CHAPTER 5: DIFFUSION IN SOLIDS

ISSUES TO ADDRESS...
How does diffusion occur? Why is it an important part of processing? How can the rate of diffusion be predicted for some simple cases? How does diffusion depend on structure and temperature?
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Chapter 5: DIFFUSION
z Why
z z z z

study Diffusion?

Heat-treated to improve their properties. Heat-treatment almost always involve atomic diffusion. z z desired results depends on diffusion rate Heat-treatment temperature, time, and/or rate of heating/cooling can be predicted by the mathematics of diffusion Steel gear Case hardened to improve hardness and resistance to fatigue diffusing excess carbon or nitrogen into outer surface layer.

z z

z z

Diffusion: The phenomenon of material transport by atomic motion. Many reactions and processes that are important in the material treatment rely on the mass transfer: z z Either with a specific solid ( at microscopic level ) z z Or from a liquid, a gas, or another solid phase.
z z z z

5.1 Introduction

This chapter covers: z z Atomic mechanism z z Mathematics of diffusion z z Influence of temperature and diffusing species of the diffusion rate
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5.1 Introduction (Contd.)

z z

Phenomenon of diffusion z z Explained using diffusion couple, formed by joining bars of two different materials having intimate contact Copper and Nickel diffusion couple z z Figure 5.1 shows as formed z z Atom locations and concentration Heated for an extended period at an elevated temperature ( but below melting temperature of both ) and cooled to room temperature.
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z z

z z

 Interdiffusion: In an alloy, atoms tend to migrate

from regions of large concentration.
Initially After some time

DIFFUSION

100% 0

Cu

Ni

100% 0 Concentration Profiles 5

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Concentration Profiles

5.1 Introduction (Contd.)

Chemical analysis reveals z Alloy region z Variation of concentration z Atoms migrated or diffused into one another Interdiffusion or impurity diffusion z Atoms of one metal diffuses into another z Net drift of atoms from high to lower concentration
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DIFFUSION
Self-diffusion: In an elemental solid, atoms
also migrate. Self-diffusion

All atoms exchanging positions are of same type No compositional Diffusion in pure metal changes
Label some atoms After some time

C A D B

C A B
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5.2 Diffusion Mechanism

z z z z

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. z z 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 (Section 4.7): z z Every atom is vibrating very rapidly about its lattice position within the crystal z z At any instant, not all vibrate with same frequency and amplitude. z z Not all atoms have same energy z z Same atom may have different level of energy at different time 8 z z Energy increases with temperature

5.2 Diffusion Mechanism (Contd.)

z Several
z Two

different models for atomic motion DIFFUSION

dominate for metallic diffusion

z VACANCY
z Involves

interchange of an atom from a normal lattice position to an adjacent vacant lattice site or vacancy z Necessitates presence of vacancies z Diffusing atoms and vacancies exchange positions they move in opposite directions z Both self- and inter-diffusion occurs by this 9 mechanism

DIFFUSION MECHANISMS
Vacancy Diffusion:
applies to substitutional impurities atoms exchange with vacancies rate depends on: --number of vacancies --activation energy to exchange.

increasing elapsed time

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5.2 Diffusion Mechanism (Contd.)

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5.2 Diffusion Mechanism (Contd.)

z z

INTERSTITIAL DIFFUSION z z Atoms migrate from an interstitial position to a neighboring one that is empty z z Found for interdiffusion of impuries such as hydrogen, carbon, nitrogen, and oxygen atoms small enough to fit into interstitial positions. z z Host or substitutional impurity atoms rarely have insterstitial diffusion Interstitial atoms are smaller and thus more mobile interstitial diffusion occurs much more rapidly then by vacancy mode There are more empty interstitial positions than vacancies 12 interstitial atomic movement have greater probability

z z

z z

INTERSTITIAL DIFFUSION

Applies to interstitial impurities. More rapid than vacancy diffusion. Simulation:

--shows the jumping of a smaller atom (gray) from one interstitial site to another in a BCC structure. The interstitial sites considered here are at midpoints along the unit cell edges.

(Courtesy P.M. Anderson)

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5.3 Steady-State Diffusion

z z

The quantity of an element that is transported within another is a function of time diffusion is a time-dependent process. Diffusion flux (J)
z z z z z z z z

z z

Rate of diffusion or mass transfer Defined as mass or number of atoms (M) diffusing through and perpendicular to a unit cross-sectional area of solid per unit time. Mathematically, J = M / (At) In differential form: J = (1/A)(dM/dt)

A: area across which diffusion is occurring t: elapsed diffusion time

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Diffusion
z

How do we quantify the amount or rate of diffusion?

kg moles (or mass) diffusing mol or J Flux = 2 (surface area )(time ) cm s m 2 s

Measured empirically
z z z z z z

Make thin film (membrane) of known surface area Impose concentration gradient Measure how fast atoms or molecules diffuse through the membrane M= J slope mass M l dM diffused J= = At A dt time
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Steady-State Diffusion
Rate of diffusion independent of time

dC Flux proportional to concentration gradient = dx

C1 C1

Ficks first law of diffusion

C2 x1 x2

C2

dC J = D dx
D diffusion coefficient

dC C C 2 C1 if linear = dx x x 2 x1

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5.3 Steady-State Diffusion (Contd.)

z z z z

If the diffusion flux does not change with time steady-state diffusion Example: z z Diffusion of a gas through a plate of metal z z Concentration (or pressure) of diffusing species on both side are held constant z z Concentration profile: Concentration versus position z z Assumed linear concentration profile as shown in figure (b)

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5.3 Steady-State Diffusion (Contd.)

z z

Concentration gradient z z Slope at a particular point on the concentration profile curve z z Concentration gradient = dC / dx For linear concentration shown in figure 5.4b: Conc. Gradient = C/x = (CA A CB B) / (xA A xB B) Ficks 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

z z

z z

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5.3 Steady-State Diffusion (Contd.)

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Example: Chemical Protective Clothing (CPC)

z z

z z z z

Methylene chloride is a common ingredient of paint removers. Besides being an irritant, it also may be absorbed through skin. When using this paint remover, protective gloves should be worn. If butyl rubber gloves (0.04 cm thick) are used, what is the diffusive flux of methylene chloride through the glove? Data: z z diffusion coefficient in butyl rubber: -8 cm2 2/s D = 110 x10-8 z z surface concentrations:

C1 = 0.44 g/cm3 C2 = 0.02 g/cm3

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 Solution assuming linear conc. gradient

glove C1 paint remover x1 x2
tb =

Example (cont).
dC C 2 C1 D J = -D x 2 x1 dx

skin l2
6D

C2

Data:

D = 110 x 10-8 cm2/s C1 = 0.44 g/cm3 C2 = 0.02 g/cm3 x2 x1 = 0.04 cm

J = (110 x 10

-8

g ( 0 .02 g/cm 3 0 .44 g/cm 3 ) = 1 .16 x 10 - 5 cm /s) ( 0 .04 cm) cm 2 s

2
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5.4 Nonsteady-State Diffusion

z z z z

Most practical diffusion situations are non-steady Non-steady z z Diffusion flux and the concentration flux at some particular point of solid vary with time z z Net accumulation or depletion of the diffusing species z z Figure shown concentration profile at three different times
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NON STEADY STATE DIFFUSION

Concentration profile, C(x), changes w/ time. dx
J(left) J(right) Concentration, C, in the box

To conserve matter: J (right) J (left) = dC dx dt dJ = dC dt dx Governing Eqn.:

equate

Fick's First Law: dC J = D or dx d2 C (if D does dJ = D not vary dx dx 2 with x)

dC d 2C =D dt dx 2

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z z z z

z z

z z

Solution for Semi-infinite Solid with constant surface concentration Assumptions z z Initial concentration C0 0 z z X = 0 at the surface and increases with distance into the solid z z Initial time = 0 Boundary conditions z C = Co z For t = 0, o at 0 x z C = Cs z For t > 0, s (Constant surface concentration) at x=0 C x C0 x C = C0 = 1 erf 0 at x = C s C0 2 Dt Solution z z erf ( ) : Gaussian error function 24 z z Values given in Table 5.1

NON STEADY STATE DIFFUSION

Copper diffuses into a bar of aluminum.
Surface conc., C s of Cu atoms

Cs

C( x,t)

bar pre-existing conc., C o of copper atoms

C o to

t1

t2

t3 position, x

General solution:

x C(x, t) C o = 1 erf 2 Dt Cs Co
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"error function" Values calibrated in Table 5.1, Callister 6e.

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EXAMPLE PROBLEM
Copper diffuses into a bar of aluminum. 10 hours at 600C gives desired C(x). How many hours would it take to get the same C(x) if we processed at 500C? Key point 1: C(x,t500C) = C(x,t600C). Key point 2: Both cases have the same Co and Cs.

Dt should be held constant. x C (x ,t) Co = 1 erf 2Dt Cs C o 5.3 x10 -13 m 2 /s Answer: 4.8x10 -14 m 2 /s

(Dt) 500C =(Dt) 600C

(Dt) 600 = 110 hr t 500 = D 500

10hrs

Note: values of D are Given here.

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Factors That Influence Diffusion

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Factors That Influence Diffusion (Contd.)

z z z z

DIFFUSING SPECIES Magnitude of diffusion coefficient (D) indicative of the rate at which atoms diffuse D depends on both the diffusing species as well as the host atomic structure
2/s Self-diffusion Fe in -Fe 3.0E(-21) m2 Vacancy Diffusion 2/s Inter-diffusion C in -Fe 2.4E(-12) m2 Interstitial Diffusion

z z

z z

z z

Interstitial is faster than vacancy diffusion

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Factors That Influence Diffusion (Contd.)

TEMPERATURE
z

Temperature has a most profound influence on the coefficients and diffusion rate Example: Fe in -Fe (Table 5.2) oC D=3.0E(-21) m2 2/s 500o oC D=1.8E(-15) m2 2/s approximately 900o six orders

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DIFFUSION AND TEMPERATURE

Diffusivity increases with T.
diffusivity D = Do
1500 1000

pre-exponential [m 2 /s] (see Table 5.2, Callister 6e ) activation energy Q [J/mol],[eV/mol] exp d (see Table 5.2, Callister 6e )

RT
300

Experimental Data:
600

10 -8 D (m 2 /s) 10 -14

gas constant [8.31J/mol-K] Q ln D = ln D0 d R T(C)

log D = log D0

1 T

Ci n -Fe

Qd 1 2.3R T

C in Fe
in Fe
Al in Al Cu Cu in -Fe in Cun ei e Zn F -F

D has exp. dependence on T Recall: Vacancy does also! D interstitial >> D substitutional

C in -Fe C in -Fe
2.0 1000K/T

10 -20

0.5

1.0

1.5

Cu in Cu Al in Al Fe in -Fe Fe in -Fe Zn in Cu
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