Polymorphism / Allotropy

• Many elements or compounds exist in more than one crystalline form under different conditions of
temperature and pressure. This phenomenon is termed polymorphism

• Polymorphism can potentially be found in any crystalline material including polymers, minerals, and
metals

• If the material is an elemental solid, the phenomenon is referred to as allotropy.

In terms of thermodynamics, there are two types of polymorphic behaviour.

• Enantiotropic

• Monotropic
 Polymorphism

• For an enantiotropic system, a plot of the free

energy against temperature shows a crossing
point threshold before the various melting
points.

• It may also be possible to revert interchangeably

between the two polymorphs by heating or
cooling, or through physical contact with a lower
energy polymorph.
 Polymorphism

For a monotropic system, plots of the free

energies of the various polymorphs
against temperature do not cross before
all polymorphs melt—

In other words, any transition from one

polymorph to another below melting
point will be irreversible.
 Polymorphism

Metal oxides Phase Conditions of P and T Structure/Space Group

Corundum-type Trigonal
α phase Ambient conditions
(R3c)
Al2O3
Cubic (Fd3m)
γ phase 773 K and 1 atm

Rutile Equilibrium phase Rutile-type Tetragonal

Anatase Metastable phase (Not stable) Tetragonal (I41/amd)
TiO2
Orthorhombic (Pcab)
Brookite Metastable phase (Not stable)

Monoclinic phase Ambient conditions Monoclinic (P21/c)

ZrO2 Tetragonal phase Above 1443 K Tetragonal (P42/nmc)
Fluorite-type phase Above 2643 K Cubic (Fm3m)
 Polytypism
• Polytypism is a special type of polymorphism wherein different polymorphs exist in different
domains of the same crystal.

• It has to do with the way that individual layers are stacked within a crystal structure.

• Polytypes have identical close-packed planes, but differ in the stacking sequence in the third
dimension perpendicular to these planes.

• Silicon carbide (SiC) has more than 170 known polytypes, although most are rare. All the polytypes
of SiC have virtually the same density and Gibbs free energy. The most common SiC polytypes are:
Phase Structure Ramsdell Notation Stacking Sequence Comment
α-SiC hexagonal 2H AB Wurtzite form
α-SiC hexagonal 4H ABCB
The most stable and
α-SiC hexagonal 6H ABCACB
common form
α-SiC rhombohedral 15R ABCACBCABACABCB
Sphalerite or zinc
β-SiC face-centered cubic 3C ABC
blende form

https://www.tf.uni-kiel.de/matwis/amat/semi_en/kap_a/basics/ba_1_1.html
 Polytypism

• A second group of materials with different polytypes are the transition metal
dichalcogenides, layered materials such as molybdenum disulfide (MoS2).

• For these materials the polytypes have more distinct effects on material properties,
e.g. for MoS2, the 1T polytype is metallic in character, while the 2H form is more
semiconducting.

• Another example is Tantalum disulfide, where the common 1T as well as 2H

polytypes occur, but also more complex 'mixed coordination' types such as 4Hb and
6R, where the trigonal prismatic and the octahedral geometry layers are mixed.

• Here, the 1T polytype exhibits a charge density wave, with distinct influence on the
conductivity as a function of temperature, while the 2H polytype exhibits
superconductivity.
 Allotropy of I ran

1800
1600
Melting, 1538 ac

1400 A4, 1394 ac

1200

·u 1000
�.,...,..,..,...,..,,,..,...,,..,..-r-r--r-r-7...,.-+- A 3 912 a C
1

800 A2, Curie Trans�ion, 770 ac

600

400

200
o�-----�
Structure changes in Fe

► aFe and 8Fe (both BCC) are known as ferrite

► yFe (FCC) is known as austenite
► Under high pressure (>10 GPa), HCP iron (cFe) can form
 Allotropy of Carbon

► Carbon can exist in many allotropic forms

► Graphite, Diamond, Fullerenes, Nanotubes, ...

Graphite
► Hexagonal graphite is the stable form at normal temperatures and pressures
► Other crystalline forms (polytypes) of graphite also exist (e. g. rhombohedral)

Carbon
atom Q r = 0.071nm

0.67nm

� 0.246nmI�
0.142nm
Layered structure of graphite and its hexagonal unit cell