6.03.

2019

Chapter 5: Diffusion
(Mass transport by atomic motion)

ISSUES 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?

Diffusion
•Many reactions and processes that are important in the
treatment of materials rely on the transfer of mass either
within a specific solid or from a liquid, a gas, or another solid
phase.

•This is necessarily accomplished by diffusion, the

phenomenon of material transport by atomic motion

Diffusion - Mass transport by atomic motion

Mechanisms
•Gases & Liquids – random motion
•Solids – vacancy diffusion or interstitial diffusion
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Diffusion
•The phenomenon of diffusion may be demonstrated with the
use of a diffusion couple, which is formed by joining bars of two
different metals together so that there is intimate contact
between the two faces;

Diffusion
•This couple is heated for an
extended period at an elevated
temperature (but below the melting
temperature of both metals), and
cooled to room temperature.

•Chemical analysis will reveal a

condition similar to that, pure
copper and nickel at the two
extremities of the couple,
separated by an alloyed region.

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Diffusion
•Concentrations of both metals vary with position. This result
indicates that copper atoms have migrated or diffused into the
nickel, and that nickel has diffused into copper.
•There is a net drift or transport of atoms from high- to low-
concentration regions.
•This process, whereby atoms of one metal diffuse into
another, is termed interdiffusion, or impurity diffusion.

Diffusion
Self-diffusion:
•diffusion also occurs for pure metals,
•but all atoms exchanging positions are of the same type.

Label some atoms After some time

C
C
A D
A
D
B
B
In an elemental solid, atoms also migrate.

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Diffusion Mechanisms
•Diffusion is just the stepwise migration of atoms from lattice site
to lattice site. In fact, the atoms in solid materials are in constant
motion, rapidly changing positions. For an atom to make such a
move, two conditions must be met:

(1) there must be an empty adjacent site

(2) the atom must have sufficient energy to break bonds with its
neighbor atoms and then cause some lattice distortion during
the displacement.

At a specific temperature some small fraction of the total

number of atoms is capable of diffusive motion, depending on
the magnitudes of their vibrational energies. This fraction
increases with rising temperature.
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Diffusion Mechanisms
Boltzman Energy
T1 Distribution curve
Number of
atoms

E1 Energy
E*
Average energy at
temperature T1

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Diffusion Mechanisms
Boltzman Energy
T2>T1 Distribution curve
Number of
atoms

E1 E2 Energy
E*
Average energy at E2>E1 Average energy at
temperature T1 temperature T2

Diffusion Mechanisms
Vacancy Diffusion:
• atoms exchange with vacancies
• applies to substitutional impurities atoms
• rate depends on:
-- number of vacancies
-- activation energy to exchange.

increasing elapsed time

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Diffusion Mechanisms
• Interstitial diffusion – smaller atoms can
diffuse between atoms.

Adapted from Fig. 5.3(b), Callister & Rethwisch 8e.

More rapid than vacancy diffusion

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Processing Using Diffusion

• Case Hardening:
-- Diffuse carbon atoms Adapted from
chapter-opening
into the host iron atoms photograph,
Chapter 5,
at the surface. Callister &
Rethwisch 8e.
-- Example of interstitial (Courtesy of
Surface Division,
diffusion is a case Midland-Ross.)

hardened gear.

• Result: The presence of C

atoms makes iron (steel) harder.

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Processing Using Diffusion

• Doping silicon with phosphorus for n-type semiconductors:
• Process: 0.5 mm
1. Deposit P rich
layers on surface.
magnified image of a computer chip

silicon
2. Heat it.
3. Result: Doped light regions: Si atoms
semiconductor
regions.

light regions: Al atoms

silicon
Adapted from Figure 18.27, Callister &
Rethwisch 8e. 13

Diffusion
• How do we quantify the amount or rate of diffusion?
• Diffusion is a time-dependent process
• In a macroscopic sense, the quantity of an element
that is transported within another is a function of time.

Diffusion Flux: The mass (or, equivalently, the number

of atoms) M diffusing through and perpendicular to a unit
cross-sectional area of solid per unit of time.

moles (or mass) diffusing mol kg

J  Flux   or
surface areatime  cm2s m2s

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Diffusion
• Measured empirically
– Make thin film (membrane) of known surface area
– Impose concentration gradient
– Measure how fast atoms or molecules diffuse through the
membrane

M=
M 1 dM mass J  slope
J  diffused
At A dt
time
The units for J are kilograms or atoms per meter squared per second:
(kg/m2-s or atoms/m2-s)

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i) Steady-State Diffusion
•Rate of diffusion independent of time: “Diffusion flux does not
change with time”.
dC
Flux proportional to concentration gradient =
dx
C1 C1 Fick’s first law of diffusion

dC
C2 C2 J  D
dx
x1 x2
x
D  diffusion coefficient
dC C C2  C1 (constant of proportionality)
if linear  
dx x x 2  x1

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Example: Chemical Protective

Clothing (CPC)
• Methylene chloride is a common ingredient of paint
removers. Besides being an irritant, it also may be
absorbed through skin. When using this paint
remover, protective gloves should be worn.
• If butyl rubber gloves (0.04 cm thick) are used, what
is the diffusive flux of “methylene chloride” through
the glove?
• Data:
– diffusion coefficient in butyl rubber:
D = 110 x10-8 cm2/s
– surface concentrations: C1 = 0.44 g/cm3
C2 = 0.02 g/cm3

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Example (cont).
• Solution – assuming linear conc. gradient
glove
C1 dC C  C1
tb 
2 J  -D  D 2
paint
6D dx x2  x1
skin
remover
C2 Data: D = 110 x 10-8 cm2/s
x1 x2 C1 = 0.44 g/cm3
C2 = 0.02 g/cm3
x2 – x1 = 0.04 cm

(0.02 g/cm3  0.44 g/cm3 ) g

J   (110 x 10 -8 cm2 /s)  1.16 x 10-5
(0.04 cm) cm2s

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Diffusion and Temperature

• Diffusion coefficient increases with increasing T.

 Qd 
D  Do exp  
 RT 

D = diffusion coefficient [m2/s]

Do = pre-exponential [m2/s]
Qd = activation energy [J/mol or eV/atom]
R = gas constant [8.314 J/mol-K]
T = absolute temperature [K]

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Diffusion and Temperature

D has exponential dependence on T
1500

1000

600

T(C)
300

10-8

D (m2/s) Dinterstitial >> Dsubstitutional

C in a-Fe Al in Al
10-14 C in g-Fe Fe in a-Fe
Fe in g-Fe

10-20
0.5 1.0 1.5 1000 K/T

Adapted from Fig. 5.7, Callister & Rethwisch 8e. (Date for Fig. 5.7
taken from E.A. Brandes and G.B. Brook (Ed.) Smithells Metals
Reference Book, 7th ed., Butterworth-Heinemann, Oxford, 1992.)

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Example: At 300ºC the diffusion coefficient and

activation energy for Cu in Si are
D(300ºC) = 7.8 x 10-11 m2/s
Qd = 41.5 kJ/mol
What is the diffusion coefficient at 350ºC?

D transform ln D
data

Temp = T 1/T

1
Qd Qd 1
lnD2  lnD0    and lnD1  lnD0   
R  T2  R  T1 
D Q  1 1
 lnD2  lnD1  ln 2   d   
D1 R  T2 T1 
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Example (cont.)
 Q  1 1 
D2  D1 exp  d   
 R  T2 T1 

T1 = 273 + 300 = 573K

T2 = 273 + 350 = 623K

  41,500 J/mol  1 1 
D2  (7.8 x 10 11 m2 /s) exp   
 8.314 J/mol - K  623 K 573 K 

D2 = 15.7 x 10-11 m2/s

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ii) Non-steady State Diffusion

• Most practical diffusion situations are nonsteady-state ones.

• The “diffusion flux” and the “concentration gradient” at
some particular point in a solid vary with time, with a net
accumulation or depletion of the diffusing species resulting.
• The concentration of diffusing species is a function of both
time and position C = C(x,t)
• In this case Fick’s Second Law is used

C  2C
Fick’s Second Law: D 2
t x

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Non-steady State Diffusion

• Copper diffuses into a bar of aluminum.
Surface conc.,
bar
C s of Cu atoms
pre-existing conc., Co of copper atoms

Cs

Adapted from
Fig. 5.5,
Callister &
Rethwisch 8e.

---Boundary Conditions:
at t = 0, C = Co for 0  x  
at t > 0, C = CS for x = 0 (constant surface conc.)
C = Co for x = 
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Solution:
C  x , t   Co  x 
 1  erf  
Cs  Co  2 Dt 

C(x,t) = Conc. at point x at CS

time t
erf (z) = error function
2 z C(x,t)

2
 e  y dy
 0
Co
erf(z) values are given on
next slide.
Adapted from Fig. 5.5,
Callister & Rethwisch 8e.

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Tabulation of Error Function Values

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Non-steady State Diffusion

• Sample Problem: An FCC iron-carbon (Fe-C) alloy
initially containing 0.20 wt% C is carburized at an
elevated temperature and in an atmosphere that
gives a surface carbon concentration constant at 1.0
wt%. If after 49.5 h the concentration of carbon is
0.35 wt% at a position 4.0 mm below the surface.
Determine the temperature at which the
treatment was carried out.

C ( x, t )  Co  x 
• Solution: Using Fick’s 2nd Law:  1  erf  
Cs  Co  2 Dt 

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Solution (cont.):
•at t=0

Cs=1.0
Co=0.20 wt% C …….. Co=0.20 wt% C …… Co=0.20 wt% C
wt% C

•at t=49.5 h

Cs=1.0
Co=0.20 wt% C
wt% C

4 mm Cx=0.35 wt% C

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C ( x , t )  Co  x 
Solution (cont.):  1  erf  
Cs  Co  2 Dt 

– t = 49.5 h x = 4 x 10-3 m
– Cx = 0.35 wt% Cs = 1.0 wt%
– Co = 0.20 wt%

C ( x, t )  Co 0.35  0.20  x 
  1  erf    1  erf ( z )
Cs  Co 1.0  0.20  2 Dt 

 erf(z) = 0.8125

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Solution (cont.):
We must now determine the value of z for which the error function
is 0.8125. An interpolation is necessary as follows

z erf(z) z  0.90 0.8125  0.7970


0.95  0.90 0.8209  0.7970
0.90 0.7970
z 0.8125 z  0.93
0.95 0.8209

Now solve for D x x2

z D
2 Dt 4z 2t

 x2  3 2
D     ( 4 x 10 m) 1h
 2.6 x 10 11 m2 /s
 4z 2t  ( 4)(0.93)2 ( 49.5 h) 3600 s
 
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Solution (cont.):
• To solve for the temperature at Qd
T 
which D has the above value, R(lnDo  lnD )
we use a rearranged form of
Equation shown on slide 19:
from Tables, for diffusion of C in FCC Fe
Do = 2.3 x 10-5 m2/s Qd = 148,000 J/mol

148,000 J/mol
 T 
(8.314 J/mol - K)(ln 2.3 x10  5 m2 /s  ln 2.6 x10 11 m2 /s)

T = 1300 K = 1027ºC

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Summary
Diffusion FASTER for... Diffusion SLOWER for...

• open crystal structures • close-packed structures

• materials w/secondary • materials w/covalent

bonding bonding

• smaller diffusing atoms • larger diffusing atoms

• lower density materials • higher density materials

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