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OBJECTIVES:

o To know what are stainless steels


o To understand how chromium makes stainless steels “stainless”
o To learn what are the stainless steel families and their features and uses
o To know the different physical and mechanical properties of stainless steels
o To know what is corrosion and how it happens
o To learn the different types of corrosion that may occur on stainless steels

METALLURGY OF STAINLESS STEELS

What are Stainless Steels?

A stainless steel is an iron-base alloy with at least 10.5 % (approximately 11%) chromium
that forms a corrosion resistant passive layer on the steel surface. They are a group of iron-
base alloys, the iron-chromium (Fe-Cr) alloys, often with nickel (Ni) additions, which “do not
rust in sea water”, “are resistant to concentrated acids” and which “do not scale at
temperatures up to 1100 °C”. (Outokumpu, 2013)

However, it is important to understand what these materials are and why they behave the way
they do. This is especially true because the word “stainless” is itself somewhat a misnomer;
these materials can stain and can corrode under certain conditions. (Covert & Tuthill, 2000)

How does chromium makes stainless steels “stainless”?

The unique corrosion resistance of stainless steels is attributed to the existence of a thin,
adherent, inactive passive film that covers the surface. This passive film is very thin (1-3 nm).
This film can be conveniently thought of as chromium oxide, but it also contains small
amounts of other elements in the alloy. If the surface is clean and free of contamination, the
film forms instantaneously on exposure to air, aerated water, nitric acid, or other oxidizing
media. (Covert & Tuthill, 2000)

The chromium in the alloy forms a self-healing protective clear oxide layer that forms
spontaneously in air. The self-healing nature of the oxide layer means the corrosion resistance
remains intact regardless of fabrication methods. Even if the material surface is cut or
damaged, it will self-heal and corrosion resistance will be maintained. (Aalco Metals Ltd.,
2005)
Because of this protective film, stainless steels do not corrode as carbon or low alloy steels or
cast irons do. These materials “rust” or corrode through constantly changing anodes and
cathodes on the surface. However, except in solutions such as hydrochloric acid, this general
corrosion or uniform attack practically never occurs on stainless steels. While factors such as
chemical environment, pH, temperature, equipment design, fabrication methods, surface
finish, contamination, and maintenance procedures can affect the corrosion of stainless steels.
(Covert & Tuthill, 2000)

STAINLESS STEEL FAMILIES

Although the corrosion resistance of stainless steels comes from the presence of Chromium,
other elements are added to enhance other properties. These elements alter the microstructure
of the steel. Stainless steels are grouped into families based on their metallurgical
microstructure. The microstructure may be composed of the stable phases of austenite or
ferrite, a “duplex” mix of these two, martensite or a hardened structure containing
precipitated micro-constituents. (Aalco Metals Ltd., 2005)

Ferritic Stainless Steels

Ferritic stainless steels are the simplest, lowest-cost stainless steels. In their minimal form,
they contain simply enough chromium to overcome their inherent level of carbon impurity
and hit the ~11% chromium in solution required for “stainlessness.” The quantity of
chromium present ranges from 10.5 to 18%. (Outokumpu, 2013)

Acoording to Aalco Metals Ltd. (2005), ferritic stainless steels have moderate corrosion
resistance. They are magnetic. These steels cannot be hardened by heat treatment. Moreover,
they are always used in the annealed condition. Most grades of ferritic stainless steels have
poor weldability.

Ferritic stainless steels are typically used in vehicle exhausts, fuel lines, cooking utensils,
architectural trim, and domestic appliances.

Austenitic Stainless Steels


According to Aalco Metals Ltd. (2005), austenitic stainless steels contain a minimum of 16%
chromium and 6% nickel. Adding nickel to stainless steel in sufficient amounts, changes the
microstructure to “austenite”.

Seventy percent of commercially produced stainless steel are austenitic. The most common
grade of austenitic stainless steel is 304. Globally, 304 accounts for more than 50% of
stainless steel consumed. A common name for 304 stainless is 18/8. This name refers to the
average composition, 18% chromium and 8% nickel.

Austenitic stainless steels have excellent corrosion resistance and weldability. They are non-
magnetic and are ductile and readily formable. They are not hardenable by heat treatment but
are rapidly work hardened with cold work. They have good performance at high temperatures
and excellent performance at low temperature. In addition, austenitic stainless steels are also
considered hygienic because of their excellent cleanability.

Applications for austenitic stainless steels include kitchen sinks, architectural applications
such as roofing, cladding, gutters, doors, windows and balustrading. They are also used in
food preparation areas and food processing equipment. Moreover, austenitic steels are also
used in heat exchangers, ovens, and chemical tanks.

Duplex Stainless Steels

Duplex stainless steels get their name from the fact that they contain both a ferritic and
austenitic microstructure (“duplex” means “composed of two parts”). They have a relatively
high chromium content of between 18 and 28%. Nickel content is moderate at 4.5 to 8%.
(Aalco Metals Ltd., 2005)

Their limitations lie in their lack of cryogenic toughness and their inability to withstand
temperatures much above 300 °C without forming embrittling phases. But between -100 and
300 °C, they are exceptional materials. (McGuire, 2008)

Duplex stainless steels have excellent corrosion resistance and increased resistance to
chloride attack. Their tensile and yield strength are higher than that of austenitic or ferritic
steels. In addition, duplex stainless steels have good weldability and formability.

Duplex stainless steels typically find application in areas like heat exchangers, marine
applications, desalination plants, and off-shore oil and gas installations. Duplex stainless
steels are also used in chemical and petrochemical plants.

Martensitic Stainless Steels

High carbon and lower chromium content are the distinguishing features of martensitic
stainless steels when compared with ferritic stainless. The smallest category of stainless steels
in usage volume is the martensitic stainless steels. This is mainly because these alloys are
limited in corrosion resistance because of the necessity of keeping alloy levels low to produce
the martensite structure. Even so, they fill an important niche as a strong, hard, and tough
alloy of fairly good corrosion resistance and as a strong, stable, high temperature alloy. The
useful alloys of martensitic stainless steel contain from roughly 11 to 18% chromium and up
to 1.0% carbon. (McGuire, 2008)
According to Aalco Metals Ltd. (2005), martensitic stainless steels have moderate corrosion
resistance. They are magnetic and heat treatable. They don’t have ability to be cold formed.
In addition, duplex stainless steels also have poor weldability.

Martensitic stainless steels are typically used for knife blades, cutlery, surgical instruments,
and fasteners. They are also used in shafts and springs.

Precipitation-Hardening Stainless Steels (PH Stainless Steels)

These are primarily iron-chromium-nickel alloys to which other elements have been added to
form compounds of small grains which precipitate when heated to intermediate or high
temperature (500 °C to 900 °C) for a period of time. When present, these small grains strain
the crystal and strengthen the alloy. They contain 11 to 18% chromium, 3 to 27% nickel and
smaller amounts of other metals. These alloys are used where a combination of high strength
and corrosion resistance is needed. These alloys can be expensive. (Covert & Tuthill, 2000)

According to Aalco Metals Ltd. (2005), precipitation hardening grades have good to
moderate corrosion resistance. They have good weldability and very high strength. PH
stainless steels are magnetic.

Precipitation hardening stainless steels are typically used in pulp and paper industry
equipment, aerospace applications, and turbine blades. Moreover, PH stainless steels are also
used in nuclear waste casks and in mechanical components.

PHYSICAL PROPERTIES

Density

Within each steel category, density usually increases with an increasing level of alloying
elements, particularly heavy elements such as molybdenum. The austenitic steels generally
have a higher density than the other stainless steel types.

Elastic modulus

This is a measure of the stiffness of the steel and is an important parameter in structural
design. The elastic modulus for stainless steels is typically ~200 GPa and shows only small
variation with composition and microstructure. The elastic modulus decreases with increasing
temperature.

Thermal Properties

The two important physical properties that show the greatest variation between the stainless
steel types are thermal expansion and thermal conductivity. These thermal properties are a
very important consideration in high temperature applications. Thermal properties also
includes specific heat.

Austenitic steels exhibit higher thermal expansion, typically 18x10-6/°C. Duplex grades show
intermediate values while carbon steel is similar to ferritic stainless steels.
Thermal conductivity for stainless steels is generally lower than for carbon steels (40
W/m°C) and decreases with increasing alloying level for each stainless steel category. A low
thermal conductivity is important for retaining heat, for example in building component and
food containers.

The specific heat capacity is the energy required to produce a specific temperature increase in
the material. For stainless steels it is around 500 J/kg°C. The specific heat capacity has
implications for heat input requirements in welding and in steelmaking.

Electrical resistivity

The electrical resistivity of steels increases with the content of alloying elements and is thus
higher for stainless steels than for carbon steels. The highest values of around 0.8 µΩm are
seen for super-austenitic grades and the lowest for the leanest ferritic grades.

Magnetic Properties

All ferritic, martensitic, duplex and PH grades are ferromagnetic, while stable austenitic
grades are not magnetizable. Small amounts of ferrite or martensite in an austenitic structure
can have appreciable effect on the magnetic properties and so must be avoided where this is
critical, for example cyclotrons and submarines. (Outokumpu, 2013)

MECHANICAL PROPERTIES OF STAINLESS STEELS

Stainless steels are often selected for their corrosion resistance, but they are at the same time
constructional materials. According to Aalco Metals Ltd. (2005), required mechanical
properties are normally given in purchase specifications for stainless steel. Minimum
mechanical properties are also given by the various standards relevant to the material and
product form. Meeting these standard mechanical properties indicates that the material has
been properly manufactured to an appropriate quality system. Engineers can then confidently
utilize the material in structures that meet safe working loads and pressures.

Tensile Strength

Tensile strength is generally the only mechanical property required to define bar and wire
products. Identical material grades may be used at various tensile strengths for completely
different applications. The supplied tensile strength of bar and wire products directly relates
to the final use after fabrication.

Yield Strength

Unlike mild steels, the yield strength of annealed austenitic stainless steel is a very low
proportion of the tensile strength. Mild steel yield strength is typically 65-70% of the tensile
strength. This figure tends to only be 40-45% in the austenitic stainless family.

Cold working rapidly and greatly increases the yield strength. Some forms of stainless steel,
like spring tempered wire, can be cold worked to lift the yield strength to 80-95% of the
tensile strength.
The different families of stainless steel tend to have different tensile and yield strengths.
These typical strengths (in MPa) for annealed material are outlined in the table below.

Ductility

The combination of high work hardening rates and high elongation / ductility makes stainless
steel very easy to fabricate. With this property combination, stainless steel can be severely
deformed in operations like deep drawing.

Ductility is normally measured as the % elongation before fracture during tensile testing.
Annealed austenitic stainless steels have exceptionally high elongations. Typical figures are
60-70%.

Hardness

Hardness is the resistance to penetration of the material surface. Hardness testers measure the
depth that a very hard indenter can be pushed into the surface of a material. Brinell, Rockwell
and Vickers machines are used. Each of these has a different shaped indenter and method of
applying the known force. Conversions between the different scales are therefore only
approximate.

Martensitic and precipitation hardening grades can be hardened by heat treatment. Other
grades can be hardened through cold working.

Mechanical Properties at Cryogenic Temperature

Austenitic stainless steels have excellent properties also at low temperatures and are usually
the only material solution for very low (cryogenic) temperature applications. Ferritic, duplex,
and martensitic grades are commonly not suitable for low temperature applications due to the
brittle behavior at very low temperatures. (Outokumpu, 2013)
Mechanical Properties at High Temperature

Creep is the time dependent slow plastic deformation of metals under a constant stress.

Most austenitic stainless steels have lower strength than the other types at temperature range
up to about 500°C. In terms of creep strength, they are superior to ferritics and the other
types. Ferritic steels have relatively high strength up to 500°C but their creep strength above
500°C is low. Duplex stainless steels behave in the same way as the ferritic stainless steels
but have higher strength at low temperatures. (Outokumpu, 2013)

CORROSION CHARACTERISTICS OF STAINLESS STEELS

Corrosion is the gradual degradation of a metal by a chemical, often electrochemical, reaction


with the surrounding environment. A result of corrosion can be loss of material properties
such as mechanical strength, appearance and impermeability to liquids and gases. Stainless
steels are often chosen because of their resistance to corrosion, but they are not immune to
corrosion. Whether a stainless steel is corrosion resistant in a specific environment depends
on the combination of the chemical composition of the stainless steel and the aggressiveness
of the environment. (Outokumpu, 2013)

Moreover, according to Outokumpu (2013), corrosion can be divided into wet corrosion and
high temperature corrosion:

 Wet (or aqueous) corrosion refers to corrosion in liquids or moist environments, and
includes atmospheric corrosion.
 High temperature corrosion denotes corrosion in hot gases at temperatures from
around 500°C to 1200°C.

All corrosion types affecting stainless steel are related to permanent damage of the passive
film, either complete or local breakdown. Factors such as chemical environment, pH,
temperature, surface finish, product design, fabrication method, contamination and
maintenance procedures will affect the corrosion behavior of stainless steel and the type of
corrosion that may occur.

How does wet corrosion happen?

Wet (or aqueous) corrosion of metals is an electrochemical process that involves an anode
and a cathode, as well as an electrolyte connecting the two. At the anode, the metal oxidizes
(corrodes) and forms rust or some other corrosion product.

At the cathode, a reduction reaction takes place. This is typically the reduction of oxygen or
hydrogen evolution:
Example:

4 Fe (s) + 3 O2 (g)  2 Fe2O3 (s)

Iron Oxygen Ferrous Oxide (known as rust)

In order to prevent corrosion, these reactions must be prevented.

Types of Corrosion Classified Under Wet Corrosion

Pitting Corrosion

Pitting corrosion is a highly localized corrosion with discrete pits on the free surface of
stainless steels as shown in the figure below. The size, shape and morphology of the pits can
vary; some pits can be quite shallow while some penetrate deep into the material. They can
also undermine the surface with attack that appears small but spreads beneath the surface.
Therefore, the full extent of pitting corrosion can be difficult to judge by just visual
inspection as it may be concealed.

Crevice Corrosion

As its name implies, this type of corrosion occurs in crevices and confined spaces. As the
oxygen content is limited inside a tight crevice, oxygen is needed for the formation of
chromium oxides, the passive layer is weakened. The figure below shows an example of
corrosion on a stainless steel valve flange.
Uniform Corrosion

Uniform corrosion occurs when the passive layer is destroyed on the whole or a large part of
the surface as shown in the figure. Thus, the anodic and cathodic reactions occur on the same
surface at constantly changing locations. Uniform corrosion can occur on stainless steels in
acids or hot alkaline solutions.

Atmospheric corrosion

In contrast to other forms of corrosion, atmospheric corrosion is not a unique form of


corrosion, but a collective term to describe the corrosion on metal surfaces in the atmosphere.
The atmosphere may be indoor or outdoor, and many different corrosion forms may be
involved. Halides, and mainly chlorides, are often involved in atmospheric corrosion as they
are abundant in our environment. Stainless steel that is exposed to an aggressive atmospheric
environment is primarily affected by staining, sometimes referred to as tea staining. The
figure below shows an atmospheric test station where samples are fully exposed.
Intergranular Corrosion

Intergranular corrosion occurs between the grain boundaries inside a metal. This type of
corrosion is well known for stainless steels which have been soaked for an excessive period
of time at temperatures between 500 and 800°C. At these temperatures, chromium will react
with carbon at the grain boundaries to form carbides. This causes chromium depletion in the
immediate vicinity of the grain boundaries. If the chromium content falls below 11%,
corrosion can easily start.

Galvanic Corrosion

Galvanic corrosion (also called “dissimilar metal corrosion”) refers to corrosion damage
induced when two dissimilar materials are coupled in a corrosive electrolyte. It occurs when
these metals are exposed to a corrosive environment like seawater. Usually, galvanic
corrosion is not a problem for stainless steels but can affect other metals in contact with them.
However, metals with much higher corrosion potential than stainless steels can cause
galvanic corrosion on the stainless steel. Corrosion potential is the property of metal and
nonmetal surfaces to lose electrons in the presence of an electrolyte. (Outokumpu, 2013)
Types of Corrosion Classified Under High Temperature Corrosion

Stainless steel can suffer high temperature corrosion and oxidation. This can occur when a
metal is exposed to a hot atmosphere containing oxygen, sulfur, halogens or other compounds
able to react with the material. (Outokumpu, 2013)

Oxidation

When the chromium content is increased from 0 to 27%, the maximum service temperature
of stainless steels increases from around 500°C to 1150°C. The passive layer of chromium
oxides become less protective at elevated temperatures and oxidation of the steel will be more
likely to occur. In addition, the presence of water vapor in the atmosphere reduces the
resistance to oxidation and thus the maximum service temperature.

Sulfidation

Different sulfur compounds are often present as contaminants in flue gases and some process
gases. Sulfidation is a process of installing sulfide ions in a material or molecule. Chromium
in the steel would react with sulfur and produce chromium sulfides instead of chromium
oxides. Moreover, the sulfide scales are generally much less protective than the
corresponding oxide scales, leading to a faster corrosion rate.

When the protective layer begins to crack, the gases will be able to penetrate through the
protective layer and continue the attack.

Carburization and Nitridation

Carburization is the formation of metal carbides in a material as a result of exposure to a


carbon containing atmosphere. Carburization of stainless steels can take place in carbon
monoxide, carbon dioxide, methane and other hydrocarbon gases at high temperatures. The
corrosion process referred to as "Metal Dusting" is a carburization process which results in
surface attack and the formation of a powdery residue. On the other hand, nitridation is the
formation of metal nitrides. The precipitation of carbides and nitrides leads to embrittlement,
a reduction in toughness and ductility.
References

Aalco Metals Ltd. (2005). Stainless steel: general information. Retrieved April 27, 2018 from
http://www.aalco.co.uk/datasheets/Stainless-Steel_St-St-Introduction_61.ashx.

Covert, R. & Tuthill, A. (2000). Stainless steels: an introduction to their metallurgy and
corrosion resistance. Dairy, food and environmental sanitation, vol. 20 (pp. 508-517).
Des Moines, Iowa: International Association for Food Protection.

McGuire, M. (2008). Stainless steels for design engineers. Materials Park, Ohio: ASM
International.

Outokumpu (2013). Handbook of stainless steel. Riihitontuntie, Espoo: Outokumpu Oyj.


University of Mindanao
Matina, Davao City

Stainless Steels:

Metallurgy

Physical Properties

Mechanical Properties

Corrosion Characteristics

Submitted by:

Jocelyn G. Corpuz
BS ChE – 3

Submitted to:

Engr. Angelita G. Fernandez


Instructor

May 3, 2018