Diffusion: Diffusion (8) Æ Transport by Atomic Motion

Diffusion [8]
¾ Diffusion Æ transport by atomic motion.
Inhomogeneous material can become homogeneous by diffusion.

Temperature should be high enough to overcome energy barrier.
1>
Applications of Diffusion
¾ Life - Breathing
¾ Nitriding / Carburizing - Surface Hardening of Steels
¾ p-n junction - Dopant Diffusion for Semiconductor
Devices
¾ Manufacturing of Plastic Beverage Bottles/MylarTM
Balloons
¾ Sputtering, Annealing - Magnetic Materials for Hard
Drives
¾ Coatings and Thin Films
¾ Thermal Barrier Coatings for Turbine Blades
2>
Diffusion of oxygen into a single-celled organisms
In a single-celled organism (such as Amoeba) the

distance is so small that diffusion is rapid enough
for the cell’s needs
maximum
distance
oxygen is 0.1 mm
carbon dioxide
3>
Diffusion of oxygen into an earthworm
diffusion takes place through
the thin skin of the worm
CO2 diffuses
O2 diffuses in out
Section through
worm’s skin
0.04mm
the blood vessels

absorb the O2 and
carry it to the body 4>
Diffusion of oxygen into a human body
each tube ends up in
a cluster of tiny air sacs.
blood supply to air sac

Human
Lung air breathed
in and out
diffusion of
oxygen
O2
diffusion of
carbon dioxide
the air passages in the lung
branch into finer and finer tubes CO2
0.03 mm
6>
Surface Hardening of Steels
¾ Furnace for heat treating steel using the carburization process.
• Case Hardening:
-- Diffuse carbon atoms
into the host iron atoms
at the surface.
-- Example of interstitial
diffusion is a case
hardened gear. 6>
¾ Schematic of a n-p-n transistor.
Electronic solid state devices
©2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning™ is a trademark used herein under license.
7>
Surface corrosion protection
¾ Hot dip galvanized parts and structures prevent corrosion.
8>
Surface heat protection
¾ A thermal barrier coating on nickel-based superalloy.
9>
Mechanisms for Diffusion
¾ Self-diffusion - The random movement of atoms

within an essentially pure material.
¾ Vacancy diffusion - Diffusion of atoms when an atom
leaves a regular lattice position to fill a vacancy in the
crystal.
¾ Interstitial diffusion - Diffusion of small atoms from
one interstitial position to another in the crystal
structure.
10>
¾ Self-diffusion: in an elemental solid, atoms also migrate.
Label some atoms After some time

C
C
A D
A
D
B
B
11>
¾ Vacancy or Substitutional Diffusion: Atom from normal lattice
position changes position with an adjacent vacancy (vacancy
lattice site). So, the atoms and vacancies travel in opposite
directions. Both self-diffusion and inter (impurity)-diffusion can
occur thus.
Source: William Callister 7th edition, chapter 5, page 112, figure 5.3(a) 12>
¾ Interstitial Diffusion: Atoms move from one interstitial site to

another (vacant) interstitial site.
Source: William Callister 7th edition, chapter 5, page 112, figure 5.3(b)
13>
¾ Interdiffusion: In an alloy, atoms tend to migrate

from regions of large concentration.
Initially After some time
Adapted
from Figs.
5.1 and 5.2,
Callister 6e.
Cu Ni
100% 100%
0 0
Concentration Profiles Concentration Profiles
14>
Activation Energy for Diffusion
¾ Activation energy: energy is required to squeeze atoms

past one another during diffusion.
©2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning™ is a trademark used
herein under license.
Q (substitutional) > Q (interstitial)

15>
Diffusion coefficient and temperature
¾ Diffusion coefficient: a constant which is a function of

diffusing species and temperature.
¾ 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]
16>
Activation Energy for Diffusion
16>
Diffusion coefficient
Si
18>
Diffusion Paths
¾ Experimentally determined activation energies for diffusion
Qsurface < Qgrain boundary < Qlattice

¾ Lower activation energy implies higher diffusivity
¾ Core of dislocation lines offer paths of lower resistance
Schematic → (PIPE DIFFUSION)
Log (D) →
Polycrystal
Ag self-diffusion:
Qgrain boundary = 110 kJ /mole
Single
QLattice = 192 kJ /mole
crystal
1/T → 19>
Type of Diffusion
20>
Rate of Diffusion – Some Definitions
¾ Diffusion coefficient (D) - A temperature-dependent
coefficient related to the rate at which atoms, ions, or
other species diffuse.
¾ D0 - a constant which is a function of jump frequency,

jump distance and coordination number of vacancies.
¾ Concentration gradient - The rate of change of

composition with distance in a nonuniform material,
typically expressed as atoms/cm3.cm or at%/cm.
¾ Fick’s first law - The equation relating the flux of

atoms by diffusion to the diffusion coefficient and the
concentration gradient.
21>
J ≡ Flux ≡
Flux
(surface area )(time )

=
2
moles (or mass) diffusing mol
or
kg
cm s m2s
22>
Simplest Case: Steady-State Diffusion
¾ The rate of diffusion is independent of time

dC
∴ Flux is proportional to concentration gradient =
dx
C1 This model is captured as

C1
Fick’s first law of diffusion
dC
C2 C2 J = −D
dx
x1 x2
x
D ≡ diffusion coefficient
dC ΔC C2 − C1
if linear ≅ = which is a function of diffusing
dx Δx x2 − x1 species and temperature
For steady state diffusionÆ concentration gradient = dC/dx is linear

23>
Example: Chemical Protective Clothing (CPC)
¾ Methylene chloride is a common ingredient in paint
removers. Besides being an irritant, it also may be
absorbed through skin. When using this paint
remover, protective gloves should be worn.
¾ If butyl rubber gloves (0.04 cm thick) are used, what
is the diffusive flux of methylene chloride through
the glove?
¾ Data:
¾ diffusion coefficient in butyl rubber:
D = 110 x10-8 cm2/s
¾ surface concentrations:
¾
C1 = 0.44 g/cm3
C2 = 0.02 g/cm3
24>
¾ Solution – assuming linear concentration gradient

glove
C1 dC C 2 − C1
J = -D ≅ −D
paint tb =
l2 dx x 2 − x1
skin
6D
remover
C2 Data: D = 110 x 10-8 cm2/s
x1 x2 C1 = 0.44 g/cm3
C2 = 0.02 g/cm3
x2 – x1 = 0.04 cm
3 3
( 0 . 02 g/cm − 0 . 44 g/cm ) g
J = − (110 x 10 -8 cm2 /s) = 1.16 x 10 -5
(0.04 cm) cm2s
25>
¾ If a person is in contact with the irritant and

more than about 0.5 gm of the irritant is deposited
on their skin they need to take a wash break.
¾ If 25 cm2 of glove is in the paint thinner can,
How long will it take before they must take a wash
break?
−5
Flux = 1.16 × 10 g
2
cm -s
2
if the exposed area of the gloves are 25 cm
how long will it take to get 0.5g of M-C onto the hands?
Flux = 25cm ∗ 1.16 × 10

2 −5 g
= 2.9 × 10−4 g
2
cm -s s
Exposure time= 0.5g ≅ 1724s = 0.48 hr
2.9 × 10−4 g
s 26>
Non-steady State Diffusion
¾ The concentration of diffusing species is a
function of both time and position C = C(x,t)
¾ This is more common – the flux varies with time!
• To conserve matter: • Fick's First Law:
J(right) − J(left) = dC dC
− J = −D or
dx dt dx
dJ = dC dJ = d2 C (if D does
− −D not vary
dx dt dx dx2 with x)
equate dx
• Governing Eqn.: J(left) J(right)
dC d2C
=D 2
dt dx Concentration,
C, in the box
Fick’s Second Law
27>
Non-steady State Diffusion
¾ Fick’s Second Law Solution

∂C ∂ 2C C ( x, t ) − Co ⎛ x ⎞
=D 2 = 1 − erf ⎜ ⎟
∂t ∂x C s − Co ⎝ 2 Dt ⎠
28>
C ( x, t ) − Co ⎛ x ⎞
Error Function Table = 1 − erf ⎜ ⎟
C s − Co ⎝ 2 Dt ⎠
29>
Example: Design of a Carburizing Treatment
¾ The surface of a 0.1% C steel gears is to be

hardened by carburizing. In gas carburizing, the
steel gears are placed in an atmosphere that
provides 1.2% C at the surface of the steel at a high
temperature. Carbon then diffuses from the surface
into the steel. For optimum properties, the steel
must contain 0.45% C at a depth of 0.2 cm below the
surface. Design a carburizing heat treatment that will
produce these optimum properties. Assume that the
temperature is high enough (at least 900oC) so that
the iron has the FCC structure.
30>
31>
32>
Diffusion and Materials Processing
¾ Sintering - A high-temperature treatment used to join

small particles compacted by powder metallurgy.
Diffusion processes during sintering and powder metallurgy.

Atoms diffuse to points of contact, creating bridges and reducing
the pore size
33>
Particles of barium magnesium Microstructure of BMT

tantalate (BMT) (Ba(Mg1/3 ceramics obtained by
Ta2/3)O3) powder are shown. This compaction and sintering of
ceramic material is useful in BMT powders.
making electronic components
known as dielectric resonators
that are used for wireless
communications.
34>
¾ Grain growth - Movement of grain boundaries by diffusion
in order to reduce the amount of grain boundary area.
Grain growth occurs as atoms diffuse across the grain boundary

from one grain to another
35>
Grain growth in alumina ceramics can be seen from the

SEM micrographs of alumina ceramics. (a) The left
micrograph shows the microstructure of an alumina
ceramic sintered at 1350oC for 150 hours. (b) The right
micrograph shows a sample sintered at 1350oC for 30
hours.
36>
¾ Diffusion bonding - A joining technique in which two surfaces
are pressed together at high pressures and temperatures.
The steps in diffusion bonding: (a) Initially the contact area is

small; (b) application of pressure deforms the surface, increasing
the bonded area; (c) grain boundary diffusion permits voids to
shrink; and (d) final elimination of the voids requires volume
diffusion 37>
Kirkendall effect
¾ Materials A and B welded together with inert marker under
diffusion
¾ Usually the lower melting component diffuses faster (say B)
A B
Marker motion
Inert Marker – thin rod of a high melting material which is basically

insoluble in A & B
38>
Kirkendall effect
D(Cu)>D(Ni)
Porosity occurs in the copper because copper diffuses faster in the nickel. 39>
Summary: Structure & Diffusion
Diffusion FASTER for... Diffusion SLOWER for...
• open crystal structures • close-packed structures
• lower melting T materials • higher melting T materials
• materials w/secondary • materials w/covalent

bonding bonding
• smaller diffusing atoms • larger diffusing atoms
• cations • anions
• lower density materials • higher density materials

39>
References
¾ CALLISTER JR, W. D. AND RETHWISCH, D. G.
Materials Science and Engineering: An Introduction, 9th edition.
John Wiley & Sons, Inc. 2014, 988p. ISBN: 978-1-118-32457-8.
¾ ASHBY, M. and JONES, D. R. H.
Engineering Materials 1: An Introduction to Properties, Applications and Design.
4th Edition. Elsevier Ltd. 2012, 472p. ISBN 978-0-08-096665-6.
¾ CALLISTER JR, W. D. AND RETHWISCH, D. G.
Fundamentals of Materials Science and Engineering: An Integrated Approach, 4th ed.
John Wiley & Sons, Inc. 2012, 910p. ISBN 978-1-118-06160-2.
¾ MITTEMEIJER, E. J.
Fundamentals of Materials Science: The Microstructure–Property Relationship Using
Metals as Model Systems. Springer-Verlag Berlin. 2010, 594p. ISBN 978-3-642-10499-2.
¾ ASKELAND, D. AND FULAY, P.
Essentials of Materials Science & Engineering, 2nd Edition.
Cengage Learning. 2009, 604p. ISBN 978-0-495-24446-2.
¾ ABBASCHIAN, R., ABBASCHIAN, L., AND REED-HILL, R. E.
Physical Metallurgy Principles, 4th Ed. Cengage. 2009, 750p. ISBN 978-0-495-08254-5.
¾ SMALLMAN, R. E. and NGAN, A.H.W.
Physical Metallurgy and Advanced Materials, 7th Edition.
Elsevier Ltd. 2007, 650p. ISBN 978-0-7506-6906-1.
Nota de aula preparada pelo Prof. Juno Gallego para a disciplina Ciência dos Materiais de Engenharia.
® 2016. Permitida a impressão e divulgação.
http://www.feis.unesp.br/#!/departamentos/engenharia-mecanica/grupos/maprotec/educacional/ 41

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Diffusion: Diffusion (8) Æ Transport by Atomic Motion

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Diffusion [8]

¾ Diffusion Æ transport by atomic motion.

Inhomogeneous material can become homogeneous by diffusion.

In a single-celled organism (such as Amoeba) the

the blood vessels

blood supply to air sac

¾ Hot dip galvanized parts and structures prevent corrosion.

¾ A thermal barrier coating on nickel-based superalloy.

¾ Self-diffusion - The random movement of atoms

¾ Self-diffusion: in an elemental solid, atoms also migrate.

Label some atoms After some time

¾ Interstitial Diffusion: Atoms move from one interstitial site to

¾ Interdiffusion: In an alloy, atoms tend to migrate

¾ Activation energy: energy is required to squeeze atoms

Q (substitutional) > Q (interstitial)

¾ Diffusion coefficient: a constant which is a function of

D = diffusion coefficient [m2/s]

¾ Experimentally determined activation energies for diffusion

Qsurface < Qgrain boundary < Qlattice

¾ D0 - a constant which is a function of jump frequency,

¾ Concentration gradient - The rate of change of

¾ Fick’s first law - The equation relating the flux of

(surface area )(time )

¾ The rate of diffusion is independent of time

C1 This model is captured as

For steady state diffusionÆ concentration gradient = dC/dx is linear

¾ Solution – assuming linear concentration gradient

¾ If a person is in contact with the irritant and

Flux = 25cm ∗ 1.16 × 10

¾ Fick’s Second Law Solution

¾ The surface of a 0.1% C steel gears is to be

¾ Sintering - A high-temperature treatment used to join

Diffusion processes during sintering and powder metallurgy.

Particles of barium magnesium Microstructure of BMT

Grain growth occurs as atoms diffuse across the grain boundary

Grain growth in alumina ceramics can be seen from the

The steps in diffusion bonding: (a) Initially the contact area is

Inert Marker – thin rod of a high melting material which is basically

Diffusion FASTER for... Diffusion SLOWER for...

• open crystal structures • close-packed structures

• lower melting T materials • higher melting T materials

• materials w/secondary • materials w/covalent

• smaller diffusing atoms • larger diffusing atoms

• lower density materials • higher density materials

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