DIFFUSION

WHY?

Many reactions/processes…
need transfer of matter from one component to another
material transport by atomic motion = diffusion

High percentage of materials processing technology –

- relies on understanding of diffusion mechanisms

Key points:
 why does diffusion occur
 how diffusion rates can be predicted
 how diffusion processes can be controlled
 why diffusion is essential to materials processing
1. INTRODUCTION
2. ATOMIC STRUCTURE AND INTERATOMIC BONDING
3. STRUCTURE OF CRYSTALLINE MATERIALS
4. IMPERFECTIONS IN SOLIDS
5. DIFFUSION

6. MECHANICAL PROPERTIES OF MATERIALS

7. DISLOCATIONS AND STRENGTHENING MECHANISMS
8. PHASE DIAGRAMS
9. PHASE TRANSFORMATION
10.THERMAL PROCESSING OF METAL ALLOYS
11.METAL ALLOYS

12.CERAMICS
13.POLYMERS
14.COMPOSITE MATERIALS
15.CORROSION AND DEGRADATION OF MATERIALS
16.ELECTRICAL PROPERTIES OF MATERIALS
17.THERMAL PROPERTIES OF MATERIALS
18.MAGNETIC PROPERTIES OF MATERIALS
19.OPTICAL PROPERTIES OF MATERIALS
EXAMPLE: Cu/Ni diffusion couple

joining of 2 dissimilar metals

need ‘intimate’ contact

between 2 metal faces

i.e. as atomically pure as possible

limited atomic transfer

occurs in this state

BUT/
heat for an extended period
below Tm for both metals

Cu atoms diffuse into Ni

Ni atoms diffuse into Cu

Interdiffusion
Economically – good way of alloying high melting point materials
(cheaper than melting)

e.g. powder metallurgy + ceramics processing

(sintering)

Self-diffusion – occurs in pure metals

i.e. atoms ‘move around’ the lattice
also occurs in atomically pure interfaces
usually undetectable

DIFFUSION MECHANISMS

atoms in solid materials – constantly moving

to move, atoms must:

•have an empty site to move to

•have sufficient energy to ‘debond’ from neighbours and cause sufficient lattice
distortion
VACANCY DIFFUSION

i.e.

↑temperature ↑no. of vacancies ↑diffusion rate

→ atoms ←vacancy sites

both interdiffusion and self-diffusion

INTERSTITIAL DIFFUSION

i.e.

Interstitial atoms – move to other interstitial sites

e.g. H, O, N, C etc. in metal lattices

i.e. small atoms!

In metal alloys – more common than vacancy distribution

(also – more interstitial vacancies than vacant lattice sites)
STEADY-STATE DIFFUSION

Diffusion = time dependent process

rate of diffusion = rate of mass transfer = diffusion flux = J

J = mass of atoms (M) passing through an area A during time t

M
J=
i.e.

At

1 dM
or J= J = kg / m 2 s
A dt
If J doesn’t change with time – steady-state diffusion
e.g. diffusion of gas through a thin metal plate (membrane)

i.e.

Plot C v. distance – linear (sometimes) = concentration profile

so = concentration gradient

dC
from this:
J =− D
dx
D = diffusion coefficient (m2/s)
-ve sign shows diffusion of atoms occurs from high C to low C

known as Fick’s First Law

EXAMPLE:

“A plate of iron is exposed to a carburizing

(carbon-rich) atmosphere on one side and a
decarburizing (carbon-deficient) atmosphere on
the other side at 700°C. If a condition of steady-
state is achieved, calculate the diffusion flux of
carbon through the plate if the concentrations of
carbon at positions of 5 and 10mm beneath the
carburizing surface are 1.2 and 0.8kg/m3
respectively. Assume a diffusion coefficient of
3 x 10-11m2/s at this temperature”

Use Fick’s first law:

C A − CB ( 1 . 2 − 0 . 8 )kg / m 3

J =− D = − ( 3 x10 −11 m 2 / s )
x A − xB ( 5 x10 −3 − 10 −2 )m

= 2.4 x 10-9kg/m2-s
NON-STEADY-STATE DIFFUSION

Concentration gradient at 3 different

More common situation times:

e.g. so – more applicable…

∂C ∂  ∂C  ∂ 2C
= D = D 2
∂t ∂x  ∂x  ∂x
Fick’s Second Law

To work effectively – need boundary conditions to be satisfied

- quite a complex solution

EXAMPLE:
semi-infinite solid (i.e very thick)
surface concentration held constant = Cs
diffusing species = gas
The picture can't be displayed.

gas partial pressure = constant

Assume:

1. Before diffusion – any existing solute atoms in the solid are random at a
concentration of C0
2. x=0 at surface and ↑ into solid
3. t=0 at instant before diffusion commences

boundary conditions: t=0, C=C0 at x=∞ and t>0, C=Cs at x=0

Cx − C0  x 
so = 1 − erf  
Cs − C0  2 Dt 
Cx = concentration at depth x after time t erf(x/2√Dt) = Gaussian error function
(tabulated)
So if C0, D and C are known – Cx at any x can be found
EXAMPLE:

Hardening of a steel surface – carburizing

hardening of a surface layer by diffusing into it extra C atoms

typically – use hot methane

Initial alloy concentration = 0.25wt%C

Heat treatment temperature = 950°C

to bring the C content at the surface to 1.20wt%

How long will it take to reach a carbon content of 0.8% at a distance 0.5mm below
the surface?

D for carbon in iron at 950°C = 1.6 x 10-11m2/s

 So: C0 = 0.25wt%C
Cs = 1.2wt%C
Cx = 0.8wt%C
T = 950°C
x = 5 x 10-4m
t = ?
From before:
Cx − C0  x 
= 1 − erf  
Cs − C0  2 Dt 
so:
0.8 − 0.25  62.5 
= 0.579 = 1 − erf  
1.2 − 0.25  t 
interpolate from tables: 0.421 = erf(0.392)

so 62.5/√t = 0.392 t = 7.1 hours

FACTORS THAT INFLUENCE DIFFUSION

Species
relative size of atoms important
small atoms travel better than large ones

reason? obvious

Temperature

↑T = ↑ in energy in atoms ↑readiness to move

i.e  − Qd 
D = D0 exp 
 RT 
D0 = temperature-independent diffusion constant
R = Gas constant = 8.31J/mol K
T = absolute temperature (K)
Qd = activation energy for diffusion

Qd = energy required to produce diffusive motion in 1 mol of atoms

EXAMPLE:

how fast will magnesium diffuse through aluminium at 400°C?

From data table:

D0 = 1.2 x 10-4m2/s
Qd = 131kJ/mol

so

D = 8.1 x 10-15m2/s
PROCESSING USING DIFFUSION

• 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.
 PROCESSING USING DIFFUSION

• Doping Silicon with P for n-type semiconductors:

• Process:

1. Deposit P rich
layers on surface.

silicon

2. Heat it…

3. Result: Doped
semiconductor
regions.

silicon