Diffusion

Atomic and ionic arrangements are never perfect.

Most materials are not pure elements, they are alloys or
blends of different elements or compounds. Different types
of atoms or ions typically diffuse or move within the
material, so the differences in their concentration are
minimized and producing homogenous, uniform
compositions that make the material thermodynamically
more stable.
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 initial concentration gradient and
temperature.
Diffusion plays a central role in;
The control of the phase transformations needed for the
heat treatment of metals and alloys.
The processing of ceramics.
The solidification and joining of materials.

Diffusion Applications and Technologies
Depending on either enhancing or limiting diffusion.
Carburization for Surface Hardening of Steels; e.g.,
teeth of a gear, to be hard and not the entire gear.
Carburization processes are used to increase the surface
hardness (using graphite powder or gaseous phase
containing carbon). Nitriding process (similar to
carburization process) at which nitrogen is introduced into
the surface of a metallic material.
Dopant Diffusion for Semiconductor Devices;

The existence of microelectronics industry is due to
the very good understanding of the diffusion of different
atoms into silicon or other semiconductors. e.g., The
creation of the p-n junction involves diffusing dopant
atoms, such as phosphorous (P), arsenic (As), boron (B),
aluminum (Al), etc., into selected ultra-small regions of
silicon wafers (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.

Conductive Ceramics;

Polycrystalline ceramics tend to be good insulators
of electricity due to their covalent and ionic bonds along
with microstructural features. Diffusion of ions, electrons,
or holes plays an important role in the electrical
conductivity of many ionically conductive ceramics (fully
stabilized zirconia ZrO2)/ used for;
Oxygen sensors in cars, touch screen displays, fuel cells,
and batteries.

Magnetic Materials for Hard Drives;

Cobalt alloys are used in the manufacture of
magnetic hard disks for PC. Producing thin layers of these
alloys by a process called sputtering at which the targets
are bombarded with ion beams. Chromium is often added
to cobalt alloy thin film to enhance their magnetic
properties by heating the sputter film to a high
temperature for a long time then annealing for allowing
diffusion of chromium atoms from grain interior to grain
boundaries.

Creation of Plastic Beverage Bottles / Aluminum-coated
PET;

For certain applications the diffusion has to be
limited e.g., the creation of certain plastic bottles, the
diffusion of carbon dioxide (CO2) must be minimized.
This is one of the major reasons why using
polyethylene terephthalate (PET) to make bottles which
ensure that the carbonated beverages they contain will not
loose their fizz for a reasonable period of time. In addition,
Helium balloons made of aluminum coated PET retain
helium much longer since the thin aluminum coating helps
minimize the occurrence of out-diffusion of helium.


Oxidation of Aluminum (aluminum oxide or rust Al2O3)

Coatings and Thin Films;

used in the manufacturing process to limit the
diffusion of water vapor, oxygen, and other chemicals e.g.,
paint to steel structures for preventing rusting, applying
zinc (Zn) coating onto steel structures (the process is
called; Hot Dip Galvanizing, at about 420C).
Thermal Barrier Coatings for Turbine Blades;

In an aircraft engine, some of the nickel superalloy-
based turbine blades are coated with ceramic oxides such
as yattria stabilized zirconia (YSZ) to protect the underlying
alloy from high temperatures, hence the name Thermal
Barrier Coatings (TBCs).
Optical Fibers and Microelectronic Components;
e.g., coating around optical fibers that made of silica
(SiO2) with polymeric materials to prevent diffusion of
water molecules. Water vapor has two related and separate
effects on the performance of glass optical fibers;
1. Incorporation of water in the form of hydroxyl group
(OH ) increases optical losses (the signal being
attenuated).
2. Water vapor attacks the glass surface causing
microcracks that lower strength of glass.

Also, using plastic coating to encase microelectronic
circuitry components such as capacitors to prevent
diffusion of water vapor or other chemicals that
deteriorate performance.
Water and Air Treatment;

In environmental engineering applications, such as
treatment of water or air, diffuse of certain ions or
molecules through a filter or an ion exchanger resin is of
great importance. In certain drug delivery applications,
diffusion of drugs or other biochemical molecules through
small capillaries carrying blood is very important to be
interested by the doctors and health care professionals.
Drift and Diffusion
Movement of small particles due to driving forces
density gradients, electric, or magnetic gradients) other
than concentration and temperature gradients (Diffusion)
is called Drift.
Examples;
An open bottle of perfume in one end of the room, the
perfume can be smelled at the other end (convective mass
transfer).
The movement of charged ions in a solution (often water
based) under an electric field produces thin layers of
metals and alloys (electroplating).
Stability of Atoms and Ions
Atoms, ions, and imperfections are not stable or at
rest in their normal positions in the crystal structures they
will move when possess thermal energy.
e.g., atom may move from its normal location in the crystal
structure to a nearby vacancy or from one interstitial site
to another or may jump across a grain boundary causing
the grain boundary to move.
As the temperature or thermal energy increases, the
ability of atoms or ions to diffuse increases also.
The rate of atom or ion movement is related to
temperature or thermal energy by the Arrhenius
equation
|
.
|

\
|

=
RT
Q
c Rate
o
exp
Where; co = constant, R = Gas constant (1.987 cal/mol*K),
T = absolute temperature (K), Q = activation energy
(cal/mol).
Or;





Plotting ln(rate) of some reaction versus 1/T, the slope of
the curve will be Q/R and consequently Q can be
calculated.
( ) ( )
RT
Q
c rate
o
= ln ln
The Arrhenius plot
of ln(rate) versus
1/T can be used to
determine the
activation energy
for a reaction.
Example;
Suppose that interstitial atoms are found to move from one
site to another at the rate of 510^8 jumps/s at 500C and
810^10 jumps/s at 800C . Calculate the activation energy
Q for the process.
Mechanisms for Diffusion
The created disorder (i.e., increased entropy) by the
vacancies (defects) that exist in the material helps
minimize the free energy and therefore, the
thermodynamic stability of a crystalline material. In
materials containing vacancies, atoms move or also jump
from one lattice position to another by a process known as
self-diffusion . Two important mechanisms by which
atoms or ions can diffuse;
Vacancy Diffusion; 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). Continuously, countercurrent
flows of atoms and vacancies called vacancy diffusion
occur. As the temp. increases the number of vacancies
increases.
Interstitial Diffusion; A small interstitial atom or ion can
move from interstitial site to another, no vacancies are
required for this mechanism. The smaller the interstitial
atoms the faster the diffuse can be. Because more
interstitial sites can exist than vacancies, interstitial
diffusion occurs more easily than vacancy diffusion.
Diffusion mechanisms in materials: (a) vacancy or
substitutional atom diffusion and (b) interstitial diffusion.
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 nickel until both
atoms are uniformly distributed.
Diffusion of
copper atoms
into nickel.
Eventually, the
copper atoms are
randomly
distributed
throughout the
nickel.
Activation Energy for Diffusion
A diffusing atom must squeeze past the surrounding
atoms to reach its new site. For this to happen, energy
must be supplied to force the atom to its new position. The
atom is originally in a low energy, relatively stable
location. For the atom to be moved to a new location it
must overcome an energy barrier that is the activation
energy Q. The thermal energy supplies atoms or ions with
the energy needed to exceed this barrier.
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.
Rate of Diffusion (Ficks First Law)
The rate at which atoms, ions, particles or other
species diffuse in a material can be measured by the flux
J.
Flux J; is the number of atoms passing through a plane of
unit area per unit time.
Ficks first law explains the net flux of atoms;





Where;
J = flux.
D = diffusivity or diffusion coefficient (cm/s).
dc/dx = concentration gradient (atoms/ cm*cm).
dx
dc
D J =
The negative sign means that the flux of diffusing
species is from higher to lower concentrations, making the
dc/dx term negative, and hence J will be positive.

Concentration may be expressed as atoms percent
(at%), weight percent (wt%), mole percent (mol%), atom
fraction, or mole fraction. The units of concentration
gradient and flux will also change respectively.

If dealing with diffusion of ions, electrons, holes, etc.,
the units of J, D, and dc/dx will reflect the appropriate
species that are being considered.

At the microscopic scale the thermodynamic driving
force for diffusion is concentration gradient.
Concentration
gradient
Factors affecting diffusion are; Temperature and
Diffusion Coefficient.
The kinetics of process of diffusion are strongly
dependent on temperature. The diffusion coefficient D is
related to temperature by an Arrhenius type equation;



Where;
Q = activation energy (cal/mol) for diffusion of species
under consideration.
R = gas constant.
T = absolute temperature (K).
Do = The pre-exponential term (similar to co) and it is a
constant for a given diffusion system.

|
.
|

\
|

=
RT
Q
D D
o
exp
Types of Diffusion
Volume diffusion; the atoms move through thecrystal
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.

Grain boundary diffusion; atoms can also diffuse along
boundaries, interfaces, and surfaces in the material. Atoms
diffuse easily by grain boundary diffusion because the
atom packing is poor in the grain boundaries. Because
atoms can more easily squeeze their way through the
disordered 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.
Composition Profile (Ficks Second Law)
Describes the dynamic, or non-steady state, diffusion
of atoms.
Ficks 2
nd
law is the differential equation;




If the diffusion coefficient is assumed not a function of
location x and the concentration (c) of diffusing species, a
simplified version of Ficks 2
nd
law can be written as
follows;
|
.
|

\
|
c
c
c
c
=
c
c
x
c
D
x t
c
|
|
.
|

\
|
c
c
=
c
c
2
2
x
c
D
t
c
Ficks 2
nd
law can assist in designing a variety of
materials processing techniques including the steel
carburizing heat treatment and dopant diffusion in
semiconductors.
Diffusion and Material Processing
Solidification, phase transformations, heat treatments, etc.
Diffusional processes become very important when
materials are used or processed at elevated temperatures.
Melting and Casting.
Sintering.
Grain Growth.
Diffusion Bonding.