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Diffusion Contd…
• Diffusion is the process by which atoms move in a material. • The fraction of atoms possessing this amplitude increases markedly
• Many reactions in solids and liquids are diffusion dependent. with rising temperature.
• Structural control in a solid to achieve the optimum properties is also • In jumping from one equilibrium position to another, an atom passes
dependent on the rate of diffusion. through a higher energy state since atomic bonds are distorted and
• Atoms are able to move throughout solids because they are not broken, and the increase in energy is supplied by thermal vibrations.
stationary but execute rapid, small-amplitude vibrations about their • As might be expected defects, especially vacancies, are quite
equilibrium positions. instrumental in affecting the diffusion process on the type and
• Such vibrations increase with temperature and at any temperature a number of defects that are present, as well as the thermal vibrations
very small fraction of atoms has sufficient amplitude to move from of atoms.
one atomic position to an adjacent one.

Diffusion: Definition Contd…

• The term inter-diffusion refers to the migration of impurity atoms; for
• Diffusion can be defined as the mass flow process in which atoms host atoms, the term self-diffusion is used
change their positions relative to neighbors in a given phase under the • Diffusion also occurs for pure metals, but all atoms exchanging
influence of thermal and a gradient. positions are of the same type; this is termed self-diffusion.
• Diffusion is the phenomenon of material transport by atomic motion. • In pure metals self-diffusion occurs where there is no net mass
• The gradient can be a compositional gradient, an electric or magnetic transport, but atoms migrate in a random manner throughout the
gradient, or stress gradient. crystal.
• Solid-state diffusion is a means of mass transport within solid • In alloys inter-diffusion takes place where the mass transport almost
materials by stepwise atomic motion. always occurs so as to minimize compositional differences.
• The process by which atoms of one metal diffuse into • Various atomic mechanisms for self-diffusion and inter-diffusion have
another is termed inter-diffusion, or impurity diffusion. been proposed.
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Diffusion: Mechanism Diffusion: Types

• From an atomic perspective, diffusion is just the stepwise migration • The most energetically favorable process involves an interchange of
of atoms from lattice site to lattice site. places by an atom and a neighboring vacancy – vacancy diffusion.
• In fact, the atoms in solid materials are in constant motion, rapidly • This process demands not only the motion of vacancies, but also the
changing positions. For an atom to make such a move, two conditions presence of vacancies.
must be met: • The unit step in vacancy diffusion is an atom breaks its bonds and jumps
(1) there must be an empty adjacent site, and into neighboring vacant site.
(2) the atom must have sufficient energy to break bonds with • In interstitial diffusion, solute atoms which are small enough to occupy
its neighbor atoms and then cause some lattice distortion during the interstitial sites diffuse by jumping from one interstitial site to another.
displacement. • The unit step here involves jump of the diffusing atom from one
interstitial site to a neighboring site.

Contd… Contd…
• Substitutional diffusion generally proceeds by the vacancy mechanism. • However, the equilibrium number of self-interstitial atoms present at
Thus interstitial diffusion is faster than substitutional diffusion by the any temperature is negligible in comparison to the number of
vacancy mechanism. vacancies. This is because the energy to form a self-interstitial is
• During self-diffusion or ring mechanism or direct-exchange mechanism, extremely large.
three or four atoms in the form of a ring move simultaneously round the
ring, thereby interchanging their positions.
• This mechanism is untenable because exceptionally high activation
energy would be required.
• A self-interstitial is more mobile than a vacancy as only small activation
energy is required for self-interstitial atom to move to an equilibrium
atomic position and simultaneously displace the neighboring atom into
an interstitial site.
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Contd…
• Diffusion in most ionic solids occurs by a vacancy mechanism.
• In ionic crystals, Schottky and Frankel defects assist the diffusion
process.
• When Frenkel defects (pair of vacancy interstial) dominate in an ionic
crystal, the cation interstitial of the Frenkel defect carries the
diffusion flux.
• If Schottky defects (pair of vacant sites) dominate, the cation vacancy
carries the diffusion flux.
• In thermal equilibrium, in addition to above defects, ionic crystal may
have defects generated by impurities and by deviation from
stochiometry.

Contd… Diffusion: Steady State

• Thus imperfections in ionic materials that influence diffusion arise in • Diffusional processes can be either steady-state or non-steady-state.
two ways: These two types of diffusion processes are distinguished by use of a
• intrinsic point defects such as Frenkel and schottky defects whose parameter called flux.
number depends on temperature, and • It is defined as net number of atoms crossing a unit area
• extrinsic point defects whose presence is due to impurity ions of perpendicular to a given direction per unit time.
different valance than the host ions. • For steady-state diffusion, flux is constant with time, whereas for non-
• The former is responsible for temperature dependence of diffusion steady-state diffusion, flux varies with time.
similar to that for self-diffusion in metals, while the latter result in a • A schematic view of concentration gradient with distance for both
temperature dependence of diffusion which is similar to that for steady-state and non-steady-state diffusion processes are shown in
interstitial solute diffusion in metals. figure
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Diffusion: Steady State

• Steady-state diffusion is described by Fick’s first law which states that
flux, J, is proportional to the concentration gradient.
• The constant of proportionality is called diffusion coefficient
(diffusivity), D (cm2/sec).
• Diffusivity is characteristic of the system and depends on the nature
of the diffusing species, the matrix in which it is diffusing, and the
temperature at which diffusion occurs.
• Thus under steady-state flow, the flux is independent of time and
remains the same at any cross-sectional plane along the diffusion
direction.

Contd… Diffusion: Non-Steady

• For the one-dimensional case, Fick’s first law is given by • Most interesting cases of diffusion are non-steady-state processes
since the concentration at a given position changes with time, and
thus the flux changes with time.
• This is the case when the diffusion flux depends on time, which
means that a type of atoms accumulates in a region or depleted from
a region (which may cause them to accumulate in another region).
• Fick’s second law characterizes these processes, which is expressed
• where D is the diffusion constant, dc/dx is the gradient of the as:
concentration c, dn/dt is the number atoms crossing per unit time a
cross-sectional plane of area A. The minus sign in the equation means
that diffusion occurs down the concentration gradient.
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Contd… Factors affecting Diffusion

• Ease of a diffusion process is characterized by the parameter D,
diffusivity. The value of diffusivity for a particular system depends on
many factors as many mechanisms could be operative.
• Diffusing species: If the diffusing species is able to occupy interstitial
sites, then it can easily diffuse through the parent matrix. On the
other hand if the size of substitutional species is almost equal to that
of parent atomic size, substitutional diffusion would be easier. Thus
size of diffusing species will have great influence on diffusivity of the
system.

Contd… Strengthening Mechanisms in Metals

• Temperature: Temperature has a most profound influence on the • Ability of a metal to deform plastically depends on ease of dislocation
diffusivity and diffusion rates. It is known that there is a barrier to motion under applied external stresses.
diffusion created by neighboring atoms those need to move to let the
diffusing atom pass. Thus, atomic vibrations created by temperature • Strengthening of a metal consists hindering dislocation motion.
assist diffusion. Dislocation motion can be hindered in many ways, thus are
• Lattice structure: Diffusion is faster in open lattices or in open strengthening mechanisms in metals.
directions than in closed directions. • Strengthening by methods of grain-size reduction, solid-solution
• Presence of defects: As mentioned in earlier section, defects like alloying and strain hardening applies for single-phase metals.
dislocations, grain boundaries act as short-circuit paths for diffusing • Precipitation hardening, dispersion hardening, fiber strengthening
species, where the activation energy is diffusion is less. Thus the and Martensite strengthening are applicable to multi-phase metallic
presence of defects enhances the diffusivity of diffusing species.
materials.
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Strengthening by Grain Size Reduction Contd…

• This strengthening mechanism is based on the fact that • The smaller the grain size, the more frequent is the pile up of dislocations.
crystallographic orientation changes abruptly in passing from one A twin boundary can also act as an obstacle to dislocation motion.
grain to the next across the grain boundary. • A grain boundary can hinder the dislocation motion in two ways:
• Thus it is difficult for a dislocation moving on a common slip plane in
one crystal to pass over to a similar slip plane in another grain, (1) by forcing the dislocation to change its direction of motion and
especially if the orientation is very misaligned. (2) discontinuity of slip plane because of disorder.
• In addition, the crystals are separated by a thin non-crystalline region, • Effectiveness of grain boundary depends on its characteristic misalignment,
which is the characteristic structure of a large angle grain boundary. represented by an angle.
• Atomic disorder at the boundary causes discontinuity in slip planes. • With decrease in grain size, the mean distance of a dislocation can travel
Hence dislocations are stopped by a grain boundary and pile up decreases, and soon starts pile up of dislocations at grain boundaries. This
against it. leads to increase in yield strength of the material.

Solid Solution Strengthening Contd…

• Adding atoms of another element that those occupy interstitial or • Pure metals are almost always softer than their alloys.
substitutional positions in parent lattice increases the strength of • Solute strengthening effectiveness depends on two factors – size difference
parent material. between solute and parent atoms, and concentration of solute atoms.
• This is because stress fields generated around the solute atoms • Solute atoms are two categories with respect to their relative
interact with the stress fields of a moving dislocation, thereby strengthening effect –
increasing the stress required for plastic deformation i.e. the impurity (1) Those produce non-spherical distortions, such as most interstitial
atoms cause lattice strain which can "anchor" dislocations. atoms, have a relative strengthening effect per unit concentration of about
• The solute atoms have more influence on the frictional resistance to three times their shear modulus,
dislocation motion than on the static locking of dislocations. (2) Those produce spherical distortion, such as substitutional atoms, have
a relative strengthening of about G/10.
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Strain Hardening Contd…

• Two most important industrial processes used to harden metals or • For a given amount of plastic strain, higher the value of n, greater is
alloys are: strain hardening and heat treatment. the strain hardening.
• Strain hardening is used for hardening/strengthening materials that • Increasing temperature lowers the rate of strain hardening, and thus
are not responsive to heat treatment. the treatment is given, usually, at temperatures well below the
• The phenomenon where ductile metals become stronger and harder melting point of the material. Thus the treatment is also known as
when they are deformed plastically is called strain hardening or work cold working.
hardening. • Most metals strain hardens at room temperature.
• Intensity of strain hardening can be gaged from the slope of the flow • The consequence of strain hardening a material is improved strength
curve, defined by the parameter strain hardening exponent, n. It is and hardness but material’s ductility will be reduced.
measure of the ability of a metal to strain harden.

Contd… Contd…
• The cold worked state is a condition of higher internal energy than the
• Strain hardening is used commercially to enhance the mechanical un-deformed metal.
properties of metals during fabrication procedures. • Although cold worked dislocation cell structure is mechanically stable, it
• In addition to mechanical properties, physical properties of a material is not thermodynamically stable.
also changes during cold working. • With increase in temperature state becomes more unstable, eventually
• There is usually a small decrease in density, an appreciable decrease reverts to strain-free condition.
in electrical conductivity, small increase in thermal coefficient of • This process of heating to attain strain-free condition is called annealing
expansion and increased chemical reactivity (decrease in corrosion heat treatment where effects of strain hardening may be removed.
resistance). • Annealing process can be divided into three distinct processes: recovery,
recrystallization and grain growth.
• It is usual industrial practice to use alternate cycles of strain hardening
and annealing to deform most metals to a very great extent.
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Precipitation Hardening Contd…

• Requisite for precipitation hardening to take place is that second phase
• Small second-phase particles distributed in a ductile matrix can must be soluble at an elevated temperature but precipitates upon
hinder the dislocation motion and thus increase the strength of a quenching and aging at a lower temperature.
material. • This limits the alloy systems which can be strengthened by precipitation
• Second-phase particles either can be introduced by mixing and hardening. For example: Al-alloys, Cu-Be alloys, Mg-Al alloys, Cu-Sn
consolidation (dispersion strengthening) or precipitated in solid state alloys.
(precipitation hardening). • If the precipitation occurs at normal ambient temperatures, it is called
natural aging.
• Precipitation hardening or age hardening is produced by solution
treating and quenching an alloy. • Some alloy systems needed to be aged at higher temperatures and the
process is known as artificial aging.
• Term ‘Age hardening’ is used to describe the process because
strength develops with time. • Most precipitation hardened alloys are limited in their maximum service
temperatures, which may lose their strength at elevated temperatures
due to over-aging.

Dispersion strengthening Contd…

• In dispersion strengthening, hard particles are mixed with matrix powder • Dislocations moving through the matrix, which is either precipitation
and consolidated and processed by powder metallurgy techniques. hardened or dispersion strengthened, have two alternatives.
• Here second phase shall have very little solubility in the matrix, even at • They can either cut through the precipitate particles or bend around
elevated temperatures. and bypass them.
• Because there is very little solubility, the particles resist growth or over- • The first alternative is possible only when the slip plane is continuous
aging to a much greater extent than the second phase particles in a from the matrix through the precipitate particle and when the stress
precipitation hardening system.
to move a dislocation in precipitate is comparable to that in matrix.
• Theoretically, at least, it is possible to produce infinite number of
dispersion-hardened systems by mixing finely divided metallic powders and • Cutting of particles is easier for small particles which can be
second phase particles (oxides, carbides, nitrides, borides, etc). considered as segregated solute atoms.
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Annealing: Recovery, Recrystallization and

Contd…
Grain Growth
• Optimum strengthening occurs during aging once the right interspacing • Annealing is an important industrial process to relieve the stresses from
of particles is achieved. cold working.
• Smaller the particles, dislocations can cut through them at lower • During cold working grain shape changes, while material strain hardens
stresses. because of increase in dislocation density.
• On the other hand, larger the particles they will be distributed at wider • Between 1-10% of the energy of plastic deformation is stored in material in
distances. the form of strain energy associated with point defects and dislocations.
• Thus it is necessary to arrest the growth of particles in precipitation • On annealing i.e. on heating the deformed material to higher temperatures
hardened alloys at right interspacing. and holding, material tends to lose the extra strain energy and revert to the
original condition before deformation by the processes of recovery and
• Over-aging allows the fine particles to coalesce into larger and fewer recrystallization. Grain growth may follow these in some instances.
particles. The interspacing is increased thereby and the yield stress
decreases.

Recovery Recrystallization
• This is the first stage of restoration after cold working where physical • This stage of annealing follows after recovery stage.
properties of the cold-worked material are restored without any • Here also driving force is stored energy of cold work. Even after
observable change in microstructure. complete recovery, the grains are still in relatively high strain energy
• The properties that are mostly affected by recovery ate those sensitive state.
to point defects, for example – thermal and electrical conductivities. • This stage, thus, involves replacement of cold-worked structure by a
• During recovery, which takes place at low temperatures of annealing, new set of strain-free, approximately equiaxed grains i.e. it is the
some of the stored internal energy is relieved by virtue of dislocation process of nucleation and growth of new, strain-free crystals to
motion as a result of enhanced atomic diffusion. replace all the deformed crystals.
• Excess point defects that are created during deformation are annihilated • It starts on heating to temperatures in the range of 0.3-0.5 Tm, which
either by absorption at grain boundaries or dislocation climbing process. is above the recovery stage.
• Stored energy of cold work is the driving force for recovery. • There is no crystal structure change during recrystallization.
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Contd… Grain Growth

• This process is characterized by recrystallization temperature which is
defined as the temperature at which 50% of material recrystallizes in • This stage follows complete crystallization if the material is left at elevated
one hour time. temperatures.
• The recrystallization temperature is strongly dependent on the purity • However, grain growth does not need to be preceded by recovery and
of a material. Pure materials may recrystallizes around 0.3 Tm, while recrystallization; it may occur in all polycrystalline materials.
impure materials may recrystallizes around 0.5-0.7 Tm. • During this stage newly formed strain-free grains tend to grow in size. This
• There are many variables that influence recrystallization behavior, grain growth occurs by the migration of grain boundaries. Driving force for
namely amount of prior deformation, temperature, time, initial grain this process is reduction in grain boundary energy i.e. decreasing in free
size, composition and amount of recovery prior to the start of the energy of the material.
recrystallization. • As the grains grow larger, the curvature of the boundaries becomes less.
• During recrystallization, the mechanical properties that were changes This results in a tendency for larger grains to grow at the expense of
during deformation are restored to their pre-cold-work values. smaller grains.
• Thus material becomes softer, weaker and ductile.

Contd…
• In practical applications, grain growth is not desirable. Incorporation
of impurity atoms and insoluble second phase particles are effective
in retarding grain growth.
• Because the driving force for grain growth is lower than the driving
force for recrystallization, grain growth occurs slowly at a temperature
where recrystallization occurs at substantially high speeds. However,
grain growth is strongly temperature dependent.