Diffusion

J. Ernesto Indacochea
University of Illinois at Chicago
Civil and Materials Engineering Dept.

Introduction
Atoms and molecules can be quite mobile at Tset in both
liquids and solids:
Drop of ink in a beaker of water
colored.
Intermixing at molecular level

spread, water evenly

diffusion

Continuous motion of H2O molecules in water at R.T.

exemplifies self-diffusion.
Atomic-scale motion (diffusion) in liquids is relatively
rapid and easily to visualize.
More difficult to visualize diffusion in rigid solids, but it
does occur.
J. Ernesto Indacochea

Diffusion in Materials

UIC

Introduction
Diffusion is related to the internal atom movement.
Heat treatments alter the properties of materials
Only possible by
atom movement

Internal structure of
material must change

Diffusion required for:

Heat treatment of metals
Manufacture of ceramics
Solidification of materials
Manufacture of transistors and solar cells
Electrical conductivity of ceramic materials

J. Ernesto Indacochea

Diffusion in Materials

UIC

Introduction
Applications of Diffusion

J. Ernesto Indacochea

Diffusion in Materials

UIC

Introduction
Difference between liquid-state and solid state diffusion is
the slower diffusion rate in the solid.
Tight atomic structure of atoms has an impact on the
diffusion of atoms or ions within the solid.
The energy requirements to squeeze most atoms or ions
through a perfect crystal structure are so high that
diffusion is nearly impossible.

J. Ernesto Indacochea

Diffusion in Materials

UIC

Vacancy Diffusion
What is needed to make solid-state diffusion practical?
POINT DEFECTS!!!

J. Ernesto Indacochea

Diffusion in Materials

UIC

Vacancy Diffusion
atom interchange from a normal lattice position to an
adjacent vacant lattice site.
the extent of vacancy diffusion is controlled by the
concentration of these defects.
the direction of vacancy motion is opposite to direction
of diffusing atoms.
both self-diffusion and interdiffusion occur by this
mechanism.

J. Ernesto Indacochea

Diffusion in Materials

UIC

Diffusion Concepts
processes reactions in solid state occur by spontaneous
rearrangement of atoms into a more stable state.
for reactions to proceed from an unreacted to a reacted
state, atoms must have enough energy to overcome an
activation energy barrier.
E

atom

Ea

vacancy

distance

J. Ernesto Indacochea

Diffusion in Materials

UIC

Diffusion Concepts
Stepwise migration of atoms from a lattice point to another.
In a solid material atoms are in constant motion.
Conditions for atom migration:
empty adjacent site.
atom must have enough energy to break bonds and cause lattice
distortion during displacement.

diffusive motion influenced by atom vibrational energies

f(T)

J. Ernesto Indacochea

Diffusion in Materials

UIC

Interstitial Diffusion
migration of interstitial atoms
from and interstitial position to
adjacent empty one. Typical
interstitial atoms: hydrogen,
carbon, nitrogen, and oxygen.
In most metals interstitial
diffusion occurs much more
rapidly than vacancy diffusion.

J. Ernesto Indacochea

Diffusion in Materials

UIC

10

Activation Energy for Diffusion

a diffusing atom must
squeeze past neighbor
atoms to reach new site.
Energy must be supplied
to force atom to its new
position activation
energy, Q.
normally less energy is
required to squeeze an
interstitial atom past the
surrounding atoms.
C. Smith; The Science of Engineering Materials; Prentice Hall

J. Ernesto Indacochea

Diffusion in Materials

UIC

11

Activation Energy for Diffusion

Diffusion System

Q
(cal/mole)

J. Ernesto Indacochea

Do
(cm2/s)

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Factors Influencing Diffusion

Diffusing Species:
the magnitude of the diffusion coefficient D is indicative
of the rate at which atoms diffuse.
temperature has a profound effect on diffusion rates:

D = DO
Qd 1
ln D = ln D o

R T
J. Ernesto Indacochea

Qd
exp

RT
Qd 1
log D = log D o

2.3 R T
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Factors Influencing Diffusion

Arrhenius plot relationship between diffusion coefficient

and reciprocal of temperature for different elements.

J. Ernesto Indacochea

Diffusion in Materials

UIC

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Factors Influencing Diffusion

Diffusing Species:
The crystal structure of the metal affects the diffusion rate:
Diffusivities of different elements in BCC-Fe are higher than in FCC-Fe
at the same temperature (e.g. 910C).
Reasons for faster diffusion in BCC compared with FCC iron:
BCC iron lattice is slightly more open; it has lower packing factor than FCC.
BCC lattice has a coordination number of 8 compared with 12 in FCC
fewer bonds must be broken when elements diffuse in BCC iron.

G.F. Carter. Principles of Physical & Chemical Metallurgy. American Society for Metals (1979)

J. Ernesto Indacochea

Diffusion in Materials

UIC

15

Factors Influencing Diffusion

Diffusion is faster along grain boundaries than

through grains:

More open structure at grain boundaries than the interior grain.

Much lower activation energy for diffusion in grain boundaries compared
transgranular diffusion.
Ag self-diffusion

G.F. Carter. Principles of Physical & Chemical Metallurgy. American Society for Metals (1979).

J. Ernesto Indacochea

Diffusion in Materials

UIC

16

Diffusion
Example: Determine Dcu in Ni at 500C.
Qd = 256 kJ/mol
DO= 2.7 x 10- 5 m2/sec
T = 500 + 273 = 773 K
R = 8.31 J/mol-K

D = 2 .7 10

256000

exp

8 .31 773

D = 1.33 x 10-22 m2/sec

J. Ernesto Indacochea

Diffusion in Materials

UIC

17

Steady State Diffusion

diffusion is a time-dependent process.

the mass transfer rate is often needed.
mass transfer = diffusion flux (J)
(kg/m2s; atoms/ m2s)

Flux: # of atoms passing

through a plane of unit area
per unit time.

M
1 dM
J =
=

A t
A dt
J. Ernesto Indacochea

Diffusion in Materials

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Steady State Diffusion

diffusion of gas out of a
gas bottle (cylinder).
Thin wall
thickness

Gas at
Pressure PA

Gas Diffusion
direction

Gas at
Pressure PB

Pressure of Diffusing Gas

PA> PB

The slope @ any point in

curve:
=

PA

C
x

C
x

A
A

C
x

B
B

PB
0

concentration vs position
plot in the solid is termed
concentration profile.
Application: purification of
hydrogen
J. Ernesto Indacochea

concentration gradient
Thickness

dC
dx

dC
J = D
dx
Constant of proportionality

Ficks first Law:

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Non-steady State Diffusion

(Ficks Second Law)
steady-state diffusion not commonly encountered in
engineering materials.
in most cases the concentration of solute atoms at any
point in the material changes with time non-steady
state diffusion.
t2

t0
J. Ernesto Indacochea

t1
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Non-steady State Diffusion

(Ficks Second Law)
for example, if C is being diffused into the surface of a
steel camshaft to harden its surface, the concentration of
C under the surface at any point will change with time as
the diffusion process progresses.

J. Ernesto Indacochea

Diffusion in Materials

UIC

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=D
t
x

Non-steady State Diffusion

(Ficks Second Law)
Ficks second law applies for non-steady state cases
Cs

C
C
=
D

t
x x

C
C
=D 2
t
x
2

Co
x

J. Ernesto Indacochea

Diffusion in Materials

UIC

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Non-steady State Diffusion

(Ficks Second Law)
To solve Ficks second law, physically meaningful boundary
conditions must be specified.
A practical and important solution is for a semi-infinite solid
in which the surface concentration is held constant:
boundary conditions:
for t = 0, C = Co at 0 x
for t >0, C = Cs at x = 0
C = Co at x =

Cx Co
= 1 erf
Cs Co
J. Ernesto Indacochea

2 Dt

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Non-steady State Diffusion

(Ficks Second Law)

J. Ernesto Indacochea

Diffusion in Materials

UIC

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Non-steady State Diffusion

(Ficks Second Law)

J. Ernesto Indacochea

Diffusion in Materials

UIC

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Non-steady State Diffusion

(Ficks Second Law)
Example:
z

Many sliding and rotating parts, such as gears, call for a hard structure in the
surface layers backed by a tough structure in the interior. The first step in
producing such parts is to diffuse carbon into the surface of a steel, raising
the level from the original level of about 0.2% carbon to 0.5-0.9% carbon for
0.005-0.050 in. (0.0127-0.127 cm).
If we place the gear in a furnace at 1000C with an atmosphere rich in
hydrocarbon gas, the surface reaches a carbon content of about 0.9% very
rapidly. The carbon content beneath the surface then rises gradually as a
function of time. Calculate the carbon content C at 0.010 in. (0.0254 cm)
beneath the surface after 10 hr (36,000 sec) at 1000C.

Solution

Cx Co
= 1 erf
Cs Co
J. Ernesto Indacochea

Cs = 0.9%; Co = 0.2%;

2 Dt

Cx = ?; x=0.01=0.0254cm;
D = 0.298 x 10-6 cm2/sec
t= 3.6 x 104 sec.
Diffusion in Materials

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Non-steady State Diffusion

(Ficks Second Law)

C 0.2
0.0254cm
x

= 1 erf

0.9 0.2

6
2
4

2 0.298 10 cm /sec 3.6 10 sec

C 0.2 = (0.7 )[1 erf (0.123 )]

x
C = 0.2 + [0.7(1 0.138)]
x
C = 0.803%C
x
J. Ernesto Indacochea

Diffusion in Materials

UIC

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