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Binary Solutions

Composition as a thermodynamic variable


Gibbs free energy of binary solutions
Entropy of formation and Gibbs free energy of an ideal
solution
Regular solutions: Heat of formation of a solution
Real solutions: interstitial solid solutions, ordered phases,
intermediate phases, compounds
Equilibrium in heterogeneous systems
Reading: Chapter 1.3 of Porter and Easterling,
Chapters 9.5, 9.6, 9.9, 9.10 of Gaskell

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Solid Solutions (terminology)


Solid solutions are made of a host (the solvent or matrix) which
dissolves the minor component (solute). The ability to dissolve is
called solubility.
Solvent: in an alloy, the element or compound present in
greater amount
Solute: in an alloy, the element or compound present in lesser
amount
Solid Solution:
9 homogeneous
9 maintains crystal structure
9 contains randomly dispersed impurities (substitutional or
interstitial)
Second Phase: as solute atoms are added, new compounds /
structures are formed, or solute forms local precipitates
Solubility Limit of a component in a phase is the maximum
amount of the component that can be dissolved in it (e.g.
alcohol has unlimited solubility in water, sugar has a limited
solubility, oil is virtually insoluble). The same concepts apply
to solid phases: Cu and Ni are mutually soluble in any amount
(unlimited solid solubility), while C has a limited solubility in
Fe.
Whether the addition of impurities results in formation of solid
solution or second phase depends the nature of the impurities,
their concentration and temperature, pressure
MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Composition as a thermodynamic variable


Real materials are almost always mixtures of different elements
rather than pure substances: in addition to T and P, composition
is also a variable.
To understand conditions for equilibrium and phase diagrams
(like the one below) we have to understand how the Gibbs free
energy of a given phase depends on composition, temperature
and pressure. Since many real experiments are performed at
fixed pressure of 1 atm, we will focus on G(T, composition).

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Gibbs free energy of a binary solution (I)


Lets consider a binary solution of A and B atoms that have the
same crystal structures in their pure states and can be mixed in
any proportions - form a solid solution with the same crystal
structure (unlimited solid solubility). Example: Cu and Ni.
1 mol of homogeneous solid solution contains XA mol of A and
XB mol of B. XA and XB are the mole fractions of A and B in
the alloy.

XA + XB = 1

Lets consider two steps of mixing:


1. Bring together XA mol of pure A and XB mol of pure B
2. Mix A and B to make a homogeneous solution
After step 1 the free energy of the system is

Gstep1 = XAGA + XBGB

X AG A

GB

Gstep1
GA

Gibbs free energy per mole


before mixing

XB

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

X BG B

Gibbs free energy of a binary solution (II)


After step 2 the free energy of the system is

G step2 = G step1 + G mix


Where Gmix is the change of the Gibbs
free energy caused by the mixing.

G mix = H mix T Smix

H mix = H step2 H step1

- heat of mixing of the components


(heat of formation of a solution)

Smix = Sstep2 Sstep1

- difference in entropy between


mixed and unmixed states (entropy of
formation of a solution)

Lets first consider an ideal solution interactions between


atoms A-A, B-B and A-B are identical, and Hmix = 0. The free
energy change upon mixing is only due to the change in
configurational entropy:

Gidmix = T Smix

Smix = Sstep2 Sstep1

Sstep1 = k Bln1 = 0 - there is only one way the atoms can be


arranged before mixing

Therefore Smix = Sstep2


MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Entropy of formation of an ideal solution (I)


Statistical definition of entropy:

S = kB ln

Statistical mechanics: if we have Ntot objects


and Nspec of them are special or different,
the number of ways the objects can be
arranged (number of microstates) is
Remember for vacancies we had
Ntot = N number of lattice sites,
Nspec = n number of vacancies.

N tot !
=
N spec !(N tot N spec )!

For mixing of NA particles of type A with NB atoms of type B:

(
N A + N B )!
=
N B! N A !

S mix = k B ln = k B ln

(N A + N B )!
N B! N A !

Using Stirling formula for big numbers: ln N! N ln N N

S mix = k B [ln (N A + N B )!-lnN A !-lnN B !] =


= kB[(NA + NB )ln(NA + NB ) - (NA + NB ) - NAlnNA + NA - NBlnNB + NB ] =

N B
NA

+ N B ln
= k B N A ln
N A + N B
NA + NB

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Entropy of formation of an ideal solution (II)


NA
XA =
NA + NB

NB
XB =
NA + NB

If the total amount of material is 1 mol, NA + NB = Avogadros


number (Na), and NA = XANa, NB = XBNa, NakB = R. Therefore

S mix

N B
NA
=
+ N B ln
= k B N A ln
N A + N B
NA + NB

= R [X A lnX A + X B lnX B ]

Gidmix = T Smix = RT[X A lnXA + X BlnXB ]


For the total Gibbs free energy of an ideal solution:

G id = G step2 = G step1 + G idmix

Gstep1 = XAGA + XBGB

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


For a nonideal solution we have to take into account heat of
formation Hmix:
G mix = H mix T Smix
MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

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

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Gibbs free energy of an ideal solution

Gidmix = T Smix = RT[X A lnXA + X BlnXB ]


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

T1

Gidmix

T2 > T1

T2

XB

1
GB T

Gid

GA T

GB T

GA T

= S
T P

id
mix

XB

Decrease of GA and GB
with T is due to the
temperature dependence
of the free energy:

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Regular solutions: Heat of formation of a solution (I)


For a nonideal solution we have to take into account heat of
formation Hmix 0:

G mix = H mix T Smix

H mix > 0

- mixing is endothermic (heat absorbed)

H mix < 0

- mixing is exothermic (heat released)

Lets account for the heat of formation Hmix 0 using a simple


model called statistical or quasi-chemical model. In this model
the heat of mixing is only related to the bond energies between
adjacent atoms. The assumption is that the interatomic distances
and bond energies are independent of composition.
B

3 types of bonds:

A A bond (energy EAA)

A B bond (energy EAB)

B B bond (energy EBB)

If there are PAA, PBB, PAB bonds of each type, the internal energy
of the solution is

E = PAA E AA + PBBE BB + PABE AB

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Regular solutions: Heat of formation of a solution (II)


Lets calculate the internal energy of the solution:

E = PAA E AA + PBBE BB + PABE AB


If z is the coordination number of an atom in a crystal, then the
number of atoms NA and NB are related to the number of bonds
as

N A z = 2PAA + PAB

PAA

N A z PAB
=

2
2

N B z = 2PBB + PAB

PBB =

N B z PAB

2
2

Using these expressions for PAA and PBB in the expression for
energy, we have

N z P
N z P
E = A AB E AA + B AB E BB + PABE AB =
2
2
2
2
E AA + E BB
NAz
N Bz

=
E AA +
E BB + PAB E AB

2
2
2

energy of unmixed components


Therefore, the energy of mixing (heat of formation Hmix) is

H mix = H step2 H step1 E mix

E AA + E BB

= PAB E AB

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Regular solutions: Heat of formation of a solution (III)


The energy of mixing (heat of formation Hmix) calculated within
statistical or quasi-chemical model is

E + E BB

H mix = PAB E AB AA

E + E BB
If E AB = AA
the solution is ideal: Hmix = 0
2

E AA + E BB
If E AB >
2

Hmix > 0 atoms will tend to be


surrounded by atoms of the same type

E AA + E BB
If E AB <
2

Hmix < 0 atoms will tend to be


surrounded by atoms of different type

But for small differences between EAB and (EAA+EBB)/2 (and for
high T) we can still consider a random arrangement of atoms in a
solution (such solutions are called regular solutions). Then

PAB = zNtotXAXB

and

Hmix = XAXB

E AA + E BB

= zN tot E AB

Hmix

0
MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

where

>0

XB

Regular solutions: Gibbs free energy (I)

Gmix = Hmix T Smix = XAXB + RT(XAlnXA + XBlnXB )

<0

For < 0, Hmix < 0 exothermic


solution mixing is favorable at all T

H mix

- TSmix
G mix

XB

For high || and low T PAB max an ordered alloy could be formed
the assumption of random mixing is
not valid, solution is not regular,
Hmix XAXB

> 0, high T

> 0, low T
H mix

H mix

G mix

G mix

- TSmix

XB

- TSmix
1

XB

For > 0, Hmix > 0 mixing (formation of A-B pairs is


avoided at low T. At high T entropy helps to mix. At low T
MSE 3050, Phase
Diagrams
Kinetics, Leonid
clustering
may
occur and
solution
is notZhigilei
regular.

Regular solutions: Gibbs free energy (II)

Gmix = Hmix T Smix = XAXB + RT(XAlnXA + XBlnXB )

Addition of a small amount of


solute always leads to the decrease
of Gmix and G. Why?

> 0, low T
H mix

G mix

- TSmix

XB

G = X A G A + X B G B + X A X B + RT[X A lnX A + X B lnX B ]

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Real solutions
For regular solutions we assumed a random arrangement of
atoms in a solution. For many real materials this is not a valid
assumption.
If < 0 the internal energy is minimized by increasing the
number of A-B bonds can lead to ordered solution at low T
if > 0 the internal energy is minimized by increasing the
number of A-A and B-B bonds can lead to clustering at low T
The arrangement of atoms is a result of compromise between the
lowest internal energy and highest entropy. Degree of clustering
or ordering decreases with increasing T since the entropy
contribution (-TS) to Gibbs free energy becomes more important.

random

ordered

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

clustering

Real solutions
If atoms A and B have different sizes, the statistical or quasichemical model will underestimate Hmix. The energy of the
elastic strain fields due to the mismatch in atomic sizes should be
taken into account.
If the size difference is large, the
contribution of the strain energy term could as important as the
chemical (bonding) term.

If the size difference between the atoms is very large, then


interstitial solid solutions are energetically favorable.

In systems with strong chemical bonding between the atoms


there is a tendency for formation of intermediate phases. The
intermediate phases can have a different crystal structure and
may be highly ordered.

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Substitutional Solid Solutions


Max solute concentration = 50 at%
e.g. Cu-Ni (unlimited solid solubility)

Factors for high solubility:


Atomic size factor - atoms need to fit solute and solvent
atomic radii should be within ~ 15%
Crystal structures of solute and solvent should be the same
Electronegativities of solute and solvent should be
comparable (otherwise new intermediate phases are
encouraged)
Generally, more solute goes into solution when it has higher
valency than solvent

Interstitial Solid Solutions


Normally, max. solute concentration 10%
e.g. 0.1 at% of C in -Fe (BCC).

Factors for high solubility:

For fcc, bcc, hcp structures the voids (or interstices) between
the host atoms are relatively small atomic radius of solute
should be significantly less than solvent.

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Equilibrium in Heterogeneous Systems (I)


Systems with two or more phases are heterogeneous systems. If
pure components A and B have different equilibrium crystal
structures, phase and phase , we have to consider two Gibbs
free energy curves, one for each phase:

GB

GA
GA

GB

0
homogeneous phase

XB

1
homogeneous phase

For compositions near cross-over of G and G, the total Gibbs


free energy can be minimized by separation into two phases.

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Equilibrium in Heterogeneous Systems (II)


Lets consider a systems with two phases and , that have
compositions XB and XB and Gibbs free energies G and G.
If the average composition of the system is XB0, the molar free
energy G+ is given by the point on a straight line that connects
G and G, and the relative number of moles of phases and
can be found by the lever rule:

M = (XB - XB0)/(XB - XB)


M = (XB0 - XB)/(XB - XB)

L1 = G
G

G+
G

L2
L1

L4

L3

XB X0B

XB

Molar free energy of the


phase mixture with molar
fractions of phases and ,
M and M

L4 = G

L3 XB X0B

=
=
M
L1 XB XB
L3 = MG

L2 X0B XB

=
=
M
L4 XB XB
L2 = MG

L3 + L2 = MG + MG = G+

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Equilibrium in Heterogeneous Systems (III)

G0
G

G1
XB1 X0B XB1
For composition XB0 the lowest Gibbs free energy is G0 for a
homogeneous system. The total Gibbs free energy can be
additionally decreased by separation into two phases, for
example with compositions XB1 and XB1 .

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Equilibrium in Heterogeneous Systems (IV)

Geq

Geq

Geq
eq
B

X0B

eq
B

The total Gibbs free energy is at minimum if phases and have


compositions

eq
B

and

eq
B

These are the equilibrium compositions of the phases.

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Intermediate phases
The intermediate phases can have a crystal structure that is
different from the one of the pure components, and an additional
Gibbs free energy curve for the intermediate phase should be
considered.

GB
GA

GB
Gmix

GA
XB

XB

If an intermediate phase have a specific composition and small


deviations from the ideal composition cause a rapid rise in G, the
phase is called compound. Compounds typically have a
stoichiometric composition (AnBm where n and m are integers).
The structure of intermediate phases is determined by
Relative atomic size: RA/RB ~ 1.1-1.6 Laves phases (e.g.
MgZn2, MgNi2); RA >> RB interstitial compounds, e.g. Fe3C
Valency: stability of phases depends on the # of valence
electrons per unit cell
Electronegativity: different electronegativity of components
leads charge transfer and formation of strong ionic bonding, e.g.
Mg2+ + Sn4- = Mg2Sn
MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Summary
Make sure you understand language and concepts:
Gibbs free energy of binary solutions, entropy and heat of
formation terms
for ideal solution
for regular solutions
Real solutions: interstitial solid solutions, ordered phases,
intermediate phases, compounds
Chemical potential and activity of a component, Henrys and
Raoults laws - not tested
Equilibrium in heterogeneous systems
Make sure you understand all the variables, as well as the
approximations, basic ideas, and graphical pictures behind these
equations:

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

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

E AA + E BB

= zN tot E AB

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei