Topic 5:

DIFFUSION IN SOLIDS
WHY STUDY DIFFUSION?
• Materials often heat treated to improve properties

• Atomic diffusion occurs during heat treatment

• Depending on situation higher or lower diffusion rates

desired

• Heat treating temperatures and times, and heating or cooling

rates can be determined using the mathematics/physics of
diffusion
Example: steel gears are “case-hardened” by
diffusing C or N to outer surface
 Topic 5:
DIFFUSION IN SOLIDS
ISSUES TO ADDRESS...
• Atomic mechanisms of diffusion

• Mathematics of diffusion

• Influence of temperature and diffusing species on

Diffusion rate
 DIFFUSION
Phenomenon of material transport by atomic or particle
transport from region of high to low concentration

• What forces the particles to go from left to right?

• Does each particle “know” its local concentration?
• Every particle is equally likely to go left or right!
• At the interfaces in the above picture, there are
more particles going right than left  this causes
an average “flux” of particles to the right!
• Largely determined by probability & statistics
 DIFFUSION DEMO
• Glass tube filled with water.
• At time t = 0, add some drops of ink to one end
of the tube.
• Measure the diffusion distance, x, over some time.

to x (mm)
t1
t2
t3
time (s)
xo x1 x2 x3
 DIFFUSION: THE PHENOMENA (1)
• Interdiffusion: In an alloy or “diffusion couple”, atoms tend
to migrate from regions of large to lower concentration.
Initially (diffusion couple) After some time

Adapted
from Figs.
5.1 and 5.2,
Callister 6e.

Cu Ni
100% 100%

0 0
Concentration Profiles Concentration Profiles
 DIFFUSION: THE PHENOMENA (2)
• Self-diffusion: In an elemental solid, atoms
also migrate.

Label some atoms After some time

C
C
A D
A
D
B
B
 DIFFUSION MECHANISMS
Diffusion at the atomic level is a step-wise migration of atoms from
lattice site to lattice site

Conditions for diffusion:

• there must be an adjacent empty site
• atom must have sufficient energy to break bonds with its
neighbors and migrate to adjacent site (“activation” energy)

Higher the temperature, higher is the probability that an atom will have
sufficient energy
 hence, diffusion rates increase with temperature

Types of atomic diffusion mechanisms:

• substitutional (through vacancies)
• interstitial
 DIFFUSION MECHANISMS
Substitutional Diffusion:
• applies to substitutional impurities
• atoms exchange with vacancies
• rate depends on:
-- number of vacancies
-- temperature
-- activation energy to exchange.

increasing elapsed time

 ACTIVATION ENERGY FOR
DIFFUSION
Initial state Intermediate state Final state

Energy Activation energy

• Also called energy barrier for diffusion

 DIFFUSION SIMULATION
• Simulation of
interdiffusion
across an interface:

• Rate of substitutional
diffusion depends on:
-- vacancy concentration
-- activation energy (which is
related to frequency of jumping).

(Courtesy P.M. Anderson)

 INTERSTITIAL SIMULATION
• Applies to interstitial impurities.
• More rapid than vacancy
diffusion (Why?).
• Interstitial atoms smaller and
more mobile; more number of
interstitial sites than vacancies

• Simulation:
--shows the jumping of a
smaller atom (gray) from
one interstitial site to
another in a BCC
structure. The
interstitial sites
considered here are
(Courtesy P.M. Anderson)
at midpoints along the
unit cell edges.
PROCESSING USING DIFFUSION (1)
• Case Hardening:
-- Example of interstitial Fig. 5.0,
Callister 6e.
diffusion is a case (Fig. 5.0 is
courtesy of
hardened gear. Surface
Division,
-- Diffuse carbon atoms Midland-
Ross.)
into the host iron atoms
at the surface.

• Result: The "Case" is

--hard to deform: C atoms
"lock" planes from shearing.
--hard to crack: C atoms put
the surface in compression.
 PROCESSING USING DIFFUSION (2)
• Doping Silicon with P for n-type semiconductors:
• Process 0.5mm
1. Deposit P rich
layers on surface.

magnified image of a computer chip

silicon
Fig. 18.0,
2. Heat it. Callister 6e.

3. Result: Doped
light regions: Si atoms
semiconductor
regions.

light regions: Al atoms

silicon
 MODELING DIFFUSION: FLUX
• Flux: amount of material or atoms moving past a unit area in unit time
Flux, J = M/(A t)

1 dM  kg  atoms 
J   or  
A dt 2 2
m s   m s 
• Directional Quantity
x-direction
y J
y

Jx Unit area A
Jz x through
z which
• Flux can be measured for: atoms
--vacancies
move.
--host (A) atoms
--impurity (B) atoms
 CONCENTRATION PROFILES & FLUX
• Concentration Profile, C(x): [kg/m3]
Cu flux Ni flux

Concentration Concentration Adapted

of Cu [kg/m 3 ] of Ni [kg/m 3 ]
from Fig.
5.2(c),
Callister 6e.

Position, x
• Fick's First Law:
Diffusion coefficient [m 2 /s]
flux in x-dir.
[kg/m 2 -s] dC
Jx  D concentration
dx gradient [kg/m 4 ]
• The steeper the concentration profile,
the greater the flux!
 STEADY STATE DIFFUSION
• Steady State: Steady rate of diffusion from one end to the other.
Implies that the concentration profile doesn't change with time.
Why?
Steady State:
J x(left) J x(right) J x(left) = J x(right)
x
Concentration, C, in the box doesn’t change w/time.
dC
• Apply Fick's First Law: J x  D
dx
dC  dC 
• If Jx)left = Jx)right , then     
dx left dx right

• Result: the slope, dC/dx, must be constant

(i.e., slope doesn't vary with position)!
 EX: STEADY STATE DIFFUSION
• Steel plate at 3
kg/ m
700C with = 1. 2 3
C1 g/m
geometry 0. 8k
=
shown: Carbon C2 Steady State =
rich straight line! Adapted
gas Carbon
from Fig. 5.4,
Callister 6e.
deficient
gas
D=3x10 -11 m 2 /s
0 x1 x2

10
• Q: How much 5m

m
m

m
carbon transfers
from the rich to C2  C 1 kg
J  D  2 .4  10 9
the deficient side? x2  x 1 m 2s
Note: Steady state does not set in instantaneously.
 STEADY STATE DIFFUSION:
ANOTHER PERSPECTIVE
• Hose connected to tap; tap turned on
• At the instant tap is turned on, pressure is high at the tap
end, and 1 atmosphere at the other end
• After steady state is reached, pressure linearly drops
from tap to other end, and will not change anymore

Tap end Flow end

Increasing time
Pressure
Steady state
 NON STEADY STATE DIFFUSION
dx
• Concentration profile,
C(x), changes J (left) J (right)
w/ time.
Concentration,
C, in the box
• To conserve matter: • Fick's First Law:
JJ(right)
(right) JJ(left) ddCC
(left)   ddCC JJ  DD or
or
dx 
dx dt
dt dx
dx
ddJJ  ddCC ddJJ  dd22CC (if
(ifDDdoes
does
  DD not
notvary
vary
dt dx dx22 with x)
dx
dx dt dx dx with x)

equate
equate
• Governing Eqn.:
dC d 2C Fick’s second law
=D 2
dt dx
 EX: NON STEADY STATE DIFFUSION
• Copper diffuses into a bar of aluminum.
Surface conc.,
C s of Cu atoms bar
pre-existing conc., C o of copper atoms
C(x,t)
Cs

t3 Adapted from
t2 Fig. 5.5,

t t1 Callister 6e.

Co o
position, x
• Boundary conditions:
For t = 0, C = C0 at x > 0
dC d 2C
For t > 0, C = Cs at x = 0 =D
C = C0 at x = ∞
dt dx 2
 EX: NON STEADY STATE DIFFUSION
• Copper diffuses into a bar of aluminum.
Surface conc.,
C s of Cu atoms bar
pre-existing conc., C o of copper atoms
C(x,t)
Cs

t3 Adapted from
t2 Fig. 5.5,

t t1 Callister 6e.

Co o
position, x
• General solution: C(x, t )  C o   x 
1  erf  
2 Dt 
Cs  Co
"error function"
Values calibrated in Table 5.1, Callister 6e.
 PROCESS DESIGN EXAMPLE
• Suppose we desire to achieve a specific concentration C1
at a certain point in the sample at a certain time

C ( x, t )  C0  x 
 1  erf  
Cs  C0  2 Dt 
becomes
C1  C0  x 
 constant  1  erf  
Cs  C0  2 Dt 

x2
  constant
Dt
 DIFFUSION DEMO: ANALYSIS
• The experiment: record combinations of
t and x that kept C constant.
to
t1
t2
t3
xo x1 x2 x3
 
C(x i, t i )  C o x
 1 erf  i
2 Dt 
 = (constant here)
Cs  Co  i 

• Diffusion depth given by:

x i  Dt i
DATA FROM DIFFUSION DEMO
ln[x(mm)]
4
BB
BBBB
3.5 B B B B
B B
3 B
B
2.5
2 Linear regression fit to data:
1.5 ln[ x(mm )]  0.58 ln[ t (min)]  2 .2
1 R2  0.999
0.5
0
0 0.5 1 1.5 2 2.5 3
ln[t(min)]

• Experimental result: x ~ t0.58

• Theory predicts x ~ t0.50
• Reasonable agreement!
 PROCESSING QUESTION
• Copper diffuses into a bar of aluminum.
• 10 hours at 600C gives desired C(x).
• How many hours would it take to get the same C(x)
if we processed at 500C, given D500 and D600?
Key point 1: C(x,t500C) = C(x,t600C).
Key point 2: Both cases have the same Co and Cs.
• Result: Dt should be held constant.
C (x, t )  Co  x 
= 1  erf  
 2Dt 
(Dt) 500ºC =(Dt) 600ºC
C s  Co

5.3 x10 -13 m 2 /s 10hrs

(Dt )600 Note: values
• Answer: t 500   110 hr of D are
D500 provided here.
4.8x10 -14 m 2 /s
 DIFFUSION AND TEMPERATURE
• Diffusivity increases with T.
pre-exponential [m 2 /s] (see Table 5.2, Callister 6e )
activation energy
 Q  [J/mol],[eV/mol]
diffusivity D  Do exp  d  (see Table 5.2, Callister 6e )
 RT 
gas constant [8.31J/mol-K]

• Remember vacancy concentration: NV = N exp(-QV/kT)

• QV is vacancy formation energy (larger this energy,
smaller the number of vacancies)
• Qd is the activation energy (larger this energy, smaller
the diffusivity and lower the probability of atomic diffusion)
 ACTIVATION ENERGY FOR
DIFFUSION
Initial state Intermediate state Final state

Energy Activation energy

• Also called energy barrier for diffusion

 DIFFUSION AND TEMPERATURE
pre-exponential [m 2 /s] (see Table 5.2, Callister 6e )
activation energy
 Q  [J/mol],[eV/mol]
diffusivity D  Do exp  d  (see Table 5.2, Callister 6e )
 RT 
gas constant [8.31J/mol-K]
• Experimental Data: NOTE: log(D) = log(D0) – Qd/(RT)
1500
1000

600

3 00
T(C)
10 -8 C in D has exp. dependence on T
-
2
D (m /s) Fe Ci
n
Recall: Vacancy does also!
-Fe Dinterstitial >> D substitutional
10 -14 C in -Fe Cu in Cu
Zn

C in -Fe Al in Al
Fe

in Cun -

Al

Fe in -Fe
Cu in Fe
F
in

in
ei e

Fe in -Fe
Al
 -F

Zn in Cu
Cu

10 -20
0.5 1.0 1.5 2.0 1000K/T
Adapted from Fig. 5.7, Callister 6e. (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.)
 SUMMARY:
STRUCTURE & DIFFUSION
Diffusion FASTER for... Diffusion SLOWER for...

• open crystal structures • close-packed structures

• lower melting T materials • higher melting T materials

• materials w/secondary • materials w/covalent

bonding bonding

• smaller diffusing atoms • larger diffusing atoms

• lower density materials • higher density materials