A Term paper about Diffusion

In Partial Fulfilment of the Requirements for

Mark C. Gordo

BSME 4A

August 2019
 Diffusion refers to the net flux of any species, such as ions, atoms, electrons, holes, and
molecules. The magnitude of this flux depends upon the concentration gradient and temperature.
The process of diffusion is central to many today’s important technologies. In materials processing
technologies, control over the diffusion of atoms, ions, molecules, or other species is key Diffusion
refers to an observable net flux of atoms or other species. It depends upon the concentration
gradient and temperature. Just as water flows from a mountain toward the sea to minimize its
gravitational potential energy, atoms and ions tend to move in a predictable fashion to eliminate
concentration differences and produce homogeneous compositions that make the material
thermodynamically more stable. There are hundreds of applications and technologies that depend
on either enhancing or limiting diffusion. The following are just few examples

In Carburization for Surface Hardening of Steels the carburization process can be used to
increase surface hardness. In carburization, a source of carbon, such as a graphite powder or
gaseous phase containing carbon, is diffused into steel components such as gears. In later
chapters, you will learn how increased carbon concentration on the surface of the steel increases
the steel’s hardness. Like the introduction of carbon, we can also use a process known as
nitriding, in which nitrogen is introduced into the surface of a metallic material. Diffusion also plays
a central role in the control of the phase transformations

In Dopant Diffusion for Semiconductor Devices the creation of the p-n junction involves
diffusing dopant atoms, such as phosphorous (P), arsenic (As), antimony (Sb), boron (B),
aluminum (Al), into precisely defined regions of silicon wafers. Some of these regions are so small
that they are best measured in nanometers. A p-n junction is a region of the semiconductor, one
side of which is doped with n-type dopants (e.g., As in Si) and the other side is doped with p-type
dopants (e.g., B in Si).

In Conductive Ceramics, diffusion of ions, electrons, or holes also plays an important role
in the electrical conductivity of many conductive ceramics, such as partially or fully stabilized
zirconia (ZrO2) or indium tin oxide (also commonly known as ITO). Lithium cobalt oxide (LiCoO2)
is an example of an ionically conductive material that is used in lithium ion batteries. These
ionically conductive materials are used for such products as oxygen sensors in cars, touchscreen
displays, fuel cells, and batteries. The ability of ions to diffuse and provide a pathway for electrical
conduction plays an important role in enabling these applications.

For instance, an atom may move from a normal crystal structure location to occupy a
nearby vacancy. An atom may also move from one interstitial site to another. Atoms or ions may
jump across a grain boundary, causing the grain boundary to move. The ability of atoms and ions
to diffuse increases as the temperature, or thermal energy possessed by the atoms and ions,
increases. The rate of atom or ion movement is related to temperature or thermal energy by the
Arrhenius equation:
−𝑸
𝑹𝒂𝒕ⅇ = 𝒄𝟎 ⅇ𝒙𝒑 ( )
𝑷𝑻

where c0 is a constant, R is the gas constant, T is the absolute temperature (K), and Q is the
activation energy (Cal mol) required to cause Avogadro’s number of atoms or ions to move. This
equation is derived from a statistical analysis of the probability that the atoms will have the extra
energy Q needed to cause movement. The rate is related to the number of atoms that move.
 Defects known as vacancies exist in materials. The disorder these vacancies create helps
minimize the free energy and, therefore, increases the thermodynamic stability of a crystalline
material. In materials containing vacancies, atoms move or “jump” from one lattice position to
another. This process, known as self-diffusion, can be detected by using radioactive tracers. As
an example, suppose we were to introduce a radioactive isotope of gold (Au198) onto the surface
of standard gold (Au197). After a period, the radioactive atoms would move into the standard
gold. Eventually, the radioactive atoms would be uniformly distributed throughout the entire
standard gold sample. Although self-diffusion occurs continually in all materials, its effect on the
material’s behavior is generally not significant.

Diffusion of unlike atoms in materials also occurs. Consider a nickel sheet bonded to a copper
sheet. At high temperatures, nickel atoms gradually diffuse into the copper, and copper atoms
migrate into the nickel. Again, the nickel and copper atoms eventually are uniformly distributed.
Diffusion of different atoms in different directions is known as interdiffusion. There are two
important mechanisms by which atoms or ions can diffuse. In self-diffusion and diffusion involving
substitutional atoms, an atom leaves its lattice site to fill a nearby vacancy (thus creating a new
vacancy at the original lattice site).

As diffusion continues, we have counterflows of atoms and vacancies, called vacancy diffusion.
The number of vacancies, which increases as the temperature increases, influences the extent
of both self-diffusion and diffusion of substitutional atoms. When a small interstitial atom or ion is
present in the crystal structure, the atom or ion moves from one interstitial site to another. No
vacancies are required for this mechanism. Partly because there are many more interstitial sites
than vacancies, interstitial diffusion occurs more easily than vacancy diffusion. Interstitial atoms
that are relatively smaller can diffuse faster.

Normally, less energy is required to squeeze an interstitial atom past the surrounding
atoms; consequently, activation energies are lower for interstitial diffusion than for vacancy
diffusion. Typical values for activation energies for diffusion of different atoms in different host
materials. We use the term diffusion couple to indicate a combination of an atom of a given
element (e.g., carbon) diffusing in a host material (e.g., BCC Fe). A low-activation energy
indicates easy diffusion. In self-diffusion, the activation energy is equal to the energy needed to
create a vacancy and to cause the movement of the atom.

The rate at which atoms, ions, particles or other species diffuse in a material can be
measured by the flux J. Here we are mainly concerned with diffusion of ions or atoms. The flux J
is defined as the number of atoms passing through a plane of unit area per unit time. Fick’s first
law explains the net flux of atoms:

ⅆ𝐶
𝐽 = −𝐷
ⅆ𝑥

where J is the flux, D is the diffusivity or diffusion coefficient, and dc/dx is the concentration
gradient . Depending upon the situation, concentration may be expressed as atom percent (at%),
weight percent (wt%), mole percent (mol%), atom fraction, or mole fraction. The units of
concentration gradient and flux will change accordingly.

The concentration gradient shows how the composition of the material varies with
distance: △c is the difference in concentration over the distance △x. A concentration gradient may
be created when two materials of different composition are placed in contact, when a gas or liquid
is in contact with a solid material, when nonequilibrium structures are produced in a material due
to processing, and from a host of other sources. The flux at a temperature is constant only if the
concentration gradient is also constant—that is, the compositions on each side of the plane in
remain unchanged. In many practical cases, however, these compositions vary as atoms are
redistributed, and thus the flux also changes. Often, we find that the flux is initially high and then
gradually decreases as the concentration gradient is reduced by diffusion. The examples that
follow illustrate calculations of flux and concentration gradients for diffusion of dopants in
semiconductors and ceramics, but only for the case of constant concentration gradient.

The kinetics of diffusion are strongly dependent on temperature. The diffusion coefficient D is
related to temperature by an Arrhenius-type equation:
−𝑄
𝐷 = 𝐷0 𝑒𝑥𝑝 ( )
𝑅𝑇
where Q is the activation energy (in units of cal mol) for diffusion of the species under
consideration (e.g., Al in Si), R is the gas constant, and T is the absolute temperature (K). D0 is
the pre-exponential term.

There are types of Diffusion. In volume diffusion, the atoms move through the crystal from
one regular or interstitial site to another. Because of the surrounding atoms, the activation energy
is large, and the rate of diffusion is relatively slow. Atoms can also diffuse along boundaries,
interfaces, and surfaces in the material. Atoms diffuse easily by grain boundary diffusion, because
the atom packing is disordered and less dense in the grain boundaries. Because atoms can more
easily squeeze their way through the grain boundary, the activation energy is low. Surface
diffusion is easier still because there is even less constraint on the diffusing atoms at the surface.
𝑎𝑡𝑜𝑚𝑠
Diffusion requires time. The units for flux are . If many atoms must diffuse to produce a
𝑐𝑚2 ⋅𝑠
uniform structure, long times may be required, even at high temperatures. Times for heat
treatments may be reduced by using higher temperatures or by making the diffusion distances as
small as possible.

In polymers, we are most concerned with the diffusion of atoms or small molecules
between the long polymer chains. As engineers, we often cite the permeability of polymers and
other materials, instead of the diffusion coefficients. The permeability is expressed in terms of the
volume of gas or vapor that can permeate per unit area, per unit time, or per unit thickness at a
specified temperature and relative humidity. Polymers that have a polar group (e.g., ethylene vinyl
alcohol) have higher permeability for water vapor than for oxygen gas. Polyethylene, on the other
hand, has much higher permeability for oxygen than for water vapor.

Diffusional processes become very important when materials are used or processed at
elevate temperatures. Melting and Casting, one of the most widely used methods to process
metals, alloys, many plastics, and glasses involves melting and casting of materials into a desired
shape. Diffusion plays a particularly important role in solidification of metals and alloys. During
the growth of single crystals of semiconductors, for example, we must ensure that the differences
in the diffusion of dopants in both the molten and solid forms are accounted for. This also applies
for the diffusion of elements during the casting of alloys.

Although casting and melting methods are very popular for many manufactured materials, the
melting points of many ceramic and some metallic materials are too high for processing by melting
and casting. These relatively refractory materials are manufactured into useful shapes by a
process that requires the consolidation of small particles of a powder into a solid mass. Sintering
is the high-temperature treatment that causes particles to join, gradually reducing the volume of
pore space between them. Sintering is a frequent step in the manufacture of ceramic components
(e.g., alumina, barium titanate, etc.) as well as in the production of metallic parts by powder
metallurgy, it is a processing route by which metal powders are pressed and sintered into dense,
monolithic components. The process in which a small amount of liquid forms and assists
densification is known as liquid phase sintering.

A polycrystalline material contains many grain boundaries, which represent high-energy

The driving force for grain growth is reduction in grain boundary area. Grain boundaries
are defects and their presence cause the free energy of the material to increase. Thus, the
thermodynamic tendency of polycrystalline materials is to transform into materials that have a
larger average grain size. High temperatures or low-activation energies increase the size of the
grains. Many heat treatments of metals, which include holding the metal at high temperatures,
must be carefully controlled to avoid excessive grain growth. In normal grain growth, the average
grain size increases steadily, and the width of the grain size distribution is not affected severely.
In abnormal grain growth, the grain size distribution tends to become bi modal.

A method used to join materials, called diffusion bonding, occurs in three steps. The first
step forces the two surfaces together at a high temperature and pressure, flattening the surface,
fragmenting impurities, and producing a high atom-to-atom contact area. As the surfaces remain
pressed together at high temperatures, atoms diffuse along grain boundaries to the remaining
voids; the atoms condense and reduce the size of any voids at the interface. Because grain
boundary diffusion is rapid, this second step may occur very quickly.

To summarize, The net flux of atoms, ions, etc., resulting from diffusion depends upon the
initial concentration gradient. The kinetics of diffusion depend strongly on temperature. In general,
diffusion is a thermally activated process and the dependence of the diffusion coefficient on
temperature is given by the Arrhenius equation. The extent of diffusion depends on temperature,
time, the nature and concentration of diffusing species, crystal structure, composition of the
matrix, stoichiometry, and point defects. Encouraging or limiting the diffusion process forms the
underpinning of many important technologies. Examples include the processing of
semiconductors, heat treatments of metallic materials, sintering of ceramics and powdered
metals, formation of amorphous materials, solidification of molten materials during a casting
process, diffusion bonding, and barrier plastics, films, and coatings.

Fick’s laws describe the diffusion process quantitatively. Fick’s first law defines the
relationship between the chemical potential gradient and the flux of diffusing species. Fick’s
second law describes the variation of concentration of diffusing species under no steady state
diffusion conditions. For a system, the amount of diffusion is related to the term Dt. This term
permits us to determine the effect of a change in temperature on the time required for a diffusion-
controlled process. The two important mechanisms for atomic movement in crystalline materials
are vacancy diffusion and interstitial diffusion. Substitutional atoms in the crystalline materials
move by the vacancy mechanism. The rate of diffusion is governed by the Arrhenius relationship
that is, the rate increases exponentially with temperature. Diffusion is particularly significant at
temperatures above about 0.4 times the melting temperature (in Kelvin) of the material.
References:

The Science and Engineering of Materials by Donald P. Askland, Prasdeep Fulay, Wendelin
Wright