 ]
少。
4 　无钴马氏体时效钢的时效强化机理
固溶态马氏体时效钢的强化主要来源于固溶、
位
错及相变强化等。很多试验表明马氏体板条间距或板
[ 28 229 ]
条宽度不受晶粒尺寸的影响 , 屈服强度与晶粒尺
寸的微弱依赖关系 ,可能是由于晶界的强化作用被板
图 1 　晶粒尺寸对无钴马氏体时效钢 ( 00N i18Mo4Ti) 条界强化、
固溶强化、
大量的位错强化所淹没造成的。
屈服强度的影响 [ 27 ] 时效处理后 ,晶粒尺寸比较小时 , 晶界面积大 , 析出相
Fig. 1 　Effect of grain size on tensile strength of Co 2free 不会在晶界产生大量偏聚 ; 当晶粒尺寸比较粗大时 ,析
maraging steel(00N i18Mo4Ti) 出相会在晶界、
板条界处偏聚 , 使晶粒内的析出相减
[ 27 ]
然而 , Sinha 等对 18N i无钴马氏体时效钢的研少 ,从而造成了强度降低。晶界上沉积相密度的增加
究认为 ,无论是固溶态还是时效态无钴马氏体时效钢 , 会形成壁垒阻碍位错的滑移 , 同时各晶粒的协调变形
其拉伸性能都不受晶粒尺寸的影响。与前者的试验结受到抑制 ,表现为塑性降低。而夹杂物在基体或晶界
果大相径庭。上的偏聚 ,则会形成微裂纹或产生沿晶断裂 ,降低材料
时效处理对无钴马氏体时效钢力学性能的影响也的韧性
[ 29 ] [ 27 ]
。 Sinha 认为拉伸性能和晶粒尺寸无关、
[ 28 ]
有人做了一些研究。图 2 是在不同时效温度下 , 时韧性随固溶温度升高而恶化 , 原因可能是由于马氏体
效时间对 T250 无钴马氏体时效钢硬度的影响。从图形貌由板块状转变成桁条状造成的。
2 中可以看出 , 当时效温度较低时 ( 450 ℃, 480 ℃) , 无钴马氏体时效钢种类繁多 , 时效析出相也不尽
T250 钢的硬度迅速上升 , 后来变化速度趋于平缓 , 不相同。现在研究应用较成熟的是 C 型含钴马氏体时
过直到 600 m in 时硬度还有上升的趋势 ; 高温时效处效钢 ,而 T型无钴马氏体时效钢的研究还比较少。
理时 ( 550 ℃, 600 ℃) , 硬度都很快达到峰值 (分别在 [ 32 ]
认为 T250 无钴马氏体时效钢的
Vanderwalker
15 m in和 5 m in ) ,此后硬度逐渐下降。
时效强化相是 N i3 (Mo, Ti) , 其析出过程为 : 首先在马
　　一般来说 ,马氏体时效钢的时效温度一旦超过该
氏体基体内发生 N i偏聚 , N i的偏聚导致逆变奥氏体
钢的 A s (奥氏体逆相变 )温度 ,组织中将会出现逆转变
的生成 ,随后 N i3 Ti在奥氏体内形核、
长大 , 其位向及
奥氏体 ,会使强度、硬度降低。 T250 钢的 A s温度是多
形状取决于奥氏体。N i3 Ti沉淀后 ,部分逆变奥氏体又
高 ,图 2 中 550 ℃、600 ℃时效曲线的变化是由于强化
变回马氏体。时效后期部分 Mo 原子代替了 Ti原子形
相长大所致 ,还是逆转变奥氏体所致都需要进一步探 [ 15 ]
成 N i3 (Mo, Ti) 。Vasudevan 采用分析电镜并辅以计
讨。
算机模拟分析电子衍射谱对 C250 和 T250 进行的研
《金属热处理》2007 年第 32 卷第 2 期 9
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究也证实了上述观点。这一结果提示我们 , 无钴马氏 App lications[ C ]. Huntington, W est V irginia: TM S, 1988: 1 2
体时效钢时效时的逆变奥氏体也可以在较低的时效温 38.
[ 2 ] 　Floreen S, Bayer A M. Development and commercialization of
度下形成 ,或者说该钢的 A s温度很低 , 且是可变的。
[ 33 ] cobalt2free maraging steels[A ]. W ilson R K. M araging Steels
尹钟大则认为 , 含钴马氏体时效钢的析出次序 : 首
Recent Developments and App lications [ C ]. Huntington,
先发生调幅分解 , 然后在 N i2Mo 2Ti富集区以原位形核 W est V irginia: TM S, 1988: 55 272.
方式析出强化相 N i3 (Mo, Ti) ,没有逆变奥氏体的中间 [ 3 ] 　何　毅 ,杨　柯 , 等 . 超纯净化 18N i ( 350 ) 马氏体时效钢
[ 16 ]
过程。沙维用场离子显微镜原子探针方法对 T300 的研究 [ J ]. 金属学报 , 2001, 37 ( 8 ) : 852 2856.
[ 4 ] 　H ickey C F, Thomas T S. M echanical p roperty characteriza2
在不同时效温度 ( 450 ～ 610 ℃) 和不同时效时间 ( 5
tion of Vascomax T2250 [ A ]. W ilson R K. M araging Steels
m in～360 h )的析出次序进行了研究 ,认为该钢的强化
Recent Developments and App lications [ C ]. Huntington,
相为 N i3 Ti和 Fe7 Mo6 , Fe7 Mo6是时效后期在 N i3 Ti边界 W est V irginia: TM S, 1988: 73 290.
上形核、
长大 ,而且时效组织中未发现逆变奥氏体。何 [ 5 ] 　何　毅 . 超高强韧化马氏体时效钢的研究 [ D ]. 沈阳 : 中
[ 10 ]
毅等人对新型无钴马氏体时效钢的研究认为 : 该钢国科学院金属研究所 , 2002.
800 ℃固溶、480 ℃时效 12 h 的析出相为纳米尺度的 [ 6 ] 　Kim Y G, Kim G S, et al. M icrostructure and mechanical
[5]
N i3 ( Ti,Mo ) , 但未涉及逆变奥氏体。对 W 250 的研 p roperties of a cobalt2free tungsten 2bearing maraging steel
[ J ]. M ater. Sci. Eng. , 1986, 79 ( 1 ) : 133 2140.
究则表明 ,该钢的主要强化相是正交结构的 N i3 W 和
[ 7 ] 　A sayama Y, et al. M echanical p roperties of a cobalt free mar2
六方结构的 N i3 Ti。过时效处理 ( 650 ℃时效 3 h )后才 aging steel containing chrom ium [ J ]. J. Japan Inst. M etals,
有 13% (体积分数 ) 的逆变奥氏体。文献 [ 15 ]认为 , 1987, 51 (1) : 76 282.
时效强化的时效初期 , 强化效果与位错切过共格区 [ 8 ] 　Tharian K T, Sivakumar D , et a1. Development of new nick2
(沉淀相 )所要求的应力有关 , 此时共格应力和沉淀相 el, cobalt2free maraging steel[ J ]. M ater. Sci. Tech. , 1991, 7
( 12 ) : 1082 21088.
内部有序化起主要作用。随着沉淀相的长大并与基体
[ 9 ] 　任怀亮 ,何肇基 ,等 . 无钴马氏体时效合金 [ J ]. 北京钢铁
保持半共格关系 ,位错切过它们所需应力逐步增加 ,屈
学院学报 , 1987, 9 ( 4 ) : 31 237.
服强度上升。沉淀相继续长大 ,尺寸达到一定值时 ,位
[ 10 ] 　何　毅 , 杨　柯 , 等 . 超高强 18N i无钴马氏体时效钢的
错只能绕过而无法切过。许多研究都表明其强化机制力学性能 [ J ]. 金属学报 , 2002, 38 (3) : 278 2282.
[ 10, 28 ]
可以用 O rawan绕过机制来解释。文献 [ 34 ]认为 , [ 11 ] 　Nageswara Rao B , Acharya A R. Charpy V 2notech impact
沉淀相的临界半径尺寸达到 15倍的 Burgers矢量 (约为 test: a partial alternate to ASTM E399 fracture testing for
3175 nm )时 ,位错就会绕过沉淀相。当沉淀相的颗粒间 routine quality control app lications[ J ]. Eng. Frac. M ech. ,
1999, 32 ( 1 ) : 39 242.
距达到某一临界值时强度达到峰值。文献 [ 10 ]计算出
[ 12 ] 　A sayama Y. H igh strength cobalt free maraging steel [ P ].
无钴马氏体时效钢峰值强度时沉淀相的临界颗粒间距
United States Patent: 4579590, 1986 204 201.
为 2513 nm ,沉淀相的直径尺寸为 817 nm。 [ 13 ] 　陈　光 ,翁宇庆 . 无钴马氏体时效钢研究进展 [ J ]. 钢铁
综上所述 ,关于无钴马氏体时效钢时效强化相的研究学报 , 1993, 5 (4) : 89 294.
析出次序、
强化相的类型、
时效过程中逆变奥氏体的形 [ 14 ] 　张　强 ,王明鉴 ,等 . 固溶处理对 T250 无钴马氏体时效
成条件、
分布、
数量及其对性能的影响都需要进行深入钢的组织及力学性能的影响 [ J ]. 材料热处理学报 ,
2004, 25 ( 6 ) : 30 234.
的研究。
[ 15 ] 　Vasudevan V K, Kim S J, et al. Precip itation reactions and
5 　结语 strengthening behavior in 18 w t pct nickel maraging steels
为了使无钴马氏体时效钢得到广泛的应用 , 特别 [ J ]. M etal Trans. , 1990, 21A (11) : 2655 22668.
是在冷变形量很大的旋压薄壁零件的生产、
应用中 ,应 [ 16 ] 　Sha W , Cerezo A , et al. A tom p robe field 2ion m icroscopy
深入研究其固溶、
时效工艺及强化机理 ; 进行无钴马氏 study of aging behavior of Co 2free maraging steel[ J ]. Sur2
face Science, 1991, 246 ( 4 ) : 278 2284.
体时效钢循环相变处理工艺及其影响因素的研究 , 探
[ 17 ] 　Decker R F, Eash J T, et al. 18% N i maraging steel [ J ].
索进一步提高其强韧性的途径 ; 研究稀土元素对无钴 Trans. ASM , 1962, 55 ( 1 ) : 58 276.
马氏体时效钢的作用及机理 , 为开发性能更好的新型 [ 18 ] 　Sha W , Cerezo A , et al. Phase chem istry and p recip itation
无钴马氏体时效钢奠定理论基础。 reactions in maraging steel: Part Ⅳ. D iscussion and conclu2
参考文献 : sions[ J ]. M etal Trans. , 1993, 24A (6) : 1253 21256.
[ 1 ] 　Decker R F, Floreen S. M araging steels— the first 30 years [ 19 ] 　姜　越 ,尹钟大 . 无钴马氏体时效钢的研究现状 [ J ]. 材
[ A ]. W ilson R K. M araging Steels Recent Developments and 料科学与工艺 , 2004, 12 ( 1 ) : 108 2112.
10 《金属热处理》2007 年第 32 卷第 2 期
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[ 20 ] 　Nagayama K, Terasak T, et al. M echanical p roperties of a [ 28 ] 　Sinha P P, et al. Effect of aging on m icrostructure and me2
Cr2N i2Mo 2A l2Ti maraging steel in the p rocess of martensitic chanical p roperties of cobalt free 18%N i ( 250grade ) marag2
transformation[ J ]. M ater. Sci. Eng. A , 2001, 308 ( 6 ) : 25 2 ing steel[ J ]. M ater. Sci. Tech. , 1998, 14 ( 1 ) : 1 29.
37. [ 29 ] 　何　毅 ,苏国跃 , 等 . 超纯净 18N i马氏体时效钢晶粒尺
[ 21 ] 　A sayama Y. Delayed failure in air environment and p recip i2 寸及其对拉伸性能的影响 [ J ]. 金属学报 , 2002, 38 ( 1 ) :
tation behavior in maraging steels[ A ]. R ichard K,W ilson. 53 257.
M araging Steels Recent Developments and App lications [ 30 ] 　朱景川 ,尹钟大 ,等 . 18N i ( 200) 马氏体时效钢的循环相
[ C ]. Huntington,W est V irginia: TM S, 1988: 237 2253. 变晶粒新工艺 [ J ]. 钢铁 , 2001, 36 (6) : 52 255.
[ 22 ] 　Decker R F. M araging steel: getting better w ith age [ J ]. [ 31 ] 　Park C N , Yong G, Kim. Effects of repeated thermal cy2
Adv. M ater Process, 1988, 133 ( 6 ) : 45 250. clings on the transformation behaviour, m icrostructure and
[ 23 ] 　Davidson J. M araging steel [ P ]. United States Patent: mechanical p roperties in a Cobalt2free Tungsten 2containing
6080359, 2000 206 227. maraing steel (W 2250 ) [ J ]. M ater. Sci. Eng. , 1990, 123
[ 24 ] 　W illiam R P, et al. The partial substitution of manganese for ( 2 ) : 255 2260.
nickel in maraging steel[ J ]. Tras. ASM , 1966, 59 (1) : 71. [ 32 ] 　Vanderwalker D M. The p recip itation sequence of N i3 Ti in
[ 25 ] 　惠卫军 ,李　荣 ,等 . 稀土对 18N i (350) 马氏体时效钢韧 Co free maraging steel [ J ]. M etall Trans, 1987, 18A ( 7 ) :
塑性的影响 [ J ]. 材料工程 , 1996 (2) : 19 223. 1191 21194.
[ 26 ] 　何　毅 ,杨　柯 ,等 . 高强度无钴马氏体时效钢的晶粒长 [ 33 ] 　尹钟大 ,李晓东 , 等 . 18N i马氏体时效钢时效机理的研
大与力学性能研究 [ J ]. 航空材料学报 , 2002, 22 ( 4 ) : 1 25. 究 [ J ]. 金属学报 , 1995, 31 ( 1 ) : 7 213.
[ 27 ] 　Sinha P P, et al. Effect of solution temperatures on m icro2 [ 34 ] 　Klish D , Rack H J. The strength and fracture toughness of
structure tensile fracture p roperties of Co 2free maraging 18N i ( 350 ) maraging steel[ J ]. M etal Trans. , 1971, 2 ( 9 ) :
steel[ J ]. Steel Res. , 1994, 65 ( 11 ) : 494 2499 3011 23020.
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第 20 卷第 5 期　　　　钢铁研究学报 Vol. 20 , No . 5
　　　　　　　　　
2008 年 5 月　　　Jo urnal of Iron and Steel Research 　May 　2008
新型 Cr2Co2 Ni2Mo 系马氏体时效不锈钢的强韧化机理

刘振宝 , 　杨志勇 , 　雍岐龙 , 　梁剑雄 , 　孙永庆 , 　李文辉 , 　宋诚一
( 钢铁研究总院结构所 , 北京 100081)
摘　要 : 研究了由我国自行研制的 Cr2Ni2Co2Mo 系高强度马氏体时效不锈钢的强韧化机理。结果表明 , 该钢在

535 ℃时效强度可达 1 940 MPa , KIC = 141 M Pa ・ m ,此时钢中析出的大量、
弥散、
细小的 Fe2 Mo 型 Laves 相是
保持超高强度的主要原因 ; 在纤细的马氏体板条界上有少量的残余奥氏体使钢具有较高的韧性。该钢具有优良
的综合性能 ,特别适合于制造新一代高强高韧、
承力的耐海洋环境腐蚀结构件 ,并在航天及航空领域潜在着应用
前景。
关键词 : 马氏体时效不锈钢 ; 强韧化机理 ; 析出相
中图分类号 : T G1421 1 　　文献标识码 :A 　　文章编号 :100120963 (2008) 0520027206
Strengthening2Toughening Mechanism of an Cr2Co2Ni2Mo

Ultra2 High Strength Maraging Stainless Steel
L IU Zhen2bao , 　YAN G Zhi2yo ng , 　YON G Qi2lo ng , 　L IAN G J ian2xio ng ,
SU N Yo ng2qing , 　L I Wen2hui , 　SON G Cheng2yi
( Instit ute for St ruct ural Materials , Cent ral Iron and Steel Research Instit ute , Beijing 100081 , China)
Abstract :The strengthening2toughening mechanism of an domestic2produced Cr2Co2Ni2Mo ultra2high strength maraging

stainless steel was st udied. The result s show t hat after aging at 535 ℃fo r 4 h t he st rengt h of t he steel may reach
1 940 MPa , and KIC can reach 141 MPa ・ m , large amo unt of p recipitates are found in t he martensite , t he p re2
cipitates are very fine and dispersedly dist ributed in t he mat rix , which greatly enhances t he st rengt h of t he steel ,
and t he residual austenites between martensitic lat hs imp rove t he to ughness of t he steel. The steel is especially sui2
ted to making a new generatio n of st ruct ural member wit h high st rengt h and high toughness , which can be used in
st rained marine enviro nment , and it can be used in t he aero space field.
Key words :maraging stainless steel ; st rengt hening2to ughening mechanism ;p recipitation p hase
　　马氏体时效不锈钢是采用低碳马氏体相变强化金成分设计、冶炼工艺及强度级别均上升了一个新

和时效强化效应叠加的手段使钢具有最高的强韧性的水平 ,尤其在提高钢的强度方面一直是该领域研
和优异的综合性能[ 1～4 ] 。该钢是当前抗拉强度与韧究的热点。自从 1997 年 Martin [ 8 ] 等申请了马氏体
性匹配最好 ,综合性能最佳的金属结构材料 ,广泛应时效不锈钢 Custo m465 专利 ( 其强度为 1 800 M Pa)
用于航空、
航天和海洋等高科技领域 ,已成为民用飞以来 ,马氏体时效不锈钢的强度级别从 1 600 M Pa
机、
战斗机、舰载飞机起落架、潜艇动力装置等承力推向了更高的水平 , 2006 年底 , 美国 Q ues Tek 新
耐蚀 ( 或高温) 部件的首选材料 [ 5～7 ] 。马氏体时效不技术有限责任公司成功研制了马氏体时效不锈钢
锈钢具有的高强、
高韧和良好的耐蚀性能是其它钢 FerriumS53 , 其强度约为 1 980 M Pa , KIC = 80
种不可替代的。在近 40 年的发展中 ,该钢无论从合 M Pa ・ m 以上 [ 9 ] 。
基金项目 : 国家高技术研究发展计划 (863) 资助项目

作者简介 : 刘振宝 (19772) ,男 ,博士生 ; 　　E2mail :liuzhenbao1977 @yahoo . co m. cn ; 　　修订日期 :2007211220
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・2 8 ・　　　　　　　　　　　　　　　　钢　铁　研　究　学　报　　　　　　　　　　　　　　　　　第 20 卷
　　20 世纪 70 年代开始 , 国内开展了马氏体时效峰值 ,随后强度和硬度随时效温度升高而降低。冲

不锈钢的研制工作 , 研制的典型钢种有 00Cr12Ni82 击功 ( A KU2 为深度 2 mm 的 U 型缺口试样的冲击功)
Cu2 AlN b ,00 Cr10 Ni10 Mo2 Ti1 和 00Cr13Ni8Mo22 随时效温度升高逐渐下降到最低点 ( 535 ℃时 ) , 然
Nb Ti [ 10～12 ] 等 10 余种。2002～2005 年 ,钢铁研究总院后再上升 [ 图 1 ( a 、
b ) ] 。总体来看 , 断面收缩率 ( Z)
成功设计并研制出新型的超低碳马氏体时效不锈钢 , 和伸长率 A 的变化不明显 ( 尤其是后者) 。但时效
( )
该钢是国内自主研发并具有自主知识产权的 Cr2Ni2 温度在 440～480 ℃时 ,断面收缩率呈现出缓慢下降
Co2Mo 系马氏体时效不锈钢 , 其强度为 1 940 MPa , 的趋势 ,在 480 ℃出现了一个较低值 ,随着时效温度
KIC = 141 M Pa ・ m
[ 7 ,13 ]
。在此 , 笔者探索性研究的升高 ,断面收缩率和伸长率缓慢上升 ,而在 535 ℃
了该钢的强韧化机理 , 深化了马氏体时效不锈钢的时断面收缩率又开始下降 [ 图 1 ( c) ] 。
强韧化理论。
3 　强韧化机理
1 　实验材料和方法
31 1 　超细马氏体板条
　　实验用料采用真空感应炉熔炼 ( V IM 3 t ) + 真　　图 2 示出了固溶处理 + 负温处理 + 535 ℃×4 h
空自耗炉重熔的双真空熔炼 . 实验钢主要成分为 : 时效处理后实验钢的 T EM 组织及板条宽度的分
01 02C2Fe213Cr24Ni213Co26Mo 。钢锭经 1 150 ℃加配。从图 2 ( a ,b) 可见 ,组织主要是细小的板条马氏
热和均匀化处理后锻成 <20 mm 、 90 mm ×90 mm 和体 ( M) 。从图 2 ( c ) 中马氏体板条的尺寸可见 , 宽度
55 mm ×55 mm 的棒材 , 并加工成试样。试样经小于 200 nm 的马氏体板条约占 70 % , 平均板条宽
1 050 ℃×60 min 固溶处理 + 空冷 ( AC) ; 负温处理度约为 197 nm ,纤细状板条马氏体在保证钢具有较
( 干冰与酒精混合溶液温度控制在 - 70 ℃) ; 然后在高强度的同时还具有良好的韧性。图 2 ( b ) 显示出
不同温度 ( t = 440～600 ℃) 下时效 , 保温 4 h 。冲击细小马氏体簇 ( M T ) 切割马氏体板条的精细结构。
试样和拉伸试样分别参照 GB/ T22921994 和 GB/ 可见马氏体板条被多个角度排列、与板条长轴呈近
T22822002 标准 ,用透射电镜 ( H2800 ) 观察和分析了 60°
的小马氏体簇切割成多段而碎化。在材料强度
钢的微观组织结构。学中 ,细化晶粒的强韧化效果通常用 Hall2Petch 公
式来描述 ,即 :
2 　实验结果
　　Re = Re0 + ky d - 1/ 2 ( 1)
　　图 1 为固溶和负温处理后时效温度对实验钢力式中 , Re0 为原始屈服强度 ; ky 为常数 ; d 为“有效晶
学性能的影响。可以看出 , 实验钢的强度 ( Rm , ReL ) 粒”尺寸。
和硬度 ( H RC) 随时效温度升高而提高 , 535 ℃时效　　Nalyer 将式 ( 1) 修正为 Re = Re0 + ky DM- 1 。此式
时 , 钢的强度 ( 1 940 M Pa ) 和硬度 ( H RC 54) 出现了被广泛应用 , 式中 DM- 1 为马氏体板条束直径 , 它与
板条的关系为 :
W
2 arcco s
　　DM = { W ln t g L π +
π +
2 4
π W
L - L arcco s } ( 2)
2 L
式中 , W 为板条宽度 ; L 为板条长度。
　　由式 (1) 可知 ,纤细的板条尺寸 ( 或有效晶粒) 和
马氏体板条宽度的细化及长度方向的细化 [ 图 2 ( b) ] ,
既是提高强度 ,又是增加韧性的主要因素[ 14 ] 。
31 2 　纳米级析出相
图 1 　固溶和负温处理后时效温度对实验钢力学性能的影响　　经 535 ℃×4 h 时效处理后 ,在板条马氏体上析
Fig1 1 　Effects of aging temperature after solution and 出了大量的、弥散的纳米级强化相。表 1 列出了不同
subzero treatment on mechanical properties 时效温度处理后析出相的尺寸分布。可看出 ,535 ℃×
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第 5 期　　　　　　　　　　刘振宝等 : 新型 Cr2Co2Ni2Mo 系马氏体时效不锈钢的强韧化机理　　・2 9 ・
图 2 　板条马氏体形貌和尺寸
Fig1 2 　Size and shape of martensite lath
表 1 　析出相尺寸分布的运动 ,是大幅度提高钢的强度的重要因素。

Table 1 　Size of precipitation phase 　　图 5 为 600 ℃×4 h 时效处理后实验钢的 T EM
时效处理制度直径/ nm 体积比/ % 组织、 SAD 图及其标定。可以看出 , 随时效温度升
535 ℃×4 h 5～10 85 高 ,Laves 相明显聚集长大 ,电子束沿 [ 112 ] M 方向入
10～20 10
> 10 5 射得到其衍射斑点经标定后可知 :[112 ] M ∥[ 185 ]L1 ∥
600 ℃×4 h 5～10 20
10～50 50
[ 232 ]L2 ∥[ 234 ]L3 ∥[ 122 ]L4 , ( 110 ) M ∥( 212 ) L1 ∥
> 50 30 ( 122) L2 ∥( 122 ) L3 ∥( 212 ) L4 , ( 110 ) M ∥( 122 ) L3 ∥
( 212) L4 。由于析出相的长大使析出相的弥散强化
4 h 时效处理后钢中有 85 %的析出相尺寸小于 10 效果下降 ,从而致使钢的强度降低。
nm 。这些析出相钉扎在位错和马氏体板条界上 , 阻　　赵振业等 [ 15 ] 在研究 01 10C214Cr212Co241 5Mo
碍了位错的移动 , 大大提高了钢的强度 , 如图 1 中钢时也发现了 Fe2 Mo 型 Laves 相 , 并得到出该相与
535 ℃×4 h 时效处理后 ,钢的强度达到峰值。马氏体晶体学的关系 , 即 : [ 2 1 10 ] ∥[ 1 11 ] M ,
　　采用 H800 透射电镜观察了 535 ℃×4 h ,600 ℃× ( 0001) L ∥( 112 ) M 。 K. J . Irvine [ 16 ] 等研究了 12Cr2
4 h 时效处理后实验钢的微观组织 , 结果示于图 3 ～ 8Mo215Co 钢在 600 ℃以上回火时 Laves 相的析出 ;
5 。可见 ,钢中主要析出相为六方结构 ( TCP 拓扑密 Kasak [ 17～19 ] 等发现 A FC277 钢在温度高于 650 ℃回
排结构 ) Fe2 Mo 型的 Laves 相 ( a = 01 474 nm , c = 火时 ,有 Laves 相沉淀 ,并推断与该钢 565 ℃回火时
01 772 nm) 。由于实验钢为低碳马氏体时效不锈钢 , 出现的硬化峰有相关 , 但并未确定其强化作用。本
在时效过程中碳化物析出量很少 , 而且也未观察到实验结合前人所得结论 , 并在超低碳 Co2Cr2Mo2Ni
碳化物。由析出相的 SAD 图及标定可知 : ( 110) M ∥ 系马氏体时效不锈钢中观察到了 Laves 相 , 并证明
( 212 ) L3 , ( 110 ) M ∥ ( 212 ) L1 ∥ ( 212 ) L2 ∥ ( 212 ) L3 , Laves 相对钢具有很强的硬化效果。
[ 115 ] M ∥[ 162 ]L1 ∥[ 261 ]L2 ∥[ 467 ]L3 , 而且可看出 , 31 3 　残余奥氏体的韧化作用
电子束沿马氏体 [ 115 ] M 方向入射 ,Laves 相呈圆球　　透射电镜观察结果表明 , 经 1 050 ℃固溶处理
状。后 ,不同时效处理的基体组织为马氏体 + 残余奥氏
　　图 4 为电子束沿马氏体 [ 112 ] M 方向入射得到体。图 6 为 535 ℃×4 h 时效处理后实验钢的透射
的 535 ℃×4 h 时效处理后实验钢析出相的微观组电镜照片。可见 , 残余奥氏体沿板条马氏体束之间
织。由图 4 ( a ,b) 可知 ,析出相细小、弥散 ,由于它们或片状马氏体周围呈薄片状分布 , 这对改善材料的
之间的位向关系不同 ,故析出相的衬度即明暗程度也韧性十分有利 , 不仅可阻止裂纹在马氏体板条间的
不同。图 4 ( c ,d) 标定结果表明 : [ 112 ] M ∥[ 592 ]L1 ∥ 扩展 ,还可以减缓板条间密集排列时位错前端引起
[ 354 ]L2 ∥[ 331 ]L3 , ( 110 ) M ∥( 112 ) L1 ∥( 112 ) L2 ∥ 的应力集中。由标定结果可知 , 残余奥氏体与马氏
( 103) L3 。析出相与基体保持良好的共格关系 , 并且体保持良好的 K2S 关系。G. Thomas[ 20 ] 在对 Fe2Cr2C
绝大多数析出相在位错线附近生成 , 它们阻碍位错系马氏体钢研究中也观察到断裂韧性与残余奥氏体
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・3 0 ・　　　　　　　　　　　　　　　　钢　铁　研　究　学　报　　　　　　　　　　　　　　　　　第 20 卷
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第 5 期　　　　　　　　　　刘振宝等 : 新型 Cr2Co2Ni2Mo 系马氏体时效不锈钢的强韧化机理　　・3 1 ・

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・3 2 ・　　　　　　　　　　　　　　　　钢　铁　研　究　学　报　　　　　　　　　　　　　　　　　第 20 卷
膜有关 ,认为稳定的残余奥氏体薄膜存在于板条马 Be and Ti in Maraging Stainless Steel [J ] . J IPI ,1969 ,207

(12) :1642.
氏体之间对韧性有利。
[ 2 ] 　魏振宇 . 马氏体时效不锈钢 [J ] . 新金属材料 ,1972 , (4) :22.
4 　讨论 [ 3 ] 　Imrie W H. Maraging Steel in t he British Aero space Indust ry

[J ] . Metal Forming ,1970 , (1 ,2) :41.
　　在本研究的 Cr2Ni2Co2Mo 系高强度马氏体时 [ 4 ] 　姜　越 , 尹钟大 , 朱景川 , 等 . 马氏体时效不锈钢的发展现状
效不锈钢成分范围内 ,强韧化机理主要包括 : 高位错 [J ] . 特殊钢 ,2003 ,24 (3) :1.

[ 5 ] 　Wilson R K. Maraging Steels2Recent Develop ment and Appli2
密度纤细板条马氏体强化及韧化作用和超细板条的
cations [J ] . Tmsaime Warrendale PA ,1988 ,1 :255.
二次细化“有效晶粒”作用 ; 沉淀析出 Laves 相的弥
[ 6 ] 　赵先存 , 黄桂煌 . 国外不锈钢现状及动向 [J ] . 国外金属材料 ,
散强化 ; 残余奥氏体薄膜分布在板条界上 ,并与其保 1980 , (5) :1.
持良好的 K2S 关系均对钢起到韧化的作用。通过 [ 7 ] 　刘振宝 , 宋为顺 , 杨志勇 , 等 . 时效对超高强马氏体时效不锈
观察 Laves 相及不同位相衍射结果发现 ,Laves 相与钢组织与性能的影响 [J ] . 材料热处理学报 ,2005 ,26 (4) :52.
[ 8 ] 　Martin. U . S , Patent s 5 ,681 ,528.
马氏体基体的晶体学关系为 : [ 21 10 ]L ∥[ 1 10 ] M ,
[ 9 ] 　Charles J , Kuehmann Ph D. Co mp utational Design of High2
(0001) L ∥( 110) M , 并且沿马氏体的 [ 1 10 ] M 方向的
St rengt h : High2 Toughness Stainless Steel for Carrier2Based
长大速度较快。 Aircraft [ EB/ OL ] . (2005211210) [ 2007211220 ] . http :/ / www.
morisan. com/ ferriums53. pdf .
5 　结论 [ 10 ] 　陆世英 , 张廷凯 . 不锈钢 [ M ] . 北京 : 原子能出版社 ,1995.
[ 11 ] 　宋为顺 , 赵先存 . 我国高强度不锈钢的发展现状和展望 [J ] .
　　(1) 实验所研究的 Cr2Ni2Co2Mo 系高强度马氏体
不锈 ,2000 ,4 (2) :1.
时效不锈钢成分范围内 ,经过 1 050 ℃×1 h ( AC) +
[ 12 ] 　陆世英 . 我国不锈钢研究与应用的回顾和进步发展的展望
- 73 ℃×8 h + 535 ℃×4 h ( AC) 处理后 ,钢的强度 [J ] . 钢铁研究学报 ,1966 ,8 (2) :64.
可达 1 940 M Pa , KIC = 141 M Pa ・ m 。 [ 13 ] 　刘振宝 , 杨志勇 . 固溶处理对新型马氏体时效不锈钢力学性
能影响研究 [J ] . 钢铁 ,2007 ,42 (3) :47.
　　( 2) 时效处理后 ,实验钢的微观组织为纤细的板
[ 14 ] 　赵振业 , 李春志 , 李　志 , 等 . 一种超高强度不锈钢细化组
条马氏体 + 少量的残余奥氏体。纤细的马氏体组织
织 TEM 研究 [J ] . 航空材料学报 ,2005 ,25 (2) :1.
使钢在具有较高强度的同时还具有良好的韧性。 [ 15 ] 　赵振业 , 李春志 , 李　志 , 等 . 一种高强度不锈钢齿轮钢强
　　( 3) 经 535 ℃×4 h 时效处理后 ,实验钢中析出化相研究 [J ] . 航空材料学报 ,2003 ,23 (1) :1.
了大量、弥散、细小的 Fe2 Mo 型 Laves 相 , 它们分布 [ 16 ] 　Irvine K J . The Develop ment of High St rengt h Steel [J ] . J of
在马氏体板条上 ,并与基体保持良好的共格关系。这 t he Iron and Steel Inst ,1962 ,200 (10) :820.
[ 17 ] 　Kasak A , Chandho k C k , Dulis E J . Develop ment of Precipi2
些析出相钉扎在位错线附近 ,显著提高了钢的强度。
tation Hardening Cr2Mo2Co Stainless Steel [J ] . Trans ASM ,
Laves 相与马氏体之间的晶体学关系为 : [ 21 10 ]L ∥ 1963 ,56 :455.
[ 1 10 ] M , ( 0001 ) L ∥( 110 ) M 。 [ 18 ] 　Versnyder F L , Beattle J R H J . The Laves and Chip hases in
　　( 4) 残余奥氏体与马氏体保持着 K2S 关系 , 残 aModified 12Cr Stainless Alloy [J ] . Trans of ASM ,1955 ,47 :
211.
余奥氏体沿板条马氏体束之间或片状马氏体周围呈
[ 19 ] 　Kout sky J , J ezek. Co mpo sition of Precipitates in Modified
薄片状分布 ,对改善材料的韧性十分有利。
12 % Chro mium Steel s in t he Range Above 550 ℃ [J ] . Jour2
nal of t he Iron and Steel Inst ,1962 ,11 :938.
参考文献 :
[ 20 ] 　Thomas G. Retained Austenite and Tempered Martensite
[ 1 ] 　Crawfird W M , Cont ractor G P. The Effect s of St rengt hening Embrit tlement [J ] . Metall Trans ,1978 ,9A (3) :439.
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　第 43 卷　第 4 期钢铁　Vol. 43 , No . 4
　2 0 0 8 年 4 月 Iron and Steel Ap ril 　2008
预先冷轧变形对马氏体时效钢强化的影响
杨卓越 , 　苏　杰 , 　陈嘉砚
( 中国钢研科技集团公司 , 北京　100081)
摘　要 : 系统研究了预先冷轧变形对马氏体时效钢强化的影响 ,研究结果表明 :510 ℃×3 h 时效引起的强度净增

加值恒定 ,与冷轧变形量无关 ,最终的强度为 :σ=σ0 +ΔσCR +ΔσAge ,即初始强度、
冷加工强化和时效强化的叠加 ,其
中只有冷加工强化 ΔσCR 随变形量变化。电子衍射花样及衍射斑强度分布证实 :510 ℃×3 h 时效后马氏体基体内
析出六方结构的 Ni 3 ( Ti ,Mo) 和正交结构的 Ni3 Mo ,冷轧变形量对时效析出行为没有明显的影响。
关键词 : 马氏体时效钢 ; 冷轧变形 ; 时效 ; 强化
Effect of Prior Cold Rolling Def ormation on

Strengthening of Maraging Steel
YAN G Zhuo2yue , 　SU J ie , 　C H EN J ia2yan
(China Iron and Steel Research Instit ute Group , Beijing 100081 , China)
Abstract : The effect of cold rolling deformatio n p rio r to aging on t he st rengt hening of a maraging steel was investi2
gated. The result s of experiment s indicated t hat t he net st rengt h increment caused by aging at 510 ℃ fo r 3 h is al2
mo st constant , irrespective of percentage of reduction in t hickness. Final st rengt h can be exp ressed as σ=σ0 +ΔσCR
+ΔσAge ,where σ0 is initial st rengt h , and ΔσCR and ΔσAge are st rengt hening cont ribution due to cold wo rking and aging
respectively , and ΔσCR is only related to percentage of reductio n in t hickness. It was co nfirmed by elect ro n diff raction
analysis t hat t he st rengt hening p recipitates are Ni3 ( Ti , Mo ) and Ni3 Mo , regardless of percentage of reductio n in
t hickness.
Key words : maraging steel ; cold rolling ; ageing ; st rengt hening
　　马氏体时效钢通过时效析出金属间化合物获得艺提供依据。
超高强度 ,同时具有足够的韧性和塑性 , 经过近 50
年的研究和应用 ,马氏体时效钢的物理冶金及制造、
1 　实验材料与方法
加工工艺已日趋成熟 , 应用领域日益拓宽。另一方研究用的 18Ni 马氏体时效钢首先由真空感应
面 ,超低碳马氏体时效钢固溶处理 ( 淬火) 形成的马炉熔炼 ,随后经过真空自耗重熔 , 其化学成分 ( 质量
氏体相对较软 ,韧性和塑性很好 ,可以冷加工成各种分数 ) 为 : 17. 89 % Ni 、10. 10 % Co 、4. 53 % Mo 、
01 86 % Ti 、
[ 1～ 4 ]
型材 ,满足各种性能要求 ,其中时效前冷轧变形 0. 12 % Al 、0. 002 7 % C 、0. 002 7 % S 、
不仅提高强度 ,而且可以改善磁性 ,作为磁性合金应 01 003 7 % P ,其余为 Fe 。由于 Co 和 Ti 含量略高 ,
用在磁滞电机转子等结构上 [ 3 ,4 ]
。一些研究表明 : 因此其强度略高于 18Ni ( 300 ) 马氏体时效钢。自耗
由于超低碳马氏体时效钢加工硬化指数较低 , 时效重熔的钢锭经 1 200 ℃×24 h 均质化处理 , 随后在
前冷轧变形强化有限 , 如 18Ni ( 350 ) 马氏体时效钢 1 160 ℃锻造开坯 , 终锻温度为 850 ℃, 重新加热至
固溶后冷轧变形 25 % 、510 ℃×3 h 时效后强度仅 820 ℃保温 1 h 后热轧 ,随后再经过 820 ℃×1 h 固
比未变形的材料提高 0. 5 %[ 1 ] , Kula 对 18Ni ( 250 ) 溶处理后冷轧成 90 mm 宽、
0. 8 mm 厚的带材 ,冷轧
马氏体时效钢也得到类似结果。但 Lee 对 18Ni 变形量 ( 厚度减小 ) 分别控制在 15 % 、30 % 、
45 % 、
( 250) 马氏体时效钢冷轧管的研究表明 : 冷轧后直接 60 %和 75 % ,从不同变形量的带材上切取板拉伸试
时效比重新固溶后时效的材料强度高出 17 % 以样 ,板拉伸试样标距长 30 mm 、
宽 10 mm ,其长度方
上 [5 ]
。本文系统研究了 18Ni 马氏体时效钢冷轧变向平行于轧制方向。加工的试样经过 510 ℃×3 h
形的强化特征 ,以便澄清上述争议 ,并为优化轧制工时效后空冷。拉伸试验在 M TS 810 上进行 ,夹头速
作者简介 : 杨卓越 (19622) , 男 ; 　　E2mail : yangzhuoyue @nercast . co m ; 　　修订日期 : 2007210212

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第4期杨卓越等 : 预先冷轧变形对马氏体时效钢强化的影响・6 7 ・
度为 1 mm/ min ,每一状态 ( 变形加时效 ) 至少 3 个　　关于冷轧变形对马氏体时效钢的强度的影响 ,

试样 ,其平均值作为拉伸性能的测定结果。早期的学者认为时效析出 δ2Ni3 Mo 和 η2Ni3 ( Ti ,
从时效带材上切取透射电镜 ( TEM) 试样 , 观察 Mo ) 金属间化合物强化 , 而 δ2Ni3 Mo 和 η2Ni3 ( Ti ,
面为轧制面 ,手工磨削至 0. 05 mm 。用双喷电解减薄 Mo ) 倾向于在位错上析出 , 因此位错分布控制随后
抛光 ,减薄液为 5 %高铬酸 + 95 %的酒精溶液 ,薄膜清时效析出相的弥散度 , 而冷加工增加材料内位错密
烘干后用 H2800 透射电镜观察 ,操作电压 200 kV 。
洗、度 ,使最终时效后 Ni3 Mo 和 Ni3 ( Ti , Mo ) 析出相弥
散度增加 ,因此最终使材料强化 [ 2 ] 。但本研究证实 ,
2 　试验结果与分析无论变形量多大 ,时效后强度的净增加值恒定 ,冷轧
2. 1 　冷变形强化行为变形并不能促进随后的时效强化 , 但冷轧变形强化
图 1 为时效前冷轧变形量对屈服、
抗拉强度的在时效后仍然保留 ,因此最终强度可用下式表达 :
影响 ,可以看出两个重要的特征 : 首先无论是否时 σ = σ0 + ΔσCR + ΔσAge
效 ,材料的强度随冷轧变形量的增加而上升 ,说明冷式中 ,σ为最终强度 ;σ0 为初始强度 , 取决于钢的成
加工对强化有明显的贡献 ,如冷轧变形 75 %的材料分 ;ΔσCR 为冷变形强度增量 , 取决于变形量 ;ΔσAge 为
比变形 15 % 的材料屈服强度和抗拉强度均高出时效强度增量 ,取决于钢的成分。
21 %以上 ,经过 510 ℃×3 h 时效后 , 屈服强度和抗 2. 2 　时效析出相
拉强度均高出 11 %以上。其次 ,不同变形量的材料图 2 为冷轧变形 15 % 、 510 ℃×3 h 时效样品析
具有几乎恒定的屈强比 ( 表 1 ) , 尽管冷轧变形量相出相的 T EM 照片 ,图 2 ( a ) 为复合电子衍射谱 ,可以
差很大 ,但时效后强度 ( 屈服、抗拉强度) 的净增加值看出存在较强的析出物衍射斑 ,其中强衍射斑点 ( 图
非常相近 ,如表 1 所示 ,经过 510 ℃×3 h 时效后 ,屈 2 ( a ) 中的 1 和 2 ) 既符合正交结构 δ2Ni3 Mo 的
服强度上升 890 ～ 916 M Pa ; 抗拉强度上升 983 ～ ( 211 )δ ,又符合六方结构η2Ni3 ( Ti ,Mo ) 的 ( 202 2 )η ,
-
1 016 M Pa 。时效后强度净增加值随机性地分布在两者的面间距仅相差 0. 05 % ,从电子衍射上无法分

上述范围内 ,与变形量无关 ,另一方面时效后强度增 -
辩 ,但复合电子衍射谱上存在弱的 ( 202 1 )η ( 图 2 ( a )
加值上限比下限仅高 2 %～3 % ,应在测试误差范围中的 3) ,证实了六方结构η2Ni3 ( Ti ,Mo ) 的存在 , 另
内。因此认为时效后强度的净增加值是恒定的。一方面 , 若仅有六方结构 η2Ni3 ( Ti , Mo ) 存在 , 则
- -
( 202 2 )η 的衍射强度应为 ( 202 1 )η 的两倍 , 但对称衍
射谱中衍射斑 2 的强度比衍射斑 3 的强度高出许多
倍 ,因此图 2 ( a) 中强衍射斑点 1 和 2 并非单纯的η2
Ni3 ( Ti ,Mo ) , 应属于 η2Ni3 ( Ti , Mo ) 的 ( 202 2 )η 和
-
Ni3 Mo 的 ( 211 )δ 的复合衍射 , 从而证实正交结构

Ni3 Mo 的存在 , 因此标定为图 2 ( b ) 的结果是合理
的 ,即图 2 ( a) 所示的复合衍射为正交结构 Ni3 Mo 的
两个变态和六方结构 Ni3 ( Ti ,Mo ) 的两个变态。用
图 2 ( a) 中的 1 和 2 得到的中心暗场像分别为图 2
( c) 和 ( d ) 。从电子衍射和相应的暗场图像得到的
图 1 　冷轧变形对拉伸强度的影响 Ni3 Mo 、 Ni3 ( Ti ,Mo ) 与马氏体基体的位向关系也符
Fig. 1 　Effect of cold rolling on tensile strength
合许多文献 [ 6 ,7 ] 报导的结果。
表 1 　拉伸试验结果
Table 1 　Results of tensile test
时效前的强度/ MPa 510 ℃×3 h 时效后的强度/ MPa
冷轧变形量/ %
ReL Rm ReL / R m ReL ΔReL Rm ΔR m ReL / Rm
15 1 040 1 070 0. 972 1 943 903 2 023 983 0. 960
30 1 070 1 097 0. 975 1 963 893 2 063 993 0. 952
45 1 117 1 157 0. 965 2 033 916 2 133 1 016 0. 953
60 1 162 1 197 0. 971 2 070 908 2 177 1 015 0. 951
75 1 267 1 303 0. 972 2 157 890 2 257 990 0. 956
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・6 8 ・钢　铁第 43 卷
(a) 选区复合电子衍射谱 ; 　( b) 电子衍射花样指数化 ; 　(c) 衍射斑 1 的暗场像 ; 　(d) 衍射斑 2 的暗场像

图 2 　冷轧变形 15 %、
510 ℃×3 h 时效样品[ 001] M 晶带轴 TEM 照片
Fig. 2 　Photographs of [ 001] M zone axis of specimen 15 % reduced by cold rolling and aged at 510 ℃ for 3 h , TEM
　　为了进一步确认时效析出相 ,从马氏体 [ 011 ] M 为从马氏体 [ 011 ] M 晶带轴观察 ,Ni3 Mo 析出相的衍

晶带轴观察得到图 3 所示的结果。从图 3 ( a ) 的电射很弱 ,根据 Ni3 ( Ti ,Mo ) 和 Ni3 Mo 与马氏体基体
-
子衍射谱上可以看出 , 由于同时存在多个 {224 0}η 的位向关系[ 6 ,7 ] , 即 ( 011 ) M / / ( 0001 )η/ / ( 010 )δ ,
- - - -
晶面族的电子衍射 , 以及多个 {202 0}η 晶面族弱衍 [ 11 1 ] M / / [ 112 0 ]η/ / [ 100 ]δ ,而 ( 224 0 )η 与 ( 400 )δ 面
射 ( 图 3 ( a ) 中箭头所指 ) , 再次证明六方结构 Ni3 间距仅相差 0. 7 % ,电子衍射是重合的 ,因此图 4 ( b)
( Ti ,Mo ) 的存在 ,与此同时 ,从电子衍射谱上观察到所示用画圆圈斑点得到的暗场像实际上是 ( 224 0 )η
-
-
Ni3 ( Ti ,Mo ) 的两种变态 , 其中变态 1 的 [ 112 0 ]η 方与 ( 400)δ 复合衍射的暗场像 ,只不过 ( 400 )δ 衍射较
- - -
向平行于 [ 11 1 ] M ; 变态 2 的 [ 112 0 ]η 方向平行于 [ 1 弱 ,暗场像以 Ni3 ( Ti ,Mo ) 为主。
- -
1 1 ] M 晶向 ,同时存在多个 ( 224 0 )η 的二次衍射 ( 图用与上述同样的方法和位向观察了冷轧变形
3 ( a) 中的 1 和 2 ) η
, 相与马氏体基体之间的位向关 75 % 、
510 ℃ ×3 h 时效的样品 , 得到与冷轧变形
- -
系为 : { 110 } M / / { 0001 }η , < 11 1 > M / / < 112 0 >η 。 15 %样品相同的结果 ( 图 4 ) ,其分析过程不再赘述。
这一结果并非意味着不存在正交结构 Ni3 Mo 。因这些结果表明 : 尽管时效前的冷轧变形量不同 ,但冷
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第4期杨卓越等 : 预先冷轧变形对马氏体时效钢强化的影响・6 9 ・
轧变形量对时效行为没有明显的影响 , 这也许是时 Maraging Steel Through Thermomechanical Treat ment s [J ] . Met 2

allurgical Transactions , 1974 , 5 (3) :685.
效后强度净增加值不受冷变形量影响的主要原因。
[ 2 ] 　Roberson J A ,Adair A M. The Effect s of Prior Deformation on
t he St rengt hening Processes in Maraging Steel [ J ] . Transac2
3 　结论
tions of t he TMS2A IME , 1969 , 245 (9) : 1937.
( 1) 马氏体时效钢时效前冷轧变形 , 未时效和 [ 3 ] 　Ahmad Z , Farooque M , Haq A U , et al . Text ure Develop2
510 ℃×3 h 时效后的强度 ( 屈服、

抗拉强度) 均随冷 ment in Dual2Phase Cold2Rolled 18 pct Ni Maraging Steel [J ] .
Metallurgical Transactions , 1997 , 28A (12) : 2459.
轧变形量的增加而上升。
[ 4 ] 　Abreu H F G , Tavares S S M , Silva J J M , et al . The Influ2
( 2) 时效引起的强度净增加值恒定 , 与冷轧变
ence of an Intermediate Austenization Heat Treat ment in t he
形量无关 ,因此最终强度可表达为 :σ=σ0 + ΔσCR + Text ure of Cold2Rolled and Aged 18 % Ni Maraging Steel [J ] .
ΔσAge ,即初始强度、冷加工强化和时效强化的叠加 , Materials Characterization , 2004 , 52 (3) : 203.
其中只有 ΔσCR 随冷轧变形量变化。 [ 5 ] 　Lee I K ,Chou C P ,Cheng C M ,et al . Effect of Heat Treat ment
( 3) 透射电镜电子衍射花样及衍射斑强度分布 on Micro st ruct ures of Flow Formed C2 250 Maraging Steel [J ] .

Materials Science and Technology , 2003 , 19 (11) : 1595.
表明 :510 ℃×3 h 时效后马氏体基体内析出六方结
[ 6 ] 　Tewari R ,Mazumder S ,Batra I S ,et al. Precipitation in 18 wt % Ni
构的 Ni3 ( Ti , Mo ) 和正交结构的 Ni3 Mo , 冷轧变形 Maraging Steel of Grade 350[J ] . Acta Materialia , 2000 , 48 (5) :
量对时效行为没有明显的影响。 1187.
[ 7 ] 　L I X D , YIN Z D. A Co mp uter2Simulated Elect ron Diff raction
参考文献 :
Analysis of Precipitates in 18Ni (350) Maraging Steel [J ] . Ma2
[ 1 ] 　Rack H J , Kalish D. Improved Fatigue Resistance of 18Ni (350) terials Letters , 1995 , 23 (426) : 269.
( 上接第 60 页)
　　( 3) 通过末道次计算出口厚度的波动可以识别参考文献 :
操作工人的卡量反馈以及钢坯的个体异常 , 从而去
[ 1 ] 　胡贤磊 ,赵　忠 , 矫志杰 , 等 . 中厚板厚度的在线软测量方法
除回归的变抗力参数中的不良数据 , 保持数据的优
[J ] . 钢铁研究学报 , 2006 , 18 (7) : 55. ( HU Xian2lei , ZHAO
良性。
Zhong , J IAO Zhi2jie , et al . On2Line Soft2Mearsuring Met hod
( 4) 实际应用表明 , 该自适应轧制模型可以在 of Plate Thickness [ J ] . Journal of Iron and Steel Research ,
无测厚仪下稳定的实现轧制力的高精度预报 , 该模 2006 , 18 (7) :55. )
型的轧制力预测偏差可以控制在 7 %以内 , 其中轧 [ 2 ] 　胡贤磊 ,邱红雷 , 刘相华 , 等 . 中厚板弹跳曲线零点漂移对轧
制力预测偏差在 5 %以内的道次可占 73 %以上 , 出制力自适应的影响 [ J ] . 钢铁研究学报 , 2003 , 15 ( 1 ) : 24.

( HU Xian2lei , Q IU Hong2lei , L IU Xiang2hua , et al . Influence
口厚度的预计算偏差一般可以控制在 0. 2 mm 以
of Zero Wave for Spring Curve on Rolling Force Adaption in
内 ,具有很强的实用性。 Plate Rolling[J ] . Journal of Iron and Steel Research , 2003 , 15
(1) :24. )
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Control of High Strength Low Alloy (HSLA) Steel Properties

Abstract:
Most HSLA steels are furnished in the as-hot-rolled condition with ferritic-pearlitic microstructure. The
exceptions are the controlled-rolled steels with an acicular ferrite microstructure and the dual-phase steels
with martensite dispersed in a matrix of polygonal ferrite. These two types of HSLA steels use the formation
of eutectoid structures for strengthening, while the ferritic-pearlitic HSLA steels generally require
strengthening of the ferrite.
Most HSLA steels are furnished in the as-hot-rolled condition with ferritic-pearlitic microstructure. The
exceptions are the controlled-rolled steels with an acicular ferrite microstructure and the dual-phase steels
with martensite dispersed in a matrix of polygonal ferrite. These two types of HSLA steels use the formation
of eutectoid structures for strengthening, while the ferritic-pearlitic HSLA steels generally require
strengthening of the ferrite.
Pearlite is generally an undesirable strengthening agent in structural steels because it reduces impact
toughness and requires higher carbon contents. Moreover, yield strength is largely unaffected by a higher
pearlite content.
Strengthening Mechanisms in Ferrite
The ferrite in HSLA steels is typically strengthened by grain refinement, precipitation hardening, and, to a
lesser extent, solid-solution strengthening. Grain refinement is the most desirable strengthening
mechanism because it improves not only strength but also toughness.
Grain refinement is influenced by the complex effects of alloy design and processing methods. For
example, the various methods of grain refinement used in the three different stages of hot rolling (that is,
reheating, hot rolling, and cooling) include:
The addition of titanium or aluminum to retard austenite grain growth when the steel is reheated for
hot deformation or subsequent heat treatment
The controlled rolling of microalloyed steels to condition the austenite so that it transforms into
fine-grain ferrite
The use of alloy additions and/or faster cooling rates to lower the austenite-to-ferrite transformation
temperature.
The use of higher cooling rates for grain refinement may require consideration of its effect on precipitation
strengthening and the possibility of undesirable transformation products.
Precipitation strengthening occurs from the formation of finely dispersed carbonitrides developed during
heating and cooling. Because precipitation strengthening is generally associated with a reduction in
toughness, grain refinement is often used in conjunction with precipitation strengthening to improve
toughness.
Precipitation strengthening is influenced by the type of carbonitride, its grain size, and, of course, the
number of carbonitrides precipitated. The formation of MC is the most effective metal carbide in the
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precipitation strengthening of microalloyed niobium, vanadium, and/or titanium steels. The number of fine
MC particles formed during heating and cooling depends on the solubility of the carbides in austenite and
on cooling rates.
Steelmaking
Precise steelmaking operations are also essential in controlling the properties and chemistry of HSLA
steels. Optimum property levels depend on such factors as the control of significant alloying elements and
the reduction of impurities and nonmetallic inclusions.
Developments in secondary steelmaking such as desulphurization, vacuum degassing, and argon

shrouding have enabled better control of steel chemistry and the effective use of microalloyed elements.
Compositional limits for HSLA steel grades described in ASTM specifications the use of vacuum degassing
equipment allows the production of interstitial-free (IF) steels. The IF steels exhibit excellent formability,
high elongation, and good deep draw/ability.
Compositions and Alloying Elements
Chemical compositions for the HSLA steels are specified by ASTM standards. The principal function of
alloying elements in these ferrite-pearlite HSLA steels, other than corrosion resistance, is strengthening of
the ferrite by grain refinement, precipitation strengthening, and solid-solution strengthening. Solid-solution
strengthening is closely related to alloy contents, while grain refinement and precipitation strengthening
depend on the complex effects of alloy design and thermo-mechanical treatment.
Alloying elements are also selected to influence transformation temperatures so that the transformation of
austenite to ferrite and pearlite occurs at a lower temperature during air cooling. This lowering of the
transformation temperature produces a finer-grain transformation product, which is a major source of
strengthening. At the low carbon levels typical of HSLA steels, elements such as silicon, copper, nickel, and
phosphorus are particularly effective for producing fine pearlite. Element such as, manganese and
chromium, which are present in both the cementite and ferrite, also strengthen the ferrite by solid-solution
strengthening in proportion to the amount, dissolved in the ferrite.
In the presence of alloying elements, the practical maximum carbon content at which HSLA steels can be
used in the as-cooled condition is approximately 0.20%. Higher levels of carbon tend to form martensite or
bainite in the microstructure of as-rolled steels, although some of the higher-strength low-alloy steels have
carbon contents that approach 0.30%.
The required strength is developed by the combined effect of:
• Fine grain size developed during controlled hot roiling and enhanced by microalloyed elements
(especially niobium)
• Precipitation strengthening caused by the presence of vanadium, niobium, and titanium in the
composition.
Nitrogen additions to high-strength steels containing vanadium are limited to 0.005% and have become
commercially important because such additions enhance precipitation hardening. The precipitation of
vanadium nitride in vanadium-nitrogen steels also improves grain refinement because it has a lower
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solubility in austenite than vanadium carbide.
Manganese is the principal strengthening element in plain carbon high-strength structural steels. It
functions mainly as a mild solid-solution strengthener in ferrite, but it also provides a marked decrease in
the austenite-to-ferrite transformation temperature. In addition, manganese can enhance the precipitation
strengthening of vanadium steels and. to a lesser extent, niobium steels.
One of the most important applications of silicon is its use as a deoxidizer in molten steel. Silicon has a
strengthening effect in low-alloy structural steels. In larger amounts, it increases resistance to scaling at
elevated temperatures. Silicon has a significant effect on yield strength enhancement by solid-solution
strengthening and is widely used in HSLA steels for riveted or bolted structures.
Copper in levels in excess of 0.50% also increases the strength of both low- and medium-carbon steels by
virtue of ferrite strengthening, which is accompanied by only slight decreases in ductility. Copper can be
retained in solid solution even at the slow rate of cooling obtained when large sections are normalized, but it
is precipitated out when the steel is reheated to about 510 to 605°C (950 to 1125°F). At about 1% copper,
the yield strength is increased by about 70 to 140 MPa regardless of the effects of other alloying elements.
Copper in amounts up to 0.75% is considered to have only minor adverse effects on notch toughness or
weldability. Copper precipitation hardening gives the steel the ability to be formed extensively and then
precipitation hardened as a complex shape or welded assembly.
The atmospheric-corrosion resistance of steel is increased appreciably by the addition of phosphorus, and
when small amounts of copper are present in the steel, the effect of the phosphorus is greatly enhanced.
When both phosphorus and copper are present, there is a greater beneficial effect on corrosion resistance
than the sum of the effects of the individual elements.
Chromium is often, added with copper to obtain improved atmospheric-corrosion resistance.
Nickel is often added to copper-bearing steels to minimize hot shortness.
Molybdenum in hot-rolled HSLA steels is used primarily to improve hardenability when transformation
products other than ferrite-pearlite are desired. Molybdenum (0.15 to 0.30%) in microalloyed steels also
increases the solubility of niobium in austenite, thereby enhancing the precipitation of NbC(N) in the ferrite.
This increases the precipitation-strengthening effect of NbC(N).
Aluminum is widely used as a deoxidizer and was the first element used to control austenite grain growth
during reheating. During controlled rolling, niobium and titanium are more effective grain refiners than
aluminum.
Vanadium strengthens HSLA steels by both precipitation hardening the ferrite and refining the ferrite grain
size. The precipitation of vanadium carbonitride in ferrite can develop a significant increase in strength that
depends not only on the rolling process used, but also on the base composition. Carbon contents above
0.13 to 0.15% and manganese content of 1% or more enhances the precipitation hardening, particularly
when the nitrogen content is at least 0.01%.
Titanium is unique among common alloying elements in that it provides both precipitation strengthening
and sulfide shape control. Small amounts of titanium (<0.025%) are also useful in limiting austenite grain
growth. However, it is useful only in fully killed (aluminum deoxidized) steels because of its strong
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deoxidizing effects, the versatility of titanium is limited because variations in oxygen, nitrogen, and sulfur
affect the contribution of titanium as carbide strengthened.
Zirconium can also be added to killed high-strength low-alloy steels to improve inclusion characteristics,
particularly in the case of sulfide inclusions, for which changes in inclusion shape improve ductility in
transverse bending.
Boron has no effect on the strength of normal hot-rolled steel but can considerably improve hardenability
when transformation products such as acicular ferrite are desired in low-carbon hot-rolled plate.
Treatment with calcium is preferred for sulfide inclusion shape control.
Controlled Rolling
The hot-rolling process has gradually become a much more closely controlled operation, and controlled
rolling is now being increasingly applied to microalloyed steels with compositions carefully chosen to
provide optimum mechanical properties at room temperature.
Controlled rolling is a procedure whereby the various stages of rolling are temperature controlled, with the
amount of reduction in each pass predetermined and the finishing temperature precisely defined. This
processing is widely used to obtain reliable mechanical properties in steels for pipelines, bridges, offshore
platforms, and many other engineering applications. The use of controlled rolling has resulted in improved
combinations of strength and toughness and further reductions in the carbon content of microalloyed HSLA
steels.
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SUSCEPTIBILITY TO BRITTLE FRACTURE

OF FLANGES IN ASTM A105.
A. Dhooge and E. Deleu, Research Center of the Belgian Welding Institute (BWI)
ABSTRACT
The incentive for the present study was a brittle fracture that occurred in a 101 mm
thick 24” welding neck flange of Class 600 according to ANSI B16.5. This
component, with a coarse grain microstructure, was installed in a high-density
polyethylene (HDPE) loop reactor and failed presumably at a temperature of -16 °C.
In this project, a large number of ASTM A105 carbon steel flanges has been
investigated with the main purpose of evaluating the material’s fracture toughness
and defect tolerance. Investigations revealed large variations in microstructure, grain
size and hardness, depending on the manufacturing route and heat treatment. Even
multiple small hydrogen cracks were found in two of the investigated 24” flanges.
Toughness has been evaluated by notch impact and CTOD fracture toughness tests
at different low temperatures. A correlation was made between microstructure, grain
size and fracture toughness. A fitness-for-purpose analysis, based on CTOD fracture
toughness, allowed to assess the risk for brittle fracture in large (24” / Class 600)
carbon steel flanges complying with ASTM A105.
1. INTRODUCTION
Codes, ASME VIII div.1 and ASME B31.3 allow carbon steel conforming to
ASTM A105 [1] for applications down to a minimum temperature of -29 °C (-20 °F).
In January 1998, Borealis Beringen (Belgium) experienced brittle fracture in a raised

face 101 mm thick 24” welding neck flange of Class 600 operating in the loop of a
reactor of an HDPE-unit since 1990. Due to a power dip in the plant, the product in
the reactor boiled at atmospheric pressure, resulting in cooling of the reactor and the
loop to about -16 °C. The line was partly plugged with solid product at the location of
the failed flange, which resulted in an uneven cooling of this flange. It was assumed
that, close to the boiling product, the temperature of the flange was about –16 °C but
about +60 °C at the location of the plug, see Figure 1. The flange cracked at the
transition between the conical and cylindrical part of the welding neck, see Figure 2,
at a location coinciding with the cold area.
Previous investigations at the Belgian Welding Institute (BWI) revealed that the
flange had a coarse grained (ASTM grain size number 5 to 6) ferrite-pearlite
microstructure, see Figure 3. The 27 J Charpy-V impact transition temperature was
about +10 °C. An additional heat treatment at BWI (normalising at 900 °C for one
hour) resulted in grain refinement to ASTM grain size number 9, see Figure 4, and in
a shift of impact transition temperature to below -30 °C.
As a result of this, a research project has been initiated with the following main
objectives:
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- to get a better understanding of the relation between microstructure, grain size,

hardness and fracture toughness properties of flanges in carbon steel
complying with ASTM A105
- to formulate recommendations and requirements for flanges actually in use in
different plants as well as for new installations.
2. INVESTIGATED MATERIAL
Within the scope of a fitness-for-purpose analysis, a series of flanges with different

sizes and of various rating classes has been fully characterised.
To achieve this, the fractured 24” / Class 600 flange from Borealis (symbolised
hereafter by FLA) has been retained for further investigation as well as two other
flanges of same size and rating class (symbolised by FLB and FLD), which were
removed from the HDPE reactor. Moreover, twenty new flanges with different sizes
and rating classes, manufactured in carbon steel conforming to ASTM A105 have
been ordered at one supplier (stockist). Flanges were obtained from three different
manufacturers together with EN10204:3.1B certificates.
An overview of all investigated welding neck flanges and most important topics is
given in Table 1. According to the relevant certificates, all flanges received a
normalising heat treatment after forging, which, according to ASTM A105, is only
mandatory for flanges above Class 300.
3. TEST PROGRAMME AND RESULTS
The investigation of in total twenty-three flanges included chemical analyses,

metallographic examinations, hardness measurements and mechanical testing
consisting of notch impact, tensile and CTOD fracture toughness tests. The main
outcome of this is given in the following paragraphs.
3.1 Metallography
The results of surface replica examinations and hardness measurements (made by

means of a portable field apparatus, type Microdur) are included in Table 1. From
this, one can observe that the original 24” flanges from the HDPE reactor had not
been normalised correctly resulting in a coarse grained microstructure.
Similarly, the twenty investigated new flanges show a large variation in grain size.
Also in this case it is clear that some of the flanges were not or incorrectly
normalised, although officially mentioned on the accompanying certificates.
Besides, the metallographic examinations on radial cross sections revealed that

microstructure, grain size and hardness can vary substantially within one and the
same flange and therefore raise questions about its homogeneity. Indeed, the
difference between minimum and maximum individual ASTM grain size numbers
measured per flange varied from 1,3 to 2,3. The mean values for each flange are
given in Table 1 and are considered within this study as the most representative
grain size for each flange separately.
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However, a correct normalising heat treatment at 910 °C for 30 minutes performed by

BWI on the unfractured flange FLD yielded a fine grain and a fairly homogeneous
microstructure (ASTM grain size number 9,8) over the whole thickness with little
variation in grain size (1,3) and hardness. This again is an indication that the heat
treatment during manufacturing in many cases has not been performed properly.
Also heat treatment trials realised on pieces extracted from the unfractured flange
FLB demonstrate that the test material is not sensitive for grain growth as longer
exposure times and higher temperatures do not really affect the grain size.
3.2 Cracks in 24” / Class 600 flange FLB and FLV
Metallographic and ultrasonic examinations have revealed multiple small cracks (up
to 2 mm long) in two of the investigated flanges, see Figure 5. The nature and
morphology of these cracks indicate that these were typical hydrogen cracks or so
called flakes. SEM investigation revealed a brittle cleavage type of fracture.
Such internal fissures are attributed to stresses produced by localised transformation

and decreased solubility of hydrogen during cooling after hot working [2]. Hydrogen
in excess of 5 ppm plays an important role in this phenomenon and can be prevented
by degassing treatments. Vacuum degassing treatments are the most efficient and
consistent way of reducing hydrogen levels to less than 3 ppm, but there are high
capital running and maintenance costs. Soaking treatments are costly and time
consuming, especially for large section sizes. Also slow cooling after forging can be
beneficial: this slow cooling operation presumably permits the hydrogen to diffuse out
of the steel and thereby minimises the susceptibility to flaking.
3.3 Mechanical properties
3.3.1 Notch impact toughness
Notch impact data obtained on longitudinal standard test samples showed that the
impact toughness of flanges with a coarse grained microstructure (including the
fractured flange FLA) is quite low, see Figure 6. The transition temperature
corresponding of such flanges with a mean impact toughness of 27 J is about
+20 °C. At the minimum operating temperature of -29 °C allowed by ASME B31.3,
these flanges possess an impact toughness of less than 10 J.
As expected, flange FLD normalised at BWI exhibits a much better impact toughness
transition behaviour with mean values of at least 40 J down to -29 °C. Impact
toughness values of nearly 27 J have been obtained even at -46 °C.
The impact data thus demonstrate that material complying with ASTM A105 can
exhibit an extremely different impact toughness transition. Indeed mean notch impact
toughness for instance at –46 °C and at +20 °C can vary respectively between 3 J
(flange FLT) and 68 J (flange FLK) and between 30 J (flange FLR) and 185 J
(flange FLJ).
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Apparently, the impact toughness is mainly governed by the grain size. A fine-
grained test material (ASTM grain size number of 9 or higher) undoubtedly leads to
a better impact toughness behaviour than a coarse-grained test material (ASTM
grain size number of 7 or lower).
To illustrate the relation between grain size and impact toughness, a summary of
mean grain sizes detected by metallography and 27 J transition temperatures for all
flanges is given in Figure 7. This figure shows that in general a fine- and a coarse-
grained material respectively possess a transition temperature below –40 °C (good
behaviour) and above 0 °C (bad behaviour). Surprisingly one 12” / Class 600 flange
(FLL) with a coarse grain microstructure has yielded an acceptable notch impact
behaviour with a 27 J transition temperature of –35 °C.
3.3.2 CTOD fracture toughness
CTOD fracture toughness tests have been done on 24 mm thick square section three
point bend specimens removed in longitudinal direction from the inner side of four
flanges with different grain sizes. All specimens were fatigue notched from the
outside of the flange while CTOD fracture toughness testing was realised according
to BS4778:Part1:1991 in the temperature range between -29 °C and +20 °C.
The test results are summarised in Table 2. The untreated, coarse-grained flanges
FLA and FLB possess a moderate fracture toughness while flange FLD, normalised
at BWI, exhibits an excellent resistance against brittle fracture initiation. Flange FLK
with the intermediate grain size (although still with a mean ASTM grain size number
of 9,1) amazingly yields by far the best CTOD fracture toughness at all temperatures.
The reason for this is that nearly all samples removed from flanges FLD and FLK
exhibited a maximum force plateau behaviour so that the results have been governed
by other material properties than the resistance against fracture initiation (strain
hardening, resistance against ductile tearing, …).
4. DISCUSSION
From the metallographic examination, it is concluded that about 40% of the

investigated flanges has not been heat treated properly after forging despite the
accompanying certification that all flanges had been normalised. This is evidenced by
the coarse grained microstructure and presence of Widmanstatten ferrite.
This is fully in line with the findings of Bartlett, Frost and Bowen [3] who have studied
the fracture toughness and defect assessment of low temperature carbon steel
flanges complying with ASTM A350. The study was typically for gas-plant piping
systems where fitness-for-purpose needs to be established at a temperature of
-64 °C. This is the lowest temperature that can be reached on theoretical grounds if
rapid depressurisation of the system occurs following a process trip or fault condition.
They also observed that many large steel flanges possess poor toughness. A
rejection rate of up to 40% (16 flanges out of a sample of 44) has been reported on
flanges ordered to ASTM A350 LF2 (requiring a minimum impact energy of 20 J at
-46 °C in a standard Charpy impact test). Problems are believed to arise because
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accompanying test certificates are often based on smaller-scale test bars supplied
from the same heat of material. While such test bars may be considered
representative of the chemical composition of the entire heat, it is unlikely that they
can represent accurately the forging and heat-treatment schedules performed
subsequently to produce the final flanges. It should be noted that although
certification anomalies are found occasionally, little evidence of in-service toughness
problems with such flanges has ever been reported.
Table 2: CTOD fracture toughness of flanges with different grain sizes

(underlined data are minimum “critical” properties)
Test temp. CTOD values Fracture behaviour

Flange
(°C) (mm) [*]
+20 0,58-0,15-0,60 m/f/m
FLA (Fractured)
0 0,36-0,14-0,12 f/f/f
ASTM 6,7
-29 0,27-0,09-0,12 f/f/f
+20 0,17-0,08-0,11 f/f/f
FLB (Untreated)
0 0,05-0,06-0,10 f/f/f
ASTM 6,2
-29 0,09-0,08-0,04 f/f/f
+20 0,41-0,44-0,60 m/m/m
FLD (Normalised at BWI)
0 0,56-0,61-0,62 m/m/m
ASTM 9,8
-29 0,62-0,59-0,55 m/f/m
+20 0,90-1,51-1,32 e/m/m
FLK (Untreated)
0 1,39-1,36-1,44 m/m/m
ASTM 9,1
-29 1,52-1,35-1,50 m/m/m
[*] m = maximum force plateau
f = unstable fracture (case “c” or “u” of BS4778)
e = end of clip gauge
The regression line of all data points given in Figure 7, each determined by means of
eighteen impact tests and about forty to fifty grain size measurements, proves that a
material should have at least an ASTM grain size number of 7,3 or 8,1 in order to
guarantee a maximum impact transition temperature of respectively -10 °C or -29 °C.
If it is accepted that the detected variation in grain size number across an entire
flange follows a normal distribution (with a measured standard deviation of 0,4) and if
it is required that at least 90% of the material should be adequate, then the mean
grain size number of the flange should be 0,5 higher than the grain size number
required above.
Because of this detected variation but also because of the deviation between the
grain size measured by replica and by metallography at the same location (due to
different orientation of both samples) one single measurement should yield a grain
size number which is at least 1,3 above the mean level assuring adequate
toughness. If the number of replicas can be increased up to four then this average
grain size should only be 0,8 above the required mean level for the flange.
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This conservative approach permits to deduce that the ASTM grain size number
determined on one single replica should be at least equal to 9,1 (=7,3+0,5+1,3) or 9,9
(=8,1+0,5+1,3) to assure sufficient toughness respectively at -10 °C or -29 °C. If
instead it is possible to prepare four replicas evenly distributed over the
circumference then the mean ASTM grain size number should be at least 8,6
(=7,3+0,5+0,8) or 9,4 (=8,1+0,5+0,8) depending on the minimum operating
temperature. More replicas are needed to further relax these requirements but this
would increase the procedural costs to unpractical levels.
These very stringent criteria are necessary because of the “limited” number of replica
examinations within this project. The correlation between the grain size detected by
replica and the mean grain size determined on radial cross sections therefore cannot
be assessed statistically. Only observed ranges of deviations can be used which
should be appropriately interpreted in order not to overestimate the material’s
fracture toughness and defect tolerance.
On the other hand, Figure 7 also demonstrates that flanges complying with
ASTM A105, have 27 J impact transition temperatures not higher than +20 °C. If
severe stresses may develop only at ambient temperatures or higher, then it is clear
that these flanges may be used without taking further precautions in the as-delivered
condition.
5. FITNESS FOR PURPOSE
If, as stated before and as general criterion, it is accepted that a pressure part can
only be exposed to design conditions of stress and strain at temperatures at or
beyond its 27 J transition temperature, then only eleven out of the twenty-three
flanges may be taken into service working at temperatures down to -29 °C. If all
flanges fabricated following the said ASTM standard should be accepted then the
minimum design temperature should be about ambient temperature.
Another possible evaluation may be developed from a fitness-for-purpose analysis

following BS 7910:1999 [4] “Guide on methods for assessing the acceptability of
flaws in metallic structures”, which is based particularly on CTOD fracture toughness.
This evaluation permitted to determine at –29 °C maximum tolerable defect sizes for
assumed stress conditions.
Indeed in the normal loading conditions of internal pressure and bolt-tightening, a

material having the tensile (yield of 290 MPa) and toughness (CTOD of 0,09 mm)
properties of those detected for the failed flange can withstand at -29 °C a sharp
surface defect at the intersection of the conical part and the pipe section of maximum
1,5 mm deep and 7,5 mm long (or any equivalent non-planar defect). Long surface
defects (even over the whole circumference) of maximum 0,7 mm deep can be
allowed under the same conditions without risk for brittle fracture.
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These conclusions are based on a Level 2A or normal assessment and includes so

called partial safety factors on applied stress, defect size and toughness valid for a
failure probability of 0,001 (events/year). It is generally advised to take account of
safety factors due to the uncertainty in input data necessary for the assessment.
If non-destructive testing is capable of detecting such flaws and if a proper repair

procedure can be realised then the risk for brittle fracture initiation in these flanges is
presumed to be acceptably small. These acceptance levels may not be viewed as
new criteria for quality control or good workmanship levels as applying a
fitness-for-purpose analysis based on an Engineering Critical Assessment or ECA
should be done only exceptionally. The occurrence of defects even acceptable to
BS7910 instead should be regarded as a need for improving the manufacturing
quality.
6. CONCLUSIONS
A first important conclusion is that in many cases, data on the certificates do not
comply with the obtained test results. Indeed impact data mentioned on certificates
are consistently higher compared to those actually measured on the forged flanges.
Also the certified heat treatment (normalisation) is either incorrect or has not been
performed at all. This results in a large grain size and poor toughness. Moreover, the
S-, Cr- and Cu-contents of one flange, although acceptable, do not correspond with
the composition mentioned on the certificate. This shows that the particular flange
has been produced from another heat than the one indicated on the certificate.
Finally, the carbon equivalent of the flanges (ranging from 0,36 to 0,47) is
systematically higher than the carbon equivalent indicated on the certificates. The
largest difference was measured on the 18” / Class 600 flange FLY (0,45 versus
0,38). This has a repercussion on the weldability of the material (hardening and cold
cracking susceptibility).
It is further concluded that the investigated 24” / Class 600 flanges removed from the
HDPE reactor have not been correctly heat treated before installation, although this
is mandatory following ASTM A105 for all flanges above Class 300.
Many small cracks were detected in two of the investigated 24” / Class 600 flanges,
which were typical hydrogen cracks (flakes).
The notch toughness strongly varies from flange to flange and is closely related to
the measured grain size. Microstructure and grain size may also vary considerably
within the same flange. However, this phenomenon has not caused a lot of scatter on
the material’s tensile, hardness and toughness properties.
Anyhow, determination of grain sizes based on replica examinations should be done

on a minimum of four locations per flange. The required mean ASTM grain size
number determined from the present investigation is 8,6 or 9,4 to assure an
appropriate toughness respectively down to -10 °C or -29 °C. Otherwise, it is unsafe
to apply ASTM A105 flanges at such conditions. The advantage of this technique is
that it can be applied on existing and on new flanges.
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http://www.tcr-arabia.com/ndt/metallographic-replication-in-situ.shtml
It is recommended to perform ultrasonic as well as replica examinations on all

flanges before putting them into service.
A fitness-for-purpose analysis following BS7910:1999 “Guide on methods for

assessing the acceptability of flaws in metallic structures” has shown that under
conditions of internal pressure and bolt-tightening a surface defect at the intersection
of the conical part and the pipe section of maximum 1,5 mm deep and 7,5 mm long
can be tolerated at –29 °C in flanges complying with ASTM A105. Long surface
defects of maximum 0,7 mm deep can be allowed under the same conditions. If such
flaws can be detected and repaired then the risk for brittle fracture initiation is virtually
excluded.
Acknowledgements
This study has been funded by the Belgian “Federaal Ministerie van Tewerkstelling
en Arbeid – Administratie van de Arbeidsveiligheid – Directie van Chemische
Risico’s”.
The author’s are grateful to the members of the steering group for their valuable
discussions and suggestions: Federaal Ministerie van Tewerkstelling en Arbeid,
Solvay, Borealis Polymers, Fina Antwerp Olefins, Fina Raffinaderij Antwerpen,
Monsanto Europe and Distrigas.
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Table 1: Overview of investigated steel flanges in carbon steel ASTM A105

Forging Normalising ASTM grain ASTM grain 27J
Hardness -
Flange Size / Class Temperature Temperature size number size number Transition
Microdur
(Certificate) (Certificate) (replica) (metallography) Temperature
FLA 24" - 600Lbs ? ? 172 6,5 6,7 15°C
FLB 24" - 600Lbs 1230°C 920°C - Still air 187 5,9 6,2 20°C
FLD 24" - 600Lbs ? 920°C - Still air 166 6,3 9,8 (*) -45°C
FLE 12" - 150Lbs ? 900°C - Still air 136 8,6 7,3 -10°C
FLF 12" - 150Lbs ? 900°C - Still air 161 7,7 7,5 -10°C
FLG 12" - 150Lbs ? 900°C - Still air 147 8,6 7,4 -5°C
FLH 12" - 150Lbs ? 900°C - Still air 149 8,4 7,4 -10°C
FLI 12" - 600Lbs ? 900°C - Still air 136 9,3 9,1 -50°C
FLJ 12" - 600Lbs ? 900°C - Still air 134 9,2 9,2 -55°C
FLK 12" - 600Lbs ? 900°C - Still air 140 8,7 9,1 -55°C
FLL 12" - 600Lbs 1180°C 910°C - Still air 151 6,1 6,9 -35°C
FLM 18" - 600Lbs 1180°C 910°C - Still air 153 9,8 9,3 -60°C
FLN 18" - 600Lbs 1180°C 910°C - Still air 164 9,4 9,2 -40°C
FLY 18" - 600Lbs 1180 °C 910°C - Still air 126 6,6 6,7 0°C
FLP 18" - 600Lbs 1180°C 910°C - Still air 153 9,5 9,5 -55°C
FLQ 24" - 150Lbs ? 900°C - Still air 153 7,2 6,9 15°C
FLR 24" - 150Lbs 1180°C 910°C - Still air 164 6,8 6,7 15°C
FLS 24" - 150Lbs 1180°C 910°C - Still air 126 6,7 6,6 5°C
FLT 24" - 150Lbs 1230°C 920°C - Still air 153 6,4 6,7 10°C
FLU 24" - 600Lbs 1180°C 910°C - Still air 153 9,4 9,2 -55°C
FLV 24" - 600Lbs 1180°C 910°C - Still air 164 9,1 8,8 < -60°C
FLW 24" - 600Lbs 1180°C 910°C - Still air 126 9,4 9,1 -60°C
FLX 24" - 600Lbs 1180°C 910°C - Still air 153 9,3 9,1 -50°C
Flanges FLA, FLB and FLD have been removed from HDPE loop reactor - Flanges FLE to FLX are new flanges
(*) ASTM grain size number after normalising
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+60 °C -16 °C
Figure 1: Uneven temperature distribution in the 24” / Class 600 flange FLA
Crack
Figure 2: Brittle fracture location in the 24” / Class 600 flange FLA
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Figure 3: Microstructure of the broken 24” / Class 600 flange FLA (ASTM grain
size number from previous investigation: 5 to 6) – same magnification as
Figure 4
Figure 4: Microstructure of the broken 24” / Class 600 flange FLA after
normalising trial at 900 °C for one hour (ASTM grain size number from previous
investigation: 9)
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Figure 5: Small hydrogen cracks in the 24” / Class 600 flange FLB
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120
100
Mean Energy (J)
80
FLA
60 FLB
FLD
40
20
0
-60 -40 -20 0 20 40 60 80
Temperature (°C)
Figure 6: Notch impact temperature transition curves for flanges removed from
the HDPE reactor (FLA = fractured flange; FLB = untreated flange with
microcracks; FLD = flange normalised at BWI)
20
Transition temperature (°C)
-20
-40
-60
-80
5 6 7 8 9 10 11
Mean ASTM grain size number (by metallography)
Figure 7: 27 J impact transition temperature against mean grain size for all
investigated flanges (open symbols = Class 150, closed symbols = Class 600)
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REFERENCES
1. ASTM A105 - 96 “Standard Specification for Carbon Steel Forgings for Piping
Components”
2. Hydrogen in steel castings.

The Casting Development Centre
Technical Bulletin No. 50
3. Fracture toughness and defect assessment of low-temperature carbon steel

flanges.
Bartlett, R.A.; Frost, S.R. and Bowen, P.
International Journal of Pressure Vessels and Piping – vol.48 – no 3 – 1991
4. BS7910:1999 “Guide on methods for assessing the acceptability of flaws in

metallic structures”
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Steel Making
金属材料与热处理技工培训视频
http://player.youku.com/player.php/sid/XMzIzODQxMg==/v.swf
Appendix A.
Menu
http://player.youku.com/player.php/sid/XMzIzODU0MA==/v.swf
http://player.youku.com/player.php/sid/XMzIzOTM4NA==/v.swf
Appendix A.
Menu
http://player.youku.com/player.php/sid/XMzIzOTQ3Ng==/v.swf
锻造方法与工艺
http://www.56.com/n_v42_/c38_/0_/12_/jixiezhizao_/zhajm_120788749021_/1631000_/0_/32564242.swf
Appendix A.
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http://www.56.com/n_v156_/c40_/24_/16_/danlin57_/121622148628_/390530_/0_/36753955.swf
http://www.56.com/n_v198_/c34_/10_/15_/mobyplay_/sc_mp4_120603129195_/879000_/0_/31186127.swf
Appendix A.
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http://www.56.com/n_v155_/c30_/21_/1_/qq251417457_/zhajm_11943676576x_/901000_/0_/22322261.swf
http://www.56.com/n_v48_/c34_/20_/6_/zhongguonian2008_/zhajm_120839889114x_/2044000_/0_/32972718.swf
Appendix A.
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Introduction to steel making: http://www.youtube.com/watch?v=8OZ-WSQmLgc
Steel Making Raw Materials: http://www.youtube.com/watch?v=8x1Hf_U-1fo
Appendix A.
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Steel making blast furnace: http://www.youtube.com/watch?v=Yov7Z0rMyHI
Steel making blast furnace: http://www.youtube.com/watch?v=KsyDQy0djs4
Appendix A.
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Steel making blast furnace: http://www.youtube.com/watch?v=D49DpD4ooB4
Steel making blast furnace: http://www.youtube.com/watch?v=sbk4FpTwEpg
Appendix A.
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Tapping the furnace: http://www.youtube.com/watch?v=4bO6kHtVL7g
Tapping the furnace: http://www.youtube.com/watch?v=8vbNkBOGMwg
Appendix A.
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Filling hot metal car: http://www.youtube.com/watch?v=ZN-vBlGoHBk
Steel Making: Iron Making: http://www.youtube.com/watch?v=b2uAUvHzi5U
Appendix A.
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How Iron is made: http://www.youtube.com/watch?v=4TR9P7fqHqE
Steel Making: http://www.youtube.com/watch?v=yvHsKmezjEw
Appendix A.
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Steel Making Part II: http://www.youtube.com/watch?v=uaeecSnLCxU
Steel Making Process: http://www.youtube.com/watch?v=V-1nKFZfjd8
Appendix A.
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Steel making process; the converter: http://www.youtube.com/watch?v=01gjqDKXghQ
Basic Oxygen Steel Making: http://www.youtube.com/watch?v=qo50KxLU_34
Appendix A.
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Electric arc furnace: http://www.youtube.com/watch?v=S8NVvKf1wVE
Electric arc furnace: http://www.youtube.com/watch?v=-j0xFBG9xNg
Appendix A.
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Electric arc furnace: http://www.youtube.com/watch?v=ijWwfcw0FOo
Slag pour: http://www.youtube.com/watch?v=zhJF_hTJ2Rw
Appendix A.
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Steel making: rolling: http://www.youtube.com/watch?v=6xnKmt_gsLs
Stee making, cold rolling: http://www.youtube.com/watch?v=wBXexkRsAJg
Appendix A.
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Hot steel descaling and rolling: http://www.youtube.com/watch?v=8QLUWo9ryhA
Steel making, tube manufacture: http://www.youtube.com/watch?v=JDMln5vitgE
Appendix A.
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Steel making, continuous casting: http://www.youtube.com/watch?v=d-72gc6I-_E
Steel making, secondary steel: http://www.youtube.com/watch?v=wtsBRF1W2oQ
Appendix A.
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Steel mill: http://www.youtube.com/watch?v=XPMeID9nQwA
Forging: http://www.youtube.com/watch?v=tLRkOupbARM
Appendix A.
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More Video:
http://www.matter.org.uk/steelmatter/raw_materials/default.htm
Appendix A.

Effect of Alloying Elements On Steels Rev.B

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Inspector Knowledge Series 04-B

Effect of steel Alloying Elements

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01 01.10.2008 For Approval Charlie C. CM Mok

Revision Change description

 The Mechanism of Strengthening.

 Carbon.  Lead  Titanium

 Carbon contents, steel classification and alloy steels.

 Thermal Processing of Metals

Introduction to Dislocations, Fourth Edition by Derek Hull, D J Bacon

Chapter One: The Mechanism of strengthening.

When the stress is sufficient to permanently deform

lattice to reduce dislocation mobility, thereby increasing mechanical strength.

1. Work hardening or strain hardening.

Plastic Deformation: Mechanical Testing:

The Nature of Dislocations

Transmission Electron Micrograph of Dislocations Transmission Electron Micrograph of Dislocations

Deformation and strengthening mechanisms

Linear Defects - Dislocations

There is a second basic type of dislocation, called screw

If the shear force is increased, the atoms will continue to

Stacking Faults and Twin Boundaries

Grain Boundaries in Polycrystals

Bulk defects occur on a much bigger scale than the rest of

Pinning points - overview.

Types of pinning points

Second phase precipitates

Dislocation slip mechanism

Following are brief description s on the methods of strengthening.

Work or Strain hardening

2. Materials and Experimental Methods

3. Results and Discussion

Figure 1. Figure 2a.

Strain Hardening and Annealing Slide Show: Full download

Dislocation and Plastic Deformation:

Grain Boundary Strengthening

Effect of Microstructural Variation on Weld Metal Cold Cracking of HSLA-100 Steel

The influence of austenite grain size on hot ductility of steel

A: Lattice distortion due to the presence of coherent precipitate:

General behaviour of the powder particles during mechanical alloying processing

Solid solution strengthening

Substitutional and interstitial solutes.

Metal Crystal Structure Atomic Radius (nm)

A nanometer (nm) equals 10-9 meter or 10 Angstrom units.

Solid solution strengthening by interstitials

Strengthening at high interstitial concentrations

Substitutional solid solution strengthening of iron

Effect of solid solution strengthening

1. C and N are interstitial elements rather than substitutional.

Iron and Its Interstitial Solid Solutions

Figure 1 : Vacancy in a BCC crystal lattice.

Figure 2 : Vacancy in a FCC crystal lattice.

Figure 3 : Vacancy in a FCC crystal lattice.

Figure 4 : Vacancy in a FCC crystal lattice.

Carbon and nitrogen in solution in α- and γ- iron

and wear resistant.

Dislocations cutting through particles:

Dislocations bowing around particle:

Some precipitation hardening materials

• 2000-series aluminum alloys (important examples: 2024 and 2019)

Precipitate hardening of stainless steel grades.

Chapter Two: The Effects of Alloying Elements on Iron-Carbon Alloys

The Mechanism of Strengthening.

Carbon. Lead Titanium

Carbon contents, steel classification and alloy steels.

Thermal Processing of Metals

Effect of grain size.

By secondary hardening, e.g. 12% Cr steel with additions.

Deformation of austenite during the transformation

Deformation after the transformation of austenite

It is used as a deoxidizing agent in nearly all steels.