Unit IV

Imperfection
in Solids

Imperfection in Solids
Point defects: stoichiometric defects and
nonstoichiometric defects. Line defects:
edge dislocations and screw dislocations.
Plane defects: stacking faults, grain
boundaries and twin boundaries. Solid
state reactions: mechanisms of migration
of ions, solid electrolytes, thermal
decomposition of solid-Type 1 and Type II
reactions.

Dr. Asha T. M.
Crystal defects
Crystal defect is an imperfection in the regular geometrical arrangement of the atoms in a
crystalline solid. These imperfections result from deformation of the solid, rapid cooling from
high temperature, or high-energy radiation (X-rays or neutrons) striking the solid. Located at
single points, along lines, or on whole surfaces in the solid, these defects influence its
mechanical, electrical, and optical behavior.

Classification of crystal defects based on the dimensionality

Based on the dimensionality, the defects in crystals are classified into three as follows:

1. Zero dimensional or point defect

2. One dimensional or line defect
3. Two dimensional or surface defects

Zero dimensional or Point defects

Those defects in the crystals which occur around an atom or particle are called point defects.
These defects occur only at or around a single lattice point. They do not extend in space in
any dimension. That’s why they are also called zero dimensional (0-D) defects. These are the
smallest possible defects in any crystalline solid material. Point defects occur when,

➢ One or more atoms of the crystal are missing from their corresponding lattice site.
➢ Atom/s is shifted from its corresponding lattice site to interstitial position in the
crystal.
➢ Foreign atoms occupy the interstitial position in the crystal lattice.
➢ Original atom of the crystal is replaced by foreign atom.

Classification of point defect

The following chart gives the summary of the classification of the point defect.

DR. ASHA T. M. 1
 I. Stochiometric defects

The compounds which obey the law of definite proportions, the law of constant composition
and the law of conservation of mass are called stoichiometric compounds. The defects in
crystals which do not disturb the stoichiometry of the compound or crystal are called
stoichiometric defects. Stoichiometric Defects can be divided into following types:

A. Vacancy Defect: The point defect which is produced when an atom goes missing
from its original lattice site is called vacancy defect. It creates vacancy in the lattice
site as shown in the diagram below. It results in a decrease in density of the
substance. Number of vacancy defects depends on the temperature of the crystal.
It occurs due to imperfect packing during crystallization.

B. Interstitial Defect: The point defect which occurs when an atom takes the
interstitial position of the lattice structure is called interstitial defect. The atom
can be of the same crystal or foreign crystal/material. If the atom is of the same
crystal, then the defect is called self-interstitial defect. It is shown below through
the diagram. This defect increases the density of the crystal. It causes atomic
distortion.

Classification of vacancy defect

Vacancy defect is further classified into two types as follows:

1. Schottky defect

Schottky defect is a type of point defect or imperfection in solids

which is caused by a vacant position that is generated in a crystal
lattice due to the atoms or ions moving out from the interior to
the surface of the crystal.
Schottky defect in crystals is observed when equal
numbers of cations and anions are missing from the lattice
(Figure on the right). Since an equal number of cations and anions
are missing, otherwise the electrical neutrality of the crystal will
get affected.
As for the density of the solid, it decreases considerably. It is a type of defect in crystals
that mostly occurs in highly ionic compounds or highly coordinated compounds. The
compound lattice has only a small difference in sizes between the anions and cations. Some
common examples of salts where Schottky defect is prominent include Sodium Chloride
(NaCl), Potassium Chloride (KCl), Potassium Bromide (KBr), Caesium Chloride (CsCl) and Silver
Bromide (AgBr).

DR. ASHA T. M. 2
Schottky Defect Calculation

The number of Schottky defects (n) present in an ionic compound containing N ions at
temperature T is given by:

n = NeE/2KT

Where, E is the energy required to create 'n' Schottky defects and K is the Boltzmann constant.

2. Frenkel defect

A Frenkel defect is another form of a point defect which is created

when an atom or cation leaves its original place in the lattice
structure to create a vacancy while occupying another interstitial
position within the solid crystal.
This defect creates vacancy defect at original site and
interstitial defect at new site (Figure on the right). The Frankel
defect is also called a dislocation defect. This defect occurs in ionic
compounds of low coordination number with smaller cation and
bigger anions.
The defect is not found in alkali metal halides because cations and anions have almost
equal sizes and cations cannot be accommodated in interstitial sites. There is also no
significant impact of the Frenkel defect on the density of the solid and therefore both the
volume and mass of the solid is preserved.
Consequences of Frenkel defect

• There is an increase in the dielectric constant as the like charge ions comes closer.
• The solids having Frenkel defect show conductivity and diffusion in solid state due to
the presence of vacant lattice sites.
• Due to the Frenkel defect, the lattice energy and stability of crystalline solid decreases.
• Entropy of the solid increases.
Frenkel defects are mostly exhibited in ionic solids where the smaller ion (usually the cation)
is dislocated. Some examples include AgBr, ZnS, AgCl, and AgI. Here the defect occurs mainly
due to the smaller size of Zn2+ and Ag+ ions. Meanwhile, silver bromide shows both types of
point defects such as Frenkel and Schottky defects.
Calculation of the number of Frenkel defects

Frenkel Defects can be calculated using the equation given below:

n= √NN∗e–ΔH/2RT
Where,

DR. ASHA T. M. 3
n = Number of Frenkel defect; = normally occupied positions; N∗ = number of available
positions; ΔH = the enthalpy formation of one Frenkel defect and R = gas constant.

Key Differences Between Schottky and Frenkel Defect

Interstitial defects

An interstitial defect is a type of point crystallographic

defect where an atom of the same or of a different type,
occupies a normally unoccupied site in the crystal structure.
When the atom is of the same type as those already
present, they are known as a self-interstitial defect.
Alternatively, small atoms in some crystals may occupy
interstitial sites, such as hydrogen in palladium.
Interstitial atoms (blue) occupy
some of the spaces within a lattice of
larger atoms (red)

II. Impurity defect

Impurity defect is defined as the foreign atoms that compress into the interstices or replace
some atoms that make up the solid. The defects in ionic compounds due to replacing ions by
ions of another compound are called impurity defects.
It is one of the point defects. In Impurity defect, the particular entity of a crystalline
solid structure consists of trace or minimum amounts of another entity. Impurity defect
occurs when foreign atoms differ from the host atoms that exist in the crystal lattice. It arises
when foreign atoms exist at the vacant interstitial sites or lattice sites.

DR. ASHA T. M. 4
 Vacancies are formed by the addition of
impurities through aliovalent ions (ion
that is substituting the original ion is of a
different oxidation state than the ion it is
replacing). The formation of vacancies in
impurity defect through aliovalent
impurity can be understood by
considering the crystallization of molten
NaCl with a small amount of SrCl2 that
results in Sr2+ which occupies some of the
sites of Na+ (Figure on the left).
Here, two Na+ ions are replaced by each Sr2+ ion. The site of one ion is occupied by impurity
ion and the other site remains empty. The number of cationic vacancies that are produced is
equivalent to that of Sr2+. Other examples for impurity defect are solid solution of AgCl and
CdCl2.

III. Non-stochiometric defects

The defects which disturb the stoichiometry of the compounds are called non-stoichiometric
defects. These defects are either due to presence of excess metal ions or deficiency of metal
ions.

A. Metal excess defects

Metal excess defect may be due to the following reasons.

i. Metal excess defect due to anion vacancy

Anionic vacancies are found in alkali halides such as NaCl and KCl. In this defect, the negative
ion is missing from the lattice site leaving behind a hole which is then occupied by an electron
to maintain electric balance. These electrons are trapped in the anion vacancies.
For example, when NaCl is heated in an atmosphere of Na vapours. The excess of Na
atoms deposits on the surface of NaCl crystal. Therefore Cl– ions then diffuse to the surface
where it combines with Na+ ions to form NaCl. This creates a vacancy at the anionic site which
will be occupied by an electron to maintain the charge neutrality. This site is known as F-
center or Farbecenter (from the original German Farbzentrum, where Farbe means color and
zentrum means center). F-centre imparts color to the crystal. The color results by excitation
of these electrons when they absorb energy from the visible light falling on the crystals.

DR. ASHA T. M. 5
Hence non-stochiometric NaCl is yellow in color, KCl is violet in color and LiCl is pink in color.

ii. Metal excess defect due to extra cation

In this defect, on heating the compound, it releases extra

cations. These cations occupy the interstitial sites in crystals
and the same number of electrons goes to neighboring
interstitial sites. Extra cations in the interstitial site can be
found in crystals that exhibit Frenkel defect such as ZnO. For
example, zinc oxide is white at room temperature, on excess
heating, it turns yellow as it loses oxygen.

ZnO → Zn2+ + ½O2 + 2e-

Now there is excess of zinc in the crystal and its formula becomes Zn1+xO. The excess Zn2+ ions
move to interstitial sites and the electrons to neighboring interstitial sites.

B. Metal deficiency defect

The defect arises when the metal shows variable

valency. In this defect, some cations are missing from
the lattice site and for maintaining its electrical
neutrality another remaining cation increase their
valency.
Example: Ferrous oxide, Nickel oxide.
It is difficult to prepare FeO in stochiometric
composition and is always found in the composition,
Fe0.95O. It may actually range from Fe0.93O to Fe0.96O.
In the crystal of FeO, some Fe2+ ions will be missing and the loss of positive charge is made up
by the oxidation of some of the Fe2+ ions into Fe3+ ions as shown in figure.

One dimensional or line defect

Line defects are a form of crystallographic defects in which the defects occur in a plane of
atoms in the middle of the crystal lattice. These defects occur when a plane of atoms misalign.
Line defects are called dislocations and occur in crystalline materials only. A dislocation or
Taylor's dislocation is a linear crystallographic defect or irregularity within a crystal structure
that contains an abrupt change in the arrangement of atoms. Dislocations are especially
important in materials science, because they help determine the mechanical strength of
materials.
In order to understand the effect of dislocations on the mechanical properties of
crystals, consider the effect of applying a shearing stress to a crystal that contains an edge
dislocation (Figure below). The top half of the crystal is pushed to the right and the bottom
half to the left. Comparing (a) and (b), the extra half-plane which terminates at 2 in (a) can

DR. ASHA T. M. 6
effectively move simply by breaking the bond 3-6 and forming a new linkage 2-6. Thus, with
a minimum of effort, the half-plane has moved one unit of distance in the direction of the
applied stress. If this process continues, the extra half-plane eventually arrives at the surface
of the crystal as in (c). In (d), it is assumed that half-planes are generated at the left-hand end
of the crystal. With each one that is generated, another one, equal and opposite in orientation
and sign, is left behind. At the left-hand side, five half-planes in the bottom part of the crystal
have accumulated at the surface. Balancing these in the top part of the crystal, three half-
planes have arrived at the right-hand end and two more (positive dislocations) are still inside
the crystal and in the process of moving out.

The process of movement of dislocations is called slip and the pile-up of half-planes at
opposite ends gives ledges or slip steps. The line AB in (d) represents the projection of the
plane over which the dislocation moves and is called the slip plane. The centre of the distorted
region is a line that passes right through the crystal, perpendicular to the paper, and
approximates to the end of the extra half-plane; this is the line of the dislocation or
dislocation line. Outside this stressed region, the crystal is essentially normal and is referred
to as the un-slipped region. A dislocation line defines the boundary between slipped and un-
slipped regions of material (Figure below).

DR. ASHA T. M. 7
Therefore, a dislocation is characterized by two vectors, viz;

i. Tangent vector, 𝐭̂: is a vector which is tangent or parallel to the dislocation line
and gives the orientation of the dislocation line. It is a unit vector.
ii. Burgers vector, ⃗𝐛: is a vector which gives the magnitude and direction of the
slip.

There are three basic types of dislocations depending on the relationship between Line
vector, t̂ and ⃗⃗
b:

A. Edge dislocation
B. Screw dislocation
C. Mixed dislocation
⃗ ꓕ 𝐭̂)
A. Edge dislocation (𝐛

A dislocation in which the Burgers vector, 𝐛⃗ is perpendicular to the line vector, 𝐭̂ is known as
the edge dislocation. Edge dislocation occurs due to the introduction or elimination of an
extra row of atoms. Region of lattice disturbance extends along an edge inside a crystal. The
inter-atomic bonds are significantly distorted only in the immediate vicinity of the dislocation
line.

There are two types of Edge dislocation, positive and negative.

 Edge dislocation is considered positive when compressive stresses present above the
dislocation line, and is represented by ┴.
 If the stress state is opposite i.e., compressive stresses exist below the dislocation line,
it is considered as negative edge dislocation, and represented by ┬.

DR. ASHA T. M. 8
 ⃗ ‖ 𝐭̂)
B. Screw dislocation (𝐛

A dislocation in which the Burgers vector, ⃗𝐛 is parallel to the line vector, 𝐭̂ is known as the
edge dislocation. The screw dislocation is slightly more difficult to visualize. Screw dislocations
can be produced by a tearing of the crystal parallel to the slip direction. If a screw dislocation
is followed all the way around a complete circuit, it would show a slip pattern similar to that
of a screw thread. Hence it can be considered as a dislocation in the lattice structure of a
crystal in which the atoms are arranged in a helical pattern that is normal to the direction of
the stress.
Imagine cutting a crystal along a plane and slipping one half across the other by a
lattice vector, the halves fitting back together without leaving a defect.

C. Mixed dislocation (𝐛⃗ 𝐧𝐨𝐭 ꓕ 𝐭̂ 𝐚𝐧𝐝 𝐛

⃗ 𝐧𝐨𝐭 ‖ 𝐭̂)
⃗ is neither parallel nor perpendicular, but some
A dislocation in which the Burgers vector, 𝐛
angles to the line vector, 𝐭̂ is known as the mixed dislocation.

Two dimensional or surface defects

A planar defect is a discontinuity of the perfect crystal structure or dislocations across a plane.
Plane defect is classified into four types as follows:

i. Free surface or external surface

ii. Grain boundary
iii. Stacking faults
iv. Twin boundary

DR. ASHA T. M. 9
 i. Free surface or external surface

Free surfaces (external surfaces) of materials are surface defects in the sense that growth of
crystal has stopped abruptly at the surface. The atoms in the free surface of a solid (or, even
liquid) have no neighbors and have no cohesive-bonds, on one side. That is why, these atoms
have higher free energy as compared to atoms inside, Figure below.
Free surfaces have surface energies that are roughly
calculated from the number of ‘broken bonds’ at the
surface. For example if the free surface is a close-
packed plane of a close-packed crystal structure such
as {111} type. An atom in free surface has six
neighbouring bonds in the surface plane, and three
bonds with atoms below this surface but the three
bonds above the surface are broken (as coordination
number is 12). Thus, three out of total twelve bonds
of an atom, that is, one quarter of bonds are missing
compared to an atom inside.
The surface energy shall be one-quarter of the cohesive energy per atom, that is, around 1 eV
for a metal such as FCC-iron. There are on an average around 1015 atoms cm-2 in a crystal
surface. So, the surface energy becomes 1015 eV cm-2.

ii. Grain boundary

A grain boundary is a general planar defect that separates regions of different crystalline
orientation (i.e. grains) within a polycrystalline solid (Figure below).
Solids generally consist of a number of crystallites or grains of varying size and
orientation. These have random crystallographic orientations. When a metal starts with
crystallization, the phase change begins with small crystals that grow until they fuse, forming
a polycrystalline structure. In the final block of solid material, each of the small crystals (called
“grains“) is a true crystal with a periodic arrangement of atoms, but the whole polycrystal
does not have a periodic arrangement of atoms, because the periodic pattern is broken at the
grain boundaries. Grains and grain boundaries help determine the properties of a material.

DR. ASHA T. M. 10
Grain boundaries are rotation boundaries. Hence grain on one side of the boundary is rotated
with respect to the grain on the other side. Rotation can be represented by a rotation axis
and rotation angle.

Based on the magnitude of rotation angle, grain boundary is classified into two:

 Small angle boundary: When the angle of rotation is small (generally < 5°), the
boundary is termed as small angle boundary. The energy associated with a small angle
boundary is small.
 Large angle boundary: When the angle of rotation is large (generally > 5°), the
boundary is termed as large angle boundary. The energy associated with a large angle
boundary is large.

Based on the relationship between rotation with respect to boundary plain, grain boundary
is classified into two:

 Tilt Boundaries: Tilt boundaries are boundaries between adjacent grains having
misorientation in such a way that lattices appear to be tilted with respect to one
another. In this case, rotation axis will be parallel to the boundary plane.

 Twist Boundaries: Twist boundaries are boundaries between adjacent grains having
misorientation in such a way that the lattices appear to be rotated (twisted) with
respect to one another. In this case, rotation axis will be perpendicular to the
boundary plane.

iii. Stacking faults

In crystallography, a stacking fault is a planar defect that can occur in crystalline materials.
Crystalline materials form repeating patterns of layers of atoms. Errors can occur in the
sequence of these layers and are known as stacking faults. The most common example of
stacking faults is found in close-packed crystal structures.

DR. ASHA T. M. 11
Face-centered cubic (fcc) structures differ from hexagonal close
packed (hcp) structures only in stacking order. Both structures
have close-packed atomic planes with sixfold symmetry — the
atoms form equilateral triangles. When stacking one of these
layers on top of another, the atoms are not directly on top of one
another. The first two layers are identical for hcp and fcc, and
labelled AB.
If the third layer is placed so that its atoms are directly above those of the first layer,
the stacking will be ABA -this is the hcp structure, and it continues ABABABAB. However, there
is another possible location for the third layer, such that its atoms are not above the first
layer. Instead, it is the atoms in the fourth layer that are directly above the first layer. This
produces the stacking ABCABCABC.
Consider a perfect crystal with ccp arrangement as shown below from which a C plane
is being removed so that the arrangement near the removed C plane becomes ABAB type
rather than ABCABC arrangement and a stacking fault is been introduced at this plane. The
arrangement of crystal appears to be perfect above and below this plane. Or in other words,
the defect is concentrated only along this plane and is therefore considered as a plane defect.

Crystal on one side of the fault is shifted by a NON-LATTICE TRANSLATION with respect to the
crystal on the other side. Therefore, stacking fault is considered as a translation boundary.
Stacking faults occur during crystal growth and are also a part of other defects.

iv. Twin boundary

Twin boundaries are a special case of a large angle grain boundary for which there is no atomic
misfit. Across the twin boundary crystallites have planes that are the mirror image of the
planes in the other crystallite. Twins are either grown-in during crystallization, or the result
of mechanical or thermal work.

DR. ASHA T. M. 12
 Figure: Difference between (a) grain boundary (GB) and (b) a twin boundary (TB)

Twin boundaries always occur in pairs and the region between two twin boundaries is known
as “twin”(Figure below).

Solid state reactions

I. Shake ’n Bake Method

The oldest, simplest and still most widely used method to make inorganic solids is to mix
together powdered reactants, perhaps press them into pellets or some other shape and then
heat in a furnace for prolonged periods. The method is not sophisticated, hence the use of
alternative names such as shake ’n bake or, beat ’n heat! It is nevertheless very effective and,
for instance, almost all the high-Tc superconductors were first prepared by this method.
Solid state reactions are intrinsically slow because, although the reactants may be well
mixed at the level of individual particles (e.g. on a scale of 1 μm or 10−3 mm), on the atomic
level they are very inhomogeneous. In order to achieve atomic level mixing of reactants,
either solid state counter diffusion of ions between different particles or liquid- or gas-phase
transport is necessary to bring together atoms of the different elements, and in the correct
ratio, to form the desired product.
Consider a typical solid state reaction, that of MgO and Al2O3 powders to form
MgAl2O4 spinel. The various processes involved in the reaction can be considered.

DR. ASHA T. M. 13
At every interface between contacting grains of MgO and Al2O3, all the ingredients necessary
to form the MgAl2O4 product are present (Figure below). The first stage, therefore, is
nucleation of small crystals with the spinel stoichiometry and structure. For nuclei to be stable
and not to disintegrate spontaneously as soon as they form, they must usually be several tens
of Angstroms across, i.e., they must be considerably larger than a single unit cell and must
therefore contain many tens of atoms. The critical size of nuclei represents a balance between
the negative free energy of formation of the spinel product and the positive surface energy
of the nuclei. If the nuclei are too small, the surface area to volume ratio is too large and the
nuclei are unstable. Nucleation tends to be difficult simply because of the large number of
ions that must get together, in the correct arrangement, to form a stable nucleus.

Figure: Idealised reaction mixture

composed of grains of MgO and Al2O3.
In practice, their shapes will be
irregular, of different size and not
arranged in such an orderly fashion.

Nucleation is greatly facilitated if it is heterogeneous and the product nuclei are able
to form on the surface of an existing structure, especially if there is some similarity in the two
structures. The MgO/Al2O3 reaction to form spinel provides two examples of possible
heterogeneous nucleation, on the surfaces of either MgO or Al2O3 grains, Figure below.

Figure: Nucleation of
MgAl2O4 spinel on (a) MgO
and (b) Al2O3. Letters A, B, C
refer to close-packed layers
of oxide ions.

At the MgO/MgAl2O4 interface, provided that the MgAl2O4 nucleus and the underlying
MgO are in the same crystallographic orientation, the oxide ion arrangement can continue
unchanged since it is ccp in both structures, with an ABC stacking sequence, Figure (a) above.
Formation of a spinel nucleus on top of an MgO structure (or substrate) is relatively easy
because of the structural similarity of MgO and spinel and the absence of any necessity to
create a stand-alone spinel nucleus with large surface area. In the MgO/spinel case, the

DR. ASHA T. M. 14
structural similarity extends to 3D since there is a common oxygen packing arrangement; this
is referred to as topotaxy.

At a suitably oriented Al2O3/MgAl2O4 interface, the situation is similar, but now the oxygen
stacking sequence changes from hcp (AB) in Al2O3 to ccp in spinel. Oriented nucleation of
spinel on an alumina substrate is still easy (the change in stacking sequence resembles that
found in stacking faults), but the structural similarity between substrate and nucleus is limited
to the 2D interface and is referred to as epitaxy.
Therefore, chemical reactions in which major structural features of one of the
reactants are preserved in the product is referred to as topochemical reactions. Epitactic and
topotactic features are common in solid state reactions, crystal growth, oriented thin film
deposition, intercalation reactions and phase transformations. Oriented nucleation, of the
kind described above, is relatively easy provided that (a) the appropriate atoms that form the
product nuclei are nearby and (b) there is good lattice matching between substrate and
nucleus.
In the MgO/Al2O3 reaction mixture, we may expect thin nuclei of spinel to form
whenever grains of MgO and Al2O3 are close together or touching because all three structures
have a close-packed oxide arrangement and lattice matching across the interfaces should be
good. Although the first few atomic layers of product nuclei may form easily, subsequent
growth or thickening of the product is more difficult because, effectively, the two reactants,
MgO and Al2O3, are no longer in contact but are separated by a rather impenetrable spinel
layer. A complex counter-diffusion process is the required in which Mg2+ ions diffuse away
from, and Al3+ ions diffuse towards, the MgO/MgAl2O4 interface, and vice versa for the
MgAl2O4/Al2O3 interface. Assuming for the moment that there is no way that the ions can
avoid the long diffusion pathway through the spinel product layer, we have the scenario
summarised in Figure below. As the reaction proceeds, the spinel layer thickens, the diffusion
pathlength increases and reaction slows.

In order to preserve local electroneutrality during reaction and throughout the

product, it is necessary that, for every three Mg2+ ions that diffuse to the right-hand
interface, two Al3+ ions must diffuse to the left-hand interface. The reactions that occur at
the interfaces may be written, ideally, as follows:

DR. ASHA T. M. 15
In cases where reactant and product are of different colour, it may be possible, in carefully
designed experiments, to observe visually the displacement of the interfaces; this is known
as the Kirkendall effect.
The spinel formation reaction is particularly slow because ions such as Mg2+ and Al3+
diffuse very slowly; typically, heating for 1 week at 1500 ◦C would be required to form a fairly
pure spinel product. The reaction can be accelerated by the following means.

▪ By partially grinding the reacted mixtures, so as to break up reactant/product

interfaces and bring fresh reactant surfaces into contact.
▪ Another way is if gas- or liquid-phase assisted transport of matter can occur,
and bring reactants together without the need for long-range solid state
diffusion.
▪ A small amount of liquid or gaseous transporting agent may be very effective
in enhancing reaction rates.

There are four main issues for consideration in planning a solid state reaction: choice of
starting materials, mixing method, container and heat treatment conditions.

1. Starting materials

Ideal starting materials should be of accurately known stoichiometry, pure and reactive.
Problems with stoichiometry and purity can arise if the reagents are sensitive to water and/or
CO2 in the atmosphere or contain transition elements in uncertain or mixed valence states.
Reagents may need to be dried, at a temperature found by trial and error, and subsequently
kept in a desiccator. For oxide synthesis, it can be useful to use oxy salt reagents, such as
carbonates, acetates or nitrates (but not sulfates, which are very stable thermally), since
these decompose during the initial stages of reaction on heating. This decomposition step
may decrease greatly the particle size of the reagent, increase its surface area and therefore
increase its potential reactivity. In addition, evolution of gases during the decomposition can
help to mix the solid reactants.

DR. ASHA T. M. 16
 2. Mixing of reactants

For solid state reaction, it is essential to bring particles of reactants into contact; this is
facilitated by increasing the surface area of the reactants. Samples are therefore mixed and
milled. This can be done manually using a mortar and pestle (agate mortars and pestles are
useful since they are non-porous, readily cleaned and should not contaminate samples); there
are also various labor-saving mechanical mixing techniques such as ball milling, in which the
mixture of reactants is placed inside a rotating container together with a number of balls of,
for instance, agate. The container is then rotated for a period of time, e.g. 3–24 h, and the
effect of the tumbling motion with the agate balls is to reduce the average particle size of the
reactants in addition to achieving an intimate mixture. High-energy milling is possible in
planetary ball mills, which are rotated at very high speed. While the mixing and milling
processes are carried out rapidly and effectively, there is a danger of contamination from the
milling media. To facilitate mixing, by whatever method, a liquid such as water or an organic
liquid is often added and then needs to be removed by drying at the end of the mixing stage.

3. Container

If atmospheric sensitivity of the desired product phase is not a problem, the reaction mixture
can simply be heated in air in a furnace in a suitable container. Prime consideration for the
container is that it should not react with the sample. Frequently-used inert containers for
oxides are boats or crucibles of

➢ Pt (but Pt reacts with Li2O, BaO and many transition metal oxides).
➢ Au (but its melting temperature, 1063 ◦C, places an upper limit on the reaction
temperatures that may be used; however, Au is generally more inert than Pt).
➢ Al2O3 (high-purity alumina is inert and high melting, but nevertheless contamination
from the reactants may occur).
➢ SiO2 glass (crucibles of pure SiO2 glass can withstand temperatures up to 1200 ◦C
before the glass softens and starts to devitrify; oxides of alkali metals, in particular,
are reactive towards SiO2).
➢ Graphite crucibles are commonly used as containers for the synthesis of sulfides,
other chalcogenides and nitrides.

4. Firing schedule

The heating schedule should be designed to:

 Cause smooth decomposition of any oxy salt reagents without excessive frothing,
melting or leakage of reagent from the container,
 Avoid melting and in particular volatilization of one or more of the reagents, and
 Apply temperatures at which the reagents react together on a reasonable timescale
(e.g. 12–24 h).

DR. ASHA T. M. 17
Reactions may be carried out in air or, if a tube furnace is available, a range of controlled
atmospheres may be used. Alternatively, sealed ampoules of silica glass or precious metals
may be used to prevent loss of volatile reagents or atmospheric attack. For known materials,
there may be recipes in the literature detailing appropriate reaction conditions, but for the
attempted synthesis of new materials, a trial-and-error approach is usually needed.

II. Combustion synthesis

In complete contrast to solid state reactions that often require heating for several days at
high temperatures to complete a synthesis, controlled explosions in reactions known
variously as combustion synthesis, self propagating high temperature synthesis, SHS, and
solid state metathesis, SSM, can give reaction products in minutes or even seconds.
In the SHS technique pioneered by Merzhanov and co-workers in Russia, starting
materials are chosen that react together exothermically. Consequently, once a reaction is
initiated, enough heat is generated for high temperatures to be attained and complete
reaction occurs rapidly. The starting materials may be classified as either ‘fuels’ or ‘oxidants’.
An example of an SHS reaction is the ‘thermite’ process for the extraction of iron:

Fe2O3 + 2Al → 2Fe + Al2O3

in which the fuel, Al, and the oxidant, Fe2O3, combine to generate temperatures of 3000 ◦C
for a brief period during reaction. In other combustion syntheses, fuels and oxidants are
additional reagents that are consumed in the reaction and do not feature in the final product;
typical fuels are hydrazine, glycine and urea; common oxidants are nitrates of one of the
reacting species.

III. Mechanosynthesis

Solid state reactions are generally high-temperature methods, but in favorable cases
reactions can be carried out simply by grinding together the reagents. High-energy milling is
necessary, often for periods of several hours, and there can be a danger of contamination
from the milling media. Nevertheless, the method is finding increasing applications as a
synthetic method. Details of just how solids react are still rather unclear; the reagents are
reduced to nanometre size with the introduction of mechanically induced crystal defects.
Although no heat is applied, high temperatures may be generated locally as the mechanical
energy is transformed into heat and this acts to speed up interdiffusion rates and formation
of the product phase on a very fine scale.
The products of mechanosynthesis may be different from those of the same
materials prepared by solid state reaction. They may be in a metastable state, with
compositional inhomogeneity, structural disorder and high vacancy concentration.

DR. ASHA T. M. 18
Solid electrolytes
Any electrochemical cell such as battery, fuel cells etc. requires an “electrolyte”. In most
cases, an ionic solution (Eg. dil. H2SO4 in a lead-acid battery) is an acceptable electrolyte. But
it is often desirable to avoid a liquid phase due to possible spillage and there is a considerable
interest in the development of solid electrolyte.

Ionic conductivity occurs in materials known variously as solid electrolytes, superionic

conductors (SIC) or fast ion conductors (FIC).

 These have a rigid framework structure within which one set of ions forms a mobile
sublattice.
 Conductivities as high as 1 Ω−1 cm−1, similar to those of strong liquid electrolytes,
occur.
 Solid electrolytes are intermediate between typical ionic solids, in which all ions are
fixed on their lattice sites, and liquid electrolytes, in which all ions are mobile.
 The structural requirements for high ionic conductivity are (i) there must be available
empty sites for ions to hop into and (ii) the energy barrier for ions to hop between
sites is small.
 High levels of ionic conduction are rare but modest amounts are common, especially
in non-stoichiometric or doped materials.

Often, solid electrolytes are stable only at high temperatures. On cooling, they may transform
to a polymorph with a low ionic conductivity and a more usual type of crystal structure, Figure
below. For example, Li2SO4 and AgI are both poor conductors at 25 ◦C but at 572 and 146 ◦C,
respectively, their structures change to give polymorphs, α-Li2SO4 and α-AgI, that have mobile
Li+ and Ag+ ions (σ ≈ 1 Ω−1 cm−1). On heating, the conductivity therefore increases dramatically
at the phase transition.

In order for significant ionic conduction to occur in crystals, certain conditions must be
satisfied:

DR. ASHA T. M. 19
 ➢ A large number of the ions of one species should be mobile (i.e. a large value of n in
the equation σ =neμ).
➢ There should be a large number of empty sites available for the mobile ions to jump
into. This is essentially a corollary of (a) because ions can be mobile only if there are
empty sites available for them to occupy.
➢ The empty and occupied sites should have similar potential energies with a low
activation barrier for jumping between neighbouring sites. It is no use having a large
number of available empty sites if either the moving ion cannot get into them or if the
sites are too small.
➢ The structure should have a framework, preferably 3D, permeated by open channels
through which mobile ions may migrate.
➢ The anion framework should be highly polarisable.

Types of solid electrolytes

❖ Mixed oxide: Cubic stabilized ZrO2(YxZr1-xO2-x/2, CaxZr1-xO2-x) and defect perovskite

Ba2In2O5, La1-xCaxMnO3-y
❖ Cationic: Na+ ion = Sodium β alumina (NaAl11O17, Na2Al16O25), NASICON
(Na3Zr2PSi2O12); Ag+ = AgI and RbAg4I5; Li+ = LiCoO2 and LiMnO2.
❖ Anionic: F- = PbF2 and AF2 (A = Ba. Sr and Ca).

Applications of solid electrolytes

They find application in the following areas

i. Gas sensors
ii. Solid oxide fuel cells
iii. Solid state batteries

Advantages Disadvantages

• Excellent physical and chemical • Reduced contact area for high-

stability capacity electrodes
• Good charging • Interface stress due to charging and
• Increased energy density (twice that discharging
of liquid electrolytes of same
volume)
• Low leakage currents
• Non flammability

DR. ASHA T. M. 20
Thermal decomposition of solid
Thermal analysis incorporates techniques in which property of the system is determined
as function of temperature.

There are mainly four types of thermal analysis as follows:

Technique Instrument Parameter measured Graph

Thermogravimetry Thermobalance Change in mass Percentage of Weight
(TG) loss verses time or temp.
Differential Thermobalance Rate of change of mass dw/dt verses temp.
Thermogravimetry
(DTG)
Differential Thermal DTA apparatus Change in temp ΔT verses temp.
Analysis (DTA) between the sample
and the reference, ΔT.
Differential Scanning Calorimeter Energy required to dH/dt verses temp.
Calorimetry (DSC) maintain zero temp.
difference between
the sample and the
reference.

1. Thermogravimetry (TG)

It is a technique in which a change in weight of a substance is recorded as a function of

temperature or time.

Sample is heated in a given environment (air, N2, CO2, He, Ar, etc.) at controlled rate. The
change in weight of a substance is recorded as a function of temperature or time. The temp.
is increased at a const. rate for a known initial weight of the substance and the changes in the
weights are recorded as a function of temp. at different time interval.


The TG curve for the decomposition of calcium Instrumentation of TG

oxalate

DR. ASHA T. M. 21
This plot of weight change or loss against temp. is called thermogravimetric curve or thermo-
gram (Figure above). The TG curves usually consist of two portions:

 Horizontal regions/ plateau: indicates region where there is no weight loss

 Curved regions: indicates region where there is no weight loss occurs

This measurement provides information about physical phenomena such as phase

transition, absorption and desorption as well as chemical phenomena including
chemisorption, thermal decomposition and solid-gas reactions (eg.: oxidation or reduction).
Instrumentation of TG is also shown in the above Figure.

2. Differential Thermogravimetry (DTG)

This technique involves the measurement of the rate of change of weight of the specimen as
it is being heated at a uniform slow rate. The DTG curve is a plot of dw/dT verse temperature
and corresponding to each curve (black color) in a TG graph, a corresponding peak (red color)
is obtained in DTG graph as shown in the Figure below.

The instrumentation for the DTG is same as that of TG.

3. Differential Thermal Analysis (DTA)

Is a technique in which temp. difference (ΔT) between the sample and thermally inert
reference material are continuously recorded as a function of temp. or time whilst the
substance and the reference are subjected to a controlled temp. programme.
The difference in temp. is called differential temp., ΔT is plotted against temp. or a
function of time. The DTA curve and the instrumental set up for DTA is shown below.
A DTA curve will consist of two types of peaks:

• Exothermic peaks (upward peaks) which are given by chemical changes like
oxidation, polymerization and catalytic reactions.

DR. ASHA T. M. 22
 • Endothermic peaks (udownward peaks) which are given by physical changes
like vaporization, sublimation and absorptions.

DTA curve Instrumentation of DTA

4. Differential Scanning Calorimetry (DSC)

Is a technique in which the energy necessary to establish zero temp. difference between the
sample and the reference material is measured as a function of temp. or time, whilst the
substance and the reference are subjected to controlled temp. programme.

Basic principle underlying this technique is that when the sample undergoes a physical
transformation such as a phase transition, more or less heat will need to flow to it than the
reference to maintain both at the same temp.
This is mainly applied in studying “phase transition” and widely used to determine
temp. and melting enthalpy, glass transition temp. and estimation of crystalline kinetics of
polymers.
The typical DSC curve and its instrumental set up is shown below.

DSC Curve Instrumentation of DSC

DR. ASHA T. M. 23