DIFFUSION IN SOLIDS

q FICK’S LAWS
q KIRKENDALL EFFECT
q ATOMIC MECHANISMS

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

q Mechanism of material transport by atomic motion

q Driven by thermal energy and a gradient
q Thermal energy → thermal vibrations → Atomic jumps

Concentration / chemical potential

Gradient Electric

Magnetic

Stress
Time dependent mechanism

Cu Ni When I bring it together, do they start diffusing ?

Ink in water diffuses immediately!

 Initial

What happens to the concentration of each species ?

Final

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

 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

q As a first approximation assume D ¹ f(t)

Steady State Diffusion

Constant flux of the species

!" $
𝐽= is a constant!
!# %

The solution to the Fick’s 1st equation – linearly varying concentration

Steady State Diffusion

Solutions to the Fick when the diffusivity is a function of the concentration

Steady state diffusion

C1 D ¹ f(c)
Concentration →

C2
D = f(c)

x →
 D ¹ f(c)
Steady state
J ¹ f(x,t)
D = f(c)
Diffusion

D ¹ f(c)
Non-steady state
J = f(x,t)
D = f(c)
Non-steady state

Flux is non-uniform!

Jx+Δx
jx

If the current density at two points x and x+Δx are different,

That means, there is accumulation/depletion.

𝜕𝑐 Δx is the small segment thickness

𝑗& − 𝑗&'(& = Δ𝑥
𝜕𝑡 C – species concentration m-3
𝜕𝑗
(𝑗&'(& −𝑗& )/Δ𝑥 =
𝜕𝑥
𝜕𝑐 𝜕𝑗
Δ𝑥 = − Δ𝑥
𝜕𝑡 𝜕𝑥

𝜕𝑐 𝜕 𝐷𝜕𝑐
=− −
𝜕𝑡 𝜕𝑥 𝜕𝑥
This is also called as the continuity equation.
 ¶
æ öc ¶ 2
c
ç ÷=D 2
è ¶t ø ¶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 Þ c ↑ as t ↑ -ve curvature Þ c ↓ as t ↑

Diffusion mechanisms

Interstitial diffusion
The solute/diffusing atom is very small!

Momentary increase in the enthalpy is

required for the interstitials to move from A
-B

While A and B are both interstitial

positions.
 Interstitial Diffusion

DHm
1 2

1 2

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

æ DH m ö
ç- ÷
n '=n e è kT ø
 § c = atoms / volume
§c=1/d3
§ concentration gradient dc/dx = (-1 / d 3)/d = - 1 / d 4
§ Flux = No of atoms / area / time = n’ / area = n’ / d 2

J n' 4
D= = 2 d =n 'd 2

1 2 - (dc / dx) d

æ - DH m ö
ç ÷
D =n d e 2 è kT ø
d
æ Q ö
On comparison ç- ÷
with D = D0 e è kT ø

d Vacant site

D0 = n d 2
d
2. Vacancy Mechanism
 Substitutional Diffusion
§ Probability for a jump a
(probability that the site is vacant) . (probability that the atom has
sufficient energy)
§ DHm → enthalpy of motion of atom
§ n’ → frequency of successful jumps

æ - DH f ö æ - DH m ö æ - DH f - DH m ö
çç ÷÷ ç ÷ çç ÷÷
n '=n e è kT ø
e è kT ø
n '=n e è kT ø

J n'
As derived for interstitial diffusion D= = 2 d 4 =n 'd 2
- (dc / dx) d

æ - DH f - DH m ö
çç ÷÷
D =n d 2 e è kT ø
Temperature dependence of diffusivity

æ Q ö
ç- ÷ Arrhenius type
D = D0 e è kT ø

For interstitial For substitutional

æ - DH m ö æ - DH f - DH m ö
ç ÷ çç ÷÷
D =n d 2 e è kT ø
D =n d 2 e è kT ø

D0 = n d 2

Δ𝐻) 𝑓𝑜𝑟 𝑖𝑛𝑡𝑒𝑟𝑠𝑡𝑖𝑡𝑖𝑎𝑙

𝑄=
Δ𝐻) + Δ𝐻* 𝑓𝑜𝑟 𝑠𝑢𝑏𝑠𝑡𝑖𝑡𝑢𝑡𝑖𝑜𝑛𝑎𝑙
 Examples of diffusion:

1. Diffusion couple

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 Þ c(+x,t) ¹ c(-x,t)
i.e. asymmetry about y-axis
A B
C1
x →

§ C(+x, 0) = C1
§ C(-x, 0) = C2
 ¶
æ öc ¶ 2
c æ x ö
ç ÷=D 2 c( x, t ) = A - B erf ç ÷
è ¶t ø ¶x è 2 Dt ø
Solution to 2o de with 2 constants
determined from Boundary Conditions and Initial Condition

§ Erf (¥) = 1
g § Erf (-¥) = -1
Erf (g ) =
2
ò exp(- u 2
)
du § Erf (0) = 0
p 0 § Erf (-x) = -Erf (x)

Exp(- u2) →

Area

0 g 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 Þ c(+x,t) ¹ 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
Applications based on Fick’s II law Carburization of steel

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

prone to degradation
q Surface hardenting of steel components like gears is done by carburizing
or nitriding
q Pack carburizing → solid carbon powder used as C source
q 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