Unit- 3 High polymers, Liquid crystals and display devices 12-12-2023

Definition: “Polymers are carbonaceous materials with large molecular

masses obtained by covalent linkages of several small repeating units
called monomers.

Polymerization: “Polymerization is the union of two or more smaller

and simpler molecules of similar or different types with or without
elimination of any part of the molecule resulting in the formation of new
covalent linkages.”

GLASS TRANSITION TEMPERATURE (Tg)

Unlike in metal article fabrication, the polymers are not melted to the liquid form to fabricate but
heated just to its softening temperature. This is referred to as glass transition temperature.

Definition of Tg: “The temperature at which a polymer abruptly transforms from a glassy state
(hard state) to a rubbery state (soft state) is called Glass Transition Temperature and denoted by
Tg.”

This transition from a hard solid state to a soft and flexible state corresponds to the beginning of
chain motion or rotation about C-C single bonds in polymers. Below Tg polymer is said to be in
a frozen state.

Parameters affecting Tg:

a) Chain flexibility: Free rotational motion imparts flexibility. Rigid structure in the polymer
chain or with bulky side chains hinder the freedom of rotation and decrease in flexibility and
increase Tg. Hence, the highly flexible polymer will have a low Tg value.
Ex: Tg of polyethylene is -1100C where as Tg of polystyrene is 1000C

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 H2 H2 H2 H2 H2
C C C C C Free rotation of C chain possible
Polythylene

H2 H H2 H H2
Free rotation of C chain hindered
C C C C C

Polystyrene

b) Intermolecular forces: The presence of a large number of polar groups in the molecular
chain leads to strong intermolecular forces such as hydrogen bonding, Van der Waals forces etc.,
and they restrict molecular mobility and hence increase Tg. Hence higher the intermolecular
forces higher the Tg.

O ------H N
O
H N

CH3
H2
C C
H Nylon 6, 6
n
hydrogen bonds between
Polypropylene polar groups

c) Branching and Cross-linking: A high degree of branching and cross-linking in the polymer,
brings the molecular chains closer and lowers the free volume reducing chain mobility. This will
increase Tg. Hence highly branched and cross-linked polymers will have higher Tg.

a) Molecular weight: High molecular weight polymers have greater density and increase in Tg.
However, Tg is not significantly affected by the molecular mass if the degree of polymerization
above 250 or the molecular mass is above 20000. (graph)

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 Significance of Tg:
i)Tg can used to evaluate the flexibility of a polymer and predict its response to mechanical
stress.
ii) Many polymers change their other physical properties like viscosity, and elastic nature also at
Tg. Hence use of a polymer at Tg concerning other properties can be decided.
iii) Different fabrication works like moulding, shaping, calendaring etc., can be conveniently
carried out with knowledge of Tg, as the entire machinery can be pre-set to that temperature.
Synthesis, Properties, and Applications of TEFLON (Poly tetra fluoro ethylene-PTFE)
Synthesis: It is made by the addition polymerization of a water emulsion of Tetra fluoro
ethylene in an aqueous or alkaline medium at 55-240oC in the presence of Benzoyl peroxide as
catalyst at 1000 PSI pressure.
n CF2 = CF2 → -(CF2 – CF 2)-n
Tetrafluoro ethylene PTFE
Properties:
1. High degree of crystallinity of 93-98 %, high melting point of 327oC and high density of 2.3g
cm-3.
2. Insoluble in most solvents and chemicals
3. Not wetted by oil and water
4. High thermal stability, strength and insulating properties.
Applications: 1. For insulation in motors, transformers coil and capacitors
2. Making industrial filters, gaskets and belts
3. As non-sticky coating on bakery trays and frying pans
4. As anti- corrosive coating
5. As non- lubricated bearing.
Synthesis, Properties, Applications of PLEXI GLASS (Poly methyl methacrylate) PMMA
Synthesis: it is made by bulk or emulsion polymerization of Methyl meth acrylate in presence
of H2O2 as initiator at 60-70 o C under atmospheric pressure.
éH COOCH 3 ù é H COOCH 3 ù
ê| | ú ê | | ú
ê ú ê ú
n êC = C ú ¾¾ ¾ ¾
¾®ê- C = C -ú
ê ú ê ú
ê| | ú ê | | ú
êëH CH 3 û ú ê
ë H CH 3 úû
n

Methylmethacrylate Polymethylmethacrylate
Methyl acrylate PMMA
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 Properties: 1. Highly transparent, thermoplastic, softening at 120o C.
2. Excellent optical properties
3. Not affected by sunlight but affected by many chemicals and some organic solvents
4. Has good dimensional stability.

Applications: 1. For making lenses, aircraft parts and light fixtures

2. Used in jewellery, windscreens and TV screens.
3. For making artificial eyes and dentures.
4. Used in emulsion paints.

Conducting Polymers

Most of the polymers are insulators, with desirable properties such as lightweight, processability,
durability, and low cost. By designing the molecular structures of polymers, chemists have
developed new materials that exhibit electrical conductivities comparable to metals while
retaining the advantages of polymers. Generally, these electrically conducting polymers are
composed of conjugated polymer chains with л-electrons delocalized along the backbone. The
polymers are converted to the electrically conductive, or doped, form via oxidation or reduction
reactions that create delocalized charge carriers. Charge balance is accomplished by
incorporating an oppositely charged counter ion into the polymer matrix.

An organic polymer with a highly delocalized pi-electron system, having electrical conductance
of the order of a conductor is called a conducting polymer.
An organic polymer can be converted into a conducting polymer if it has
c Linear structure
c Extensive conjugation in the polymeric backbone (pi-back bone)
The conducting polymers are synthesized by doping, in which charged species are introduced in
organic polymers having pi-back bone. The important doping reactions are:
c Oxidative doping (p-doping)
c Reduction doping (n-doping)
c Protonic acid doping (p-doping)
c Normally electrons in a polymer are localized and do not take part in conducting but
doping can create delocalized electrons and is responsible for conduction.
Mechanism of conduction:
Band theory of solids has been used to explain the conduction mechanism in conducting
polymers. The neutral polymer (insulator) be transferred into a conductor by doping with an
electron donor (reducing dopant such as sodium naphthalide) or an electron acceptor (like iodine
vapour, FeCl3, iodine in CCl4, HBF4, perchloric acid and benzoquinone)
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 The removal of an electron from the polymer pi-back bone using a suitable oxidizing agent leads
to the formation of a delocalized radical ion called polaron.
A second oxidation of a chain containing polaron, followed by radical recombination yields two
charge carriers on each chain. The positive charge sites on the polymer chains are compensated
by anions (I3- ) formed by the oxidizing agent during doping.
The delocalized positive charges on the polymer chain are mobile, not the dopant anions. Thus,
these delocalized positive charges are current carriers for conduction. These charges must move
from chain to chain as well as along the chain for bulk conduction. On doping polyacetylene
using iodine in CCl4, for partial oxidation, the conductivity increases from 10-5 S. cm-1 to 103-105
S.cm-1.

polyacetylene

I oxidation
I2 in CCl4
-
-e,- + I3

Radical ion
-
I3
II oxidation
- -
-e, + I3
-
I3
-
I3

Recombination of radicals

- Conducting
I3 polyacetylene
polymer
- (p-doped)
I3

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 Liquid crystals

Q- What are liquid crystals? Explain molecular ordering positional and orientational order
in solid, liquid and liquid crystals. Mention general applications of liquid crystals.
Definition: Liquid crystals (LCS) may be defined as a distinct state of matter, in which the
degrees of molecular ordering (positional and orientation order) lie between an ordered
anisotropic crystalline state and a completely disordered isotropic liquid state.

The terms mesophase and mesogen also refer to the liquid crystal state. Liquid crystals exhibit
optical anisotropy, i.e., they possess different optical properties when light is incident in different
directions. Liquids, however, exhibit optical isotropy i.e., they exhibit the same optical property
irrespective of the direction of the incident light. All LCS are organic molecules with rod or disk
shape.
Positional and orientational order in solids, liquids and liquid crystals :

Figure 1: Positional and orientational order in solids, liquids and liquid crystals

In a solid crystal state, the molecules are highly ordered. Each molecule occupies a definite
position in a more or less rigid arrangement and immobile rigid arrangement and orients in a
preferred direction.

In a liquid state, the molecules neither occupy specific positions nor remain oriented in a
particular manner. The molecules are overcome with cohesive forces of attraction and are
somewhat free to move at random colliding with one another and changing their position
abruptly.

The intermediate state between the solid state and the liquid state exists another metastable state
is called the Liquid crystalline phase, wherein the molecules are free to move but are oriented in
a particular manner.

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 For example: Solid cholesteryl benzoate (CB) on heating becomes hazy liquid, which on further
heating turns into a clear and transparent liquid. On cooling these changes were observed exactly
at the same temperature. Between 145oC and 179oC the temperature at which it converts into the
liquid crystalline state is called phase transition temperature. The temperature at which the
transition from liquid crystalline state to isotropic liquid (179oC) state is called clearing
temperature.

The structure of cholesteryl benzoate is given below.

Figure 2: Structure of cholesteryl benzoate

General applications of liquid crystals: liquid crystals find application in areas of science and
engineering, particularly in display systems. Devices using liquid crystalline displays (LCD)
have the advantage of low power consumption at lesser cost and are hence widely used in
electro-optic displays like mobile communication, high-resolution T.V displays, calculators,
aircraft cockpits etc. Liquid crystal also finds application in temperature sensors, thermography,
pressure sensors etc.

Q- What is a director? Explain its significance.

Director and its significance: In a liquid crystal the molecule passes orientational order i.e. the
molecule tends to remain in a particular direction. The direction of the preferred orientation of
molecules in a liquid crystalline phase is called a director. Since molecules are in constant
motion they spend more time pointing in that direction than in any other direction. Hence the
extent of orientational order can be described by taking an average angle ϴ made by different
molecules with the director.

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 Director Director

Solid state Liquid crystalline state

Figure 3: Director in solid state and liquid crystalline state

Significance of director :

1. An average angle of 00 indicates perfect orientation and can expected in solid crystals.
2. Liquid crystals exhibit a smaller average angle (0 -50) with the director.
3. An average angle greater than 450 indicates no orientational order as found in liquids.

Q- Discuss the classification of liquid crystals with a suitable example (Or) Explain the
molecular ordering in Thermotropic and Lyotropic liquid crystals.
Classification of Liquid crystals: Liquid crystals are classified into two main categories
namely
(i) Thermotropic
(ii) Lyotropic
(i)Thermotropic liquid crystals: The class of compounds that exhibits crystalline
behaviour or variation of temperature alone is called thermotropic Lcs. More no. of
thermotropic Lcs are formed from organic molecules with a rod-like shape.

Thermotropic liquid crystals are further classified into Nematic, Smectic, and
Chiral liquid crystals.

Lyotropic liquid crystals: Liquid crystals that are obtained by mixing the two
components - organic solids compound (amphiphilic) and polar solvent. Increasing
the concentration of one of the components till the liquid phase is obtained such
liquid crystals are called lyotropic liquid crystals. The amphiphilic or amphiphile
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 compound possesses two groups that differ greatly in their solubility properties.
One part of the molecule has a ‘hydrophilic head’ which is highly soluble in H 2 O.
While the other part has a hydrophobic or lyophobic tail which is highly soluble in
hydrocarbon solvents.

Figure 4: Lyotropic mesophase

In the lyotropic phase, the water is sandwiched between the polar heads of adjacent layers of
amphiphilic molecules. Example:

1. Soap water mixture

2. DNA
3. Synthetic polypeptides
4. Biological compounds such as proteins, and nucleic acid, also exhibit a lyotropic type of
liquid crystalline behavior in water.

Q- What is a homologous series? Explain liquid crystalline behaviour in homologous PAA

homologous series.

A series of compounds of the same type wherein successive members differ in their molecular
formula by CH2 group is called a homologous series. The composition of any homologous series
can be expressed by a general formula cnH2n+1.

The thermal stability of a liquid crystal compound depends on its structure. Therefore, the
thermal stability of members of a homologous series change with a change in the number of C-
atoms in the chain. On heating a liquid crystalline compound, it undergoes change from a highly
ordered arrangement in a solid state to a disordered isotropic liquid through an anisotropic liquid

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 crystalline state. It is interesting to study the phase transition that occurs on heating in
homologous series of a liquid crystal.

When the transition temperatures are plotted for a homologous series against the number of C-
atoms in the n-alkyl chain of the molecule, certain smooth transition curves are obtained. For a
given series, the upper curve represents the transition from liquid crystalline state to the isotropic
liquid state (clearing temperature) and the lower curve shows the transition from solid state to
liquid crystalline state (transition temperature). The region between the two curves gives the
range of temperature at which the liquid crystalline state exists.

Generally, the first few homologous are purely nematic, the middle will form both nematic and
smectic mesophases and the higher homologous do not show significant variation.

PAA homologous series: The liquid crystal of para azoxy anisole (PPA) is stable between 1180
and 1350C. PAA has more than 12 homologous which are formed when –CH2 groups are added
to its side chain. A plot of the transition temperature against the number of C-atoms in the PAA
is shown in Fig.

CH3O N=N OCH3

Isotropic liquid

140
emperatu
Nematic
Temperature in oC

Liquid
120 crystal
Smectic state
100

80
Solid

4 6 8 10 12

Number of carbon atoms

Figure 5: Phase transaction temperature against the number of C-atoms in PAA

From the Figure, the phase transition of PAA is given by

1. When the group (side chain) contains 1-5 C-atoms, the transition is from solid to nematic, and
nematic to isotropic liquid.
2. Homologous containing 6-10 C-atoms show a transition from solid to smectic, smectic to
nematic before melting into a liquid.

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 3. When the number of C-atoms is greater than 10, shows a transition from solid to smectic, and
smectic to liquid.

Q- Explain the display mechanism in liquid crystals. Or how is liquid utilized in display
systems?

Display systems
This is used in information display systems, where liquid crystals control the brightness or
darkness of parts of a display device. Numbers can be created in numeric displays which have
seven segments (also called pixels). Alphabets can be displayed in a fourteen-segment
arrangement.

A numeric display consists of seven segments for each digit. Each segment is a liquid crystal.
Light emitted by each crystal can be independently controlled so that any digit can be displayed.
When an electric field is applied to a segment, the liquid crystal is deformed and when polarized
light is incident, it gets brightened. By using dichroic dyes, the contrast between bright and dark
areas can be enhanced and the required colours can be obtained.

One of the most important effects of the electrooptic effect (of nematic and chiral liquid crystals)
is in liquid display systems (LCD). Electro-optic effect of liquid crystal controls the brightness
and darkness of emergent light.

LCD requires a very small current. Most of the display in LCD watches and calculators is
composed of 7 segments. Each seven-segment section can display one number. The 14-segment
LCD uses alphabets. Light from the area of each segment is controlled independently and the
creation of any digits or alphabets is possible. 5x7 matrix segments are used for numbers, letters
and figures.

A 7-segment display (Figure) consists of seven segments for each digit (each segment represents a liquid
crystal). Light from the area of each of the seven segments or pixels is controlled independently and
creation of any of the ten digits becomes possible. When an electric field is applied to a segment, the
liquid crystal in that segment undergoes deformation (is activated) and when polarized light is incident,
the segment gets brightened. A typical liquid crystal display cell (reflection mode) and the electrical
circuit with four rows and two columns for a digit to appear are shown in the below Figures.

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 Transparent electrodes Glass plates

Seal
Liquid Reflector

Figure 6: Representation of a liquid crystal display (reflection mode pixel) where the liquid
crystal is embedded between two glass plates

In the Figure, when a voltage is applied to

i) Row 1 column I activate the liquid crystal in area a which gets brightened.

ii) Row 2 column I activates the liquid crystal in an area d which gets brightened.

iii) Row 3 column I activates the liquid crystal in an area e which gets brightened.

iv) Row 1 column II activates the liquid crystal in an area b which gets brightened.

v) Row 2 column II activates the liquid crystal in an area c which gets brightened.

vi) Row 3 column II activates the liquid crystal in an area f which gets brightened.

vii) Row 4 column II activates the liquid crystal in an area g which gets brightened.

For example, to get the number 139 on the display (Fig. b) an electric field is applied between
row 2 and column II (operation v) and between row 3 and column II (operation vi) to give ‘1’

In the second digit operations (i), (v), (vi) and (vii) give ‘3’

In the third digit operations (i), (ii), (iv), (v), (vi) and (vii) give ‘9’. Thus, the digit 139 appears
on the display.

To enhance the difference in the brightness between dark (turned OFF, voltage removed) and
bright areas (turned ON, voltage applied), dyes are used. Dyes used in liquid crystal displays are
called dichroic dyes and give desired colours to the displays with good contrast.

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 Column I Column II

Row 1

b c

Row 2

d
Row 3

e f

Row 4

(a)

(b)

Figure 7: Seven-segment LCD for a digit; each row is connected to two segments and each
column is connected to three or four segments; a, to g are the LCD cells. (b) display of
number 139

Display Devices

Organic Light-Emitting Diodes (OLED) and their Applications

OLEDs are thin-film organic semiconductor light-emitting devices. also known as organic
electroluminescent (organic EL) diode, is a light-emitting diode (LED) in which the emissive
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 electroluminescent layer is a film of organic compound that emits light in response to an electric
current. This organic layer is situated between two electrodes; typically, at least one of these
electrodes is transparent.

OLED consist of a thin film of organic material sandwiched between two electrodes (anode and
cathode). The anode is transparent and made of indium tin oxide. A cathode is reflective and
made of metal. When an external potential is applied across electrodes, positive and negative
charges (holes from the anode and electrons from the cathode) are injected. These electrons and
holes shift inside the material and recombine to form excitons, emitting photons in the process.

Based on their number of layers, OLEDs can be classified as two-layer and three-layer OLEDs.
In two-layer OLEDs, electrons are injected from the cathode into the lowest unoccupied
molecular orbital. Simultaneously, holes are injected from the anode into the highest occupied
molecular orbital. The figure given below depicts a bilayer light-emitting display.

Figure 8: OLED
An OLED consists of:
1. Substrate: Regarded as the base of an OLED, it is made up of a thin translucent glass or foil
material.
2. Anode: It is also called an emitter. Its main function is to emit electrons when a voltage is
applied across terminals.
3. Cathode: A cathode is the topmost part of OLED displays. It injects electrons when a
potential difference is applied across terminals.
4. Organic layer: The layer above the anode is called the organic layer. It contains a conductive
polymer made of hydrogen or carbon molecules.
5. Conductive layer: This layer is made of organic plastic molecules and helps to move holes
from the anode.
6. Emissive layer: This layer is made of organic materials, it helps to transport electrons from
the cathode.
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 Properties of OLED:
i. OLEDs make it easier to fabricate flexible displays.
ii. OLEDs fit in as these consume less power and provide a high-quality display.
iii. The current OLED technology provides remarkable color fidelity, high efficiency and
operation stability, high reliability and readability.
Applications of OLED: are mainly used
i. in digital devices such as high-end television systems,
ii. computer monitors,
iii. pocket-size systems such as Android phones,
iv. media players,
v. digital cameras,
vi. portable gaming consoles and mini-screens.
Quantum dot-based light-emitting diodes (QDLEDs / QLEDs) are a new form of light-
emitting technology based on nanoparticles, and their structures are similar to the OLED
technology. However, in this technology, a layer of quantum dots is placed between electron and
hole-transporting layers, like a sandwiched structure. A quantum dot display is a display
device that uses quantum dots (QD), semiconductor nanocrystals which can produce pure
monochromatic red, green, and blue light. Photo-emissive quantum dot particles are used in LCD
backlights and/or display color filters. Quantum dots are excited by the blue light from the
display panel to emit pure basic colors, which reduces light losses and color crosstalk in color
filters, improving display brightness and color gamut.

Design of QLEDs

QDs are composed of nanoparticles with a range of diameters from 5 - 20nm. When charge carriers (electrons and
holes) are confined to such tiny particles, the larger band gap of the surrounding substance creates a barrier. When
the charge carriers (electron–hole pairs) eventually recombine, a characteristic photon is emitted.
QLED consist of a thin film of quantum dot materials sandwiched between two electrodes
(anode and cathode). When an external potential is applied across electrodes, positive and
negative charges (holes from the anode and electrons from the cathode) are injected. These
electrons and holes recombine to emit photons.

QLEDs or QDLED is considered a next-generation display technology after OLED displays. The structure of a
QDLED is analogous to that of an OLED. An applied electric field causes electrons and holes to move into the
Quantum dot layer, where they are captured in the Quantum dot layer, emitting photons. QDLEDs are a genuine
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 example of electroluminescence. They provide the hard-to-reach blue end of the spectrum and are the key to
opening any number of exciting technological developments.

Figure 9: QLED
Properties of QDLEDs

a. QLEDs are a reliable, energy-efficient, tunable colour solution for display and lighting
b. QLEDs are characterized by pure and saturated emission colours with narrow bandwidths.
c. Quantum dots (QDs) have many unique optical properties such as high photoluminescence
(PL) quantum yield (QY), high colour purity,
d. Size-tunable emission wavelength and solution-processed synthesis, make them promising
materials for next-generation light-emitting diodes (LEDs) in display and lighting applications

Application of QLEDs: Quantum dot light-emitting diodes (QD-LEDs) are widely recognized
as great alternatives to organic light-emitting diodes (OLEDs) due to their enhanced
performances. For the last ten years, OLEDs have been predominantly used in flat panel display
technologies because of their ability to produce bright, smooth pictures. They find the following
applications
(i) Quantum dots have revolutionized the field of light-emitting diodes. Quantum dots can
provide a wide variety of colors depending on their size and composition The color emitted by a
light-emitting diode can be tuned by either decreasing or increasing the size of quantum dots of
the particular material used. These find application in some crucial fields such as display and
lighting technology.
(ii) These can be effectively used in night vision, data communication, agriculture, and
horticulture.
(iii) Quantum dot light-emitting diodes (QLEDs) are cost-effective electroluminescence devices
ideal for large-area display and lighting applications.

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