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Chapter Outline

Diffusion - how do atoms move through solids?

Diffusion mechanisms

Vacancy diffusion

Interstitial diffusion

Impurities

The mathematics of diffusion

Steady-state diffusion (Fick’s first law)

Nonsteady-State Diffusion (Fick’s second law)

1

Cont’d

Factors that influence diffusion:

Diffusing species

Host solid

Temperature

Microstructure

Atomic mobility

Tracer diffusivity in binary alloys

Diffusion in ternary alloys

High diffusivity paths

Diffusion in multi phase binary solutions

2

Cont’d

What is diffusion?

Diffusion: the movement of particles in a solid

from an area of high concentration to an area of

low concentration, resulting in the uniform

distribution of the substance.

Diffusion is process which is NOT due to the

action of a force, but a result of the random

movements of atoms.

Heat causes atoms to vibrate.

3

Mechanisms of diffusion

Interdiffusion: In an alloy, atoms tend to migrate

from regions of high conc. to regions of low conc.

After some time

Initially

Cu Ni Cu Ni

4

Cont’d

Before After

5

Cont’d

Self-diffusion: In an elemental solid, atoms also

migrate.

Label some atoms After some time

C

C

A D

A

D

B

B

Diffusion in pure metal changes

6

Cont’d

Atoms in solids are in constant motion rapidly changing positions.

Diffusion is just the stepwise migration of atoms from a lattice site

to other lattice site.

Two conditions for movement:

1. There must be an empty adjacent site

2. Atom must have sufficient energy to break bonds with neighbor

atoms.

Atomic vibration:

Every atom is vibrating very rapidly about its lattice position within

the crystal.

At any instant, not all vibrate with same frequency and amplitude.

Not all atoms have same energy.

Same atom may have different level of energy at different time.

Energy increases with temperature.

7

Vacancy Diffusion

• Involves interchange of an atom from a normal

lattice position to an adjacent vacant lattice site or

vacancy.

• Necessitates presence of vacancies.

• Substitutional diffusion generally proceeds by the

vacancy mechanism.

• Diffusing atoms and vacancies exchange

positions.

• They move in opposite directions.

• Both self- and inter-diffusion occurs by this

mechanism. 8

Cont’d

Vacancy Diffusion:

Applies to substitutional impurities

Atoms exchange with vacancies

Rate depends on:

1. Number of vacancies;

2. Activation energy to exchange.

9

Cont’d

To jump from lattice site to lattice site, atoms need energy

to break bonds with neighbors, and to cause the necessary

lattice distortions during jump. This energy comes from the

thermal energy of atomic vibrations (Eav ~ kBT)

10

Cont’d

Interstitial diffusion:

Interstitial diffusion – smaller atoms can

diffuse between atoms.

11

Cont’d

Interstitial diffusion is generally faster than

vacancy diffusion because bonding of

interstitials to the surrounding atoms is

normally weaker and there are many more

interstitial sites than vacancy sites to jump to.

Requires small impurity atoms (e.g. C, H, O) to

fit into interstices in host.

12

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.

13

Diffusion Flux

The quantity of an element that is transported within another is a

function of time. Diffusion is a time-dependent process.

The flux of diffusing atoms, J, is used to quantify how fast

diffusion occurs. The flux is defined as either in number of atoms

diffusing through unit area and per unit time (e.g., atoms/m2-

second) or in terms of the mass flux - mass of atoms diffusing

through unit area per unit time, (e.g., kg/m2-second).

Mathematically: J = M / (At)

In differential form: J = (1/A)(dM /dt)

Where M is the mass of atoms diffusing

through the area A during time t.

14

Cont’d

How do we quantify the amount or rate of diffusion ?

moles (or mass) diffusing mol kg

J Flux or

surface areatime 2

cm s m2s

• Measured empirically

– Make thin film (membrane) of known surface area

– Impose concentration gradient

– Measure how fast atoms or molecules diffuse through the

membrane

M=

M l dM mass J slope

J

At A dt diffused

time

15

Steady-State Diffusion

Rate of diffusion independent of time

Flux proportional to concentration gradient =

dC

C2 C2 J D

dx

x1 x2

x

D diffusion coefficient

dC C C2 C1

if linear

dx x x2 x1

16

Cont’d

state diffusion

Example:

Diffusion of a gas through a plate of metal

Concentration (or pressure) of diffusing species on both side

are held constant

Concentration profile: Concentration versus position

Assumed linear concentration profile as shown in figure (b)

17

Cont’d

Concentration gradient = dC / dx

For linear concentration shown in the above:

Conc. Gradient = ΔC/Δx = (CA – CB) / (xA – xB)

Fick’s first law: For steady-state diffusion, the

flux is proportional to the concentration gradient

J = -D(dC/dx)

D: diffusion coefficient (sq. m per second )

-ve sign: direction of diffusion from a high to a

low concentration

18

Cont’d

Example problem

19

Cont’d

J = -D(dC/dx)

Diffusion coefficient is the measure of

mobility of diffusing species.

DO : temperature-independent preexponential

(m2/s)

Qd– the activation energy for diffusion (J/mol )

R – the gas constant (8.31 J/mol-K)

T – absolute temperature (K)

20

Cont’d

The above equation can be rewritten as

can be estimated by plotting lnD versus 1/T or logD versus

1/T. Such plots are Arrhenius plots.

Qd/2.3R, intercept of ln Do

21

Diffusion coefficient (D)

• Diffusivity D depends on:

Diffusion mechanism

Temperature of diffusion

Type of crystal structure (bcc > fcc)

Crystal imperfections

Concentration of diffusing species

22

Cont’d

Example: At 3000c the diffusion coefficient and

activation energy for Cu in Si are:

D(3000c) = 7.8 x 10-11 m2/s

Qd = 41.5 kJ/mol

R=8.314J/ mol.ok

What is the diffusion coefficient at 3500c?

ANSWER: D2 = 15.7 x 10-11 m2/s

23

Non-steady-State Diffusion: Fick’s second law

The concentration of diffusing species is a

function of both time and position C = C(x,t)

In this case Fick’s Second Law is used

d Cx d d Cx

= D

dt d x d x

In words, The rate of change of composition at position x with

time, t, is equal to the rate of change of the product of the

diffusivity, D, times the rate of change of the concentration

gradient, dCx/dx, with respect to distance, x.

24

Non-steady-State Diffusion: Fick’s second law

25

Cont’d

26

Cont’d

Solution of this equation is concentration

profile as function of time, C(x,t):

Cs

at t = 0, C = Co for 0 x

at t > 0, C = CS for x = 0 (constant surface

conc.)

C = Co for x =

27

Cont’d

C x - Co x CS

= 1 - erf

C s - Co 2 Dt

C(x,t) = Conc. at point x at C(x,t)

time t

erf (z) = error function Co

erf(z) values are given in Table 5.1

28

Cont’d

Tabulation of Error Function Values

29

Cont’d

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.

30

Cont’d

Selected Values of Do and Ea for Diffusion Systems

31

Diffusion Coefficient

32

Cont’d

Factors that influence diffusion

Temperature - diffusion rate increases very rapidly

with increasing temperature.

Diffusion mechanism – diffusion by interstitial

mechanism is usually faster than by vacancy

mechanism.

Diffusing and host species - Do, Qd are different for

every solute, solvent pair.

Microstructure - diffusion is faster in polycrystalline

materials compared to single crystals because of the

accelerated diffusion along grain boundaries.

33

Atomic mobility

Atomic diffusion is a diffusion process whereby the

random thermally-activated movement of atoms in a

solid results in the net transport of atoms.

The rate of transport is governed by the diffusivity

and the concentration gradient.

Segregation to grain boundaries, interfaces &

dislocations is of great technological importance. For

example the diffusion of C,or N to dislocations in

mild steel is responsible for strain ageing and blue

brittleness.

The segregation of impurities such as Sb, Sn, P and

As in low alloy steels produces temper

embrittlement.

34

Cont’d

Segregation to grain boundaries affects the mobility

of the boundary & has an effect on recrystallization

and grain growth.

The problem of atom migration can be solved by

considering the thermodynamic condition for

equilibrium; namely the chemical potential of an

atom must be the same everywhere.

An alternative way to describe a flux of atom is to

consider a net drift velocity(v) super imposed on the

random jumping motion of each diffusing atom. The

drift velocity is related to the flux by:

JB= VB CB ---------1

35

Cont’d

Since atoms always migrate so as to remove

differences in chemical potential is reasonable to

suppose that the drift velocity is proportional to

the chemical potential gradient,i.e

VB= -MB -----------2

Where MB is a constant of proportionality known

as atomic mobility. From 1 & 2

JB=-MBCB ------------3

( ) is the chemical force for migration of atoms.

36

High diffusivity paths

In this section diffusion along dislocations,

interfaces, grain boundaries& free surfaces are

discussed. It will become apparent that under

certain circumstances diffusion along these

defects can be the dominant diffusion path.

Diffusion along the grain boundaries & free surfaces

It is experimentally found that diffusion along

grain boundaries & free surfaces can be described

by:

Db=Dbo

Or

DS=DS0

37

Cont’d

Where Db & DS are the grain boundary and surface

diffusivities, Dbo & DS0 are the frequency factors.

Qb & Qs are experimentally determined values of

activation energies for diffusion.

In general, at any temperature the magnitude of Db &

DS relative to the diffusivity through defect free

lattice D1 are such that:

DS >Db>D1

This mainly reflects the relative ease with which

atoms can migrate along free surfaces, interior

boundaries & though the lattice. 38

MULTIPHASE DIFFUSION IN BINARY

AND TERNARY SOLID-STATE SYSTEMS

high temperature, interdiffusion will occur.

Depending on the nature of the starting materials,

temperature & annealing time, a new concentration

distribution of the element is set up.

If the materials are completely miscible at that

temperature, the concentration profiles are more or

less smooth without any discontinuity.

If however they are only partially miscible or if they

react to form new phases, discontinuities in the

concentration profile occur which are closely related

to the phase diagram of the system.

39

Cont’d

40

Cont’d

THE END!!!

41

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