Chapter 2

Brief Review of Liquid Crystals

Abstract Examined and summarized the types of liquid crystals. Analyzed

structural characteristics of smectic, nematic and cholesteric liquid crystals. It is
noted that cholesteric liquid crystals are helically twisted structure, the pitch of the
helix which is temperature dependent and individual chemical properties of
liquid-crystalline compounds of cholesterol. Results on the influence of temperature
on rheological properties of cholesteric liquid crystals are presents.

This chapter describes briefly main ideas of liquid crystals, their structure and
properties. Such approach seems reasonable since it does not require searching
corresponding publications.

2.1 Liquid-Crystal State of Matter and Kinds

of Liquid Crystals

There are three phase states of the matter, namely crystalline, liquid, and gaseous. In
each of them a given substance has certain characteristics typical only for this
substance. For crystalline substances these characteristics are the temperature and
heat of melting, for liquids—the boiling temperature and the heat of vaporization.
These and other characteristics of substances in different phase states are used to
identify them.

2.1.1 History of Liquid Crystal Discovery

At the end of the 19th century Austrian scientist Fridrich Reinitzer from the Institute
of Plant Physiology studied two substances extracted from carrot, namely
light-colored hydrocarotin and dark-red carotin. He knew from publications that
hydrocarotin was similar to cholesterol; at least they had like compositions and
chemical properties. However, Reinitzer did not decide to consider hydrocarotin as

© Springer International Publishing Switzerland 2016 37

S. Ermakov et al., Liquid Crystals in Biotribology,
Biological and Medical Physics, Biomedical Engineering,
DOI 10.1007/978-3-319-20349-2_2
38 2 Brief Review of Liquid Crystals

pure cholesterol without a thorough study of its chemical and physical properties.
Most probably, hydrocarotin was a mixture of cholesterol compounds or one of
cholesterol derivatives, as Reinitzer believed. To clarify the situation, he decided to
study some pure cholesterol derivatives especially as their physical and chemical
properties were studied poorly. Moreover, the chemical formula of cholesterol had
not been determined certainly. Reinitzer hoped to solve this problem at the same
time. If all or almost all would be known about cholesterol it would be easier to
identify components extracted from hydrocarotin at least by comparison.
This work took one and a half year. Reinitzer used industrial cholesterol. He
refined it thoroughly and determined its physical and chemical properties. Using
element analysis methods he derived the precise chemical formula of cholesterol—
C27H46O.
This result was a great achievement in the chemistry of natural substances.
Reinitzer also described in detail cholesterol derivatives. In addition to cholesterol
acetate and bromeacetate, he synthesized and studied nitrocholesterol and choles-
terolbenzoate. Two esters, namely cholesterolacetate and cholesterolbenzoate, were
of special interest.
Both substances in the solid phase are white fine-crystalline powders. When
Reinitzer determined the melting temperature by melting in glass capillaries he saw
that they became colored. At that time nobody understood that strange fact of
coloring of colorless compounds in melting. Reinitzer described the coloring of
cholesterolacetate as follows: “When cooling melted cholesterolacetate one is
surprised by very nice color appeared before cholesterolacetate thickens. This
phenomenon is seen in long capillaries used to determine the melting temperature,
yet it is better if the substance is melted between a table and cover glasses. In
reflected light bright emerald color appears in some areas which is rapidly spread
over the whole specimen bulk and then transforms to blue-green, in places to
dark-blue, then to yellow-green, orange, red, and, finally, dark-red”.
Cholesterolbenzoate demonstrated slightly different behavior: two colored areas
appeared in it, one of them was one-color and the other—multicolor just as in case
of cholesterolacetate. It appeared at lower temperatures. No such effect was
observed up that time.
Another interesting phenomenon also was not observed. Reinitzer found two
melting points of cholesterolbenzoate.
Many chemists, Reinitzer’s contemporaries, studied cholesterol derivatives
encountered serious difficulties when determining their melting points. The
researchers failed to determine the melting point of cholesterol derivatives and
established the presence of an amorphous, tar-like phase. Reinitzer observed just
this amorphous tar-like phase appearing in cholesterolbenzoate melting. But unlike
his colleagues, Reinitzer studied it more thoroughly. He managed to find that at a
temperature of 145.5 °C the white fine cholesterolbenzoate powder transformed into
a turbid, hardly transparent liquid. Initially he attributed turbidity to the presence of
impurities but additional studies shown no impurities. As cholesterolbenzoate was
heated further, the turbidity disappeared suddenly. This occurred at 178.5 °C.
2.1 Liquid-Crystal State of Matter and Kinds of Liquid Crystals 39

Reinitzer was first who found that a new turbid phase appeared between the solid
phase and the usual melt in cholesterolbenzoate melting. The color of that phase
depended on the temperature and vanished in transition to the usual melt but
sometimes it remained in the solid phase if the latter was rapidly overcooled.
Reinitzer was not only a chemist, he was also proficient in technical microscopy.
For this reason he used an opportunity to examine the colored phase with common
and polarizing microscopes. He observed a very interesting phenomenon. The
turbid phase appeared from the transparent melt as drops with jagged edges seen at
a great magnification. This gave Reinitzer cause to call the drops star-like aggre-
gates. In further cooling of the substance the star-like aggregates expanded and a
multiphase system formed. Brooklets of a liquid flew over a brightly colored
background and played. Reinitzer called them “oily grooves”.
The oily groves became transparent if the polarizers were crossed, i.e. they
shown marked double refraction. The colored background rotated the light polar-
ization plane. In other words, it possessed optical activity. The rotation angle of the
polarization plane was very high and depended on the light wavelength.
All these facts arrived Reinitzer to a conclusion that in case of cholesterolacetate
and cholesterolbenzoate he dealt with a rare variety of physical isomerism when
several substances of the same chemical composition had different structures and
physical properties.
Reinitzer attempted to separate these two isomers but he failed. Then he decided
to send the substances to Professor Otto Leman being a famous researcher in
physical methods of crystal study. He was a skilful experimenter got excellent
training in experimental physics and crystallography at the Strasbourg University
and examined the growth and solution of crystals with a polarizing microscope.
The samples were sent on March 14, 1888. At that time Leman studied unusual
mechanical properties of silver iodide. At temperatures above 146 °C this cubic
crystal did not cleave and crumble to small pieces in compression. It changed its
shape easily like melted sealing-wax or rosin. It could be rolled into a thin sheet by
the slight touch of a common needle.
Such behavior of silver iodide crystals was beyond concepts of those days. The
ductility of metals was explained by their polycrystalline structure but in that case a
monocrystal was considered whose lattice could not deform so greatly, as it was
believed.
Attempting to answer the questions arisen Leman received the samples from
Reinitzer. The study of properties of the substances sharpened still more the issues of
a high ductility of the compounds showing the crystal-like behavior. The thorough
investigation of cholesterolbenzoate properties with exchange of opinions con-
cerning different aspects of the problem with Reinitzer and other specialists and the
discovery of some nitrooxyphenol esters by Hatterman with properties similar to
those of cholesterolbenzoate gave rise to new ideas on the behavior of crystals. Their
essence was expressed in the Leman’s letter to Reinitzer: “Physicists always show
great interest to the fact that there are crystals whose ductility allows one to call them
liquid crystals”. However, Leman avoided using this term in his papers. He gingerly
called cholesterol compounds fluid crystals and nitrooxide compounds—drop-liquid
40 2 Brief Review of Liquid Crystals

crystals. The latter definition resulted from the fact that these compounds had a less
viscosity and were shaped as spherical drops in mixtures with fluids.
Analyzing the situation with silver iodide, cholesterolbenzoate, and nitrooxide
compounds Leman supposed that if such ductile crystals as silver iodide existed
which hardly retained their weight why crystals totally incapable of retaining their
shape should not exist? They will run into a fluid while their physical properties
should be anisotropic like those of other crystals and they should grow from
oversaturated solutions. Cholesterolbenzoate was undoubtedly one of such liquid
crystals.
That reasoning of Leman resulted in the discovery of liquid crystals. Solid
crystals having a right spatial arrangement and totally disordered isotropic liquids
were bridged by viscous-fluid and absolutely liquid drop-fluid crystals. Leman
believed that the solid crystals retained well their weight that caused their poly-
hedral shapes. Liquid crystals of silver iodide, cholesterolacetate, and cholester-
olbenzoate hardly retained their weight and for this reason sometimes they had a
polyhedral shape while smoothed and deformed. Finally, drop-fluid crystals of
nitrooxide compounds were absolutely incapable of retaining their weight and their
equilibrium shape was a spherical drop.
This Leman’s understanding formed finally in 1890.
Leman really considered both liquid and drop-fluid crystals as crystals while
realizing clearly that these substances differed from solid crystals in their structure.
Anisotropy and homogeneity are the main attributes of real crystals. Anisotropy is
the dependence of crystal properties on the direction. It results in optical anisotropy
appearing as double refraction. Homogeneity implies equal properties along parallel
directions. It causes a geometrically right, periodical arrangement of particles
making up the crystal, i.e. the existence of a lattice.
Liquid crystals are anisotropic but their fluidity is incompatible with the exis-
tence of the lattice. For this reason Leman supposed that those phenomena
(anisotropy and fluidity) could be explained satisfactory if the right spatial
arrangement of molecules was considered as a minor factor, as a mode of stacking
implemented only in slow crystallization. This stacking mode can be disordered by
an enough high deforming force but this does not affect the nature of crystal.
According to Leman, the essence of crystal is the anisotropy resulted from the
anisotropy of molecules themselves. Leman wrote: “The proper anisotropy of
molecules which produces indirectly the right structure of a body is an essential and
main attribute of crystal rather than the right arrangement of the molecules in the
right system of points”.
Another equally important feature of crystal is its ability to grow in oversaturated
solutions. As Leman noted, both non-deformed and deformed (without a lattice)
crystals grow with the same rates while amorphous bodies do not grow.
Afterwards this view of Leman arrived him to some erroneous conclusions
which luckily did not influence scientific progress but hampered the recognition of
liquid crystals.
Reinitzer’s and Leman’s results introduced new, revolutionary ideas in science
which encountered a suspicious reaction of most physicists and chemists rather than
2.1 Liquid-Crystal State of Matter and Kinds of Liquid Crystals 41

made a sensation in the scientific community. The discovery of liquid crystals

followed by a long period of their study and recognition.
This is a brief history of the discovery of liquid crystals. The development of
liquid crystal research is described in more detail in book [1] specially devoted to
this problem.
It took more than two decades to recognize the existence of the liquid-crystal
state of the matter. This is not surprising since, according to the understanding of
many physicists and chemists of the beginning of the 20th century, the phrase
“liquid crystals” was nonsensical. This is Leman’s blame. It was he who proposed
the expression “liquid crystal” unfortunate at that time.
Afterwards French physicist Fridel corrected Leman’s mistake and proposed the
term “mesomorphous state” as a synonym of the term “liquid-crystal state” formed
from the Greek word “mezos” meaning intermediate. Indeed, the liquid-crystal state
is the fourth phase state of the matter and takes an intermediate position between the
crystalline and liquid states.

2.1.2 Classes of Liquid Crystals

At present thermotropic and liotropic liquid crystals are distinguished. The class of
thermotropic liquid crystals is formed by the substances which transit to the
liquid-crystal state with elevating temperature. In this case the following phase
transitions are considered: solid–liquid crystal–isotropic liquid. They are phase
transitions of the first kind and can be successfully registered by the differential
thermometry method (Fig. 2.1). When the isotropic liquid is cooled down the phase
transitions are repeated in the reverse sequence.
The temperature of the transition solid–liquid crystal is called the melting tem-
perature Tm. The temperature of the transition liquid crystal–isotropic liquid is called
the elucidation temperature Te. The term results from the fact that many crystals in
the mesophase are turbid liquids scattering light considerably. The scattering dis-
appears and the melt becomes transparent in transition to the isotropic liquid.
Liotropic liquid crystals are the substances which form the liquid-crystal phase
when dissolving them in water or other solvents. As a rule, the phase appears within
a strictly certain range of the concentration of the substance being dissolved in the
solvent. Potassium n-alconate soap is a typical example of liotropic liquid crystals.
Nowadays liotropic liquid crystals are very attractive for researchers. This is due to
the fact that liotropic liquid-crystal phases are typical for more materials than
thermotropic ones and to a great role of liotropic liquid crystals in biology. Note
that myosin being an albumen contained in the contracting substance of the mus-
cular tissue, desoxyribose nucleic acid playing a leading role in the transfer of
heritable data, many polypeptides, ferments and other substances of biological
origin are capable of forming the liotropic liquid-crystal phase [2, 3]. It is also found
that liquid crystals are of great importance in metabolic processes in living
organisms.
42 2 Brief Review of Liquid Crystals

Θ, rel. units

8 78,2 C

64,0 C
exo
heating
6

4 cooling
83,4 C
endo

75,2 C

0 20 40 60 80 100 120 t, min

Fig. 2.1 Phase transition temperatures of cholesterolpelargonate

Like solid crystals, liquid crystals show the anisotropy of properties which is
always closely related to the anisotropy of the matter structure [4]. Apparently,
proceeding from this fact German chemist Vorlender supposed that liquid crystals
were formed mainly from the organic compounds whose molecules had an elon-
gated cigar-like shape, i.e. shown the anisotropy of the structure. His predictions
had come true. It should be noted that earlier Leman assumed the structure of
molecules of liquid-crystal substances to be anisotropic.
It is found that the substances with flat disc-shaped molecules also form the
liquid-crystal phase. Such substances are called discotic liquid crystals or discotics.
Elongated cigar-shaped molecules of the liquid crystal are always in thermal
motion. The direction of their major axes continuously changes relatively to a
certain direction. To mark the direction of predominant orientation the unit vector
n is used which is called “director”. The director characterizes phenomenologically
the long-range order of molecules.
Because of the thermodynamic least free energy principle the elongated or
disc-shaped structure of liquid crystal molecules a certain arrangement of the
molecules appears in the mesophase. The pattern of the arrangement is governed by
both the structure of the liquid crystal molecules and thermodynamic conditions.

2.2 Classification and Structure of Liquid Crystals

The classification of liquid crystals was proposed by French physicist Fridel in the
beginning of the 19th century and is based on molecular arrangement. Like Reinitzer
and Leman, he examined microscopically thin layers of liquid crystals formed on a
table glass in melting. He found that irrespective of the chemical structure of the
2.2 Classification and Structure of Liquid Crystals 43

compounds liquid crystals formed a limited number of kinds of optical pictures. Fridel
related the kind of the optical picture observed with the arrangement of molecules in
the samples and proposed the classification of liquid crystals on this basis.
He divided liquid crystals into smectic (from the Greek word “smegma” meaning
soap) and nematic (from the Greek word “nema” meaning thread) crystals. Nematic
liquid crystals are divided into properly nematic and cholesteric crystals. Two
following facts resulted in such division. The first fact was that no mesogens were
found passing consecutively the nematic and cholesteric mesophases. The second
fact was that it was possible to transform a properly nematic liquid crystal into a
cholesteric one and vice versa by external effects such as mechanical deformation,
electric and magnetic fields.
In smectic liquid crystals molecules are arranged so that their major axes are
parallel and their centers of mass lie in one plane. Major axes of the smectic
molecules or the director n form an angle β with the normal to this plane (Fig. 2.2).
The location of the centers of mass of the molecules results in the formation of
smectic layers. It is apparently that the thickness of the layers depends on the molecule
length and the angle between the director n and the location plane of the centers of mass.
By the pattern of arrangement in the layers smectic liquid crystals are divided
into two groups: with structured and non-structured layers. In smectic crystals with
structured layers the centers of mass of the molecules form a two-dimensional
lattice in the layer. The director can be oriented relatively to the layer both normally
(Fig. 2.2a, b) and at an angle (Fig. 2.2c, d). Smectic crystals with structured layers
are ordered better than crystals with non-structured layers. In smectic crystals of
both groups the mutual slip of layers can occur and in most cases the rotation of
molecules about their major axes is possible.
In non-structured layers molecules of the smectic crystal are distributed chaot-
ically (Fig. 2.2a, c). This group consists of several subgroups of smectic crystals
which differ in the angle of director orientation relatively to the normal to the layer.

Fig. 2.2 Structure diagram of (a) (c)

smectic liquid crystals with
non-structured (a) and
structured (b) layers n β

(b) (d)

n β

n
44 2 Brief Review of Liquid Crystals

Smectic crystals for which β = 0 (Fig. 2.2a) belong to the first subgroup. Therefore,
in these crystals major axes of the molecules are perpendicular to smectic layers. Such
crystals are commonly called smectics A. They are most widespread among smectic
crystals.
The second subgroup consists of non-structured smectic crystals for which β ≠ 0.
They are called smectics C (Fig. 2.2c). Among them are smectics C with a small
(β < 30°) and great (β ≈ 45°) angle between the director and the normal to the layer.
With elevating temperature smectics C with the small slope angle transform into
smectics A. However, the smectics C are known for which the angle β depends on
the temperature within a certain temperature range and can decrease down to zero
while other smectics with the small slope angle show no temperature dependence of
the slope angle β.
Smectics C with the great angle β do not transform into smectics A and their
angle β is independent of the temperature.
If molecules of the smectic substance are chiral, i.e. twisted about their major
axes, the twisted smectic mesophase C* is formed (Fig. 2.3).
In such smectics the director rotates along the taper generatrix when passing
from one layer to another.

Fig. 2.3 Smectic C*

mesophase
2.2 Classification and Structure of Liquid Crystals 45

In smectics B centers of mass of molecules in layers are located at points of the

hexagonal lattice and the director is perpendicular to layers (Fig. 2.4).
A similar location of centers of mass is typical for smectics H but the director n is
inclined to layers (Fig. 2.5).
If the smectic H forms a compound with chiral molecules the quasi-hexagonal
arrangement remains but when passing from layer to layer the director rotates along
the taper generatrix as in case of the smectic C*. This smectic is called smectic H*.
The quasi-hexagonal arrangement of centers of mass of molecules in layers is
also typical for smectics E but unlike other smectics with structured layers the
rotation of the molecules about their major axes is hampered. As the director is
perpendicular to the layers, rhombic arrangement occurs (Fig. 2.6).
In smectics G the arrangement of centers of mass of molecules and the ham-
pering of rotation about major axes are the same as in smectics E but the director is
inclined to the layer plane (Fig. 2.7).
Smectics D have the cubic body-centered structure (Fig. 2.8).
It consists of structure units containing many molecules; they are called micelles
(from the Greek word mica meaning grain). In nematic liquid crystals molecules are
parallel to each other and their centers of mass are arranged chaotically unlike
smectic crystals (Fig. 2.9).

Fig. 2.4 Smectic

B mesophase

Fig. 2.5 Smectic

H mesophase
46 2 Brief Review of Liquid Crystals

Fig. 2.6 Smectic

E mesophase

Fig. 2.7 Smectic

G mesophase

Fig. 2.8 Smectic

D mesophase

Fig. 2.9 Structure diagram of

nematic liquid crystal
2.2 Classification and Structure of Liquid Crystals 47

In this case layers typical for smectics are not formed and long-range order exists
only in respect to the orientation of major axes of the nematic crystal.
Cholesteric liquid crystals are formed by cholesterol derivatives (esters), yet they
may contain substances of other classes.
Cholesteric liquid crystals typically consist of molecular layers; each of them
demonstrates the molecular arrangement specific for nematics when centers of mass
lie in the molecular plane chaotically. The director also lies in the layer plane [5]. The
thickness of the molecular layer called also a quasi-nematic layer [6] is 0.5–0.6 nm.
In transition from one molecular layer to another the director rotates by a small angle
relatively to the director of the underlying layer. This angular shift accumulates in
the sequence of the layers and, generally, ends of the molecules or the director end
move along a spiral (Fig. 2.10). Apparently, the lead P of the spiral is

2p
P¼ d ð2:1Þ
a

where α is the shift (twist) angle of the director in transition from layer to layer; d is
the thickness of the molecular layer of the cholesteric crystal.
According to the results reported in [7], the angular shift of the director in
transition from layer to layer in cholesteric crystals is 15 angular minutes on the
average. Other authors give the value of about 0.5° [8]. Further thorough studies
have shown that the twist angle α depends on both the temperature and the
molecular structure of the cholesteric liquid crystal as well as some other factors
[9–11].
Taking α = 0.5° and d = 0.6 nm we obtain that the lead of the cholesteric spiral is
400 nm.
It is apparently that in the molecular layers corresponding to the director twist
angles of 0°, π, and 2π the major axes of liquid crystal molecules have the same
orientation (Fig. 2.10) that makes the layers indistinguishable. Then the distance
S = P/2 is the period of the specific lattice of the cholesteric liquid crystal. It is easy
to note that in cholesteric crystals the molecular orientation is repeated at a distance
equal to the period S. However, the molecules can move freely and exchange their
positions in each molecular layer but their spiral arrangement with the period
S remains unchanged.

P = 2S 400 nm

Fig. 2.10 Structure diagram of cholesteric liquid crystal

48 2 Brief Review of Liquid Crystals

Macrolayers consisting of many molecular or quasi-nematic layers in which the

spiral arrangement is retained along the certain direction at a distance of one or
more lattice periods are called monocrystal layers of cholesteric liquid crystals
(Fig. 2.11). Such layers can be formed between bearing surfaces.
We presented in general outline the classification of liquid crystals. Apparently,
it is far from the total scientific classification whose main attribute is predictability.
The presented classification does not possess predictability and is mainly of the
descriptive character. Therefore, often it may occur that newly synthesized liquid
crystals show mesophases which can not be classified according to this scheme.
Such mesophases are called exotic. Future studies will allow researchers to refer
many of them to the already known kinds and groups. Yet, the possibility of
appearing new arrangement modes among exotic mesophases can not be ruled out.
This substance forms the discotic mesophase within the temperature range
81.2–87 °C. One of these new arrangement modes has been found recently. It
appears in the so-called disc-shape crystals or discotics (Fig. 2.12). Their molecules
have the symmetric branched formula which can be approximated by a flat disc. For
example, benzol-hexa-n-heptanoate contains such molecules.
Discotics demonstrate the layered molecular arrangement like smectic crystals
[3, 12]. Their molecules lie in the layer planes forming close hexagonal packing
shown in Fig. 2.13.
The classification presented above shows that though some liquid crystals have
the solely mesophase typical only for the given crystal in many liquid crystals

Fig. 2.11 Monocrystal layers of cholesteric liquid crystal between bearing surfaces

Fig. 2.12 The molecule of C7H15

disc-shape crystals H15C 7 O
C
C O O
O O C7H15
O C
C O
H15C7 O O
O O C
C
O C7H15
C7H15
2.2 Classification and Structure of Liquid Crystals 49

Fig. 2.13 Discotic mesophase

N N
N N N A
A A N N Ch N A A
G A N Ch A G A G
C B B A A G G G
B B C B
B B

Fig. 2.14 Some cases of polymesomorphism of liquid crystals: I isotropic fluid, S solid crystal,
N nematic, A, B, C, and G corresponding smectics, Ch cholesteric

different phase transformations occur with varying temperature and several meso-
phases change consecutively. As experiments have shown, there are certain regu-
larities of changing mesophases. Figure 2.14 illustrates some cases of the
polymesomorphism of liquid crystals known presently.
It is seen in the figure that in transition from the solid crystal to isotropic liquid
through different mesophases a sequence of the mesophases occurs with decreasing
ordering degree: the smectic, cholesteric, and nematic mesophases.
The same regularity is typical for the smectic mesophase. If the solid crystal
melts initially the smectic crystals appear with structured layers and only at higher
temperatures the smectics with non-structured layers are formed.
The smectic C always exists at lower temperatures than the smectic A. As for
polymesomorphism with the mesophase G, Fig. 2.14 shows that it behaves like the
mesophase C and often precedes the mesophase B with decreasing temperature.
50 2 Brief Review of Liquid Crystals

2.3 Properties of Liquid Crystals

2.3.1 Optical and Electrical Properties of Liquid Crystals

An original molecular architecture of monocrystalline layers of cholesteric crystals

causes some specific optical properties. First of all, this is optical activity, i.e. the
ability of the crystals to rotate the polarization plane of linearly polarized light
passing the crystal layer. Alpha-quartz crystals considered quite optically active
rotate the polarization plane of light by approximately 20° per one millimeter of the
crystal thickness while the cholesteric monocrystalline layer of the same thickness
rotates the polarization plane by an angle of about 18,000° [7]. Such gross optical
activity is typical only for cholesteric liquid crystals. Nematic and smectic crystals
do not possess optical activity.
However, one can give the structure of the cholesteric to the nematic by twisting
it between the bearing surfaces. Additives of cholesteric liquid crystals to nematics
result in the formation of the cholesteric structure.
Circular dichroism is another typically crystal property of cholesteric liquid
crystals. It causes the division of natural white light into two components by the
cholesteric crystal. The electric vector of one of the components rotates clockwise
and that of the other component rotates counter-clockwise. Depending of the
structure of liquid crystal molecules one of the components passes the crystal while
another component reflects from it causing the certain color of the cholesteric
substance. This phenomenon is called the selective reflection of light and results
from changes in the spiral lead of cholesterics with varying temperature. It should
be noted that the selective reflection of light governs the action of liquid-crystal
thermoindicating films applied in medicine, engineering and life, for example, in
liquid-crystal room thermometers [13, 14]. The systematic description of optical
properties of cholesteric liquid crystals is presented in monograph [15].
Like cholesteric liquid crystals, nematic and smectic crystals possess double
refraction. However, it occurs at a certain orientation of the director relatively to the
light propagation direction.
Double refraction proves the anisotropy of the refractive index that is caused by
the anisotropy of the permittivity of liquid crystals. There are refractive indices of
the light polarized along (n||) and perpendicularly to (n⊥) the director. Similarly,
there are permittivities for the orientation of the director along (ε||) and perpen-
dicularly to (ε⊥) the electric field direction. The difference Δε = ε||−ε⊥ is called the
dielectric anisotropy of the liquid crystal. It can be both positive and negative. The
dielectric anisotropy results from the anisotropy of liquid crystal molecules, their
structure, and the nature of atoms contained in the molecules.
Liquid crystals also possess the anisotropy of magnetic properties. The differ-
ence of the diamagnetic susceptibilities measured along major axes (χ||) of liquid
crystal molecules and perpendicularly to the axes (χ⊥) is called the anisotropy of the
diamagnetic susceptibility (Δχ). It can be both positive and negative. For nematic
2.3 Properties of Liquid Crystals 51

and smectic crystals Δχ > 0 and for pure cholesterol ethers Δχ < 0. However, for
some cholesterics Δχ > 0 [16].
The anisotropy of electrical and magnetic properties of liquid crystals provides
the possibility of the orientation of their molecules under the effect of electric and
magnetic fields. The direction of major axes of liquid crystal molecules in electric
and magnetic fields is governed by the sign of the dielectric and diamagnetic
anisotropies, respectively. If the anisotropy is positive the major axes of molecules
are parallel to the field direction and if it is negative the orientation is perpendicular.
Frideriks and his colleagues observed first the effect of changes in the nematic
orientation in electric field. For this reason this effect is generally called the
Frideriks transition. These experiments have shown that there is a limiting thickness
of the layer between the bearing surfaces, for example between flat and convex
glasses, at which the re-orientation of molecules occurs under a given magnetic
field strength [17]. The threshold character of the Frideriks transition is caused by a
quite strong adhesion between liquid crystal molecules and the bearing surfaces. It
occurs only when the magnetic field strength is enough high to overcome the
adhesion of the nematic crystal to the bearing surfaces.
The orientation effect of electric field is complicated by the electric conductivity
of liquid crystals. The electric conductivity is anisotropic and can cause substance
motion and the redistribution of electric fields. All this induces a number of new
effects such as magnetoelectricity, electrohydrodynamic instability etc. whose
nature is described in papers [8, 14, 18–21].

2.3.2 Peculiarities of Formation of Liquid-Crystal

Layers on Solid Surfaces

In liquid crystals the director can rotate not only in electric and magnetic fields but
also under the effect of the bearing surfaces. They are, for example, the walls of a
flat capillary formed by glasses.
The bearing surfaces can orient the director parallel, normally, or at an angle to
them. In the first case when major axes of molecules are parallel to the surface the
orientation is called planar or plane. Their optical properties are similar to those of
a plate of the optically positive monocrystal cut parallel to the crystal optical axis.
The optical axis is the direction in the monocrystal along which light propagates
without double refraction. In the second case when the major axes of molecules are
perpendicular to the bearing surfaces the orientation is homeotropic. In its optical
properties such structure is similar to a plate of the optically positive monocrystal
cut perpendicularly to the optical axis.
The orientation mode on the bearing surface is governed by its nature, prepa-
ration technique, and the liquid crystal nature. Under given conditions the orien-
tation is implemented at which the free energy of liquid crystal molecules on the
bearing surface is minimal. It is apparently that the orientation effects are possible
52 2 Brief Review of Liquid Crystals

only when liquid crystal molecules are attracted to the solid surface by certain
intermolecular forces. These forces, hence the energy of interaction, are governed
by a number of factors. The surface preparation technique is believed the main
factor [16].
The energy of interaction between the liquid crystal and bearing surface can be:
(a) comparable with the energy of intermolecular interaction in the liquid crystal;
(b) much less than the intermolecular interaction energy in the crystal.
In the first case the strong adhesion of liquid crystal molecules to the bearing
surface occurs; in the second case the adhesion is weak. It is difficult to predict
which of the cases appears in the experiment. In practice empirical rules are used. It
is found that the strong adhesion is easier to implement than the weak one.
A number of methods of providing a certain orientation of liquid crystal mole-
cules on the bearing surface have been developed. They are divided into mechanical
and chemical methods. The mechanical methods involve the producing of the ori-
enting microrelief on the bearing surface. This is achieved by surface machining
with polishing pastes in the certain direction. The appeared microgrooves orient
molecules of nematic and cholesteric crystals parallel to the surface (Fig. 2.15).
Liquid crystals are also oriented on the surfaces rubbed with soft materials like
wool, paper, and leather.
The required microrelief can be also produced by depositing thin, about 20 nm
thick, metal or oxide films onto the bearing surfaces at a certain angle. If the flow of
the substance under deposition is perpendicular to the surface liquid crystal mol-
ecules are oriented mainly parallel to it. If the substance is deposited at blunt angles
(more than 80°) the molecule orientation is “oblique”. In this case the director n is
inclined to the bearing surface at an angle of 20°.
As a rule, the mechanical methods provide a strong adhesion of liquid crystal
molecules to the bearing surface. The orientation of the molecules along microrelief
grooves is more profitable from the energy viewpoint that the transverse orientation.
According the results reported in [16, 22], for the sinusoidal profile with the
wavelength of 20 nm and the amplitude of 1 nm the energy gain at the parallel
orientation in comparison with the perpendicular one is 8 · 10−5 J/m2. This provides
so strong adhesion that to rotate liquid crystal molecules normally to microrelief
grooves it is necessary to apply electric field with the strength of 6 · 108 V/m or
magnetic field with the strength of 6 · 108 A/m.

Fig. 2.15 Orientation of liquid crystal molecules along microrelief grooves

2.3 Properties of Liquid Crystals 53

As a rule, major axes of smectic liquid crystals are oriented normally to the
bearing surface. In its close vicinity a smectic film copies the surface microrelief.
As the distance from the bearing surface increases, the distortion of smectic films
decreases and, finally, disappears at all. The thickness of the distorted smectic film
on finely polished surfaces reaches 1 mm and more [14].
The chemical methods of orientation are based on the use of chemical com-
pounds which are deposited onto the bearing surface or introduced directly into the
liquid crystal and produce a certain surface structure because of physisorption and
chemisorption on the bearing surfaces. These substances are called orientants. As a
rule, their molecules contain active end groups and a hydrocarbon radical. The end
groups interact with the surface and the hydrocarbon radicals are oriented either
normally or parallel to the substrate depending on their length. Liquid crystal
molecules are placed between the hydrocarbon radicals and oriented parallel to
them. Thus, the corresponding orientation of liquid crystal molecules appears.
It should be noted that the great number of orientants providing a strong
adhesion in most cases includes surfactants. The surfactants initiate the homeotropic
orientation of nematic and cholesteric liquid crystals [22].
The analysis of the described orientation methods has shown that, as a rule, their
application varies the energy state of the surface. Interactions on the solid–liquid
interface are described phenomenologically by the surface tension. The use of this
approach for the liquid crystal–solid system yielded the empirical rule according to
which the homeotropic orientation occurs in the cases when the critical surface
tension (σc) of the solid is less than the surface tension of the liquid crystal (σlc). If
σc > σlc the planar orientation of liquid crystal molecules appears [22, 23]. The
author of [22] proposed to call it the rule of Fridel-Kreig-Kmetz (FKK rule).
Though the rule was verified by a great number of experiments it is not true in some
cases.
The studies have shown that when using FKK rule one should consider the sign
of the dielectric anisotropy, the nature of forces (polar or dispersion) causing the
surface tension, and the pattern of the solid surface microrelief. Paper [22] sum-
marizes the study results which are presented in Table 2.1.
Here we should mention the ability of liquid crystals to orient molecules of
dissolved substances parallel to their major axes. This effect is called the “guest-
host” effect. Dichroic dyes which absorb light depending on the molecule orien-
tation and light polarization make the “guest-host” effect visible. If a small amount
of the dye (the guest) is added to the nematic crystal (the host) dye molecules are
oriented by nematic molecules parallel to their major axes. The nematic arrange-
ment is retained in this case.
If the nematic crystal with the dye additive is placed into a flat capillary the
liquid crystal has certain color at the planar orientation. In electric field normal to
the capillary walls the nematic changes its color. This proves that the Frideriks
transition resulted in the re-orientation of both nematic and dye molecules. The
behavior of the “guest” is governed by the behavior of the “host”.
54 2 Brief Review of Liquid Crystals

Table 2.1 Orientation possible in substrate—liquid crystal interaction substrate

Пoдлoжкa Пoдлoжкa — жидкий кpиcтaлл
Material Microrelief pattern σк > σжк σк < σжк
Δε > 0a Δε < 0 Δε > 0 Δε < 0
Activated oxides and diacids (polar surface) Smooth surface ⊥2 xb Heт cлyчaeв
Symmetrical grooves ⊥ || Ecть σк > σжк
Non-symmetrical
grooves
3D valleysd || ⊥
Wet oxides, polymers, and fatty acid Smooth surface x x ⊥5 ⊥5
derivatives Symmetrical grooves || || ⊥ ⊥
Non-symmetrical
grooves
3D valleysd ⊥e ⊥e || ||
a
Δε characterizes the polarity of liquid crystal
b
this case is poorly confirmed by experiments
⊥, ||,
c
, homeotropic, planar, and inclined orientations
d
regular set of 3D alternating peaks and valleys
e
homeotropic orientation resulted from 3D relief independent of liquid crystal nature and appearing due to zero
interactions

2.3.3 Rheological Properties of Liquid Crystals

The anisometric structure of molecules of liquid crystals influences their rheological

behavior.
The viscosity of liquid crystals, like that of common fluids, decreases with
temperature elevation. However, nematics and some cholesterics demonstrate a
substantial viscosity variation at temperatures of the transition liquid crystal phase
—isotropic fluid. In most cases the viscosity rises. The viscosity increment of
nematics is insignificant [24–26].
Cholesteric liquid crystals are characterized by an almost jump-like viscosity rise
by several orders of magnitude. According to the results of [16], the viscosity of
cholesterolacetate increases by approximately six orders of magnitude at the elu-
cidation point. However, the measurements of the viscosity of cholesterolformiate
with varying temperature carried out in a rotation viscometer did not show so great
viscosity rise at the elucidation point (Fig. 2.16). This can result from errors of the
measuring techniques or the discrete mode of temperature variation in the
experiments.
There are liquid crystals whose viscosity decreases under similar conditions [1].
The described viscosity variations occur at low shear rates. The rheological nature
of liquid crystals changes depending on the shear rate. According to the results of
[24], at shear rates less than 10−3 c−1 the cholesteric liquid crystal shows the
non-Newtonian flow mode. Within the range from 10 to 103 c−1 the hydrodynamic
flow orients liquid crystal molecules and the viscosity does not depend on the shear
rate similarly Newtonian fluids. The isotropic fluid of cholesteric liquid crystals
behaves in the same manner as the Newtonian fluid.
2.3 Properties of Liquid Crystals 55

η, mPa·s
D=145,8 1/s
D=1312,0 1/s

1000

100

10 o
90 95 100 105 110 T, C

Fig. 2.16 Temperature dependence of viscosity of cholesterolformiate

In the liquid crystal phase the viscosity of liquid crystals depends on the ori-
entation of the director relatively to the flow. Tsvetkov [24] and other researchers
have shown that the orientation of nematics by magnetic field perpendicular to the
axis of the capillary in which the liquid crystal flows increases the effusion time, i.e.
the viscosity. If the magnetic field direction coincides with the capillary axis
direction the time of liquid crystal effusion decreases. This proves that liquid
crystals possess the viscosity anisotropy. The viscosity is less if molecules are
oriented along the flow. The viscosity anisotropy of liquid crystals appears only at a
slow flow velocity. Otherwise the orientation effect of magnetic or electric field is
too weak since the orientation in the liquid crystal flow becomes dominating.
According to the results reported in [16, 27], the direction of major axes of
nematic molecules appearing in the flow does not coincide with the flow direction.
As I.Ya. Frenkel shown [27], the major axes of anisometric molecules are oriented
at an angle of 45° to the flow direction. This angle can be less than 45° at high shear
rates and it decreases with increasing shear rate. However, according to the cal-
culation results from [16], the orientation angle does not depend on the shear rate
but is governed by the ratio of anisotropic viscosities. Experimental verification
confirmed the theoretical predictions.

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New York, 1979), p. 316
56 2 Brief Review of Liquid Crystals

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