Advanced Ship Building

Materials
Lesson – 2
LESSON OUTLINE

▪ USES OF FOLLOWING PLASTICS AND THEIR PROPERTIES

– CELLULOID
– VULCANITE EBONITE
– BAKELITE
– TERYLENE
– POLYVINYL CHLORIDE
– LAMINATED PLASTICS
CELLULOID

▪ Celluloids are a class of materials produced by mixing nitrocellulose and camphor,

often with added dyes and other agents.
▪ Once much more common for its use as photographic film before the advent of
safer methods, celluloid's common contemporary uses are table tennis balls,
musical instruments, combs, office equipment, and guitar picks
▪ Nitrocellulose (NC), also called cellulose nitrate, is the oldest thermoplastic.
▪ It was invented by Alexander Parkes in 1855 and later commercialized under the
trademarks Parkesine, Xylonite and Celluloid.
▪ It is synthesized by reacting cellulose fibers with an aqueuos solution of nitric and
sulfuric acid.
▪ The average degree of nitration will be affected by the water content,
composition of the bath, immersion time, and reaction condition. NC's with
about 2 nitrate groups per glucose repeat unit are often chosen in plastics and
lacquers. A higher nitrate content is used in explosives.
CELLULOID

▪ Plastics made from NC have excellent mechanical properties including high impact resistant
but have poor weathering and heat stability and are not resistant to dilute acids and bases,
but are insoluble and stable in water and nonpolar solvents.
▪ To achieve the desired properties, other additives such as camphor, dyes, stabilizers and
fillers are often added.
▪ Nitrocellulose is highly combustible which makes it too hazardous for many applications.
▪ Today, NC is mainly used as an inexpensive binder in products like (flexographic) printing
inks, fast drying lacquers, baked-on enamels, and adhesives.
▪ In several of these applications, NC is modified (reacted) with other resins such as alkyd and
amino resins.
▪ The dilution with other ingredients such as camphor greatly reduces the flammability of NC.
This blend is called celluloid. It is used for handles of fountain pens, tools and brushes; for
eyeglass frames; and in the past, for motion picture film.
VULCANITE EBONITE

▪ Ebonite is a brand name for a material generically known as hard rubber,

and is obtained by vulcanizing natural rubber for prolonged periods.
▪ Ebonite may contain from 25% to 80% sulphur and linseed oil.
▪ Its name comes from its intended use as an artificial substitute for ebony
wood.
▪ The material has also been called vulcanite, although that name formally
refers to the mineral vulcanite.
VULCANITE EBONITE

▪ The sulphur percentage and the applied temperatures and duration

during vulcanizing are the main variables that determine the technical
properties of the hard rubber polysulfide elastomer.
▪ The occurring reaction is basically addition of sulphur at the double bonds,
forming intramolecular ring structures, so a large portion of the sulphur is
highly cross-linked in the form of intramolecular addition.
▪ As a result of having a maximum sulphur content up to 40%, it may be
used to resist swelling and minimize dielectric loss.
▪ The strongest mechanical properties and greatest heat resistance is
obtained with sulphur contents around 35% while the highest impact
strength can be obtained with a lower sulphur content of 30%.
VULCANITE EBONITE

▪ The rigidity of hard rubber at room temperature is attributed to the van

der Waals forces between the intramolecular sulphur atoms.
▪ Raising the temperature gradually increases the molecular vibrations that
overcome the van der Waals forces making it elastic.
▪ Hard rubber has a content mixture dependent density around 1.1 to 1.2.
▪ When reheated hard rubber exhibits shape-memory effect and can be
fairly easily reshaped within certain limits.
▪ Depending on the sulphur percentage hard rubber has a thermoplastic
transition or softening temperature of 70 to 80 °C (158 to 176 °F).
BAKELITE

▪ Bakelite or polyoxybenzylmethylenglycolanhydride was the first plastic

made from synthetic components.
▪ It is a thermosetting phenol formaldehyde resin, formed from a
condensation reaction of phenol with formaldehyde. It was developed by
the Belgian-American chemist Leo Baekeland in Yonkers, New York, in
1907.
▪ The creation of a synthetic plastic was revolutionary for its electrical
nonconductivity and heat-resistant properties in electrical insulators,
radio and telephone casings and such diverse products as kitchenware,
jewellery, pipe stems, children's toys, and firearms.
BAKELITE

▪ Making Bakelite is a multi-stage process. It begins with heating of phenol and

formaldehyde in the presence of a catalyst such as hydrochloric acid, zinc
chloride, or the base ammonia.
▪ This creates a liquid condensation product, referred to as Bakelite A, which is
soluble in alcohol, acetone, or additional phenol. Heated further, the product
becomes partially soluble and can still be softened by heat.
▪ Sustained heating results in an "insoluble hard gum". However, the high
temperatures required to create this tends to cause violent foaming of the
mixture when done at standard atmospheric pressure, which results in the
cooled material being porous and breakable.
▪ Baekeland's innovative step was to put his "last condensation product" into an
egg-shaped "Bakelizer". By heating it under pressure, at about 150 °C (300 °F),
Baekeland was able to suppress the foaming that would otherwise occur. The
resulting substance is extremely hard and both infusible and insoluble
BAKELITE

▪ Bakelite has a number of important properties. It can be moulded very

quickly, decreasing production time. Mouldings are smooth, retain their
shape and are resistant to heat, scratches, and destructive solvents.
▪ It is also resistant to electricity, and prized for its low conductivity. It is not
flexible.
▪ Phenolic resin products may swell slightly under conditions of extreme
humidity or perpetual dampness.
▪ When rubbed or burnt, Bakelite has a distinctive, acrid, sickly-sweet or
fishy odour.
TERYLENE

▪ Polyethylene terephthalate, commonly abbreviated PET, PETE, or the

obsolete PETP or PET-P, is the most common thermoplastic polymer resin
of the polyester family.
▪ This is used in fibres for clothing, containers for liquids and foods, and
thermoforming for manufacturing, and in combination with glass fibre for
engineering resins.
▪ It may also be referred to by the brand names Terylene in the UK, Lavsan
in Russia and the former Soviet Union, and Dacron in the US.
TERYLENE

▪ The majority of the world's PET production is for synthetic fibres (in
excess of 60%), with bottle production accounting for about 30% of global
demand.
▪ In the context of textile applications, PET is referred to by its common
name, polyester, whereas the acronym PET is generally used in relation to
packaging.
▪ Polyester makes up about 18% of world polymer production and is the
fourth-most-produced polymer after polyethylene (PE), polypropylene
(PP) and polyvinyl chloride (PVC).
▪ PET consists of polymerized units of the monomer ethylene
terephthalate, with repeating (C10H8O4) units.
TERYLENE

▪ PET is commonly recycled, and has the number "1" as its resin
identification code (RIC).
▪ Depending on its processing and thermal history, polyethylene
terephthalate may exist both as an amorphous (transparent) and as a
semi-crystalline polymer.
▪ The semicrystalline material might appear transparent (particle size less
than 500 nm) or opaque and white (particle size up to a few micrometres)
depending on its crystal structure and particle size.
TERYLENE

▪ The monomer bis(2-hydroxyethyl) terephthalate can be synthesized by

– The esterification reaction between terephthalic acid and ethylene glycol with water
as a by-product (this is also known as a condensation reaction).
– or by transesterification reaction between ethylene glycol and dimethyl terephthalate
(DMT) with methanol as a by-product.
– Polymerization is through a polycondensation reaction of the monomers (done
immediately after esterification/transesterification) with water as the by-product.
TERYLENE - PROPERTIES

▪ PET in its natural state is a colourless, semi-crystalline resin.

▪ Based on how it is processed, PET can be semi-rigid to rigid, and it is very
lightweight.
▪ It makes a good gas and fair moisture barrier, as well as a good barrier to
alcohol (requires additional "barrier" treatment) and solvents.
▪ It is strong and impact-resistant. PET becomes white when exposed to
chloroform and also certain other chemicals such as toluene.
▪ About 60% crystallization is the upper limit for commercial products, with
the exception of polyester fibres.
TERYLENE - PROPERTIES

▪ Like glass, amorphous PET forms when its molecules are not given enough time
to arrange themselves in an orderly, crystalline fashion as the melt is cooled.
▪ At room temperature the molecules are frozen in place, but, if enough heat
energy is put back into them by heating above glass transition temperature, they
begin to move again, allowing crystals to nucleate and grow. This procedure is
known as solid-state crystallization.
▪ When allowed to cool slowly, the molten polymer forms a more crystalline
material. This material has spherulites containing many small crystallites when
crystallized from an amorphous solid, rather than forming one large single
crystal.
▪ Light tends to scatter as it crosses the boundaries between crystallites and the
amorphous regions between them. This scattering means that crystalline PET is
opaque and white in most cases. Fibre drawing is among the few industrial
processes that produce a nearly single-crystal product.
TERYLENE – INTRINSIC VISCOSITY

▪ One of the most important characteristics of PET is referred to as intrinsic

viscosity (IV).
▪ The intrinsic viscosity of the material, found by extrapolating to zero
concentration of relative viscosity to concentration which is measured in
decilitres per gram (dℓ/g).
▪ Intrinsic viscosity is dependent upon the length of its polymer chains but
has no units due to being extrapolated to zero concentration.
▪ The longer the polymer chains the more entanglements between chains
and therefore the higher the viscosity. The average chain length of a
particular batch of resin can be controlled during polycondensation.
TERYLENE – INTRINSIC VISCOSITY

▪ The intrinsic viscosity range of PET:

– Fiber grade:
▪ 0.40–0.70 -Textile
▪ 0.72–0.98 -Technical, tire cord
– Film grade:
▪ 0.60–0.70 BoPET (biaxially oriented PET film)
▪ 0.70–1.00 Sheet grade for thermoforming
– Bottle grade:
▪ 0.70–0.78 Water bottles (flat)
▪ 0.78–0.85 Carbonated soft drink grade
– Monofilament, engineering plastic
▪ 1.00–2.00
POLYVINYL CHLORIDE

▪ Polyvinyl chloride (PVC) is the world's third-most widely produced synthetic

plastic polymer (after polyethylene and polypropylene).
▪ About 40 million tons of PVC are produced each year.
▪ PVC comes in two basic forms: rigid (sometimes abbreviated as RPVC) and
flexible.
▪ The rigid form of PVC is used in construction for pipe and in profile applications
such as doors and windows.
▪ It is also used in making bottles, non-food packaging, food-covering sheets, and
cards (such as bank or membership cards).
▪ It can be made softer and more flexible by the addition of plasticizers, the most
widely used being phthalates.
POLYVINYL CHLORIDE

▪ In this form, it is also used in plumbing, electrical cable insulation,

imitation leather, flooring, signage, phonograph records, inflatable
products, and many applications where it replaces rubber. With cotton or
linen, it is used in the production of canvas.
▪ Polyvinyl chloride is produced by polymerization of the vinyl chloride
monomer (VCM), as shown
POLYVINYL CHLORIDE

▪ About 80% of production involves suspension polymerization.

▪ Emulsion polymerization accounts for about 12%, and bulk polymerization
accounts for 8%.
▪ Suspension polymerization affords particles with average diameters of 100–180
μm, whereas emulsion polymerization gives much smaller particles of average
size around 0.2 μm.
▪ VCM and water are introduced into the reactor along with a polymerization
initiator and other additives. The contents of the reaction vessel are pressurized
and continually mixed to maintain the suspension and ensure a uniform particle
size of the PVC resin. The reaction is exothermic and thus requires cooling. As the
volume is reduced during the reaction (PVC is denser than VCM), water is
continually added to the mixture to maintain the suspension.
▪ The polymerization of VCM is started by compounds called initiators that are
mixed into the droplets. These compounds break down to start the radical chain
reaction.
POLYVINYL CHLORIDE

▪ Typical initiators include dioctanoyl peroxide and dicetyl peroxydicarbonate,

both of which have fragile oxygen-oxygen bonds. Some initiators start the
reaction rapidly but decay quickly, and other initiators have the opposite effect.
▪ A combination of two different initiators is often used to give a uniform rate of
polymerization. After the polymer has grown by about 10 times, the short
polymer precipitates inside the droplet of VCM, and polymerization continues
with the precipitated, solvent-swollen particles. The weight average molecular
weights of commercial polymers range from 100,000 to 200,000, and the
number average molecular weights range from 45,000 to 64,000.
▪ Once the reaction has run its course, the resulting PVC slurry is degassed and
stripped to remove excess VCM, which is recycled. The polymer is then passed
through a centrifuge to remove water. The slurry is further dried in a hot air bed,
and the resulting powder is sieved before storage or pelletization. Normally, the
resulting PVC has a VCM content of less than 1 part per million.
POLYVINYL CHLORIDE

▪ Other production processes, such as micro-suspension polymerization

and emulsion polymerization, produce PVC with smaller particle sizes (10
μm vs. 120–150 μm for suspension PVC) with slightly different properties
and with somewhat different sets of applications.
▪ PVC may be manufactured from either naphtha or ethylene feedstock.
However, in China, where there are substantial stocks, coal is the main
starting material for the calcium carbide process
▪ The acetylene so generated is then converted to VCM which usually
involves the use of a mercury-based catalyst. The process is also very
energy intensive with much waste generated.
POLYVINYL CHLORIDE

▪ Micro Structure –
– The polymers are linear and are strong.
– The monomers are mainly arranged head-to-tail, meaning that there are chlorides on
alternating carbon centres.
– PVC has mainly an atactic stereochemistry, which means that the relative stereochemistry
of the chloride centres are random.
– Some degree of syndiotacticity of the chain gives a few percent crystallinity that is
influential on the properties of the material.
– About 57% of the mass of PVC is chlorine. The presence of chloride groups gives the
polymer very different properties from the structurally related material polyethylene.
– The density is also higher than these structurally related plastics
POLYVINYL CHLORIDE

▪ Additives –
– The product of the polymerization process is unmodified PVC.
– Before PVC can be made into finished products, it always requires conversion into a
compound by the incorporation of additives such as heat stabilizers, UV stabilizers,
plasticizers, processing aids, impact modifiers, thermal modifiers, fillers, flame retardants,
biocides, blowing agents and smoke suppressors, and, optionally, pigments.
– The choice of additives used for the PVC finished product is controlled by the cost and
performance requirements of the end use specification (underground pipe, window
frames, intravenous tubing and flooring all have very different ingredients to suit their
performance requirements).
– Previously, polychlorinated biphenyls (PCBs) were added to certain PVC products as flame
retardants and stabilizers.
POLYVINYL CHLORIDE

▪ Properties –
– PVC has high hardness and mechanical properties. The mechanical properties enhance
with the molecular weight increasing but decrease with the temperature increasing.
– The elastic modulus can reach 1500–3,000 MPa.
– The soft PVC (flexible PVC) elastic limit is 1.5–15 MPa.
– The heat stability of raw PVC is very poor, so the addition of a heat stabilizer during the
process is necessary in order to ensure the product's properties.
– Traditional product PVC has a maximum operating temperature around 60 °C (140 °F)
when heat distortion begins to occur.
POLYVINYL CHLORIDE

▪ Properties –
– Melting temperatures range from 100 °C (212 °F) to 260 °C (500 °F) depending upon
manufacture additives to the PVC.
– The linear expansion coefficient of rigid PVC is small and has good flame retardancy, the
limiting oxygen index (LOI) being up to 45 or more. The LOI is the minimum concentration
of oxygen, expressed as a percentage, that will support combustion of a polymer and
noting that air has 20% content of oxygen.
– As a thermoplastic, PVC has an inherent insulation that aids in reducing condensation
formation and resisting internal temperature changes for hot and cold liquids.
– PVC is a polymer with good insulation properties, but because of its higher polar nature
the electrical insulating property is inferior to non-polar polymers such as polyethylene
and polypropylene.
– Since the dielectric constant, dielectric loss tangent value, and volume resistivity are high,
the corona resistance is not very good, and it is generally suitable for medium or low
voltage and low frequency insulation materials.
POLYVINYL CHLORIDE

▪ Chlorinated PVC
– PVC can be usefully modified by chlorination, which increases its chlorine content to or
above 67%.
– Chlorinated polyvinyl chloride, (CPVC), as it is called, is produced by chlorination of
aqueous solution of suspension PVC particles followed by exposure to UV light which
initiates the free-radical chlorination.
– The reaction produces CPVC, which can be used in hotter and more corrosive
environments than PVC.
LAMINATED PLASTICS

▪ Lamination is the technique/process of manufacturing a material in

multiple layers, so that the composite material achieves improved
strength, stability, sound insulation, appearance, or other properties from
the use of the differing materials, such as plastic.
▪ A laminate is a permanently assembled object created using heat,
pressure, welding, or gluing.
▪ Laminated plastics are a special form of polymer-matrix composite
consisting of layers of reinforcing materials that have been impregnated
with thermosetting resins, bonded together, and cured under heat and
pressure.
LAMINATED PLASTICS

▪ The cured laminates, called high-pressure laminates, are produced in

more than 70 standard grades, based on National Electrical Manufacturers
Association (NEMA) specifications.
▪ Laminated plastics are available in sheet, tube, and rod shapes that are
cut and/or machined for various end uses.
▪ The same base materials are also used in moulded-laminated and
moulded-macerated parts.
▪ The moulded-laminated method is used to produce shapes that would be
uneconomical to machine from flat laminates, where production
quantities are sufficient to warrant mould costs.
LAMINATED PLASTICS

▪ Strength of a moulded shape is higher than that of a machined shape

because the reinforcing plies are not cut, as they are in a machined part.
The moulded-macerated method is used for similar parts that require
uniform strength properties in all directions.
▪ Other common forms of laminated plastics are composite sheet laminates
that incorporate a third material bonded to one or both surfaces of the
laminate.
▪ Metals most often used in composites are copper, aluminium, nickel, and
steel. Copper-clad sheets (one or both sides) for printed-circuit and
multilayer boards comprise the largest volume of metal composite sheet
laminates.
▪ Non-metallic include elastomers, vulcanized fibre, and cork. Composite
metal/plastic materials are also produced in rods and tubes.
LAMINATED PLASTICS

▪ Vulcanized fibre is another product often classified with the laminated

plastics because end uses are similar. Vulcanized fibre is made from
regenerated cotton cellulose and paper, processed to form a dense
material (usually in sheet form) that retains the fibrous structure.
▪ The material is tough and has good resistance to abrasion, flame, and
impact.
LAMINATED PLASTICS - RESINS

▪ Phenolics are the most widely used resin in laminated plastics. These low-
cost resins have good mechanical and electrical properties and resistance
to heat, flame, moisture, mild acids, and alkalies. Most paper and cloth-
reinforced laminates are made with phenolics.
▪ Polyesters are used for both electrical and mechanical service requiring
moderate heat resistance. The resins are usually mineral filled to improve
dimensional stability and flame retardancy and to reduce cost.
▪ Melamine resins are used primarily in electrical-grade laminates because
of their excellent resistance to arcing and tracking, high mechanical
strength, and good resistance to alkalies.
LAMINATED PLASTICS - RESINS

▪ Epoxies are recommended for applications requiring resistance to

chemicals and humid environments. They have low moisture absorption
and good dimensional stability, mechanical strength, bond strength, and
fungus resistance.
▪ Silicones, used primarily with glass-cloth reinforcement, have very high
heat resistance (to 550 °F). Laminates based on silicones have low
moisture absorption, and they maintain their electrical properties over a
wide range of service conditions.
▪ Polyimide binders extend the use-temperature range of glass laminates
upward. These resins can also withstand lengthy solder-bath exposure
without blistering.
LAMINATED PLASTICS - REINFORCEMENTS

▪ Papers are the lowest-cost reinforcing materials used in making

laminates. Types include kraft, alpha, cotton linter, and combinations of
these. Papers provide excellent electrical properties, good dimensional
stability, moderate strength, and uniform appearance.
▪ Cotton cloth is used for applications requiring good mechanical strength.
The lighter-weight fabrics are not as strong but have excellent
machinability.
▪ Asbestos, in the form of paper, mat, or woven fabric, provides excellent
resistance to heat, flame, chemicals, and wear.
LAMINATED PLASTICS - REINFORCEMENTS

▪ Glass-fibre reinforcements, in woven fabric or mat, form the strongest

laminates. These laminates also have low moisture absorption and
excellent heat resistance and electrical properties.
▪ Nylon fabrics provide excellent electrical and mechanical properties and
chemical resistance, but laminates reinforced with these materials lack
dimensional stability at elevated temperatures.