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Feb 10, 2014

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Callister Materials slides

Attribution Non-Commercial (BY-NC)

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Callister Materials slides

Attribution Non-Commercial (BY-NC)

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Chapter 5: Diffusion

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?

Chapter 5 - 1

Diffusion

Diffusion - Mass transport by atomic motion

_______________ ! Gases & Liquids random (___________) motion ! Solids ________ diffusion or __________ diffusion

Chapter 5 - 2

Diffusion

__________: In an alloy, atoms tend to __________

from regions of _____ conc. to regions of _____ conc.

Initially After some time

Adapted from Figs. 5.1 and 5.2, Callister & Rethwisch 8e.

Chapter 5 - 3

1 !

12/10/09 !

Diffusion

Self-diffusion: In an elemental solid, ________

also migrate.

Label some atoms After some time

C A D B

C A B D

Chapter 5 - 4

Diffusion Mechanisms

Vacancy Diffusion:

_______ exchange with __________ ! applies to ____________ impurities atoms rate depends on: --number of _________ --activation _________ to exchange.

Chapter 5 - 5

Diffusion Simulation

Simulation of interdiffusion across an interface: Rate of ____________ diffusion depends on:

-- ___________concentration -- frequency of ___________.

Chapter 5 - 6

2 !

12/10/09 !

Diffusion Mechanisms

! ___________ diffusion smaller atoms can diffuse between _________.

Chapter 5 - 7

Case ___________:

-- Diffuse carbon atoms into the host iron atoms at the surface. -- Example of interstitial diffusion is a case hardened gear.

Adapted from chapter-opening photograph, Chapter 5, Callister & Rethwisch 8e. (Courtesy of Surface Division, Midland-Ross.)

Chapter 5 - 8

______silicon with phosphorus for n-type semiconductors: 0.5 mm Process:

1. Deposit __ rich layers on surface.

magnified image of a computer chip

silicon!

2. ________ 3. Result: Doped _____________ regions.

light regions: Si atoms

silicon

Adapted from Figure 18.27, Callister & Rethwisch 8e. Chapter 5 - 9

3 !

12/10/09 !

Diffusion

! How do we quantify the amount or rate of diffusion?

J ! Flux !

moles (or mass) diffusing mol kg = or (surface area )(time ) cm2s m2s

! Measured empirically

! Make thin film (___________) of known surface area ! Impose ______________ gradient ! Measure how fast atoms or molecules diffuse through the membrane M= mass diffused

J=

M l dM = At A dt

J ! slope time

Chapter 5 - 10

Steady-State Diffusion

Rate of ___________ independent of time Flux proportional to ____________ gradient =

C1 C1

dC dx

___________ of diffusion

C2 x1 x x2

C2

J = !D

dC dx

if linear

dC "C C2 ! C1 # = dx "x x2 ! x1

Chapter 5 - 11

! _________________ 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 (____ cm thick) are used, what is the diffusive flux of _______________ through the glove? ! Data: ! diffusion coefficient in butyl rubber: D = ________________ ! surface concentrations: C1 = 0.44 g/cm3 C2 = 0.02 g/cm3

Chapter 5 - 12

4 !

12/10/09 !

Example (cont).

! Solution assuming ___________ conc. gradient

glove C1 paint remover

!2 6D

tb =

J =-D

Data:

skin C2

dC C ! C1 " !D 2 dx x2 ! x1

x1 x2

Chapter 5 - 13

Diffusion coefficient increases with increasing _____.

# ! Qd & ! !! ( ! D =! Do exp%$ ! RT ' !

D = __________ coefficient [m2/s] Do = pre-exponential [m2/s] Qd = _________ energy [J/mol or eV/atom] R = gas constant [_______________] T = absolute temperature [K]

Chapter 5 - 14

D has _______________ dependence on T

1500 1000 600 300

C in *Fe Fe i

n F )e

* in Fe -Fe

C in

)-F e

Al in Al

10-20

0.5

1.0

1.5

1000 K/T

Adapted from Fig. 5.7, Callister & Rethwisch 8e. (Date for Fig. 5.7 taken from E.A. Brandes and G.B. Brook (Ed.) Smithells Metals Reference Book, 7th ed., Butterworth-Heinemann, Oxford, 1992.) Chapter 5 - 15

5 !

12/10/09 !

Example: At 300C the diffusion coefficient and activation __________ for _____________ are D(300C) = 7.8 x 10-11 m2/s Qd = 41.5 kJ/mol What is the diffusion ________ at 350C?

D

transform data

Temp = T

ln D

1/T

"

$ 1 1' & # ) % (

Qd R

&1# $ $T ! ! % 1"

Chapter 5 - 16

Example (cont.)

& Q D2 = D1 exp$- d % R , 1 1 )# * *T - T ' '! 1 (" + 2

& - 41,500 J/mol , 1 1 )# D2 = (7.8 x 10 -11 m2 /s) exp$ * '! % 8.314 J/mol - K + 623 K 573 K ("

D2 = _____________

Chapter 5 - 17

! The ___________ of diffusing species is a function of both time and position C = C(x,t) ! In this case ________________ Law is used

____________ Law

!C ! 2C =D 2 !t !x

Chapter 5 - 18

6 !

12/10/09 !

Chapter 5 - 19

Copper diffuses into a bar of ___________.

Surface conc., Cs of Cu atoms bar _____________________, Co of copper atoms

Cs

Adapted from Fig. 5.5, Callister & Rethwisch 8e.

B.C.

Chapter 5 - 20

Solution:

C (x , t )' Co & x # = 1 ' erf $ ! Cs ' Co % 2 Dt "

CS

2 #

"

z 0

e ! y dy

C(x,t) Co

Chapter 5 - 21

7 !

12/10/09 !

! Sample Problem: An FCC iron-carbon alloy initially containing ___________ is carburized at an elevated temperature and in an atmosphere that gives a surface carbon concentration constant at 1.0 wt%. If after _____ the concentration of carbon is 0.35 wt% at a position _____ below the surface, determine the temperature at which the treatment was carried out. ! Solution: use Eqn. 5.5

C( x, t ) ' Co & x # = 1 ' erf $ ! Cs ' Co % 2 Dt "

Chapter 5 - 22

Solution (cont.):

! t = 49.5 h ! Cx = 0.35 wt% ! Co = ________

- erf(z) = ______

Chapter 5 - 23

Solution (cont.):

We must now determine from Table 5.1 the value of z for which the error function is 0.8125. An interpolation is necessary as follows z 0.90 z 0.95 erf(z) 0.7970 0.8125 0.8209

z ! 0.90 0.8125 ! 0.7970 = 0.95 ! 0.90 0.8209 ! 0.7970

z = 0.93

z=

x 2 Dt

D=

x2 4 z 2t

Chapter 5 - 24

8 !

12/10/09 !

Solution (cont.):

! To solve for the temperature at which D has the above value, we use a rearranged form of Equation (5.9a);

T =

Qd R(lnDo ! lnD )

from Table 5.2, for diffusion of C in FCC Fe Do = 2.3 x 10-5 m2/s Qd = 148,000 J/mol - T=

148,000 J/mol (8.314 J/mol - K)(ln 2.3 x10 !5 m2 /s ! ln 2.6 x10 !11 m2 /s)

T = 1300 K = _______

Chapter 5 - 25

! Methylene chloride is a common ingredient of paint removers. Besides being an irritant, it also may be ___________ through skin. When using this paint remover, protective gloves should be worn. ! If butyl rubber gloves (______________) are used, what is the breakthrough time (tb), i.e., how long could the gloves be used before methylene _________ reaches the hand? ! Data (from Table 22.5) ! diffusion coefficient in butyl rubber: D = 110 x10-8 cm2/s

Chapter 5 - 26

! Solution assuming linear conc. _____________

glove C1 paint remover skin

tb =

!2 6D

C2 x1 x2

Equation from online CPC Case Study 5 at the Student Companion Site for Callister & Rethwisch 8e (www.wiley.com/ college/callister)

! = x2 ! x1 = 0.04 cm

D = 110 x 10-8 cm2/s

(0.04 cm)2 (6)(110 x 10 -8 cm2 /s)

tb =

= 240 s = 4 min

Chapter 5 - 27

9 !

12/10/09 !

Summary

Diffusion FASTER for...

open crystal structures materials w/secondary bonding smaller diffusing atoms lower density materials

close-packed structures materials w/covalent bonding larger diffusing atoms higher density materials

Chapter 5 - 28

10 !

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