DIFFUSION IN SOLIDS

 FICK’S LAWS
 KIRKENDALL EFFECT
 ATOMIC MECHANISMS

Diffusion in Solids
P.G. Shewmon
McGraw-Hill, New York (1963)
 H2 diffusion direction

Ar H2

Movable piston
with an orifice Piston motion

Ar diffusion direction Piston moves in the

direction of the slower
moving species
Kirkendall effect

 Materials A and B welded together with Inert marker and given a diffusion
anneal
 Usually the lower melting component diffuses faster (say B)
A B

Marker motion

Inert Marker – thin rod of a high melting material which is basically

insoluble in A & B
 Diffusion

 Mass flow process by which species change their position relative to

their neighbours
 Driven by thermal energy and a gradient
 Thermal energy → thermal vibrations → Atomic jumps

Concentration / chemical potential

Gradient Electric

Magnetic

Stress
 Flux (J) (restricted definition) → Flow / area / time [Atoms / m2 / s]

 Assume that only B is moving into A

 Assume steady state conditions → J  f(x,t) (No accumulation of matter)
 Fick’s I law
Diffusion coefficient/ diffusivity
No. of atoms dn dc
crossing area A   DA Cross-sectional area
per unit time dt dx Concentration gradient

Matter transport is down the concentration gradient

Flow direction
A

 As a first approximation assume D  f(t)

J  atoms / area / time  concentrat ion gradient

dc
J
dx
dc
J  D
dx
1 dn dc
J  D
A dt dx

dn dc Fick’s first law

  DA
dt dx
 Diffusivity (D) → f(A, B, T)

Steady state diffusion

C1 D  f(c)
Concentration →

C2
D = f(c)

x →
 D  f(c)
Steady state
J  f(x,t)
D = f(c)
Diffusion

D  f(c)
Non-steady state
J = f(x,t)
D = f(c)
Fick’s II law
x
Accumulation  J x  J x  x

 J 
Accumulation  J x   J x  x 
Jx Jx+x  x 

 c   J   Atoms 1    Atoms 
 x  J x   J x  x   m 3 s .m   m 2 s    J 
 t   x      

 c  J  c    c 
 x   x      D  Fick’s first law
 t  x  t  x  x 

 c    c  D  f(x)  c   2c
   D   D 2
 t  x  x   t  x
  c   2c
 D 2
 t  x

RHS is the curvature of the c vs x curve

c →
c →

x→ x→

LHS is the change is concentration with time

+ve curvature  c ↑ as t ↑ ve curvature  c ↓ as t ↑

 
 c  2
c  x 
 D 2 c( x, t )  A  B erf  
 t  x  2 Dt 
Solution to 2o de with 2 constants
determined from Boundary Conditions and Initial Condition
 Erf () = 1
  Erf (-) = -1
Erf    
2
 exp u 2

du  Erf (0) = 0
 0  Erf (-x) = -Erf (x)
Exp( u2) →

Area

0  u →
 Applications based on Fick’s II law Determination of Diffusivity

A & B welded together and heated to high temperature (kept constant → T0)

t2 > t1 | c(x,t1) t1 > 0 | c(x,t1) t = 0 | c(x,0)

f(x)|t
C2 Non-steady
Flux state
Concentration →

f(t)|x

Cavg  If D = f(c)
↑t  c(+x,t)  c(-x,t)
i.e. asymmetry about y-axis
A B
C1
x →

 C(+x, 0) = C1  A = (C1 + C2)/2

 C(x, 0) = C2  B = (C2 – C1)/2
Temperature dependence of diffusivity

 Q 
  Arrhenius type
D  D0 e  kT 
Applications based on Fick’s II law Carburization of steel

 Surface is often the most important part of the component, which is

prone to degradation
 Surface hardenting of steel components like gears is done by carburizing
or nitriding
 Pack carburizing → solid carbon powder used as C source
 Gas carburizing → Methane gas CH4 (g) → 2H2 (g) + C (diffuses into steel)

CS

C1
x → 0

 C(+x, 0) = C1  A = CS
 C(0, t) = CS  B = CS – C1
Approximate formula for depth of penetration

x  Dt
ATOMIC MODELS OF DIFFUSION

1. Interstitial Mechanism
2. Vacancy Mechanism
3. Interstitialcy Mechanism
4. Direct Interchange and Ring
 Interstitial Diffusion

Hm
1 2

1 2

 At T > 0 K vibration of the atoms provides the energy to overcome the energy
barrier Hm (enthalpy of motion)
  → frequency of vibrations, ’ → number of successful jumps / time

 H m 
 
 ' e  kT 
  c = atoms / volume
c=1/3
 concentration gradient dc/dx = (1 /  3)/ =  1 /  4
 Flux = No of atoms / area / time = ’ / area = ’ /  2

J ' 4
D  2   ' 2
1 2  (dc / dx) 

  H m 
 
D   2 e  kT 

 Q 
On comparison  
with D  D0 e  kT 

 Vacant site

D0    2

 Substitutional Diffusion
 Probability for a jump 
(probability that the site is vacant) . (probability that the atom has
sufficient energy)
 Hm → enthalpy of motion of atom
 ’ → frequency of successful jumps

  H f    H m    H f  H m 
     
 ' e  kT 
e  kT 
 ' e  kT 

J '
As derived for interstitial diffusion D  2  4  ' 2
 (dc / dx) 

  H f  H m 
 
D   2 e  kT 
Calculated and experimental activation energies for vacancy Diffusion

Element Hf Hm Hf + Hm Q

Au 97 80 177 174

Ag 95 79 174 184
Interstitial Diffusion

  H m 
 
D   2 e  kT 

 D (C in FCC Fe at 1000ºC) = 3  1011 m2/s

Substitutional Diffusion

  H f  H m 
 
D   2 e  kT 

 D (Ni in FCC Fe at 1000ºC) = 2  1016 m2/s

DIFFUSION PATHS WITH LESSER RESISTANCE

Experimentally determined activation energies for diffusion

Qsurface < Qgrain boundary < Qlattice

Lower activation energy automatically implies higher diffusivity

 Core of dislocation lines offer paths of lower resistance

→ PIPE DIFFUSION

 Diffusivity for a given path along with the available cross-section for
the path will determine the diffusion rate for that path
 Comparison of Diffusivity for self-diffusion of Ag →
single crystal vs polycrystal

Schematic
 Qgrain boundary = 110 kJ /mole
 QLattice = 192 kJ /mole
Log (D) →

Polycrystal

Single
crystal
1/T →
← Increasing Temperature