9th APRIL,2018
final initial
α(Tfinal Tinitial )
initial
linear coefficient of
thermal expansion (1/K or 1/°C)
5
Thermal Expansion
• If the curve is not symmetric, the average position in
which the atom sits shifts with temperature.
• Bond lengths therefore change (usually get bigger for
increased T).
• Thermal expansion coefficient is nonzero.
Bond energy
r(T1)
r(T5)
T5
bond energy vs bond length
curve is “asymmetric”
T1
THERMAL EXPANSION: COMPARISON
(10-6/K) •Thermal expansion
Material
• Polymers at room T mismatch is a major
Polypropylene 145-180 problem for design of
Polyethylene 106-198
Polystyrene 90-150 everything from
Teflon 126-216 semiconductors to
• Metals
bridges.
increasing
Aluminum 23.6
Steel 12
Tungsten 4.5
•Particularly an issue
Gold 14.2 in applications where
• Ceramics temperature changes
Magnesia (MgO) 13.5
Alumina (Al2O3) 7.6 greatly (esp. engines).
Soda-lime glass 9 Why does generally
Silica (cryst. SiO2) 0.4
decrease with increasing
bond energy?
Selected values from Table 19.1, Callister 6e.
Thermal Shock Resistance For Brittle
materials e.g
• Occurs due to: nonuniform heating/cooling ceramics
• Ex: Assume top thin layer is rapidly cooled from T1 to T2
rapid quench
s
tries to contract during cooling T2 Tension develops at surface
resists contraction T1 s E l (T1 T2 )
Temperature difference that Critical temperature difference
can be produced by cooling: for fracture (set s = sf)
quench rate sf
(T1 T2 ) (T1 T2 ) fracture
k E l
set equal
sf k
• (quench rate) for fracture Thermal
Shock Resistance (TSR) E l
sf k
• Large TSR when is large
E l
Numerical example important 12
These all are members of ceramic material
They belong to Amorphous Type.
E – Young’s Modulus
v = poisson ratio
α = Thermal expansion Coefficient
Thermal
• Application:
Protection System
Re-entry T
Space Shuttle Orbiter Distribution
(400-1260C):
• Silica tiles
-- large scale application -- microstructure:
~90% porosity!
Si fibers
bonded to one
another during
heat treatment.
100 mm
25
Linear polymer - Any polymer in which molecules are in the form
of spaghetti-like chains.
Thermoplastics - Linear or branched polymers in which chains of
molecules are not interconnected to one another.
Thermosetting polymers - Polymers that are heavily cross-linked
to produce a strong three dimensional network structure.
Elastomers - These are polymers (thermoplastics or lightly cross-
linked thermosets) that have an elastic deformation > 200%.
SUMMARY
Diffusion
Diffusion Mass transport by atomic motion. Diffusion is
a consequence of the constant thermal motion of
atoms, molecules and particles that results in
material moving from areas of high to low
concentration-.
Mechanisms
• Brownian motion is the seemingly random
movement of particles suspended in a liquid or gas.
• Solids – vacancy diffusion or interstitial diffusion.
35
We need a way of splitting up the Gibbs free energy of a phase among the various
components of the phase--how does the Gibbs free energy of a phase vary with
composition--We address these issues by defining a partial Gibbs free energy for each
component at constant pressure and temperature and constant composition of other
components, called the partial molar Gibbs free energy or chemical potential
A partial molar property is a thermodynamic
quantity which indicates how an extensive
property of a solution or mixture varies with
changes in the molar composition of the mixture
at constant temperature and pressure
Diffusion Mechanism
Vacancy diffusion
Interstitial diffusion
45
Activation Energy
G H TS
G Vibration frequency:
Energy
Atom position
Jump Frequency :
H m
D D0 exp
RT 46
Vacancy Diffusion
• Applies to substitutional impurities
• Atoms must hop to open vacancy
• Rate depends on probability of overcoming migration activation
energy, Qm
pQ = Bexp(-Hm/kT)
And
• Probability of a vacancy
pv = Nv/N = exp(-Hv/kT)
• Here is Diffusion Coefficient is:
D = D0 exp(-Hd/kT)
where Hd = Hm + Hv
48
Interstitial Diffusion
where D0 is a pre-exponential
factor (m2/s) and Hd = Hm
51
Data
Interstitial diffusion in Fe Self-diffusion data for metals
isotope
x=0
52
Other Diffusion Mechanisms
Direct exchange
Zener ring
53
LAW’S OF DIFFUSION
Adolf Eugen Fick was a German-born physician
Fick’s first law - The equation relating the flux of atoms by
diffusion to the diffusion coefficient and the concentration
©2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning™ is a trademark used herein under license.
gradient.
Diffusion coefficient (D) - A temperature-dependent coefficient
related to the rate at which atoms, ions, or other species diffuse.
Concentration gradient - The rate of change of composition with
distance in a nonuniform material, typically expressed as
atoms/cm3.cm or at%/cm.
©2003 Brooks/Cole, a division of Thomson Learning, Inc.
Thomson Learning™ is a trademark used herein under
license.
DIFFUSION FLUX
Non-steady State Diffusion
• The concentration of diffusing species is a function of both time and
position C = C(x,t)
• In this case Fick’s Second Law is used
Fick’s second law - The partial differential equation that describes
the rate at which atoms are redistributed in a material by diffusion.
Fick’s Second Law C 2C
D 2
t x
57
MECE 3345 Materials Science V. Diffusion in Solids
58
MECE 3345 Materials Science V. Diffusion in Solids
dn
J D J J12 J 21
dx
2 Lattice parameter
a
D
Average stay time at interstitial site
11 2
Einstein formula D : jump distance
6
Simple cubic FCC BCC
a
2
a
3
a
1 2 2
1 1
6
12 8 59
MECE 3345 Materials Science V. Diffusion in Solids
B
dn
J D
dx n: number density
x
Position
J
x
Position
60
MECE 3345 Materials Science V. Diffusion in Solids
n1 n2
c
c
concentration
t2
concentration
t1 A A
A
B
B x
x x
Position x
J
x
Position
J12 J 21
61
MECE 3345 Materials Science V. Diffusion in Solids
n
ns
t increases
concentration
ns ns
n0
t=0
n0 n0
0 0 0 x
x=0 x=∞ x=0 x=∞ Position
Solution to the Fick’s second law
Fixed surface concentration.
n x ( t ) n0 x
1 erf , erf: Gaussian error function
ns n0 2 Dt
62
MECE 3345 Materials Science V. Diffusion in Solids
2 x 2
Error function erf x e d
0
63
Applications of Diffusion