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Chapter: 6
DIFFUSION
Engineering Materials
Learning Objectives
After studying this chapter you should be able to do the
following:
Name and describe the two atomic mechanisms of
diffusion. Indicate which type of diffusion occurs more
rapidly, and then explain why this is so.
Distinguish between steady-state and non-steady state
diffusion.
(a) Write Ficks first and second laws in equation form,
and define all parameters. (b) Note the kind of diffusion
for which each of these equations is normally applied.
Define all parameters of Ficks second law for diffusion.
Calculate the diffusion coefficient for some material at a
specified temperature, given the appropriate diffusion
constants.
Give a brief definition of diffusion.
Engineering Materials
Explain the terms interdiffusion and self-diffusion.
Given the mass of material diffusing through a cross-sectional
area over a specified time period, compute the diffusion flux.
Define the terms concentration profile and concentration
gradient.
For steady-state diffusion through a metal sheet, determine the
diffusion flux given values for the diffusion coefficient, the
sheet thickness, and the concentrations of diffusing species at
both surfaces.
Cite the driving force for steady-state diffusion.
Cite two factors that influence diffusion rate (i.e., the
magnitude of the diffusion coefficient).
Given the pre-exponential, Do, the activation energy, the
absolute temperature, and the gas constant, be able to compute
the value of the diffusion coefficient.
Engineering Materials
Diffusion
Diffusion
What is diffusion?
Diffusion is material
transport by atomic
motion.
Inhomogeneous
materials can become
homogeneous
by
diffusion.
For an active diffusion
to
occur,
the
temperature should
be high enough to
overcome
energy
barriers to atomic
motion.
properties of materials.
Desirable properties of sliding parts (e.g. gears and shafts): soft core for high
fracture toughness; and hard surface for better wear resistance.
Solution:
Enriching carbon content at the surface by
diffusion carburizing
Industrial Applications of
Diffusion Processes: Gas Purification
Industrial Applications of
Diffusion Processes: Doping of Silicon Wafers
Galvanized coating
Steel
Examples of diffusion
A balloon filled with helium will deflate a little bit every
day, because helium atoms diffuse out of the balloon
through its wall
When spaghetti is cooked, water molecules diffuse into
the spaghetti strings, making them thicker and more
flexible.
Heat diffuses through the walls of a mug filled with hot
coffee
A sugar cube in a glass of water that is not stirred will
dissolve slowly and the sugar molecules will
Types of Diffusion
1. Inter-diffusion: In an alloy, atoms tend to
migrate from regions of high conc. to regions of
low conc.
After some time
Initially
Types of Diffusion
2. Self-diffusion: In an elemental solid, atoms
also migrate.
Label some atoms
C
A
D
B
Diffusion Mechanisms
1. Vacancy Diffusion:
Two conditions to occur:
i.
there must be an empty adjacent site available
ii.
the atom must have sufficient energy to break bonds
with its neighbor atoms and then cause some lattice
distortion during the displacement.
Both self-diffusion and inter-diffusion occur by this
mechanism
Diffusion Mechanisms
Vacancy---Self Diffusion
Vacancy
Vacancy
Atom
Diffusion Mechanisms
2. Interstitial diffusion
A small interstitial atom moves
interstitial site to another.
No vacancy is needed or created.
from
one
Interstitial diffusion
Simulation
of
the
vacancy
mechanism
Simulation of the
direct interstitial
mechanism
Steady-state diffusion:
Steady state diffusion: Diffusion flux does not
change with time
Concentration of diffusion species on both
surface of the plate are held constant
Diffusion flux (J): Mass (or, equivalently, the
number of atoms) M diffusing through and
perpendicular to a unit cross-sectional area
of solid per unit of time
J = M/At
A; area across which diffusion occurring
and t: elapsed diffusion time.
J= (1/A) (dM/dt)
J: kg/m2 -s or atoms/m2 s
Steady-state diffusion:
Flux;
The flux during
diffusion is defined
as the number of
atoms passing
through a plane of
unit area per unit
time
Flux can be measured
for:
--vacancies
--host atoms
--impurity atoms
Steady-state diffusion:
When concentration C is
plotted vs. position (or
distance, the resulting curve
is termed the concentration
profile:
The slope at particular point
on this curve is
the
concentration gradient
Concentration gradient:
=C /x (kg/m3)
Steady-state diffusion:
The flux is proportional to the
concentration gradient through
the expression
J = -D (C)/ (x)
D:
diffusion
coefficient
(m2)/sec
Negative sign: the expression
indicate
the
direction
of
diffusion
is
shown
the
concentration
gradient,
from
high
to
a
low
concentration
Ficks first law
Steady-state diffusion:
EXAMPLE
At a particular temperature, the diffusion coefficient for Pb in naturally occurring
28
2
ZrSiO4 is
D 8.310
cm s
Find the value of the concentration gradient where the flux of lead, J, is equal to
g
J 5.0 10 2
cm s
30
ANSWER
dC
J D
dx
dC
J
dx
D
dC
5 1030 g s
cm2 s
cm2
dx
8.3 1028
dC
3 g
6.02 10 4
cm
dx
Steady-state diffusion:
plate of iron is exposed to a carburizing (carbon-rich) atmosphere on one side
and a decarburizing (carbon-deficient) atmosphere on the other side at 700C
(1300F). If a condition of steady state is achieved, calculate the diffusion flux
of carbon through the plate if the concentrations of carbon at positions of 5
and 10 mm beneath the carburizing surface are 1.2 and 0.8 kg/m3, respectively.
Assume a diffusion coefficient of 310-11m2/s at this temperature.
Steady-state diffusion:
A sheet of steel 1.5mm thick has nitrogen atmosphere on both sides at
1200C and is permitted to achieve a steady-state diffusion condition. The
diffusion coefficient for nitrogen in steel at this temperature is 610-11m2/s,
and the diffusion flux is found to be 1.210-7kg/m2-s. Also, it is known that
the concentration of nitrogen in the steel at the high-pressure surface is 4
kg/m3. How far into the sheet from this high-pressure side will the
concentration be 2.0 kg/m3? Assume a linear concentration profile.
Steady-state diffusion:
Example
You want to select a polymer for making plastic bottles that can
be used for storing carbonated beverages. What factors would
you consider in choosing a polymer for this application?
SOLUTION
First, since the bottles are to be used for storing carbonated
beverages, a plastic material with a small diffusivity for
carbon dioxide gas should be chosen.
The bottles should have enough strength so that they can
survive a fall of about six feet. This is often tested using a
drop test.
The surface of the polymer should also be amenable to
printing of labels or other product information.
The effect of processing on the resultant microstructure of
polymers must also be considered
Non-steady-state diffusion
Ficks Second Law
1. The concentration gradient at a specific point along the
diffusion path changes with time, t.
2. This transient condition is represented by a second-order
differential equation also known as Fick's second law.
dC d
dC
[ D. ]
dt dx
dx
3.
dC
d C
D. 2
dt
dx
1. For t =0, C = C0 at 0 x
2. For t > 0, C = Cs at x = 0, C = C0
at x =
Cs C x
x
erf (
)
C s Co
2 Dt
erf(z)
erf(z)
erf(z)
0.0000
0.55
0.5633
1.3
0.9340
0.025
0.0282
0.60
0.6038
1.4
0.9523
0.05
0.0564
0.65
0.6420
1.5
0.9661
0.10
0.1125
0.70
0.6778
1.6
0.9763
0.15
0.1680
0.75
0.7111
1.7
0.9838
0.20
0.2227
0.80
0.7421
1.8
0.9891
0.25
0.2763
0.85
0.7707
1.9
0.9928
0.30
0.3286
0.90
0.7969
2.0
0.9953
0.35
0.3794
0.95
0.8209
2.2
0.9981
0.40
0.4284
1.00
0.8427
2.4
0.9993
0.45
0.4755
1.1
0.8802
2.6
0.9998
0.50
0.5205
1.2
0.9103
2.8
0.9999
Cs - Co
0.8 0.25
1.2 0.25
0.5789
x
1 erf
2 Dt
x
erf
= 0.421
2 Dt
= 0.392 =
2[ (1.6 x 10-11 m2/s)1/2] ( t)1/2
2 Dt
t = 7.1 h
SOLUTION
SOLUTION (Continued)
SOLUTION
SOLUTION
2. Temperature:
- higher temp, higher diffusion rate. (higher D values)
Diffusion Coefficient:
Do
D Do e
Q
(
)
RT
SUMMARY:
STRUCTURE & DIFFUSION
Diffusion FASTER for...
close-packed structures
materials w/secondary
bonding
materials w/covalent
bonding
cations
anions
Summary
Steady-state diffusion
In general diffusion rate (J) can be defined as the rate of mass (M) transfer per unit
time (t) per unit cross-sectional area (A).
If the rate of diffusion does not change with time, it is governed by
Ficks First Law