Ch5: Diffusion
Ch5: Diffusion
Chapter Five Contents:
Introduction to Diffusion.
Diffusion Mechanisms.
Steady-state Diffusion.
Diffusion and Temperature.
Nonsteady-state Diffusion.
Factors that Influence Diffusion.
2 Ch5:MME237 Lecturer: Mr. Thabet Elrabei 2/19/2021
Introduction to Diffusion
• Diffusion: Mass transport by atomic motion.
• Mechanisms:
Gases & Liquids – random (Brownian) motion.
Solids – vacancy diffusion or interstitial diffusion.
3 Ch5:MME237 Lecturer: Mr. Thabet Elrabei 2/19/2021
Introduction to Diffusion
• Why Study Diffusion?
• Diffusion plays a crucial role in:
Alloying metals: bronze, silver, gold.
Strengthening and heat treatment processes.
• Hardening the surfaces of steel.
High temperature mechanical behavior.
Phase transformations.
• Mass transport during FCC to BCC.
Environmental degradation.
• Corrosion, etc.
4 Ch5:MME237 Lecturer: Mr. Thabet Elrabei 2/19/2021
Introduction to Diffusion
• DIFFUSION DEMO:
• Glass tube filled with water.
• At time t = 0, add some drops of ink to one end of the tube.
• Measure the diffusion distance, x, over some time.
• Compare the results with theory.
5 Ch5:MME237 Lecturer: Mr. Thabet Elrabei 2/19/2021
Introduction to Diffusion
• How do atoms move in Solids?
• Why do atoms move in Solids?
• Diffusion, simply, is atoms moving from one lattice site to another in a
stepwise manner.
Transport of material by moving atoms.
• Two conditions are to be met:
An empty adjacent site.
Enough energy to break bonds and cause lattice distortions during
displacement.
• What is the energy source?
HEAT.
• What else?
Concentration gradient.
6 Ch5:MME237 Lecturer: Mr. Thabet Elrabei 2/19/2021
Introduction to Diffusion
• DIFFUSION: THE PHENOMENA (1)
• Interdiffusion: In an alloy, atoms tend to migrate from regions
of large concentration.
Initially After some time
100%
0
Concentration Profiles
7 Ch5:MME237 Lecturer: Mr. Thabet Elrabei 2/19/2021
Introduction to Diffusion
• DIFFUSION: THE PHENOMENA (2)
• Self-diffusion: In an elemental solid, atoms also migrate.
Label some atoms (use isotopes) After some time
C
A
D
B
8 Ch5:MME237 Lecturer: Mr. Thabet Elrabei 2/19/2021
Introduction to Diffusion
• More examples in 3-D.
9 Ch5:MME237 Lecturer: Mr. Thabet Elrabei 2/19/2021
Diffusion Mechanisms
• Diffusion Mechanisms (I): Vacancy Diffusion.
Energy is needed to generate a vacancy, break bonds, cause
distortions. Provided by HEAT.
Atom moves in the opposite direction of the vacancy.
10 Ch5:MME237 Lecturer: Mr. Thabet Elrabei 2/19/2021
Diffusion Mechanisms
• Diffusion Mechanisms (II): Interstitial Diffusion.
Smaller atoms can diffuse between atoms.
Much faster than vacancy diffusion, why ? Smaller atoms like B,
C, H, O. Weaker interaction with the larger atoms. More vacant
sites, no need to create a vacancy.
11 Ch5:MME237 Lecturer: Mr. Thabet Elrabei 2/19/2021
Diffusion Mechanisms
• Diffusion Mechanisms (III): Substitutional Diffusion.
Applies to substitutional impurities.
Atoms exchange with vacancies.
Rate depends on:
• Number of vacancies.
• Activation energy to exchange.
12 Ch5:MME237 Lecturer: Mr. Thabet Elrabei 2/19/2021
Diffusion Mechanisms
• PROCESSING USING DIFFUSION:
1. 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.
• Hard to deform: C atoms "lock"
planes from shearing.
• Hard to crack: C atoms put the
surface in compression.
13 Ch5:MME237 Lecturer: Mr. Thabet Elrabei 2/19/2021
Diffusion Mechanisms
2. Doping:
Doping silicon with phosphorus
0.5 mm
for n-type semiconductors.
• Process:
1. Deposit P rich layers on surface.
magnified image of a computer chip
silicon
2. Heat it.
light regions: Si atoms
3. Result: Doped semiconductor regions.
silicon light regions: Al atoms
14 Ch5:MME237 Lecturer: Mr. Thabet Elrabei 2/19/2021
Steady-state Diffusion
• How do we quantify the amount or rate of diffusion?
moles (or mass)diffusing mol kg
J Flux or
surface areatime cm s m2s
2
• Measured empirically:
Make thin film (membrane) of known surface area.
Impose concentration gradient.
Measure how fast atoms or molecules diffuse through the
membrane.
M=
M l dM mass J slope
J diffused
At A dt
time
15 Ch5:MME237 Lecturer: Mr. Thabet Elrabei 2/19/2021
Steady-state Diffusion
• MODELING DIFFUSION: FLUX
• Flux:
• Directional Quantity (anisotropy ?)
• Flux can be measured for:
Vacancies.
Host (A) atoms.
Impurity (B) atoms. Diffusion is a time-dependent process.
16 Ch5:MME237 Lecturer: Mr. Thabet Elrabei 2/19/2021
Steady-state Diffusion
• CONCENTRATION PROFILES & FLUX:
• Concentration Profile, C(x): [kg/m3]
Cu flux Ni flux
Concentration Concentration
of Cu [kg/m3] of Ni [kg/m3]
Position, x
• Fick's First Law:
• The steeper the concentration profile, the greater the flux.
17 Ch5:MME237 Lecturer: Mr. Thabet Elrabei 2/19/2021
Steady-state Diffusion
• Concentration Gradient: dC/dX (kg/m³).
The slope at a particular point on concentration profile.
(a) Steady-state diffusion across a thin plate. (b) A linear concentration
profile for the diffusion situation in (a).
18 Ch5:MME237 Lecturer: Mr. Thabet Elrabei 2/19/2021
Steady-state Diffusion
• Steady State: the concentration profile doesn't change with
time.
dC
• Apply Fick's First Law: J x D
dx
dC dC
• If (Jx)left = (Jx)right , then
dx left dx right
• Result: the slope, dC/dx, must be constant.
(i.e., slope doesn't vary with position).
19 Ch5:MME237 Lecturer: Mr. Thabet Elrabei 2/19/2021
Steady-state Diffusion
• Example (1): Steady State Diffusion.
• Steel plate at 700º C.
• How much carbon transfers from the rich to the deficient side?
20 Ch5:MME237 Lecturer: Mr. Thabet Elrabei 2/19/2021
Steady-state Diffusion
• Example (2): 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
21 Ch5:MME237 Lecturer: Mr. Thabet Elrabei 2/19/2021
Steady-state Diffusion
• Solution : assuming linear conc. gradient.
dC C2 C1
J -D D
dx x2 x1
Data: D = 110 x 10-8 cm2/s
C1 = 0.44 g/cm3
C2 = 0.02 g/cm3
x2 – x1 = 0.04 cm
-8 2 (0.02 g/cm3 0.44 g/cm3 ) g
J (110 x 10 cm /s) 1.16 x 10-5
(0.04 cm) cm2s
22 Ch5:MME237 Lecturer: Mr. Thabet Elrabei 2/19/2021
Diffusion and Temperature
• Diffusion coefficient increases with increasing T.
Qd
D Do exp
R T
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]
23 Ch5:MME237 Lecturer: Mr. Thabet Elrabei 2/19/2021
Diffusion and Temperature
• D has exponential dependence on T.
1500
1000
600
300
T(C)
10-8
D (m2/s)
D interstitial >> Dsubstitutional
10-14 C in a-Fe Al in Al
C in g-Fe Fe in a-Fe
Fe in g-Fe
10-20
0.5 1.0 1.5 1000 K/T
24 Ch5:MME237 Lecturer: Mr. Thabet Elrabei 2/19/2021
Diffusion and Temperature
• Example: At 300ºC the diffusion coefficient and activation energy
for Cu in Si are:
D(300ºC) = 7.8 x 10-11 m2/s , Qd = 41.5 kJ/mol
Qd
What is the diffusion coefficient at 350ºC? D Doexp
R T
D transform data ln D
Temp = T 1/T
Qd 1 Qd 1
lnD2 lnD0 and lnD1 lnD0
R T2 R T1
D2 Qd 1 1
lnD2 lnD1 ln
D1 R T2 T1
25 Ch5:MME237 Lecturer: Mr. Thabet Elrabei 2/19/2021
Diffusion and Temperature
Qd 1 1
D2 D1 exp
R T2 T1
T1 = 273 + 300 = 573 K
T2 = 273 + 350 = 623 K
11 2 41,500 J/mol 1 1
D2 (7.8 x 10 m /s) exp
8.314 J/mol - K 623 K 573 K
D2 = 15.7 x 10-11 m2/s
26 Ch5:MME237 Lecturer: Mr. Thabet Elrabei 2/19/2021
Nonsteady-state Diffusion
• Concentration profile, C(x), changes w/ time.
Fick’s Second Law.
27 Ch5:MME237 Lecturer: Mr. Thabet Elrabei 2/19/2021
Nonsteady-state Diffusion
• Nonsteady-State Diffusion.
Copper diffuses into a bar of aluminum.
Surface conc.,
C s 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 (const. surf. conc.)
C = Co for x =
28 Ch5:MME237 Lecturer: Mr. Thabet Elrabei 2/19/2021
Nonsteady-state Diffusion
C x ,t Co x
1 erf
Cs Co 2 Dt
C(x,t) = Conc. at point x at time t.
erf (z) = error function
2 z y 2
0
e dy
erf(z) values are given in Table 5.1
29 Ch5:MME237 Lecturer: Mr. Thabet Elrabei 2/19/2021
Nonsteady-state Diffusion
30 Ch5:MME237 Lecturer: Mr. Thabet Elrabei 2/19/2021
Nonsteady-state Diffusion
• 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:
C( x ,t ) Co x
1 erf
Cs Co 2 Dt
31 Ch5:MME237 Lecturer: Mr. Thabet Elrabei 2/19/2021
Nonsteady-state Diffusion
• 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
We must now determine from Table 5.1 the value of z for which the
error function is 0.8125. An interpolation is necessary as follows:
32 Ch5:MME237 Lecturer: Mr. Thabet Elrabei 2/19/2021
Nonsteady-state Diffusion
z erf(z)
z 0.90 0.8125 0.7970
0.7970 0.90
0.95 0.90 0.8209 0.7970
0.8125 z
0.8209 0.95
z = 0.93
Now solve for D
z
x x2
D
2 Dt 4z 2t
x2 3 2
( 4 x 10 m) 1h
D 2.6 x 1011 m2 /s
4z 2t ( 4)(0.93)2 ( 49.5 h) 3600 s
33 Ch5:MME237 Lecturer: Mr. Thabet Elrabei 2/19/2021
Nonsteady-state Diffusion
• To solve for the temperature at which D has above value, we
use a rearranged form of Equation:
Qd
T
R(lnDo lnD)
• From Table 5.2, for diffusion of C in FCC Fe:
Do = 2.3 x 10-5 m2/s Qd = 148,000 J/mol
148,000 J/mol
T
(8.314 J/mol - K)(ln 2.3x105 m 2 /s ln 2.6x1011 m 2 /s)
T = 1300 K = 1027°C
34 Ch5:MME237 Lecturer: Mr. Thabet Elrabei 2/19/2021
Nonsteady-state Diffusion
35 Ch5:MME237 Lecturer: Mr. Thabet Elrabei 2/19/2021
Factors that Influence Diffusion
• Temperature - diffusion rate increases very rapidly with
increasing temperature.
• Diffusion mechanism – diffusion by interstitial mechanism is
usually faster than by vacancy mechanism.
• Diffusing and host species – Do, Qd are different for every
solute, solvent pair.
• Microstructure - diffusion is faster in polycrystalline materials
compared to single crystals because of the accelerated
diffusion along grain boundaries.
End of Chapter Five…
36 Ch5:MME237 Lecturer: Mr. Thabet Elrabei 2/19/2021
