Solution for homogeneization (separation of variables)

Let us consider a system with a relatively long time of annealing such that
system may reach to homogenization.

Time is rather relative. In a small system, relatively small time can be considered
as long time because it will not take much time to homogenize. On the other hand
in a large system, even longer time also may not be sufficient.

We have seen that the concentration in a particular system (with specific

diffusion coefficient) varies with the position, x and time, t.

We make an assumption here that these two variables are separable, so that we
can write
C = X(x)T(t)

Following partial differentiation gives
∂C ∂T ∂ 2C ∂2 X
=X =T
∂t ∂t ∂x 2 ∂x 2

Substituting in Fick’s second law (considering constant D)

∂T ∂2 X 1 ∂T 1 ∂ 2 X
X = DT ⇒ =
∂t ∂x 2 DT ∂t X ∂x 2

We have now separated the variables, t and x in two different sides.

Both the sides should be equal to the same constant value. For the sake of
further derivation, we consider it as -λ2. Choosing this is rather convenience and
also the need. 1 ∂T
= −λ2
DT ∂t
∂T
= −λ2∂t
T

Integration yields
T t
∂T
∫T T D ∫ ∂t
2
= − λ
o o

T To is the value correspond to time, t = 0.

ln = −λ2 Dt
To
(
T = To exp − λ2 Dt )

This relation explains the reason for taking the negative sign. We want to relate
the decrease in inhomogeneity with the increase in time. This relation explains
that T decreases exponentially with the increase in time.

Further,
1 ∂2 X
2
= −λ2
X ∂x
∂2 X 2
2
+ λ X =0
∂x

Solution to this equation after integration gives (and since λ2 use will be always
positive for positive or negative values of λ.).
(
X ( x) = A' sin λx + B ' cos λx ) A´ and B´ are the constants come from integration

Combining these two solutions we get

( ) (
C ( x, t ) = A' sin λx + B ' cos λx To exp − λ2 Dt )
(
= ( A sin λx + B cos λx ) exp − λ2 Dt )

Note that this solution holds for any value of λ. If there are different values of λ,
the solution will be the sum of all solutions:
∞
C ( x, t ) = ∑ ( Am sin λm x + Bm cos λm x ) exp − λm Dt( 2
)
m =1

The constants, Am, Bm and λm should be determined based on a particular

situation or problem we are interested.

Let us consider a thin plane sheet, with thickness h, where concentration of the
substance, which should be diffused from both sides is kept uniformly before start
of the diffusion out. Further, we make the situation such that the concentration at
the surfaces of the sheet is always kept zero, we can write the boundary condition
as
C = Co, 0 < x < h at t = 0
C = 0, for x = 0 and x = h at t > 0

Following second boundary condition, C will be zero at x =0 at any time
only if Bm = 0. Further, C will be zero at x = h only if λm = mπ/h, where m is a positive
integer.

After replacing these values, we find

∞
 mπ   m 2π 2 
C ( x, t ) = ∑  Am sin x  exp − 2 Dt 
m =1  h   h 

Now following first boundary conditions for t=0
∞
 mπ 
Co = ∑  Am sin x
m =1  h 

From this for the final relation, we need to find the value of Am.

nπ

For that we multiply Sin xdx both the sides and integrate x in the
range of 0 to h. h

h ∞  h

 nπ  nπ mπ
∫o o  h  ∑
C sin  x  dx = 

m =1 
Am∫
o
sin
h
x sin
h
xdx 



In the right hand side, all integrals will be zero except for only one value n=m.
When n=m the value of the integral is h/2.

so we get
h
2  mπ 
Am = ∫ Co sin  x dx
ho  h 

Integration of this shows the value of 0 for even values of m and 4Co /nπ for any odd
values of m.

We can change the summation integer values such that we can use this relation of
every integers. That means it will give odd m values for every integers.

Am = Ai = 4Co / (2 j + 1) j = 0, 1, 2.........

So the solution can be written as

4Co ∞
1 (2 j + 1)πx  (2 j + 1)2 π 2 
C ( x, t ) = ∑
π j =0 2 j + 1
sin
h
exp −
h 2
Dt 
 
Note:
This solution is the summation of all the terms for j equal to zero to infinity.
However, it must be clear from the relation that values for every successive j
decreases exponentially (note the negative sign inside the exponent).
So it should be possible to represent the concentration curve with first few values of j.

So extrapolate the discussion further, let us calculate the value for j =0 and 1 after
time t.
4Co πx  π2 
C j = 0 ( x, t ) = sin exp − 2 Dt  for j =0
π h  h 

4Co 1 3πx  9π 2 
C j =1 ( x, t ) = sin exp − 2 Dt  for j =1
π 3 h  h 

If we take the ratio, we find
C j = 0 ( x, t )  8π 2 
= 3 exp 2 Dt 
C j =1 ( x, t )  h 

As explained earlier, this solution can be used where the thickness of the system is
relatively small so that it can reach to homogeneous in reasonable time frame.

So this also depends on the diffusion coefficient at that particular temperature of
interest.

Suppose, we consider h = 4 Dt

Then the ratio is 417. That means if we neglect from even the second term, it will
give hardly 0.2% error.

It should be decided based on the system. Because if we have h = 10 Dt , the ratio is
6.6. If we neglect the second term, we will introduce around 15% error.

So it depends on the system/temperature how many terms should be considered

 Calculation of diffusion parameters
Carburization is an important technique to harden steel, where roughly a particular
carbon concentration at a particular depth is required for required hardness

Suppose initial carbon content in the

steel is Co = 0.20 wt%

Concentration of carbon on the

surface is brought suddenly to Cs= 1.15
wt%

Suppose we know that the diffusion

coefficient of carbon is D = 1.6x10-11 m2/s
(950oC)

Problem 1: how much time it will take to

achieve carbon content of C(x) = 0.75
wt% at 0.5 mm below the surface

C (x ) − C o  x 
= 1 − erf  
C S − Co  2 Dt 

So we should use this relation.
C (x ) − C o  x   62.5 
= 1 − erf   0.4210 = erf  
C S − Co  2 Dt   t 

So it can be seen as erf(z) is equal to 0.4210 and we need to find

corresponding Z value.

In most of the cases, the exact value cannot be found from the table directly.

For example, z for erf(z) of 0.4187 and 0.4284 are tabulated. Our value of
interest is in the middle of this range.

Since we are considering a very small part of the actual distribution or curve,
we can take a average value from a linear function following

Z erf(z) That means

0.39 0.4187  62.5 
z? 0.4210 erf (0.392) = erf  
 t 
0.4 0.4284
 62.5 
0.392 =  
z − 0.39 0.4210 − 0.4187  t 
= t = 25,400 s = 7.1 hrs
0.40 − 0.39 0.4284 − 0.4187
z = 0.392 So the answer is it will take 7.1 hrs
Problem 2: How much time it will take to achieve carbon content of
C(x) = 0.75 wt% at a position 0.8 mm below the surface?

C ( x ) − Co  x 
= 1 − erf  
C S − Co  2 Dt 

C ( x ) − Co
Since = constant
C S − Co

We can write

x1 x2
=
2 Dt1 2 Dt 2

x1 (0.5mm) and t1 (7.1 hrs) is known from the previous example. D is

constant. So t2 can be calculated for 0.8mm (calculate yourself!)
 Problem on diffusion couples

Let us consider a diffusion couple between NB-= 0.3 and NB+= 0.7 atomic fraction.
After annealing the couple for 25hrs, we find the concentration of NB= 0.6 at distance
2.5 micron. Calculate the diffusion coefficient in this case

C B ( x ) − C B− 1   x 
= 1 + erf  
+
CB − CB −
2   
 2 DB t 
For constant Vm
N B ( x ) − N B− 1   x 
= 1 + erf  
+
NB − NB −
2   
 2 DB t 
N B ( x) = 0.6, N B− = 0.3, N B+ = 0.7
x = 2.5µm = 2.5x10 −6 m,
t = 25hrs = 90000s
 x 
erf   = 0. 5
2 D t 
 B 

Z erf(z)
z − 0.47 0.5 − 0.4937 x
0.47 0.4937 = = 0.477
0.48 − 0.47 0.5027 − 0.4937 2 Dt
z? 0.5
z = 0.477
0.48 0.5027 D = 7.63x10 −17 m 2 / s

Further in the same couple, we find NB=0.4
at the location x=-0.25

Now let us calculate the diffusion coefficient

N B (x ) − N B− 1   x 
= 1 + erf  
+
NB − NB −
2   
 2 DB t 

N B ( x) = 0.4, N B− = 0.3, N B+ = 0.7

x = −2.5µm = −2.5x10 −6 m,
t = 25hrs = 90000 s

0.4 − 0.3 1   −x 
= 1+ erf  
0.7 − 0.3 2  2 D t 
 B 
erf (− z ) = −erf ( z )
 x 
erf   = 0 .5
2 D t 
 B 

Then following similar procedure we can determine the diffusion coefficient, which
will be the same as what we calculated before!

This should be the case, since we consider the constant diffusion coefficient for our
analysis