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 7 - 1
 WHY STUDY Diffusion?

Materials of all types are often heat treated to improve their

properties. The phenomena that occur during a heat
treatment almost always involve atomic diffusion.

Often an enhancement of diffusion rate is desired; on

occasion measures are taken to reduce it.

Heat-treating temperatures and times, and/or cooling rates

are often predictable using the mathematics of diffusion and
appropriate diffusion constants.

Chapter 7 - 2
 WHY STUDY Diffusion?

The steel gear shown on this page

has been case hardened; that is,
its hardness and resistance to
failure by fatigue have been
enhanced by diffusing excess
carbon or nitrogen into the outer
surface layer.

Chapter 7 - 3
 Diffusion
Diffusion - Mass transport by atomic motion
- The phenomena that occur during a heat
treatment almost always involve atomic diffusion.

Mechanisms
• Gases & Liquids – random (Brownian) motion
• Solids – vacancy diffusion or interstitial diffusion

Inter-diffusion – atoms of one metal diffuse into

another.
self-diffusion - Diffusion also occurs for pure metals,
but all atoms exchanging positions are of the same
type.
Chapter 7 - 4
 Diffusion
• Interdiffusion: In an alloy, atoms tend to migrate from regions
of high conc. to regions of low conc.
after high temp.( below melting temp.) - heat treatment
Initially After some time

Copper-Nickel
Chapter 7 - 5
Chapter 7 - 6
Diffusion

Chapter 7 -
 Diffusion Simulation

Microstructure of the 4.0 mass% iron decarburized for 1 min at

a 1293 K, b 1353 K, and c 1413 K with 4.0 mass% C
Hong et al. (2019). Mechanism of Carbon Diffusion in the Iron Sheet During Gas– Solid Decarburization. Trans Indian Inst Met. 72(2), 335-342.

Chapter 7 - 8
Chapter 7 - 9
 ATOMIC VIBRATIONS
• Every atom in a solid material is vibrating very rapidly about its
lattice position within the crystal.

• At any instant of time not all atoms vibrate at the same

frequency and amplitude, nor with the same energy.

• With rising temperature, this average energy increases, and, in

fact, the temperature of a solid is really just a measure of the
average vibrational activity of atoms and molecules.

• Many properties and processes in solids are manifestations of

this vibrational atomic motion.

• For example, melting occurs when the vibrations are vigorous

enough to rupture large numbers of atomic bonds.

Chapter 7 - 10
 Diffusion Mechanisms
Vacancy Diffusion:
• atoms exchange with vacancies
• applies to substitutional impurities atoms
• rate depends on:
-- number of vacancies (increases with rising temp.)
-- activation energy to exchange. (increases with rising temp.)

increasing elapsed time

Chapter 7 - 11
 Diffusion Mechanisms
Rate of substitutional diffusion depends on:
--vacancy concentration.

Chapter 7 -
 Diffusion Mechanisms
• Interstitial diffusion – smaller atoms can
diffuse between atoms.

More rapid than vacancy diffusion

Chapter 7 - 13
Diffusion Mechanisms

Chapter 7 -
 Processing Using Diffusion
• Case Hardening:
-- Diffuse carbon atoms
into the host iron atoms
at the surface.
-- Example of interstitial
diffusion is a case
hardened gear.
• Result: The presence of C
atoms makes iron (steel)
harder and more resistance
to failure by fatigue (cyclic
loading).

- hard to deform: C atoms "lock"

planes from shearing.
-hard to crack: C atoms put the
surface in compression. Chapter 7 - 15
 Processing Using Diffusion
• Doping silicon with phosphorus for n-type semiconductors:
• Process: 0.5 mm
1. Deposit P rich
layers on surface.
magnified image of a computer chip

silicon
2. Heat it.
3. Result: Doped light regions: Si atoms
semiconductor
regions.

light regions: Al atoms

silicon
Chapter 7 - 16
 Diffusion
Diffusion flux (J), defined as the mass (or, equivalently, the number of atoms) M
diffusing through and perpendicular to a unit cross-sectional area of solid per unit
of time.
• How do we quantify the amount or rate of diffusion?

• Measured empirically
– Make thin film (membrane) of known cross-sectional area
– Impose concentration gradient
– Measure how fast atoms or molecules diffuse through the
membrane

M=
mass J  slope
diffused
time
Chapter 7 - 17
Chapter 7 - 18
Fick`s first law of diffusion

Steady-State Diffusion
Rate of diffusion independent of time
Flux proportional to concentration gradient =

C 1 C1 Fick’s first law of diffusion

C2 C2

x1 x2 D  diffusion coefficient
x
A negative sign because from
higher to lower concentration

Chapter 7 - 19
 One practical example of steady-state
diffusion is found in the purification of
hydrogen gas. One side of a thin sheet of
palladium metal is exposed to the impure gas
composed of hydrogen and other gaseous
species such as nitrogen, oxygen, and water
vapor. The hydrogen selectively diffuses
through the sheet to the opposite side, which
is maintained at a constant and lower
hydrogen pressure

Chapter 7 - 20
Chapter 7 - 21
 Example: Chemical Protective
Clothing (CPC)
• Methylene chloride 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 (0.04 cm thick) are used, what
is the diffusive flux of methylene chloride through the
glove?
• Data:
– diffusion coefficient in butyl rubber:
D = 110 x10-8 cm2/s
– surface concentrations: C1 = 0.44 g/cm3
C2 = 0.02 g/cm3

Chapter 7 - 22
 Example (cont).
• Solution – assuming linear conc. gradient
glove
C1 2
tb =
6D
paint skin
remover
C2 Data: D = 110 x 10-8 cm2/s
x1 x 2 C1 = 0.44 g/cm3
C2 = 0.02 g/cm3
x2 – x1 = 0.04 cm

Chapter 7 - 23
Example

Chapter 7 - 24
Chapter 7 -
Chapter 7 -
 Diffusion and Temperature

• Diffusion coefficient increases with increasing T

Qd
D = Do exp -
RT

D = diffusion coefficient [m2/s]

Do = pre-exponential [m2/s]
Qd = activation energy [J/mol or eV/atom]
R = gas constant [8.314 J/mol-K]
T = absolute temperature [K]

Chapter 7 - 27
 Diffusion and Temperature
D has exponential dependence on T
1500

1000

600

300
T(°C)
10-8

D (m2/s) Dinterstitial >> Dsubstitutional

C in α-Fe Al in Al
10-14 C in γ-Fe Fe in α-Fe
Fe in γ-Fe

10-20
0.5 1.0 1.5 1000 K/T

Ex. For the self-diffusion of Fe in α-Fe, the diffusion coefficient

increases approximately six orders of magnitude (from 3.0x10-21 to
1.8x10-15 m 2 /s) in rising temperature from 500 to 900 C (see table)
Chapter 7 - 28
Example: At 300°C the diffusion coefficient and
activation energy for Cu in Si are
D(300°C) = 7.8 x 10-11 m2/s
Qd = 41.5 kJ/mol
What is the diffusion coefficient at 350°C?

Qd
D transform ln D D = Do exp -
data RT

Temp = T 1/T

Chapter 7 - 29
 Example (cont.)

T1 = 273 + 300 = 573 K

T2 = 273 + 350 = 623 K

D2 = 15.7 x 10-11 m2/s Chapter 7 - 30

 Non-steady State Diffusion
• Most practical diffusion situations are nonsteady-
state ones. That is, the diffusion flux (J) and the
concentration gradient (dC/dx) at some particular
point in a solid vary with time.

• The concentration of diffusing species is a function of

both time and position C = C(x,t)
• In this case Fick’s Second Law is used

Fick’s Second Law

Chapter 7 - 31
 Non-steady State Diffusion
• Copper diffuses into a bar of aluminum.
Surface conc.,
Cs of Cu atoms bar
pre-existing conc., Co of copper atoms

Cs

B.C. at t = 0, C = Co for 0  x  ∞
at t > 0, C = CS for x = 0 (constant surface conc.)
C = Co for x = ∞
Chapter 7 - 32
 Non-steady State Diffusion

C(x,t) = Conc. at point x at CS

time t
erf(z) = error function
C(x,t)
erf(z)
Co

*erf=error function=the standard normal

cumulative probability Chapter 7 - 33
erf(z) values

Chapter 7 - 34
Chapter 7 - 35
Chapter 7 - 36
 Example
• For some applications, it is necessary to harden the surface of a steel (or
ironcarbon alloy) above that of its interior. One way this may be accomplished is
by increasing the surface concentration of carbon in a process termed
carburizing; the steel piece is exposed, at an elevated temperature, to an
atmosphere rich in a hydrocarbon gas.
• Consider one such alloy that initially has a uniform carbon concentration of 0.25
wt% and is to be treated at 950°C (1750 F). 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 1.6x10-
11 m2/s.
• Solution: Since this is a nonsteady-state diffusion problem in which the surface
composition is held constant, Equation

• is used.

Chapter 7 - 37
 Solution
• Values for all the parameters in this expression except time t are specified in the
problem as follows:

• We must now determine the value of z for which the error function is 0.4210. An
interpolation is necessary, as

Chapter 7 - 38
Solution

Chapter 7 - 39
 Example
• Sample Problem: An FCC iron-carbon alloy initially
containing 0.20 wt% C is carburized at an elevated
temperature and in an atmosphere that gives a
surface carbon concentration constant at 1.0 wt%. If
after 49.5 h the concentration of carbon is 0.35 wt%
at a position 4.0 mm below the surface, determine
the temperature at which the treatment was carried
out.

• Solution:

Chapter 7 - 40
Solution (cont.):

– t = 49.5 h x = 4 x 10-3 m
– Cx = 0.35 wt% Cs = 1.0 wt%
– Co = 0.20 wt%

 erf(z) = 0.8125

Chapter 7 - 41
Solution (cont.):
We must now determine from Table the value of z for which the
error function is 0.8125. An interpolation is necessary as follows

z erf(z)
0.90 0.7970
z 0.8125 z = 0.93
0.95 0.8209

Now solve for D

Chapter 7 - 42
 Qd
Solution (cont.): D = Do exp -
RT
• To solve for the temperature at
which D has the above value,
we use a rearranged form of
Equation;
R = gas constant [8.314 J/mol-K]
from Table (next slide), for diffusion of C in FCC Fe
Do = 2.3 x 10-5 m2/s Qd = 148,000 J/mol

T = 1300 K = 1027°C
Chapter 7 - 43
A Tabulation of Diffusion Data

Chapter 7 - 44
 Example
• Using the data in Table Diffusion Data, compute the
diffusion coefficient for magnesium in aluminum at
550 °C.
• Solution: Q
• This diffusion coefficient may be determined by D = D exp -
d
o RT
R = gas constant [8.314 J/mol-K]

• applying Equation 5.8; the values of D0 and Qd from Table are 1.2x10-4 m2/s
and 131 kJ/mol, respectively. Thus,

Chapter 7 - 45
 Summary
Diffusion FASTER for... Diffusion SLOWER for...

• open crystal structures • close-packed structures

• materials w/secondary • materials w/covalent

bonding bonding

• smaller diffusing atoms • larger diffusing atoms

• lower density materials • higher density materials

Carbon steel is an iron-carbon alloy in which the carbon content

usually varies from 0.15% to 1.5% Chapter 7 - 46
Questions?

Chapter 7 - 47
 HOMEWORK
1. Determine the carburizing time necessary to achieve a carbon
concentration of 0.30 wt% at a position 4 mm into an iron–
carbon alloy that initially contains 0.10 wt% C. The surface
concentration is to be maintained at 0.9 wt% C, and the
treatment is to be conducted at 1100C. Use the diffusion data
for γ-Fe in Table.

Chapter 7 - 48