Diffusion in Solids

A schematic illustration of an atomic diffusion

 Diffusion
Diffusion is material transport by atomic motion. Inhomogeneous materials can
become homogeneous by diffusion. For an active diffusion to occur, the
temperature should be high enough to overcome energy barriers to atomic
motion.

Mechanisms:

•Gases & Liquids – random

(Brownian) motion

•Solids – vacancy diffusion or

interstitial diffusion
 Diffusion
• Interdiffusion: In an alloy, atoms tend to migrate from regions of high
concentration to regions of low concentration at elevated temperature.
Initially After some time

Adapted from
Figs. 5.1 and
5.2, Callister
7e.

Interdiffusion (or impurity diffusion) occurs in response to a concentration

gradient.
 Self-Diffusion
• Self-diffusion is diffusion in one-component material, when all atoms that
exchange positions are of the same type.

Label some atoms After some time

C
C
A D
A
D
B
B
 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

To jump from lattice site to lattice site, atoms need energy to break bonds with
neighbors, and to cause the necessary lattice distortions during the jump. This
energy comes from the thermal energy of atomic vibrations (Eav ~ kT).

Materials flow (the atom) is opposite the vacancy flow direction.

 Diffusion Mechanisms
Interstitial diffusion is generally faster than vacancy diffusion because
bonding of interstitials to the surrounding atoms is normally weaker, and there
are many more interstitial sites than vacancy sites to jump to.

Requires small impurity atoms (e.g. C, H, O) to fit into interstices in host.

More rapid than vacancy diffusion.

 Diffusion – Thermally Activated
Process

In order for atom to jump into a

vacancy site, it needs to posses
Ea enough energy (thermal energy) to
break the bonds and squeeze through
its neighbors. The energy necessary for
motion, Ea, is called the activation
energy for vacancy motion.

Schematic representation of the diffusion of an atom from its original position

into a vacant lattice site. At activation energy Ea has to be supplied to the atom
so that it could break inter-atomic bonds and to move into the new position.
 Diffusion Simulation

• Simulation of interdiffusion
across an interface:

• Rate of substitutional diffusion

depends on:

--vacancy concentration
--frequency of jumping

(Courtesy P.M. Anderson)

 Diffusion Processing
• 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. The surface of the
gear is more harder than inside.
 Diffusion Processing
• 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
semiconductor
light regions: Si atoms
regions.

silicon
light regions: Al atoms
 Diffusion
The flux of diffusing atoms, J, is used to quantify how fast diffusion occurs.

• How do we quantify the amount or rate of diffusion?

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

moles (or mass)diffusing mol kg

J  Flux   or
surface areatime cm s m2s
2

M=
M l dM J  slope
J  mass
At A dt diffused
time
 Steady-State Diffusion
Steady state diffusion: the diffusion flux does not change with time.
Concentration profile: concentration of atoms/molecules of interest as
function of position in the sample.
Concentration gradient: dC/dx: the slope at a particular point on
concentration profile.
dC
Flux proportional to concentration gradient =
dx

C1 C1
Fick’s first law of diffusion

C2 dC
C2
J  D
x1
dx
x2
x
D  diffusion coefficient
dC C C2  C1
if linear  
dx x x2  x1
 Example Problem 1:
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 a 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
 Example (cont).
• Solution – assuming linear concentration gradient:

glove dC C2  C1
J -D  D
C1 dx x2  x1
paint 2
tb  skin
6D
remover Data: D = 110 x 10-8 cm2/s
C2 C1 = 0.44 g/cm3
x1 x2 C2 = 0.02 g/cm3
x2 – x1 = 0.04 cm

-8 2 (0.02 g/cm3  0.44 g/cm3 ) g

J   (110 x 10 cm /s)  1.16 x 10-5
(0.04 cm) cm2s
Diffusive flux of methylene
chloride through the glove
 Example Problem 2
A plate of Iron is exposed to a carburizing (carbon-rich) atmosphere on one side
and a decarburizing (carbon-deficient) on the other side at 700 C (1300 F). If
a condition of steady state is achieved, calculate the diffusion flux of carbon
through the plate if the concentration of carbon at positions of 5 and 10 mm
(5x10^-3 and 10^-2) beneath the carburizing surface are 1.2 and 0.8 kg/m3,
respectively. Assume a diffusion coefficient of 3x10^-11 m2/s at this
temperature.

Solution: Fick’s first law is utilized to determine the diffusion flux. Substitution of
the values above into the expression yields:

J -D
dC C  C1
 D 2
(1.2  0.8)
J   (3x10^ 11)
dx x2  x1 (5 x10^ 3  10^ 2)

J = 2.4x10^-9 kg/m2-s
 Diffusion and Temperature
Temperature dependence of the diffusion coefficient, follows the Arrhenius
dependence. Diffusion coefficient exponentially 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]
 Diffusion and Temperature
D has exponential dependence on T
1500

1000

600

300
T(C)
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 7e. (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.)
 Example Problem 3
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
Q  1  Q  1
lnD2  lnD0  d   and lnD1  lnD0  d  
R  T2  R  T1 
D2 Q  1 1
 lnD2  lnD1  ln  d   
D1 R  T2 T1 
 Example (cont.)
 Qd  1 1 
D2  D1 exp    
 R  T2 T1 

T1 = 273 + 300 = 573 K

T2 = 273 + 350 = 623 K

11 2   41,500 J/mol  1 1 

D2  (7.8 x 10 m /s) exp    
 8.314 J/mol - K  623 K 573 K 

D2 = 15.7 x 10-11 m2/s Diffusion coefficient at 350ºC

 Non-steady State Diffusion
In most real situations the concentration profile and the concentration gradient
change with time. The change of the concentration profile is given in this case
by a differential equation, Fick’s Second Law.

C  2C Solution of this equation is

Fick’s Second Law: D 2 concentration profile as function of
t x time, C(x,t):

• Copper diffuses into a bar of aluminum.

Surface conc.,
Cs of Cu atoms bar
pre-existing conc., Co of copper atoms

Cs
B.C. at t = 0, C = Co for 0  x  
at t > 0, C = CS for x = 0
(const. surf. conc.)
C = Co for x = 
 Solution
CS
C x ,t   Co  x 
 1  erf  
Cs  Co  2 Dt 
C(x,t)
C(x,t) = Conc. at point x at
Co
time t
erf (z) = error function
2 z y 2

  0
e dy

erf(z) values are given

in Table 5.1
 Example Problem 4
An FCC iron-carbon 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 hrs 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: use Eqn. 5.5  1  erf  
Cs  Co  2 Dt 
 C( x ,t )  Co  x 
Solution (cont.): Cs  Co
 1  erf  
 2 Dt 

– t = 49.5 hrs 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
 Solution (cont.):
We must now determine from Table 5.1 the value of z for which the error
function is 0.8125. An interpolation is necessary as follows:

z  0.90 0.8125  0.7970

z erf(z) 
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
( 4 x 10 m) 1h
D      2.6 x 1011 m2 /s
 4z 2t  ( 4)(0.93)2 ( 49.5 h) 3600 s
 
Diffusion coefficient
 Diffusion of Different Species

Smaller atoms diffuse more readily than bigger ones, and diffusion is faster in
open lattices or in open directions.
 Solution (cont.):
• To solve for the temperature at which
D has above value, we use a
Qd
rearranged form of Equation (5.9a); T
R(lnDo  lnD)
from Table 5.2, 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 2.3x105 m2 /s  ln 2.6x1011 m2 /s)

T = 1300 K = 1027°C The temperature at which the

treatment was conducted.
 Example Problem 5:
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 breakthrough time (tb), i.e., how long could the gloves be
used before methylene chloride reaches the hand?

• Data (from Table 22.5)

– diffusion coefficient in butyl rubber:
D = 110 x10-8 cm2/s
 Example (cont).
• Solution – assuming linear conc. gradient

glove
C1
2
paint skin
tb  Equation 22.24
remover 6D
C2
x1 x 2
  x2  x1  0.04 cm

D = 110 x 10-8 cm2/s

(0.04 cm)2
tb   240 s  4 min
-8 2
(6)(110 x 10 cm /s)

Time required for breakthrough ca. 4 min

 References

1. Callister Jr., W.D. “Materials Science and Engineering: An Introduction,” 7th

edition, John Wiley & Sons, 2006.
2. Smith, W.F. and Hashemi, J. “Foundations of Materials Science and
Engineering,” McGraw-Hill, 2004.
3. David Brandon and Wayne D Kaplan “Microstructural Characterization of
Materials,” John Wiley and Sons, In., 1999.
4. Leonid Zhigilei “Introduction to the Science and Engineering of Materials,”
University of Virginia, 2007.
5. [Link]
usion/examples/[Link]