Advanced Materials Science

Lecture 3: Diffusion
 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
 DIFFUSION IN SOLIDS

Topics to be discussed...
• Atomic mechanisms of diffusion

• Mathematics of diffusion

• Influence of temperature and diffusing species on

Diffusion rate
 DIFFUSION
• Phenomenon of material transport species (particles, atoms, ions,
molecules) through a medium (gas, liquid, solid) from a region of high to
low concentration without bulk motion.

• Diffusion in crystalline solids (solid-state diffusion) takes place only by

defects; in a perfect structure, there can be no diffusion

• Many essential processes take place by solid-state diffusion: Reactions,

synthesis, mixing, doping, permeation, ionic conduction, sintering, grain
growth, creep, corrosion.

• These comprise the synthesis, fabrication, utilization, and breakdown of

materials
 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

 Interstitial Diffusion Mechanism

• Diffusion involves atoms that migrate from an interstitial

position to an empty interstice.
• Generally faster than vacancy diffusion because bonding
of interstitials to the surrounding atoms is normally weaker
(atoms are more mobile) and there are many more
interstitial sites than vacancy sites.
• Requires small impurity atoms (e.g. C, H, O) to fit into
interstices in host.
 ACTIVATION ENERGY FOR DIFFUSION
Initial state Intermediate state Final state

Energy Activation energy

• The energy required to produce the movement of 1 mole of atoms by diffusion.

• Also called energy barrier for diffusion
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.
 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/m3] of Ni [kg/m3]
from Fig.
5.2(c),
Callister 6e.

Position, x
• Fick's First Law:
flux in x-dir. Diffusion coefficient [m2/s]
[kg/m2-s] dC
J x  D concentration
dx gradient [kg/m4]
• 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.
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)!
Example Problem 1
 EX: STEADY STATE DIFFUSION
m3
/
. 2kg
• Steel plate at =
1
g
3
/m
C1 . 8k
700ºC with =
0
C2
geometry Carbon Steady State =
rich straight line! Adapted
shown:
gas Carbon
from Fig. 5.4,
Callister 6e.
deficient
gas
D=3x10-11m2/s
0 x1 x2

10
• Q: How much 5m

m
m

m
carbon transfers
from the rich to C2  C1  9 kg
J  D 2.4 10
the deficient side? x2  x1 m2s
 Example Problem 2

• A sheet of BCC iron 2 mm thick was exposed to a

carburizing gas atmosphere on one side and a
decarburizing atmosphere on the other side at 675°C.
After having reached steady state, the iron was quickly
cooled to room temperature. The carbon concentrations
at the two surfaces of the sheet were determined to be
0.012 and 0.00758 wt%. Compute the diffusion
coefficient if the diffusion flux is 1.40x10-8 kg/m2-s.
• Hint: convert the concentrations from weight percent to
kilograms of carbon per cubic meter of iron.
 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) dC dC
dC
 dC
(left)  
JJ   D
D or
or
dx
dx dt
dt dx
dx
dJ dC dJ dd22CC (if
(ifDDdoes
does
dJ  dC dJ   D
D not
notvary
vary
dt dx dx22 with x)
dx
dx dt dx dx with x)

equate
equate
• Governing Eqn.: 2
dC d C 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-existingconc., C o of copper atoms
C(x,t)
Cs

t3 Adapted from
t2 Fig. 5.5,
t1 Callister 6e.

C o to
position, x
• Boundary conditions:
For t = 0, C= Cs at x=0
dC d2C
C = C0 at x > 0 =D 2
For t > 0, C = Cs at x = 0 dt dx
C = C0 at x = ∞
 EX: NON STEADY STATE DIFFUSION
• Copper diffuses into a bar of aluminum.
Surface conc.,
C s of Cu atoms bar
pre-existingconc., C o of copper atoms
C(x,t)
Cs

t3 Adapted from
t2 Fig. 5.5,
t1 Callister 6e.

C o to
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
Example Problem
 Example Problem 2

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   (Dt)500ºC =(Dt)600ºC
Cs  Co  2Dt 

5.3x10-13m2/s 10hrs
(Dt)600 Note: values
• Answer: t 500   110hr of D are
-
D500 provided here.
14
4.8x10 m /s2
 DIFFUSION AND TEMPERATURE
• Diffusivity increases with T.
pre-exponential [m2/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 (the larger this energy,
smaller the diffusivity and lower the probability of atomic
diffusion)
 Diffusion of different species

Smaller atoms diffuse more readily

Diffusion faster in open lattices or in open directions

 ACTIVATION ENERGY FOR
DIFFUSION
Initial state Intermediate state Final state

Energy Activation energy

• Also called energy barrier for diffusion

 DIFFUSION AND TEMPERATURE
pre-exponential [m2/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

300
T(C)
10-8 C i D has exp. dependence on T
n
-
2
D (m /s) Fe Ci Recall: Vacancy does also!
n
-Fe Dinterstitial>> Dsubstitutional
10-14 C in -Fe Cu in Cu
Zn Fe i e

C in -Fe Al in Al
Fe

in Cun -

Al

Fe in -Fe
Cu in Fe

in
i n

Fe in -Fe
Al
-F

Zn in Cu
10-20
Cu

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.)
 Diffusion – Temperature Dependence
dC Diffusion coefficient is the measure of
J  D
dx mobility of diffusing species.
Qd   D exp   Qd
D  D0 exp 
   

 RT  0
 kT 

D0 – temperature-independent (m2/s)
Qd – the activation energy (J/mol or eV/atom)
R – the gas constant (8.31 J/mol-K)
or
kB - Boltzman constant ( 8.6210-5 eV/atom-K)
T – absolute temperature (K)
Qd  1  Qd  1 
ln D ln D0    or log D log D0   
R T  2.3R  T 

Arrhenius Plots
(lnD) vs. (1/T) or (logD) vs. (1/T)
Diffusion – Temperature Dependence (II)

Graph of log D vs. 1/T has slope of –Qd/2.3R,

intercept of ln Do
Qd  1 
log D log D 0   
2.3R  T 

 log D1  log D 2 
Q d  2.3R  
 1 T1  1 T2 
 Diffusion – Temperature Dependence (III)

Arrhenius plot:
Diffusivity for metallic systems
 Diffusion: Role of the microstructure (I)

Diffusion coefficients depends on diffusion path

Grain boundaries and surfaces less restrictive
Example Problem
 Factors that Influence Diffusion
 Temperature - diffusion rate increases very rapidly
with increasing temperature

 Diffusion mechanism - interstitial is usually faster

than vacancy

 Diffusing and host species - Do, Qd is different for

every solute, solvent pair

 Microstructure - diffusion faster in polycrystalline vs.

single crystal materials because of the rapid diffusion
along grain boundaries and dislocation cores.
 Diffusion and Materials Processing

 Sintering - A high-temperature treatment used to join

small particles.
 Powder metallurgy - A method for producing monolithic
metallic parts.
 Dielectric resonators -Hockey puck-like pieces of
ceramics such as barium magnesium tantalate (BMT)
or barium zinc tantalate (BZN).
 Grain growth - Movement of grain boundaries by
diffusion in order to reduce the amount of grain
boundary area.
 Diffusion bonding - A joining technique in which two
surfaces are pressed together at high pressures and
temperatures.
 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