05-05-2020

Amazing World of Materials: Diffusion

Nature and Properties of Materials

C Prof. Kamal K. Kar

Advanced Nanoengineering Materials Laboratory
Department of Mechanical Engineering
118
1968-2001-2020
and Materials Science Programme
Indian Institute of Technology Kanpur
http://home.iitk.ac.in/~kamalkk/index.htm
[email protected]

Advanced
Nanoengineering
De
Materials Laboratory

Why study diffusion?

• Materials often heat treated to improve properties

• Atomic diffusion occurs during heat treatment

• Depending on situation higher or lower diffusion rates desired

• Heat treating temperatures and times, and heating or

cooling rates are critical factors for diffusion

Example: steel gears are “case-hardened” by diffusing

C or N to outer surface

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Important Concepts

 Applications of Diffusion
 Activation Energy for Diffusion
 Mechanisms for Diffusion
 Rate of Diffusion (Fick’s First Law)
 Composition Profile (Fick’s Second Law)
 Factors Affecting Diffusion

Applications:1

• Furnace for heat treating steel using carburization.

• Carburizing is the addition of carbon to the surface of low-carbon
steels at temperatures ranging from 1560°F to 1740°F.
• Hardening is achieved when a high carbon martensitic case with
good wear and fatigue resistance is superimposed on a tough,
low-carbon steel core.

http://www.americanmetaltreatinginc.com/carburizing.htm

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Applications: Why advantages?

• Case Hardening:
-- Example of interstitial
diffusion is a case
hardened gear.
-- Diffuse carbon atoms
into the host iron atoms
at the surface.

• Result: The "Case" is

--hard to deform: C atoms
"lock" planes from shearing.
--hard to crack: C atoms put
the surface in compression.

Another Applications: 2 (hard disk)

Thomson Learning™ is a trademark used herein under license.
©2003 Brooks/Cole, a division of Thomson Learning, Inc.

Schematic of the
microstructure of the Co-Pt-
Ta-Cr film after annealing.

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Another Applications: 2 (hard disk)

Thomson Learning™ is a trademark used herein under license.

©2003 Brooks/Cole, a division of Thomson Learning, Inc.
Schematic of the
microstructure of the Co-Pt-
Ta-Cr film after annealing.

Most of the chromium

diffuses from the grains to the
grain boundaries after the
annealing process.

This helps improve the

magnetic properties of the
hard disk. http://www.asylumresearch.com/Gallery/Materials/Materials.shtml

Applications: 3: Galvanization
• Hot-dip galvanizing is a form of galvanization. It
is the process of coating iron, steel, or
aluminum with a thin zinc layer, by passing
the metal through a molten bath of zinc at a
temperature of around 860 °F (460 °C).
• When exposed to the atmosphere, the pure zinc
(Zn) reacts with oxygen (O2) to form zinc oxide
(ZnO), which further reacts with carbon dioxide
(CO2) to form zinc carbonate (ZnCO3), a dull grey,
fairly strong material.
• In many environments, the steel below the
coating will be protected from further corrosion. A hot-dip galvanizing 'kettle' with fume hood
•Galvanized steel is widely used in applications
where rust resistance is needed.

Galvanized steel and coils

popular for applications in
industrial goods, automobile
components, precision
tubes, consumer durable
and many more.
Galvanized i-beams.

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Applications: 4: Thermal barrier coating

Thermal barrier coatings (TBC) with a ceramic topcoat are widely used
for protecting highly loaded gas turbine components against overheating.
For example, on internally cooled turbine blades the ceramic topcoat maintains a
high temperature difference between the outer surface and the underlying metallic
substrate.

Applications: 5: Doping by diffusion (IC Chip)

• 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.
3. Result: Doped light regions: Si atoms
semiconductor
regions.

light regions: Al atoms

silicon

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Diffusion: Definition/Mechanism

Diffusion - Mass transport by atomic motion. Diffusion is a

consequence of the constant thermal motion of atoms,
molecules and particles that results in material moving from
areas of high to low concentration.
Mechanisms
• Solids – vacancy diffusion or interstitial diffusion.

Concentration / chemical potential

Gradient Electric

Magnetic

Stress

Diffusion: Definition

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Diffusion: Definition: Interdiffusion

• Interdiffusion (impurity diffusion): In an alloy, atoms tend

to migrate from regions of high concentration to regions of low
concentration.
Initially After some time

Diffusion: Definition: Self-diffusion

• Self-diffusion: In an elemental solid, atoms also migrate.

Specific atom movement After some time

C
C
A D
A
D
B
B

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Diffusion: Mechanisms

• Atoms in solid materials are in constant motion, rapidly

changing positions.
• For an atom to move, 2 conditions must be met:
1. There must be an empty adjacent site, and
2. The atom must have sufficient (vibrational) energy to
break bonds with its neighboring atoms and then cause
lattice distortion during the displacement.
At a specific temperature, only a small fraction of the
atoms is capable of motion by diffusion. This fraction
increases with rising temperature.
• There are 2 dominant models for metallic diffusion:
1. Vacancy Diffusion
2. Interstitial Diffusion

Vacancy Diffusion

Vacancy Diffusion:
• atoms exchange with vacancies
• applies to substitutional impurity atoms

• rate depends on:

-- number of vacancies
-- activation energy to exchange.

increasing elapsed time

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Interstitial Diffusion

• Interstitial diffusion – smaller atoms (H, C, O, N) can

diffuse between atoms.

More rapid than vacancy diffusion due to more mobile small atoms
and more empty interstitial sites.

Diffusion

• Flux: amount of material or atoms moving past a unit area in unit time
Flux, J = DM/(A Dt)

• Directional Quantity

• Flux can be measured for:

--vacancies
--host (A) atoms
--impurity (B) atoms

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Steady State Diffusion: Thin Plate

dC
Flux proportional to concentration gradient =
dx

C1 C1 Fick’s first law of diffusion

dC
C2 C2 J = −D
dx
x1 x2
x
D  diffusion coefficient
dC DC C2 − C1
if linear  =
dx Dx x 2 − x1

Example 1: 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 are worn.
• If butyl rubber gloves (0.04 cm thick) are used, what is the
diffusive flux of methylene chloride through a glove?

• Data:
– diffusion coefficient for butyl rubber:
D = 110 x10-8 cm2/s
– surface concentrations: C = 0.44 g/cm3
1
C2 = 0.02 g/cm3

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Example 1: Chemical Protective Clothing (CPC)

• Solution – assuming linear conc. gradient

glove
C1 dC C − C1
tb =
2 J = -D  −D 2
paint
6D dx x 2 − x1
skin
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

(0.02 g/cm3 − 0.44 g/cm3 ) g

J = − (110 x 10-8 c m2 /s) = 1.16 x 10-5
(0.04 cm) c m2s

Diffusion: Effect of Temperature

Initial state Intermediate state Final state

Energy Activation energy

• Also called energy barrier for diffusion

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Diffusion: Effect of Temperature

• Diffusion coefficient increases with increasing T.

 Qd 
D Do exp−
= 
 RT 

D = diffusion coefficient [m 2/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]

Activation energy - energy required to produce the movement of 1

mole of atoms by diffusion.

Diffusion: Effect of Other Factors

• The diffusing species, host material and temperature

influence the diffusion coefficient.
• For example, there is a significant difference in magnitude between self-
diffusion and carbon interdiffusion in α iron at 500 °C.

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Nonsteady State Diffusion

• Concentration profile, C(x), changes w/ time.

Nonsteady State Diffusion

• Concentration profile,
C(x), changes
w/ time.

• To conserve matter: • Fick's First Law:

• Governing Eqn.:
Fick’s second law

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 c   2c  x 
  = D c( x, t ) = A − B erf  
 t  x 2  2 Dt 
Solution to 2o de with 2 constants
determined from Boundary Conditions and Initial Condition

Nonsteady State Diffusion: Example

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Nonsteady State Diffusion: Example

• Example : 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: use Eqn. 6.5

C( x,t ) − Co  x 
= 1− erf 
Cs − Co  2 Dt 

Nonsteady State Diffusion: Example

C( x,t ) − Co  x 
= 1− erf  
Cs − Co  2 Dt 

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

C( x,t ) − Co 0.35 − 0.20  x 

= = 1− erf  = 1− erf(z)
Cs − Co 1.0 − 0.20  2 Dt 

 erf(z) = 0.8125

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Nonsteady State Diffusion: Example

Nonsteady State Diffusion: Example

We must now determine from Table 6.1 the value of z for which the
error function is 0.8125. An interpolation is necessary as follows

z − 0.90 0.8125− 0.7970

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

Now solve for D x x2

z= D=
2 Dt 4 z 2t

 x2  −3 2
D =   = (4 x 10 m) 1h
= 2.6 x 10−11 m2/s
 4z t  (4)(0.93) (49.5 h) 3600s
2 2
 

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− Qd 
D Doexp RT 
=

• To solve for the temperature at

Qd
which D has the calculated T=
value, we use a rearranged R(lnD − lnDo )
form of Equation (6.9a);
from Table 6.2, for diffusion of C in FCC Fe
Do = 2.3 x 10-5 m2/s Qd = 148,000 J/mol

 T=
148,000 J/mol
(8.314 J/mol- K)(ln2.6x10−11 m2 /s − ln 2.3x10−5 m2 /s)

T = 1300 K = 1027°C

Diffusion Paths

Experimentally determined activation energies for diffusion

Qsurface < Qgrain boundary < Qlattice

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Single Crystal vs Polycrystal

Schematic ▪ Qgrain boundary = 110 kJ /mole

▪ QLattice = 192 kJ /mole
Log (D) →

Polycrystal

Single
crystal
1/T →
← Increasing Temperature

Summary: Structure and 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

• lower density materials • higher density materials

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FGENCs with gradation of magnetic fillers

0
0
-5

-10
Reflection Loss (dB)

-10

Reflection Loss (dB)

-15 -20

-20 -30

Volume fraction of iron powder in SBR

-25
-40 Vf = 0.39 in UDEC
front side: Vf = 0.30 in FGEC
-30 Vf = 0.35 in UDEC
front side: Vf = 0.18 in FGEC -50
-35
9 10 10 10
0.00E+000 5.00E+009 1.00E+010 1.50E+010 2.00E+010 0.0 5.0x10 1.0x10 1.5x10 2.0x10
Frequency (Hz) Frequency (Hz)

(a) (b)
Fig. Comparison of UDEC (uniformly dispersed elastomeric composites) with FGEC for (a)
Vf = 0.35 and (b) Vf = 0.39.

Applications: 5: Doping by diffusion (IC Chip)

• Integrated circuits (ICs), found in

numerous electronic devices have
been fabricated using doping
techniques.

• The base material for these ICs is

silicon that has been “doped” with
other materials.

• More precisely, controlled

concentrations of impurities have
been diffused into specific regions
of the device to change the
properties (improve electrical
conductivity).

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Example 2

Example 2: At 300ºC the diffusion coefficient and activation

energy for Cu in Si are:

D(300ºC) = 7.8 x 10-11 m2/s Qd = 41,500 J/mol

What is the diffusion coefficient at 350ºC?

 Qd 
D = Doexp− RT 

Qd  1  Q  1 
lnD300 = lnD0 −   and lnD350 = lnD0 − d  
R  T300  R  T350 
D350 Q  1 1 
 lnD350 − lnD300 = ln =− d  − 
D300 R  T 350 T 300 

Example 2

 Q  1 1 
D2 = D1 exp− d  − 
 R  T2 T1 

T1 = 273 + 300 = 573K

T2 = 273 + 350 = 623K

 − 41,500 J/mol 1 1 
D2 = (7.8 x 10−11 m2/s)exp  − 
 8.314 J/mol- K  623K 573K 

D2 = 15.7 x 10-11 m2/s

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 c   2c  x 
  = D c( x, t ) = A − B erf  
 t  x 2  2 Dt 
Solution to 2o de with 2 constants
determined from Boundary Conditions and Initial Condition

▪ Erf () = 1
 ▪ Erf (-) = -1
Erf ( ) = exp(− u )du
2
 
2
▪ Erf (0) = 0
0 ▪ Erf (-x) = -Erf (x)

Exp(− u2) →
Area

0  u →

Determination of Diffusivity

A & B welded together and heated to high temperature (kept constant → T0)

t2 > t1 | c(x,t1) t1 > 0 | c(x,t1) t = 0 | c(x,0)

f(x)|t
C2 Non-steady
Flux
state
Concentration →

f(t)|x

Cavg ▪ If D = f(c)
↑t  c(+x,t)  c(-x,t)
i.e. asymmetry about y-axis
A B
C1
x →

▪ C(+x, 0) = C1 ▪ A = (C1 + C2)/2

▪ C(−x, 0) = C2 ▪ B = (C2 – C1)/2

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Example

• Copper diffuses into a bar of aluminum.

Surface concentration
Cs of Cu atoms bar
pre-existing concentration Co of copper atoms
• 10 hours at 600˚C gives C(x).
• How many hours would it take to get the same C(x) if processed at 500˚C?
C( x,t ) − Co  x 
= 1− erf 
Cs − Co  2 Dt 

115.5 hrs
• Answer:

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