Lquid Crystals

Liquid Crystals
Liquid crystals are compounds which show intermediate

characteristic between crystalline solid and isotropic liquid.
1
Liquid crystalline phases possess many properties correspond to liquid,
e.g., they can still flow like liquid and can coalesce to droplets.
On the other hand, they are similar to crystal as they exhibit anisotropy in
their optical, mechanical, electrical, and magnetic properties.
Materials that exhibit such unusual phases are often called mesogens
(i.e., they are mesogenic) and the various phases in which they could exist
are termed mesophases.
T
Crystalline solid Liquid crystal Isotropic liquid
2
Nematic Isotropic
The most technologically and commercially important class of LCs to date:

4-pentyl-4'-cyanobiphenyl (5CB) 3
The history of liquid crystals began in 1888 when an Austrian botanist,
Friedrich Reinitzer observed ‘double melting’ behaviour of cholesteryl
benzoate (Figure).
Cholesteryl benzoate melted into a cloudy liquid at 145.5oC; as the
temperature rose to 178.5oC, it suddenly became clear. He also observed
some unusual colour behaviour upon cooling; a pale blue colour appeared as
the clear liquid turned cloudy and followed by a bright blue-violet colour as
the cloudy liquid crystallized.
Figure: Cholesteryl benzoate

A German physicist, Otto Lehmann later made detailed observations using
polarizing optical microscope and named this state of matter as ‘liquid crystal’
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Classification of liquid crystals
1. Thermotropic LCs, whose mesophase formation is temperature
(T) dependent, and
2. Lyotropic LCs, whose mesophase formation is concentration and
solvent dependent.
Thermotropic liquid crystals:
Thermotropic transition occur in most liquid crystals, and they are
defined by the fact that the transitions to the liquid crystalline
state are induced thermally. That is, one can arrive at the liquid
crystalline state by raising the temperature of a solid and/or
lowering the temperature of a liquid.
➢ Low molar mass liquid crystals
➢ High molar mass liquid crystals
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Cholesteric
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(i) Low molecular mass calamitic liquid crystals can be classified
into three main phases which are nematic, cholesteric and
smectic.
Nematic phase
The nematic liquid crystal is the one with the least order and
highest symmetry with the most liquid-like structure in which one
or two molecular axes are oriented parallel to one another,
resulting in an orientational long range order.
For instance, an angular distribution of the long molecular axis
around a particular direction, the director n, while the molecules’
centers of mass are isotropically distributed in all three
dimensions.
The nematic liquid crystals exhibit marble like texture under
observation of polarized optical microscope (POM).
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Figure: Molecular arrangement and texture of nematic liquid crystal.
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Cholesteric phase
The cholesteric phase often known as the chiral nematic liquid
crystal which tends to align in a helical manner. This property
results from synthesis of cholesteric liquid crystal. It is obtained
through addition of chiral molecules to a nematic liquid crystal.
Some materials such as cholesterol ester are naturally chiral. The
phase occurs as a slowly twisted nematic phase which is rod –
shaped and in layered structure
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Smectic phase
Smectic liquid crystal possesses positional order which mean the
position of the molecules is correlated in some ordered pattern.
The occurrence of the phase is usually at the temperature below
the nematic phase. The term “smectic” is came from the Greek
word “soap”. There are many types of smectic phases which are
smectic A, smectic C, smectic C*(ferroelectrics). In each layered
structure of a smectic A liquid crystal, the molecules are in
random position, but directionally ordered with their long axis
normal to the plane of the layer. Under the observation of POM,
it exhibits focal-conic texture as shown in Figure.
The molecules of smectic C liquid crystal are in random position
within each layer. Formation of smectic C phase require
molecules that are either non-chiral or form a racemic mixture.
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Figure: Molecular
arrangement and
texture of smectic
liquid crystal
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Discotic
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(ii) High molar mass liquid crystals (i.e., liquid crystalline polymers)
(a) Main chain liquid crystalline polymers (MCLCPs)
(b) Side chain liquid crystalline polymers (SCLCPs)
Figure : Schematic representation of (a) MCLCPs and (b) SCLCPs.

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Melting
Crystallization
Glass Transition
Figure: DSC thermograms and

POM images of a SCLCP
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Structure-property relations
Figure: A general structural template for calamitic liquid crystals.

A and B are core units: aromatic (e.g., 1,4-phenyl, 2,6-naphthyl,
2,5-pyrimidinyl, etc.); alicyclic (e.g., trans-1,4-cyclohexyl);
heterocyclic (pyridine, thiophene, benzoxazole and benzothiazole).
To maintain linearity and polarizability anisotropy of the core, the
rings can be directly linked or may be joined by a linking group Y,
which can be stilbene (-CH=CH-), ester (-COO-), imine (-CH=N-), azo
(-N=N-) and acetylene (-CC-) groups.
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The rigid cores themselves are usually not sufficient to generate liquid
crystal phases.
Flexible terminal groups (R1 and R2) are often introduced to the rigid
cores directly or through linking groups X and Z in order to lower the
melting point and stabilize the molecular alignment in the liquid
crystal phase.
Alkyl (CnH2n+1) or alkoxy (CnH2n+1O) chains are the most frequently used
terminal groups.
Both flexibility and rigidity must be in balance in order to exhibit LC
properties.
M and N are small lateral substituents (e.g., -F, -Cl, -CH3, -CN, etc.) that
are often used to modify the mesophase type and physical properties.
Lateral substituents can disrupt the molecular packing, yet are often
advantageous for the formation of liquid crystal phases
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Lyotropic LCs
Lyotropic LCs are two-component systems where an amphiphile is
dissolved in a solvent. In blends of different components phase
transitions may also depend on concentration and these liquid
crystals are called lyotropic. Thus, lyotropic mesophases are
concentration and solvent dependent. The amphiphilic compounds
are characterized by two distinct moieties, a hydrophilic polar
"head" and a hydrophobic "tail". Examples of these kinds of
molecules are soaps (Figure a) and various phospholipids like those
present in cell membranes (Figure b).
In the recent years, Lyotropic liquid crystalline materials have been
widely used as display devices and lyotropics are also important for
biological systems, e.g. membranes.
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Figure: Chemical structure and cartoon representation of (a) sodium
dodecylsulfate (soap) forming micelles, and (b) a phospholipids
(lecitine), present in cell membranes, in a bilayer lyotropic liquid
crystal arrangement. 21
Applications of LCs and SCLCPs
LC materials :
Watches, clocks, stereos, calculators, personal organizers, laptop
computers, portable notebooks computers, vehicle clocks,
speedometers, navigation and positional aids, mobile phones, flat
desktop monitors, wave plates, polarizers, notch filters, medical
displays, spectrometers, chemical and biological sensors, actuators
and so on.
SCLCPs:
High-tensile strength fibers, self-strengthened materials,
optoelectronic materials, reversible data storage devices,
elastomeric products, thermal or barometric sensors,
chromatographic separations, solid polymer electrolytes, separation
membranes, display materials and so forth.
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Liquid Crystals

Liquid crystals are compounds which show intermediate

The most technologically and commercially important class of LCs to date:

Figure: Cholesteryl benzoate

Figure : Schematic representation of (a) MCLCPs and (b) SCLCPs.

Figure: DSC thermograms and

Figure: A general structural template for calamitic liquid crystals.

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