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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 G


dependence of G of a one-
component system on T:
G
= S
T P
2G S c
2 = = P T
T P T P T

We have also discussed the GA


dependence of the Gibbs free
energy from composition at a
given T: GB

G = XAGA + XBGB + Hmix T Smix G

0 XB 1
MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei
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 T1
A
G liquid
B
G liquid
A G solid

G liquid

0 XB 1

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:
liquid
GA and G liquid
B will increase more rapidly than G solid
A

and G solid
B Why?
The curvature of the G(XB) curves will decrease. Why?

Eventually we will reach T2 melting point of pure


component A, where G liquid
A = G solid
A

G solid
B
T2 G liquid
G liquid
A =G solid
A
B

G solid

G liquid

0 XB 1

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.

T3 G solid
B
G liquid
A

G solid
G solid
A G liquid
B

G liquid

solid solid +
liquid liquid

X1 X2
0 XB 1

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 Gliquid


A and G liquid
B
continue
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

T4
G liquid
A

G liquid
G liquid
B = G solid
B

G solid
A

G solid

0 XB 1

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

G liquid G solid
B
A
T3
G solid
G solid
A G liquid
B

G liquid
T1
solid solid +
s liquid liquid
l
T T1
s
T2 T2
l
T3

l T4 T4
T5
s
0 XB 1

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


3050, line
Solidus
MSE Phaseseparates solid
Diagrams and from
Kinetics, liquid
Leonid + solid
Zhigilei
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 at equilibrium in this temperature range.

Liquidus
L
Temperature

liquid solution

+L

Solidus
liquid solution
+
crystallites of
solid solution

A 20 40 60 80 B
polycrystal
solid solution 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. Locate composition and temperature in diagram
2. In two phase region draw the tie line or isotherm
3. Note intersection with phase boundaries. Read compositions
at the intersections.
The liquid and solid phases have these compositions.

Xliquid
B
XB 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. Locate composition and temperature in diagram
2. In two phase region draw the tie line or isotherm
3. 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 two-
phase region is analogous to a lever
balanced on a fulcrum.

W 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 = m
100 C at = X B 100
n Bm + n Am
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
mB
C wt = 100
mB + mA
where mA and mB are the weights of the components in the
system.
mA mB where AA and AB are atomic
n Am = n Bm =
AA AB weights of elements A and B.

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei


Composition Conversions

C Bwt A A
Weight % to Atomic %: C atB = wt 100
CB AA + CA AB wt

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

Atomic % to Weight %: C atB A B


C Bwt = at 100
CBA B + CAA A at

C atA A A
C wt
A = at 100
CBA B + CAA A at

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 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

G T1 G T2 < T1 G liquid
G solid

G solid
G liquid

0 XB 1 0 XB 1

T
G T3 < T2
G liquid T1
liquid
T2
G solid
T3 1+2
0 XB 1 0 XB 1
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


T
G
liquid

T1
T2
1+2
0 XB 1 0 XB 1

0 XB 1

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei


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

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.

G G T2 < T1
G liquid T1 G liquid

G solid
G solid

0 XB 1 0 XB 1

G T3 < T2 T liquid
liquid
G
T1
1+l 2+l
T2
G solid T3 1 2
1+2

0 XB 1 0 XB 1

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.

G T1 G T2 < T1


liquid
liquid

0 XB 1 0 XB 1

T
G T3 < T2 liquid
T1

+l
+l
T2

liquid T3
+

0 XB 1 0 XB 1

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.

T
G T1 liquid


+l
+l

liquid T1
+

0 XB 1 0 XB 1

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 - Minimum of G(XB)
dX B

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 ]

dG
= -G A + G B + 2 X B + RT - ln(1 - X B )
(1 - X B ) + lnX + X B =

dX B (1 - X B ) B
XB

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

X
= G B - G A + (1 2XB ) + RTln B GB - G A + + RTln(XB ) = 0
1 - XB

if XB is small (XB 0) Minimum of G(XB)


(GB >> GA)

G GA +
XB exp B
RT

Solid solubility of B in increases


exponentially with temperature
(similar to vacancy concentration)

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei


Temperature dependence of solubility (III)

liquid
+l +l

T1
+

0 XB 1

G GA +
XB exp B
RT

XB XB vs. T T vs. XB
T

T
Te XB

supersaturation with B
phase separation and
precipitation of B-rich intermediate
phase or compound

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei


Eutectic systems - alloys with limited solubility (I)

Liquidus
liquid
Solidus
Temperature, C

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 co-
exist 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

B
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


Temperature, C

Composition, wt% Sn

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


Temperature, C

(0-2 wt. % of tin)


solidification proceeds in the
same manner as for
isomorphous alloys (e.g. Cu-
Ni) that we discussed earlier.

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


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


T liquid

0 XB 1

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei


Monotectic system
Limit of liquid
T + L1
immiscibility

Lower
Upper solidus L1 liquidus
Monotectic point L1 + L2
L2
Lower solidus
+ L2
+L2
Monotectic isotherm
+

0 XB 1
F.N. Rhines, Phase Diagrams in Metallurgy, 1956

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 T1 G T2 < T1
G
G liquid

G liquid G
0 XB 1 0 XB 1
T3 < T2 T liquid
liquid
G G T1
T2
G
T3
`
`
G 0 XB 1
0 XB 1
At low temperatures, strong attraction between
unlike atoms can lead to the formation of
ordered
MSE phase
3050, Phase `. and Kinetics, Leonid Zhigilei
Diagrams
Binary solutions with Hmix < 0 - intermediate phases
If attraction between unlike atoms is very strong, the ordered
phase may extend up to the liquid.

T
liquid


+
+

0 XB 1
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


T
liquid


+
+

0 XB 1

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei


T
liquid


+
+

0 XB 1

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei


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

T liquid

0 XB 1
Increasing
liquid negative Hmix
T

`
0 XB 1
T
liquid



+
+

0 1
XBand Kinetics, Leonid Zhigilei
MSE 3050, Phase Diagrams
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
MSE phases
3050, Phase in theandsystem.
Diagrams 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 T
liquid liquid
+l +l
l l
l+ + l+AB +

+ + AB

AB
+ + AB

0 XB 1 0 XB 1
non-stoichiometric stoichiometric
Common stoichiometric compounds:
compound AB A6B5 A5B4 A4B3 A3B2 A5B3
composition, at% 50.0 45.5 44.4 42.9 40.0 37.5

compound A2B A5B2 A3B A4B A5B A6B


composition, at% 33.3 28.6 25.0 20.0 16.7 14.3
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
l

+l Eutectic
l +

temperature
+
+
Eutectoid
temperature
+

Eutectoid Eutectic
composition 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


Temperature
l

+l
l +

+
+
Eutectoid
temperature
+

Composition

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


Temperature + liquid liquid

+
+ liquid

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
MSE 3050, entire
Phase ( +and
Diagrams Fe3Kinetics,
C) phase field:
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


Reconstruction of Baroque organs (TRUESOUND EU project)
Baroque-style organ reconstructed in
rgryte Nya Kyrka, Gothenburg, Sweden

Components of reed pipes


MRS Bulletin
Vol 32, March
MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei 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
solubility
MSE 3050,at 920C,
Phase but is 32.5
Diagrams wt.% - maximum
and Kinetics, solubility after crystallization.
Leonid Zhigilei
The Gibbs phase rule (I)

Lets consider a simple one-component system.

P liquid
solid
In the areas where only one phase
is stable both pressure and
temperature can be independently gas
varied without upsetting the phase
equilibrium there are 2 degrees
of freedom. 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 = - Ph-1 equations
P = P = P = - Ph-1 equations

A = A = A = ... - Ph-1 equations


C sets of equations
= = = ...

B

B

B - Ph-1 equations

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.

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.

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 Elements of phase diagrams:
language and concepts:
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
Microconstituent Peritectoid ( + )
Primary phase +

Solvus line, Solubility limit

Austenite, Cementite, Ferrite
Pearlite Compound, AnBm
Hypereutectoid alloy
Hypoeutectoid alloy
Ternary alloys A useful link:
Gibbs phase rule http://www.soton.ac.uk/~pasr1/index.htm
MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei