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Each element
- 3 different states: gas, liquid, solid
- at Tm - solid & liquid are in equilibrium
- at Tb - liquid & gas are in equilibrium
Tm & Tb
depend on pressure (p) but p has very
little effect on solid.
Fig 4.1
- on the lines in this diagram there are 2 phases in equilibrium with each other.
- at the triple point all 3 phases are in equilibrium with each other.
The border between the liquid and gas states of the substance is called the vapor pressure curve.
- For a given temp, it tells us the vapor pressure
- The vapor pressure ends at critical point
Critical point- The temp above which the gas cannot be liquidfied no matter how much pressure is applied.
(kinetic energy is too great for attractive forces to overcome, regardless of the applied pressure.)
- or beyond the critical point: liquid continuously transforms to gas.
At a given pressure there is a defined Tm and a defined Tb
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n no. of component
p no. of phase
f no. of degree of freedom
Eg. 1 component 1 phase:
f = 2
pressure and temp
At the triple point; n = 1, p = 3 :
f = 13+2 =0
means only specific values of temp and pressure that
3 phases are in equilibrium with each other.
Tm & Tb depend only little on pressure (for solid), therefore Gibbs phase rule can be modified
f = np+1
p constant
At melting temp:
f = 12 +1=0
n=2
p =1:
p =2:
= np+2
3. Monotectic system
- miscibility gap occurs both in the solid and
liquid states. Fig 4.7 Fe-Pb
4. Complete solubility in the liquid state but limited
solubility in the solid state
- the solubility increase with increasing temp,
- if a miscibility gap exists only at temp below the solidus
temp, the melt solidifies as a solid solution and upon
cooling this solution decomposes into 2 phases. Fig 4.8
5. Complete solubility in liquid state and the max. temp of a
miscibility gap is higher than the solidus temp
- a point of intersection of the solidus temp with the solvus line of
the miscibility gap, the three phases (melt + 2 phases) are in
equilibrium.
(f = n p +1 = 2 3 + 1 = 0)
-There is solidification region has a cigar shape this phase
diagram is called peritectic phase diagram. Fig. 4.9
peritectic reaction:
L + 1 <==> 2 ( conc.= cp)
occur at Tp which is between melting temp of both components
- Occur when Tm of both components are very different.
Thermodynamics of alloys
G = H TS
G = Gmin
(T, p = constant)
H - enthalpy
T - temp
S - entropy
p - pressure
S > 0 T up TS up
G down and Gmin at equilibrium
G of pure metal depending on temp. Fig 4.19
The free energy of crystal (Gc) & melt (Gm) change differently with temp
At melting temp: Gm = Gc liquid and solid in equilibrium
For pure element:
entropy = vibrational entropy + configuration entropy
(entropy of mixing)
S
= Sv + Sm
For alloys with 2 components A and B:
Total no. of atom N = no. of atom A + no. of atom B
N
= NA + NB
The atomic concentration of A: cA = NA/N
The atomic concentration of B: cB = NB/N = c
The entropy of mixing:
Sm = - N k {c lnc + (1 c) ln (1 c)}
c < 1, Sm > 0
-TS = -T(Sv + Sm) ~ -TSm
Fig. 4.20:
Sm curve is symmetry:
c = 0.5 slope = 0
c=0
slope = -
c=1
slope = +
S
=
c 0:1 c
lim
G = H TS
H does not change markedly with temp.
G(c) vary with -TS
Fig 4.21
T1 :
TA & TB:
T2 :
T3 :
Solid solutions
Primary solid solution or terminal solid solution
solid solution next to the pure component.
Intermediate solid solution phase with finite
composition range discrete from primary solid solution
Types of solid solutions Fig. 4.26
1. Interstitial solid solution - only H, B, C, N
2. Substitutional solid solution
-Interstitial site usually smaller than the size of the smallest atom
-Interstitial atom causes elastic distortion energy
-the size of interstitial atom elastic energy will rapidly increase decrease the solubility
-elastic distortion increase the free energy of the solid solution increase destabilizes the solid solution
Fig. 4.27 shows the determination of composition of the phases
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IV Crystal structures
Single atom:
only one electron can occupy in on energy state.
Bring 2 atoms closer: e- in one atom needs to change its energy state or this energy state needs to split
into two levels.
N atoms together:
the energy state split into N energy level quasi continuous energy band.
In crystal: if the adjacent electronic state is a large energy different, the band gap is large. Therefore, the
energy of an additional electron can drastically increase at certain concentrations of valence
electrons. VEC valence electron concentration (no. of valence electrons per atom)
The critical electron density of this band gap depends on crystal structure; bcc has higher electron density in
the band gap than fcc.
If Zn (2 valence e-) added in Cu (1 valence e-) to form solid solution (fcc)
- no. of valence e- in the band gap drastically increase
- The critical valence electron concentration (VEC) of fcc is reached. fcc is not stable.
- bcc becomes more favorable (with increasing Zn atoms).
- Therefore the second phase will be formed and
stability of the second phase can be determined
by free energy diagram.
Fig. 4.31 shows the effect of VEC of the various alloys.
- Base metal: Cu
- alloying element: Zn(2), Ga(3), Ge ( 4), As (5 )
- Increasing valence e- the solubility decrease.
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A:B =1:1
A:B =1:1
Note: the ordered and disorder structure are not equivalent even though they cannot be discriminated.
The ordered atomic distribution low entropy
Degree of ordered decreases with increasing temperature. If the exchange energy, Ho, is very small
disordered structure will be exist.
and at higher temperature disordered solid solution
Cu-Au : at T<390oC ordered structure formed
Tc : the critical temp is the temp that ordered state changes to disordered state.
Ni-Al system:
Ni3Al and NiAl are the ordered phases and remain ordered up to melting point
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s =
p- x
1- x
G(s) = H TS
in equilibrium
dG/ds = 0
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If the alloying element is so small that it can fit in the interstitial sites of the other component, the
requirement is r/R = 0.59. For example:
- AB type compound if all octahedral interstitial sites of fcc are occupied, NaCl lattice.
- This phases have a very sharply defined upper solubility limit since all interstitial sites are occupied,
no more alloying elements can be dissolved, Fig 4.47. This phase is called Hgg phase high
stability. Fig. 4.47a Hgg phase TaC has high melting temperature ~ 3988 o C.
- Crystal structure of the Hgg phase is not necessary the same lattice of the pure component.
eg. Ta is bcc, TaC is fcc which C atoms occupy in octahedral interstitial of fcc, Fig 4.47b.
(Ta2C is Hgg phase with hexagonal structure, Fig. 4.47.)
- Hgg phase AB4 : interstitial sites in the center of fcc are occupied.
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