HELWAN UNIVERSITY

FACULTY OF ENGINEERING
MECHANICAL ENGINEERING DEPARTMENT

Post Grad. Ph.D. Program

Smart Materials Technology

Diffusion

By

Eng. Ahmed Hegazy Khallaf

Under Supervision of

Prof. Dr. Mohamed El-Shennawy

Professor in Mechanical Engineering Department
Faculty of Engineering, Helwan University
 Diffusion

1. Introduction:
Many reactions and processes that are
important in the treatment of materials rely on the
transfer of mass either within a specific solid
(ordinarily on a microscopic level) or from a
liquid, a gas, or another solid phase. This is
necessarily accomplished by diffusion, the
phenomenon of material transport by atomic
motion. The phenomenon of diffusion may be
demonstrated with the use of a diffusion couple,
which is formed by joining bars of two different
metals together so that there is intimate contact
between the two faces; this is illustrated for Fig. 1 A copper–nickel diffusion
couple before a high-temperature
copper and nickel in Fig.1, which includes heat treatment.
schematic representations of atom positions and
composition across the interface.

This couple is heated for an extended

period at an elevated temperature (below the
melting temperature of both metals), and cooled
to room temperature. Chemical analysis will
reveal a condition similar to that represented in
Fig. 2 – namely, pure copper and nickel at the 2
extremities of the couple, separated by an alloyed
region. Concentrations of both metals vary with
position as shown in Fig. 2c. This result indicates
that copper atoms have migrated or diffused into
Fig. 2 A copper–nickel diffusion
the nickel, and that nickel has diffused into couple after a high-temperature
heat treatment.

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copper. This process, whereby atoms of one metal diffuse into another, is
termed inter-diffusion, or impurity diffusion.

2. Diffusion Mechanisms:
Any theory of atom diffusion in solids should start with a discussion
of diffusion mechanisms. We must answer the question: ‘How does this
particular atom move from here to there?’ In crystalline solids, it is
possible to describe diffusion mechanisms in simple terms. The crystal
lattice restricts the positions and the migration paths of atoms and allows
a simple description of each specific atom displacements. This contrasts
with a gas, where random distribution and displacements of atoms are
assumed, and with liquids and amorphous solids, which are neither really
random nor really ordered.

2.1. Interstitial Mechanism:

Solute atoms, which are considerably smaller than the solvent
atoms, are incorporated on interstitial sites of the host lattice thus
forming an interstitial solid solution. Interstitial sites are defined by the
geometry of the host lattice. In fcc and bcc lattices, for example,
interstitial solutes occupy octahedral and/or tetrahedral interstitial sites
(Fig. 6.1). An interstitial solute can diffuse by jumping from one
interstitial site to one of its neighboring sites as shown in Fig. 6.2. Then
the solute is said to diffuse by an interstitial mechanism.

Fig. 3 Octahedral and tetrahedral interstitial sites in the BCC (left) and FCC (right) lattice

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 To look at this process more closely, we consider the atomic
movements during a jump. The interstitial starts from an equilibrium
position, reaches the saddle-point configuration where maximum lattice
straining occurs, and settles again on an adjacent interstitial site. In the
saddle-point configuration neighboring matrix atoms must move aside
to let the solute atom through. When the jump is completed, no
permanent displacement of the matrix atoms remains.

2.2. Vacancy Mechanism:

One mechanism involves the interchange of an atom from a
normal lattice position to an adjacent vacant lattice site or vacancy, as
represented schematically in Fig. 4. This mechanism is termed vacancy
diffusion. Of course, this process necessitates the presence of
vacancies, and the extent to which vacancy diffusion can occur is a
function of the number of these defects that are present; significant
concentrations of vacancies may exist in metals at elevated
temperatures. Because diffusing atoms and vacancies exchange
positions, the diffusion of atoms in one direction corresponds to the
motion of vacancies in the opposite direction. Both self-diffusion and
inter-diffusion occur by this mechanism; for the latter, the impurity
atoms must substitute for host atoms.

Fig. 4 Schematic representations of vacancy diffusion

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 In most metal alloys, interstitial diffusion occurs much more
rapidly than diffusion by the vacancy mode, because the interstitial
atoms are smaller and thus more mobile. Furthermore, there are more
empty interstitial positions than vacancies; hence, the probability of
interstitial atomic movement is greater than for vacancy diffusion.

3. Diffusion States:
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 of solid
per unit of time. In mathematical form, this may be represented as:

𝑀
𝐽=
𝐴𝑡
Where A denotes the area a cross which diffusion is occurring and t
is the elapsed diffusion time. 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).

There are two types of diffusion:

1. Steady-state diffusion.

2. Nonsteady-state diffusion.

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 4. Factors influence diffusion:
4.1. Diffusing species:
The diffusing species as well as the host material influence the
diffusion coefficient. For example, there is a significant difference in
magnitude between self-diffusion and carbon inter-diffusion in iron at
500 °C, the D value being greater for the carbon inter-diffusion
(3x10^-21 vs. 2.4 x10^-21 m2/s). The magnitude of the diffusion
coefficient D is indicative of the rate at which atoms diffuse.
Coefficients, both self and inter-diffusion, for several metallic systems
are listed in (Table 1). This comparison also provides a contrast between
rates of diffusion via vacancy and interstitial modes as discussed earlier.
Self-diffusion occurs by a vacancy mechanism, whereas carbon diffusion
in iron is interstitial.
Table 1 Diffusion coefficient for self and inter-diffusion

Self-diffusion
Inter-diffusion

4.2. Temperature:
Temperature has a most profound influence on the coefficients
and diffusion rates. For example, for the self-diffusion of Fe in α-Fe, the
diffusion coefficient increases approximately six orders of magnitude
diffusion (from 3.0x10^-21 to 1.8 x10^-15 m2/s) in rising temperature from
500 °C to 900 °C (Table 2).

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 Table 2 A Tabulation of Diffusion Data

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.

𝑑𝐶
𝐽 = −𝐷
𝑑𝑥
Where:

J: is the diffusion flux

D: is the diffusion coefficient

: is the concentration gradient

5. Applications of diffusion:
There are many applications of the diffusion in the industry. One of
the most important application of diffusion is surface hardening.
SURFACE HARDENING, a process that includes a wide variety of
techniques, is used to improve the wear resistance of parts without
affecting the more soft, tough interior of the part. This combination of hard
surface and resistance to breakage upon impact is useful in parts such as a
cam or ring gear, bearings or shafts, turbine applications, and automotive

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components that must have a very hard surface to resist wear, along with
a tough interior to resist the impact that occurs during operation. Most
surface treatments result in compressive residual stresses at the surface that
reduce the probability of crack initiation and help arrest crack propagation
at the case-core interface. Further, the surface hardening of steel can have
an advantage over through hardening because less expensive low-carbon
and medium carbon steels can be surface hardened with minimal problems
of distortion and cracking associated with the through hardening of thick
sections.

There are two distinctly different approaches to the various methods

for surface hardening (Table 3):

 Methods that involve an intentional buildup or addition of a new layer.

 Methods that involve surface and subsurface modification without
any intentional buildup or increase in part dimensions
Table 3 Engineering methods for surface hardening of steels

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 5.1. Diffusion in Surface hardening:
Diffusion methods modify the chemical composition of the surface
with hardening species such as carbon, nitrogen, or boron. Diffusion
methods may allow effective hardening of the entire surface of a part and
are generally used when a large number of parts are to be surface hardened.
In contrast, selective surface-hardening methods allow localized
hardening. Selective hardening generally involves transformation
hardening (from heating and quenching), but some selective-hardening
methods (selective nitriding, ion implantation, and ion beam mixing) are
based solely on compositional modification.

Fig. 5 Diffusion application in surface hardening

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 References
[1] William D. Callister, “Materials Science and Engineering: An
Introduction 8e”, John Wiley & Sons, 2010.
[2] J. Dossett and G.E. Totten, “Introduction to Surface Hardening of
Steels”, ASM Handbook, Volume 4A, Steel Heat Treating
Fundamentals and Processes, 2013.
[3] Diffusion Mechanism Chapter.

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