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Lecture 08 - Diffusion in Solids PDF

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154 views23 pages

Lecture 08 - Diffusion in Solids PDF

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icagayle V
Copyright
© © All Rights Reserved
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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?

1
DIFFUSION DEMO
• Glass tube filled with water.
• At time t = 0, add some drops of ink to one end
of the tube.
• Measure the diffusion distance, x, over some time.
• Compare the results with theory.

2
WHY STUDY DIFFUSION?
• Materials of all types are often heat treated to improve their
properties.
•The phenomenon that occur during heat treatment is almost
always involved atomic diffusion.

Definition:

Diffusion – Mass transport by atomic motion.


DIFFUSION: THE PHENOMENA (1)
• Interdiffusion: In an alloy, atoms tend to migrate
from regions of large concentration.
Initially After some time

Adapted
from Figs.
5.1 and 5.2,
Callister 6e.

3
DIFFUSION: THE PHENOMENA (2)
• Self-diffusion: In an elemental solid, atoms
also migrate.

Label some atoms After some time

C
A
D
B

4
DIFFUSION MECHANISMS
Substitutional Diffusion:
• applies to substitutional impurities
• atoms exchange with vacancies
• rate depends on:
--number of vacancies
--activation energy to exchange.

5
DIFFUSION SIMULATION
• Simulation of
interdiffusion
across an interface:

• Rate of substitutional
diffusion depends on:
--vacancy concentration
--frequency of jumping.

(Courtesy P.M. Anderson)

6
INTERSTITIAL SIMULATION
• 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 (Courtesy P.M. Anderson)

unit cell edges.


7
PROCESSING USING DIFFUSION
• Case Hardening:
--Diffuse carbon atoms Fig. 5.0,
Callister 6e.
into the host iron atoms (Fig. 5.0 is
courtesy of
at the surface. Surface
Division,
--Example of interstitial Midland-
Ross.)
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.

8
PROCESSING USING DIFFUSION
• Doping Silicon with P for n-type semiconductors:
• Process:
1. Deposit P rich
layers on surface.

silicon
Fig. 18.0,
2. Heat it. Callister 6e.

3. Result: Doped
semiconductor
regions.

9
MODELING DIFFUSION: FLUX
• Flux:

• Directional Quantity

• Flux can be measured for:


--vacancies
--host (A) atoms
--impurity (B) atoms
10
CONCENTRATION PROFILES & FLUX
• Concentration Profile, C(x): [kg/m3]
Cu flux Ni flux

Concentration Concentration Adapted


of Cu [kg/m3] of Ni [kg/m3]
from Fig.
5.2(c),
Callister 6e.

Position, x
• Fick's First Law:

• The steeper the concentration profile,


the greater the flux!
11
STEADY STATE DIFFUSION
• Steady State: the concentration profile doesn't
change with time.

dC
• Apply Fick's First Law: J x = −D
dx
 dC   dC 
• If Jx)left = Jx)right , then   = 
 dx  left  dx  right

• Result: the slope, dC/dx, must be constant


(i.e., slope doesn't vary with position)!
12
EX: STEADY STATE DIFFUSION
• Steel plate at
700C with
geometry
shown:
Adapted
from Fig.
5.4,
Callister 6e.

• Q: How much
carbon transfers
from the rich to
the deficient side?

13
NON STEADY STATE DIFFUSION
• Concentration profile,
C(x), changes
w/ time.

• To conserve matter: • Fick's First Law:

• Governing Eqn.:

14
EX: NON STEADY STATE DIFFUSION
• Copper diffuses into a bar of aluminum.

C(x,t)
Cs

t3 Adapted from
t2 Fig. 5.5,
t1 Callister 6e.
t
Co o
position, x
• General solution:

"error function"
Values calibrated in Table 5.1, Callister 6e.
15
EX: NON STEADY STATE DIFFUSION

For some applications, it is necessary to harden the


surface of a steel and one way this may be accomplished is by
increasing the surface concentration of carbon in a process
called Carburization.

Consider an alloy that initially has a uniform


concentration of 0.25 wt% and is to be treated at 9500C. If the
concentration of carbon at the surface is brought to and
maintained at 1.20 wt%, how long will it take to achieve a
carbon content of 0.80 wt% at a position 0.5 mm below the
surface? DC = 1.6 x 10-11 m2/s.
PROCESSING QUESTION
• 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.
• Result: Dt should be held constant.

Note: values
• Answer: of D are
provided here.
16
DIFFUSION DEMO: ANALYSIS
• The experiment: we recorded combinations of
t and x that kept C constant.

 
C(x i , t i ) − Co x
= 1− erf  i 
 = (constant here)
Cs − Co  2 Dt i 

• Diffusion depth given by:


DIFFUSION AND TEMPERATURE
• Diffusivity increases with T.

• Experimental Data:

D has exp. dependence on T


Recall: Vacancy does also!
Dinterstitial >> Dsubstitutional
C in -Fe Cu in Cu
C in -Fe Al in Al
Fe in -Fe
Fe in -Fe
Zn in Cu

Adapted from Fig. 5.7, Callister 6e. (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.)
Assignment #5

The diffusion coefficients for iron in nickel are given at two


temperatures:
T(K) D(m2/s)
1273 9.4 x 10-16
1473 2.4 x 10-14
a) Determine the values of Do and the activation energy Qd..
b) What is the magnitude of D at 11000 C?
SUMMARY: STRUCTURE & DIFFUSION
Diffusion FASTER for... Diffusion SLOWER for...

• open crystal structures • close-packed structures

• lower melting T materials • higher melting T materials

• materials w/secondary • materials w/covalent


bonding bonding

• smaller diffusing atoms • larger diffusing atoms

• cations • anions

• lower density materials • higher density materials

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