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He Way To Somewhere: Sub-Topics Diffusion Diffusion Processes in Industry
He Way To Somewhere: Sub-Topics Diffusion Diffusion Processes in Industry
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Sub-topics
Diffusion
1 Diffusion processes in industry
RATE PROCESSES IN SOLIDS
At any temperature different from absolute zero all atoms, irrespective
of their state of aggregation (gaseous, liquid or solid), are constantly in
motion diffusion
Diffusion refers to the net flux of any species, such as ions,
atoms, electrons, holes, and molecules.
Flux = (conductivity) x (driving force)
this diffusion constant (D) reflects The term “gradient” describes the
the mobility of the diffusing variation of a given property as a
species in the given environment function of distance
2
NON-SPONTANEOUS PROCESSES
For process to be started,
the atoms should have 2.
1. sufficient energy to
overcome an activation
energy barrier. Q=activation energy
State 1
State 2
Involves reduction in energy
3
Or
Energy change is negative
DIFFUSION
As T of the system is increased, more and more molecules will attain the
activation energy level.
In statistical mechanics, Maxwell– Probability ~ exp(-∆E/RT)
Boltzmann statistics describes the
distribution of material particles R– Boltzman constant = 1.38
over various energy states and x10 -23 J/atom K 4
probabilities to find a particle in
definite state:
WHAT IS DIFFUSION?
5
SELF-DIFFUSION
C
C
A D
A
D
B
B t
6
VACANCY OR SUBSTITUTIONAL DIFFUSION
Why, in general, is
the activation energy
for self diffusion higher
for materials of high
melting point?
7
ATOMIC DIFFUSION IN SOLIDS
Examples:
9 Movement of smoke particles in air :
Very fast.
9 Movement of dye in water :
Relatively slow.
9 Solid state reactions : Very restricted
movement due to bonding.
8
Diffusion processes may be divided into two types:
(a) steady state and (b) non-steady state.
HOW FAST DOES DIFFUSION OCCUR?
Cu flux Ni flux
Concentration Concentration
of Cu [kg/m3] of Ni [kg/m3]
Position, x
• Concentration Profile, C(x): [kg/m3]
Steady state diffusion takes place at a constant rate - that is, once
the process starts the number of atoms crossing a given interface (the
flux) is constant with time.
This means that throughout the system dc/dx = constant and dc/dt = 0.
11
PROBLEM - CONCENTRATION GRADIENT
atoms/m2 s
Kg/m2 s Kg/m3
13
PROBLEM - SEMICONDUCTOR DOPING
One way to manufacture transistors, which amplify
electrical signals, is to diffuse impurity atoms into a
semiconductor material such as silicon (Si).
Problem: Suppose a silicon wafer 0.1 cm thick, which
originally contains one phosphorus atom for every 10
million Si atoms, is treated so that there are 400 P-
atoms for every 10 million Si atoms.
Calculate the concentration gradient (a) in atomic
percent/cm and (b) in atoms/(cm3 x cm)
The lattice
parameter of 14
silicon is 5.4307 A.
DIFFUSIVITY
Diffusivity depends on
16
EFFECT OF TEMPERATURE ON DIFFUSION
A large activation energy results in a relatively small diffusion coefficient.
19
DESIGN OF AN IRON MEMBRANE
A cylinder 3 cm in diameter
and 10 cm long contains a gas
that includes 0.5 x1020 N atoms
per cm3 and 0.5 x1020 H atoms
per cm3 on one side of an iron
membrane.
Gas is continuously introduced to the pipe to assure a constant
concentration of nitrogen and hydrogen.
The gas on the other side of the membrane includes a constant 1
1018 N atoms per cm3 and 1 x 1018 H atoms per cm3.
The entire system is to operate at 700 C (at this T iron has the BCC
structure).
Design an iron membrane that will allow no more than 1% of the
nitrogen to be lost through the membrane each hour,
while allowing 90% of the hydrogen to pass through the membrane
per hour. 20
TYPES OF DIFFUSION
In volume diffusion, the atoms move through the crystal
from one regular or interstitial site to another. Because of
the surrounding atoms, the activation energy is large and
the rate of diffusion is relatively slow.
Atoms can also diffuse along boundaries, interfaces, and
surfaces in the material. Atoms diffuse easily by grain
boundary diffusion, because the atom packing is
disordered and less dense in the grain boundaries.
Because atoms can more easily squeeze their way through
the grain boundary, the activation energy is low.
Surface diffusion is easier still because there is even less
constraint on the diffusing atoms at the surface.
21
TUNGSTEN -THORIUM DIFFUSION COUPLE
Consider a diffusion couple between pure tungsten
and a tungsten alloy containing 1 at% thorium.
After several minutes of exposure at 2000°C, a
transition zone of 0.01 cm thickness is established.
What is the flux of thorium atoms at this time if
diffusion is due to
(a) volume diffusion,
(b) grain boundary diffusion, and
The lattice parameter of
(c) surface diffusion? BCC tungsten is 3.165 Å.
22
NONSTEADY-STATE DIFFUSION
Concentration of solute atoms at any point in metal changes with
time in this case.
C(x,t)
Cs
t3
t2
to t1
Co
position, x
24
15
SOLUTION
One practically important solution is for a semi-infinite solid in which the
surface concentration is held constant.
Frequently, the source of the diffusing species is a gas phase, the partial
pressure of which is maintained at a constant value.
Furthermore, the following assumptions are made:
1.Before diffusion, any of the diffusing solute
atoms in the solid are uniformly distributed with
concentration of C0 .
2. x at the surface is zero and increases with
distance into the solid.
3. The time is taken to be zero before
the diffusion process begins.
25
FICK’S SECOND LAW – SOLUTION
26
TABULATION OF ERROR FUNCTION VALUES
27
CARBURIZING
Diffusing carbon
atoms
Low
carbon
Steel part
Carbon Gradients
In Carburized metals
• Result:
--hard to deform: C atoms
"lock" planes from shearing.
--hard to crack: C atoms put
the surface in compression. 28
INDUSTRIAL APPLICATIONS OF DIFFUSION –
CASE HARDENING
Sliding and rotating parts needs to have
hard surfaces.
30
TIME COMPUTATION
31
DIFFUSIVITY DATA FOR SOME METALS
32
PROBLEM: TIME FOR DIFFUSION
Carburizing: the steel piece is exposed, at an elevated temperature, to an
atmosphere rich in a hydrocarbon gas, such as methane (CH4 ).
Consider an alloy that initially has a uniform carbon concentration
of 0.25 wt% and is to be treated at 950 C. If the concentration of carbon at
the surface is suddenly 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?
The diffusion coefficient for carbon in iron at this temperature is 1.6 x 10 -11
m2/s.
33
DESIGN PROBLEM
The wear resistance of a steel gear is to be improved by hardening its
surface. This is to be accomplished by increasing the carbon content
within an outer surface layer as a result of carbon diffusion into the
steel; the carbon is to be supplied from an external carbon-rich gaseous
atmosphere at an elevated and constant temperature.
The initial carbon content of the steel is 0.20 wt%, whereas the surface
concentration is to be maintained at 1.00 wt%. In order for this treatment
to be effective, a carbon content of 0.60 wt% must be established at a
position 0.75 mm below the surface.
Specify an appropriate heat treatment in terms of temperature and time
for temperatures between 900C and 1050 C. Use data in Table for the
diffusion of carbon in γ-iron. The gas const = 8.31 J/mol K
34
DESIGN OF A MORE ECONOMICAL HEAT
TREATMENT
10 h are required to successfully carburize a batch of 500 steel
gears at 900°C, where the iron has the FCC structure.
We find that it costs $1000 per hour to operate the carburizing
furnace at 900°C and $1500 per hour to operate the furnace at
1000°C.
Is it economical to increase the carburizing temperature to
1000°C?
What other factors must be considered?
35
SUMMARY:
STRUCTURE & DIFFUSION
20