Matano

Materials Engineering (MAEN 123)
Igor Medved
Department of Materials Engineering and Chemistry, Czech Technical University, Prague
MAEN 123 p. 1
The Boltzmann-Matano
method
About the method
The basic idea
The parabolic law
Example
Application of Matano
Formula for D
Model of a profile
A solution to diffusion
equation
The Boltzmann-Matano method
equation
Example of experimental
data
MAEN 123 p. 2
About the method
method
About the method

The basic idea
The method is used to calculate the diffusion coefficient D (or thermal diffusivity a) as
a function of concentration C (temperature T ) in a 1D transport of mass (heat)
It converts the diffusion equation (heat equation)
The parabolic law
C
h
C i
=
D(C)
t
x
x
Example
or
T
h
T i
=
a(T )
t
x
x
Formula for D
Model of a profile
equation
equation
data
into a more easily solved ordinary differential equation

The rudiments of the method were proposed by L. Boltzmann
Austrian physicist (1844 1906) known especially for developing the theory of statistical mechanics
C. Matano determined experimentally the diffusion coefficients as a function of

concentration in metal alloys
Japanese physicist (1905 1947) who also studied fibers
MAEN 123 p. 3
The basic idea
method
Apply the Boltzmann transformation
About the method

The basic idea
The parabolic law
in the diffusion equation
Example
C
h
C i
=
D(C)
,
t
x
x
Formula for D
Model of a profile
equation
2 t
where C = C(x, t) is a function of space and time

Since we have
d
x
d
d
=
=
=
t
t d
2t d
4( t)3 d
equation
data
d
1
d
=
=
,
x
x d
2 t d
the diffusion equation becomes

dC
1
d h
1 dC i
=
D(C)
,
2t d
2 t d
2 t d
i.e.,
dC
d h
dC i
2
=
D(C)
d
d
d
This is an ordinary differential equation, unlike the diffusion equation (which is a partial differential equation):
this time C = C() is a function of
MAEN 123 p. 4
The parabolic law
method
Why to use the transformation
About the method
2 t
The basic idea

The parabolic law
d h
dC i
dC
2
=
D(C)
,
d
d
d
Example
Formula for D
Model of a profile
equation
equation
data
From the transformed equation, i.e.,

we immediately see that C() = const is its solution

So, what is the time t needed for a given concentration value to arrive at a certain position x?
The solution C() = const says that this time is proportional to the square of the distance,
t x2 ,
which is usually called the parabolic law (recall that a parabola is a graph of a quadratic function)
MAEN 123 p. 5
Example
method
About the method
The basic idea

Example of the profiles for the moisture content Wm (plays the role of the concentration C ) in a porous
concrete
Taken from M.I. Nizovtsev et al., International Journal of Heat and Mass Transfer 51 (2008) 41614167
The parabolic law

Example
Formula for D
Model of a profile
equation
equation
data
MAEN 123 p. 6
method
About the method
The basic idea
The parabolic law

Example
Formula for D
Model of a profile
In 1933 Matano applied the transformed equation to study diffusion in alloys

In his experiment two alloys with different concentration of diffusing atoms (species) are put into contact and the
concentration C at a fixed time t can be extracted as a function of the x coordinate.
The limiting concentration values on the left and right are denoted as CL and CR , respectively
The initial conditions are

CL
for x < 0
C(x, t = 0) =
CR
for x > 0
Example of a diffusion couple magnesium + lithium:
equation
equation
data
MAEN 123 p. 7
Formula for D
method
To obtain a formula for the diffusion coefficient D , let us integrate the equation
dC
d h
dC i
2
=
D()
d
d
d
About the method

The basic idea
The parabolic law
Example
over from a chosen value =

We get
Formula for D
Model of a profile
equation
equation
to = (where C = CR )
h
n d(C C ) o
d(C CR ) i
dC
R
d = D()
= D( )
=
d
d
d
Therefore,
D( ) =
data

dC
d d
d(CCR )
d
=
2
If we know the concentration profile C() from experiment, then we can calculate the integral in the nominator
and the derivative in the denominator, and the formula yields the value of the diffusion coefficient D at =
we get the dependence of D on
Subsequently, if we express via C (by inverting the profile C()), then from D() we get the desired
dependence of D on the concentration C
These calculations are usually performed numerically
MAEN 123 p. 8
Model of a profile
method
The profile C() is usually S-shaped:
A frequent approximation of the profile is
About the method

The basic idea
The parabolic law
Example
Formula for D
Model of a profile
equation
equation
data
C(x, t) =
x
CL + CR
CR CL
+
erf a ,
2
2
2 t
i.e.,
CR CL
CL + CR
+
erf(a)
2
2
C() =
Here erf is the error function defined as
2
erf y =
u2
du
MAEN 123 p. 9
A solution to diffusion equation
method
About the method
It turns out that the erf approximation is actually a solution to the diffusion equation with a constant diffusion
coefficient D , i.e., to the equation
dC
d h dC i
d2 C
2
=
D
=D
d
d
d
d 2
The basic idea

The parabolic law
(III.1)
Example
Indeed, observing that
d 2
d erf y
=
dy
dy
Formula for D
Model of a profile
equation
u2
du
2 y2
= e
,
for the profile
equation
C() =
data
CL + CR
CR CL
+
erf(a)
2
2
we have
d2 C
CR CL
2
2
(a)2
=
a
(a
)
e
d 2
2
2
dC
CR CL
2
=
a e(a) ,
d
2
Consequently, the left-hand side of equation (III.1)
LHS = 2
CR CL
2 (a)2
a e
2
is equal to the right-hand side
RHS = D
provided Da
2
CR CL
2
a (a2 ) e(a) ,
2
=1
MAEN 123 p. 10
A solution to diffusion equation
method
So, we conclude that if Da
= 1, i.e., a = 1/ D, then
x
CR CL
CL + CR
+
erf a ,
C(x, t) =
2
2
2 t
About the method

The basic idea
The parabolic law
i.e.,
Example
C(x, t) =
Formula for D
Model of a profile
equation
equation
x
CL + CR
CR CL
+
erf
2
2
2 Dt
is indeed a solution to the diffusion equation with a constant diffusion coefficient D
There are also other known solutions to the diffusion equation, depending on the initial and boundary conditions
data
MAEN 123 p. 11
Example of experimental data
method
About the method
The basic idea
For the above-discussed example of the profiles for the moisture content Wm (that plays the role of the
concentration C ) taken from M.I. Nizovtsev et al., International Journal of Heat and Mass Transfer 51 (2008)
41614167, the resulting dependence of the moisture diffusion coefficient Dm on the moisture content Wm
is:
The parabolic law

Example
Formula for D
Model of a profile
equation
equation
data
MAEN 123 p. 12

Matano

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Materials Engineering (MAEN 123)

The Boltzmann-Matano method

About the method

About the method

The parabolic law

into a more easily solved ordinary differential equation

C. Matano determined experimentally the diffusion coefficients as a function of

Japanese physicist (1905 1947) who also studied fibers

The basic idea

Apply the Boltzmann transformation

About the method

in the diffusion equation

where C = C(x, t) is a function of space and time

The parabolic law

Why to use the transformation

About the method

The basic idea

From the transformed equation, i.e.,

we immediately see that C() = const is its solution

The parabolic law

In 1933 Matano applied the transformed equation to study diffusion in alloys

About the method

over from a chosen value =

The profile C() is usually S-shaped:

A frequent approximation of the profile is

About the method

Here erf is the error function defined as

A solution to diffusion equation

About the method

The basic idea

Indeed, observing that

for the profile

Consequently, the left-hand side of equation (III.1)

is equal to the right-hand side

A solution to diffusion equation

So, we conclude that if Da

About the method

is indeed a solution to the diffusion equation with a constant diffusion coefficient D

Example of experimental data

The parabolic law

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