Diffusion

What is Diffusion?
One of the most
fundamental processes
that controls the rate at
which many
transformations occur
is the diffusion of
atoms

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Our Goals Today!
Name and describe the
atomic mechanisms of
diffusion!

Distinguish between steady-state

and non-steadystate diffusion !

Apply Fick’s first and second laws

for carburization case!
Diffusion
The phenomenon
of material
transport by
atomic motion

why do atoms move?

Stability of atoms
Imperfections could be introduced
into the lattice of a crystal. These
imperfections are not stable or at
rest.

Atoms posses some thermal energy and they

will move. They may move from a normal
lattice point to occupy nearby vacancy or
move from one interstitial site to another.
 (1) Vacancy
(3) Interstitial
impurity

(4) and (5) (2) self-interstitial

substitutional
impurities
Substitutional/vacancy diffusion Diffusion
Mechanism
Vacancy
For an atomic to make a motion,
there are two conditions that need
to be met:
Position of
1. There must be an empty
substitutional atom
after diffusion
adjacent site
2. The atom must have sufficient
Interstitial diffusion energy to break bonds with its
neighbor atoms and then cause
This mechanism:
Position of interstitial
atom after diffusion 1. Small impurities such as some lattice distortion during
hydrogen, carbon, nitrogen, the displacement.
and oxygen
2. No vacancies is required
3. More rapid Activation Energy
Diffusion is a time-dependent process—it is necessary to know how
fast diffusion occurs, or the rate of mass transfer  diffusion flux
(J)

“defined as the mass (or, equivalently, the number of

atoms) M diffusing through and perpendicular to a unit
cross-sectional (A) area of solid per unit of time (t)”

     
J J J
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 concentration gradient

  Δ𝐶
¿
Δ𝑥
  𝐶 𝐴 −𝐶𝐵
¿
𝑥 𝐴 − 𝑥𝐵

  𝑑𝐶
𝐽 =− 𝐷
𝑑𝑥
If the diffusion flux does not Fick’s 1st law
change with time, a steady-state D is called the diffusion coefficient,
condition exists. which is expressed in square meters
10 per second
A plate of iron is exposed to a carburizing (carbon-rich) atmosphere on one side
and a decarburizing (carbon-deficient) atmosphere on the other side at 700 ˚C
(1300 ˚F). If a condition of steady state is achieved, calculate the diffusion flux of
carbon through the plate if the concentrations of carbon at positions of 5 and 10
mm (5 x 10-3 and 10-2 m) beneath the carburizing surface are 1.2 and 0.8 kg/m3,
respectively. Assume a diffusion coefficient (D) of 3 x 10-11 m2/s at this temperature

D = 3 x 10-11 m2/s XA = 5 x 10-3 m

A B CA = 1.2 kg/m3 XB = 10-2 m
5 mm CB= 0.8 kg/m3
10 mm

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 Most practical diffusion situations are non-steady-state.
the diffusion flux and the concentration gradient at some particular point in a solid
vary with time
 
J

 
=
2
 
𝑑 𝐶
¿−𝐷 2
𝑑𝑥

Fick’s 2nd law

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It is assumed that in this equation D is not vary with x
 1. Before diffusion, any of the diffusing solute atoms in the solid
are uniformly distributed with concentration of C0.
2. The value of x at the surface is zero and increases with distance
into the solid.
3. The time is taken to be zero the instant before the diffusion
process begins.

These conditions are simply stated as follows:

Initial condition:
4. For t = 0, C = C0 at 0 ≤ x ≤ ∞
Boundary conditions
5. For t > 0, C = Cs (the constant surface concentration) at x = 0
6. For t > 0, C = C0 at x = ∞

where Cx represents the concentration at depth x after time t. The expression erf(x2/√Dt) is the Gaussian error
function
13
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 x 0 1 2 3 4 5 6 7 8 9

ERF Table
0.0 0.00000 0.01128 0.02256 0.03384 0.04511 0.05637 0.06762 0.07886 0.09008 0.10128
0.1 0.11246 0.12362 0.13476 0.14587 0.15695 0.16800 0.17901 0.18999 0.20094 0.21184
0.2 0.22270 0.23352 0.24430 0.25502 0.26570 0.27633 0.28690 0.29742 0.30788 0.31828
0.3 0.32863 0.33891 0.34913 0.35928 0.36936 0.37938 0.38933 0.39921 0.40901 0.41874
0.4 0.42839 0.43797 0.44747 0.45689 0.46623 0.47548 0.48466 0.49375 0.50275 0.51167
0.5 0.52050 0.52924 0.53790 0.54646 0.55494 0.56332 0.57162 0.57982 0.58792 0.59594
0.6 0.60386 0.61168 0.61941 0.62705 0.63459 0.64203 0.64938 0.65663 0.66378 0.67084
0.7 0.67780 0.68467 0.69143 0.69810 0.70468 0.71116 0.71754 0.72382 0.73001 0.73610
0.8 0.74210 0.74800 0.75381 0.75952 0.76514 0.77067 0.77610 0.78144 0.78669 0.79184
0.9 0.79691 0.80188 0.80677 0.81156 0.81627 0.82089 0.82542 0.82987 0.83423 0.83851
1.0 0.84270 0.84681 0.85084 0.85478 0.85865 0.86244 0.86614 0.86977 0.87333 0.87680
1.1 0.88021 0.88353 0.88679 0.88997 0.89308 0.89612 0.89910 0.90200 0.90484 0.90761
1.2 0.91031 0.91296 0.91553 0.91805 0.92051 0.92290 0.92524 0.92751 0.92973 0.93190
1.3 0.93401 0.93606 0.93807 0.94002 0.94191 0.94376 0.94556 0.94731 0.94902 0.95067
1.4 0.95229 0.95385 0.95538 0.95686 0.95830 0.95970 0.96105 0.96237 0.96365 0.96490
1.5 0.96611 0.96728 0.96841 0.96952 0.97059 0.97162 0.97263 0.97360 0.97455 0.97546
1.6 0.97635 0.97721 0.97804 0.97884 0.97962 0.98038 0.98110 0.98181 0.98249 0.98315
1.7 0.98379 0.98441 0.98500 0.98558 0.98613 0.98667 0.98719 0.98769 0.98817 0.98864
1.8 0.98909 0.98952 0.98994 0.99035 0.99074 0.99111 0.99147 0.99182 0.99216 0.99248
1.9 0.99279 0.99309 0.99338 0.99366 0.99392 0.99418 0.99443 0.99466 0.99489 0.99511
2.0 0.99532 0.99552 0.99572 0.99591 0.99609 0.99626 0.99642 0.99658 0.99673 0.99688
2.1 0.99702 0.99715 0.99728 0.99741 0.99753 0.99764 0.99775 0.99785 0.99795 0.99805
2.2 0.99814 0.99822 0.99831 0.99839 0.99846 0.99854 0.99861 0.99867 0.99874 0.99880
2.3 0.99886 0.99891 0.99897 0.99902 0.99906 0.99911 0.99915 0.99920 0.99924 0.99928
2.4 0.99931 0.99935 0.99938 0.99941 0.99944 0.99947 0.99950 0.99952 0.99955 0.99957
2.5 0.99959 0.99961 0.99963 0.99965 0.99967 0.99969 0.99971 0.99972 0.99974 0.99975
2.6 0.99976 0.99978 0.99979 0.99980 0.99981 0.99982 0.99983 0.99984 0.99985 0.99986
2.7 0.99987 0.99987 0.99988 0.99989 0.99989 0.99990 0.99991 0.99991 0.99992 0.99992
2.8 0.99992 0.99993 0.99993 0.99994 0.99994 0.99994 0.99995 0.99995 0.99995 0.99996
2.9 0.99996 0.99996 0.99996 0.99997 0.99997 0.99997 0.99997 0.99997 0.99997 0.99998
3.0 0.99998 0.99998 0.99998 0.99998 0.99998 0.99998 0.99998 0.99999 0.99999 0.99999
3.1 0.99999 0.99999 0.99999 0.99999 0.99999 0.99999 0.99999 0.99999 0.99999 0.99999
15 3.2 0.99999 0.99999 0.99999 1.00000 1.00000 1.00000 1.00000 1.00000 1.00000 1.00000
 For some applications, it is necessary to harden the surface of a steel (or iron–carbon alloy) above that of its
interior. One way this may be accomplished is by increasing the surface concentration of carbon in a process
termed carburizing; the steel piece is exposed, at an elevated temperature, to an atmosphere rich in a
hydrocarbon gas, such as methane (CH4).

Consider one such alloy that initially has a uniform carbon concentration of 0.25 wt% and is to be treated at
950°C (1750°F). If the concentration of carbon at the surface is suddenly brought to and maintained at 1.20 wt
%, how long will it take to achieve a carbon content of 0.80 wt% at a position 0.5 mm below the surface? The
diffusion coefficient for carbon in iron at this temperature is 1.6 × 10 -11 m2/s

C0 = 0.25 wt% C
Cs = 1.20 wt% C
Cx = 0.80 wt% C
x = 0.50 mm = 5 × 10-4 m   62.5
0.5790=1−
D = 1.6 × 10-11 m2/s √𝑡
  62.5
0 .4210=𝑒𝑟𝑓
√𝑡
0.4210=erf
  (¿𝑧)¿
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   62.5   62.5   62.5
0.5790=1− 0 .4210=𝑒𝑟𝑓 𝑧= 0.4210=erf
  (¿𝑧)¿
√𝑡 √𝑡 √𝑡
We must now determine from Erf table, the value of z for which the error function is 0.4210. An interpolation is necessary, as

  62.5  √ 𝑡 = 62.5   62.5 2

0.392=
√𝑡 0.392 𝑡 =⌊ 0.392 ⌋ =25420 𝑠 7.1 hour!

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 FACTORS THAT INFLUENCE
1. Diffusing Species DIFFUSION 2. Temperature

D interstitial >> D substitutional

C in α-Fe Al in Al
C in γ–Fe Fe in α-Fe
Fe in γ–Fe
Temperature has a profound influence on the coefficients and
diffusion rates (D). For example, rising temperature from 500˚C to
900˚C  for the self-diffusion of Fe in α-Fe, D increases
approximately six orders of magnitude (from 3.0 x 10-21 to 1.8 x 10-18
m2/s) in. The temperature dependence of the diffusion coefficients is

D = D0 exp
 

D0 = a temperature-independent preexponential (m2/s)

Qd = the activation energy for diffusion (J/mol or eV/atom)
R = the gas constant, 8.31 J/mol∙K or 8.62 × 10-5 eV/atom∙K
T = absolute temperature (K)
Diffusion Coefficient
Determination

Using the data in Table, compute the D for

magnesium in aluminum at 550°C.
Solution
This D may be determined by applying
Equation  D = D exp
0

the values of D0 and Qd from Table are 1.2 ×

10−4 m2/s and 130 kJ/mol, respectively. Thus,
 How long will it take to carburize a 0.20% C steel at 900C so that the
carbon content will be 0.40% at a depth of 1 mm when the carbon
concentration at the surface is assumed to be 1.0%? It has been known
that the value of D0 and Q is 0.21 cm2/s and 33.8 kcal, respectively.
C0 = 0.20 wt% C
Cs = 1.0 wt% C
Cx = 0.40 wt% C
 0.4 −0.2 10-3   𝑥
x = 1 mm = 10-3 m
D0 = 0.21 cm2/s 1.0− 0.2
=1-  𝑒𝑟𝑓
√ 𝐷𝑡
0.75=erf
( 2 √ 𝐷𝑡 )
Qd = 33.8 kcal

We must now determine from Erf table, the value of x for which the error
function is 0.75. An interpolation is necessary!
   𝑧 − 0.80 0.75 −0.7421
= =0.8134
0.85− 0.80 0.7707 −0.7421

  𝑥 𝒙𝟐
= 0.8134 ; 𝑥=1.63 √ 𝐷𝑡 ; 𝒕 =
2 √ 𝐷𝑡 𝟐 . 𝟔𝟓 𝑫

D0 = 0.21 cm2/s
Qd = 33.8 kcal
R= 1.987 × 10−3 kcal·mol−1 ·K−1
 

D = 1.1 x 10-7 cm2/s

 Since the depth is 0.1 cm, then: