INTRODUCTION TO MATERIALS SCIENCE

Course Code: PHY-657

Credit Hours: Three (3)

Diffusion

Dr. Ejaz Ahmed

Department of Physics

Abdul Wali Khan University Mardan

 Diffusion Flux (J)
Diffusion is a time-dependent process—that is, in a macroscopic sense, the quantity of an element that is
transported within another is a function of time.
Often it is necessary to know how fast diffusion occurs, or the rate of mass transfer.
This rate is frequently expressed as a diffusion flux (J), defined as the mass (or, equivalently, the number of

atoms) M diffusing through and perpendicular to a unit cross-sectional area A of solid per unit of time t. In
mathematical form, this may be represented as
𝑴
𝑱=
𝑨𝒕
In differential form, this expression becomes
𝟏 𝒅𝑴
𝑱=
𝑨 𝒅𝒕
The units for J are kilograms or atoms per meter squared per second
(𝒌𝒈/𝒎𝟐 − 𝒔 or 𝒂𝒕𝒐𝒎𝒔/𝒎𝟐 − 𝒔).
 Steady-State Diffusion
If the diffusion flux does not change with time, a steady-state
condition exists.
One common example of steady-state diffusion is the diffusion of atoms
of a gas through a plate of metal for which the concentrations (or
pressures) of the diffusing species on both surfaces of the plate are held
constant.
When concentration C is plotted versus position (or distance)
within the solid x, the resulting curve is termed the concentration
profile; the slope at a particular point on this curve is the
concentration gradient:
C𝒐𝒏𝒄𝒆𝒏𝒕𝒓𝒂𝒕𝒊𝒐𝒏 𝑮𝒓𝒂𝒅𝒊𝒆𝒏𝒕 = 𝒅𝑪Τ𝒅𝒙
In the present treatment, the concentration profile is assumed to be linear, as
depicted in Figure. For diffusion problems, it is sometimes convenient to
express concentration in terms of mass of diffusing species per unit volume of
solid (𝒌𝒈/𝒎𝟑 or 𝒈/𝒄𝒎𝟑).
 Steady-State Diffusion (cont.)
The mathematics of steady-state diffusion in a single (x) direction is
relatively simple, in that the diffusion flux is proportional to the
concentration gradient through the expression
𝒅𝑪 𝒅𝑪 𝑪𝑨 − 𝑪𝑩
𝑱∝− 𝑱 = −𝑫 = −𝑫
𝒅𝒙 𝒅𝒙 𝒙𝑨 − 𝒙𝑩

The constant of proportionality D is called the diffusion coefficient, which is

expressed in square meters per second. The negative sign in this
expression indicates that the direction of diffusion is down the concentration
gradient, from a high to a low concentration. Above Equation is sometimes called Fick’s first law.

The diffusion coefficient (D) is the mass of the substance diffuses through a unit surface in a
unit time at a concentration gradient of unity. The dimension of D in the SI system is a square
meter per second (𝒎𝟐/𝒔) which is also called diffusivity.
 Steady-State Diffusion (cont.)

➢ Sometimes the term driving force is used in the context of what compels a reaction to
occur. For diffusion reactions, several such forces are possible; but when diffusion is
according to steady state diffusion Equation, the concentration gradient is the
driving force.
➢ One practical example of steady-state diffusion is found in the purification of
hydrogen gas. One side of a thin sheet of palladium metal is exposed to the impure
gas composed of hydrogen and other gaseous species such as nitrogen, oxygen, and
water vapor. The hydrogen selectively diffuses through the sheet to the opposite side,
which is maintained at a constant and lower hydrogen pressure.
 Non-steady-State Diffusion
Most practical diffusion situations are nonsteady-state
ones. That is, 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. This is illustrated in Figure, which
shows concentration profiles at three different diffusion
times. Under conditions of nonsteady state, use of Fick’s
first law Equation is no longer convenient; instead, the Figure:
partial differential equation Concentration profiles for
nonsteady-state diffusion taken at
𝝏𝑪 𝝏 𝝏𝑪
= 𝑫 three different times, and 𝒕𝟏 , 𝒕𝟐 , 𝒕𝟑 .
𝝏𝒕 𝝏𝒙 𝝏𝒙

known as Fick’s second law, is used.

 Nonsteady-State Diffusion

If the diffusion coefficient is constant (i.e., independent of composition (which should

be verified for each diffusion situation)), above equation simplifies to

𝝏𝑪 𝝏𝟐 𝑪
= 𝑫 𝟐
𝝏𝒕 𝝏𝒙

Fick’s second law—diffusion equation for nonsteady-state diffusion (in one direction).

Solutions to this expression (concentration in terms of both position and time) are
possible when physically meaningful boundary conditions are specified.
 NON-STEADY-STATE DIFFUSION
One practically important solution is for a semi-infinite solid (A bar of solid is considered to be semi-infinite
if none of the diffusing atoms reaches the bar end during the time over which diffusion takes place. A bar of
length l is considered to be semi-infinite when 𝒍 > 𝟏𝟎 𝑫𝒕) in which the surface concentration is held
constant. Frequently, the source of the diffusing species is a gas phase, the partial pressure of which is
maintained at a constant value. Furthermore, the following assumptions are made:
1. Before diffusion, any of the diffusing solute atoms in the solid are uniformly distributed with
concentration of 𝑪𝒐
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.
For 𝒕 = 𝟎, 𝑪 = 𝑪𝒐 𝒂𝒕 𝟎 ≤ 𝒙 ≤ ∞
For 𝒕 > 𝟎, 𝑪 = 𝑪𝒔 𝐭𝐡𝐞 𝐜𝐨𝐧𝐬𝐭𝐚𝐧𝐭 𝐬𝐮𝐫𝐟𝐚𝐜𝐞 𝐜𝐨𝐧𝐜𝐞𝐧𝐭𝐫𝐚𝐭𝐢𝐨𝐧 𝒂𝒕 𝒙 = 𝟎
𝑪 = 𝑪𝒐 𝐚𝐭 𝒙 = ∞ 𝝏𝑪 𝝏𝟐 𝑪
Application of these boundary condition to equation = 𝑫 𝟐 yields the solution
𝝏𝒕 𝝏𝒙
𝑪𝒙 − 𝑪𝒐 𝒙
= 𝟏 − 𝒆𝒓𝒇
𝑪𝒔 − 𝑪𝒐 𝟐 𝑫𝒕
 NON-STEADY-STATE DIFFUSION (cont.)
where 𝑪𝒙 represents the concentration at depth x after time t. The expression 𝒆𝒓𝒇 𝒙Τ𝟐 𝑫𝒕 is
the Gaussian error function, values of which are given in mathematical tables for various values
𝒙Τ𝟐 𝑫𝒕; a partial listing is given in below Table.
Table: Tabulation of Error Function Values

This Gaussian error 𝟐 𝒛 −𝒚𝟐

function is defined by 𝐞𝐫𝐟 𝒛 = න 𝒆 𝒅𝒚
𝝅 𝟎 where 𝒙Τ𝟐 𝑫𝒕 has been replaced by the variable z.
 NON-STEADY-STATE DIFFUSION (cont.)

The concentration parameters that appear in Equation

𝑪𝒙 −𝑪𝒐 𝒙
= 𝟏 − 𝒆𝒓𝒇
𝑪𝒔 −𝑪𝒐 𝟐 𝑫𝒕

are noted in given figure, a concentration profile taken

at a specific time. The Equation thus demonstrates the
relationship between concentration, position, and
time—namely, that 𝑪𝒙 being a function of the
dimensionless parameter 𝒙Τ 𝑫𝒕 may be determined at Figure:
Concentration profile for nonsteady-state
any time and position if the parameters 𝑪𝒐 , 𝑪𝒔 and D diffusion; concentration parameters relate
to Equation.
are known.
 NON-STEADY-STATE DIFFUSION (cont.)
Suppose that it is desired to achieve some specific
concentration of solute, 𝑪𝟏 in an alloy; the left-hand side
of Equation now becomes
𝑪𝟏 − 𝑪𝒐
= 𝒄𝒐𝒏𝒔𝒕𝒂𝒏𝒕
𝑪𝒔 − 𝑪𝒐
This being the case, the right-hand side of this same
expression is also a constant, and subsequently

𝒙 𝒙𝟐
= 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 or = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝟐 𝑫𝒕 𝑫𝒕 Figure:
Concentration profile for nonsteady-state
diffusion; concentration parameters relate
to Equation.
Some diffusion computations are thus facilitated on the
basis of this relationship.
 Non-steady-State Diffusion Time Computation
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. 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; assume
that the steel piece is semi-infinite.
𝑪𝒙 − 𝑪𝒐 𝒙
Solution 𝑪𝒐 = 𝟎. 𝟐𝟓 𝒘𝒕. % 𝑪 = 𝟏 − 𝒆𝒓𝒇
𝑪𝒔 − 𝑪𝒐 𝟐 𝑫𝒕
𝑪𝒔 = 𝟏. 𝟐𝟎 𝒘𝒕. % 𝑪
𝑪𝒙 = 𝟎. 𝟖𝟎 𝒘𝒕. % 𝑪 𝟎. 𝟖𝟎 − 𝟎. 𝟐𝟓 𝟓 × 𝟏𝟎−𝟒 𝒎
= 𝟏 − 𝒆𝒓𝒇
𝒙 = 𝟎. 𝟓 𝒎𝒎 = 𝟓 × 𝟏𝟎−𝟒 𝒎 𝟏. 𝟐𝟎 − 𝟎. 𝟐𝟓
𝟐 𝟏. 𝟔 × 𝟏𝟎−𝟏𝟏 𝒎𝟐ൗ 𝒕
𝑫 = 𝟏. 𝟔 × 𝟏𝟎 −𝟏𝟏 𝒎 𝟐
ൗ𝒔 𝒔
Non-steady-State Diffusion Time Computation (cont.)
Non-steady-State Diffusion Time Computation (cont.)
𝟏ൗ
𝟔𝟐. 𝟓 𝒔 𝟐
𝟎. 𝟒𝟐𝟏𝟎 = 𝒆𝒓𝒇
𝒕
We must now determine from Table 5.1 the value of z for which the error function is 0.4210. An interpolation
is necessary, as
𝟏ൗ
𝒛 𝒆𝒓𝒇 𝒛 Therefore, 𝟔𝟐. 𝟓 𝒔 𝟐
= 𝟎. 𝟑𝟗𝟐
0.35 0.3794 𝒕
𝑧 0.4210
0.40 0.4284 And solving for t, we find

𝒛−𝟎.𝟑𝟓 𝟎.𝟒𝟐𝟏𝟎−𝟎.𝟑𝟕𝟗𝟒
= 𝟏ൗ 𝟐
𝟎.𝟒𝟎−𝟎.𝟑𝟓 𝟎.𝟒𝟐𝟖𝟒−𝟎.𝟑𝟕𝟗𝟒 𝟔𝟐. 𝟓 𝒔 𝟐
𝒕= = 𝟐𝟓, 𝟒𝟎𝟎 𝒔 = 𝟕. 𝟏 𝒉
𝟎. 𝟑𝟗𝟐
𝒛 = 𝟎. 𝟑𝟗𝟐
𝒕 = 𝟕. 𝟏 𝒉