CHAPTER 5
Diffusion in Solids
(Callister p 180-194)
Study Theme outcomes: After studying this chapter the students
should be able to
- describe the diffusion mechanism
- distinguish between steady and unsteady state diffusion process
- Understand the difference between Fick’s first law and second
law.
- Application of diffusion in industry.
- Factors that influence the diffusion coefficient
-Solve problems based on knowledge gained in this chapter
regarding diffusion
5.1 Atomic Diffusion in Solids.
Solid-state diffusion: The process whereby atoms and ions move
(migrate) through the crystal lattice. Diffusion occurs because of
the atoms having vibration energy, which assists them to jump
from one position in the crystal lattice to another. The higher the
temperature, the higher the jump rate and thus diffusion.
Importance of diffusion: processing of materials, like heat
treatment of steel and doping of micro-electronic components,
creep, recrystallization etc. involve atomic movements.
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Example of experimental proof of diffusion:
When two metals are brought in close contact at elevated
temperature (e.g. copper and nickel).
Cu Ni at t0 : pure Cu and pure Ni
100
%Cu
t t2 t1
50
at t : homogenous solid
solution of Cu and Ni
5.2 Diffusion Mechanisms
Vacancy or substitutional diffusion
Atoms can move from one atomic site to another if there are
vacancies in the lattice for the atoms to move. The activation
energy for the movement is provided by the thermal vibration of
the atoms.
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Fig 5.1: Energy requirements for atoms to move
(Ref: Ashby Fig. 13.9)
Interstitial diffusion
Small atoms (eg. carbon) can diffuse by moving from one
interstitial position to another, without permanently displacing
the atoms in the matrix (parent) crystal lattice. Interstitial
diffusion requires less activation energy and is, therefore, more
rapid than substitutional diffusion. Interstitial spaces need not
be created as vacancies are.
Fig 5.2: Schematic of Interstitial diffusion (Ref: Callister Fig. 7.3)
5.3 Steady State Diffusion
Consider the diffusion of solute atoms within the lattice of the
solvent. Diffusion will occur if a concentration gradient of solute
atoms exist:
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Fig 5.3: Steady State Diffusion Profile (Ref: Callister Fig. 7.4)
Steady-state diffusion occurs if CA and CB remain constant with
time and if the concentration gradient (dC/dx) remains
unchanged. Under these conditions, the flux (J) of solute atoms,
which moves from plane xA to plane xB, is given by Fick's First
Law:
J = - D dc/dx (1)
J = Diffusion flux (kg/m2.s or atoms/m2.s)
D = Diffusivity (diffusion coefficient) with units (m2/sec.)
5.4 Non-steady State Diffusion
Steady-state diffusion is not commonly encountered in
engineering materials. In most cases non-steady state diffusion,
in which the concentration of solute atoms at any point in the
material changes with time, takes place.
Example: Diffusion of carbon into the surface of a steel camshaft
or gear. (Surface hardening by carburization)
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For cases like these, Fick's Second Law must be applied:
dCx = d (D dCx) …………………(2)
dt dx dx
The solution to (2), is dependant on the application
One of the applications, and thus solutions to the differential
equation is for example:
Consider the case of gas A (solute) diffusing into solid B.
As the time of the diffusion increases, the concentration of solute
atoms at any point will also increase. However, the surface
concentration of the solute will remain constant.
Fig 5.4: Profile for nonsteady state condition at various times
(Ref: Callister Fig. 7.5 & 7.6)
In this case, the solution to equation (2) is as follows:
Cs Cx x
erf
Cs C0 2 Dt
erf = Error Function (Callister Table 7.1)
Cs = surface concentration of A
C0 = initial uniform concentration of A in the solid
Cx = concentration of A at distance x at time t
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x = distance from the surface
D = diffusivity of A in B at temp. T
Table for diffusivities of some systems.
See also Callister ex. Problem 7.2 & 7.3
Gallium (Ga) is diffused into a silicon wafer with no previous Ga in
it, at a temperature of 1100C for 3h. What is the depth below the
surface at which the concentration is 1022 atoms/m3 if the surface
concentration is 1024 atoms/m3?
Given: At 1100C: D = 7,0 x 10-17 m2/s.
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.5.4 Factors that influence D
Type of diffusion mechanism
Temperature
Temperature dependence of D:
D D 0 e Q/RT
With D0 = temperature independent constant (m2/s)
Q = activation energy (J/mol) (Callister Table 7.2)
See: Callister ex. Problem 7.4 & 7.5
Type of crystal structure of the solvent.
Compare for example the D values for C in Fe in Table 4.4.
The BCC – Fe has a lower APF and larger inter-atomic
opening for diffusion to occur.
Type of crystal defects present.
The less densely packed the atoms, for example at grain
boundaries, and the higher the vacancy concentration, the
higher the diffusivity.
Concentration of diffusing species. - Complex
5.5 Industrial Applications of Diffusion Processes
1) Heat treatment of engineering components.
All types of heat treatment require re-arrangement of atoms by
diffusion.
2) Case hardening of steel components by carburizing.
# See Callister p 180
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# See Callister ex. Prob. 7.1.
Class example: Calculate the time in minutes to gas carburize a
gear of 1020 steel at 927 oC to a concentration of 0,4 % C at a
depth of 0,7 mm. Surface concentration of C is 0,9 % and initial
concentration of the steel is 0,2 % C. D 927 = 1,28 x 10-11 m2/s
(143 min.)
3) Impurity diffusion into silicon wafers for integrated micro-
electronic circuits ("doping").
. Refer Callister Chapter 7 for problems
Assignment: See problems on clickUP
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