EMA5001 Lecture 6

Determining Diffusion
Coefficient & Matano Analysis
 Measurement of Diffusion Coefficient

❑With analytical solutions

Diffusion into semi-infinite bar
▪ Tracer (Self) diffusion coefficient CB
▪ Really dilute solid solution (interstitial or
substitutional type)
~
D = DB = DB* t1
Analytical solution to Fick’s 2nd law exists:
 x2 
C B ( x, t ) =
N
exp −  0
Dt  4 Dt  lnCB
x
For a given time t1, if concentration profile is 1
measured, as CB(x), Slope = −
4 Dt1
then

ln C B ( x ) = ln
N 1
− x2 t1
Dt1 4 Dt1 0 x2
Plotting lnCB(x) vs. x2, the slope can give DB

EMA 5001 Zhe Cheng 6 Determine D & Matano Analysis 2

 Diffusion Coefficient for Regular
Solid Solution
❑Diffusion coefficients DB , DB , and
~ A A A
D all change with concentration
A B A
❑NO analytical solutions for Fick’s 2nd A A A
Law
C   C  J’B
= D  C2 C1
t x  x  J’A
❑Matano gave a graphical solution C
Initial conditions C2
C (x > 0) = C1; C (x < 0) = C2 c

Boundary conditions
C1
C (x → ∞) = C1; C (x → -∞) = C2 ;
0 x
dC
=0
dx x → 

EMA 5001 Zhe Cheng 6 Determine D & Matano Analysis

 Boltzmann Transformation

❑From Fick’s 2nd Law C   C 

= D 
Introduce  =
x t x  x 
t
All partial differential terms in Fick’s 2nd law equation are transformed:
 x 
 
C dC  dC  t  x dC 1  x  dC  dC
=  =  = − 3/ 2  =−    = − 
t d t d t 2t d 2t  t  d 2t d
 x 
 
C dC  dC  t  1 dC
=  =  = 
x d x d x t d
  C  d  C   d  1 dC   1 d  dC  1
 D  =  D   =  D    = D 
x  x  d  x  x d  t d  x t d  d  t

1 d  dC 
=  D 
t d  d  
EMA 5001 Zhe Cheng 6 Determine D & Matano Analysis 4
 Matano Analysis (1)

❑Continue from previous Boltzmann transformation

Right side of Fick’s 2nd Law becomes   C  1 d  dC 
D =  D 
x  x  t d  d 

Left side of Fick’s 2nd Law becomes C  dC

=− 
t 2t d

C   C 
Fick’s 2nd Law = D 
t x  x 

 dC 1 d  dC 
is transformed as −  =  D 
2t d t d  d 

1 dC d  dC 
We have −  = D 
2 d d  d 

EMA 5001 Zhe Cheng 6 Determine D & Matano Analysis 5

 Matano Analysis (2)

❑Continue from previous

1 dC d  dC 
We have −  = D 
2 d d  d 
1  dC 
Multiply both sides with dλ: − dC = d  D 
2  d 
 dC 
c c
1
Integrate with respect to C from C1 to c, −  dC =  d  D 
2 C1 C1 
d  
Put  = x / t back into the equation
1
c
x
c
 dC dx 
We have −  dC =  d  D  

2 C1 t C1  dx d ( x / t ) 
 dC 
c c
1
For any given time t (i.e., t constant), −
2 t C1  xdC = t C1  D dx 
d

 dC 
c c
1
Re-arrange, −
2t C1 xdC = C1d  D dx 
EMA 5001 Zhe Cheng 6 Determine D & Matano Analysis 6
 Matano Analysis (3)

❑Continue from p.6

 dC 
c c
1
We have −
2t  xdC =
C1
C1  D dx 
d

 dC   dC 
c
1
Integration on right side gives −
2t C1 xdC =  D dx C =c −  D dx C =C1
dC
Consider boundary condition of =0
dx C =C 1

 xdC = D(c )
1 dC
We have −
2t C1
dx C =c

Therefore, interdiffusion coefficient for C = c is D (c ) = −

1
 xdC 
dx
2t C1
dC C =c

EMA 5001 Zhe Cheng 6 Determine D & Matano Analysis 7

 Determination of Matano Interface

❑Continue from previous Original Matano

c interface interface
D (c ) = −
1 dx
 xdC 
C
2t dC C2
C1 C =c
c
c
❑Note the value of
integration term C1  xdC
C1
depends on selection of origin (0, 0)! 0 0’ x x'
→ Where?
dx
❑Note as c → C2 , the deferential term approaches infinity
dC C =c
i.e., from boundary condition:
dC dx
=0 →
dx x →
dC C →C 2

❑To make diffusion coefficient D finite when C = C2,

C2

 x' dC → 0
the selection of origin/coordinate system
must make the integration term satisfy C1
EMA 5001 Zhe Cheng 6 Determine D & Matano Analysis 8
 Physical Meaning of Matano Interface

❑Continue from previous 𝑐

1 𝑑𝑥′
𝐷 𝑐 =− න 𝑥′𝑑𝐶 ⋅ ቮ
2𝑡 𝑑𝐶
𝐶1 𝐶=𝑐
❑Physical Meaning of Matano Interface
▪ Averaged position weighed with respect to concentration if concentration profile
C(x) is invertible to the form of x (C)
▪ The interface where the total net number of atoms lost on one side of the
interface due to diffusion equals the total net number of atoms gained on the
other side of the interface
▪ The interface “across which an equal number of atoms have crossed in both
directions”
http://www.matter.org.uk/matscicdrom/manual/df.html

EMA 5001 Zhe Cheng 6 Determine D & Matano Analysis 9