MTSH601 TEST 1 MEMO 27 -2-2018

Time : 2hr DIFFUSION MARKS: 90

1. What is a thermal barrier coating? Where are such coatings used? (3)

In an aircraft engine, some of the nickel superalloy-based turbine blades are coated with ceramic
oxides such as yttria stabilized zirconia (YSZ). These ceramic coatings protect the underlying alloy
from high temperatures; hence, the name thermal barrier coatings (TBCs). The diffusion of oxygen
through these ceramic coatings and the subsequent oxidation of the underlying alloy play a major
role in determining the lifetime and durability of the turbine blades.

2. Cite two reasons why interstitial diffusion is normally more rapid than vacancy diffusion (4)

When a small interstitial atom or ion is present in the crystal structure, the atom or ion moves
from one interstitial site to another. No vacancies are required for this mechanism. Partly because
there are many more interstitial sites than vacancies, interstitial diffusion occurs more easily than
vacancy diffusion. Interstitial atoms that are relatively smaller can diffuse faster.
Less energy is required to squeeze an interstitial atom past the surrounding atoms; hence,
activation energies are lower for interstitial diffusion than for vacancy diffusion.

3. Aluminum metal oxidizes more readily than iron but aluminum is considered to be a metal
that usually does not “rust?” (3)
Aluminum does not “rust.” In reality, aluminum oxidizes (rusts) more easily than iron; however,
the aluminum oxide (Al2O3) forms a very protective but thin coating on the aluminum’s surface
preventing any further diffusion of oxygen and hindering further oxidation of the underlying
aluminum. The oxide coating does not have a color and is thin and, hence, invisible. This is why we
think aluminum does not rust.

4. Define Fick’s first law and write it as an equation and explain the different terms. (3)
Fick’s first law states that under steady state condition, the flux of the flowing particles is directly
proportional to the concentration gradient
J = -D dc
dx

J – flux; D – diffusion coefficient dc/dx – concentration gradient

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5. State Fick’s second law. Write down the differential equation of Fick’s second law and its
solution.
(3)
The partial differential equation that describes the rate at which atoms are redistributed in
a material by diffusion.

6. Distinguish between steady state diffusion and non- steady state diffusion. (4)
Steady State Diffusion:
If the diffusion flux does not change with time a steady state condition exist. Steady-state diffusion
is the situation wherein the rate of diffusion into a given system is just equal to the rate of
diffusion out, such that there is no net accumulation or depletion of diffusing species--i.e., the
diffusion flux is independent of time.
Non Steady State Diffusion: If the diffusion flux and the concentration gradient at some particular
point in a solid varies with time there will be a depletion /accumulation of diffusing species. Then
there is a non steady state of diffusion

7. Explain the process sintering with a diagram. What is the driving force for sintering? (5)
Sintering is the high-temperature treatment that causes particles to join, gradually reducing the
volume of pore space between them. Sintering is a frequent step in the manufacture of ceramic
components

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8. Why does grain growth occur? What is meant by the terms normal and abnormal
grain growth? (4)
A polycrystalline material contains a large number of grain boundaries, which represent high-
energy areas because of the inefficient packing of the atoms. A lower overall energy is obtained in
the material if the amount of grain boundary area is reduced by grain growth. Grain growth
involves the movement of grain boundaries, permitting larger grains to grow at the expense of
smaller grains’
In normal grain growth, the average grain size increases steadily and the width of the grain size
distribution is not affected severely. In abnormal grain growth, the grain size distribution tends to
become bi-modal (i.e., we get a few grains that are very large and then we have a few
grains that remain relatively small).

9. Define diffusion bonding and explain the different steps in this bonding with diagrams. (5)

A method used to join materials, called diffusion bonding, occurs in three steps. The first step
forces the two surfaces together at a high temperature and pressure, flattening the surface,
fragmenting impurities, and producing a high atom-to-atom contact area. As the surfaces remain
pressed together at high temperatures, atoms diffuse along grain boundaries to the remaining
voids; the atoms condense and reduce the size of any voids at the interface. Because grain
boundary diffusion is rapid, this second step may occur very quickly. Eventually, however, grain
growth isolates the remaining voids from the grain boundaries. For the third step—final
elimination of the voids—volume diffusion, which is comparatively slow, must occur. The diffusion
bonding process is often used for joining reactive metals such as titanium, for joining dissimilar
metals and materials, and for joining ceramics.

10. Define the following: (6)

10.1. flux
Flux : The number of atoms or other diffusing species passing through a plane of unit area per unit
time. This is related to the rate at which mass is transported by diffusion in a solid.
10.2. Purple plague Formation of voids in gold- aluminum welds due to unequal rates of diffusion
of the two atoms eventually failure of the weld can occur.
10.3. Kirkendal effect Physical movement of an interface due to unequal rates of diffusion of the
atoms within the material.

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11. The diffusion coefficients for iron in nickel are given at two temperatures

11.1. Determine the values of D0 and the activation energy Qd . (6)

D1 = D0 exp {-Q/RT1} ln D1 = lnD0 -Q/RT1 ………(1)

D2 = D0 exp {-Q/RT2} ln D2 = lnD0 -Q/RT2 …………(2)

−Q 1 1
(1)-(2) ln D1 - ln D2 = [ − ]
R T1 T2

−R( ln D 1−ln D 2) −8.31(ln 9.4 × 10−16 −ln 2.4 ×10−14 ¿ ¿)

Q= 1 1 = 1 1
− −
T1 T2 1273 1473

Q= 258707 J/mol

9.4 ×10−16
D1
D1 = D0 exp {-Q/RT1} D0 = = −258707 = 3.9×10−5 m2/s
exp ⁡¿ ¿ exp (
8.31 ×1273 )

11.2. What is the magnitude of D at 11000C ? (5)

D1 = D0 exp {-Q/RT1}

258707
D = 3.9×10−5 m2/s exp {- } = 5.97 ×10−15 m2/s
8.31× 1373

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12. A sheet of FCC iron 5.0 mm thick is exposed to a carburizing gas on one side and a
decarburizing gas on the other at 525°C. After reaching steady state, the iron membrane is
quenched to room temperature, and the Carbon concentrations at each side of the membrane
are 0.085 and 0.0018 wt%. Calculate the diffusion coefficient if the diffusion flux is 2.36 x10 -9
kg/m2.s. [Density of Carbon is 2.25 g/cm3 and Iron is 7.87 g/cm3]. (10)

Convert wt% to kg/m3

C c × 1000 0.08 5 ×1000

=6.68 kg C /m3
Concentration of Carbon 0.085 wt %= C c C Fe = 0.08 5 99.915
+ +
ρC ρFe 2.25 7.87
C c × 1000 0.001 8 ×1000
=0.142 kg C /m3
Concentration of Carbon 0.0018 wt %= C c C Fe = 0.001 8 99.9982
+ +
ρC ρFe 2.25 7.87

dc dx
J= -D D = -J
dx dc

∆ c ( 6.68−0.142 ) kg /m3
= = 1.31×10 3 kg C/m3.m Fe
∆x 5 ×10−3 m

Flux J = 2.36 ×10 -9 kg/m2-s.

J
2 .36× 10−9 kg /m2 . s −12
D= dc = 3
=1.80 ×10 m2/s
dx 1.31×10 kg C /m 3. m

13. The steady-state diffusion flux through a metal plate is 5.4 × 10 -10 kg/m2-s at a temperature
of 727 0C and when the concentration gradient is -350 kg/m4. Calculate the diffusion flux at
1027 0C for the same concentration gradient and assuming an activation energy for diffusion of
125000 J/mol. (10)

dc −Q dc
J= -D = = D0 exp {- }
dx RT dx

J 5.4 ×10−10
D0 = −Q dc = −125000 =5.27×10−6 m2 / s
exp {− }
RT dx
exp {
8.31 ×1000 }
−350 kg/m 4

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 dc −Q dc
J= -D = = D0 exp {- }
dx RT dx

−125000 J / mol
= 5.27×10−6 m2 / s exp {- }×−350 kg /m 4
8.31× 1300

Diffusion flux J = 1.7×10−8 kg/m 2 s

14. A copper-nickel diffusion couple is fashioned. After a 700-h heat treatment at 1100 0C, the
concentration of Cu is 2.5 wt% at the 3.0-mm position within the nickel. At what temperature
must the diffusion couple need to be heated to produce this same concentration (i.e., 2.5 wt%
Cu) at a 2.0-mm position after 700 h? The pre-exponential and activation energy for the
diffusion of Cu in Ni are 0.65 cm 2/s and 61500 cal/mol. (9)

X x12 x22
=constant =
√D D1 D2

D1 = D0 exp {-Q/RT1}

61500 cal/mol
D =0.65 cm2/s exp {- } = 1.06 ×10−10 cm2/s
1.987 ×1373

x22 0.22
D2 = 2 × D 1 = ×1.06 ×10−10 cm2/s =4.69×10−11 cm2/s
x1 032

Q
D1 = D0 exp {-Q/RT1} T= =
R (ln D 0−lnD 2)
61500
−11
1.987(ln 0.65−ln 4.69 ×10 cm2/ s)

Temperature T = 1325K

15. An FCC iron–carbon alloy initially containing 0.35 wt% C is exposed to an oxygen rich and
virtually carbon-free atmosphere at 1400 K .Under these circumstances the carbon diffuses from
the alloy and reacts at the surface with the oxygen in the atmosphere; that is, the carbon
concentration at the surface position is maintained essentially at 0 wt%C. (This process of
carbon depletion is termed decarburization.) At what position will the carbon concentration be
0.15 wt% after a 10-h treatment? (10)

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the diffusion coefficient for carbon in FCC iron at this temperature.

D = D0 exp( −Q
RT )
−32900
D = 0.23 exp(
1.987 ×(1400) )
D = 0.23 exp (-11.83)

D = 1.68 ×10−6 cm2/s

C s−C x
C s−C 0
= erf ( 2 √xDt )
0−0.15
0−0.35
= erf ( 2 √xDt )
0.4286= erf ( 2 √xDt )
Z erf z
0.40 = 0.4284
Z = 0.4286
0.45 = 0.4755

Z−0.4 0 0.4286−0.4284
0. 45−0.4 0
= 0.4755−0.4284

Z = 0.4002

x
= 0.4002
2 √ Dt

−6
D = 1.68 ×10 cm 2 /s

Time t = 10 hours × 3600 s/h = 3.6 × 10 4 s

cm2 cm2
√ Dt =
√ 1.68× 10−6
s
× 3.6 ×104 s 2.034 ×10−6
s
×17.28 ×104 s = 0.246

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 x = 2 √ Dt ×0.4002 = 2× 0.246× 0.4002=¿0.196 cm

Depth = x = 0.196 cm

R = 1.987 cal/mol.K or 8.31 J/mol.K or 8.62× 10-5 eV /atom .K

Table 1: Diffusion data for selected materials

Diffusion Couple Q (cal/mol) D0 (cm2/s)

Interstitial diffusion:  
C in FCC iron 32900 0.23
C in BCC iron 20900 0.011
N in FCC iron 34600 0.0034
N in BCC iron 18300 0.0047
H in FCC iron 10300 0.0063
H in BCC iron 3600 0.0012

Table 2: Tabulation of Error Function Values

Z erf(z) Z erf(z) Z erf(z)
0 0 0.55 0.5633 1.3 0.9340
0.025 0.0282 0.60 0.6039 1.4 0.9523
0.05 0.0564 0.65 0.6420 1.5 0.9661
0.10 0.1125 0.70 0.6778 1.6 0.9763
0.15 0.1680 0.75 0.7112 1.7 0.9838
0.20 0.2227 0.80 0.7421 1.8 0.9891
0.25 0.2763 0.85 0.7707 1.9 0.9928
0.30 0.3286 0.90 0.7970 2.0 0.9953
0.35 0.3794 0.95 0.8209 2.2 0.9981

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0.40 0.4284 1.0 0.8427 2.4 0.9993
0.45 0.4755 1.1 0.8802 2.6 0.9998
0.50 0.5205 1.2 0.9103 2.8 0.9999