MEN 200

Diffusion

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MEN 200 Science of materials
 Topic to Address

– How does diffusion occur?

– Why is it an important part of processing?

– How can the rate of diffusion be predicted for

some simple cases?

– How does diffusion depend on structure

and temperature?

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MEN 200 Science of materials
 Diffusion

Definition: is the process of MASS TRANSFER by atomic

motion
– Interdiffusion: In an alloy, atoms tend to migrate from regions
of high concentrations to regions of low concentrations
– Self-diffusion: In an elemental solid, atoms also migrate.

Mechanisms
– Gases & Liquids: random (Brownian) motion
– Solids:
• vacancy diffusion
• interstitial diffusion
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MEN 200 Science of materials
 Interdiffusion Demonstration
Interdiffusion: In an alloy, atoms tend to migrate from regions of high
concentrations to regions of low concentrations
Ex: Copper and Nickel
Cu Ni Cu Ni
Heated
at elevated Temp.
Then
cooled
to room Temp.
Initially After some time

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MEN 200 Science of materials
 Self-diffusion Demonstration

Self-diffusion: In an elemental solid, atoms also migrate.

Pure metal Pure metal

C
C
After some time
A D
A
D
B
B

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MEN 200 Science of materials
 Diffusion Mechanisms
Conditions for diffusion: (from atomic perspective)
– There must be an empty atomic site
– The atom must have sufficient energy to break bonds with its neighbor atoms

Vacancy Diffusion: atoms exchange with vacancies, applies to substitutional

impurities atoms too.
Rate depends on:
--number of vacancies
--activation energy to exchange.

increasing elapsed time

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MEN 200 Science of materials
 Diffusion Mechanisms
Interstitial Diffusion: It involves atoms that migrate from an interstitial position to
a neighboring one that is empty (interdiffusion).

Impurity atoms: Hydrogen, Carbon, Nitrogen and Oxygen

(small enough to fit into the interstitial positions)

Interstitial diffusion occurs much more rapidly than diffusion by the vacancy mode

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MEN 200 Science of materials
 Diffusion Mechanisms
Interstitial Diffusion: It involves atoms that migrate from an interstitial position to
a neighboring one that is empty (interdiffusion).

Impurity atoms: Hydrogen, Carbon, Nitrogen and Oxygen

(small enough to fit into the interstitial positions)

Interstitial diffusion occurs much more rapidly than diffusion by the vacancy mode

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MEN 200 Science of materials
Processing Using Diffusion

Case Hardening:
– Diffuse carbon atoms into the host
iron atoms at the surface.
– Example of interstitial diffusion is a
case hardened gear.

Result: The presence of C atoms makes iron (steel) harder.

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MEN 200 Science of materials
Processing Using Diffusion
Doping: silicon with phosphorus for n-type semiconductors:

Process: 0.5 mm

1. Deposit P rich layers on surface.

silicon magnified image of a computer chip

2. Heat it.

light regions: Si atoms

3. Result: Doped semiconductor regions.

silicon

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light regions: Al atoms
MEN 200 Science of materials
 Diffusion
– Diffusion is a time dependent process
– We need to quantify HOW MUCH MASS of an element is transported
within another element as a function of time

The diffusion flux: J  Flux  moles (or mass) diffusing  mol2 or kg2
surface area time cm s ms

In mathematical form In differential form

M N 1 dM 1 dN
J J J J
At At A dt A dt

M : mass diffusing
N : number of moles diffusing
A : The area across which diffusion is occurring
t : the elapsed diffusing time
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MEN 200 Science of materials
 Steady State Diffusion
– When the diffusion flux does not change with time = constant
C : Concentration of the diffusing species

The concentration gradient The diffusion flux: (Fick’s first law)

(in kg/m4) dC '' dC ''
J  D
dx dx
D Diffusion coefficient m2/s

In this case
dC '' C '' C A''  CB''
 
dx x x A  xB

Steady state diffusion 12

MEN 200 Science of materials
 Nonsteady-State Diffusion
Definition: The diffusion flux and the concentration gradient at some
particular point in a solid vary with time

Fick’s second law

C ''   C ''  D :Diffusion coefficient

  D 
t x  x  C '' :Concentration of the
diffusing species (Kg/m3)
D Constant

C ''  2C '' Concentration profile for

D 2 Nonsteady-State diffusion
t x

Solutions are possible only when physically meaningful boundary

conditions are specified.
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MEN 200 Science of materials
 Semi-infinite solid
A solid bar is assumed to be semi-infinite if none of the diffusing atoms
reaches the bar end during the time over which diffusion takes place.

Fick’s second law

C ''  2C '' Semi infinite bar
D 2
t x

Boundary conditions
1. Before diffusion, the diffusing solute atoms
initially in the solid, are uniformly t  0, C ''  C0'' at 0  x  
distributed with concentration of C0’’
2. The value of x at the surface is zero and
increases with distance into the solid. t  0, C ''  Cs'' at x  0

3. The time is taken to be zero the instant

before the diffusion process begins t  0, C ''  C0'' at x  
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MEN 200 Science of materials
 Semi-infinite solid
C ''  2C ''
D 2
t x Semi infinite bar

Solution of Fick’s second law

C x''  C0''  x 
 1  erf  
Cs''  C0''  2 Dt 

C x'' Concentration of the diffusing species (Kg/m3) at depth x after time t

 x 
erf   Is the Gaussian error function
 2 Dt 
Concentration profile for
nonsteady-state diffusion

erf z  
2 z
 e  y dy
2

 0

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MEN 200 Science of materials
 Gaussian Error Function
Function erf z  
2 z

 y2
e dy
 0

If the value is not in the table, interpolate between given values

z  1.17
1.2  1.17 0.9103  erf ( z )
z1  1.1 erf ( z1 )  0.8802  erf ( z)  0.9013
1.2  1.1 0.9103  0.8802
z2  1.2 erf ( z2 )  0.9103

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MEN 200 Science of materials
 Factors That Influence Diffusion
Self diffusion occurs by a vacancy mechanism (number of vacancies)
Interdiffusion occurs by an interstitial mechanism (activation energy)

D :is indicative of the rate at which atoms diffuse

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MEN 200 Science of materials
 Factors That Influence Diffusion
Temperature has the most profound influence on the coefficients and
diffusion rates

T  500o C T  900o C
Example: Iron α-Fe D  3.0 1021 m2 / s D  1.8 1015 m2 / s

The diffusion coefficient as a function of temperature

D0 a temperature independent pre-exponential (m2/s)

 Qd 
  Qd the activation energy for diffusion (J/mol or eV/atom)
D  D0 e  RT 
R the gas constant, 8.31 J/mol-K or 8.62 × 10-5 eV/atom-K
T absolute temperature (K)

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MEN 200 Science of materials
 Factors That Influence Diffusion
The diffusion coefficient as a function of temperature
 Qd 
 
D  D0 e  RT 

log

Qd  1 
log D  log D0   
2.3R  T 

1
y  log D, x 
T
Qd
m , b  log D0
2.3R

y  b  mx

Experimentally, the values of Qd and

D0 are determined from these plots Plot of logD versus (1/T) 19
MEN 200 Science of materials
 Steady State Diffusion
Problem 5.6:
The purification of hydrogen gas by diffusion through a palladium sheet
was discussed in Section 5.3. Compute the number of Kilograms of
hydrogen that pass per hour through a 6-mm-thick sheet of palladium
having an area of 0.25 m2 at 600oC. Assume a diffusion coefficient of
1.7×10-8 m2/s, that the concentrations at the high- and low pressure
sides of the plate are 2.0 and 0.4 kg of hydrogen per cubic meter of
palladium, and that steady-state conditions have been attained

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MEN 200 Science of materials
 Steady State Diffusion
Problem 5.6:

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MEN 200 Science of materials
 Steady State Diffusion
Problem 5.6:

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MEN 200 Science of materials
 NonSteady State Diffusion
Problem 5.11:
Determine the carburizing time necessary to achieve a carbon
concentration of 0.30 wt% at a position 4 mm into an iron-carbon alloy that
initially contains 0.10 wt% C. The surface concentration is to be maintained
at 0.90 wt% C, and the treatment is to be conducted at 1100oC. Use the
diffusion data for γ-Fe in Table 5.2.

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MEN 200 Science of materials
 NonSteady State Diffusion
Problem 5.11:

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MEN 200 Science of materials
 NonSteady State Diffusion
Problem 5.11:

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MEN 200 Science of materials
 NonSteady State Diffusion
Problem 5.25:
The steady state diffusion flux through a metal plate is 7.8×10-8 Kg/m2-s at a
temperature of 1200o C (1473 K) and when the concentration gradient is -500
kg/m4. Calculate the diffusion flux at 1000o C (1273 K) for the same
concentration gradient and assuming an activation energy for diffusion of
145000 J/mol.

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MEN 200 Science of materials
 NonSteady State Diffusion
Problem 5.25:

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MEN 200 Science of materials
 NonSteady State Diffusion
Problem 5.25:

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MEN 200 Science of materials