Highlights:
1. Know what diffusion is (material transport by atomic motion) and how its action
during processing affects materials properties (annealing depends on diffusion).
2. Know diffusion mechanisms (vacancy and interstitial).
3. Understand the concept of a diffusion flux (amount of material transported) and
the concept of steady state (no change in flux).
4. Understand the relationship between distance and time in unsteady state diffusion
problems.
5. Understand factors that influence diffusion rate (species, temperature, etc.).
Notes:
Throughout Chapter 6, two repeated
examples of engineering problems for
which diffusion is important are:
1)
2)
Diffusion into the surface of a Si wafer to create p-n junctions, and transistors.
Transistors are created from the top surface of a Silicon wafer down. This is
illustrated by the Figure below, where the concentration of an n-type or p-type
dopant increases with time during a diffusion process. We will learn about Si
dopants in Chapter 12.
________________________________________________________________________
Chapter 6 turns chapter 5 into chapter 3.
Diffusion turns crystals with point defects, line defects, and grain boundaries, into
perfect crystals.
Show figures 6.1 and 6.2. This configuration is known as a diffusion couple.
Interdiffusion, or impurity diffusion, may be desired or undesired.
Desirable-
This type of diffusion depends on the presence of vacancies and therefore increases
with the vacancy concentration as the temperature increases. Motion of vacancies in
one direction is equivalent to motion of atoms in the opposite direction.
B)
Steady-state Diffusion
Diffusion is time-dependent, the amount of matter transferred depends on time and is
characterized by the diffusion flux J.
J=
J(t) =
1 M
A t
Eventually, steady-state conditions may be reached, and the diffusion flux no longer
changes with time. The concept of a steady state is an important one, and we will divide up
diffusion problems into steady state and unsteady state diffusion.
Example
Steady state diffusion of a gas through a plate of metal, where the gas pressure on either side
of the plate is kept constant. Show figure 6.4.
dc
c -c
= slope of line in figure 6.4b = A B
dx
x A - xB
J=-D
dC
dx
The negative sign ensures that the flux goes from the high to the low concentration regions.
This concentration gradient can be the driving force for a reaction. The quantity D is the
diffusivity and describes the rapidity with which material A can diffuse into material B.
The configuration in figure 6.4 can be used for hydrogen purification. Take a mixture of H,
O, and N on the left-hand side. DH >> DO, DN, so only hydrogen diffuses through at a
significant rate. Why doesnt this reach eventual steady state conditions, which is not useful
for hydrogen purification? Discuss this extensively in class. Pd membranes are used
commercially for separating H gas, which diffuses through Pd much faster than other gases.
Example Problem:
We want to use the equation above, Ficks first law of diffusion. However, the units of
diffusion flux and concentration are inconsistent, so we need to use equations (5.12) to
convert from wt% to kg C/m3 Fe.
C1 " =
C1
C1
CC =
C2
x1000
0.012
0.012
99.988
+
7.87 g / cm 3 2.25 g / cm 3
x1000
C C = 0.270 kg / m 3
Similarly, 0.075 wt% C can be converted to 1.688 kg/m3. Now we can substitute into Ficks
first law above:
J=-D
1.4 x10
dC
dx
(0.270 1.688 kg / m )
sec = D
(1.0 x10 m )
3
kg / m
into a Si surface or the surface of a machine tool. The former allows alteration of the
electrical properties of Si, and the latter allows hardening of the surface of cutting tools.
This is encountered more often than steady-state diffusion. Unsteady-state diffusion is
governed by Fick's second law:
C C
=
D
t x x
Assuming D is constant (bad assumption in practice):
2
C
C
=D
t
x2
Since many of you have not had differential equations yet, you may not be able to follow
this discussion, but you should still be able to use the final equations. We need to employ
the following boundary conditions
For t = 0, C = C 0 at 0 x
For t = 0 , C = C s , the constant concentration at x = 0
C = C 0 at x =
Including these three boundary conditions Fick's second law (equation 6.4b) can be solved
to yield
x
C x - C0
= 1 - erf
C s - C0
2 Dt
The error function(erf) is tabulated in Table 6.1, it is just a mathematical function that can
only be represented by an integral, you can use it just by looking up values in a table and
interpolating. You will not need to calculate error functions numerically, but for your
curiosity erf(x) is:
2 x - y2
erf(x) =
e dy
0
The error function erf(x) can also be calculated from the infinite series,
3
1 x 5 1 x7
x
erf(x) = x - +
+ ...
3 2! 5 3! 7
x
1 - erf
= constant ,
2 Dt
or
x
= constant
Dt
Both the diffusing species and the host material affect D (Show table 6.2, figure 6.7).
B)
Temperature
D = D0 e -Q d /RT
ln D = ln D0 -
Qd
RT
or
log D = log D0 -
Qd
2.303RT
Therefore, a plot of ln D versus 1/T should yield a straight line with slope -Qd/R and
intercept ln D0.
Example problem:
From figure 6.7, determine the activation energy and preexponential factor for Al diffusion in Al.
Easiest approach:
Select two points on the straight line, as far apart as possible for
maximum accuracy, and call their coordinates (D1, T1) and (D2, T2). I read two points as
(1000/T, D) = (1.10 K-1, 10-12 m2/sec) and (1.65 K-1, 10-18 m2/sec). Since 1/T is usually
graphed instead as 1000/T, you need to read the graph carefully.
T1 =
1000
= 909.1 K
1.10 K 1
D1 = 10 12 m 2 / sec
T2 =
1000
= 602.4 K
1.66 K 1
D2 = 10 18 m 2 / sec
Substitute into the last of the three equations above for each point:
log D1 = log D0 -
Qd
2.303RT1
log D2 = log D0 -
Qd
2.303RT2
D
Qd 1 1
log 1 =
2.303R
D
2
T2 T1
Now you can substitute values for D1, T1, D2, and T2 to determine the activation energy
Qd.
10 12 m 2 / sec
Qd
1
1
=
log 18 2
(
)
2.303
J
mol
K
K
K
8
.
31
/
602
.
4
909
.
1
m
10
/
sec
Qd = 205 kJ / mol
This differs from the value given in Table 6.2 (144 kJ/mol), and I cannot reconcile the
difference between these two answers. Once you have Qd, D0 can be determined by
substitution into either of the two equations for (D1, T1) or (D2, T2). Using the former:
(205,000 J / mol )
2.303(8.31 J / mol K )(909.1 K )
log D0 = 0.217
D0 = 0.61 m 2 / sec
This disagrees wildly with the typical values for D0 shown in Table 6.2. However, I
cannot find my mistake in this problem.
Example problem:
Consider a diffusion couple between metals A and B. After a 30-hr heat treatment at
1400K, the concentration of A is 3.2 wt% at a distance of 1.5 mm from the interface. If an
identical diffusion couple is instead heated 1200K for 30 hr, at what position will the
concentration be 3.2 wt%? Assume that the preexponential factor and activation energy for
diffusion are 1.8x10-5 m2/sec and 152 kJ/mol, respectively, and that the surface
concentration of A is 100 wt%.
Straightforward solution:
Start with the solution to Ficks 2nd law:
x
C x - C0
= 1 - erf
C s - C0
2 Dt
Now substitute in the correct numbers to determine Cs, which will require using the erf table
6.1. We will eventually need to calculate the diffusion coefficient D at each of these
temperatures. From equation (6.8):
D = D0 e - Q
/RT
3.2 - 0
1.5 x10 3 m
= 1 - erf
11
2
Cs - 0
2 [3.84 x10 m / sec ][30 x 3600 sec]
3.2
= 1 - erf (0.368 )
Cs
Interpolating:
0.368 0.35
y 0.3794
=
0.4 0.35
0.4284 0.3794
y = 0.397, or erf (0.368) = 0.397
3.2
= 1 - 0.397
Cs
C s = 5.31 wt %
Now we have to substitute back in again:
x
3.2 - 0
= 1 - erf
12
2
729.5 x = 0.368
x
C x - C0
= 1 - erf
2
Dt
C s - C0
Now note that for both heat treatments, Cs and Cx and C0 are the same, so the entire lefthand side of this equation is the same. For these two heat treatments, the entire right-hand
side of the equation must also be the same. Therefore,
x1
= 1 - erf x 2
1 - erf
2 D t
2 D t
1 1
2 2
x12
x 22
=
D1 t 1
D2 t 2
Substituting into this equation, using the D values calculated above:
x 22
(1.5 mm ) 2
=
4.35 x10 12 m 2 / sec ( 30 hr )
3.84 x10 11 m 2 / sec ( 30 hr )
x 2 = 0.50 mm
We obtained the same answer without doing the erf and erf-1 calculation.