Kinetics of Materials Lecture1

1.Consider two heat chambers at temperature T1 and T2 (T1>T2). By connecting these

two chambers using a metal bar of length L and cross-sectional area A. Prove that the
entropy production rate (σ) associated with the heat flow process is proportional to
the product of heat flux and temperature gradient?

L
T1 δ A T2

2. Describe how the apparent thermal conductivity and entropy production rate (𝜎𝜎̇ ) of
a conductor in below different measurement conditions. (a) Under a thermal driving
force (temperature gradient) only, (b) Connecting to a voltmeter and under a thermal
driving force

3. Consider a thermoelectric material was subjected to a temperature gradient which

value is 3600 K/cm (the left is high T and the right is low T), and the value of the generated
electric field was 7 V/cm. Please calculate entropy production rate (𝜎𝜎𝜎) for the materials.
(ρ=1000 ohm-1 cm-1 , S=0.2 mV/K, κ=0.01 W/cm K, Tav=600K )(Assume NO EM and TM
happen) (Hint: Calculate JQ, Jq => 𝜎𝜎𝜎 )

4. (a) What is the Petier effect? (b) What is Peltier coefficient and working principle of
a thermoelectric cooler device assembled by connecting material A and material B to
a battery. (c) To reach the highest efficiency of this device, how to choose material A
and B? Please explain it by the working mechanism mentioned in (b).

HW
1.Explain (i) thermodynamic equilibrium; (ii) Steady-state flow process. Why does the
local equilibrium need to be assured for describing a kinetic process driven by
various driving forces?
In handout p.11, 20, 22, 23, 25
2.Describe how the apparent electrical conductivity of a conductor changes with
measurement conditions. (a) isothermal, (b) adiabatic. (c) Please explain your results
in (a-b).
(a)ρ = Lqq
𝐿𝐿𝐿𝐿𝑄𝑄−𝐿𝐿𝐿𝐿𝐿𝐿
(b) ρ = Lqq - 𝐿𝐿𝐿𝐿𝐿𝐿
Kinetics of Materials Lecture2
1. (a)Write down the flux expression for thermomigration and describe the atomic flow
direction in a material with a negative "heat of transport ". (b) Write down the flux
expression for stress-migration and describe the atomic flow direction in a material
subjection to a stress gradient.

2. Steel is an alloy of iron with tiny amount of carbon. (a) Consider a spherical steel ball
annealed at high temperature for carbon homogenization. Draw a schematic plot of
carbon concentration along the radial direction of the steel ball after it was cooled
down to room temperature in air. List your assumptions and justify your answer from
kinetic viewpoints. (b) If an empty steel cylinder (i.e. tube shape) annealed at high
temperature and quenched to room temperature, draw a schematic plot of carbon
concentration in the radial direction. List your assumptions and justify your answer
from kinetic viewpoints.

3. A diffusion couple including inert wires was made by plating pure copper on to a
block of a-brass with a composition Cu-30wt%Zn. After 56 days at 785 °C the marker
velocity was determined as 2.6×10-8 mm/s. Microanalysis showed that the
∂X Zn
composition at the markers was XZn=0.2, XCu=0.8, and was 0.1 mm-1. From an
∂x

analysis of the complete penetration curve the interdiffusivity at the markers was
calculated as 4.5×10-13 m2/s. (a)Use this data to calculate the intrinsic diffusivity DCu
and DZn in brass at 20 % Zn. (b)How would you expect the interdiffusivity, DCu and DZn
to vary as a function of composition?

4. There is a single crystalline Si line (thickness 1μm, width 1μm,100 μm long) and
silicon has a diamond cubic crystal structure. (a) If the Si line is across two temperature
reservoirs at 300 K and 600 K, what is the vacancy concentration gradient along the Si
line when a local equilibrium is assumed? (b) Would you expect the apparent Qtrans
of is more positive or negative? Make your assumptions if it is necessary and Provide
your reasoning in details.

5.At 800K, considering a metallic hollow ball of inner radius 3 nm and outer radius of
5.2 nm: (a) Calculate the equilibrium vacancy concentration at the inner and outer
surface? (b) What is the value of the vacancy flux (Jv)? (c) Due to the presence of Jv,
the outer radius of this hollow ball was reduced to 5 nm and inner one to 2.25 nm.
Please estimate the time it takes. (Data: vacancy formation energy 0.92 eV, surface
energy 1.83 J/m2 , atomic volume 1.18x10-23 cm3 , 1 eV=1.6x10-19 J; kB=8.617x10-5 eV/K;
D=10-13 cm2/s)

HW
1.What is the critical product for electromigration? Derive the expression of the
critical product.
In handout p.31
2.Consider an Al line (0.5 μm x 0.5 μm x 5 μm). Deff= 10-15cm2/s at 150˚C. The Al line
is subjected to an electric current 4 mA at 150˚C. Please estimate the stress caused
by extrusion at the anode side. (β=-10e, ρ=3.85×105 Ω-1cm-1, Ω =1.66×10-23cm3, kB=
8.617x10-5eV/K)
𝐴𝐴Ω
∆σ~7.8 ∗ 1021
𝑐𝑐𝑐𝑐3
Kinetics of Materials Lecture3
1.Consider two diffusion samples as follows:

A B
x1 x1
x x
The amount of diffusion species is the same for both samples. It takes a time of t1 for
the sample A to have a concentration equal to c1 at the location x=x1. If C(x1,2t1)=c1/2
for the sample B. Derive the expression of diffusivity of diffusion species in terms of x1
and t1.

2. Deposit a thin layer of Cu0.6 Ni0.4 alloy film (0.1 µm) on a Ni foil. Assume that the
dominant diffusion specie is Cu. The pre-factor and activation energy of interdiffusivity
are 6×10−8 cm2/𝑠𝑠 and 0.98 eV, respectively. (a) Calculate the interdiffusivity at 600⁰C.
(b) What is the diffusion length of copper measured from the original interface after
thermal treatment at 600⁰C for 10 days. (c) What is the concentration of copper in Ni
at the distance of 1.5 µm from original interface after thermal treatment at 600⁰C for
10 days. k=8.617x10-5 eV/K

3. Considering the gas carburizing of a gear of steel (0.15 wt.% C) at 900⁰C. Calculate
the time necessary to increase the carbon content to 0.35 wt.% at 0.5 mm below the
surface of the gear. Assume the carbon content at the surface to be 1.15 wt.% and the
nominal carbon content of the steel gear before carburizing is 0.15 wt%. Diffusivity of
C in γ iron at 900⁰C=1.28x10-11 m2/s.

4. Consider a Ni/Cu0.7 Ni0.3 /𝑁𝑁𝑁𝑁 diffusion sample. The Cu0.7 Ni0.3 layer is 0.1 µm thick
and both Ni parts are 10 µm thick. Given the Cu diffusivity in Cu-Ni alloy with D0 =
6 × 10−8 cm2 /s and EA = 0.98 eV, (a) Calculate the Cu diffusivity at 450⁰C. (b) What
is the Cu concentration in the middle of the sample after annealing at 450⁰C for 10 h?
k=8.617 × 10−5 eV/K

5.(a) What is the Mantano interface in a diffusion couple? (b)Consider an A/B diffusion
couple. If the interdiffusivity increases with increasing concentration CA, how does the
CA profile look like after a time? Explain why. (c) label location of the original A/B
junction and the Mantano interface in the plot. Explain why.
HW
1.Assume the water content in a free-standing polymer film of 20 µm in thickness is
0.12 wt.% when the film is fully soaked with water at room temperature. Consider
water desorption in the film under vacuum. Calculate the water content at 1 µm
beneath the film surface after putting the film in a vaccum chamber for 30 min. The
diffusivity of water in polymer film is 10−12 𝑐𝑐𝑐𝑐2/𝑠𝑠 at room temperature.
0.10846wt%
2.By welding thick pure Cu and Zinc plates together to form a diffusion couple, it is
intended to form a layer of α-brass in between Cu and Zn. If the diffusion couple is
thermally treated at 800oC for 10 hours, (a) what is the thickness of the brass with a
composition of 20 to 30 at. % Zn assuming the interdiffusivity is 10-13 cm2/s at 800 oC
2.688*10−5 𝑐𝑐𝑐𝑐
Kinetics of Materials Lecture4
1. The self-diffusivity of FCC crystal for diffusion by a vacancy mechanism is written
below
𝑓𝑓 𝑓𝑓
𝑆𝑆𝑣𝑣𝑚𝑚 +𝑆𝑆𝑣𝑣 −(𝐻𝐻𝑣𝑣𝑚𝑚 +𝐻𝐻𝑣𝑣 )
𝐷𝐷∗ = 𝑓𝑓𝑎𝑎2 𝜐𝜐 exp� � exp� �
𝑘𝑘 𝑘𝑘𝑘𝑘

Find the expression of self-diffusivity of HCP crystal through vacancy-mediated

mechanism. The lattice constant for HCP is a and c(=1.633a).

2. Consider <100> SD self-interstitial defect in Cu (FCC). Assume the atomic jump

frequency Γ ′ =108 s-1, a=0.291 nm, nSD=6x1012 cm-3, nSD=1.62x1023 cm-3 (a) Calculate
the self-diffusivity of Cu through SD interstitialcy diffusion mechanism by assuming
correlation factor f=1. (b) When the Cu is subjected to a tension stress along [100]
direction, SD concentration along [100] direction, nSD[100], become 3x1012 cm-3,
calculate nSD[100] after releasing the stress for 1 ns.

3.Consider an ionic solid NaCl. The major defect mechanism is Na×Na = Na∙𝑖𝑖 + VNa ′

with a defect formation enthalpy of ∆𝐸𝐸. What is the expression of self-diffusivity of

Na in NaCl in terms of lattice constant a, atomic jump rate 𝚪𝚪 ′ and correlation factor f
and ∆𝐸𝐸? What is the activation energy for self-diffusion of Na ions in NaCl?

4.Consider vacancy concentration in a pure ionic solid A2B. Assuming that the same
vacancy volume for V ’A and V..B. (a) What is the ratio of [V..B]/.[V ’A]? (b) If the
Schottky defect formation energy and V..B. migration energy are Hfs and HmB, what is
the activation energy of B ions diffusing in A2B through vacancy mechanism?

5. Considering the diffusion of the CaO doped-ZrO2 ionic solids is through vacancy
mechanism (FCC packing of Zr). Assume the Schottky defect dominates the diffusion
at high temperature region. Please plot the figures of (a) ln[D0] vs (1/T) (b) ln[V0] vs
(1/T) (c) logD0 vs logPO2, and explain how [D0] and [V0] in doped-ZrO2 varies as the
function of temperature in the intrinsic dominate, oxygen deficient dominate and
impurity dominate region.
HW
1. Please derive the mean-square displacement <R2> in the diffusion from a (a) point
source in 3D and (b) line source in 2D. Please labelling C (R,τ) and how to get <R2>

(a)6Dτ
(B)2Dτ
2. Write down the expression of diffusivity in terms of atomic jump frequency and
lattice constant for single crystal Si (diamond crystal structure) through vacancy-
mediated diffusion?

1 ′ 𝟐𝟐
𝚪𝚪 𝒂𝒂 𝑿𝑿𝒗𝒗 𝒇𝒇
8
Kinetics of Materials Lecture5
1. Assume a polycrystalline Cu line of thickness t, width w and length L, which has a
grain size of dimension d, and the thickness of grain boundaries is δ. The self-
diffusivities of Cu atoms along crystal, grain boundaries and surface are DXL, DB and DS
respectively. DB(100oC)=3×10-15 cm2/s, DB(350 oC)=1.2×10-9 cm2/s, DS(100 oC)=1×10-12
cm2/s, DS(350 oC)=1×10-8 cm2/s. k=8.617×10-5 eV/K (a) What are activation energies of
grain boundary diffusion and surface diffusion in Cu? (b) Wha t is the expression of
effective diffusivity along the Cu line? Assume surface diffusion occurs in a surface
layer of thickness δ?

2.Consider a polycrystalline AL line of 0.5 μm x 0.5 μm x0.5 μm in size. The lattice

diffusivity and grain boundary diffusivity are 1.5x10-19 cm2/s and 6x10-11 cm2/s at 100
oC, and 1.0x10-11 cm2/s and 5x10-7 cm2/s at 350 oC (a) calculate the activation energies

(eV) for lattice diffusion and grain boundary diffusion, respectively. (b) calculate the
effective diffusivity (<D>) of Al line at 150 oC.

3.Considering the Fisher’s analysis of grain boundary diffusion. Assume the isolated
boundary case, write down the diffusion equation, initial conditions and boundary
conditions for the region inside the grain and along the grain boundary. You do not
need to solve the equation.

HW
1. Assume atoms diffuse into a moving grain boundary laterally from its edges and
diffuse out through its front face into the forward grain with a diffusivity DXL. Derive
the penetration depth of atoms in the case of moving grain boundary (moving velocity
vGB).
DXL
the penetration depthλ= 𝑉𝑉

2.Please describe the magnitude of diffusion length of crystal and grain boundary in
contrast of grain size s and interatomic distance λ in (A)multiple boundary diffusion
regime, (B)intermediate regime, and (C)boundary only regime respectively
In handout p.8
Kinetics of Materials Lecture 6

1.(a)How to identify whether a chemical reaction is elementary reaction or non-

elementary reaction? (b)How does the ln(k) v.s. 1/T plot look like for a catalyzed
reaction? Explain why. (c)Under what condition can we assign a zero-order rate
equation to a chemical reaction?

2. Considering an irreversible decomposition reaction AR. 25 % of A is converted

to R in a 1 hour. If this is the (a) zero order (6 points) or (b) first order (6 points) or (c)
second order reaction, how much longer would it take to reach 50 % conversion of A?

3. For a non-elementary reaction A+BAB under a steady-state approximation, you

may consider it following a two-step procedure as below. 2AA2* and A2* +B↔AB+A
(a) what is the generation rate of A2*? (b)what is the expression of [A2*]? (c) What is
the generation rate of AB product?

4. Consider an aqueous reaction of A  R, the concentration of A in the reactor was

recorded and listed in the table. (a) Find the rate equation (10 pts) (b) If CA0=600
mole/m3, what is the conversion fraction of reactant after 2 hrs in the batch reactor.
(10 pts)

T, min: 0 100 200 300 400

CA, mole/m3: 1000 500 333 250 200
1 XA (F)1−n −1 1−n
Information:− ln(1 − XA ) = kt；C = kt；t F = �(1−n) CA0
A0 1−XA k

HW
1.Describe the factors affecting the reaction rate in a batch reactor for homogeneous
reaction.
In handout p.8
2. (a)Consider a series reaction A → R → S. The activation energies for A→R and
R → S are E1 and E2, respectively. Plot the logarithm of the overall rate constant k
versus 1/T if E1 > E2 .(b)Consider two parallel reactions, A → X1 → R (k1 , with E1 )
and A → X2 → R (k 2 , with E2 ). X1 and X2 are intermediates. Plot the logarithm of
the overall rate constant k versus 1/T if E1 > E2 .
(a)p.19 (b) p.19
Kinetics of Materials Lecture 7
1. Consider the oxidation of Si substrate. Given the parameters of dry oxidation
in the table below. (a) If the oxide is grown at 1100⁰C, whether diffusion or
reaction process is the rate-determining step when t=3 hours. Justify your answer
numerically. (b) Calculate the oxide thickness grown at 1100⁰C for 3 hr. (c)
Calculate the activation energy for O2 diffusion in Si O2. ( kB= 8.617 × 10-5eV/K)

Temperature A(µm) B(𝜇𝜇𝜇𝜇2 /ℎ𝑟𝑟) τ (hr)

(⁰C)
1000 0.165 0.0117 0.37
1100 0.09 0.027 0.076

2. Consider a reaction:a A(from gas) +B→product (liquid)，(a) Pls formulate the

distance of the reaction plane from the G/L interface for the instantons
reaction?(b) What is the minimum CB required to move the reaction plane to the
G/L interface?

3.Consider a reaction A (g→l) + bB(l)→R(s/l/g) with a rate equation -

rA=KCaCb；kAga=0.01 mol/hr*m3*Pa；fl=0.01；kAla=20 hr-1；DAl=10-5
m2/hr；DBl=10-6 m2/hr；a=100 m-1, liquid folm thickness=5 x 10-5 m. The
reactor conditions are PA=100 Pa, CB=1 mol/m3, k=107 m3/mol*hr and HA=4 x
103 Pa*m3/mol. (a)What is the value of liquid film enhancement factor? (b)
Calculate the transport/reaction resistance for each transport or reaction step
and identify the major rate-limiting step. (c)What is the overall reaction rate?

4.To remove gas A from the mixture gas, mixture gas containing gas A was bubbled
through B solution in a packed column to remove gas A from the mixture gas by the
following irreversible 2nd order chemical reaction: A (g) +B (l)  R(s/l/g) (a) What
kind of chemical reaction it is? (Instantaneous, fast or?) Why? (b) What is the overall
reaction rate? (c) Please draw the interface behavior for this fluid-fluid reaction.
𝑚𝑚𝑚𝑚𝑚𝑚
𝑘𝑘𝐴𝐴𝐴𝐴 𝑎𝑎 = 0.01 ℎ𝑟𝑟∙ 𝑚𝑚3 ∙𝑃𝑃𝑃𝑃 ; 𝑓𝑓𝑙𝑙 = 0.01 ; 𝑘𝑘𝐴𝐴𝐴𝐴 𝑎𝑎 = 20 ℎ𝑟𝑟 −1 ; 𝐷𝐷𝐴𝐴𝐴𝐴 = 10−5 𝑚𝑚2 /ℎ𝑟𝑟; 𝐷𝐷𝐵𝐵𝐵𝐵 =

10−6 𝑚𝑚2 /ℎ𝑟𝑟; 𝑎𝑎 = 100 𝑚𝑚−1 ;. PA= 100 Pa; CB= 3 mole/m3 ; k=104 m3/mol⋅hr,
HA=4x102 Pa m3/mol; liquid film thickness (x0)= 5x10-5 m

5. Hydrogen sulfide is absorbed by a solution of methanolamine (MEA) in a

packed column. At the top of the column, gas is at 20 atm and it contains
 0.1 % of H2S, while the absorbent contains 250 mol/m3 of free MEA. The
diffusivity of MEA in solution is 0.64 times that of H2S. The reaction is
normally regarded as irreversible and instantaneous. H2S + RNH2 →HS- +
RNH3+
(a)Find the rate of absorption of H2S in MEA solution in mol/s×m3.
(b)Location the major resistance in (a)?
(c) Find the rate of absorption of H2S in pure water in mol/s×m3.
(d)To find out whether it is worthwhile using MEA absorbent, determine how
much faster is absorption with MEA compared to absorption in pure water. (20
points)
Data: kAl∙a=0.03 s-1 ; kAg∙a= 60 mol/s m3 atm;
HA = 10-4 atm×m3/mol, Henry's law constant for H2S in water.

HW
1. Consider a fluid-fluid reaction A (g→l) + bB(l)→R(s/l/g) with a rate equation
-rA=kCACB. (a) What is the rate determination step for the case of extremely high
reaction rate and high concentration of CB?? Explain why. (b)Formulate the rate
equation in term of the transport coefficient in the region indicated in (a).
(a) transpoet in gas film
(b)-rA’’’’=kAgPA