Nuclear Materials

REVIEW – DIFFUSION &

SUPERPLASTICITY

Mark Daymond daymond@queensu.ca

Queen’s University
KINGSTON, ONTARIO, CANADA.

point defects in crystals

substitutional interstitial

vacancy self-interstitial solute atoms

atom (SIA)

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 Equilibrium Concentrations:
Point Defects
• Equilibrium concentration varies with temperature!

No. of defects Activation (formation) energy

 Q 
 exp  
Nv
 v
No. of potential
N  k T 
defect sites.
Temperature
Boltzmann's constant

(8.62 x 10 -5 eV/atom-K)
Each lattice site
is a potential
vacancy site
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equilibrium concentration of vacancies

entropy/enthalpy of formation

S v  H v
X ve  exp  exp
k kT

S v
exp 3
k

H v  about 1 eV
4

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 equilibrium concentration of
Self Interstitial Atoms (SIAs)
S i  H i
X ie  exp  exp
k kT

S i
exp 3
k

H i  about 4 eV
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interstitial diffusion
entropy/enthalpy of migration
vibration frequency

S mi  H mi
i  zi i exp  exp
k kT
number of available sites
 H mi
Di  1 i i2  D0i  exp
6 kT

jump distance

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 vacancy diffusion

S mv  H mv
v  zv h exp  exp
k kT

 H mv
Dv  1 v 2  D0 v  exp
6 kT

For an atom to self diffuse it needs a vacancy next to it....
Vacancy Diffusion:
• atoms exchange with vacancies
• applies to both self diffusion and diffusion of substitutional impurity
atoms
• rate depends on:
-- number (actually density) of vacancies
-- activation energy to exchange
-- frequency of jumping

increasing elapsed time

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 Self diffusion
DA  1  2 A vacancy concentration*
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S m  H m
A  zX v exp  exp
k kT
S  H v S  H m
 z exp v  exp  exp m  exp
k kT k kT
 (H v  H m )
DA  D0  exp
kT
H sd  H v  H m
* for an atom to diffuse, it must be adjacent to a vacancy
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Diffusion distance
- diffusion of a single atom or vacancy occurs by
random walk
- the direction of each jump is uncorrelated with
the previous one
- statistically, after n jumps, it moves a distance
n1/2 jumps from its initial position, i.e., after a time
t the distance from the initial position is:

r   t
r  2 .4 Dt
10

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 Importance of point defects for
nuclear materials
• As we will see in later lectures, the diffusion
properties of vacancies and SIA’s are important
because they are generated by irradiation, and, in
general do not have their equilibrium concentrations
• Processes that depend on vacancy concentration are
accelerated by irradiation
• Solute redistribution can occur
• Redistribution of vacancies and SIA’s can cause
macroscopic dimensional changes

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tensile stress-strain curve

True stress = L/A

d
stresses and strains can only
d be accurately calculated up to this
point where necking is assumed to
start

Engineering stress = L/A0

= ln (1+e)
al = ln (1+a)
ul = ln(1+u)

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 condition of load instability (maximum load)

P  A
at maximum load dP  dA  Ad  0
dA d
hence 
A 
to maintain dL dA d
  d 
constant volume
L A 
d
hence 
d

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Incipient Neck in Specimen

A, 

A+A, 
A,  increasing

A, 

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 work hardening exponent (n) and
strain rate sensitivity (m)

  ln      
n    
  ln      
  ln  
m 
  ln  

At low temperatures, n is high, m is low

At high temperatures, n is low, m is high

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when m = 0
   d  d ln  
    n
   d  d ln  
We’ve already seen d
instability occurs when 
d

n 

 n

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

When m ≠ 0
 1 A  n 
 1  
A m A   

Necking occurs when A 0
is negative and  is positive A
n
1  0

 n
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superplasticity

 1 A  n 
  1  
 m A  

rate of necking

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 References
• B.D. Cullity and S.R. Stock, The elements
of X-ray Diffraction, third edition, Prentice
Hall Inc., 2001, Chapter 2
• D.A. Porter and K.E. Easterling, Phase
Transformations in Metals and Alloys,
second edition, Stanley Thornes
(Publishers) Ltd., Chapter 2

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