Lecture 4

MKT 1122 MATERIALS SCIENCE
Lecture-4
(Diffusion in Solids)
Umut Karagüzel
Yildiz Technical University

Diffusion in Solids
Diffusion is the phenomenon of material transport by atomic

motion. Atoms of one element make atomic movements in the
crystal lattice of another element.
Diffusion
Couple
Pure copper and nickel at the two extremities of the couple,
separated by an alloyed (mixed) region. Concentrations of both
metals vary with position.
Copper atoms have migrated or diffused into the nickel, and
nickel atoms have diffused into copper. This process, whereby
atoms of one metal diffuse into another, is known interdiffusion,
or impurity diffusion.
Diffusion also occurs for pure metals, but all atoms exchanging
positions are of the same type; this is termed self-diffusion,
and will not cause any composition change.
Pre-conditions for diffusion:

(1) There must be empty adjacent sites (vacancies), and
(2) The atoms must have sufficient energy to break bonds with
its neighbor atoms and make movements in the crustal. This
energy is vibrational in nature and supplied by heating (heat
energy).
Mechanisms of Diffusion
a. Vacancy Diffusion b. Intersitital Diffusion

mechanism involves the mechanism involves atoms
interchange of an atom from a that migrate from an interstitial
normal lattice position to an position to an empty
adjacent vacant lattice site or neighboring one. This
vacancy. the diffusion of atoms in mechanism is found for
one direction corresponds to the interdiffusion of small atoms
motion of vacancies in the such as H, C, N, O to fit into
opposite direction. the interstitial positions.
Interstitial diffusion occurs much more rapidly than diffusion
by vacancy transport mode, because the interstitial atoms are
smaller and more mobile. There are also more empty interstitial
positions than vacancies.
Diffusion is a time-dependent process. The quantity of an
element or number of atoms being transported in another
element’s crystal is a function of time.
Diffusion flux (J) is the rate of diffusion and expresses
how fast (and much) diffusion occurs. It is defined as the
mass (or the number of atoms) (M) diffusing through and
perpendicular to a unit cross-sectional area (A) of solid per
unit of time (t). In differential form:
J: diffusion flux (kg/m2 .s) or (atoms/m2 .s),
M: mass or atoms diffused (kg) or (atoms),
A: cross sectional area the diffusion occurs (m2),
t: diffusion time (s).
a. STEADY STATE DIFFUSION
Steady State Diffusion occurs when the diffusion flux does not
change with time.
When concentration of diffused atoms C is plotted versus position
(or distance in x direction) within the solid the resulting curve is
termed the concentration profile.
Steady-state diffusion in one direction (say in x) is expressed
mathematically by Fick’s First Law:
D is diffusion coefficient (m2/s) and the negative sign indicates,

the concentration gradient decreases from high to low
concentration in the direction (x) of diffusion.
The term Driving force is used to define a factor accelerating

the process.
The driving forces for diffusion:

1. Concentration gradient (concentration difference)
2. Diffusion coefficient (Temperature, activation energy)
Diffusion coefficient D:
Do : Temperature independent pre-exponential constant

(m2/s), (but it is a function of solute and solvent elements),
Qd : Activation energy for diffusion (J/mol) or (eV/atom), (it
also depends on solute and solvent elements),
R : Gas constant (8.31 J/mol.K) or (8.62 x 10-5 eV/atom.K)
T : Absolute process temperature (K).
Naturel logarithm of both sides yields a line equation:
ln D ln Do
ln Do
(Convenience of
Arrhenius type
equations!!!)
Solute Solvent
atoms atoms
Diffusion Data for Different Couples

Diffusion coefficient (D) as a function of temperature
B. NON-STEADY STATE DIFFUSION
Practical diffusion applications are in non-steady state. Diffusion

flux and the concentration gradient at a particular point vary with
time.
Under conditions of non-steady state Fick’s Second Law is used
to construct a relationship between process parameters, time,
concentrations and temperature.
If the diffusion coefficient is assumed as independent of

composition:
Solution of the expression (concentration in terms of both

position and time) is possible if physically meaningful boundary
conditions are specified and a special function (error
function) is used.
1. Before diffusion, solute atoms in the solid are uniformly
distributed with concentration of C0.
2. The value of x at the surface is zero and increases into the
solid.
3. The time is zero at the time diffusion process begins.
Cx : concentration of diffused species at depth x, after time t

Cs : concentration of diffused species on the surface of the solid
(Concentration of diffused atoms in the process environment),
Co : initial concentration of diffused atoms in the solid.
D : diffusion constant
t: time for diffusion
erf : Gaussian Error function.
A graphical method can also be used for the solution of Fick’s 2nd Law
FACTORS AFFECTING DIFFUSION
• Temperature
• Diffusing species (Solute-Solvent Atoms)
• Concentration Difference (Cs – Co)
• Diffusion Zone
An Implementation of Solid State Diffusion Process
Carburizing (“sementasyon” in Turkish) is a thermo-chemical
surface heat treatment applicable to low carbon steels.
Carbon is playing a very effective role in strength and hardness of

steel. Higher the C concentration yields harder or stronger steel.
But steels with high C content exhibit extremely brittle behavior

and may be very dangerous for certain mechanical engineering
applications, because of resulting sudden and unexpected
fracture failures.
When we need high hardness only on the surface or near the

surface of a machine part (like shafts, springs etc.), we select a
low carbon steel at the beginning and then we apply carburizing
treatment (i.e. a surface hardening heat treatment) to the steel.
Carburizing is done at sufficiently high temperatures in C
rich atmosphere (i.e. in a high temperature furnace) by
holding the work piece enough time.
During the process C atoms diffuse through the surface of

low C steel work piece and increase the carbon concentration.
Higher process temperature and/or longer holding time result

thicker C reach layer (i.e. case) on the surface.
In other words, to control the case depth is possible only if

diffusion process is controlled properly. The process is also
known as “case hardening” process.
Case
Case (Carburized
Thickness, t
Layer) with high C
Core (center)
with low C
C
Diffusion
Diameter, D
Example:
Consider a steel bar with 0.25% C concentration is being carburized.

The furnace atmosphere has 1.2% C potantial and temperature is
maintained at 950 C. How long does it take to achieve a carbon
concentration of 0.80% at a position 0.5 mm below the surface?
Co = 0.25 %
Cs = 1.20 %
Cx = 0.80 %
x = 0.5 mm = 5 x 10-4 m
T = 950oC = 1223 K
Do = 2 x 10-5 m2/s (for C in γ-Fe) (from Table 5-2)
Qd = 148,000 J/mol (for C in γ-Fe) (from Table 5-2)
R = 8.31 J/mol.K
Answer: a. Analytical 10.4 hours, b. Graphical 11.3 hours

Z? 0.4210
Lineer Interpolation is used to find intermediate value for Z
y=z
x = erf(z)
0.58
0.75

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MKT 1122 MATERIALS SCIENCE

Yildiz Technical University

Diffusion is the phenomenon of material transport by atomic

Pre-conditions for diffusion:

a. Vacancy Diffusion b. Intersitital Diffusion

D is diffusion coefficient (m2/s) and the negative sign indicates,

The term Driving force is used to define a factor accelerating

The driving forces for diffusion:

Do : Temperature independent pre-exponential constant

Naturel logarithm of both sides yields a line equation:

Diffusion Data for Different Couples

Practical diffusion applications are in non-steady state. Diffusion

If the diffusion coefficient is assumed as independent of

Solution of the expression (concentration in terms of both

Cx : concentration of diffused species at depth x, after time t

FACTORS AFFECTING DIFFUSION

Carbon is playing a very effective role in strength and hardness of

But steels with high C content exhibit extremely brittle behavior

When we need high hardness only on the surface or near the

During the process C atoms diffuse through the surface of

Higher process temperature and/or longer holding time result

In other words, to control the case depth is possible only if

Consider a steel bar with 0.25% C concentration is being carburized.

Answer: a. Analytical 10.4 hours, b. Graphical 11.3 hours

Lineer Interpolation is used to find intermediate value for Z

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