AES 402A - MATERIALS SCIENCE & ENGINEERING

DIFFUSION
A.) INTRODUCTION
Reactions and process that are important in the treatment of materials to improve their properties
such as casehardening of iron & steel rely on transfer of mass either within the specific solid, or
from gas , from liquid, or another solid phase. This is accomplished by DIFFUSION, a
phenomenon of mass transport by atomic motion. From an atomic perspective for diffusion to
occur, two conditions must be met : a.) there must be an adjacent empty site, b.) atoms must
have sufficient energy to break bonds with its neighbor atoms & then cause some lattice distortion
during the displacement.
When two different metals are placed in intimate contact face-to-face, and heated at elevated
temperature for an extended period, atoms of both metals will diffuse into each other. This is
known as inter-diffusion or impurity diffusion. Diffusion also occur in pure metals, and is termed as
self-diffusion.
Case hardening of steel by CARBURIZING, NITRIDING, and CYANIDING process
involves the diffision phenomenon --> This is assigned as students' research report.
B.) DIFFUSION MECHANISM
Several models of atomic diffusion had been proposed, and of these ; two dominate for metallic
diffusion :
1.) Vacancy diffusion - involves the interchange of atoms from a normal lattice position to an
adjacent vacantsite. Refer to illustration below.
2.) Interstitial diffusion - involves migration of atoms from an interstitial position to a neighboring
interstitial one that is empty. Refer to the illustration below. For most metal alloy, this type
occurs much more rapidly than the vacancy type, because the intertitial atoms are smaller thus
more mobile, & there are more empty interstitial positions than vacancies.

vacancy

Vacancy diffusion Interstitial diffusion

C.) STEADY STATE DIFFUSION - Fick's first law
Diffusion flux ( J ) is the amount of mass ( or equivalent number of atoms ) diffussing through
and perpendicular to the unit cross-sectional area of solid per unit time.
A steady state diffusion is one in which the diffusion flux ( J ) does not change with time, as in the
example of a diffusion of atoms of a gas thru a metal plate for which the concentration (or
pressure) of the diffusing species on both surfaces of the plate are held constant as shown :

PA > PB and constant CA

Concentration
PA direction of profile
PB diffusion of
gaseous species

CB XA XB

The concentration gradient = dC/dx., is assumed linear =

where :
Fick's 1'st Law : J = diffusion flux, kg/m 2-sec
D = diffusion coeffcient, m 2/sec.

Sample problem # 1 : A steel plate is exposed to a carburizing atmosphere on one side at 700
deg C. , If thecondition of steady state is achieved, calculate the diffusion flux of carbon thru the
plate if the concentration ofcarbon at positions 5 and 10 mm beneath the surface are 1.2 and 0.8
 kg/m3, respectively.. The diffusion coefficient is assumed at 3 x 10-11 m2/sec.

D.) NONSTEADY-STATE DIFFUSION - Fick's second law.

The most practical diffusion situations are the nonsteady state ones; ie, the diffusion flux and the
concentration gradient at some particular point in a solid vary with time, with a net accumulation or
depletion of the diffusing species resulting.
Analytical solution to Fick's second law
Fick's second law : equation for a semiinfinite plate with a
constant surface concentration with the
following initial and boundary conditions:
– t = 0, C = Co at 0 ≤ x ≤ ∞
– for t > 0, C = Cs at x = 0 and
C = Co at x = ∞

(z)
where ( z ) =

where CX represents the concentration at the depth x after time t . The expression erf ( x /2(D t) 1/2
is a Gaussian error function ; of which the partial listing of values are given in the table below.
The above equation demonstrates the relationship between concentration, position, and time. CX
being the function of a dimensionless parameter x /(D t)1/2, maybe determined at any time and
position if the parameters CO , CS , and D are known. Suppose it is desired to achieve some
specific concentration of solute , C1 , in an alloy: the left hand of the equation now becomes :

(C1 - C0) / (CS - C0) = constant

This being the case, the right hand side of the equation is also a constant, and subsequently :

x / 2(D t)1/2 = constant , or x2 / (D t) = constant, or

(D t)1 = (D t)2 = constant

Concentration profile

Tabulation of the Gaussian Error Function Values ( partial )

z erf( z ) z erf( z ) z erf( z )
0 0 0.55 0.5633 1.3 0.9340
 0.025 0.0282 0.60 0.6039 1.4 0.9523
0.05 0.0564 0.65 0.6420 1.5 0.9661
0.10 0.1125 0.70 0.6778 1.6 0.9763
0.15 0.1680 0.75 0.7112 1.7 0.9838
0.20 0.2227 0.80 0.7421 1.8 0.9891
0.25 0.2763 0.85 0.7707 1.9 0.9928
0.30 0.3286 0.90 0.7970 2.0 0.9953
0.35 0.3794 0.95 0.8209 2.2 0.9981
0.40 0.4284 1.00 0.8427 2.4 0.9993
0.45 0.4755 1.01 0.8802 2.6 0.9998
0.50 0.5205 1.20 0.9103 2.8 0.9999

Sample problem # 2 - A steel alloy with an initial carbon content of 0.25 wt % is to be carburized at
950 degrees C by exposing it to a gas containing carbon that brought and maintain the carbon
concentration at the steel surface at 1.2 %. How long will it take to achieve a carbon content of 0.8
wt % at a position 0.5 mm below its surface ? The diffusion coefficient at this temperature is 1.6 x
10-11 m2/sec. Assume the alloy piece is semi-infinite.

Solution:
Given: Co = 0.25 wt% , Cs = 1.20 wt% Cx = 0.80 wt% , x = 0.50 mm D = 1.6 x 10-11 m2/s

(Cx – Co)/(Cs – Co) = 1 - erf [ x/(2(Dt)1/2) ]

(0.80 – 0.25)/(1.20 – 0.25) = 1-erf [(5x10-4) /(2(1.6x10-11t)1/2)]
0.57895 - 1 = - erf (z)
0.4210 = erf (z) = erf [ x/(2(Dt)1/2) ] ; hence z = x/(2(Dt)1/2)
the corresponding value of z at erf(z) = 0.4210 is found by
interpolation using Table 5.1, z = 0.392 (refer to table below)

therefore, z = 0.392 = x/(2(Dt)1/2) = [(5x10-4) /[(2)(1.6 x10-11t)1/2]

0.392 = 62.5 /(t1/2 )
t = (6.25/0.392)2 = 25420 sec = 7.06 hrs.

Sample problem # 3 - The diffusion coefficient of aluminum in copper is at 500 & 600 degrees C
are 4.8 x 10-14 , and 5.3 x 10-13 m2/sec, respectively. Determine the time at 500 degrees C that will
produce the same diffusion result ( in terms of concentration of Cu at some specific point in Al ) as
a 10-hr heat treatment at 600 degrees C.
 Solution :
The composition in both diffusion situations will be equal at the same position (i.e. x is also a
constant), hence :
Dt = constant
(Dt) at 500oC = (Dt) at 600oC
diffusion time, t at 500oC = (Dt) at 600oC / (D) at 500oC = (5.3 x 10-13 m2/s)(10 hr)/4.8 x 10-14 m2/s
= 110.4 hours

E. FACTORS THAT INFLUENCE DIFFUSION

1.) Diffusing species - the diffusing species influence the diffusion coefficient. An example is
in iron. There is a significant difference in the magnitude of self, & carbon interdiffusion in
a-iron, the D value being greater in interdiffusion. Self diffusion occurs by via vacancy
mechanism, while carbon diffusion is interstitial.
TABULATION OF DIFFUSION DATA

Diffusing Host Do Activation Energy, Qd Calculated Values

species Metal (m2/sec) kJ/mole eV/atom T ( OC) D (m2/sec)
Fe a -Fe 2.8 x 10-4
251 2.60 500 3.0 x 10-21
(BCC) 900 1.8 x 10-15
Fe g -Fe 5.0 x 10-5 284 2.94 900 1.1 x 10-17
(FCC) 1100 7.8 x 10-16
C a -Fe 6.2 x 10-7 80 0.83 500 2.4 x 10-12
900 1.7 x 10-10
C g -Fe 2.3 x 10-5 148 1.53 900 5.9 x 10-12
1100 5.3 x 10-11
Cu Cu 7.8 x 10-5 211 2.19 500 4.2 x 10-19
Zn Cu 2.4 x 10-5 189 1.96 500 4.0 x 10-18
Al Al 2.3 x 10-4 144 1.49 500 4.2 x 10-14
Cu Al 6.5 x 10-5 136 1.41 500 4.1 x 10-14
Mg Al 1.2 x 10-4 131 1.35 500 1.9 x 10-13
Cu Ni 2.7 x 10-5 256 2.65 500 1.3 x 10-22

2.) Temperature - has the most profound influence on coefficient and diffusion rates. Diffusion
coefficients are related to temperature by :

D = Do x exp [-Qd / (RT)]

where : DO = temperature-independent preexponential (m2/sec)
Qd = activation energy ( J/mole, cal/mole, or eV/mole )
O O
R = gas constant ( 8.31 J/mol- K , 1.987 cal/mol- K ,
-5 O
8.62 x 10 eV/atom- K )
O
T = absolute temperature, K
This can also be expressed in logarithmic form as :

ln D = ln Do - (Qd / R)(1/T) , or
log D = log Do - (Qd/2.3R)(1/T)
which now is straight line equation y = mx + b.

Sample problem # 4 - Compute the diffusion coefficient for magnesium in aluminum at 550 deg
C, using the data in the table above.

Solution:
D = Do x exp [-Qd / (RT)] can be used
from the diffusion data tabulation above:
 the host metal is aluminum
the diffusing specie is magnesium, its Do when diffusng in aluminum = 1.2 x 10-4 m2/s
and its activation energy, Qd = 131,000 J/mol, and R = 8.31 J/mol-K
D = (1.2*10-4)*exp[-131000/(8.31*(550+273))] = 5.8*10-13 m2/s