Module-2 BCHES202

MODULE 2
Polymers and Memory Devices
Polymers
Polymers (Greek, poly=many and meros=part) are very high molecular mass substances
and are formed by the repeated combination of large number of simple units called
monomers through covalent bonds.
Monomers are simple molecules with 2 or more bonding sites through which each can link to the
other monomers to form a polymer chain, hence called as ‘’building blocks”. Examples: Vinyl
chloride, adipic acid, hexamethylene diamine, styrene etc. The process by which these simple
molecules, i.e., monomers are converted into polymers is called as polymerization. This may be
shown for a monomer M as given below.

The first synthetic organic polymer polyvinylchloride was synthesized in 1838 by accidentally.
Later, polystyrene was discovered in 1839.
Molecular weights of Polymers
The polymer product is a mixture of chains of different lengths but of definite molecular weight.
Thus, it is not possible to assign a definite molar mass to a polymer. It is usual to adopt statistical
method methods for calculating the average molecular weights of polymers. Two important
averaging methods are:
a) Number Average Molecular Weight/Molar mass (Mn)
b) Weight Average Molecular Weight/ Molar mass (Mw)
Number Average Molecular Weight/Molar mass
It is the ratio of the sum of molar masses of individual molecules to the total number of molecules
in the mixture.
Let a polymer chain consists of ‘n’ polymer chains of which n1 molecules have M1 molecular
weight, n2 molecules have M2 molecular weight……till ni with Mi molecular weight. then,

.
Weight Average Molecular Weight/ Molar mass (Mw)
In a mixture if, w1 is the mass of polymer with molar mass M1, w2 with molar mass M2…. till wi
with molar mass Mi, then,

𝑤
But number of moles n= 𝑀 and w=nM
Therefore replacing w1 by n1M1, w2 by n2M2……..wi by niMi in equation (2) we have,

𝑀𝑤
Usually, Mw is greater than Mn and therefore 𝑀𝑛 is greater than or equal to one. This ratio is called
distribution ratio.

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𝑀𝑤
If =1 the polymer is homogeneous and contains polymers of same chain length. The higher
𝑀𝑛
the deviation of the ratio from 1, the higher is the degree of heterogeneity of the polymer.
The key difference between number average and weight average molecular weight is that the
number average molecular weight refers to the mole fraction of molecules in a polymer
sample whereas the weight average molecular weight is the weight fraction of molecules in a
polymer sample.
Numerical Problems on Number average and weight average molar masses

1. A polystyrene polymer contains 5, 10, 15 and 20 molecules of with x= 100,

120, 150 and 200 respectively. Calculate number average and weight average molar masses of
the polymer.
Solution:
Molar mass of monomer= (8x12) + (8x1) =104
n1 = 5, M1= DP X Molar mass of monomer
M1 = 100 X 104 =10,400
Similarly,
n2 = 10, M2 = 120 X 104 = 12,480
n3 = 15, M3 = 150 X 104 = 15,600
n4 = 20, M4 = 200 X 104 = 20,800
𝑛1 𝑀1 + 𝑛2 𝑀2 + 𝑛3 𝑀3+ 𝑛4 𝑀4
𝑀𝑛 =
𝑛1 + 𝑛2 + 𝑛3 + 𝑛4
(5 × 10400) + (10 × 12480) + (15 × 15600) + (20 × 20800)
=
5 + 10 + 15 + 20

= 16536 g/mol
𝑛1 𝑀12 + 𝑛2 𝑀22 + 𝑛3 𝑀32 + 𝑛4 𝑀42
𝑀𝑤 =
𝑛1 𝑀1 + 𝑛2 𝑀2 + 𝑛3 𝑀3+ 𝑛4 𝑀4

5 × (1.04 × 104 )2 + 10 × (1.248 × 104 )2 + 15 × (1.56 × 104 )2 + 20 × (2.08 × 104 )2

=
826800
=17418.36 g/mol
2. Calculate the number average and weight average molar masses of polymer with
following composition.

Monomer molar mass= 3x12+6x1=42

n1 = 25, M1 = 400 X 42 = 16800

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n2 = 35, M2 = 800 X 42 = 33600

n3 = 40, M3 = 600 X 42 = 25200

∑ 𝑛𝑖 𝑀𝑖 (25 ×16800)+(35×33600)+(40×25200)
𝑀𝑛 = ∑ 𝑛𝑖
= = 26040 g/mol
25+35+40

∑ 𝑛𝑖 𝑀𝑖225×(1.68×104 )2 +35×(3.36×104 )2 +40×(2.5200×104 )2

𝑀𝑤 = ∑ 𝑛 𝑀 = = 27638.7 g/mol
𝑖 𝑖 (25 ×16800)+(35×33600)+(40×25200)
Conducting Polymers
Introduction: Conducting polymers are organic polymers which conduct electricity.
Conductivity polymers show excellent chemical, thermal and oxidative stability due to low
hydrogen content and aromatic structure. They are used in the manufacturing of chemical
sensors, electro-magnetic shielding, antistatic coatings, corrosion inhibitors, etc. They are also
used in compact electronic devices such as polymer-based transitions, light-emitted diode
(LEDs), and lasers.
Examples: Polyacetylene, Polypyrrole, Polyaniline, etc

Synthesis of Polyacetylene: Acetylene is

polymerized using a mixed catalyst of alkyl
aluminium and titanium tetraalkoxides
(Ziegler-Natta Catalyst).

Conducting mechanism of polyacetylene

a. In the neutral chain of polyacetylene, it is a linear
structure and has extensive conjugation but does not
conduct electricity. In order to make it conducting, a
charge has to be created by adding oxidizing agent
(acceptor, positive charge is created) or reducing
agent (donor, negative charge is created).
b. On addition of an acceptor (A), electron is pulled by
A and it becomes A- and a positive charge is created.
Another pi- electron remains on the carbon atom(as
one pi- electron is taken by A). Positive and negative
charge are present next to each other and are called
exitons and such a system is called as polaron.
c. If one more A is added, it again takes off an electron and creates a positive charge. Two positive
charges are created (dications) and because of like charge, they move away from each other, such a
system is called bipolaron or soliton.
d. And thus there is conduction.

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Applications of polyacetylene
1. Doped polyacetylene offers a particularly high electrical conductivity therefore it can be used
in electric wiring or electrode material in lightweight rechargeable batteries.
2. Used as a sensor to measure glucose concentration.
3. Use in electronic devices such as light-emitting diodes, water purification devices, hydrogen
storage, and biosensors.
Preparation, properties, and commercial applications of Graphene oxide (GO)
Graphene Oxide (GO), the monomolecular sheets of graphite oxide is a compound of carbon,
oxygen, and hydrogen in variable ratios obtained by treating graphite with strong oxidizers. GO
sheets have been used to prepare a strong paper like material and have recently attracted
substantial interest as a possible intermediate for the manufacture of graphene.
Preparation: Many methods have been developed to synthesize GO. However, in general, it is
prepared by chemical methods (Hummer’s- Offeman method).
Step 1: The oxidation of graphite to graphitic oxide is achieved by treating graphite with mixture
of con. H2SO4, sodium nitrate (NaNO3) and potassiumpermanganate (KMnO4). The completion of
the oxidation method can be judged by the presence of graphitic oxide in the final product or
with the help of carbon to oxygen ratio. The carbon to oxygen ratio should be between 2.1 to 2.9

Step 2. The prepared graphite oxide can easily form dispersion in organic solvents (DMF, THF,
NMP and ethylene glycol) and exfoliated into individual, single layer graphene oxide sheets in
this step.

Properties
1. GO particles are highly hydrophilic.
2. They form stable aqueous dispersions in a wide range of concentrations.
3. They form stable dispersions in a number of organic solvents like DMF, THF, NMP andethylene
glycol owing to hydrogen bonding between hydroxyl groups on their surface and solvent
interface.
4. Thin films of GO exhibit a high optical transparency.
Applications
1. Large area reduced grapheme oxide (rGO) transparent electrodes can become indispensable
components of low-cost flexible solar cells based on organic material.
2. GO and rGO are distinctly associated with electrodes for energy storage systems- super
capacitors and lithium batteries.
3. The controllable resistivity of partially reduced GO films and good ability for chemical
functionalization is the key property for making chemical and biological sensors for a broad
range of applications.
4. It opens the wide area of applications in electronic devices including active elements likefield
effect transistors (FETs) and organic light emitting devices (OLEDs).

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Memory Devices
Introduction:
• Memory devices are electronic components used to store data and instructions temporarily or
permanently.
• They are essential components in modern electronic devices such as computers,smartphones, and
digital cameras.
• Memory devices can be classified into volatile and non-volatile memory, with volatile memory
losing its contents when power is removed and non-volatile memory retaining its contents.
• Memory devices are organized into a hierarchy based on speed, capacity, and cost, with the CPU
cache being the fastest and most expensive type of memory.
• Memory technologies are constantly evolving, with new types of memorydevices being developed
for faster, more energy-efficient, and more reliable memory.

Basic concepts of electronic memory

• Electronic memory is a type of storage technology that uses semiconductormaterials to store digital
data.
• Electronic memory devices are known for their speed and compact size, making them ideal for use
in electronic devices.
• Electronic memory devices can be both read from and written to, meaningthat data can be stored and
retrieved as needed.
• Electronic memory devices store digital data using binary code, which is asystem of representing
information using only two symbols 0 and 1.
• Memory cells are small units of semiconductor material that can store a single bit of information.
The most common types of memory cells are DRAM and SRAM cells.
• Multiple memory cells are organized into arrays, which consist of rows andcolumns of memory cells.
The organization of the memory array determines how data is accessed and how quickly it can be
accessed.
• Memory devices can be categorized based on whether they allow for both reading and writing of
data (RAM) or used for storing fixed data that cannot be altered (ROM).
• Non-volatile memory is a type of memory that retains stored data even when the power is turned
off. This contrasts with volatile memory, which requires power to retain stored data.
• Flash memory is a type of non-volatile memory that can be erased and rewritten multiple times. It
is commonly used in memory cards, USB drives, and solid-state drives.

Classification of electronic memory devices

(Based on the device structure or the electronic component employed in the device)

1. Transistor-Type Memory Devices:

➢ Transistor-based memory refers to memory technologies that utilize transistors as the
primary component for storing and accessing data.
➢ Transistors are semiconductor devices that can amplify or switch electronic signals, making

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them a fundamental building block of modern electronics.

➢ Transistors are used to create memory cells that can store and retrieve data in a digital format.
➢ Each memory cell typically consists of one or more transistors along with other supporting
components.
➢ The state of the transistors determines the stored data, representing binary values such as 0s
and 1s.

2. Capacitor-Type Memory Devices:

➢ Capacitor-based memory refers to memory technologies that utilize capacitors as the primary
component for storing and retaining data.
➢ Capacitors are electronic components that can store and release electrical charge.
➢ Capacitors are used to create memory cells that can store and retrieve data in a digital format.
➢ Each memory cell typically consists of a capacitor and additional circuitry for accessing and
manipulating the stored charge.
➢ The presence or absence of charge in the capacitor represents the binary states of data,
typically 0s and 1s.

3. Resistor-Type Memory Devices:

➢ Resistor-based memory refers to memory technologies that utilize resistors as the primary
component for storing and accessing data.
➢ In these memory technologies, the resistance of the memory elements is altered to represent
different data states.
➢ This resistance change is typically achieved by applying voltage or current pulses to the
memory element.
➢ One notable example of resistor-based memory is Resistive Random-Access Memory
(ReRAM), also known as Resistive RAM or RRAM. (still in the research and development stage,
and their commercial adoption and widespread use are yet to be fully realized.)

4. Charge Transfer-Type Memory Devices:

➢ Charge transfer-based memory refers to memory technologies that store and retrieve
data by transferring electric charges within the memory elements.
➢ These memory technologies rely on the movement of charges to represent and
manipulate data.
➢ Charge transfer type memory consists of an array of closely spaced capacitors that can
store and transfer electric charges.
➢ Data is stored in the form of charge packets, and by controlling the voltage applied to the
capacitors, the charges can be transferred and read out sequentially. Example: Charge-
Coupled Devices (CCDs).

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Types of organic memory devices:

Organic memory devices refer to electronic devices that utilize organic materials for data storage
and retrieval. These materials often exhibit unique properties, such as high flexibility, low-cost
production, and compatibility with large-area manufacturing processes. Here are some examples
of organic memory devices:
1. Organic Field-Effect Transistors (OFETs): OFETs, by applying an electric field, the charge
distribution in the organic semiconductor layer can be altered, leading to changes in
conductivity and storage of information.
2. Organic Electrochemical Transistors (OECTs): OECTs employ organic materials that can
reversibly undergo redox reactions. The redox processes modulate the conductivity of the
device, enabling data storage and retrieval.
3. Organic Resistive Random-Access Memory (RRAM): Organic RRAM devices use organic
materials with resistive switching behavior. By applying voltage, the resistance of the organic
layer can be altered, allowing for multiple resistance states that can represent data.
4. Polymer Memory Devices: Various types of polymers, such as ferroelectric polymers or
conductive polymers, can be employed for data storage. These materials exhibit properties
like polarization or electrical conductivity changes that can be utilized for memory
applications.
Organic memory materials
(a) Organic molecules
Organic molecules can indeed be used as organic memory materials. Organic memory materials
are materials that can store information, similar to the way that traditional computer memory
works.
There are several examples of organic molecules that have been studied as potential organic
memory materials. Here are a few common examples:
1. Bistable [2]Rotaxanes: These are molecular machines that
consist of a ring threaded onto a molecular axle. The ring can
move along the axle, allowing the rotaxane to adopt different
states. In a bistable [2]rotaxane, the ring can be locked into
two different positions, which correspond to the two different
states of the memory element.

2. Diarylethenes: These are photochromic

molecules that can switch between two
different configurations when exposed to
light. This property can be used to create a
memory element that can be switched
between two different states using light.

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3. Spiropyrans: These are also photochromic

molecules that can switch between two
different configurations when exposed to light.
They have been studied as potential memory
materials, particularly in the form of thin films.

4. Polydiacetylenes: These are polymers that can undergo a

reversible color change in response to changes in temperature
or pressure. This property can be used to create a memory
element that can be switched between two different states.

(b) Polymeric materials

Polymeric materials have received considerable attention as organic memory materials due to
their unique properties such as flexibility, low cost, and easy processing.
Polymeric materials have also been studied as potential organic memory materials. Here are a
few common examples:
1. Polyvinylidene fluoride (PVDF): PVDF is a piezoelectric polymer
that can generate an electric charge in response to mechanical stress.
This property has been exploited to create memory elements based
on the deformation of the material.

2. Polyaniline (PANI): PANI is a conducting polymer that can be used

to create memory elements based on the modulation of its
conductivity. PANI can be synthesized in different forms such as
nanowires, thin films, and nanoparticles, making it a versatile
material for memory applications.

3. Polycarbonate (PC): PC is a thermoplastic polymer that can

be used to create memory elements based on the reversible
deformation of the material. PC has good mechanical
properties, making it a suitable material for flexible memory
devices.

4. Polyethylene oxide (PEO): PEO is a water-soluble

polymer that can be used to create memory elements based
on the modulation of its electrical conductivity. PEO has
been used to create resistive switching memory devices.

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(c) Organic inorganic hybrid materials

Organic-inorganic hybrid materials have received considerable attention as potential organic
memory materials due to their unique combination of properties. These materials can exhibit
improved performance compared to their individual organic or inorganic components, making
them promising candidates for memory applications.
Organic-inorganic hybrid materials have also been studied as potential organic memory
materials. Here are a few common examples:
1. Metal-organic frameworks (MOFs): MOFs are porous materials made up of metal ions or
clusters connected by organic ligands. MOFs have been studied as potential memory materials
due to their high surface area and tunable properties. Memory effects in MOFs have been
observed due to changes in the conformation of the organic ligands.
2. Hybrid perovskites: Hybrid perovskites are materials that have a crystal structure similar to
that of the mineral perovskite. These materials consist of an inorganic framework that is filled
with organic cations. Hybrid perovskites have been studied as potential memory materials
due to their unique properties such as high charge carrier mobility and tunable bandgap.
3. Nanocellulose-based hybrids: Nanocellulose is a renewable and biodegradable material
that can be functionalized with organic molecules to create hybrid materials. Nanocellulose-
based hybrids have been studied as potential memory materials due to their high mechanical
strength, low toxicity, and tunable properties.
4. Hybrid polymers: Hybrid polymers consist of both organic and inorganic components and
have been studied as potential memory materials due to their unique properties. For example,
hybrid polymers based on siloxane and organic moieties have been studied as potential
memory materials due to their high thermal stability and tunable properties.

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