Liquid Crystals by Imran Aziz

Introduction to Liquid
Crystals
MOHAMMAD IMRAN AZIZ
Assistant Professor
PHYSICS DEPARTMENT
SHIBLI NATIONAL COLLEGE, AZAMGARH
(India).
aziz_muhd33@yahoo.co.in
Contents
 Properties of liquid  Lyotropic
crystals  structures
 Types of liquid crystals  application
 Thermotropic  NIOSOMES
 nematic
 smectic
 cholesteric
Synergistic Effects of Surfactants
 Observed when surfactants having relatively similar
structure or ionic property are mixed
 Resulted in the formation of liquid crystal structures or
complexes at the interface by intermolecular
interactions between surfactants
 Examples
 Anionic and nonionic in synthetic latex emulsion
polymerisation,
 Mixture of a dispersant and a hydrating agent to
increase dispersion stability in agricultural chemicals
STATES OF MATTER
 Common states:
 solid
 liquid
 gas
 Mattercan exist in
other states
LIQUID CRYSTALS
A state that occurs between a solid & a liquid
 Possess properties characteristics of both liquids
& crystalline solids
 Also possess properties not found in either
liquids or solids
 Mayresponse to external perturbations & some
changes colour with temperature
Crystals vs Liquid Crystals
A crystal is a highly ordered structure which possesses
long-range positional & orientational order
 For many substances these two types of order are
destroyed simultaneously when the crystal melts to form
a liquid
 Forsome substances, these orders are destroyed in
stages. These are liquid crystals. E.g. Slide 17
Properties of liquid crystals
 Liquid crystal can flow like a liquid, due to loss of positional order
 Liquid crystal is optically birefringent, due to its orientational order
 Transition from crystalline solids to liquid crystals caused by a change of
temperature – gives rise to THERMOTROPIC liquid crystals
 substances that are most likely to form a liquid crystal phase at a certain
temperature are molecules that are ELONGATED & have some degree
of RIGIDITY. Try slide 29
Typical chemical structures
 cholesterol ester
 phenyl benzoates
 surfactantssuch as
polyethylene-oxides, alkali
soaps, ammonium salts,
lecithin
 paraffins
 glycolipids
 cellulose derivatives
Typical applications
 LCD displays
 dyes (cholesterics)
 advanced materials (Kevlar)
 membranes
 temperature measurement (by changing colours)

 solvents for GC, NMR, reactions, etc.
Drug delivery
Types of liquid crystals
Thermotropic
 Phase transition depends on temperature
 Nematic
 Smectic
 Cholesteric
Lyotropic
 Phasetransition depends on temperature &
concentration
As temperature increases…..
 The first liquid crystal phase is the smectic A, where there
is layer-like arrangement as well as translational and
rotational motion of the molecules.
 A further increase in temperature leads to the nematic
phase, where the molecules rapidly diffuse out of the initial
lattice structure and from the layer-like arrangement as well.
 At the highest temperatures, the material becomes an
isotropic liquid where the motion of the molecules changes
yet again.
Nematic
 Simplest form is a
nematic liquid crystal
i.e. long-range
orientational order
but no positional
order
 The preferred direction
is known as director
Nematic…
 Despite the high degree of orientational order, nematic phase
as a whole is in disorder i.e. NO MACROSCOPIC ORDER
(orientation within a group is similar but not from one group to
another)
 Structure of nematic phase can be altered in a number of ways.
E.g. electric or magnetic field or treatment of surfaces of the
sample container
 Thus, possible to have microscopic order & macroscopic order
 Nematic liquid crystals are widely used in electro-optic display
devices
Cholesteric
 The first liquid crystal that was observed through a polarising microscope is
cholesteryl benzoate. Thus, CHOLESTERIC liquid crystal OR chiral nematic liquid
crystal
 E.g. cholesteryl benzoate: LC @ 147C, isotropic @ 186C
 Cholesteric liquid crystals have great potential uses as
- sensors
- Thermometer
- fashion fabrics that change colour with temperature
- display devices
- In CHOLESTERIC phase, there is
orientational order & no positional order,
BUT, director is in HELICAL ORDER.
 The structure of cholesteric depends on
the PITCH, the distance over which the
director makes one complete turn
 One pitch - several hundred nanometers
 Pitch is affected by:-
 Temperature
 Pressure
 Electric & magnetic fields
Smectic
 SMECTIC phase occurs at temperature below
nematic or cholesteric
 Molecules align themselves approx. parallel & tend

to arrange in layers
 Not all positional order is destroyed when a
crystal melts to form a smectic liquid crystal
 Chiral smectic C liquid crystals are useful in LCDS
LIQUID CRYSTAL POLYMERS
 Can form nematic, cholesteric, smectic
 When liquid crystal polymers solidify, the liquid
crystal structure ‘freeze in’
 This results in materials of high tensile strength
& in some cases unusual electro-optical
behaviour
 E.g. Kevlar aramid fibre – bullet-proof vest &
airplane bodies (aromatic polyamide)
Examples of phase changes
Cholesteryl myristate
71C 79C 85C

solid smectic A cholesteric isotropic
4, 4’-di-heptyloxyazoxybenxene
74C 94C 124C
solid smectic C nematic isotropic
Thermotropic vs Lyotropic
THERMOTROPIC LYOTROPIC
 Absence of solvent  Insolvent
 Rigid organic molecules  Surfactants
 Depends on Temperature
 Depends on Temperature,
 Structures:
Concentration, salt, alcohol
 Smectic
 Structures:
 Nematic
 Cholesteric  Lamellar
 Hexagonal etc
Structure formation in surfactant solution
monolayer
rod hexagonal
micelle
Oil/alcohol REVERSE
HEXAGONAL
Reverse micelle
Formation of MICROEMULSION bilayer
Effect of temperature and concentration on the
structure of lyotropic liquid crystals
SURFACTANT VESICLES
[A] Phospholipids (e.g. lecithin) + H2O ---->
phospholipid vesicles or liposomes
[B] Liposomes + (long chain) stearylamine ------->
tve charge liposome (carriers for DNA)
[C] Liposomes + dicetyl phosphate -----

- ve charge liposome
Vesicles
 Bilayers that fold into a 3D structure
 Vesicles form because they get rid of
the edges of bilayers, protecting the
hydrophobic chains from the water, but
they still allow for relatively small
layers.
 Lipids found in biological membranes
spontaneously form vesicles in
solution.
Application of Liposomes
 can encapsulate:
 drugs,
 proteins,
 enzymes
 administered intravenously, orally or intramuscularly
 decrease toxicity
 increase specificity of drug uptake
 enable slow release
Problems with phospholipids
 phospholipids undergo oxidative

degradation
 handling & storage must be under nitrogen
 expensive
Formation of liquid crystals using surfactants
[A] Anionic
e.g. alkane sulfonates
[B] Cationic
e.g. hexadecyl trimethyl ammonium bromide
[C] Amphoteric
e.g. alkyl betaines
 Due to toxicity of ionic surfactants, the vesicles are not used for drug delivery
[D] Non-ionic
e.g. alcohol ethoxylates R-O-(CH2CH2O) m H m: 2-20, R :
mixed; alkyl group C8C18
Niosomes
 Non-ionic + cholesterol -> NIOSOMES
 These vesicles prolong the circulation of entrapped
drug
 Properties depend on
1. Composition of bilayer
2. Method of production
e.g. cholesterol & single alkyl-chain non-ionic
surfactant with a glyceril head group
Examples of niosome applications
 Ketoconazole niosomes were prepared by using surfactant
(Tween 40 or 80), cholesterol and drug
Satturwar PM; Fulzele SV; Nande VS; Khandare, JN Indian Journal of
Pharmaceutical Sciences. 2002 Mar-Apr; 64(2): 155-8
 Use for topical immunisation - Bovine serum albumin (BSA)loaded

niosomes composed of sorbitan monostearate/sorbitan trioleate
(Span 60/Span 85), cholesterol and stearylamine as constitutive
lipids
Sanyog Jain1, S. P. Vyas2, Journal of Pharmacy and Pharmacology Vol.
57, No. 9, pages 1177 (2005)
The three states of mater?
solid liquid gas
Which state is a soap bubble in?
The fourth state of mater…
heat
0oC
e.g.: ice -> water
heat heat
The new liquid state showed birefringence!
145.5oC 178.5oC
Fredrich Reinitzer, Otto Lehmann, 1888
e.g.: cholesteryl benzoate
Orientational order but no positional order!

Is liquid crystal more like solid or
liquid?
Latent heat: the energy required to cause phase transition.
H2O
80 cal/g of ice -> water,
540 cal/g water -> steam.
Cholesteryl myristate:
65 cal/g of solid -> LC, 7 cal/g LC- liquid.
The structure of LC
solid liquid crystal liquid
Director
If random, <θ > = 57o
Types of liquid crystals
Discotic
Chiral nematic
LC in an electric field
Orientation of a dipole in
an electric field
LC film in an electric field

Light & polarization
Incoming
Interaction of light with LC
Reflected
beam
Ex Ey Ex Ey beam
Ex Ey
Refracted beam
Incoming
Reflected
beam
Ex Ey Ex Ey beam
Birefringence
Ex Ey
Refracted beam
LCs under a polarization
microcope
Aligning liquid crystals
“rubbing”
“polishing”
Liquid crystal display
The operation of a pixel in LCD
Other cool
Thermochromic Ink
gadgets from LCs
Polymeric LC
Interactive art using

iridescent coloring… Optoelectronic computers…
Lyotropic LCs
• Thermotropic: pure substance melts to form LC.
•Lyotropic LCs: mixtures of two substances that

separate into different regions in liquid.
micelles Lamellar bilayers
vesicles
Other liquid crystals in nature…
Iridescent color
Introduction
 Liquid crystals are very important in the study of optics,
chemistry and polymer science. The discovery of the liquid
crystal happened over a century and since this time the
phenomena has been applied to many products in our
society. This presentation will cover the properties, different
phases and uses of liquid crystals. It will also give illustrations
of liquid crystals from the micro perspective.
What are liquid crystals ?
Liquid crystals form from organic compounds and is thought of
as the phase of matter between the solid and liquid state of a
crystal.This phenomena was discovered in 1888 by Austrian
chemist Frederich Reinitzer.
Phases
Nematic Phase
 Molecules in this phase

are long and rod-like in
shape. They are free to
move in space.
Chiral Nematic
 This phase is composed

of nematic molecules in
a helical structure about
the layer normal.
 The distance that it takes
for the molecules to
complete one turn is
called the pitch.
λ = n*p*cosθ
Smectic Phase
 This phase can be
reached at lower
temperatures than the
nematic phase.
 Molecules align
themselves in layers.
(They are restricted to
their plane.)
 More order and higher
viscosity
Columnar Phase
 Characterized by its stacked columns of molecules.
 Discovered in 1977 by Chandrasekhar
Order Parameter
S = ½<(3cos²θ-1)>
The order parameter in a liquid crystal
range from 0.3 to 0.9
Electric field Effects
 Ifan electric field is
applied to a liquid
crystal the molecules
will align in the same
direction as the field.
Twisted Nematic
 This is called the
twisted nematic liquid
crystal and the spacing
between the planes
change with
temperature. The
spacing is associated
with the wavelengths of
light.
Uses of Liquid Crystals
 Flat screen television
 Wristwatches
 Laptop screens
 Digital clocks
 Thermometers
 Switchable windows
Conclusion
 We know today that many chemical compounds can exist
in the liquid crystal state, such as cholesteryl benzoate.
Thanks to the scientists that worked so diligently toward
understanding this phenomenon, the world can focus on
ways to make this product useful in society. Over the last
century many applications such as the detection of hot
points in microcircuits, the findings of fractures or tumors
in humans and the conversion of infared images have
become accessible due to the understanding of pitch in a
liquid crystal.
Liquid Crystal Materials
C N
Broad Classification
Lyotropics Thermotropics
amphiphilic molecules, polar and non-polar molecules consisting of a rigid core and
parts form liquid crystal phases over certain flexible tail(s) form liquid crystal phases
concentration ranges when mixed with a over certain temperature ranges.
solvent
hydrophobic
non-polar tail flexible tail
+
-
hydrophilic
polar headaziz_muhd33@yahoo.co.in rigid core
The Lyotropic Phases
micelle
cross section
reverse
micelle
cross section
The Thermotropic Liquid Crystal Molecule
Chemist’s Physicist’s
View CN Engineer’s
View
• Shape Anisotropy
• Length > Width
The molecule above (5CB) is ~2 nm × 0.5 nm

Geometrical Structures of
Mesogenic Molecules
Low Molecular Weight High Molecular Weight

(polymers)
disk-like ( )n
rod-like ( )n
most practical applications

The Liquid Crystal Phase
Crystal Nematic LC Isotropic

Temperature
The Nematic Director n
n
director
θ
Long H H H H
Molecular
Axis H H
O C N
H C C
H H H H
H C C H H
H H H
The local average axis
of the long molecular axis
Other Liquid Crystal Phases
z n
n n
θ
Smectic C Smectic A Nematic

Temperature
Chirality
The methyl group on the 2nd carbon atom
on the alkyl chain of the molecules extends
out of the plane of the paper and the hydro-
gen atom extends into the plane of the paper.
Therefore the 2nd carbon can be thought of
as a right or left handed coordinate system
left-handed right-handed H H H H H
mirror images
H-C-C-C-C-C C N
H H H H H non-chiral
H H H H
H
H-C-C-C-C-C C N
CH
non-superimposable aziz_muhd33@yahoo.co.in3
H H H H chiral (RH)
The Chiral Nematic
Ordinary Nematic Chiral Nematic
CN
CN
director
pitch
n
P
The Chiral Smectic C: Ferroelectrics
C10H21 O CH 3
N
COO CH 2 CH C 2H5
µ
Eye- dipole moment µ
fin - chiral
ferroelectric LC has a
dipole moment perp-
aziz_muhd33@yahoo.co.in endicular to its long
axis, and is chiral.
The Chiral Smectic: TGB
Twisted Grain Boundary (TGB)
A twisted grain boundary smectic A phase (frustrated) - TGBA*
R
Discotic Liquid Crystal
C
R C
O O
C O R
C
O
O
O
C
R O
O
O O C
example: R=OCOC11 H23 R
C O
R
Discotics Liquid Crystals
n
Nematic discotic phase

Columnar, columns of molecules
in hexagonal lattice
Polymer Liquid Crystals
Combining the properties of liquid crystals and polymers
Main Chain Side Chain
mesogenic moieties are mesogenic moieties
connected head-to-tail attached as side chains
on the polymer backbone
rigid
semi-flexible
Polymer Liquid Crystals
forming nematic liquid crystal phases
side-chain
main-chain aziz_muhd33@yahoo.co.in
Example of Side-Chain Polymer LCs
R1
-(-CH2-C-)X- O
O C-O-(CH2)n-O C-O R2
• Too slow for display applications (switching times ~ 0.5-1 s

• Useful for other applications such as:
• Optical filters
• Optical memory
• Alignment layers for low molecular weight LCs
• Non-linear optic devices (optical computing)
The Order Parameter
n
1
θ S = P 2 (cos θ=
) θ
(3 cos− 2
1)
2
∫ θdΩ
2
cos
1
cos 2 θ = Ω = no order
∫ dΩ Ω
3
cos 2( θ =0 o) =1 perfect order

n
S = P 2 (cos θ=
) 1 perfect crystal
S = P 2 (cos θ=
)
0 isotropic fluid
Maier-Saupe Theory - Mean Field Approach
Interactions between individual molecules are represented by a

potential of average force n
V ( cosθ ) = − vP
2 ( cos) θ <2P >
θ ψ
• {V: minimum} when phase is ordered (∝-P2(cosθ ))
• {V: V=0} when phase is disordered (∝<P2(cosθ )>) φ
• factor for intermolecular strength (∝ ν )
From Statistical Mechanics (Self Consistency)

1
∫ P ( cos θ ) exp (β vP cos

2 ( θ ) <P
2 2 > (
θ
)d cos ))
< P2 >= 0
1
∫ exp ( β vP (cosθ ) <P

0
2
2 > d) cos
(θ )
β =(kT)-1
Maier-Saupe Theory - Mean Field Approach
n
1.0
Order Parameter, S
Isotropic
Fluid
Nematic
0.0 Liquid
Crystal
-0.6 n
Temperature
Landau-de Gennes Theory
1 2 1 3 1 4 1
f = f 0+ aS − bS + cS+ ∇ (S− ) GS
L 2
zδ( )
2 3 4 2
a=α ο (T-T*), α ο , b, c, T*, L are phenomenological constants
G is a surface interaction strength
Good near NI transition

Order Parameter, S
surface
aziz_muhd33@yahoo.co.in Predicts order near
Temperature surface
Optical Anisotropy: Birefringence
ordinary ray (no, ordinary index of refraction)
extraordinary ray (ne, extraordinary index

of refraction)
Optical Anisotropy: Birefringence
ordinary wave n =no
1 cos 2 θ sin 2θ
extraordinary wave 2
= 2
+ 2
n no ne
optic
axis
For propagation along the optic

axis, both modes are no

Birefringence Example: 1/4 Wave Plate
What is minimum d for circular polarized

liquid crystal 1/4 wave plate ? linear polarized
Unpolarized
d LC: ∆ n=0.05
polarizer
1
Ne = No +
4 Takes greater number of e-waves
ned nod 1 than o-waves to span d, use
= +
λ λ 4 ∆ n=0.05
1 λ 589 nm
d= = = 2,950
nm= 2.95mµ
4 ∆n 4 (0.05 ) aziz_muhd33@yahoo.co.in
Creating Deformations with a
Field and Surface - Bend Deformation
E or B
Field and Surface - Splay Deformation
E or B
Field and Surface - Twist Deformation
E or B
Elastic Constant K22 :
Temperature Dependence
K ∝S 2 T
( )
7
P -a
zo
K22 (x 10-12 Newton)
6 xy
ph
en
eto
le
5
P-a
z ox
4 y an
iso
le (P
AA
)
3
2
-30 -20 -10
aziz_muhd33@yahoo.co.in 0
T-T NI (°C)
Effects of an Electric Field
n y
E x
θ ε n = sin θx+ cosθ y
E = Eo y
ε
1 1
fe = εo∆ ε ( E⋅ n ) = ε o∆ ε Eo
2 2
θ2
cos Electric Free Energy Density
2 2
df 1
Γe = e = εo∆ ε Eo sin ( 2 θ )
2
Electric Torque Density
dθ 2
Using ∆ ε = 5 and E=0.5 V/µ m
1 1
ε o ∆ε Eo = ( 8.85× 10 −12C 2 /N ) ( ) ( )
2 2
⋅ m 2
5 0.5
× 10 V /m =
6
5.5N /m 2
2 2
Freedericksz Transition -
The Threshold I
y E n
z
E Ec θ
y x
d x n At some critical E
field, the director
rotates, before Ec
nothing happens
(
n = cos θ ( z ) ,sinθ (z ),0 )
1
2 VOL
{
Fd = ∫ K 11∇⋅ ( n+) K 22 ⋅∇×
2
(n +
n )K
2
n(
×∇×
33 )
n dV
2
}
2
0  dθ 0
K 22  − 
 dz
The Threshold II
1 2 1 2 E-field
Fe = ∫ εo∆ ε (⋅E n dV
) = ∫ ε∆o ε E θsindV
2
2 VOL 2 VOL free energy
1  
2
 dθ
d
 2
F = Fd + Fe= ∫ − ∆oε Eε θdz total
2
K
 22  sin
20  dz  
 free energy
 
∂F d  ∂ F  Minimize free energy with
−  = 0
∂θ dz   dθ ‘Euler’ Equation
 ∂  dz 
  
The Threshold III
 d 2θ
K 22  2 + εo∆εE 2
θ cos
sin θ= 0 differential equation
 dz 
π K 22  π  10N −11
soln.
ETH = =  −6 
d εo ∆ε  ×
5 10 m ( 8.85 ×10 −12
C 2
/ Nm2
)
(10) small θ
V V
mid-layer tilt (deg)

≈ 200,000 = 0.2
m µm
threshold
 V
VTH =ETHd =  0.2  (5 mµ= ) volt
1
 µm
1.0 E/Ec
Defects
s=1/2 s=-1
s=-1/2
s=+1 s=+1 s=+1
The singular line

(disclination) is pointing
out of the page, and director
s=+2 orientation changes by
s=3/2 2π s on going around the
line (s is the strength)

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Introduction to Liquid

 Types of liquid crystals  application

 temperature measurement (by changing colours)

 E.g. cholesteryl benzoate: LC @ 147C, isotropic @ 186C

 Cholesteric liquid crystals have great potential uses as

- fashion fabrics that change colour with temperature

 Molecules align themselves approx. parallel & tend

71C 79C 85C

[C] Liposomes + dicetyl phosphate -----

 phospholipids undergo oxidative

 Use for topical immunisation - Bovine serum albumin (BSA)loaded

solid liquid gas

Which state is a soap bubble in?

e.g.: ice -> water

Orientational order but no positional order!

solid liquid crystal liquid

If random, <θ > = 57o

LC film in an electric field

Interactive art using

•Lyotropic LCs: mixtures of two substances that

 Molecules in this phase

 This phase is composed

The molecule above (5CB) is ~2 nm × 0.5 nm

Low Molecular Weight High Molecular Weight

most practical applications

Crystal Nematic LC Isotropic

Smectic C Smectic A Nematic

A twisted grain boundary smectic A phase (frustrated) - TGBA*

Nematic discotic phase

• Too slow for display applications (switching times ~ 0.5-1 s

cos 2( θ =0 o) =1 perfect order

Interactions between individual molecules are represented by a

From Statistical Mechanics (Self Consistency)

∫ P ( cos θ ) exp (β vP cos

∫ exp ( β vP (cosθ ) <P

Good near NI transition

extraordinary ray (ne, extraordinary index

For propagation along the optic

axis, both modes are no

What is minimum d for circular polarized

2 VOL 2 VOL free energy

mid-layer tilt (deg)

s=+1 s=+1 s=+1

The singular line

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