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Materials Engineering
Diffusion is material transport by atomic motion. Mechanisms of Diffusion. Factors affecting diffusion.

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An Introduction, William D. Callister, Jr.

1

Objectives of Chapter 5

Examine the principles and applications of diffusion in materials.

Diffusion how do atoms move through solids?

Diffusion mechanisms

Vacancy diffusion

Interstitial diffusion

Impurities

The mechanism of diffusion

Steady-state diffusion (Ficks first law)

Factors that influence diffusion

Diffusion species

Host solid

Temperature

Microstructure

What is diffusion?

Diffusion is material transport by atomic motion.

an active diffusion to occur, the temperature should be high enough to

overcome energy barriers to atomic motion.

4

Self-diffusion

The random movement of atoms within an

essentially pure material. (Self-diffusion is a

diffusion in one-component material, when all atoms that

exchange positions are of the same type.)

Vacancy diffusion

Diffusion of atoms when an atom leaves a

regular lattice position to fill a vacancy in the

crystal.

Interstitial diffusion

Diffusion of small atoms from one interstitial

position to another in the crystal structure.

Department of Mechanical Engineering

Self Diffusion

Self-diffusion: In an elemental solid, atoms also migrate.

C

A

D

B

Vacancy Diffusion

Vacancy diffusion

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 ~ kT)

7

Interstitial Diffusion

Interstitial diffusion

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.

Substitutional Diffusion

Substitutional Diffusion:

applies to substitutional impurities

atoms exchange with vacancies

rate depends on:

--number of vacancies

--activation energy to exchange.

Ionic Diffusion

2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning is a trademark used herein under license.

other anion sites. Smaller cations tend to diffuse faster

10

Interdiffusion

In an alloy, atoms tend to migrate from regions of

large concentration to regions of low concentration.

Initially

100%

11

0

Concentration Profiles

Department of Mechanical Engineering

2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning is a trademark used herein under license.

12

Figure: Diffusion of

copper atoms into

nickel. Eventually,

the copper atoms are

randomly distributed

throughout the nickel

Diffusion coefficient (D) m2/sec

A temperature-dependent coefficient related to

the rate at which atoms, ions, or other species

diffuse.

The change of composition with distance in a

non-uniform material, typically expressed as

atoms/cm3.cm or at%/cm or kg/cm3.cm.

13

Diffusion Flux

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

occurs. The flux is defined as either the number of atoms diffusing

through a 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).

J = M / At (1/A) (dM/dt) (Kg m-2 s-1)

where M is the mass of atoms diffusing through the unit area A per unit time t.

14

2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning is a trademark used herein under license.

during diffusion

is defined as the

number of atoms

passing through a

plane of unit area

per unit time

15

Steady-State Diffusion

Steady state diffusion: the diffusion flux does not change with time.

Concentration profile: concentration of atoms/molecules of interest as function of

position in the sample.

Concentration gradient: dC/dx (Kg.m-4): the slope at a particular point on

concentration profile.

16

Concentration Profile, C(x): [kg/m3]

Cu flux Ni flux

Concentration

of Cu [kg/m3]

Concentration

of Ni [kg/m3]

Adapted

from Fig.

5.2(c),

Callister 6e.

Position, x

The concentration gradient is often called the driving force in diffusion

temperature

Diffusion and host species: D= f (T, D0, Qd) is different for every

solute, solvent pair

materials because of the accelerated diffusion along grain

boundaries and dislocation cores.

18

a vacancy site, it needs to

possess enough energy

(thermal energy) to break the

bond and squeeze through its

neighbor. The energy

necessary for motion, Em, is

called the activation energy for

vacancy motion.

be supplied to the atom so that

it can break inter-atomic bonds

to move into the new position.

19

Diffusion couple - A combination of elements

involved in diffusion studies

2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning is a trademark used

herein under license.

Figure:

- A high energy is

required to

squeeze atoms

past one another

during diffusion.

This energy is the

activation energy

Q.

20

- Generally more

energy is required

for a substitutional

atom than for an

interstitial atom

Department of Mechanical Engineering

Diffusion coefficient is the measure of

mobility of diffusing species.

Qd the activation energy for diffusion (J/mol or eV/atom)

R the gas constant (8.31 J/mol-K or 8.6210-5 eV/atom-K)

T absolute temperature (K)

The above equation can be rewritten as

estimated by plotting ln D versus 1/T. Such plots are Arrhenius plots.

21

22

Arrhenius plot of

diffusivity data for some

metallic systems

23

Smaller atoms diffuse more readily than big ones, and diffusion is faster in open

lattices or in open directions

24

general the diffusivity is greater through less restrictive structural

regions grain boundaries, dislocation cores, external surfaces.

25

Case Hardening:

--Diffuse carbon atoms

into the host iron atoms

at the surface.

--Example of interstitial

diffusion is a case

hardened gear.

--hard to deform: C atoms

"lock" planes from shearing.

--hard to crack: C atoms put

the surface in compression.

26

Fig. 5.0,

Callister 6e.

(Fig. 5.0 is

courtesy of

Surface

Division,

MidlandRoss.)

Diffusion FASTER for...

close-packed structures

materials w/secondary

bonding

materials w/covalent

bonding

cations

anions

27

Summary

Make sure you understand language and concepts:

Activation energy

Concentration gradient

Diffusion

Diffusion coefficient

Diffusion flux

Driving force

Ficks first law

Interdiffusion

Interstitial diffusion

Self-diffusion

Steady-state diffusion

Vacancy diffusion

28

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