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Equilibrium
Phase: properties and chemical composition are
homogeneous
Components: different elements or chemical compounds
System vs surrounding
Equilibrium
Gibbs free energy
G = H TS
Stable equilibrium is defined as the system
at minimum G
dG = 0
G G
dG = SdT + VdP = S , =V
T P P T
Single Component System
L = Hl Hs
L: Latent heat of melting at Tm
Eg. = transformation:
: fcc, dense : bcc
V = V V > 0
H = H H < 0
( is high-temperature phase)
Fig. 1.5 Effect of pressure on the equilibrium
dP phase diagram for pure iron.
<0
dT
Single Component System
L T
G = H TS
Tm
T = Tm T > 0
Fig. 1.6 Difference in free energy between
liquid and solid close to the melting point. The
curvature of the GS and GL lines has been
ignored.
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Suppose that A and B, solvent and solute, respectively, form a system, either
single phase or two phase. Then
XA + XB = 1
G = X AG A + X B GB + Gmix
Gmix = H mix TS mix
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Fig. 1.8 Variation of G1 (the free energy before mixing) with alloy
composition (XA of XB).
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For ideal solutions,
H mix = 0
S mix = R ( X A ln X A + X B ln X B )
contribucin termica
S = k ln w w : cantidad de estados distinguibles
k: constante de Boltzman
y contribucin configuracional
( N + N B )!
= k ln A
N A! N B !
NA + NB: sitios posibles a ocupar los atomos
NA! NB!: modos posibles a ser ocupados
Since H = 0 for ideal solution,
G = X A G A + X B G B + RT ( X A ln X A + X B ln X B )
AGmix=RT(XalnXa + XblnXb)
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El descenso de Ga y Gb es debido
a la entropa termica de ambos
componentes
Fig. 1.10 The molar free energy (free energy per mole of solution)
for an ideal solid solution. A combination of Figs. 1.8 and 1.9.
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En una reaccin qumica, se libera o absorbe energa
Chemical potential: medida de la energa que cada sustancia genera por mol
cuando tomos son aadidos o removidos
G '
dG'=uadna (T,p,nb constantes) A =
energa molar parcial n A T , P, nB
G : Gibbs energy of the whole system, Extensive
ua y ub varian sistematicamente
con la composicin para una
solucin ideal
Fig. 1.11 The relationship between the free energy curve for a
solution and the chemical potentials of the components.
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actividad qumica: mide la diferencia
entre la energa molar de un componente los potenciales qumicos de A y B para una
puro y la que posee cuando esta en solucin composicin XB surge del valor de la tg
Fig. 1.12 The relationship between the free energy curve and
chemical potentials for an ideal solution.
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Regular solution la mezcla es endotermica o exotermica
3 tipos de enlace:
H mix = PAB AH es debido a las energias de enlace de los atomos
The free energy curves of regular solutions vary with temperature and the sign of :
G = X AG A + X B GB + X A X B + RT ( X A ln X A + X B ln X B )
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Fig. 1.14 The variation of Hmix with composition for a regular solution.
para soluciones endotermicas
AHmix < 0
A = G A + RT ln a A
a A : Activity
aA
ln = (1 X A ) 2
X A RT
aA Fig. 1.16 The relationship between molar free
= A = activity coefficient energy and activity.
XA
Raoult's law: A 1
Henry's law: A constant
Fig. 1.17 The variation of activity with composition (a) aB (b) aA. Line 1: ideal
solution (Raoults law). Line 2: Hmix<0. Line 3: Hmix>0.
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Real solutions
Random solution is not attained for 0
Ordered substitutional depende del valor de E. Si E<0 la energia interna del sistema
Clustering se reduce por el aumento de enlaces A-B
Si E>0 se reduce la energia interna por el incremento de enlaces
Random interstitial A-A y B-B
SRO vs LRO
CuAu, Cu3Au and many other intermetallics show LRO.
A superlattice forms in materials with LRO.
Fig. 1.19 (a) Random A-B solution with a total of 100 atoms and XA=XB=0.5, PAB~100,
S=0. (b) Same alloy with short-range order PAB=132, PAB(max)~200, S=(132-100)/(200-
100)=0.32
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Cu y Au son fcc y totalmente miscibles
a altas temperaturas los tomos de Cu o Au pueden ocupar cualquier sitio y la celda se considera fcc, con
un ordenamiento atmico en cada punto de la celda
Fig. 1.20 Ordered substitutional structures in the Cu-Au system: (a) high-
temperature disordered structure, (b) CuAu superlattice, (c) Cu3Au superlattice.
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Fig. 1.21. Part of the Cu-Au phase diagram showing the regions where the
Cu3Au and CuAu superlattices are stable.
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Fig. 1.22 The five common ordered lattices, examples of which are: (a) L20: CuZn,
FeCo, NiAl, FeAl, AgMg; (b) L12: Cu3Au, Au3Cu, Ni3Mn, Ni3Fe, Ni3Al, Pt3Al, Pt3Fe;
(c) L10: CuAu, CoPt, FePt; (d) D03: Fe3Al, Fe3Si, Fe3Be, Cu3Al; (e) D019: Mg3Cd,
Cd3Mg, Ti3Al, Ni3Sn. (After R.E. Smallman, Modern Physical Metallurgy, 3rd edition,
Butterworths, London, 1970.)
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Intermetallic Phase and Intermediate Phase:
rango estrecho de composiciones
depende del tipo de enlace interatomico
Fig. 1.23 Free energy curves for intermediate phases: (a) for an intermetallic compound
with a very narrow stability range, (b) for an intermediate phase with a wide stability
range.
Equilibrium in Heterogeneous Systems
ad y cf: son las energias libres molar de alfa y beta
g:interseccin de be y dc
A = A
B = B
Also,
aA = aA
aB = aB Fig. 1.27 (a) Alloy X0 has a free energy G1 as a mixture of 1+1.
(b) At equilibrium, alloy X0 has a minimum free energy Ge when it is
a mixture of e+e.
Definicin grfica de actividad
Fig. 1.29 The derivation of a simple phase diagram from the free energy curves
for the liquid (L) and solid (S).
Binary Phase Diagrams
Fig. 1.30 The derivation of a phase diagram where Hsmix > HLmix = 0. Free
energy v. composition curves for (a) T1, (b) T2, and (c) T3.
Binary Phase Diagrams
At Tm , GS = GL
At T > Tm , GS < GL
Two-phase region (S + L) corresponds to the common tangent region of
the free energy curves of S and L.
Note that the compositions of S and L differ in the two-phase region.
When A and B atoms dislike each other,
H mix > 0
In this case, the free energy curve at low temperature has a region of
negative curvature,
i.e.,
d G
2
< 0
dX B
2
Fig. 1.31 (a) Phase diagram when HSmix < 0; (b) as (a) but even more
negative HSmix. (After R.A. Swalin, Thermodynamics of Solids, John
Wiley, New York, 1972)
Binary Phase Diagrams
Simple Eutectic Systems
Hm>>0 and the miscibility gap extends to the melting temperature.
Fig 1.32 The derivation of a eutectic phase diagram where both solid phases have the
same crystal structure. (After A.H. Cottrell, Theoretical Structural Metallurgy,
Edward Arnold, London, 1955,Sir Alan Cottrell.)
Binary Phase Diagrams
Fig. 1.33 The derivation of a eutectic phase diagram where each solid phase has a
different crystal structure. (After A. Prince, Alloy Phase Equilibria, Elsevier,
Amsterdam, 1966.)
Binary Phase Diagrams
Phase diagrams containing intermediate phases
Fig. 1.35 Free energy diagram to illustrate that the range of compositions over which a phase is
stable depends on the free energies of the other phases in equilibrium.
Binary Phase Diagrams
The Gibbs Phase Rule
F=CP+2
F : Degree of freedom
P : Number of phases
C : Number of components
S = X V SV R ( X V ln X V + (1 X V ) ln(1 X V ))
At equilibrium, dG / dX v = 0
X ve = exp( Gv / RT ) = exp(S v / R ) exp( H v / RT )
Gv = H v TS v
2
P =
r
The pressure difference results in a free energy difference:
G = P V
(Gibbs-Thomson Eq.)
2Vm
G =
r
The G-T equation states that small particles shrink while large particles grow.
The Influence of Interface on
Equilibrium
Suppose a system containing two particles embedded in , one spherical and
another one with a planar (r = ) interfaces. It can be shown that a transfer of a
small amount of , dn, from the large to small particle will increase the system free
energy by
dG = Gdn
dA 2Vm
=
dn r
Fig. 1.38 The effect of interfacial energy on the solubility of small particles.
The Influence of Interface on
Equilibrium
X = exp( (GB + ) / RT )
= X exp(2Vm / RTr )
X (1 + 2Vm / RTr )
Ternary Equilibrium
XA+XB+XC = 1
Fig. 1. 41 (Cont.) (b) A tangential plane construction to the free energy surfaces defines
equilibrium between s and l in the ternary system. (c) Isothermal section through a ternary
phase diagram obtained in this way with a two-phase region (L+S) and various tie-lines.
The amounts of l and s at point x are determined by the lever rule. (After P. Haasen,
Physical Metallurgy, Cambridge University Press, Cambridge, 1978.)
Fig. 1.42 Isothermal sections through Fig. 1.44. (After A. Prince, Alloy
Phase Equilibria, Elsevier, Amsterdam, 1966.)
Fig. 1.43 A projection of the liquidus surfaces of Fig. 1.44 onto the Gibbs triangle.
Fig. 1.44 The equilibrium solification of alloy X. (After A. Prince, Alloy Phase
Equilibria, Elsevier, Amsterdam, 1966.)
Fig. 1.45 A vertical section between points 1, 2 and X in Fig. 1.44.
(After A. Prince, Alloy Phase Equilibria, Elsevier, Amsterdam, 1966.)
Additional Thermodynamic
Relationships for Binary Solutions
Fig. 1. 46 Evaluation of the change in chemical potential due to a change in composition. (After
M. Hillert, in Lectures on the Theory of Phase Transformations, H.I. Aaronson (Ed.), The
Americal Society for Metals and The Metallurgical Society of AIME, New York, 1969.)
Additional Thermodynamic
Relationships for Binary Solutions
d A d B d ( B A ) dG d 2G
= = = d = dX B
XB XA 1 dX B dX B
2
d 2G
X A d A = X B d B = X A X B dX B
dX 2
For a regular solution,
G = X AG A + X B GB + X A X B + RT ( X A ln X A + X B ln X B )
d 2G RT
= 2
dX 2
X AXB
B = GB + RT ln B X B
d B RT d ln B RT
= 1 + = I
dX B X B d ln X B XB
and
d 2G
X AXB = RT I
dX 2
The Kinetics of Phase Transformations
Overcoming the activation barrier,
Ga, by thermal activation is possible
with a probability of
(
exp G a / RT )
Therefore, the rate of transition of
states is proportional to the rate defined
as
( ) (
rate exp G a / RT exp H a / RT )
Fig. 1.47 Transformations from initial to
final state through an activated state of
The above equation was first derived higher free energy.
empirically and is known as Arrhenius
rate equation.