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Binary phase diagrams

Binary phase diagrams and Gibbs free energy curves Binary solutions with unlimited solubility Relative proportion of phases (tie lines and the lever principle) Development of microstructure in isomorphous alloys Binary eutectic systems (limited solid solubility) Solid state reactions (eutectoid, peritectoid reactions) Binary systems with intermediate phases/compounds The iron-carbon system (steel and cast iron) Gibbs phase rule Temperature dependence of solubility Three-component (ternary) phase diagrams

Reading: Chapters 1.5.1 1.5.7 of Porter and Easterling, Chapter 10 of Gaskell

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Binary phase diagram and Gibbs free energy


A binary phase diagram is a temperature - composition map which indicates the equilibrium phases present at a given temperature and composition. The equilibrium state can be found from the Gibbs free energy dependence on temperature and composition. We have discussed the dependence of G of a onecomponent system on T:
G = S T P
2G cP S = = T 2 T T P P

We have also discussed the dependence of the Gibbs free energy from composition at a given T:

G A G B

G = XAGA + XBGB + Hmix T Smix

0
MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

XB

Binary solutions with unlimited solubility


Lets construct a binary phase diagram for the simplest case: A and B components are mutually soluble in any amounts in both solid (isomorphous system) and liquid phases, and form ideal solutions. We have 2 phases liquid and solid. Lets consider Gibbs free energy curves for the two phases at different T

T1 is above the equilibrium melting temperatures of both


pure components: T1 > Tm(A) > Tm(B) the liquid phase will be the stable phase for any composition.

G solid B G
solid A

T1
G solid G liquid B

G liquid A

G liquid

XB

G id = X A G A + X BG B + RT[X A lnXA + X BlnXB ]


MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Binary solutions with unlimited solubility (II)


Decreasing the temperature below T1 will have two effects: GA
liquid solid and G liquid G will increase more rapidly than B A

and G solid B

Why? Why?

The curvature of the G(XB) curves will decrease. Eventually we will reach

T2 melting point of pure

solid component A, where G liquid = G A A

liquid A

=G

solid A

T2
G solid G liquid

G solid B G liquid B

XB

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Binary solutions with unlimited solubility (III)


For even lower temperature T3 < T2 = Tm(A) the Gibbs free energy curves for the liquid and solid phases will cross.

G liquid A G solid A

T3
G solid

G solid B

G liquid B G liquid
solid solid + liquid liquid

X1

XB

X2

As we discussed before, the common tangent construction can be used to show that for compositions near cross-over of Gsolid and Gliquid, the total Gibbs free energy can be minimized by separation into two phases.

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Binary solutions with unlimited solubility (IV)


As temperature decreases below T3
liquid continue Gliquid and G A B solid solid to increase more rapidly than GA and GB

Therefore, the intersection of the Gibbs free energy curves, as well as points X1 and X2 are shifting to the right, until, at T4 = Tm(B) the curves will intersect at X1 = X2 = 1

G liquid A

T4
G liquid
solid G liquid = G B B

G solid A G solid

XB

At T4 and below this temperature the Gibbs free energy of the solid phase is lower than the G of the liquid phase in the whole range of compositions the solid phase is the only stable phase.
MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Binary solutions with unlimited solubility (V)


Based on the Gibbs free energy curves we can now construct a phase diagram for a binary isomorphous systems

liquid A

T3

G solid B G solid G liquid B G liquid

G solid A

T1
solid solid + liquid

liquid

T2

T1 T2

T3
T4

T4

T5

XB

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Binary solutions with unlimited solubility (VI)


Example of isomorphous system: Cu-Ni (the complete solubility occurs because both Cu and Ni have the same crystal structure, FCC, similar radii, electronegativity and valence).

Liquid

Liquidus line

Solidus line

Solid solution

Liquidus line separates liquid from liquid + solid MSE 3050, line Phaseseparates Diagrams and Kinetics, Leonid Zhigilei Solidus solid from liquid + solid

Binary solutions with unlimited solubility (VII)


In one-component system melting occurs at a well-defined melting temperature. In multi-component systems melting occurs over the range of temperatures, between the solidus and liquidus lines. Solid and liquid phases are in equilibrium in this temperature range.

Liquidus Temperature

L +L
Solidus

liquid solution

liquid solution + crystallites of solid solution B

polycrystal solid solution

20 40 60 80 Composition, wt %

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Interpretation of Phase Diagrams For a given temperature and composition we can use phase diagram to determine: 1) The phases that are present 2) Compositions of the phases 3) The relative fractions of the phases Finding the composition in a two phase region: 1. 2. 3. Locate composition and temperature in diagram In two phase region draw the tie line or isotherm Note intersection with phase boundaries. Read compositions at the intersections.

The liquid and solid phases have these compositions.

XB Xliquid B

Xsolid B

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Interpretation of Phase Diagrams: the Lever Rule Finding the amounts of phases in a two phase region: 1. 2. 3. Locate composition and temperature in diagram In two phase region draw the tie line or isotherm Fraction of a phase is determined by taking the length of the tie line to the phase boundary for the other phase, and dividing by the total length of tie line

The lever rule is a mechanical analogy to the mass balance calculation. The tie line in the twophase region is analogous to a lever balanced on a fulcrum.

W
Derivation of the lever rule:

1) All material must be in one phase or the other: W + W = 1 2) Mass of a component that is present in both phases equal to the mass of the component in one phase + mass of the component in the second phase: WC + WC = Co 3) Solution of these equations gives us the Lever rule. W = (C0 - C) / (C - C) and W = (C- C0) / (C - C)
MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Composition/Concentration: weight fraction vs. molar fraction Composition can be expressed in Molar fraction, XB, or atom percent (at %) that is useful when trying to understand the material at the atomic level. Atom percent (at %) is a number of moles (atoms) of a particular element relative to the total number of moles (atoms) in alloy. For two-component system, concentration of element B in at. % is nB

C at =

A nB + n m m

100

C at = X B 100

Where nmA and nmB are numbers of moles of elements A and B in the system. Weight percent (C, wt %) that is useful when making the solution. Weight percent is the weight of a particular component relative to the total alloy weight. For two-component system, concentration of element B in wt. % is

C wt =

mB 100 mB + mA

where mA and mB are the weights of the components in the system.

nA m =

mA AA

nB m =

mB AB

where AA and AB are atomic weights of elements A and B.

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Composition Conversions Weight % to Atomic %:

C at B

wt CB AA = wt 100 wt CB AA + CA AB

wt C at A AB C A = wt 100 wt CB AA + CA A B

Atomic % to Weight %:

wt CB

C at BAB = at 100 at CBA B + CAA A C at AA A = at 100 at CBA B + CAA A

wt A

Of course the lever rule can be formulated for any specification of composition:

ML = (XB - XB0)/(XB - XBL) = (Cat - Cato) / (Cat - CatL) M = (XB0 - XBL)/(XB - XBL) = (Cat0 - CatL) / (Cat - CatL)
WL = (Cwt - Cwto) / (Cwt - CwtL) W = (Cwto- CwtL) / (Cwt - CwtL)
MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Phase compositions and amounts. An example.

Co = 35 wt. %, CL = 31.5 wt. %, C = 42.5 wt. % Mass fractions: WL = S / (R+S) = (C - Co) / (C - CL) = 0.68 W = R / (R+S) = (Co - CL) / (C - CL) = 0.32

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Development of microstructure in isomorphous alloys Equilibrium (very slow) cooling

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Development of microstructure in isomorphous alloys Equilibrium (very slow) cooling Solidification in the solid + liquid phase occurs gradually upon cooling from the liquidus line. The composition of the solid and the liquid change gradually during cooling (as can be determined by the tie-line method.) Nuclei of the solid phase form and they grow to consume all the liquid at the solidus line.

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Development of microstructure in isomorphous alloys Non-equilibrium cooling

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Development of microstructure in isomorphous alloys Non-equilibrium cooling Compositional changes require diffusion in solid and liquid phases Diffusion in the solid state is very slow. The new layers that solidify on top of the existing grains have the equilibrium composition at that temperature but once they are solid their composition does not change. Formation of layered (cored) grains and the invalidity of the tie-line method to determine the composition of the solid phase. The tie-line method still works for the liquid phase, where diffusion is fast. Average Ni content of solid grains is higher. Application of the lever rule gives us a greater proportion of liquid phase as compared to the one for equilibrium cooling at the same T. Solidus line is shifted to the right (higher Ni contents), solidification is complete at lower T, the outer part of the grains are richer in the low-melting component (Cu). Upon heating grain boundaries will melt first. This can lead to premature mechanical failure.

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Binary solutions with a miscibility gap


Lets consider a system in which the liquid phase is approximately ideal, but for the solid phase we have Hmix > 0

T1
G solid G liquid

T2 < T1
G solid

G liquid

0
G
G

XB

1
T3 < T2

0
T T1

XB

liquid

T2
G solid

liquid

T3 0
XB

1+2

XB

At low temperatures, there is a region where the solid solution is most stable as a mixture of two phases 1 and 2 with compositions X1 and X2. This region is called a miscibility gap.
MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Eutectic phase diagram


For an even larger Hmix the miscibility gap can extend into the liquid phase region. In this case we have eutectic phase diagram.

liquid

T1
G solid

G
G liquid G solid

T2 < T1

0
G
G
liquid

XB

1
T3 < T2

0
T T1 T2 T3

XB

liquid
1+l 2+l

G solid

1+2

XB

XB

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Eutectic phase diagram with different crystal structures of pure phases


A similar eutectic phase diagram can result if pure A and B have different crystal structures.

T1

T2 < T1

liquid

liquid

0
G

XB

1
T

XB

T3 < T2

liquid

T1 T2

liquid +l + +l

T3
XB

XB

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Temperature dependence of solubility


There is limited solid solubility of A in B and B in A in the alloy having eutectic phase diagram shown below.

T1

liquid

T
liquid

+l

+l +

T1
XB

XB

The closer is the minimum of the Gibbs free energy curve G(XB) to the axes XB = 0, the smaller is the maximum possible concentration of B in phase . Therefore, to discuss the temperature dependence of solubility lets find the minimum of G(XB).

G reg = X A G A + X BG B + X A X B + RT[X A lnX A + X BlnX B ]


dG =0 dX B

- Minimum of G(XB)

See problem 1 of hw #4

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Temperature dependence of solubility (II)


G reg = X A G A + X BG B + X A X B + RT[X A lnX A + X BlnX B ]
= (1 - X B )G A + X BG B + (1 - X B )X B + RT[(1 - X B )ln(1 - X B ) + X BlnXB ]
(1 - X B ) + lnX + X B = dG = -G A + G B + 2 X B + RT - ln(1 - X B ) B (1 - X B ) dX B XB

= -GA + GB + 2 XB + RT[- ln(1- XB ) + lnXB ] =


XB = G B - G A + (1 2XB ) + RTln 1- X GB - G A + + RTln(XB ) = 0 B
if XB is small (XB 0) (GB >> GA) Minimum of G(XB)

G GA + XB exp B RT

Solid solubility of B in increases exponentially with temperature

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Eutectic systems - alloys with limited solubility (I)

Liquidus Solidus Temperature, C

liquid

Solvus

+ Copper Silver phase diagram

Composition, wt% Ag

Three single phase regions ( - solid solution of Ag in Cu matrix, = solid solution of Cu in Ag matrix, L - liquid) Three two-phase regions ( + L, +L, +) Solvus line separates one solid solution from a mixture of solid solutions. Solvus line shows limit of solubility
MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Eutectic systems - alloys with limited solubility (II)


Lead Tin phase diagram

Temperature, C

Invariant or eutectic point Eutectic isotherm

Composition, wt% Sn

Eutectic or invariant point - Liquid and two solid phases coexist in equilibrium at the eutectic composition CE and the eutectic temperature TE. Eutectic isotherm - the horizontal solidus line at TE. Eutectic reaction transition between liquid and mixture of two solid phases, + at eutectic concentration CE. The melting point of the eutectic alloy is lower than that of the components (eutectic = easy to melt in Greek).

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Eutectic systems - alloys with limited solubility (III)


Compositions and relative amounts of phases are determined from the same tie lines and lever rule, as for isomorphous alloys

A
Temperature, C

Composition, wt% Sn

For points A, B, and C calculate the compositions (wt. %) and relative amounts (mass fractions) of phases present.

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Development of microstructure in eutectic alloys (I)


Several different types of microstructure can be formed in slow cooling an different compositions. Lets consider cooling of liquid lead tin system as an example.

In the case of lead-rich alloy (0-2 wt. % of tin) solidification proceeds in the same manner as for isomorphous alloys (e.g. CuNi) that we discussed earlier.

Temperature, C

L +L

Composition, wt% Sn

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Development of microstructure in eutectic alloys (II)


At compositions between the room temperature solubility limit and the maximum solid solubility at the eutectic temperature, phase nucleates as the solid solubility is exceeded upon crossing the solvus line.

L
Temperature, C

+L +

Composition, wt% Sn
MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Development of microstructure in eutectic alloys (III) Solidification at the eutectic composition


No changes above the eutectic temperature TE. At TE all the liquid transforms to and phases (eutectic reaction).

Temperature, C

Composition, wt% Sn

L +
MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Development of microstructure in eutectic alloys (IV) Solidification at the eutectic composition


Compositions of and phases are very different eutectic reaction involves redistribution of Pb and Sn atoms by atomic diffusion (we will learn about diffusion in the last part of this course). This simultaneous formation of and phases result in a layered (lamellar) microstructure that is called eutectic structure.

Formation of the eutectic structure in the lead-tin system. In the micrograph, the dark layers are lead-reach phase, the light layers are the tin-reach phase.
MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Development of microstructure in eutectic alloys (V) Compositions other than eutectic but within the range of the eutectic isotherm
Primary phase is formed in the + L region, and the eutectic structure that includes layers of and phases (called eutectic and eutectic phases) is formed upon crossing the eutectic isotherm.

L + L +

Temperature, C

Composition, wt% Sn
MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Development of microstructure in eutectic alloys (VI)


Microconstituent element of the microstructure having a distinctive structure. In the case described in the previous page, microstructure consists of two microconstituents, primary phase and the eutectic structure.

Although the eutectic structure consists of two phases, it is a microconstituent with distinct lamellar structure and fixed ratio of the two phases.
MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

How to calculate relative amounts of microconstituents?


Eutectic microconstituent forms from liquid having eutectic composition (61.9 wt% Sn) We can treat the eutectic as a separate phase and apply the lever rule to find the relative fractions of primary phase (18.3 wt% Sn) and the eutectic structure (61.9 wt% Sn):

We = P / (P+Q) (eutectic)

W = Q / (P+Q) (primary)

Temperature, C

Composition, wt% Sn
MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

How to calculate the total amount of phase (both eutectic and primary)?
Fraction of phase determined by application of the lever rule across the entire + phase field:

W = (Q+R) / (P+Q+R) ( phase) W = P / (P+Q+R) ( phase)

Temperature, C

Composition, wt% Sn
MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Binary solutions with Hmix < 0 - ordering


If Hmix < 0 bonding becomes stronger upon mixing melting point of the mixture will be higher than the ones of the pure components. For the solid phase strong interaction between unlike atoms can lead to (partial) ordering |Hmix| can become larger than |XAXB| and the Gibbs free energy curve for the solid phase can become steeper than the one for liquid.

G
G

T1

T2 < T1
G liquid

G liquid

G XB

0
G G
liquid

1
T T1

XB
liquid

T3 < T2

T2
G G
`

T3
XB

XB

At low temperatures, strong attraction between unlike atoms can lead to the formation of MSE 3050, Phase Diagrams ordered phase `. and Kinetics, Leonid Zhigilei

Binary solutions with Hmix < 0 - intermediate phases


If attraction between unlike atoms is very strong, the ordered phase may extend up to the liquid.

liquid

XB

In simple eutectic systems, discussed above, there are only two solid phases ( and ) that exist near the ends of phase diagrams. Phases that are separated from the composition extremes (0% and 100%) are called intermediate phases. They can have crystal structure different from structures of components A and B.

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Hmix<0 - tendency to form high-melting point intermediate phase

liquid

0
T

XB
liquid

1
Increasing negative Hmix

0
T

XB
liquid

MSE 3050, Phase Diagrams XBand Kinetics, Leonid Zhigilei

Phase diagrams with intermediate phases: example


Example of intermediate solid solution phases: in Cu-Zn, and are terminal solid solutions, , , , , are intermediate solid solutions.

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Phase diagrams for systems containing compounds


For some systems, instead of an intermediate phase, an intermetallic compound of specific composition forms. Compound is represented on the phase diagram as a vertical line, since the composition is a specific value. When using the lever rule, compound is treated like any other phase, except they appear not as a wide region but as a vertical line

intermetallic compound

This diagram can be thought of as two joined eutectic diagrams, for Mg-Mg2Pb and Mg2Pb-Pb. In this case compound Mg2Pb (19 %wt Mg and 81 %wt Pb) can be considered as a component. A sharp drop in the Gibbs free energy at the compound composition should be added to Gibbs free energy curves for the existing phases in the system. MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Stoichiometric and non-stoichiometric compounds


Compounds which have a single well-defined composition are called stoichiometric compounds (typically denoted by their chemical formula). Compound with composition that can vary over a finite range are called non-stoichiometric compounds or intermediate phase (typically denoted by Greek letters).

T
liquid +l + l+ + l

T
liquid +l + AB
AB

l+AB

+ AB

XB

XB

non-stoichiometric Common stoichiometric compounds:


compound composition, at% compound composition, at% AB 50.0

stoichiometric

A6B5 A5B4 A4B3 A3B2 A5B3 45.5 44.4 A3B 25.0 42.9 A4B 20.0 40.0 A5B 16.7 37.5 A6B 14.3

A2B A5B2 33.3 28.6

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Eutectoid Reactions
The eutectoid (eutectic-like in Greek) reaction is similar to the eutectic reaction but occurs from one solid phase to two new solid phases. Eutectoid structures are similar to eutectic structures but are much finer in scale (diffusion is much slower in the solid state). Upon cooling, a solid phase transforms into two other solid phases ( + in the example below) Looks as V on top of a horizontal tie line (eutectoid isotherm) in the phase diagram.

Cu-Zn

Eutectoid

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Eutectic and Eutectoid Reactions


Temperature

Eutectoid temperature

+l

l +

Eutectic temperature

Eutectoid composition

Eutectic composition

Composition The above phase diagram contains both an eutectic reaction and its solid-state analog, an eutectoid reaction

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Peritectic Reactions
A peritectic reaction - solid phase and liquid phase will together form a second solid phase at a particular temperature and composition upon cooling - e.g. L + These reactions are rather slow as the product phase will form at the boundary between the two reacting phases thus separating them, and slowing down any further reaction.

Temperature

+ liquid
+

liquid

+ liquid

Peritectoid is a three-phase reaction similar to peritectic but occurs from two solid phases to one new solid phase ( + = ).

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Example: The IronIron Carbide (FeFe3C) Phase Diagram In their simplest form, steels are alloys of Iron (Fe) and Carbon (C). The Fe-C phase diagram is a fairly complex one, but we will only consider the steel part of the diagram, up to around 7% Carbon.

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Phases in FeFe3C Phase Diagram -ferrite - solid solution of C in BCC Fe Stable form of iron at room temperature. The maximum solubility of C is 0.022 wt% Transforms to FCC -austenite at 912 C -austenite - solid solution of C in FCC Fe The maximum solubility of C is 2.14 wt %. Transforms to BCC -ferrite at 1395 C Is not stable below the eutectic temperature (727 C) unless cooled rapidly -ferrite solid solution of C in BCC Fe The same structure as -ferrite Stable only at high T, above 1394 C Melts at 1538 C Fe3C (iron carbide or cementite) This intermetallic compound is metastable, it remains as a compound indefinitely at room T, but decomposes (very slowly, within several years) into -Fe and C (graphite) at 650 - 700 C Fe-C liquid solution

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

C is an interstitial impurity in Fe. It forms a solid solution with , , phases of iron Maximum solubility in BCC -ferrite is limited (max. 0.022 wt% at 727 C) - BCC has relatively small interstitial positions Maximum solubility in FCC austenite is 2.14 wt% at 1147 C FCC has larger interstitial positions Mechanical properties: Cementite is very hard and brittle - can strengthen steels. Mechanical properties of steel depend on the microstructure, that is, how ferrite and cementite are mixed. Magnetic properties: -ferrite is magnetic below 768 C, austenite is non-magnetic Classification. Three types of ferrous alloys: Iron: less than 0.008 wt % C in ferrite at room T Steels: 0.008 - 2.14 wt % C (usually < 1 wt % ) -ferrite + Fe3C at room T Examples of tool steel (machine tools for cutting other metals): Fe + 1wt % C + 2 wt% Cr Fe + 1 wt% C + 5 wt% W + 6 wt % Mo Stainless steel (food processing equipment, knives, petrochemical equipment, etc.): 12-20 wt% Cr, ~$1500/ton Cast iron: 2.14 - 6.7 wt % (usually < 4.5 wt %) heavy equipment casing
MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Eutectic and eutectoid reactions in FeFe3C Eutectic: 4.30 wt% C, 1147 C

L + Fe3C

Eutectoid: 0.76 wt%C, 727 C

(0.76 wt% C) (0.022 wt% C) + Fe3C


Eutectic and eutectoid reactions are very important in heat treatment of steels MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Development of Microstructure in Iron - Carbon alloys Microstructure depends on composition (carbon content) and heat treatment. In the discussion below we consider slow cooling in which equilibrium is maintained. Microstructure of eutectoid steel (I)

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Microstructure of eutectoid steel (II) When alloy of eutectoid composition (0.76 wt % C) is cooled slowly it forms perlite, a lamellar or layered structure of two phases: -ferrite and cementite (Fe3C) The layers of alternating phases in pearlite are formed for the same reason as layered structure of eutectic structures: redistribution C atoms between ferrite (0.022 wt%) and cementite (6.7 wt%) by atomic diffusion. Mechanically, pearlite has properties intermediate to soft, ductile ferrite and hard, brittle cementite.

In the micrograph, the dark areas are Fe3C layers, the light phase is ferrite

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Microstructure of hypoeutectoid steel (I) Compositions to the left of eutectoid (0.022 - 0.76 wt % C) hypoeutectoid (less than eutectoid -Greek) alloys.

+ + Fe3C

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Microstructure of hypoeutectoid steel (II) Hypoeutectoid alloys contain proeutectoid ferrite (formed above the eutectoid temperature) plus the eutectoid perlite that contain eutectoid ferrite and cementite.

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Microstructure of hypereutectoid steel (I) Compositions to the right of eutectoid (0.76 - 2.14 wt % C) hypereutectoid (more than eutectoid -Greek) alloys.

+ Fe3C + Fe3C

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Microstructure of hypereutectoid steel

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Microstructure of hypereutectoid steel (II) Hypereutectoid alloys contain proeutectoid cementite (formed above the eutectoid temperature) plus perlite that contain eutectoid ferrite and cementite.

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

How to calculate the relative amounts of proeutectoid phase ( or Fe3C) and pearlite? Application of the lever rule with tie line that extends from the eutectoid composition (0.75 wt% C) to ( + Fe3C) boundary (0.022 wt% C) for hypoeutectoid alloys and to ( + Fe3C) Fe3C boundary (6.7 wt% C) for hipereutectoid alloys.

Fraction of phase is determined by application of the lever rule across the entire ( +and Fe3 C) phase field: MSE 3050, Phase Diagrams Kinetics, Leonid Zhigilei

Example for hypereutectoid alloy with composition C1 Fraction of pearlite: WP = X / (V+X) = (6.7 C1) / (6.7 0.76) Fraction of proeutectoid cementite: WFe3C = V / (V+X) = (C1 0.76) / (6.7 0.76)

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

The most important phase diagram in the history of civilization

pearlite
naturally formed composite: hard & brittle ceramic (Fe3C) + soft BCC iron (ferrite)

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Pearlite for Piano Wire


Piano wire requirements: high strength - hit by a hammer in piano creep resistance does not go out of tune quickly acoustic properties Re-bar for highways and construction Railroad tracks

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Pearlite for Piano Wire


Cool Fe - 0.8 wt.%C from FCC austenite (~1100 C) to BCC ferrite + cementite (~600 C) hold at ~600 C for several minutes

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Pearlite for Piano Wire

Cool to room temperature

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Pearlite for Piano Wire

cementite and ferrite plates

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Pearlite for Piano Wire


Wire drawing

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Pearlite for Piano Wire


Wire drawing

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Pearlite for Piano Wire


heat back up to 1100 C all ferrite and cementite disappear 100% austenite cool Fe-0.8 wt%C from austenite (~1100 C) to ferrite + cementite (~600 C) hold at ~600 C for several minutes cool to room temperature draw wire heat back up to 1100 C all ferrite and cementite disappear 100% austenite

over & over & over

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Pearlite for Piano Wire


ceramic soft bcc iron ceramic soft bcc iron

naturally formed composite!

material

Youngs modulus 81 124 110 200 200 10

density strength yield, y 2.5 8.9 8.8 7.9 7.8

strength tensile, TS

rock(marble) copper bronze iron steel(mild) wood piano wire

60 145 50 220 4000

400 310 200 430 40

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Reconstruction of Baroque organs (TRUESOUND EU project)


Baroque-style organ reconstructed in rgryte Nya Kyrka, Gothenburg, Sweden

Components of reed pipes


MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

MRS Bulletin Vol 32, March 2007, 249-255

Reconstruction of Baroque organs (TRUESOUND EU project)


nondestructive measurements of composition on ~30 organs produced from 1624 to 1880 (neutron, X-ray diffraction, SIMS) Zn is soluble in Cu Pb is insoluble in Cu and is distributed non-uniformly in the alloy

Cu Zn phase diagram

Cu Pb phase diagram

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Reconstruction of Baroque organs (TRUESOUND EU project)


Surprisingly constant Zn concentration: ~26 wt.% from 1624 to 1790 ~32.5 wt.% from 1750 All historical tongues and shallots are made of -brass (fcc solid solution of Zn in Cu)

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Reconstruction of Baroque organs (TRUESOUND EU project)

Before 1738 Zn was only available as zinc oxide (ZnO) or zinc carbonate (ZnCO3) and brass was produced by mixing solid Cu and gas-phase Zn in a process called cementation: pieces of Cu, coal, and ZnCO3 are heated to above Tb of Zn (907C) but below Tm of Cu (1083C) ZnCO3 is reduced and evaporated Zn diffuses into hot solid Cu Heating much above 907C was not economical temperature was kept slightly above this temperature experienced craftsman can estimate temperature from the color of a furnace within ~20C the process was taking place at ~920C Zn concentration in brass is determined by solidus concentration maximum solubility of Zn in solid Cu (26 wt.% at 920C) 1738: patent on distilling metallic Zn from ZnCO3, 1781: patent on alloying brass from metallic Zn concentration of Zn in Cu is no longer limited by the MSE 3050,at Phase Diagrams and Kinetics, Leonid Zhigilei solubility 920C, but is 32.5 wt.% - maximum solubility after crystallization.

The Gibbs phase rule (I) Lets consider a simple one-component system. P In the areas where only one phase is stable both pressure and temperature can be independently varied without upsetting the equilibrium there are 2 degrees of freedom. solid liquid

gas T

Along the lines where two phases coexist in equilibrium, only one variable can be independently varied without upsetting the two-phase equilibrium (P and T are related by the Clapeyron equation) there is only one degree of freedom. At the triple point, where solid liquid and vapor coexist any change in P or T would upset the three-phase equilibrium there are no degrees of freedom. In general, the number of degrees of freedom, F, in a system that contains C components and can have Ph phases is given by the Gibbs phase rule:

F = C Ph + 2
MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

The Gibbs phase rule (II) Lets now consider a multi-component system containing C components and having Ph phases. A thermodynamic state of each phase can be described by pressure P, temperature T, and C - 1 composition variables. The state of the system can be then described by Ph(C-1+2) variables. But how many of them are independent? The condition for Ph phases to be at equilibrium are: T = T = T = P = P = P =
= = A A A = ...

- Ph-1 equations - Ph-1 equations - Ph-1 equations C sets of equations - Ph-1 equations

= = = ...
B B B

Therefore we have (Ph 1)(C + 2) equations that connect the variables in the system. The number of degrees of freedom is the difference between the total number of variables in the system and the minimum number of equations among these variables that have to be satisfied in order to maintain the equilibrium.

F = Ph(C + 1) (Ph 1)(C + 2) = C Ph + 2 F = C Ph + 2 - Gibbs phase rule


MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

The Gibbs phase rule example (an eutectic systems)

F = C Ph + 2 P = const F = C Ph + 1 C=2 F = 3 Ph

In one-phase regions of the phase diagram T and XB can be changed independently. In two-phase regions, F = 1. If the temperature is chosen independently, the compositions of both phases are fixed. Three phases (L, , ) are in equilibrium only at the eutectic point in this two component system (F = 0).

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Multicomponent systems (I)


The approach used for analysis of binary systems can be extended to multi-component systems.

wt. %

wt. %

wt. % Representation of the composition in a ternary system (the Gibbs triangle). The total length of the red lines is 100% : XA +XB + XC =1

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Multicomponent systems (II)


The Gibbs free energy surfaces (instead of curves for a binary system) can be plotted for all the possible phases and for different temperatures. G

The chemical potentials of A, B, and C of any phase in this system are given by the points where the tangential plane to the free energy surfaces intersects the A, B, and C axis.
MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Multicomponent systems (III)


A three-phase equilibrium in the ternary system for a given temperature can be derived by means of the tangential plane construction. G

For two phases to be in equilibrium, the chemical potentials should be equal, that is the compositions of the two phases in equilibrium must be given by points connected by a common tangential plane (e.g. l and m). The relative amounts of phases are given by the lever rule (e.g. using tie-line l-m). A three phase triangle can result from a common tangential plane simultaneously touching the Gibbs free energies of three phases (e.g. points x, y, and z). Eutectic point: four-phase equilibrium between , , , and liquid
MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

An example of ternary system

The ternary diagram of Ni-Cr-Fe. It includes Stainless Steel (wt.% of Cr > 11.5 %, wt.% of Fe > 50 %) and Inconeltm (Nickel based super alloys). Inconel have very good corrosion resistance, but are more expensive and therefore used in corrosive environments where Stainless Steels are not sufficient (Piping on Nuclear Reactors or Steam Generators).

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Another example of ternary phase diagram: oil water surfactant system

Drawing by Carlos Co, University of Cincinnati

Surfactants are surface-active molecules that can form interfaces between immiscible fluids (such as oil and water). A large number of structurally different phases can be formed, such as droplet, rod-like, and bicontinuous microemulsions, along with hexagonal, lamellar, and cubic liquid crystalline phases.

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Summary
Make sure you understand language and concepts: Elements of phase diagrams: Eutectic (L + ) L +

Common tangent construction Separation into 2 phases Eutectic structure Eutectoid ( + ) Composition of phases Weight and atom percent Miscibility gap + Solubility dependence on T Intermediate solid solution Peritectic ( + L ) Compound +L Isomorphous L Tie line, Lever rule Liquidus & Solidus lines Peritectoid ( + ) Microconstituent + Primary phase Solvus line, Solubility limit Austenite, Cementite, Ferrite Compound, AnBm Pearlite Hypereutectoid alloy Hypoeutectoid alloy A useful link: Ternary alloys http://www.soton.ac.uk/~pasr1/index.htm Gibbs phase rule

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

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