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Diffusion in Solids
Diffusion: One mechanism by which atoms or molecules move in known as diffusion. Diffusion is a process of mass
transport that involves the movement of one atomic species into another. In its simplest form, it occurs by random atomic jumps
from one position to another and takes place in the gaseous, liquids, and solid states for all classes of materials. Since diffusion
involves atomic jumps, it becomes more rapid at higher temperatures because of the higher thermal energy of the atoms (the rate
of diffusion can be modelled using the Arrhenius equation). The diffusion rate also depends on the openness of the structure, being
generally more rapid for less densely packed structures. Consequently diffusion is most rapid in thegaseous state and least rapid in
the solid state. Even though it is least rapid in the solid state, solid-state diffusion has extremely important practical consequences
for engineering materials. IN addition to its importance from a scientific point of view many industrial processes having
significant economic consequences involve diffusion. In this regard it should be noted that diffusion can occasionally lead to a
degradation in the engineering properties and thus also has important economic implications. For example, diffusion of oxygen
into jet engine components can cause severe embrittlement failure. (see fig 6.1)
Practical Examples of Diffusion:
The controlled diffusion of phosphorus(P), Boron (B) or other dopants (Beneficial impurities) into wafers is of fundamental
importance to the microelectronics industry. Thecontrolled diffusion of oxygen and carbon dioxide through a silicon-based rubber
membrane in a heart lung machine permits surgeons to operate on the human heart. The control diffusion of oxygen through a
ZrO2 (Zirconium oxide) membrane is the basis of the sensing devices used to monitor and control air/ fuel mixtures in internal
combustion engines. These are but a few of the many commercial applications of diffusion.

Another important industrial process involving diffusion is the carburization of steels. Carburisation increases the carbon content
in the near-surface region. The extra carbon combines with the iron to form strong iron carbide particles having excellent wear
resistance. The carburized surface is ideal for application such as gears and crankshafts in automotive engines, where there is
considerable friction and where the surface must be wear-resistant. One method by which steels are carburized into heat them to
high temperatures in a Co/Co2 atmosphere in which the ratio of these gases is adjusted to maintain a desired surface concentration
of C, under these conditions, carbon atoms are deposited on the surface, and with time they move into the body of the part being
carburized. By allowing sufficient time, a carbon-rich layer near the surface can be produced. Intuitively, we expect the thickness
of this layer to depend on factors such a time, temperature, and the carbon concentration at the surface. Figure6.2a shows an
example of a carburized surface.
As a final example of diffusion, consider the coating of turbine blade used in jet engine. Turbine blade operates at
temperatures as high as 1100 c in an environment containing highly corrosive combusting products. They are fabricated from Nibase alloys, which although strong and relatively resistant to oxygen attack, would none the less be completely oxidized over the
time if not protected. One technique that is widely used for coating turbine blades is to deposit Al on the surface of the super alloy
via dissociation of AlF3 gas. The Al and Ni in the super alloy inter diffuse and react to form NiAl (plus other secondary phases).
This diffusion coating is highly resistant to oxidation and protects the base alloy. Figure 6.2b shows a section of a typical coated
turbine blade.
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There are also examples of diffusion processes that lead to a degradation of engineering properties. For example, consider the
microelectronic circuit, composed of a silicon wafer containing diffused impurities, described above. The performance of such
circuits depends critically on the spatial distribution of the impurity atoms in the diffusion zone. While the circuit may originally
have the ideal impurity distribution, it is possible for this distribution to change from the ideal during use of the device through a
combination of driving forces such as temperature and electric fields. For example, the heating that occurs as a result of current
flow within these devices can result in additional unwanted diffusion of the impurity atoms and attendant loss of function.
Diffusion mechanisms: There are two main mechanisms of diffusion of atoms in a crystalline lattice, namely
(1) Vacancy or substitutional mechanism and
(2) Interstitial mechanism
Vacancy Diffusion: Atoms can move in crystal lattices from one atomic site to another if there is enough activation energy
provided by the thermal vibration of the atoms and if there are vacancies or other crystal defects in the lattice for atoms to
move into. Vacancies in metals and alloys are equilibrium defects, and therefore some are always present to enable
substitution diffusion of atoms to take place. As the temperature of the metal increases, more vacancies are present and more
thermal energy is available, and so the diffusion rate is higher at higher temperatures.
Consider the example of vacancy diffusion show in Fig. 6.3 on a (111) plane of copper atoms in a copper crystal lattice. If an
atom next to the vacancy had sufficient activation energy, it can move into the vacant site and thereby contribute to the selfdiffusing of copper atoms in the lattice. The activation energy for self-diffusion is equal to the sum of the activation energy to
form a vacancy and the activation energy to move the vacancy note that in general as the melting point of the metal is higher,
the activation energy is also higher. This relationship exists because the higher-melting temperature metals tend to have
stronger bonding energies between their atoms.
During self-diffusion or substitution solid-state diffusion, atoms must break the original bonds among atoms and replace these
with new bonds. This process is assisted by having vacancies present, and thus it can occur at lower activation energies. In
order for this process to occur in alloys, there must exist solid solubility of one type of atom in another. Thus, this process is
dependent on the rules of solid solubility because of these differences in chemical bonding and solid solubility and other
factors substitution diffusion data must be obtained experimentally. With time these measurements are made more precisely
and hence these data may change with time.
Diffusion can also occur by the vacancy mechanism is solid solutions. Atoms size differ Nance and bonding energy
differences between the atoms are factors that affect the diffusion rate.

Interstitial Diffusion Mechanisms: The interstitial diffusion of atoms in crystal lattices takes place when atoms move from one
interstitial site to another neighbouring interstitial site without permanently displacing any of the atoms in the matrix crystal
lattice (Fig.6.4). For the interstitial mechanism to be operative the size of the diffusing atoms must be relatively small
compared to the matrix atoms, small atoms such as hydrogen, oxygen, nitrogen, and carbon can diffuse interstitially in some
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metallic crystal lattices. For example carbon can diffuse interstitially in Bcc iron and FCC iron. In the interstitial diffusion of
carbon in iron, the carbon atoms must squeeze between the iron matrix atoms.

Rate of Diffusion-Fick's Laws: Diffusion is a time-dependent process, that is in a microscopic sense the quantity of an
element that is transported within another is a function of time. Often, it is necessary to know how fast the diffusion occurs
steady-state Diffusion (Fick's First law) consider the diffusion of solute atoms in the x direction between two parallel atomic
planes perpendicular to the paper separated by a distance x as shown in Fig 6.5 . We will assume that over a period of time the
concentration of atoms at plane I is C1and that of plane 2 is C2. That is, there is no change in the concentration of solute
atoms at these planes for the system with time. Such diffusion conditions are said to be steady-state conditions. This type of
diffusion takes place when a non-reacting gas diffusions through a metal soil. For example, steady-state diffusion conditions
are attained when hydrogen gas diffusion through a soil of palladium if the hydrogen gas is at high pressure on one side and
low pressure on the other.
If in the diffusion system no chemical interaction occurs between lower concentrations. The flux or flow of atoms in this type
of system can be represented by the equation
J= -D dc/dx
Where J= flux or net flow of atoms
"
D= proportionality constant called the diffusivity (atomic conductivity) or diffusion coefficient
dc/dx= concentration gradient
A negative sign is used because the diffusion is from a higher to a lower concentration i.e there is a negative diffusion
gradient.
This equation is called the Fick's First law of diffusion and states that for steady state diffusion conditions(that is no change in
system with time), the net flow of atoms by atomic diffusion is equal to the diffusivity by atomic diffusion is equal to the
diffusivity D times the diffusion gradient dc/dx.

Factors Affecting Diffusion: The diffusion rate depends on many variable of which the followings are important.
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1. The Types of diffusion mechanism: Whether the diffusion is interstitially or substitution will affect the diffusivity. Small
atoms can diffuse interstitially in the crystal lattice of larger solvent atoms. For examples, carbon diffusion interstitially
in the Bcc or Fcc iron lattices. Copper atoms diffuse substitution in an aluminium solvent lattice since about the same
size.
2. The temperature at which the diffusion takes place greatly affects the value of the diffusivity. As the temperature is
increased, the diffusivity also increases. For all the systems by comparing the 500c values with those for 1000c it has
been found that the temperature dependence f the diffusion rate of many diffusion system can be expressed by the
following Arrhenius-type equation:
D= Doe Q/RT
Where D = Diffusivity, m2/s
Do= proportionality constant, m2s, independent of temperature in range for which equation is valid
Q= activation energy of diffusing species, s/mol or cal/mol
T= temperature, K
3 Crystal structure: The type of crystal structure of the solvent lattice is important. For example, the diffusivity of carbon
in Bcc iron is 10-12 m2s at 500c, which is much greater than 5*10-15m2s, the value for the diffusivity of carbon is Fcc
iron at the same temperature. The reason for this difference is that the Bcc crystal structure has a lower atomic packing
factor of 0.68 as compared to that of the Fcc crystal structure, which is 0.74. Also, the interatomic spaces between the
iron atoms are can diffuse between the iron atoms in the Bc structure more easily than in the Fcc one.
4 Crystal imperfections: The type of crystal imperfections present in the region of solid-state diffusion is also important.
More open structures allow for more rapid diffusion of atoms. For example, diffusion takes place more rapidly along
grain boundaries than in the grain matrix in metals and ceramics. Excess vacancies will increase diffusion rates in metals
and alloys.
5 Concentration of the diffusing: The concentration of the diffusing species is important in that higher concentrations of
diffusing solute atoms will affect the diffusivity. This aspect of solid-state diffusion is very complex.
Non-Steady-state Diffusion (Fick's second law):
Steady state diffusion in which conditions do not change with time is not commonly encounter with engineering
materials. In most cases non-steady state diffusion in which the concentration of solute atoms at any point in the material
changes with time takes place. For examples, if carbon is being diffused into the surface of a steel camshaftto harden its
surface, the concentration of carbon under the surface at any point will change with time as the diffusion process
progresses. For non steady state diffusion in which the diffusivity is independent of time, Fick's second law of diffusion
applies, which is
Dcx/dt= d/dx(d dcx/dx)
This law states that the rate of compositional changes is equal to the diffusivity times the rate of change of the
concentration gradient.
If the D is assumed to be independent of composition, the equation simplifies to
Dt/dt= (D d2c/dx2)
Even though D may vary with concentration, the particular solution to this equation in which a gas is diffusing into a
solid is of great importance of some engineering diffusion processes and is used to solve some practical industrial
diffusion problems.
Let us consider the case of a gas A diffusing into a solid B, as shown in Figure 6.6a. As the time of diffusing increases the
concentration of solute atoms at any point in the x direction will also increase, as indicated for times t, and t2 in figure
6.6b.
If the diffusivity of gas A in solid B is independent of position, then the solution to Fick's second law can be written as
follows
Cs-Cx/Cs-Co= erf (x/2 dt)
Where Cs= is the surface concentration of element in gas diffusing into the surface.
Co= the initial uniform concentration of element is solid:
Cx= the concentration of element at distance x form surface at time t.
X= the distance from surface
D= the diffusivity of diffusing solute element
T= time
Erf= is a the error function which is a mathematical function existing by agreed definition and is used in solution of
Fick's second law.
KirkendallEfffect: One of the major breakth- roughs in diffusion measurements occurred in the 1940s when the
kirkendall effect was discovered. In binary substitution alloys the diffusion of both constituents may occur
simultaneously, leading to a phenomenon known as interdiffusion. If the intrinsic diffusion coefficients of compounds A
and B are unequal (CDa# Db) the kirkendal effect will result.
For example, if a pure copper and brass alloy are in intimate contact and held at a high temperature, the interface between
them moves while diffusion is taking place. If markers such as molybdenum wires are placed as shown in figure 6.7 the
distance between them will continuously decreases

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This indicates that more material is following out of the brass region (70% cu- 30% zn) than is flowing in from the pure
copper region. This is because the diffusion coefficient of zinc atoms is about seventimes greater than that of copper
atoms, accounting for much faster movement of zinc atoms than copper atoms. Since the diffusion confidents of copper
(Dc4) and zinc (Dzn) vary with composition and temperature, their ratio also will change with composition and
temperature.
For such a system an overall chemical diffusion coefficient has been defined by Darkens as
D= CbDa+ CaDb
WhereCa and Cb are concentration of the constituents A and B and Da and Db are their respective diffusion coefficients.
In polycrystalline substance we may also have diffusing through grain boundaries , and free surfaces. If diffusion
occurspredominantly along grain bound arise, Fick's law cannot be applied directly, since the diffusion flux will depend
on the nature and extent of the grain boundary regions as well as on the temperature, composition, and concentration
gradient.

Kirkendall Effect in Mgo/ Fe2O3 system: If reduction and oxidation take place homogeneously along the phase
boundaries, the Fe2O3 and Mzo blocks will move away from each other because the same amount of oxygen is
transported from a shell with a large radius to a shell with a smaller radius. Voidsgrowth will thus occur in this situation.
Diffusion- Controlled Process: The rates of many processes are controlled by atom diffusion of these processes, the most
important include solid state phase transformations, solid liquid phase transformationsoxidation, the high temperature
electrical conduit of ionic solids, the high temperature plastic deformation of practically all materials, and sintering (the
bonding between particles that occur when they are placed in intimate contact and heated to high temperature) All of
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these processes reflect the basic nature of the rate controlling diffusion mechanism; they are thermally activated
processes that occur rapidly only when the temperature is high enough to allow for rapid atomic mobility. One of the
most important of the diffusion controlled processes is oxidation. All metals (except gold) tend to form oxides in air or in
aqueous solutions at room temperature, since the free energy of the oxide phase is lower than the sum of the separate free
energies of the metal and oxygen. Consequently a large amount of free energy must be supplied to reverse this process in
refining naturally occurring ores to pure metals so that they can be used for engineering purposes. Similarly, metals will
tend to oxidize and return to their equilibrium state the rusting of iron via typical example of a naturally occurring
oxidation process. Oxidation that occurs in aqueous environments such as water or dilute acids is called corrosion and is
sessions engineering problem. Fortunately, oxidation is usually a slow process at ambient temperatures. The reason for
this is that once the surface of a metal begins to oxidize (Fig6.8) subsequent oxidation can take place only when oxygen
ions diffuse through the oxide and react with the metal ions at the metal oxide interface or when metal ions diffuse
through the oxide and react with oxygen ions at the oxide-oxidant interface. As the oxide thickens, the diffusions distance
increases and the rate of oxidation decreases.

Diffusion: Can be defined be defined as the mass flow process in which atoms change their positions relative to
neighbours in a given phase under the influence of thermal and a gradient. The gradient can be a compositional gradient,
an electric or magnetic gradient, or stress gradient.
Diffusion mechanisms: Diffusion mechanisms are basically two type vacancy mechanism and interstitial diffusion
mechanism
Vacancy mechanism: Diffusion mechanism of substitution solutes and solvent atoms since a vacancy can jump from one
lattice site into a neighbouring one, a vacancy flux in one direction is equivalent to the atom transport in the opposite
direction.
Interstitial (mechanism of) diffusion: Diffusion by atomic jumps from one interstice to an adjacent one. Only
interstitial solute atoms can diffuse in such a way because their atomic radius is close to that of an interstice. This
mechanism is characterized by smaller activation energy than that found in vacancy mechanisms. Activation energy: The
additional energy required above the average energy for a thermally activated reaction to take place.
Arrhenius rate equation: An empiricalequation that describes that rate of areactions a function of temperature and an
activation energy barrier
Fick's first lawof diffusion in solids: The flux of a diffusing species proportional to the concentration gradient at
constant temperature.
Fick's second law of diffusion in solids: The rate of changer of composition is equal to the diffusivity times the rate of
change of the concentration gradient at constant temperature.
Diffusivity: a measure of the rate of diffusion in solids at a constant temperature. Diffusivity D can be expressed by the
equation D=Doe -2/rt, where Q is the activation energy and T is the temperature in kelvin's Do and are constants
Steady-state conditions: For a diffusions system there is no change in the concentration of the diffusing species with
time at different places in the system
Non-steady state conditions: for a diffusing system the concentration of the diffusing species changes with time at
different places in the system.
Carburization: A heat treatment process for steels to harden the surface using a gaseous or solid source of carbon. The
carbon diffusion into the surface makes the surface harden and more abrasion resistance.
Conductive ceramics: Ceramic materials that are good conductors of electricity as a result of their ionic and electronic
charges carriers electrons, holes, or ions) are known as conductive ceramic. Examples of such materials are stabilized
zirconia, indium tin oxide, etc.
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Diffusion: Diffusion is a phenomenon by which the net flux of atoms, ions, or other species diffuse within a material due
to change in temperature and concentration gradient.
Diffusion bonding: A joining technique in which two surfaces are pressed together at high pressures and temperature
diffusions of atoms to the interface fills in voids and process a strong bond between the surfaces.
Diffusion coefficient (D): It is a temperature dependent coefficient which relates to the rate at which atoms, ions or other
species diffuse. The diffusion coefficient depends on temperature, the composition and microstructure of the lost material
and also concentration of diffusing species.

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