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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
We have also discussed the dependence of the Gibbs free energy from composition at a given T:
G A G B
0
MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei
XB
G solid B G
solid A
T1
G solid G liquid B
G liquid A
G liquid
XB
and G solid B
Why? Why?
The curvature of the G(XB) curves will decrease. Eventually we will reach
liquid A
=G
solid A
T2
G solid G liquid
G solid B G liquid B
XB
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.
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
liquid A
T3
G solid A
T1
solid solid + liquid
liquid
T2
T1 T2
T3
T4
T4
T5
XB
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
Liquidus Temperature
L +L
Solidus
liquid solution
20 40 60 80 Composition, wt %
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.
XB Xliquid B
Xsolid B
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
nA m =
mA AA
nB m =
mB AB
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
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
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
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.
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.
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
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
T1
T2 < T1
liquid
liquid
0
G
XB
1
T
XB
T3 < T2
liquid
T1 T2
liquid +l + +l
T3
XB
XB
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).
- Minimum of G(XB)
See problem 1 of hw #4
G GA + XB exp B RT
liquid
Solvus
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
Temperature, C
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).
A
Temperature, C
Composition, wt% Sn
For points A, B, and C calculate the compositions (wt. %) and relative amounts (mass fractions) of phases present.
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
L
Temperature, C
+L +
Composition, wt% Sn
MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei
Temperature, C
Composition, wt% Sn
L +
MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei
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
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
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:
Temperature, C
Composition, wt% Sn
MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei
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
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.
liquid
0
T
XB
liquid
1
Increasing negative Hmix
0
T
XB
liquid
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
T
liquid +l + l+ + l
T
liquid +l + AB
AB
l+AB
+ AB
XB
XB
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
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
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
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 ( + = ).
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.
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
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
L + Fe3C
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)
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
Microstructure of hypoeutectoid steel (I) Compositions to the left of eutectoid (0.022 - 0.76 wt % C) hypoeutectoid (less than eutectoid -Greek) alloys.
+ + Fe3C
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.
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
Microstructure of hypereutectoid steel (II) Hypereutectoid alloys contain proeutectoid cementite (formed above the eutectoid temperature) plus perlite that contain eutectoid ferrite and cementite.
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)
pearlite
naturally formed composite: hard & brittle ceramic (Fe3C) + soft BCC iron (ferrite)
material
strength tensile, TS
Cu Zn phase diagram
Cu Pb phase diagram
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 = 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).
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
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
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
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).
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.
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