CHAPTER 5

Diffusion in Solids

(Callister 9th ed (7): p 180-194)

Callister 10th ed: p130-143; p 146-147
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 5.1 Outcomes

 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
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 5.2 Solid state diffusion
What is solid state diffusion?

• The process whereby atoms move (migrate)

through the crystal lattice

• Diffusion occurs as a result of the atoms having

vibration energy, which assists them to move
from one position in the crystal lattice to another.

• The higher the temperature, the higher the rate

of movement and thus faster diffusion

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 Solid state diffusion
How does it take place?
1. Interstitial diffusion
Here the small atoms such as C or N in iron, can move
through the lattice by using the interstitial voids
2. Substitutional diffusion
Here the atoms must make use of vacancies to enable
movement

Alloy atoms or “self” atoms (i.e. self-diffusion) are

found in substitutional diffusion 4
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 5.3 Use of solid state diffusion
Where is it typically found or used?
i) Surface hardening of gear teeth
by diffusion enrichment of C or N

i) Diffusion bonding of metals

Apply pressure at high

temperatures
Titanium wing structure of
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fighter air craft
 Use of solid state diffusion
Where is it typically found or used (contn’d)?
iv) Doping of P or B atoms into Si for transistors

v) Heat treatment of precipitation hardenable alloys

Some B Al-4%Cu
atoms still alloy ppt
in solid hardened
solution 24 h at
130°C

vi) Annealing or softening of cold worked alloys

Dislocations anneal out with diffusion by using vacancies. 6
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 5.4 Concentration gradients in
diffusion
The diffusion process;
If we couple a block of Cu with one of Ni and heat it up to above
600°C for a few hours, interdiffusion will take place
At time t = 0 After some time

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 5.5 The activation energy QD for diffusion
Vacancy or substitutional vs interstitial diffusion
Atoms in substitutional diffusion can move from one atomic
site to another if there are vacancies in the lattice for the
atoms to move into. The Activation energy for the
movement is provided by the thermal vibration of the atoms
In substitutional diffusion a
significant amount of energy QDV
(=Em) is still required to move the
atom in spite of the presence of a
Vacancy vacancy.
diffusion
The activation energy QDI (=GS) in
interstitial diffusion is far smaller.

Em > Ei or QDV > QDi

Em for vacancy diffusion ES for Interstitial diffusion 8
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 5.6 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
Concentration
gradient: Definition
Steady state diffusion
CA – CB = ∆C
XA – XB ∆X takes place when the
concentration gradient
remains fixed, i.e.
CA and CB remain
constant over the entire
diffusion time.

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 Steady State Diffusion
Examples of steady state diffusion

1. Extraction of pure 2. Initial stages of 3. Breathing of air

Hydrogen from an an illness when the while sitting stationary
impure gas by body uses all of the and body consumes a
diffusion through a Pd medicine while the steady amount of
membrane. Note only supply is constant oxygen
H atoms can diffuse,
not H2 molecules 2/8/2024 10
 Steady State Diffusion
dC ∆C C2 − C1
C1 C1 if linear ≅ =
dx ∆x x2 − x1

C2 C2 Under these conditions, the

flux (J) of solute atoms,
x1 x2
x which moves from plane x1 to
plane x2, is given by Fick's
First Law
dC
J = −D J = Diffusion flux (kg/m2.s or atoms/m2.s)
dx D = Diffusivity (diffusion coefficient)
with units (m2/sec.)

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 Steady State Diffusion
Example 1:
A steel plate at 700 oC is exposed to a Carbon rich atmosphere
on the one side and a Carbon deficient atmosphere on the
other side. Calculate the flux of Carbon when the equilibrium C
concentration 5 and 10 mm below the surface are 1.2 and 0.8
kg/m3 respectively. D = 3 x 10 -11 m2/s.

Solution:
Use Fick's first law: J = - D dc/dx

= - D ( CA –CB) / (xA – xB)

= - 3 x 10 –11(1.2 – 0.8)/( 5 x 10-3 – 10x10-3)
J = 2.4 x 10-9 kg/m2s
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 Steady State Diffusion
Example 2:
Calculate the mass H2 per hr. which is purified by diffusing it
through a 5 mm thick plate of Pd with surface area of 0.2 m2 .
There is 1.5 kg/m3 H2 on the one side and 0.3 kg/m3 H2 on the
other side of the plate. Let D = 1 x 10-8 m2/s.

Solution:
: J = -D dC/dx
= - 1x 10-8 ( 1.5 – 0.3)/ (0 – 5x 10-3)
= 2.4 x 10-6 kg/m2.s

But m = J x A = 2.4 x 10-6 x 3600 x 0.2

m = 1.73 x 10-3 kg/hr
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 5.7 Non-steady State Diffusion
Steady state diffusion is not commonly found in engineering
materials. In most cases non-steady state diffusion, in which
the concentration gradient of solute atoms at any point in
the material changes with time, is used.
Example: Diffusion of carbon or nitrogen into the surface of
a steel gear. (Sfce. hardening by carburization or nitriding)

CS = Constant supply of C in a Large gear after carburising

CO/CO2/CH4 gas mixture. C0 = %C in the
14
steel before carburisation 2/8/2024
 Non-steady State Diffusion
The concentration of diffusing species is a function of both
time and position C = C(x,t)
∂C ∂ 2C
Fick's Second Law applies =D 2
∂t ∂x
In CS constant, the solution to the equation is:
Cs − Cx  x 
= erf  
Cs − C0  2 D t 

Erf = Error Function (Callister Table 7.1)

Cs = surface concentration of A
In carburisation CS C0 = initial uniform conc. of A in the solid
is kept constant in Cx = conc. of A at distance x at time t
the fixed supply
X = distance from surface
gas of CO/CO2/CH4
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D = diffusivity of A in B at temp. T 15
 Non-steady State Diffusion
The erf-function (See also Excel)

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 Non-steady State Diffusion
Example 1:
Gallium (Ga) is diffused into a silicon wafer with no
previous Ga in it, at a temp. of 1100°C 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 1100°C: D = 7.0 x 10-17 m2/s

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 Non-steady State Diffusion
Solution: Fick's second law:
Cs − Cx  x 
= erf  
Cs − C0 2 Dt
with Cs = 1024 , Cx = 1022 , C0 = 0.

(CS – CX)/(CS – C0) = (1024 - 1022 ) / ( 1024 – 0)

= 1 – 0.01 = 0.99

= erf ( x / {2 √ 7 x 10-17 x 3 x 60 x 60)}

= erf ( x/ 1.74 x 10-6) = 0.99 = erf Z

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 Non-steady State Diffusion
Solution (cont’d)
Let {x / 1.74 x 10-6} = Z then erf Z = 0.99
From Table 5.1:
erf (Z) = 0.9891 Z = 1.8
erf (Z) = 0.99 Z?
erf (Z) = 0.9928 Z = 1.9

By interpolation between 0.9891 and 0.9928 for erf

(Z) = 0.99
Z = 1.8241 = {x / 1.74 x 10-6}
Therefore: x = 3.17 x 10-6 m
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 Non-steady State Diffusion
Example 2: Carburising of the teeth of a gear

Continuous miner
Hardness gradient Pinion Gear
650

Vickers microhardness (300 g load)

600

550

500

450

400

350

300
0 0.5 1 1.5 2 2.5 3

Hardness from the surface inwards (mm)

The hardness of the gear teeth increases

near the surface because of the higher %C
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 Non-steady State Diffusion
Example 2: Carburising of the teeth of a gear
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 0.5
mm. The surface concentration of carbon is maintained at
0.9 % and the initial concentration of the steel is 0.2 %C.
D 927 = 1.28 x 10-11 m2/s
Cs − Cx  x 
Solution: Fick's second law = erf  
Cs − C0 2 Dt
with Cs = 0.9 % , Cx = 0.4 % , Co = 0.2 %

(CS – CX)/(CS – C0) = (0.9 – 0.4)/(0.9 – 0.2)

= 0.5 / 0.7 = 0.7143
= erf ( 0.5 x 10-3 / {2 √ 1.28 x 10- 11x t )}
= erf ( 69.88 / √t ) = erf Z
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 Non-steady State Diffusion
Example 2 Solution (cont’d):

Let 69.88 / √t = Z then erf Z = 0.7143

erf (Z) = 0.7122 Z = 0.75

erf (Z) = 0.7143 Z?
erf (Z) = 0.7421 Z = 0.8

By interpolation between 0.7122 and 0.7421 for

erf (Z) = 0.7143
Z = 0.755 = 69.88 / √t
t = 8567 s = 143 min.

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 5.8 The Diffusion Coefficient D
The Diffusivity or Diffusion Coefficient D follows an
Arrhenius equation with temperature:

with D0 = temp. independent constant (m2/s)

Q = activation energy (J/mol)
R = Universal gas constant 8.134 J/(mol.K)
T = temperature in degrees K (°C + 273)

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 The Diffusion Coefficient D
The diffusion coefficient D is affected by:
1. The type of diffusion:
Substitutional vs Interstitial diffusion: QDS >> QDI
I. Therefore: D(Substitusional) << D(Interstitial)

The activation energy

QDS (=Gv) >> QDI (=GS)

24
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 The Diffusion Coefficient D
The diffusion coefficient D is affected by (cont’d):
2. The type of lattice

FCC Fe
BCC Fe atoms
atoms (>910°C)
(<910°C)

The BCC metals have a loose-packed lattice structure

The FCC metals have a close-packed lattice structure
Interstitial diffusion of C in Fe is therefore much
faster in the BCC lattice than in the FCC lattice
DI (BCC) > DI(FCC) and also DV(BCC) > DV(FCC)
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 The Diffusion Coefficient D
The diffusion coefficient D is affected by (cont’d):
3. The temperature T
At higher temperatures one has more vacancies for
substitutional diffusion and vibration of atoms is
higher.

Note the much higher D for

diffusion of C in BCC Fe vs
in FCC Fe at about 910°C

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 The Diffusion Coefficient D

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 5.9 References
Chapter 5
Slide no Reference
1 Toshiba: https://www.elprocus.com/different-types-of-transistor-and-their-functions/
https://www.indiamart.com/proddetail/mechanical-gears-8094879873.html
4 https://www.google.com/search?q=diffusion+in+metals+and+alloys&rlz=1C1GYPO_enZA781ZA781&source=lnms&tbm=isc
h&sa=X&ved=0ahUKEwjC4OWB7I3gAhUiRxUIHSXiBJwQ_AUIDigB&biw=1367&bih=594#
5 http://diffusioninsolidsees.blogspot.com/2010/07/solid-state-fabrication-of-metal-matrix.html;
https://www.slideshare.net/RohitKatarya/spf-db-presentation-finla8
WF Hosfor and RM Caddell, “Metal Forming”: Mechanics and Metallurgy”, 2ed, Prentice0Hall (1993)p103
6 Nicholson et al, Phil Mag 3(1953)p531
7 Material Science and Engineering Callister 9e Fig 7.1 p 181-182
8 https://www.tf.uni-kiel.de/matwis/amat/iss/kap_5/illustr/s5_2_3a.html
9 Material Science and Engineering Callister 9e Fig 7.4 p 184
10 Univ. Birmingham: https://www.birmingham.ac.uk/research/activity/metallurgy-materials/hydrogen/themes/hydrogen-
purification.aspx
https://www.slideshare.net/uapnazmul/liposomal-drug-delivery-system
14 Metlab: https://www.metlabheattreat.com/carburizing.html
15 Material Science and Engineering Callister 9e Fig 7.5 p 185
17 Material Science and Engineering Callister 9e, p 187
21 Broken pinion gear, UG mining equipment, WE Stumpf (2017)
23 https://www.ipsenusa.com/processes-and-resources/articles-and-white-papers/make-your-atmosphere-furnace-work-for-you
27 Material Science and Engineering Callister 9e Fig 7.7; p 191
28 Material Science and Engineering Callister 9e, table 7.2, p190

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