Four Elements of Materials Science

OVERVIEW OF THE COURSE

Processing Structure Properties Performance

Chemical Synthesis Atomic/Molecular 1St. Mechanical 7 Cost

Melting Bond structure 2 Electrical Reliability
Casting Crystal Structure3 Optical 8 Efficiency
Annealing Defect Structures 4 Thermal Service Life
Sintering Microstructure 6 Magnetic ...
Diffusion 5 Energy Band Structure
....

Chapter 5-
 Rate of Processes

Chemical Kinetics Transport Phenomenon

Matter Energy

Mass Transport Heat Transfer

DIFFUSSION

Chapter 5-
 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
Lithium Ion Battery Carburization

Semiconductor
Aluminium does not rust!!

Chapter 5-
 Diffusion
Diffusion - Mass transport by atomic motion

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.

to x (mm)
t1
t2
t3
time (s)
xo x1 x2 x3

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
• What is the energy source ?
– HEAT !
• What else ?
– Concentration gradient !
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.

Cu Ni
100% 100%

0 0
Concentration Profiles 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
C
A D
A
D
B
B

Chapter 5- 4
 Diffusion Mechanisms

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

increasing elapsed time

Chapter 5- 5
 Diffusion Mechanisms
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-
Chapter 5-
 PROCESSING USING DIFFUSION
• 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-
 Diffusion
• How do we quantify the amount or rate of diffusion?

moles (or mass) diffusing mol kg

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

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

M 1 dM M=
J  mass J slope
At A dt diffused
time
Chapter 5-
 MODELING DIFFUSION: FLUX
RATE OF MATERIAL TRANSPORT
• Diffusion Flux: Material
1 dM  kg  atoms 
J   or  
A dt 2 2
m s   m s 
• Directional Quantity (anisotropy?) 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
Chapter 5-
Diffusion is a time-dependent process !
 CONCENTRATION PROFILES & FLUX
• Concentration Profile, C(x): [kg/m3]
Cu flux Ni flux

Concentration Concentration Adapted from

of Cu [kg/m 3 ] of Ni [kg/m 3 ]
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!

Concentration gradient is the DRIVING FORCE !
Chapter 5- 11
Concentration Gradient

Chapter 5-
 EX: STEADY STATE DIFFUSION
• Steel plate at 3
kg/m
700º C = 1. 2 3
C1 k g/m
. 8
=0
Carbon C2 Steady State =
rich straight line! Adapted from
gas Carbon
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 9 kg
J  D  2 .4  10
the deficient side? x2  x 1 m 2s

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
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

-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

Chapter 5 -
 Temperature Effect !

The diffusion depends on temperature because;

a- # of vacancies in the vicinity
b- thermally activated successful jumps

Chapter 5 -
Effect of Temperature

 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]

interstitial
Chapter 5 -
 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]

The diffusion depends on temperature because;

a- # of vacancies in the vicinity
b- thermally activated successful jumps Chapter 5 -
 Diffusion and Temperature
D has exponential dependence on T
1500

1000

600

300
T(C)
10-8
C

D (m2/s)
in

Ci
n Dinterstitial >> Dsubstitutional
-

-Fe
Fe Fe i

C in -Fe Al in Al
Fe

10 -14
C in -Fe Fe in -Fe
n
i

-

Al
n

Fe in -Fe
Fe

in
-Fe

Al

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.
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:
1500
1000

600

300
T(C)
10 -8 C in D has exp. dependence on T
- Recall: Vacancy does also!
2
D (m /s) Fe Ci
n
-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., Chapter 5 - 19
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1 Qd  1 
lnD2  lnD0    and lnD1  lnD0   
R  T2  R  T1 
D2 Qd  1 1 
 lnD2  lnD1  ln    
D1 R  T2 T1 
Chapter 5 -
 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

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-
 Self-Diffusion

The activation energy for self-diffusion increases as the

melting point of the metal increases.
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-
 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-
 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  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)

y 2
 e dy
 0
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  x 
• Solution: use Eqn. 5.5  1  erf  
Cs  Co  2 Dt 

Chapter 5 -
 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

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 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 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 2.3 x10 5 m2 /s  ln 2.6 x10 11 m2 /s)

T = 1300 K = 1027°C

Chapter 5 -
 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,
t1 Callister 6e.

C o to
position, x
  x 
• General solution: C(x, t ) C o  
1 erf  
2 Dt 
Cs  Co
C (x, t) = concentration at “ Gaussian error
any time and position ! function"
Chapter 5- 15
 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:
J (right)  J (left) dC
  dC J  D or
dx dt dx
dJ  dC dJ  d2 C (if D does
 D not vary
dx dt dx dx 2 with x)

equate
• Governing Eqn.:
dC d 2C
=D 2
dt dx Chapter 5- 14
 DIFFUSION DEMO: ANALYSIS
• The experiment: we recorded 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  = (constant here)
Cs  Co 2 Dt 
 i 

• Diffusion depth given by:

x i  Dt i
Chapter 5- 17
 Example 5.3
• Copper diffuses into a bar of aluminum.
• 10 hours at 600C gives desired C(x).
• How many hours would it take to get the same C(x)
if we processed at 500C?
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
Chapter 5- 16
Size Impact on Diffusion

Smaller atoms diffuse faster!

Chapter 5-
 Important
• Temperature - diffusion rate increases with
increasing temperature (WHY ?)
• Diffusion mechanism – interstitials diffuse faster
(WHY ?)
• 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 (WHY ?)

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 WHY ? • anions

• lower density materials • higher density materials

Chapter 5- 20
Chapter 5-
Chapter 5-