CHAPTER 5:

DIFFUSION IN SOLIDS

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?

Chapter 5- 1
 Diffusion

Diffusion - Mass transport by atomic motion,

the movement of atoms from lattice site to
lattice site
atoms diffuse from high to low concentrations
self diffusion – atoms change positions within
pure material
Mechanisms
• Gases & Liquids – random (Brownian) motion
• Solids – vacancy diffusion or interstitial
diffusion
Chapter 5-
 Why Study Diffusion ?

• Diffusion plays a crucial role in…

– Alloying metals => bronze, silver, gold
– Strengthening and heat treatment processes
• Hardening the surfaces of steel
– High temperature mechanical behavior
– Phase transformations
• Mass transport during FCC to BCC
– Environmental degradation
• Corrosion, etc.

Chapter 5-
 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.
• Compare the results with theory.

Chapter 5- 2
How do atoms move in Solids ?
Why do atoms move in Solids ?
• Diffusion, simply, is atoms moving from one lattice
site to another in a stepwise manner
– Transport of material by moving atoms
• Two conditions are to be met:
– An empty adjacent site
– Enough energy to break bonds and cause lattice distortions
during displacement – can be vibrational energy
• What is the energy source ?
– HEAT !
• What else ?
– Concentration gradient !
Chapter 5-
 Diffusion
• Interdiffusion: In an alloy, atoms tend to migrate
from regions of high conc. to regions of low conc.
Initially After some time

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

Chapter 5-
 DIFFUSION: THE PHENOMENA (1)
• Interdiffusion: In an alloy, atoms tend to migrate from
regions of large concentration.
Initially After some time

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

100%

0
Concentration Profiles
Chapter 5- 3
 DIFFUSION: THE PHENOMENA (2)
• Self-diffusion: In an elemental solid, atoms also
migrate.

Label some atoms (use isotopes) After some time

C
A
D
B

Chapter 5- 4
More examples in 3-D !

Chapter 5-
 Diffusion Mechanisms (I)

Energy is needed to generate a vacancy, break bonds, cause

distortions. Provided by HEAT , kT !
Atom moves in the opposite direction of the vacancy !
Chapter 5-
 Diffusion Mechanisms (II)
Interstitial Diffusion

Much faster than vacancy diffusion, why ? Smaller atoms like B,

C, H, O. Weaker interaction with the larger atoms. More vacant
sites, no need to create a vacancy !
Chapter 5-
 Diffusion Mechanisms (III)
Substitutional Diffusion:
• applies to substitutional impurities
• atoms exchange with vacancies
• rate depends on:
--number of vacancies
--activation energy to exchange.

Chapter 5- 5
PROCESSING USING DIFFUSION (1)
• Case Hardening:
--Diffuse carbon atoms Fig. 5.0,
Callister 6e.
into the host iron atoms (Fig. 5.0 is
courtesy of
at the surface. Surface
Division,
--Example of interstitial Midland-
Ross.)
diffusion is a case
hardened gear.

• Result: The "Case" is

--hard to deform: C atoms
"lock" planes from shearing.
--hard to crack: C atoms put
the surface in compression.

Chapter 5- 8
 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 chapter-opening photograph,
Chapter 18, Callister 7e. Chapter 5-
 Steady State Diffusion
• When diffusion is a function of time
• How do we quantify the amount or rate of diffusion?
moles (or mass) diffusing mol kg
J º Flux º = or
(surface area)(time ) 2
cm s m2s
• Surface area = A, time = t
• Measured empirically
– Make thin film (membrane) of known surface area
– Impose concentration gradient
– Measure how fast atoms or molecules diffuse through the
membrane
– When J is constant then have steady state diffusion

M l dM M=
J= = mass J  slope
At A dt diffused
time
Chapter 5-
 MODELING DIFFUSION: FLUX
RATE OF MATERIAL TRANSPORT
• Diffusion Material
Flux:

• Directional Quantity (anisotropy

?)

• Flux can be measured for:

--vacancies
--host (A) atoms
--impurity (B) atoms
Chapter 5- 10
Diffusion is a time-dependent process !
 CONCENTRATION PROFILES & FLUX
• Concentration Profile, C(x): [kg/m3]
Cu flux Ni flux

Concentration Concentration Adapted

of Cu [kg/m3] of Ni [kg/m3]
from Fig.
5.2(c),
Callister 6e.

Position, x
• Fick's First Law:

• The steeper the concentration profile, the greater the

flux!
Concentration gradient is the DRIVING FORCEChapter
! 5- 11
Concentration Gradient

Chapter 5-
 STEADY STATE DIFFUSION
• Steady State: the concentration profile doesn't
change with time.

• Apply Fick's First Law:

Why is the
minus sign ?
• If Jx)left = Jx)right , then

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

(i.e., slope doesn't vary with position)!
Chapter 5- 12
 EX: STEADY STATE DIFFUSION
• Steel plate at
700º C

Adapted
from Fig.
5.4,
Callister 6e.

• Q: How much
carbon transfers
from the rich to
the deficient side?

Chapter 5- 13
 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

Chapter 5 -
 Example (cont).
• Solution – assuming linear conc. gradient
glove
C1 dC C2 - C1
tb =
2
J =-D @ -D
paint skin
6D dx x2 - x1
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

-8 2 (0.02 g/cm3 - 0.44 g/cm3 ) -5 g

J = - (110 x 10 cm /s) = 1.16 x 10
(0.04 cm) cm2s

Chapter 5 -
Example Problem 7.2.1

Chapter 5 -
 Diffusion and Temperature

• Diffusion coefficient increases with increasing T.

 Qd 
D = Do exp-
 RT 

D = diffusion coefficient [m2/s]

Do = temperature independent pre-exponential [m2/s]
Qd = activation energy [J/mol or eV/atom]
R = gas constant [8.314 J/mol-K or 8.62 x 10-5 eV/atom-K]
T = absolute temperature [K]

Chapter 5 -
 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.)

Chapter 5 -
 DIFFUSION AND TEMPERATURE
• Diffusivity increases with T.

• Experimental Data:

D has exp. dependence on T

Recall: Vacancy does also!
Dinterstitial >> Dsubstitutional
C in a-Fe Cu in Cu
C in g-Fe Al in Al
Fe in a-Fe
Fe in g-Fe
Zn in Cu

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 Chapter 5 - 19
Book, 7th ed., Butterworth-Heinemann, Oxford, 1992.)
Example: At 300ºC the diffusion coefficient and
activation energy for Cu in Si are
D(300ºC) = 7.8 x 10-11 m2/s  Qd 
Qd = 41.5 kJ/mol D = Do exp- ÷
 RT 
What is the diffusion coefficient at 350ºC?

D transform ln D
data

Temp = T 1/T

Qd æ1ö Qd æ1ö
lnD2 = lnD0 - çç ÷÷ and lnD1 = lnD0 - çç ÷÷
R è T2 ø R è T1 ø
D2 Qd æ 1 1ö
\ lnD2 - lnD1 = ln =- çç - ÷÷
D1 R è T2 T1 ø
Chapter 5 -
 Example (cont.)
é Qd æ 1 1 öù
D2 = D1 expê- çç - ÷÷ú
ë R è T2 T1 øû

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

Chapter 5 -
 Fick’s Second Law ; Non-steady
state Diffusion
• In most practical cases, J (flux) and dC/dx
(concentration gradient) change with time (t).
– Net accumulation or depletion of species diffusing
• How do we express a time dependent concentration?

Concentration at a point x ? Flux, J, changes

Changing with time at any point x !
Chapter 5-
 Assumptions for Solving Fick’s
Second Law
• Assume that have a semi infinite solid (no
diffusion atoms reach end of the solid during time
of diffusion) and surface concentration is constant
– Diffusing solute atoms in the solid are uniformly
distributed with a concentration C0 before diffusion
– Value of x at the surface = 0 and increases with
distance into the solid
– Time = 0 before diffusion begins

Chapter 5-
How do we solve this partial differential
equation ?

• Use proper boundary conditions:

– t=0, C = C0, at 0 ≤ x ≤ ∞
– t>0, C = Cs, at x = 0
C = C0, at x = ∞

Chapter 5-
 Fick’s 2nd Law Has the Form

• Cx is the concentration
at depth x after time t
• erf (x/2[Dt]1/2) is the
C( x, t ) - Co æ x ö Gaussian error
= 1 - erf ç ÷ function
Cs - Co è 2 Dt ø

Chapter 5-
Creating a Specific Concentration C1
in an Alloy

• (C1-C0)/(Cs-C0) is equal to a constant

• x/2(Dt)1/2 is equal to a constant
• x2/Dt is equal to a constant

Chapter 5-
 Non-steady State Diffusion
• Copper diffuses into a bar of aluminum.
Surface conc.,
Cs of Cu atoms bar
pre-existing conc., Co of copper atoms

Cs

Adapted from
Fig. 5.5,
Callister 7e.

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 = 
Chapter 5 -
 Solution:
C (x ,t )- Co æ x ö
= 1 - erf ç ÷
Cs - Co è 2 Dt ø

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

time t
erf (z) = error function
2 z -y 2 C(x,t)
=
p ò 0
e dy
Co
erf(z) values are given in
Table 5.1

Chapter 5 -
 Non-steady State Diffusion
• Sample Problem: 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 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 æ x ö
• Solution: use Eqn. 5.5 = 1 - erf ç ÷
Cs - Co è 2 Dt ø

Gaussian error function

Chapter 5 -
 C( x ,t ) - Co æ x ö
Solution (cont.): = 1 - erf ç ÷
Cs - Co è 2 Dt ø

– 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

Chapter 5 -
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 4 z 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
 
Chapter 5 -
 Solution (cont.):
• To solve for the temperature at Qd
T=
which D has above value, we R(lnDo - lnD )
use a rearranged form of
Equation (5.9a);
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

Chapter 5 -
 Table 7.2.1
Values for the error function

Chapter 5 -
 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
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

Chapter 5 -
 Example (cont).
• Solution – assuming linear conc. gradient
glove
2
C1
tb = Equation 22.24
paint skin 6D Given in web chapters !
remover
C2
 = x2 - x1 = 0.04 cm
x1 x2
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

Chapter 5 -
EX: NON STEADY STATE DIFFUSION
• Copper diffuses into a bar of aluminum.

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  x 
o = 1 - erf  ÷
-  2 Dt 
Cs Co
C (x, t) = concentration at “Gaussian error function"
any time and position !
Chapter 5- 15
 NON STEADY STATE DIFFUSION
• Concentration profile,
C(x), changes
w/ time.

• To conserve matter: • Fick's First Law:

• Governing Eqn.:

Chapter 5- 14
Example Problem 7.2.2

Chapter 5-
continued on next slide
Chapter 5-
continued on next slide
Chapter 5-
Example Problem 7.2.3 (continued)

Chapter 5-
 DIFFUSION DEMO: ANALYSIS
• The experiment: we recorded combinations of
t and x that kept C constant.

= (constant here)

• Diffusion depth given by:

Chapter 5- 17
 DATA FROM DIFFUSION DEMO

• Experimental result: x ~ t0.58

• Theory predicts x ~ t0.50
• Reasonable agreement!
Chapter 5- 18
 Example 5.3
• 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?
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.

Note: values
• Answer: of D are
provided here.
Chapter 5- 16
Size Impact on Diffusion

Smaller atoms diffuse faster

Chapter 5-
Fast Tracks for diffusion !
eg. self-diffusion of Ag :
-Areas where lattice is pre-
strained can allow for faster
diffusion of atoms
-Less energy is needed to
distort an already strained
lattice !

Chapter 5-
 Important
• Temperature - diffusion rate increases with
increasing temperature
• Diffusion mechanism – interstitials diffuse faster
• Diffusing and host species - Do, Qd is different for
every solute - solvent pair
• Microstructure - grain boundaries and dislocation
cores provide faster pathways for diffusing species,
hence diffusion is faster in polycrystalline vs.
single crystal materials.

Chapter 5-
Example Problem 7.2.4

continued on next slide

Chapter 5-
Example Problem 7.2.4 (continued)

continued on next slide

Chapter 5-
Example Problem 7.2.4 (continued)

Chapter 5-
 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

• cations • anions

• lower density materials • higher density materials

Chapter 5- 20