CHAPTER 6: DIFFUSION IN SOLIDS

Diffusion- Steady and Non-Steady State

Gear from case-hardened

steel (C diffusion)

Diffusion - Mass transport by atomic motion

ISSUES TO ADDRESS...
How does diffusion occur?

Mechanisms
Gases & Liquids random (Brownian) motion
Solids vacancy diffusion or interstitial diffusion

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?

MatSE 280: Introduction to Engineering Materials

MatSE 280: Introduction to Engineering Materials

D.D. Johnson 2004, 2006-08

Simple Diffusion

D.D. Johnson 2004, 2006-08

Inter-diffusion
Interdiffusion: In alloys, atoms tend to migrate
from regions of large concentration.

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.

This is a diffusion couple.

After some time

Initially
Adapted from
Figs. 6.1 - 2,
Callister 6e.

100%
0
Concentration Profiles
MatSE 280: Introduction to Engineering Materials

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MatSE 280: Introduction to Engineering Materials

D.D. Johnson 2004, 2006-08

Substitution-diffusion:vacancies and interstitials

Self-diffusion

applies to substitutional impurities

atoms exchange with vacancies
rate depends on (1) number of vacancies;
(2) activation energy to exchange.

Self-diffusion: In an elemental solid, atoms also migrate.

Label some atoms

After some time

C
A
D

Number (or concentration*)

of Vacancies at T
E

n k T
ci = i =e B
N
k BT gives eV
* see web handout for derivation.

E is an activation energy
for a particular process
(in J/mol, cal/mol, eV/atom).

MatSE 280: Introduction to Engineering Materials

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Substitution-diffusion

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Inter-diffusion across Interfaces

Vacancy Diffusion:
applies to substitutional impurities
atoms exchange with vacancies
rate depends on (1) number of vacancies;
(2) activation energy to exchange.

Rate of substitutional
diffusion depends on:
- vacancy concentration
- frequency of jumping.

(Courtesy P.M. Anderson)

increasing elapsed time

MatSE 280: Introduction to Engineering Materials

D.D. Johnson 2004, 2006-08

Why should interstitial diffusion be faster than by vacancy mode of diffusion?

MatSE 280: Introduction to Engineering Materials

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Diffusion Mechanisms

Processing using Diffusion

Interstitial diffusion smaller atoms diffuse between atoms.

Case Hardening:
-Diffuse carbon atoms into the
host iron atoms at the surface.
-Example of interstitial diffusion
is a case hardened gear.

Fig. 6.0, Callister 6e.

(courtesy of Surface
Div., Midland-Ross.)

Result: The "Case" is

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

More rapid than vacancy diffusion

MatSE 280: Introduction to Engineering Materials

MatSE 280: Introduction to Engineering Materials

D.D. Johnson 2004, 2006-08

Modeling rate of diffusion: flux

Processing using Diffusion

Flux:

Doping Silicon with P for n-type semiconductors:

Process:
1. Deposit P rich
layers on surface.

Directional Quantity

silicon

Flux can be measured for:

Fig. 18.0,
Callister 6e.

2. Heat it.
3. Result: Doped
semiconductor
regions.

- vacancies
- host (A) atoms
- impurity (B) atoms
A = Area of flow

Empirically determined:
Make thin membrane of known surface area
Impose concentration gradient
Measure how fast atoms or molecules diffuse
through the membrane

silicon
MatSE 280: Introduction to Engineering Materials

D.D. Johnson 2004, 2006-08

D.D. Johnson 2004, 2006-08

MatSE 280: Introduction to Engineering Materials

diffused
mass
M

J slope
time

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Steady-state Diffusion: J ~ gradient of c

Steady-State Diffusion
Steady State: concentration profile not changing with time.

Concentration Profile, C(x): [kg/m 3]

Cu flux Ni flux
Concentration
of Cu [kg/m3]

Adapted from Fig. 6.2(c)

Concentration
of Ni [kg/m3]

Position, x
Fick's First Law: D is a constant!

Apply Fick's First Law:

If Jx)left = Jx)right , then

The steeper the concentration profile, the greater the flux!

MatSE 280: Introduction to Engineering Materials

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

(i.e., slope doesn't vary with position)!
MatSE 280: Introduction to Engineering Materials

D.D. Johnson 2004, 2006-08

Steady-State Diffusion
Rate of diffusion independent of time

C1 C1

x1

C2

x2

D.D. Johnson 2004, 2006-08

Example: Chemical Protection Clothing

dC
dx

Ficks first law of diffusion

C2

if linear

J~

dC
dx
dC
dC

=
dx left dx right
Jx = D

dC
J = D
dx
D diffusion coefficient

dC C C2 C1

=
dx
x
x2 x1

Methylene chloride is a common ingredient of paint removers.

Besides being an irritant, it also may be absorbed through skin.
When using, 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:
D in butyl rubber:
D = 110 x10 -8 cm 2/s
surface concentrations: C1 = 0.44 g/cm 3 C2 = 0.02 g/cm 3
Diffusion distance:
x2 x1 = 0.04 cm
glove
C1
l2

paint
remover

tb =

6D

skin

C2

Jx = -D

C2 - C1
x 2 - x1

= 1.16 x 10-5

g
cm2 s

x1 x2
MatSE 280: Introduction to Engineering Materials

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MatSE 280: Introduction to Engineering Materials

D.D. Johnson 2004, 2006-08

Example: Diffusion of radioactive atoms

Example: C Diffusion in steel plate

Steel plate at 700 0C with geometry shown:
Adapted from Fig.
5.4, Callister 6e.

700 C
Knowns:
C1= 1.2 kg/m 3 at 5mm
(5 x 103 m) below surface.

Surface of Ni plate at 1000 0C contains

50% Ni63 (radioactive) and 50% Ni (non-radioactive).
4 microns below surface Ni 63 /Ni = 48:52
Lattice constant of Ni at 1000 C is 0.360 nm.
Experiment shows that self-diffusion of Ni is 1.6 x 10 -9 cm 2/sec
What is the flux of Ni 63 atoms through a plane 2 m below surface?

C2 = 0.8 kg/m 3 at 10mm

(1 x 102 m) below surface.

C1 =

(4Ni / cell )(0.5Ni 63 / Ni )

(0.36x 109 m )3 / cell

= 42.87x 1027 Ni 63 / m 3

D = 3 x10 -11 m 2/s at 700 C.

Q: In steady-state, how much carbon transfers

from the rich to the deficient side?

C2 =

(41.15 42.87)x 1027 Ni 63 / m 3

D.D. Johnson 2004, 2006-08

(4 0)x 106 m

= +0.69x 1020 Ni 63 / m 2 s

How many Ni 63 atoms/second through cell?

MatSE 280: Introduction to Engineering Materials

(0.36x 109m )3 / cell

= 41.15x 1027 Ni 63 / m 3

2
= (1.6x 1013
m /sec)

(4Ni / cell )(0.48Ni 63 / Ni )

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J (0.36nm )2 = 9 Ni 63 / s
D.D. Johnson 2004, 2006-08

Where can we use Ficks Law?

Fick's law is commonly used to model transport processes in
foods,
clothing,
biopolymers,
pharmaceuticals,
porous soils,
semiconductor doping process, etc.

Non-Steady-State Diffusion
Concentration profile,
C(x), changes w/ time.

To conserve matter:

Fick's First Law:

Example
The total membrane surface area in the lungs (alveoli)
may be on the order of 100 square meters and have
a thickness of less than a millionth of a meter, so it is
a very effective gas-exchange interface.
CO2 in air has D~16 mm 2/s, and, in water, D~ 0.0016 mm 2/s

MatSE 280: Introduction to Engineering Materials

D.D. Johnson 2004, 2006-08

Governing Eqn.:

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D.D. Johnson 2004, 2006-08

14

Non-Steady-State Diffusion: another look

Non-Steady-State Diffusion: C = c(x,t)

concentration of diffusing species is a function of both time and position

Concentration profile,
C(x), changes w/ time.

Rate of accumulation C(x)

C
dx = J x J x+dx
t
Using Ficks Law:

C
J
J
dx = J x (J x + x dx) = x dx
t
x
x

C
J

C
= x = D

t
x
x
x
c
t

MatSE 280: Introduction to Engineering Materials

D.D. Johnson 2004, 2006-08

c
x

D
14

c
x

at t > 0, C = C S for x = 0 (fixed surface conc.)

C = Co for x =
2

Adapted from Fig. 6.5,

Callister & Rethwisch 3e.

MatSE 280: Introduction to Engineering Materials

D.D. Johnson 2004, 2006-08

Example: Non-Steady-State Diffusion

If after 49.5 h the concentration of carbon is 0.35 wt% at a position 4.0 mm below
the surface, what temperature was treatment done?

C(x,t)
2

B.C. at t = 0, C = Co for 0 x

FCC iron-carbon alloy initially containing 0.20 wt% C is carburized at an elevated

temperature and in an atmosphere that gives a surface C content at 1.0 wt%.

Cu diffuses into a bar of Al. CS

c
Fick's Second "Law": c D

Cs

Ficks
2nd Law

Non-Steady-State Diffusion

Copper diffuses into a bar of aluminum.

Fick's Second "Law"

If D is constant:

c
Fick's Second "Law" c D 2

Solution
C( x, t ) Co 0.35 0.20
x
=
= 1 erf
= 1 erf ( z )
Cs Co
1.0 0.20
2 Dt

Co

Using Table 6.1 find z where erf(z) = 0.8125. Use interpolation.

Solution:

z 0.90
0.8125 0.7970
=
0.95 0.90 0.8209 0.7970
"error function Values calibrated in Table 6.1

erf (z) =
MatSE 280: Introduction to Engineering Materials

z=

x
2 Dt

D=

erf(z)

0.90
z
0.95

0.7970
0.8125
0.8209

x2

4 z 2t
x2
(4 x 103 m)2
1h
D = 2 =
= 2.6 x 1011 m2 /s
2
4z t (4)(0.93) (49.5 h) 3600 s

e y dy

D.D. Johnson 2004, 2006-08

Now solve for D

So, z = 0.93

erf(z) = 0.8125

15

MatSE 280: Introduction to Engineering Materials

D.D. Johnson 2004, 2006-08

Example: Processing
Solution (cont.):

To solve for the temperature at which D

has the above value, we use a rearranged
form of Equation (6.9a);
D=D0 exp(-Qd/RT)

Qd
T =
R(lnDo lnD )

Copper diffuses into a bar of aluminum.

10 hours processed at 600 C gives desired C(x).
How many hours needed to get the same C(x) at 500 C?
Key point 1: C(x,t500C) = C(x,t600C).
Key point 2: Both cases have the same C o and Cs.

From Table 6.2, for diffusion of C in FCC Fe

Do = 2.3 x 10 -5 m2 /s Qd = 148,000 J/mol

D = 2.6 x 1011 m2 /s

Result: Dt should be held constant.

C(x,t) Co

T=

Cs Co

148,000 J/mol
(8.314 J/mol-K)(ln 2.3x105 m2 /s ln 2.6x1011 m2 /s)

Note
D(T) are T dependent!
Values of D are provided.

Answer:

T = 1300 K = 1027C

MatSE 280: Introduction to Engineering Materials

x
= 1 erf

2 Dt

MatSE 280: Introduction to Engineering Materials

D.D. Johnson 2004, 2006-08

Diffusion Analysis

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16

Data from Diffusion Analysis

The experiment: we recorded combinations of

t and x that kept C constant.

x
C(x i,t i ) Co
i
= 1 erf

Cs Co
2 Dt i

= (constant here)

Experimental result: x ~ t0.58

Theory predicts x ~ t0.50 from
Close agreement.

Diffusion depth given by:

MatSE 280: Introduction to Engineering Materials

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17

MatSE 280: Introduction to Engineering Materials

D.D. Johnson 2004, 2006-08

Diffusion and Temperature

Diffusion and Temperature

in
-

10-20

T = absolute temperature [K]

Q

1
Note: ln D = ln D0 d
R T

Q 1
log D = log D d
0 2.3R T

MatSE 280: Introduction to Engineering Materials

0.5

300

1.0

MatSE 280: Introduction to Engineering Materials

D.D. Johnson 2004, 2006-08

Ci

z-axis

T(C)

n
-Fe

in
Al

1.0

1.5

1000 K/T

FCC Fe has both higher activation energy Q and D 0 (holes larger in FCC).
BCC and FCC phase exist over limited range of T (at varying %C).
Hence, at same T, BCC diffuses faster due to lower Q.
Cannot always have the phase that you want at the %C and T you want!
which is why this is all important.
MatSE 280: Introduction to Engineering Materials

D.D. Johnson 2004, 2006-08

Al

Fe
Fe e i n
e
F
-F
in
Fe

10-20

300

600

10-14

0.5

1000

1500

D (m 2/s)

in

D0=6.2x10 7(m 2/2)

Q=0.83 eV/atom
T = 900 C D=1.7x10 10(m 2/2)

bcc-Fe:

10-8

1000 K/T

Connecting Holes, Diffusion, and Stress

Is C in fcc Fe diffusing faster than C in bcc Fe?

D0=2.3x10 5(m 2/2)

Q=1.53 eV/atom
T = 900 C D=5.9x10 12(m 2/2)

1.5

Cu in Cu
Al in Al
Fe in -Fe
Fe in -Fe
Zn in Cu

Adapted from Fig. 6.7, Callister & Rethwisch 3e.

(Data for Fig. 6.7 from E.A. Brandes and G.B. Brook (Ed.) Smithells Metals
Reference Book, 7th ed., Butterworth-Heinemann, Oxford, 1992.)

Example: Comparing Diffuse in Fe

(Table 6.2)
fcc-Fe:

C in -Fe
C in -Fe

Al

R = gas constant [8.314 J/mol-K]

Dinterstitial >> Dsubstitutional

in

Qd = activation energy [J/mol or eV/atom]

n
-Fe
Al

10-14

(see Table 6.2)

Ci

Fe
n
Fe Fe i
e
-F
in
Fe

Do = pre-exponential

D (m 2/s)

[m 2/s]

[m 2/s]

T(C)

D = diffusion coefficient

10-8

600

Adapted from Fig. 6.7,

Qd

D = Do exp
RT

1000

Experimental Data:
1500

Diffusivity increases with T exponentially (so does Vacancy conc.).

D.D. Johnson 2004, 2006-08

Red
octahedral fcc
Green + Red octahedral bcc
FCC represented as a BCT cell, with relevant holes.

MatSE 280: Introduction to Engineering Materials

D.D. Johnson 2004, 2006-08

Other Types of Diffusion (Beside Atomic)

Inter-diffusion (diffusion couples)

Flux is general concept: e.g. charges, phonons,

Cu flux Ni flux

Charge Flux j = 1 dq = 1 d(Ne)

q
A dt

jq =

e = electric chg.
N = net # e- cross A

dt

dV
j =
dx

Defining conductivity
(a material property)
Ohms Law

Solution: Ficks 2nd Law

x
Vx Vs
= erf

V0 Vs
2 t

I 1V
V
=
=
A AR
l

Heat Flux
(by phonons)

Q=

1 dH 1 d(N )
=
A dt
A dt

Defining thermal conductivity

(a material property)
Or w/ Thermal Diffusivity:

h=

Q =

cV

dT
dx

N = # of phonons with
avg. energy
Solution: Ficks 2nd Law

C1

Concentration
of Cu
[kg/m3]
Concentration

Cu flux Ni flux

of Cu [kg/m3]

C2

Concentration
of Ni [kg/m3]
Concentration
of Ni [kg/m3]

C0

Position, x
Position, x

C1x C0
x
= erf
2 Dt
C1 C0

Assuming DA = DB:
For C2x

C0 = (C1+C2)/2

Curve is symmetric about C0, erf ( z ) = erf ( z )

x
Tx Ts
= erf

T0 Ts
2 ht

Q = cV T

MatSE 280: Introduction to Engineering Materials

interface

D.D. Johnson 2004, 2006-08

MatSE 280: Introduction to Engineering Materials

D.D. Johnson 2004, 2006-08

Kirkendall Effect: What is DA > DB?

Diffusion in Compounds: Ionic Conductors

Kirkendall studied Mo markers in Cu-brass (i.e., fcc Cu 70Zn30).

Symmetry is lost: Zn atoms move more readily in one direction
(to the right) than Cu atoms move in the other (to the left).

Unlike diffusion in metals, diffusion in compounds involves

second-neighbor migration.
Since the activation energies are high, the Ds are low unless
vacancies are present from non-stoichiometric ratios of atoms.

Cu70 Zn 30

Cu

concentration

Cu

t=0

Zn
Mo wire markers

After diffusion

When diffusion is asymmetric, interface moves away markers,

i.e., there is a net flow of atoms to the right past the markers.
Analyzing movement of markers determines DZn and DCu.
Kirkendall effect driven by vacancies, effective for T > 0.5 Tmelt.
MatSE 280: Introduction to Engineering Materials

D.D. Johnson 2004, 2006-08

e.g., NiO
There are
Schottky defects

Ni

Ni

Ni

Ni

Ni

Ni2+ O2 Ni

Ni2+ O2

Ni

O2

Ni

Ni2+

Ni

Ni

Ni

Ni

Ni

The two vacancies cannot accept neighbors because they have

wrong charge, and ion diffusion needs 2nd neighbors with high
barriers (activation energies).
MatSE 280: Introduction to Engineering Materials

D.D. Johnson 2004, 2006-08

Diffusion in Compounds: Ionic Conductors

Ds in an ionic compound are seldom comparable because of size, change
and/or structural differences.
Two sources of conduction: ion diffusion and via e- hopping from ions of variable
valency, e.g., Fe 2+ to Fe 3+, in applied electric field.

e.g., ionic
In NaCl at 1000 K, DNa+~ 5D Cl ,whereas at 825 K DNa+ ~ 50D Cl!
This is primarily due to size rNa+ = 1 A vs r Cl=1.8 A.

e.g., oxides
In uranium oxide, U4+(O2) 2, at 1000 K (extrapolated), D O ~ 10 7 DU.
This is mostly due to charge, i.e. more energy to activate 4+ U ion.
Also, UO is not stoichiometric, having U 3+ ions to give UO 2-x, so that the
anion vacancies significantly increase O 2- mobility.

e.g., solid-solutions of oxides (leads to defects, e.g., vacancies)

If Fe1-xO (x=2.5-4% at 1500 K, 3Fe 2+ -> 2Fe3+ + vac.) is dissolved in MgO
under reducing conditions, then Mg2+ diffusion increases.
If MgF2 is dissolved in LiF (2Li+ -> Mg 2+ + vac.), then Li + diffusion increases.
All due to additional vacancies.

MatSE 280: Introduction to Engineering Materials

D.D. Johnson 2004, 2006-08

Example: solid-oxide fuel cell (SOFC)

Ionic Conduction: related to fuel cells

Molten salts and aqueous electrolytes conduct charge when placed in
electric field, +q and q move in opposite directions.
The same occurs in solids although at much slower rate.
Each ion has charge of Ze (e = 1.6 x 10 19 amp*sec) ,
so ion movement induces ionic conduction
Conductivity
= n Ze is related to mobility, , which is
related to D via the Einstein equations: = ZeD / k BT
Hence
nZ 2 e2
nZ 2 e2
ionic =
D=
Do eQ / RT
k BT
k BT
nZ 2 e2
Q
log10 ionic ~ ln
Do
k BT
2.3RT

So, electrical conduction can be used

determine diffusion data in ionic solids.

e.g., What conductivity results by Ca 2+ diffusion in CaO at 2000 K?

CaO has NaCl structure with a= 4.81 A, with D(2000 K)~10 -14m2/s, and Z=2.

nCa2+ =

4
cell
= 3.59x10 28 / m 3
cell (4.81x10 10 m)3

MatSE 280: Introduction to Engineering Materials

nZ 2 e2
1.3x10 5
D~
k BT
ohm cm
D.D. Johnson 2004, 2006-08

Ceramic Compounds: Al2O3

SOFC is made up of four layers, three of

which are ceramics (hence the name).
A single cell consisting of these four layers
stacked together is only a few mm thick.
Need to stack many, many together to
have larger DC current.
Overall: H 2 + 1/2O 2 H2O

Holes for diffusion

H2 2H++2e
O2 + 2H+ + 2e H2O
Image: http://www.ip3.unipg.it/FuelCells/en/htfc.asp

S. Hailes SOFC (2004 best): Thin-film of Sm-doped Ceria electrolyte (CeO 2, i.e. Sm xCe1-x O 2-x/2)
and BSCF cathode (Perovskite Ba0.5 Sr0.5 Co0.8 Fe0.2 O3-d ) show high power densities over 1
W/cm2 at 600 C with humidified H 2 as the fuel and air at the cathode.
MatSE 280: Introduction to Engineering Materials

D.D. Johnson 2004, 2006-08

Unit cell defined by Al ions: 2 Al + 3 O

MatSE 280: Introduction to Engineering Materials

D.D. Johnson 2004, 2006-08

10

Summary: Structure and Diffusion

Diffusion FASTER for...

Diffusion SLOWER for...

open crystal structures

close-packed structures

lower melting T materials

higher melting T materials

materials w/secondary
bonding

materials w/covalent
bonding

smaller diffusing atoms

larger diffusing atoms

cations

anions

lower density materials

higher density materials

MatSE 280: Introduction to Engineering Materials

D.D. Johnson 2004, 2006-08

11