Liquid Crystals: Crystals in Liquid Phase or Crystalline Liquid?

By Clare Teo and Tay Li Kim

You often come across liquid crystal displays (LCDs): the numbers displayed on a digital watch, the
High definition LCD televisions or even laptop. LCDs are very prevalent but they have only been around
for around thirty years. The Britannica Concise Encyclopedia defines a liquid crystal as a substance
that flows like a liquid but maintains some of the ordered structure characteristic of a crystal. Liquid
crystals constitute an interesting state of matter with properties intermediate between those of true
liquids and those of crystals. Unlike glasses, liquid-crystal states are thermodynamically stable.

Although this is a relatively rare phenomenon, hundreds of organic substances possess an

intermediate phase or even a succession of distinct phases. These are called mesophases or
mesomorphic phases, and the substances themselves are usually called liquid crystals.

A Brief History of Liquid Crystals

An experiment in 1888 by an Austrian botanist, Friedrich Reinitzer on cholesteryl benzoate crystals led
to the discovery of liquid crystals. When cholesteryl benzoate crystals were heated to 145.5oC,
Reinitzer observed that a viscous and cloudy liquid. However, on raising the temperature to 178.5oC,
the liquid became transparent. On cooling, the exact opposite transformation took place. These
changes were accompanied by an abrupt change in volume and by an absorption or emission of heat.
It was only in the later half of the 20th century that the first stable, room temperature liquid crystal was
made and there was no looking back.

Fredrich Reinitzer Cholesteryl benzoate

Applications of Liquid Crystals

Liquid crystals have many applications. They are used as displays in digital wristwatches, calculators,
and panel meters. They can be used to record, store, and display images which can be projected onto
a large screen. Direct and active-matrix liquid-crystal displays (LCDs) are used in several areas from
laptop computers to communication equipment such as television teleconferencing systems, portable
and high-definition television (HDTV), and video games.

Liquid crystals are used in panel displays

in laptops, television teleconferencing
systems, portable and high-definition
television (HDTV), and video games

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Liquid crystal thermography can be used as a safe and effective means for evaluation of complex pain
states associated with arthritis, soft tissue injuries and back-pain diseases. It facilitates identification of
the damage to the nervous system. In case of nerve injuries, a temperature increase is observed in the
area of the nerve distribution, which becomes colder during later stages of the injury. The technique
has proved useful in studying hemophilia, tumors of the extremities, arthritis and vascular conditions,
including the complications of diabetes.

Clinical thermography, otherwise known as infrared imaging, is based on

a careful analysis of skin surface temperatures as a reflection of normal
or abnormal human physiology. The procedure is commonly performed
either by the direct application of liquid crystal plates to a part of the body,
or via an ultra-sensitive medical infrared camera through a sophisticated
computer interface.

Thermochromic Liquid Crystals (TLC's) are highly sensitive materials that respond to temperature.
Liquid crystals change from black to a rainbow of colors and then back to black again upon heating.
Upon cooling the reverse color change occurs. They became popular with the well-known mood ring
and are now available in a wide variety of useful and exciting products.

Thermochromic Liquid Crystals (TLC's) respond to

temperature changes by changing colours from
black to a rainbow of colors and then back to black
again upon heating. Thus they became popular
with the well-known mood ring and key chains

There are some limitations to using liquid crystals. Unfortunately, liquid crystals are very difficult to
work with and require highly specialized printing and handling techniques. Liquid crystals are also
more expensive than other thermochromic inks. They are adversely effected by high temperatures,
ultra violet light, and strong solvents or chemicals.

Structure of liquid crystals

Molecules in condensed states of matter are packed closely together and thus they tend to align
themselves parallel to one another. This is what happens in liquid crystals due to specific
intermolecular interactions that favour this tendency. Thermal agitation opposes this, resulting in the
actual structure of liquid crystals being a delicate balance of the two effects. Hence the structure can
change with a variation of only a few degrees.

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In order for a molecule to display the characteristics of a liquid crystal, it must be rigid and rod-shaped.
This is accomplished by the interconnection of two rigid cyclic units. The interconnecting group should
cause the resulting compound to have a linear planar conformation. Linking units containing multiple
bonds such as -(CH=N)-, -N=N-, -(CH=CH)n-, -CH=N-N=CH-, etc. are used since they restrict the
freedom of rotation. These groups can conjugate with benzene rings, enhancing the anisotropic
(directionally dependent) polarisability. This increases the molecular length and maintains the rigidity.
An example is terephthal-bis-(4-n-butylaniline), called TBBA, whose molecular structure can be
represented as

When melting occurs, the orderly structure in a substance normally disappears at the melting point as
thermal motion of particles begins to predominate. When a mesophase exists, the orderliness only
partially disappears. Several intermediate structures are observed.

In the first type, the layers of molecules persist since the centers of the molecules tend to lie in layers.
However, these layers of molecules can slide over one another, thus the order between any two
successive layers is destroyed. Within each layer, these centers are distributed randomly as in an
ordinary liquid. This type of mesophase is described as smectic, derived from the Greek word meaning
‘soap’ because the consistency of these phases is reminiscent of that of a soft soap.

The second type of mesophase is called nematic where the degree of order here is less than that of
smectic phase. The molecules are no longer in arranged in layers but they display a preferred
orientation. The centers of the molecules are in completely random positions as do those of a normal
liquid.

Some substances pass from the crystalline state through the smectic phase to the normal isotropic
liquid state; others pass through the nematic phase instead. Other liquids follow the sequence
crystal→smectic→nematic→isotropic liquid. A variety of nematic liquid phase is known as cholesteric
where the molecules have a special property: chirality. This means that the molecules are asymmetrical
in such a way that they cannot be made to conincide with their image in a plane mirror by simple
movements like displacement or rotation. It is analogous to a right hand which can be considered as
the image of a left-hand but will not fit into a left-hand glove.

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In a sheet of perfectly oriented nematic phase, the molecules have their axes parallel to the walls of the
glass slides and thus have the same direction. However, in a cholesteric, the asymmetry of the
molecules causes those in one layer to make a small angle with those in the adjacent one. The process
is repeated from one layer to another, so that in the whole specimen, the molecules are turned through
an angle proportional to the distance from the solid surface. The structure is therefore helical and is
characterized by the distance between two layers that have the same direction, between which the
molecules have rotated through 180°.

Twist of the liquid crystal director. Chiral

liquid crystals spontaneously form twist in
the nematic phase and a precession of tilt
in the Smectic C phase.

The helical structure gives cholesterics very special optical properties-enormous optical rotatory power
which is several thousand degrees per millimeter or one hundred times greater than that of common
optically active solids and liquids. For a given angle of incidence, there is a wavelength which is
reflected much more than the others, so that when illuminated by white light, the sheet appeared
coloured. For instance, a sheet appears blue under grazing incidence but green or yellow when the
angle of incidence is closer to the normal. In addition, the colour that is observed depends on the
periodicity and hence on the temperature with which it therefore varies. The colour change is quite
appreciable with a variation of only 0.1°C.

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Operations of LCDs

Light coming from the right of the assembly is polarized by a

filter, it then passes through glass plates enclosing a liquid
crystal cell, a second polarizer rotated at 90 degrees, and
finally a color filter. Depending on the orientation of the liquid
crystal, more or less light can get through the pixel.

In summary, liquid crystals provide remarkable examples of the advances made in our knowledge of
the structure of matter only very recently, but achieved using relatively simple and well-known
experimental techniques. Due to its developed technological applications, liquid crystals have been
noted to be the phase of the future.

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Review Questions

1 Which of the following chemical compounds can form liquid crystals?

A B

C D

2 Which of the following is an example of a chiral molecule that occurs in the cholesteric phase?

A CH3CH(CH2CH3)CH3 B CH3C(CH3)2CH3

C CH3CH2CH(CH3)CH2CH2CH3 D CH3CH2CH(CH2CH3)CH2CH2CH3

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Reference
plc.cwru.edu/tutorial/enhanced/files/lc/apps/Apps.htm
www.colorchange.com/Liquid%20Crystal-APP.htm
www.pubmedcentral.nih.gov/
plc.cwru.edu/tutorial/enhanced/files/lc/chem/chem.htm
‘Principles of Modern Chemistry’ by Oxtoby & Machtrieb
‘The Structure of Matter’ by Andre Guinier

Ans : 1A 2C