PST-502 POLYMER

SCIENCE & TECHNOLOGY

LABORATORY

Prepared by Burcu Sarı & Yelda Meyva

PRIMARY CHARACTERIZATION OF POLYMERIC MATERIALS

What is the Polymer?

A polymer is a macromolecule built up by the repetition of small and simple chemical units
which are called as monomer. The chemical reaction of creating polymers from monomers is
known as a polymerization. The substances are includes mainly C, H, O, N (few other elements
such as F, Cl, S, Si, etc.)

Name Monomer Polymer

Ethylene CH2=CH2 Polyethylene -(CH2-CH2)-
CH=CH2 Polyvinylchloride (PVC) -(CH-CH2)-
Vinyl chloride
Cl Cl

Styrene
Polystyrene
Polymerization reaction types;

• Condensation (Step-Growth Polymerization)

• Addition (Chain-Growth Polymerization)

Classification of Polymers

➢ According to Origin

Polymers can be classified as natural (occur in nature and water-based) and artificial polymers
according to their origin. Natural polymers have proteins, natural rubber, starch, silk, wool,
cellulose. Natural rubber does not handle easily (sticky), but it has very good properties and
durability. So, synthetic rubber is preferable because different monomers can be mixed in
various proportions resulting in a wide range of physical, mechanical and chemical properties.
Man-made polymers are called as artificial polymers such as PE, PVC, PS, PMMA.

Chemical Structure of Starch

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 Chemical Structure of PMMA

➢ According to Polymerization Process

• Condensation Polymers

Terephthalic acid Ethylene glycol

Polymerization of Polyester

Two polyfunctional molecules react with each other and eliminate one small molecule.

• Addition Polymers

Free Radical Polymerization Polystyrene

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These polymers are produced by chain reactions. This reactions start with decomposition of a
relatively unstable initiator.

➢ According to Structure of Main Chain

• Homochain Polymers: contains only C atom in the main chain.

• Heterochain Polymers: contains atoms other than C in the main chain. They can generally
be produced by condensation polymerization.

➢ According to Structural Forms of Chains

• Linear Polymers: Two functional groups can form the long chain linear polymers.
• Branched Polymers: Bi and tri functional polymers can form these long chains with side
branches.
• Network (Cross-linked) Polymers: 3D polymers include long chains connected up into
network by chain crosslinking. At first, crosslinks between polymer chains makes the
polymer more elastic. However, the number of crosslinks increase, the polymer becomes
more rigid.

➢ According to Thermal Behavior

• Thermoplastics: They can be reheated to change shape and no chemical changes occur
during this process. They have linear or branched structure such as nylon, polyurethane
(PU), polypropylene (PP), acrylonitrile butadiene styrene (ABS).

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  Highly recyclable
 Aesthetically superior finishes
 High impact resistance (impact strength: the absorbed energy by the material
with sudden impact and strike)
 Reshaping capacity
 Chemical resistant

 Generally more expensive than thermosets

 Can melt if heated

• Thermosets: They are highly cross-linked polymers such as epoxy, phenol. The network
structure is stable. Cannot melt or flow upon heating. They decompose at high
temperatures. Thermosets are durable with high temperature performance and have
found applications of areas including electronic chips, polymer coatings and dental
fillings.

 More resistant to high temperatures than thermoplastics

 Highly flexible design
 Excellent aesthetic appearance
 Cost effective

 Cannot be recycled (if we heat it decomposes)

 More difficult to surface finish
 Cannot be reshaped

• Elastomers: They are also known as rubber. They have low glass transition temperature.
They are highly flexible, so if the force is applied to the elastomers, they will change
their shape and then come back to the original shape with removing the force. They have
different types such as thermoplastic elastomers, the proteins resilin and elastin,
polysulfide rubber, elastolefin.

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Glass Transition Temperature

If the temperature decreases below Tg, the polymer behaves brittle. Above Tg, the polymer
becomes more rubber like. It can be determined by using differential scanning calorimetry
(DSC), dynamic mechanical analysis (DMA) or dilatometer.

We can also classify the polymers what they consist of their nature.

Polyolefins

A polyolefin is a polymer produced from a simple olefin, or alkene as a monomer.

Common examples are LDPE, HDPE, PP, etc. Primary characteristics:

❖ Low melting point

❖ Easy ignition
❖ Neutral vapor
❖ Fiber characteristic for PP
❖ Wax odor
❖ Flammable

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Styrenics

Polymers formed by polymerizing styrene as a homopolymer and styrene and other

monomers as a copolymer. Common examples are PS, styrene acrylonitrile (SAN),
acrylonitrile butadiene styrene (ABS), etc. Primary characteristics:

❖ Easy ignition
❖ Neutral vapor
❖ No fiber character
❖ Styrenic (sweet) odor
❖ Flammable
❖ Black fumes when burning

Acrylics

Polymers formed by polymerization of acrylics and methacrylics in homopolymers and

heteropolymers. Common examples are PMMA, PMA, etc. Primary characteristics:

❖ Neutral vapor
❖ No fiber character
❖ Garlic like odor (acrylic odor)
❖ Flammable
❖ Degradation (unzipping reaction)

Halogenated Polymers

Polymers including halogens such as Cl, F, Br. Common examples are PVC, PTFE
(Teflon), etc. Primary characteristics:
❖ No melting
❖ Flame retardant
❖ Generally acidic vapor
❖ No fiber character
❖ Degradation (Yellowing in PVC)
❖ Acidic odor

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Polyesters

Polyester is a category of polymers which contain the ester group in their main chain.
Common examples are PET, PBT, PEN, etc. Primary characteristics:
❖ Relatively high melting temperature
❖ Neutral vapor
❖ Fiber character
❖ Typical odor
❖ Flammable

Polyamide

A polyamide is a polymer which has peptit bonds. They can occur both naturally such
as wool and silk or artificially such as nylon, aramids. Primary characteristics:
❖ Relatively high melting temperature
❖ Basic vapor
❖ Fiber character
❖ Cheese like odor
❖ Flammable

Some important polymers and their chemical structures:

PE

PP

PS

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Polymethyl methacrylate (PMMA)

Polyvinyl chloride (PVC)

Polytetrafluoroethylene (PTFE) (Teflon)

Polyethylene terephthalate (PET)

Nylon 6, 6

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Experimental Part

Behavior upon heating

o Small glass tubes

o Bunsen burner
o Litmus paper

• Melting behavior
• Fiber characteristics
• Degradation and decomposition behavior
• Acidic/Basic/Neutral gases

Behavior in flame

o Ceramic tiles
o Bunsen burner

• Flame retardancy (when we remove flame, burning decreases sharply)

• Burning Behavior (color of the flame)

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 Polymer Names U1 U2 U3

Melting Behavior

Fiber Characteristics

Decomposition/Degradation
Behavior

Acidity of flue gases

Flame Retardancy

Burning Behavior

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CRYOSCOPY

The aim of this experiment is to learn colligative properties and to determine the number
average molecular weight of the polymer using freezing point depression method.

Colligative Properties

Some of the properties of solutions are independent of the nature of the solute. They depend
only on the amount of dissolved particles in solution. These properties are called as colligative
properties. Freezing point temperature, boiling point temperature and osmotic pressure can be
given as examples. Anti-freeze technology was developed based on this property.

∆𝑇𝑓 = 𝐾𝑓 × 𝑚 × 𝑖

∆𝑇𝑓 : freezing point depression

𝐾𝑓 : cryoscopic constant [°C kg/mol]

𝑚: molality [mol solute/kg solvent]

𝑖: van’t Hoff factor, number of ions

For substances which do not dissociate in water, such as sugar, i=1. For solutes that completely
dissociate into two ions, i=2 such as NaCl or three ions i=3 such as MgCl2.

Used Chemicals

Azobenzene Benzene PEG

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PEGs have many industrial, food and pharmaceutical uses. The molecular weights of PEGs are
determined by the number of ethylene glycol units incorporated into each PEG polymer and
vary from 300 grams per mole to 10,000,000 grams per mole. The molecular weight in turn
determines the characteristics of each type or category of PEG. Low molecular weight PEGs,
containing two-to-four ethylene glycol units per polymer, are clear, watery liquids. PEGs
containing up to 700 ethylene glycol units per polymeric product are clear, thick liquids. PEGS
having 1,000 or more ethylene glycol units per polymeric product are waxy solids. PEGs are
non-toxic, colorless, odorless, nonirritating and difficult evaporate. They are soluble in many
organic solvents. All of them dissolve in water and do not change the color, odor or taste of the
water.

The characteristics of PEGs make them excellent materials for use in the pharmaceutical
industry. PEGs are used as lubricants and are employed in a variety of pharmaceutical products
as solvents, dispensing agents, delivery liquids for medications, fillers for tablets, as suppository
bases, in ophthalmic solutions and as a treatment for constipation. PEGs are also used in
veterinary products.

In manufacturing processes, PEGs are used as water-based coatings, anti-dusting agents in

agricultural products, brighteners in electroplating, cleaners and detergents, moisturizers in
cosmetic products, dye carriers for paints and inks, packaging products, non-stick agents for
molded products, color stabilizers for paper, ceramics manufacture, a softener and anti-static
agent in textile manufacture and in soldering fluxes.

Experimental Procedure

Mechanic
stirrer

Digital
thermometer

Assume that the system is adiabatic.

Soln.

Ice
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Mechanical stirring is important to obtain homogenous mixture and to avoid crystallization of
the solution.

➢ 25 mL pure benzene → freezing point (F.P): ?

➢ 0.1 g Azobenzene + 10 mL Benzene
F.P
2 mL ΔTf Slope=Kf benzene
3 mL
5 mL
molality

➢ 0.1 g PEG + 10 mL Benzene

F.P
2 mL ΔTf 𝐾𝑓 𝑏𝑒𝑛𝑧𝑒𝑛𝑒
Slope= ̅̅̅̅̅
𝑀𝑛
3 mL
5 mL

c (g/L)
∆𝑇𝑓 1
lim =
𝑐→0 𝑐 ̅̅̅̅
𝑀𝑛

In real, molecular weight of used PEG is 1000 g/mol. Make your discussions and compare
your calculated value with it.

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SYNTHESIS OF NYLON 6 AND NYLON 6,10

Introduction

Nylons have amide group (R-C=O-NH2), so it can be said that they are in polyamide group.
There are many nylon types such as Nylon 6,6, Nylon 6,10, Nylon 6,12, Nylon 4,6, Nylon 6,
Nylon 12. The two most important kinds of nylon are Nylon 6,6 and Nylon 6. These two nylons
have almost identical properties. Both were invented in the late 1930s. Nylon 6,6 was
discovered first. It was invented in the US by Wallace Carothers who was working for DuPont.
Not long after that Nylon 6 was invented in Germany by Paul Schlack who was working for I.
G. Farben. Nylons are used during World War II in military applications such as parachutes
and flak vests due to scarce of silk.

Nylons are some of the most important fibers produced commercially. If you have ever slept in
a tent or used a toothbrush, you have used nylon fibers. But, nylon can be more than just fibers.
It is also used for self-lubricating gears and bearings. Nylon-clay composites are used to make
underhood automobile parts.

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Properties of Nylons

They have optimum strength and toughness due to intermolecular forces. The most important
intermolecular force is hydrogen bonding. These hydrogen bonds make crystals of nylon very
strong, because they hold the nylon chains together very tightly. In addition, they have good
thermal and chemical resistance. However, they have low resistance to strong acids and
alcohols. They are prone to grabbing moisture from the environment. While their impact
strength and ductility increase with moisture, their mechanical strength decreases.

Usage Areas

• Automotive

They can be used for handles and radiator grill in automotives. For this purpose, they should be
dyeable, UV resistant, also have good surface appearance and mechanical strength.

• Electric

They can be used for low voltage switch gears.

• Sport

They can be used for ski bindings and roller skate due to their high impact strength and
mechanical strength.

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Polymerization Reactions

All polymerizations are investigated in two categories: Step-Growth and Chain-Growth

polymerizations. Both polymerizations are used to make nylons. Making nylon from a diacid
and a diamine is a step-growth polymerization. Making nylon from lactams is usually a chain-
growth polymerization.

In a step-growth system, we start off with monomers. The monomers combine and grow into
dimers, trimers, tetramers, and so forth. The molecules get bigger and bigger, but only when
the polymerization reaches high conversion, we have high molecular weight polymers.

But, in a chain growth system, we start off with monomers, and the monomers quickly form
high molecular weight polymers. These are high molecular weight polymers present in your
test tube just after you start the polymerization. So, we won’t have dimers, trimers, and other
oligomers. A growing polymer chain grows so fast that it reaches high molecular weight
quickly.

Ring Opening Polymerization

Strong base

Has not enough reactivity

The new molecule formed also has negatively-charged nitrogen, an amine anion. This is
unstable species, so it will abstract a proton from another molecule of e-caprolactam.

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Synthesis of Nylon 6,10

Interfacial Polymerization

An aqueous phase has one monomer and an organic solution containing second monomer.
Polyamide is the most common polymer for this process. Two solutions must be immiscible.
The rate of the reaction is high, this reaction mechanism tends to produce a small number of
long polymer chains of high molecular weight.

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Experimental Procedure of Nylon 6

❖ Disposable test tube

❖ Test tube holder
❖ Bunsen burner
❖ Glass rod
❖ e-caprolactam
❖ Metallic sodium in oil
• Put e-caprolactam in the test tube.
• Use the tube holder and move the test tube around the flame of the bunsen burner.
• Add a spatula tip of Na when the mixture in the tube melts.
• Keep heating the tube for 2-4 more minutes with moving around the flame in order to
prevent hot spots.
• When polymerization occurs, the mixture will become more viscous.
• If polymerization does not occur within several minutes, cool to just above the
solidification temperature, add more Na and reheat.

Caution! Adding too much initiator or heating too long will lead to low molecular weight and
brittle fibers. Also, heating too slowly allows the active species (the sodium salt of caprolactam)
to react with moisture in the air; and it will no longer be able to initiate polymerization.

The most exciting part of the experiment involves pulling fibers from the molten polymer. The
polymer is ready when the viscous mass no longer bubbles freely. Fibers are drawn by dipping
a glass rod into the polymer and rapidly drawing out the solidifying material. It may be
necessary to let the polymer cool some to get just the right combination of viscosity and
strength. These fibers will stretch under tension to complete polymer orientation and are then
very tough.

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Experimental Procedure of Nylon 6,10

❖ Hexamethylene diamine (1 g)
❖ Sebacoyl chloride (1 g)
❖ Hexane (25 mL)
❖ Two 50 mL beakers
❖ Glass stirring rod

• Dissolve about 1 g of hexamethylene diamine in 25 mL of water in a 50 mL beaker and

add 1-2 drops of phenolphthaleine.
• Add some azobenzene in 25 mL hexane.
• Gently pour the solution in the hexamethylene diamine/water solution.
• Get 1 mL of sebacoyl chloride using a syringe. Add it into hexane phase. A film will
form at interface. Slowly wind up the thread as you draw it out.

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SOLUTION POLYMERIZATION OF POLYSTYRENE

Introduction

Polystyrene is a synthetic aromatic polymer which can be produced from monomer styrene. It
can be in foam or solid form. Polystyrene is one of the most widely used plastics, it is produced
several billion kilograms per year. It has inherent transparency, however can be colored with
additives.

Advantages of PS

 Inexpensive and rigid plastic

 High impact polystyrene → by adding rubber → toughness and impact strength increase
 Good flow properties; so good processability and fast molding cycle
 High heat resistance
 Food contact acceptable

Disadvantages of PS

 Poor solvent resistance

 Homopolymer forms of PS are brittle
 Poor thermal stability
 Subject to stress and environmental cracking
 Poor barrier properties

Applications of Polystyrene

➢ Foam packaging and insulation

➢ Model cars and airplanes
➢ Toys
➢ Hairdryers, computers, and kitchen appliances

What is the Polymerization?

Polymerization is a process of reacting monomer molecules come together in a chemical

reaction to form two or three dimensional structures of polymer chains.

Main categories according to mechanisms;

 Condensation Polymerization (Step-Growth Polymerization)

 Addition Polymerization (Chain-Growth Polymerization)

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Condensation Polymerization

Condensation polymers form:

• when bifunctional monomers react to form a long chain polymer molecule

• small molecules, such as water, are eliminated during the reaction

Examples: Polyesters, polyamides, proteins and polysaccharides such as cellulose

dicarboxylic acid + diol

terephthalic acid + ethylene glycol → PET

Addition Polymerization

Initiation and Propagation Steps

Termination

By combination

By disproportionation

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Differences Between Condensation and Addition Polymerization

Condensation Polymerization Addition Polymerization

Any two molecular species can react Only monomer adds to the growing chain
Monomer disseapers early in the rxn. Monomer conc. decreases linearly
Polymer MW increases steadily throughout the High MW polymers at once, MW changes little
rxn. throughout the rxn.

Long rxn. time is required Long rxn. time affect MW little

Polymerization Processes
Bulk Polymerization

This type of polymerization is the most economical one because it requires neither solvent nor
emulsifier and affords high-purity polymers. However, the gel effect, with its consequences
(high viscosity, low diffusion rates, small heat conductivity) makes difficult its control. So,
explosion can be occurred if there is no an appropriate cooling system. The initiator must be
soluble in the monomer melt and organic peroxides are commonly used.

Initiator Monomer

The increase in viscosity, which is the first cause for the gel effect, makes difficult the stirring
of the reaction medium and thus the removal of the heat produced upon polymerization. The
viscosity increases at later stages of the polymerization, giving the formed polymer chains lower
mobility, making them less probable to terminate themselves. However, the monomers existing
in the reaction medium at those stages have much higher mobility, so that they keep on
propagating and we have high yield compared as other techniques.

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Solution Polymerization

Solution polymerization is often used in research laboratories because high yields can be
achieved without facing the difficulties associated with the gel effect.

Solvent

Initiator Monomer

The initiator must be soluble in the reaction medium. At the end of the polymerization, the
polymer is recovered by evaporation of the solvent or by precipitation. Free radical
polymerization in solution is seldom used in industrial processes due to the cost of the solvent,
the cost of its removal, and toxicological and environmental concerns it causes; it is, however,
sometimes utilized to obtain high-purity products or when the solvent is water (for the
polymerization of acrylamide).

Suspension Polymerization

One way to remove the heat that builds up in bulk polymerization due to the gel effect is to
disperse water-insoluble monomers as small droplets (10-500 µm) in an aqueous phase
containing “suspending" agents such as poly(ethylene oxide), poly(vinyl alcohol),
hydroxypropylcellulose, fatty acids. Initiators must be monomer soluble. The control of the
temperature is obtained by stirring the dispersed phase and cooling the walls of the reactor. In
addition, surfactants (in low proportions) can improve stabilization of the particles. Beyond a
certain yield, the particles can agglomerate and induce a coalescence of the medium that can be
prevented by addition of mineral powders.

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Emulsion Polymerization

Emulsion polymerizations proceed in a completely different way and result in the formation of
particles with size ranging between 0.05-5 µm. Continuous medium is water, however it is also
possible to carry out reverse emulsion polymerization in organic solvents in which the monomer
is insoluble. Initiators must be water-soluble such as S2O8K2, H2O2. Another major difference
with suspension polymerization lies in the presence of a emulsifier or surfactant in a proportion
well above its critical micellar concentration (CMC). When the initiator decomposes,
hydrophobic radicals are generated which add to the monomer present in the aqueous phase; as
more monomer molecules are added, the growing radical becomes increasingly hydrophobic
and surface active.

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Experimental Procedure

 Used Chemicals
CN CN
H3C C N N C CH3
CH3 CH3

Styrene AIBN (Azobisisobutyronitrile)

Toluene

Toluene Ethanol

 Take 25 mL styrene and 50 mL toluene and mix them well.

 Add 0.125 g of AIBN to the mixture as an initiator.

 Heat the mixture to the 100 °C about 60 minutes in a 2-necked balloon to reflux.

 Pour the polymer into 150 mL of ethanol solution.

 Finally, the precipitated polymer is isolated by suction and can be dried at 80 °C.

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DETERMINATION OF VISCOSITY AVERAGE MOLECULAR WEIGHT OF
POLYMERS BY DILUTE SOLUTION VISCOSITY TECHNIQUE

What is the Viscosity?

The molecular friction within a fluid that produces flow resistance. Viscosity is one the most
characteristics of fluids.

How is Viscosity Measured?

• Ostwalt Capillary Viscometer

• Falling Ball Viscometer

• Gardner Viscometer

• Cone and Plate Viscometer

• Rotating Parallel Disc Viscometer

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Ostwald Capillary Viscometer

Viscosity Types

Relative Viscosity
Relative viscosity (ηr) is the ratio of the viscosity of the solution (η) to the viscosity of the
solvent (ηs).

Specific Viscosity

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Reduced Viscosity

Inherent Viscosity

Intrinsic Viscosity

c : concentration of polymer in the solution

ᵑ : viscosity of the solution
ᵑ0 : viscosity of the pure solvent

C→0 to eliminate polymer-polymer interactions

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Huggin’s Equation

ηsp : specific viscosity.

c : concentration (be careful about units, make sure everything cancels out)
[n]: intrinsic viscosity.
k' is a constant; also called as Huggins constant

Kraemer Equation

ηrel : relative viscosity

c : concentration
[η] : intrinsic viscosity

Mark-Houwink Equation

K : constant
a : a scalar which relates to the shapes of polymer in the solution
Mv : experimental viscosity average molecular weight

• a: 0 hard spheres

• a: 0.5-0.8 random coil (in good solvent)

• a: 1 stiff coils (rigid)

• a: 2 rods (liquid crystalline polymers)

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Polymer Solutions

• End to end distance; r

• Radius of gyration; s

• Debye’s Equation:

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Long Chain Interactions

• The long chain interactions become appear in good solvents.

• If temperature increases, volume increases and long chain interactions will increase

Short Chain Interactions

• Short chain interactions become appear in theta solvent and theta temperature.

• In theta temperature, long chain polymer-polymer interations are compensated for by the
solvent-polymer interactions.

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Experimental Procedure

• Heat the water-bath to the temperature of 25 °C.

• Measure the flux time for 15 mL pure toluene

• Then, pour the pure toluene to the waste and measure the flux time for 15 mL 0.5 g/dl of
PS solution (S1)

• Add 5 ml of toluene to S1 to obtain solution S2, then measure the flux time

• Add 5 ml of toluene to S2 to obtain solution S3, then measure the flux time

• Add 5 ml of toluene to S3 to obtain solution S4, then measure the flux time

Calculations

• Calculate the concentrations of the solution S1, S2, S3 and S4

• By applying graphical method, obtain the intrinsic viscosity

• Make a table of c (g/dl), flux time (sec.), relative, specific, reduced, and inherent
viscosities

• Calculate the viscosity average molecular weight (Mv) with Mark-Houwink equation

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MECHANICAL TESTS FOR POLYMERS

Purpose is to conduct on the mechanical properties of polymers and perform tensile testing
method on a polymer sample.

• Types of Mechanical Test

Tensile, Flexural, Impact, Fatique, Hardness, Tear…

• Tensile Testing
Tensile tests measure the force required to break a specimen. Tensile test gives a stress-
strain diagrams used to determine key properties such as tensile strength, modulus, strain.

• Stress-Strain Diagram
This diagram gives a plot of stress (σ) versus strain (ε) during tensile test.
Stress is calculated by dividing the amount of force (F) applied by the machine in the
axial direction by its cross-sectional area (A). Stress, in metric system, is usually
measured in N/m2 or Pa. σ = F/A
Strain represents the displacement between particles in the body relative to the initial
length. ε=(l-l0)/l0, where l0 is starting or initial length (mm) and l is stretched length (mm).

The constant of proportionality is called the elastic modulus or Young’s modulus.

Young's Modulus = Stress / Strain

Hooke’s law is used in elastic region. If the stress exceeds the proportional limit, the strain
is no longer proportional to the stress. The polymer do not return to its original shape
when the stress is removed in plastic region.

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Equipment
Universal testing machine

Sample
Thermoplastic/Thermoset/Elastomer samples

Experimental Procedure

• A polymer (dog bone sample) is gripped at both ends by an apparatus, which slowly
pulls lengthwise on the piece until it fractures.

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• The pulling force is called a load, which is plotted against the material length change,
or displacement.
• The load is converted to a stress value and the displacement is converted to a strain
value.

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POLYMER MATRIX COMPOSITES (PMCs) (Synthesis of Novolac Resin)

Purpose of this experiment is to produce polymer matrix composite in order to obtain a material
has enhanced mechanical, chemical and thermal properties. This experiment consists of two
parts and is conducted in two weeks. In the first week, thermoset novolac resin is obtained and
in the second week, novalac is mixed with the reinforcement materials and additives in order to
obtain a polymer matrix composite product (Bakalite) having required properties.

Basic Concepts:

Composite: Composites can be defined as materials that consist of two or more chemically and
physically different phases (matrix and dispersed phases) separated by a distinct interface.

Matrix phase is the primary phase having a continuous character. It holds the dispersed phase
and shares the load with it.

Dispersed (reinforcing) phase is embedded in the matrix to reinforce properties of matrix.

The basic difference between blends and composites is that the two main constituents in the
composites remain recognizable while these may not be recognizable in blends.

Bakalite is a composite produced by combination of novolac resin (matrix) and wood flour
(reinforcement).

Phenolic Resins:
The phenolic resins are condensation products of phenol and formaldehyde.

Phenolic resins are divided into two classes:

i-Novolac (acidic conditions Formaldehyde < Phenol)

ii-Resoles (basic conditions Formaldehyde > Phenol)

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Novolac:

The reaction continues with additional phenol, and splitting off of water.

Resole

Methylol phenol can react with itself to form a longer chain methylol phenolic

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Or it can form benzyl ether

Or it can react with phenol to form a methylene bridge.

The main differences between Novolac and Resol resins are:

1) Resole phenolic resins are produced by using alkaline catalysts, whereas novolac resins are
produced via acidic catalysts.
2) Resole phenolic resins are produced via B-staging while novolacs are made by
prepolymerization.
3) Resole phenolic resins are methylol-bearing resins while novolacs are non- methylol-
bearing resins.
4) Resoles typically have a shelf life of less than 1 year (less than 60 days), whereas novolacs
have an infinite shelf life.
5) Resoles split off water when they cure while novolacs give off ammonia when they cure.
6) Novolac resins are twice more dimensionally stable than resoles.
7) Resoles are typically casting and bonding resins, whereas molding compounds are made
from novolacs (some molding compounds can be made from resoles).
8) Resoles are usually liquids while novolacs are solids.

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Chemicals
Phenol
Formaldehyde
Oxalic Acid
Water
Hexamethylene Tetramine
Magnesium Oxide
Magnesium Stearite
Calcium Carbonate
Wood Flour

Apparatus and Glassware

Thermometer
Condenser
Heater
Magnet
Graduate Cylinder

Prelaboratory Work
• Discuss the composite, reinforcement and matrix terms.
• Discuss the difference between thermoset, thermoplastic and elastomer.
• Discuss the main differences between novolac and resole resins.

Experimental Procedure

1) 32.5 g phenol, 3.5 ml water, 0.25 g oxalic acid dehydrate and 23.1 g formaldehyde are put
into 2 necked flask and condenser is placed. Add magnet. After it was refluxed about 30 minutes
at 250 °C, the same amount of oxalic acid is added and it is continued for refluxing for 60
minutes more. Then, about 200 mL hot water is poured. To observe clearly phase separation of
polymer and water, system is not filtered and waited to the next week.

2) The upper layer of the water is poured carefully and the remaining water is removed by
heating until no more water is remained. The resulting product is taken into a pot wrapped up
in Al foil. After freezing the product with liquid nitrogen, it is broken into pieces with a hummer.
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Four different sets are prepared (Table 1). They are blended by a ball mill. The sets are placed
into a mold. They are pressed under 150 kg/cm2 about 200 °C for 10 minutes.

Table 1. Compositions of composite samples prepared in the experiment

Chemicals I II III IV
Novolac 5 5 5 5
HMTA 0.85 0.85 0.25 0.85
Wood flour 3 8 3 -
Calcium carbonate - - - 1
Magnesium oxide 0.25 0.25 0.25 0.25
Magnesium stearate 0.50 0.50 0.50 0.50

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PRODUCTION OF POLYURETHANE FOAM

Purpose is to synthesize polyurethane and to produce polyurethane foam.

Prelaboratory Work

• Types of Polymerization Techniques

• Chemical Reaction of Polyurethane Synthesis
• Blowing Reaction of Polyurethane Foam
• Types of Polyurethane Foams
• Industrial Processing Methods of Polyurethane Foam

Chemicals

Polyol
Toluene diisocyanate (TDI)
Diaminoethanol catalyst
Silicone Oil
Water as blowing agent

Apparatus and Glassware

Thermometer
Beaker
Glass Fish
Pipet
Graduated Cylinder
Al-Foil
Hot Plate

Experimental Procedure

- Put 20 g of polyol into 100 ml baker. Add magnetic stirrer and mix polyol continuously
while heating on hot-plate. When temperature reaches to 35°C, add 3 g of TDI.
(Caution: TDI is toxic!) Stir the mixture at 35 °C for 30 minutes.
- Close top of the beaker by Al-foil. Heat the mixture to 90°C, wait for 30 minutes. (Be
careful! Temperature may increase immediately)
- Cool the beaker to room temperature. Add additional 4.5 g TDI, 1 g of silicone oil and
7-10 drops of diaminoethanol. Stir the medium until obtaining a homogenous mixture.
- Do an Al- foil cup. Pour the mixture into the cup. Add 2 ml of water with an injector to
the cup, and wait for foaming.

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DIFFERENTIAL SCANNING CALORIMETRY

Purpose of this experiment is to determine thermal behavior of polymer sample by using DSC
technique.

Chemicals

PET

Instrument

Scinco DSC N-650

Prelaboratory Work

• Thermal properties of polymers

• Types of thermal analysis used for polymers
• Basic principle of DSC
• Percent crystallinity of polymers.

Experimental Procedure

Engineering polymer sample PET is used. Polymer samples should be free from impurities;
including monomers, water and solvent.

Control operations manual for instrument for proper methods of:

- Temperature and heat calibration verification.

- Sample pan type and crimping of the sample pan.

- Loading sample in pan.

- Operating temperature controller and setting temperature limits.

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