Lecture 3

Polymorphism
 Polymorphism’ comes from the Greek word, Polus = many and
morph = shape. Thus it is defined as the ability of a substance to
exist as two or more crystalline phases that have different
arrangements or conformations of the molecules in the crystal lattice.
 It essentially means that in different polymorphs, the same molecule
exists in different ways.
 If this difference is because of packing, it is termed as packing
polymorphism and if it is due to difference in conformation, it is called
conformational polymorphism.
 As a result of polymorphism, molecules have different arrangements
in the unit cell of its crystal and thus display different physical
properties.
 These include different packing properties,
thermodynamic properties such as solubility, free energy,
melting point, etc., spectroscopic properties, kinetic
properties such as dissolution rate, stability, and
mechanical properties such as hardness, compatibility,
tableting, tensile strength, etc.
 Polymorphism is very important in those areas of
chemical research where full characterization of a
material has a pivotal role in determining its ultimate use,
e.g., in pharmaceutical, pigment, agrochemical, explosive
and fine chemical industries. It is interesting to note that
polymorphism has left an impression even on the history
of our world
 The particular advantage of polymorphism is that the
chemical identity of the material remains unchanged from
one polymorph to another, so that a direct correlation
between activity and solid state structure may be made.
 Why does the same chemical, say paracetamol, exist in
different ways in the solid state?
 The answer is not simple but it is definite that their free
energy difference cannot be huge.
 So some forms are slightly unstable compared to others
and we can have a functional classification based on this
factor.
 Types of Polymorphism
 Polymorphs are categorized into two types, monotropes and
enantiotropes, depending upon their stability with respect to
the range of temperatures and pressures. If one of the
polymorphs is stable (i.e., has lower free energy content and
solubility) over a certain temperature range and pressure,
while the other polymorph is stable over a different
temperature range and pressure, then the two polymorphs are
said to be enantiotropes.
 On the other hand, sometimes only one polymorph is stable at
all temperatures below the melting point, with all the other
polymorphs being unstable. These polymorphs are said to be
monotropes .
 Both types of polymorphs can be easily understood by
looking at the graphs. In Figure 1a,
polymorph A is stable below temperature Tt (transition
temperature), having lesser free energy GA than
polymorph B.
 But as the temperature increases and becomes more
than Tt, free energy G B of polymorph B becomes less
than GA; thus polymorph B becomes more stable than
polymorph A.
 This gives rise to an enantiotropic system of solid
phases. For an enantiotropic system, a reversible
transition can be observed at a definite transition
temperature at which the free energy curves cross,
before the melting point is reached .
 Whereas in Figure 1b, the polymorph A has its free energy
less than the other polymorphs throughout the range below
the melting point.
 For a monotropic system, the free energy curves do not
cross, and therefore no reversible transition can be observed
below the melting point; the polymorph with higher free energy
curve and solubility is the unstable polymorph.
 Generally, it is possible to distinguish between monotropes
and enantiotropes from their heats of fusion. An endothermic
polymorphic transition indicates enantiotropes whereas an
exothermic one indicates monotropes.
 Other than Differential Scanning Calorimetric (DSC) analysis,
there are a number of efficient ways to characterize
polymorphs
 We all know that millions of molecules must aggregate to
form a crystal. In this process, if there are energetically
viable alternate pathways, molecules may choose any of
these ways depending upon the crystallization conditions
 This leads to the different polymorphs. Thus formation of
a large enough aggregate (i.e., nucleation) is an
important step in the formation of a polymorph.
Nucleation of Polymorphs
 Consider the simple case of evaporation of a sugar solution kept in a
beaker. As time passes, more and more molecules of water leave the
beaker progressively concentrating the solution and at a stage (very
near to saturation but above it) many sugar molecules come closer to
form aggregates.
 These will have their characteristic curve of change in Gibbs free
energy vs. aggregate size as shown in Figure 2. The Gibbs free
energy difference between the new phase (that is, the aggregate)
and the old phase (that is, the sugar solution) is composed of two
terms:
 (1) The difference in Gibbs free energy between the two phases in
macroscopic quantities (usually called the volume term, ΔGv), and
(2) the difference in Gibbs free energy caused by the interfacial
energy (called the surface term,ΔGs)
 The total free energy cost, ΔGtot, of forming a nucleus of a spherical
crystal of radius r in a liquid (here sugar solution) is the sum of these
two:


 Where ɤ is the interfacial free energy, ƿ is the density of the

saturated solution and Δμ is the chemical potential difference
between the new phase and the old phase..Examination of Figure 2
shows that till a critical size r* is reached, the Gibbs free energy
change increases, and then onwards ΔG decreases as a result of
which an aggregate with r > r* (i.e., a nucleus) can spontaneously
grow.
 However molecules can also leave the aggregate leading to
complete dissolution of the aggregate

 The surviving aggregates may not be similar, depending upon how

the molecules arrange themselves; they can be of different types,
which compete among themselves to grow in size and to give a
particular nucleus.
 The aggregate present in largest numbers will form the nucleus that
grows further to give a particular polymorph. It is this primary
crystallization process involving formation of critical nuclei which
gives rise to polymorphs.
 This is a general mechanism that explains the usual situation of
crystallization in which polymorphs are crystallized depending upon
the conditions prevailing. We have learned that “who (aggregates)
survives succeeds”.
 What are the factors that determine such a survival? There are many.
Molecular conformations, hydrogen bonding, packing arrangements
and lattice energies are a few to cite.
 But, in forming an aggregate which grows and to a nucleus then to a
specific polymorph, the role of intermolecular interactions is
paramount
Role of Intermolecular Interactions
 The intermolecular interactions like van der Waals interactions,
coulombic interactions, hydrogen bonding, and steric
repulsions play an important role in determining the
arrangement of molecules in a crystal.
 Even the cooperative action of very weak interactions like C-
H…O hydrogen bonding, π… π, X…X (X = halogen), and C-
H… π interactions can significantly contribute towards
stabilizing a specific molecular arrangement in a crystal.
 These weak interactions are strong enough to cause changes
in torsion angles, thereby giving different conformations and a
particular molecular conformation which is near the most
stable equilibrium conformation is often stabilized.
 As these interactions are weak and various molecular
conformations can have nearly the same energy, the
molecules can crystallize in different crystal forms.
 Molecules capable of possessing torsional degrees of freedom
give rise to different conformations that may be preserved in
different crystal forms.
 The existence of different conformations of the same molecule
in different polymorphic modifications is termed conformational
polymorphism. Among polymorphic modifications,
conformational polymorphs have the major share.
 Sometimes polymorphs crystallize simultaneously when
conformations are very close energetically and structurally,
and nucleation rates are of the same order of magnitude. If
two or more polymorphs crystallize under identical conditions,
then it is known as concomitant polymorphism.
 Although there is a plethora of examples of
conformational polymorphism, two of them, which
are shown here, are biologically active compounds. One
of the recent examples is ‘Eflucimibe’ a new acyl-
coenzyme A: Cholesterol O-acyl transferase (ACAT)
inhibitor drug.
 This drug crystallizes simultaneously in two polymorphic
forms A and B which differ by a conformational change of
the phenol group in the crystal lattice, that occurs through
a rotation of the bond connecting the amide nitrogen and
aromatic ring
Polymorphism in Elements and Inorganic
Materials
 Polymorphism in the case of elements is termed as ‘Allotropism’. The
simplest example, as discussed in the beginning, is that of carbon to
which the new entrants are fullerenes and carbon
nanotubes.
 Other examples include phosphorous (P4) in cubic (white),
monoclinic (purple) and orthorhombic (black) forms; Sb in
rhombohedral (grey), cubic (grey), hexagonal (metallic)
forms.
 Boron exists in different allotropes such as tetragonal, rhombohedral,
orthorhombic, monoclinic and hexagonal forms. A large number of
other elements like actinides and molecular elements exist in
polymorphic forms which interconvert with change of conditions like
temperature and pressure
 A typical example is that of uranium:

Uranium (U)orthorhombic →(U)tetragonal (941 K) → (U)bcc (1047 K).

 Polymorphism is also abundant in inorganic minerals that

are known by their common names e.g., ZnS is known in
forms referred to as wurtzite and sphalerite; CaCO3 as
calcite, aragonite and valerite; TiO2 is known as rutile,
brookite and anatase.
Polymorphism in Pharmaceutical Compounds
 Most drugs are formulated and marketed in crystalline form.
Many of the drug molecules are highly functionalized and can
self-organize in several ways in the solid state with nearly the
same lattice energies. Often solvent may be incorporated in
the crystal lattice. These features and the conformational
flexibility of molecules are the primary driving forces for the
existence of crystal polymorphism in active pharmaceutical
ingredients (APIs).
 This makes the study of polymorphism and crystallization of
pharmaceutical compounds highly important. Nowadays,
research on polymorphism and material properties of active
drug compounds and excipients (excipients are ingredients
included in a pharmaceutical preparation for the purpose of
improving its physical qualities) is an integral part of drug
development.
 The knowledge of solid-state properties in an early stage of drug
development helps to avoid manufacturing problems, to fine-tune the
performance of drugs and provides space for innovations
Drugs that were previously known to exist only in a single form are
now shown to have various polymorphic forms.

 This has perplexed pharmaceutical companies and now they have to

investigate crystal polymorphism in order to optimize the physical
properties of a pharmaceutical solid before the drug development
Paracetamol, also known as acetaminophen, is the most widely used
antipyretic (fever suppressant) and analgesic (pain killer) in the
world.
 Though the drug seems to be simple, it has been shown to exist in
two polymorphic forms. One is monoclinic Form-I (P21/n), which is
marketed whereas Form-II is orthorhombic (Pbca).

 Similarly, Famotidine which is an excellent histamine H2 receptor

antagonist is also found to exist in two different polymorphic forms,
metastable polymorph B and stable polymorph A. Piroxicam, a non-
steroidal, anti-inflammatory drug widely prescribed all over the world
exists in three forms I, II and III.
 The last example discussed here is of Norfloxacin. It is
the widely used synthetic broad spectrum antibacterial
fluoroquinolone for the treatment of prostate and urinary
tract infections.
 This drug exists in two anhydrous polymorphs (A and B),
an amorphous form and several hydrated forms. Of the
two anhydrous polymorphs, Form B is the most stable at
room temperature. But the commercial sample of
norfloxacin used is the Form A, which is metastable at
room temperature.
 All these examples clearly show that it is highly important
to make the required polymorphic form, as the other form
may not show the desired effects. Usually the form that is
most stable is preferred in market formulation as the
metastable form may transform to other stable forms.
 But it is a universally accepted rule that the metastable
form has higher solubility than the stable form and this
form converts into the stable form as a result of
spontaneous change but the reverse never happens.
 Thus, whenever possible, metastable forms having high
solubility that can survive for years without changing to
the stable form are selected for formulation.
 This means that, forms that have considerable activation
barrier in moving from metastable state to stable state
would be selected.
 That is, careful evaluation of both thermodynamic
parameters (tendency toward formation of more stable
polymorphs) and kinetic parameters (which lead to
formation of metastable polymorphs) is of high
importance in crystallization process of such
compounds.
 there remain two cases of polymorphism to be
considered:

 The first one is due to the possible rotation about single bonds in a
molecule leading to several possible conformations, thus called
conformational polymorphism.
 In the second type of polymorphism, the molecules possess quasi
the same conformation, but possess different intermolecular
interactions, leading to different arrangements between the
molecules.
 This is then called packing polymorphism. It should be noted at this
point that generally, polymorphs are numbered in the order of their
discovery
Some Practical Aspects of Relative Stabilities of
Polymorphs
 Knowledge of the enantiotropic or monotropic nature of the
relationship between polymorphs can be used to steer crystallization
processes to obtain a desired polymorph at the exclusion of an
undesired one. For a dimorphic system there are four possibilities:
 1) The thermodynamically stable form in a monotropic system: no
transformation can take place to another form, and no precautions
need be taken to preserve that form or to prevent a transformation.
 2) The thermodynamically stable form in an enantiotropic system:
precautions must be taken to maintain the thermodynamic conditions
(temperature, pressure, relative humidity, etc.) at which the G curve
for the desired polymorph is below that for the undesired one
 3) The thermodynamically metastable form in a monotropic system: a
kinetically controlled transformation may take place to the undesired
thermodynamically stable form.
 To prevent such a transformation it may be necessary to employ
drastic conditions to reduce kinetic effects (e.g. very low
temperatures, very dry conditions, storage in the dark).
 4) The thermodynamically metastable form in an enantiotropic
system: the information for obtaining and maintaining this form is
essentially found in the E/T diagram.
 Therefore, it is of practical importance (e.g. pre-formulation studies of
a drug substance) to determine whether a system of concomitant
polymorphs is monotropic or enantiotropic to enable the choice of
and control over the desired
Elements and inorganic compounds
 Generally, polymorphism in inorganic chemistry is often related
to different forms of the elements like the many forms of sulfur,
the different carbon structures, like diamond, graphite, or
fullerene or even the different phases a, b, c of a pure metal

 One of the first discoveries of ‘‘polymorphism’’ was in reality a

form of what is still called ‘‘allotropism’’ (coined from Greek
‘‘other’’ + ‘‘to turn’’ = other turn, other behavior).

 The allotropism concept was first used by one of the founding

fathers of modern chemistry, Berzelius in 1841.43 At this time,
the allotropy was used to define elements in their different
forms, e.g. for sulphur,44 silicon and carbon.
 Allotrope as the different forms of the same element in which the
chemical bonding, and hence the connectivity, between atoms of the
same element is different and may have different discrete molecular
units, irrespective of the state.

Non-metallic allotropes
 A systematic overview of the different types of inorganic allotropes
begins with the non-metallic allotropes and the various and well-
known forms of carbon.
 Carbon presents many allotropic forms

 Diamond
 Diamond is probably the most well known carbon allotrope. The
carbon atoms are arranged in a lattice, which is a variation of the
face-centered cubic crystal structure. It has superlative physical
qualities, most of which originate from the strong covalent bonding
between its atoms. Each carbon atom in a diamond is covalently
bonded to four other carbons in a tetrahedron.
 These tetrahedrons together form a three-dimensional network of six
membered carbon rings in the chair conformation, allowing for zero
bond-angle strain. This stable network of covalent bonds and
hexagonal rings is the reason that diamond is so incredibly strong as
a substance.
 As a result, diamond exhibits the highest hardness and thermal
conductivity of any bulk material. In addition, its rigid lattice prevents
contamination by many elements.
 The surface of diamond is lipophillic and hydrophobic, which means
it cannot get wet by water but can be in oil. Diamonds do not
generally react with any chemical reagents, including strong acids
and bases. Uses of diamond include cutting, drilling, and grinding;
jewelry; and in the semi-conductor industry.

 Graphite
 Graphite is another allotrope of carbon; unlike diamond, it is an
electrical conductor and a semi-metal. Graphite is the most stable
form of carbon under standard conditions and is used in
thermochemistry as the standard state for defining the heat of
formation of carbon compounds.
 There are three types of natural graphite:
 Crystalline flake graphite: isolated, flat, plate-like particles with
hexagonal edges
 Amorphous graphite: fine particles, the result of thermal
metamorphism of coal; sometimes called meta-anthracite
 Lump or vein graphite: occurs in fissure veins or fractures, appears
as growths of fibrous or acicular crystalline aggregates

 Graphite has a layered, planar structure. In each layer, the carbon

atoms are arranged in a hexagonal lattice with separation of 0.142
nm, and the distance between planes (layers) is 0.335 nm.
 The two known forms of graphite, alpha (hexagonal)
and beta (rhombohedral), have very similar physical properties
(except that the layers stack slightly differently). The hexagonal
graphite may be either flat or buckled.
 The alpha form can be converted to the beta form through
mechanical treatment, and the beta form reverts to the alpha form
when it is heated above 1300 °C.

 Graphite can conduct electricity due to the vast electron

delocalization within the carbon layers; as the electrons are free to
move, electricity moves through the plane of the layers.

 Graphite also has self-lubricating and dry lubricating properties.

Graphite has applications in prosthetic blood-containing materials
and heat-resistant materials as it can resist temperatures up to 3000
°C.
 A single layer of graphite is called graphene. This material displays
extraordinary electrical, thermal, and physical properties.
 It is an allotrope of carbon whose structure is a single planar sheet of
sp2 bonded carbon atoms that are densely packed in a honeycomb
crystal lattice.
 The carbon-carbon bond length in graphene is ~0.142 nm, and
these sheets stack to form graphite with an inter-planar spacing of
0.335 nm.
 Graphene is the basic structural element of carbon allotropes such
as graphite, charcoal, carbon nanotubes, and fullerenes. Graphene
is a semi-metal or zero-gap semiconductor, allowing it to display high
electron mobility at room temperature.

 Graphene is an exciting new class of material whose unique

properties make it the subject of ongoing research in many
laboratories.
Amorphous Carbon
 Amorphous carbon refers to carbon that does not have a crystalline
structure. Even though amorphous carbon can be manufactured, there
still exist some microscopic crystals of graphite-like or diamond-like
carbon.
 The properties of amorphous carbon depend on the ratio of sp2 to
sp3 hybridized bonds present in the material. Graphite consists purely
of sp2 hybridized bonds, whereas diamond consists purely of
sp3 hybridized bonds.
 Materials that are high in sp3 hybridized bonds are referred to as
tetrahedral amorphous carbon (owing to the tetrahedral shape formed
by sp3 hybridized bonds), or diamond-like carbon (owing to the
similarity of many of its physical properties to those of diamond).
 Fullerenes and Nanotubes

 Carbon nanomaterials make up another class of carbon

allotropes. Fullerenes (also called buckyballs) are
molecules of varying sizes composed entirely of carbon
that take on the form of hollow spheres, ellipsoids, or
tubes.
 Bucky balls and Bucky tubes have been the subject of
intense research, both because of their unique chemistry
and for their technological applications, especially in
materials science, electronics, and nanotechnology.
.
 Carbon nanotubes are cylindrical carbon molecules that
exhibit extraordinary strength and unique electrical
properties and are efficient conductors of heat.
 Carbon nanobuds are newly discovered allotropes in
which fullerene-like “buds” are covalently attached to the
outer side walls of a carbon nanotube. Nanobuds
therefore exhibit properties of both nanotubes and
fullerenes
 Glassy Carbon

 Glassy or vitreous carbon is a class of carbon widely used as an

electrode material in electrochemistry as well as in prosthetic devices
and high-temperature crucibles.

 Its most important properties are high temperature resistance,

hardness, low density, low electrical resistance, low friction, low
thermal resistance, extreme resistance to chemical attack, and
impermeability to gases and liquids.
 Other Allotropes

 Other allotropes of carbon include carbon nanofoam,

which is a low-density cluster assembly of carbon atoms
strung together in a loose three-dimensional web; pure
atomic and diatomic carbon; and linear acetylenic
carbon, which is a one-dimensional carbon polymer with
the structure -(C:::C)n-.
Metallic allotropes
 Usually, pure metals adopt one of three preferential
crystal lattices: body centered cubic (BCC), face centered
cubic (FCC) or hexagonal close packed (HCP).
 These three types of crystal lattices represent the
structures of 90% of the metallic elements under
standard conditions.
 This arises from the fact that most of the metals have a
coordination number of their atoms of 8 to 12 and that the
structures are built using the hard sphere model to best
fill space
 The BCC and FCC crystal structures belong to the cubic
crystal system whereas the HCP belongs to the hexagonal
system.
 In the FCC and HCP system, each metal atom is
surrounded by twelve other metal atoms whereas in the BCC
system, there are only eight neighbor atoms.
 The atom packing/density is larger in the two systems, FCC and
HCP (74%), than in the BCC one (68%).
 In terms of polymorphism,
related to atom connectivity, it
would thus be reasonable to
consider a transition between
FCC and HCP as polymorphic
transition, while the one
between BCC and FCC or HCP
is not.

 For example, in the case of the

iron, the transition between the
e-ferrite and the c-austenite is a
polymorphic transition but the
transition between c-austenite
and a-ferrite is not .
 These different crystal structures have a direct impact on the
metal properties.
 For example, lead (Pb) and gold (Au), which belong to the FCC
lattice, are plastic metals because of the presence of a lot of planes
along which rows of atoms can slide: the slip planes.
 In comparison, metals like titanium or cobalt, which possess an HCP
structure with less slip planes, are harder to deform. This property of
deformation of metals under stress is called the plasticity (ductility:
tensile stress and malleability: compressive stress).
 The metal crystal structure can however change depending on the
conditions, namely pressure and temperature .
 A good example of such metal phase transitions is iron (Fe). The iron
manufacturing and processing is an ancient knowledge that was
passed on through the centuries.
 Nowadays the production of iron and its derivatives is well
understood and controlled, using tools such as the phase diagram
and the transition temperature point.
 It is a very good case study for the allotropism of metals and alloys
and is also very important for the industry.
 Iron adopts two different packing types upon heating: BCC
(a-ferrite) at low temperature then FCC (c-ferrite) upon
heating, and back to a BCC system (d-ferrite) at even higher
temperature
 This BCC system of d-ferrite has a larger distance between the iron
atoms than the one of a-ferrite.
 Since the connectivity of the atoms in these two phases is the same,
they are considered as polymorphs
 Several important modifications of properties arise from these
allotropic/polymorphic transformations. For example, the cell volume
decreases, but the density, the number of bonds between atoms and
the solubility towards carbon increase from BCC to FCC.
 The carbon solubility is very low in the case of the BCC a-ferrite,
however in the FCC c-austenite, it is higher due to the larger
distance between the Fe atoms.
 Thus, the carbon can be more easily inserted into the host structure
of the FCC lattice. By a rapid quenching of the FCC structure, doped
with carbon, the BCT (body centered tetragonal) forms (a9-
martensite) can be obtained.
 The connectivity between atoms change between
the FCC and BCT lattice, thus, this transformation is
allotropic.
 The BCT, body centered tetragonal, lattice can be seen as a
deformed BCC lattice. This deformed BCC lattice of iron and carbon
is commonly called steel or martensite .
 This leads us to the subject of alloy formation, solid
solutions and, in particular, steel and its processing, into
which we will now make a short excursion.

 Alloys/solid solutions – hard as rock: the steel!. The steel and

iron industry is one of the pillars of the industrial development and
has a huge economic impact on our society since the
Middle Ages and even before. Its manufacturing process and
development are strongly correlated with the allotropic properties of
the iron and its capability to solvate carbon and many other metals
and additives.
 One of the most important examples of the use of the
properties of the iron-carbon alloy is the tempering.
 This ancient method is employed in forging to improve and fine tune
mechanical properties (hardness, toughness, ductility, …) out of a
mix of iron with low carbon content by rapid cooling (quenching) from
high temperature.
 By using this type of technique, carbon-containing austenite (c-Fe +
C) can be transformed into the metastable phase of carbon-
containing martensite (a9-Fe + C) which yields a very hard steel
 The allotropic transformations that occur inside the iron–
carbon alloy are related to the transition that we
described for the iron case. In addition, in the case of
theses alloys, two or more phases can coexist, for
example ferrite can coexist with Fe3C (cementite), and
are dependent on the total carbon content
 The transformations can happen following two different
ways:
 (i) Slow transformation, which is accompanied by
diffusion of atoms and the redistribution of carbon
between the phases, which leads to the formation of
several distinct phases. The thermodynamically more
stable phases are formed (slow heating/cooling).
 (ii) Rapid transformation, achieved by quick shear or
thermal stress mechanisms, which implies a collective
movement of atoms without redistribution of atoms
between phases, which is called displacive
transformation (super cooling).
 The metastable, kinetic phases can be obtained in this
way. This is in essence the principle of the
quenching/tempering .
 For the Fe–C solid alloy, it has been shown that allotropic
transitions have a strong impact on the final physical
properties of the material:
 several very important properties of steel depend directly
on these phenomena:
 solubility difference of carbon in the different phases of
iron
 crystal shape
 the morphology
 composition of grain
 the physical properties, for examples plasticity,
toughness or hardness depend on it
 The ‘Devil’s’ metal: the tin (Sn).
 It has been shown that the iron–carbon allotropism
allows to obtain a stronger material, the steel, with
tunable physical properties. now, the ‘‘negative’’
effects of allotropism on the properties of a metal will
be presented on behalf of tin.
 Tin has a historically interesting allotropism. It is
known from the antiquity and was mainly used in
bronze alloys (mix of Cu and Sn).
 It possesses several phases and undergoes allotropic transitions.
The so called tin pest is an allotropic transformation of white (BCT)
b-Sn to grey (FCC) a-Sn. The physical properties and the aspect of
the white and grey tin are totally different.
 The white tin is ductile, metallic with a silvery shine, while grey
tin is brittle, nonmetallic, darker, less smooth, and it tends to form
a powder
 This transition from white to grey tin occurs below 13.2 ̊C.
The kinetic of the transition is relatively slow but once nuclei of grey
a-Sn are already formed and contaminate the white b-Sn, the kinetic
of conversion becomes fast, as an autocatalytic process (within
several hours up to days for a total conversion depending on the
temperature).
 Even bronze (an alloy of Cu and Sn) can undergo a
similar process if prolonged storage at low temperature
occurs. This transition affects mainly the tin by increasing
its unit cell volume and decreasing its electronic
conductivity
 Some well-known stories relate the effect of this tin pest
on the human activities:
 In 1812, the tin buttons on the clothes of Napoleon’s
soldiers were attacked by tin disease and crumbled in the
harsh Russian winter of 1812. Napoleon was thus
unprepared for the Russian winter ‘‘right down to the
buttons’’.
 In 1850, Organ pipes made of tin in the old castle church
at Reitz crumbled into gray powder during the winter, one
of many such occurrences in cold northern European
Cathedrals.
 Before the chemical explanation was available, this was
sometimes attributed to the work of the devil.
 In 1912, Captain Robert Scott and his entire expedition to
the South Pole perished. This tragedy has been
attributed to an attack of tin disease. The kerosene for
the return journey was stored in cans soldered with tin.
The fuel escaped out of the cans resulting in the loss of
all the lives to the Antarctic cold.

 Even today, tin is still widely used, mainly for solder

purposes. In order to fix the allotropic transition problem,
some lead, bismuth and other heavy metals are now
added to form stable alloys.
 From this example, we can conclude that an allotropic
transition can cause important changes in properties like
ductility or conductivity of materials, e.g. changing a
conducting metal into an insulator.

 The transition in itself is in principle reversible but the

structural/mechanical damages on the material are not,
and integrity is completely lost as in the case of tin.
Ceramics and minerals: the ‘fake’ diamond

 Let us now turn towards binary compounds, for which also some
examples are chosen.
 Zirconia-based materials are used as a simulant of gems and
diamond, as electro ceramic, and also for dental implants
because of its biocompatibility and high fracture toughness.

Pure zirconia, ZrO2, however, undergoes a process of unit cell
expansion during its manufacturing process (sintering/heating).
 The ZrO2 crystal system changes from a monoclinic crystal
system at low temperature to a tetragonal one upon heating
and finally ends in a cubic system at high temperature

 This volume expansion causes internal stress

during the cooling process leading to cracks, fractures, and thus in
homogeneity in the material, which is therefore prone to major
failure.
 One solution found to prevent this was to add some yttria (yttrium
oxide) and/or other oxides to the zirconia in order to fill the voids in
the structure and stabilize the tetragonal metastable form or even the
cubic form with a high content of dopant (electro ceramics)

 By doing this, a polymorphic transformation can be turned into a

useful process.

 Thus, when cracks form in the metastable tetragonal material via an

external source, the induced local stress delivers energy to the
system and will trigger the polymorphic transition from the tetragonal
to the monoclinic system, causing a decrease of the unit cell volume
and an overall contraction of the material in the concerned stress
zone.
 Thus, the crack, an unwanted physical default, is
self-healed by the polymorphic transition and the corresponding
volume reduction of the material With the zirconia, the impact of
polymorphic transformations on the properties of a simple metal
oxide (ceramic) are given:
 In the following part, two examples of silicates polymorphism will be
presented: the olivine and the perovskite, which play a major role in
the geology and geodynamism of our planet .
 The olivine and derivatives (MgFe)2SiO4 and
MgSiO3:
 from the crust to the core Olivines and perovskites
represent the structure type of the most abundant
minerals on earth.
 Olivine polymorphs with the composition (Mg,Fe)2SiO4
are mainly found under the crust of the upper Earth’s
mantle, while the perovskite forms of composition
MgSiO3 can be found deeper in the lower mantle, down
to the boundaries of the outer core
 In the upper mantle, the polymorphic transitions of olivine
to more tightly packed structures can be summarized as
Fig.
 The first polymorphic
transformation of the a- to b-form
relates directly to one of the well-
known seismic discontinuities in
geology and geophysics at 410 km
of depth, corresponding to 13–14
GPa.
 The next transition from the b- to
the c-form occurs even deeper at
17–19 GPa. At 23–25 Gpa and
660 km depth, a new mineral,
perovskite, and oxide are formed
by the disproportionation of
Ringwoodite, the c-form Fig. of
olivine, under high pressure and
temperature, corresponding to
another major seismic discontinuity
 The perovskite possesses also a polymorphic form. It has
been proven that at even higher pressure near the
mantle-core boundary conditions, the perovskite
transforms into a new polymorph, the post-perovskite
(Fig).
 This post- perovskite has a strong influence on the third
big discontinuity in the earth’s mantle, the D99 layer, a
200 km thick layer of post-perovskite and iron doped
species
 These three discontinuities are considered as the main
sources of the seismic phenomena and are strongly
linked to the plate tectonic mechanism and also to
geomagnetism by thermal coupling between the core and
lower mantle.
Thank you