DIFFUSION OF SOLIDS

NILESH PANCHOLI
B.E. ( Mech.), M.E. (Mech.), Ph. D.
Email: nhpancholi@gmail.com
www.nileshpancholi.com
 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?
 Diffusion
Diffusion - Mass transport by atomic motion

Mechanisms
• Gases & Liquids – random motion
• Solids – vacancy diffusion or interstitial diffusion
 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.
 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.
 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 !
 Diffusion
• Interdiffusion: In an alloy, atoms tend to migrate
from regions of high conc. to regions of low conc.
Initially After some time
• Interdiffusion: In an alloy, atoms tend to migrate from
regions of large concentration.
Initially After some time

100%

0
Concentration Profiles
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• Self-diffusion: In an elemental solid, atoms also
migrate.

Label some atoms (use isotopes) After some time

C
A
D
B

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More examples in 3-D !
 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 !
 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 !
 Diffusion Mechanisms (III)
Substitutional Diffusion:
• applies to substitutional impurities
• atoms exchange with vacancies
• rate depends on:
--number of vacancies
--activation energy to exchange.

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• Case Hardening:
--Diffuse carbon atoms
into the host iron atoms
at the surface.
--Example of interstitial
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.

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 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 l dM
J  M=
At A dt mass J  slope
diffused
time
 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
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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/m 3] of Ni [kg/m 3]
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 FORCE !11
Concentration Gradient
 STEADY STATE DIFFUSION
• Steady State: the concentration profile doesn't
change with time.

dC
• Apply Fick's First Law: J x  D
dx Why is the
 dC   dC  minus sign ?
• 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)!
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 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?

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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
 Example (cont).
• Solution – assuming linear conc. gradient
glove
C1
paint tb 
2
skin
6D
remover
C2 Data: D = 110 x 10-8 cm2/s
x1 x2 C1 = 0.44 g/cm3
C2 = 0.02 g/cm3
dC C  C1
J -D  D 2 x2 – x1 = 0.04 cm
dx x 2  x1

-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
 Temperature Dependency !

What is the probability to find

a vacancy at a nearest site ?

Atom has to break bonds and

“squeeze” thru => activation
energy, Em ≈ 1 eV .
 Diffusion and Temperature
• Diffusion coefficient increases with increasing T.

 Qd 
D  Do exp 
 R T 

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]
 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
 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

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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
ln D2  ln D0    and ln D1  ln D0   
R  T2  R  T1 
D Q  1 1
 ln D2  ln D1  ln 2   d   
D1 R  T2 T1 
 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

 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 !
 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 = ∞
 NON STEADY STATE
DIFFUSION
• Concentration profile,
C(x), changes
w/ time.

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

• Governing Eqn.:

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 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 = 
 Solution:
C  x , t   Co  x 
 1  erf  
Cs  Co  2 Dt 
C(x,t) = Conc. at point x at
time t CS
erf (z) = error function

2 z y 2 C(x,t)

  0
e dy
Co
erf(z) values are given in
Table 6.2
 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 )  C o  x 
 1  erf  
Cs  Co  2 Dt 
• Solution:
 Solution  Co
C( x , t ) (cont.):  x 
 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
 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 4z 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
 
 Solution (cont.):
Qd
from Table 5.2, for T
diffusion of C in FCC R(ln Do  ln D )
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
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
 Example (cont).
• Solution – assuming linear conc. gradient
glove
C1
2
paint skin tbEquation 22.24 Given in web chapters !
remover 6D
C2
D = 110 x 10-8 cm2/s
x1 x2
  x 2  x1  0. 04 c m

(0.04 cm) 2
tb   240 s  4 min
-8 2
(6)(110 x 10 cm /s)

Time required for breakthrough ca. 4 min

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

 
C(x i , t i )  Co x
 1 erf  i 
 = (constant here)
Cs  Co  2 Dt i 

• Diffusion depth given by:

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DATA FROM DIFFUSION DEMO

• Experimental result: x ~ t0.58

• Theory predicts x ~ t0.50
• Reasonable agreement!
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• 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.
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Size Impact on Diffusion

Smaller atoms diffuse faster

 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 ?)
 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

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