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Fiber & Rubber Industries

Chapter 7

Basics: Production of Fibers

Types of Spinning
Please Refer (applicable to this lecture) Polyamides, or Nylon Fiber
o Shreve’s CPI, 5e, Chapter 35 & 36 Polyesters
o CPI Vol-II, 2e, S.C. Bhatia – Chapter 4 & 5 Rayon
o Dryden’s Outlines of Chemical Technology, 3e, Chapter – V Rubber: SBR
CHEG
EC 603311 Chemical Process Industries
TechnologyII II 3 cr Production; Fabrication
Fibers
o A fiber filament is a thread-like structure of varying length, capable of
being woven or spun into larger units. Natural fibres such as cotton,
wool, silk & linen are being replaced to an appreciable extent by
synthetic fibers.
o The price of synthetic fibres is over 4 times that of cotton, but less
than the cost per kg for wool. All of the synthetic fibres have one or
more advantages in terms of high tensile strength, good temperature
stability, & excellent resistance to chemicals, abrasion, solvents &
moisture.
o These synthetics are prepared from molten linear polymers or a
solution of polymers by extrusion through a die containing 20-15000
small holes, solidifying, & collecting a group of threads as a filament.
This process is called spinning.

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Refer: Dryden’s OCT, p- 627 #Back
Synthetic fibers
Although many classes of fiber based on synthetic polymers have been
evaluated as potentially valuable commercial products, four of them
dominate the market; Nylon, Polyester, Acrylic, Polyolefin.
These four account for approximately 98% by volume of synthetic fiber
production, with polyester alone accounting for around 60%.
Fiber Spinning
Fiber spinning is used to manufacture synthetic
fibers. A filament is continuously extruded through
an orifice and stretched to diameters of 100 mm and
smaller.
The drawing and cooling processes determine the
morphology and mechanical properties of the final
fiber. For example ultra high molecular weight HDPE
fibers with high degrees of orientation in the axial
direction have extremely high stiffness !!
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How to differentiate various Spinning processes

For more information:

Shreve’s CPI: Chapter 35, Man made fiber and film industries, page 668. 5
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Types of Spinning
o Melt spinning: It is used for polymers that can be melted. The
polymer solidifies by cooling after being extruded from the
spinneret. It can be applied to polyamide (Nylon), polyesters,
polyurethanes and polyolefins (PP & HDPE).

o Dry Spinning: A solution consisting of a fiber-forming material and a

solvent is extruded through a spinneret. A stream of hot air impinges
on the jets of solution emerging from the spinneret, the solvent
evaporates, and solid filaments are left behind.

o Wet Fiber spinning: This process is used for polymers that need to be
dissolved in a solvent to be spun. The spinneret is submerged in a
chemical bath that causes the fiber to precipitate, and then solidify, as
it emerges. The process gets its name from this "wet" bath. Rayon,
& spandex are produced via this process.

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Polyamides
There are two principal types of materials included under the
polyamides, each type having a number of polymers.
o Diamine-dibasic acid condensation polymers - a prime example is the
first and well-known "nylon”, also called 6,6-Nylon or Nylon 66.
o In this nomenclature the first number designates the number of
carbon atoms in the diamine, the second is for the carbon atoms in
the dibasic acid. Experimentally, amines from 2-10 carbon atoms have
been condensed with acids from 2-18 carbon atoms.
o Single ring structure monomers containing the NH-group-linear
polymers form when the ring opens. Best example of this polymer is
polycaprolactam or 6-Nylon. The number refers to the total carbon
atoms in the ring; this number can vary from 5 to 12.

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Refer: Dryden’s OCT, p- 632
 Polyamides, or Nylon Fiber

Nylon-6,6
Nylon-6,6 is made from two monomers each of which contain 6 carbon
atoms - hence its name.
• One of the monomers is a 6 carbon acid with a -COOH group at each
end - hexanedioic acid.
• The other monomer is a 6 carbon chain with an amino group, -NH2,
at each end. This is 1,6-diaminohexane (also known as hexane-1,6-
diamine).

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 Polyamides, or Nylon Fiber

Production of Nylon-6,6
o Nylon salt is first prepared by mixing the amine and acid in aqueous
solution and adjusting the pH to 7.8.
o The salt is concentrated under vacuum
and then charged to an autoclave.
Here the rest of the water is removed
and the temperature gradually is
raised to 280°C to complete
polymerization and remove water of
condensation.
o The final product with a molecular
weight range of 12,000-16,000 is
extruded as a ribbon onto chilling
rolls, then to a chipper for producing
small chips suitable for storage and
rehandling.
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Refer: Dryden’s OCT, p- 635
 Polyamides, or Nylon Fiber

Production of Nylon-6,6
o When nylon fibers are produced, the chips are melted, metered
through high pressure pumps, filtered and passed through a melt
spinnerette.
o The extruded filaments
harden immediately on
air cooling and can be
wound on bobbins at
speeds of 750 meters
per minute or higher.
o The thread is stretched
to about 4 times its
original length in cold
drawing to give the
fiber desirable textile
properties.
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Refer: Dryden’s OCT, p- 635 #Back
Polyesters
o The polymers formed by condensation of polyfunctional acids or
esters with polyfunctional alcohols are called polyesters.
o When monomer acids and alcohols are used and some trifunctional
groups are present, the polymers produced are termed alkyd resins
for use largely in high grade paints and varnishes.
o The linear polyesters are formed from bifunctional groups and are
suitable for fibers and films. Outstanding examples of this group are
the Dacron fiber-Mylar film products formed from condensation of
dimethyl terephthalate and ethylene glycol.
Basic Chemistry of Dacron-Mylar Polyesters

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Refer: Dryden’s OCT, p- 639 #Back
 Polyesters

Production of Polyesters
o Dimethyl terephthalate is the ester prepared from crude terephthalic
acid which comes from oxidizing p-xylene. The ester allows for easier
control of the polymerization with glycol as it is more soluble in
ethylene glycol. The ester interchange reaction prior to polymerization
proceeds smoothly in the presence of alkali. Methanol is removed
continuously in a fractionating column.
o The reaction starts rapidly at 160°C and rises to 230°C before all of the
methyl groups are removed. Polymerization then proceeds at 275°C
and vacuum is applied to remove water of condensation.
o The formation of diethylene glycol and its condensation is an
undesirable side reaction which will affect polymer properties if
present to any extent.
o The polymer is melt spun to produce Dacron fiber and roll-extruded to
give Mylar film.
o Dye or coloring for the finished product must be done in the melting
stage because of the chemical inertness of the polyester.
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Refer: Dryden’s OCT, p- 639 #Back
Rayon
o Viscose is known as the poor man's silk. The industry is dying out
worldwide due to material constraints and adverse environmental
effects. The main raw material is wood pulp, a forest-based material,
and the production process generates toxic effluents.
o Viscose itself suffers from some deficiencies; it is a weak fiber,
especially when wet. The industry has hardly grown over the last few
years, as many weavers have switched over to newer fibers like
polyester.

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Refer: Dryden’s OCT, p- 632 #Back
 Rayon

Production of Viscose Rayon

o Cellulose wood pulp sheets or cotton
linters are placed in a steeping press and
contacted with 18% aqueous NaOH for
2-4 hours at room temperature.

o The excess alkali is pressed out with a

hydraulic ram,
o & the sheets are shredded to crumbs
and
o aged for 2-3 days, depending on
temperature (20-25°C). Aging has a
direct bearing on the viscosity of the
xanthate solution.

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Refer: Dryden’s OCT, p- 633 #Back
 Rayon

Production of Viscose Rayon

o CS2 is added in a rotating drum
mixer (barratte) over a three-hour
period.

o The orange cellulose xanthate is

transferred to the solubilizer where
it is mixed into dilute caustic to
produce an orange-colored viscous
solution containing 7-8% cellulose
and 6.5-7% NaOH.

o After digesting for 4-5 days at room

temperature, the solution is filtered
and fed to spinning machines.

15
Refer: Dryden’s OCT, p- 632 #Back
 Rayon

Production of Viscose Rayon

o For spinning viscose rayon, the extrusion spinnerettes are made of
platinum or gold alloys with anywhere from 20-1,500 orifices of 0.1-
0.2 mm diameter for continuous filament yarns and 3,000-15,000
holes of 0.05-0.1 mm diameter for staple or short fiber shapes.
o As the solution is extruded from the spinnerette, it contacts the acid
bath which precipitates the filaments without causing them to stick
together or break.
o The filament group is
wound and transferred to
a series of plastic reels
where processing
treatments of washing,
desulfurizing, bleaching,
and conditioning take
place continuously and in
that order.
Refer: Dryden’s OCT, p- 633 16
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Elastomer Polymerization Processes
o Elastomer is an elastic polymer which returns to original dimensions
when stretched considerably from its original shape.
o Under the broad classification is the rubber group. A true rubber,
whether natural or synthetic, must elongate at least 200 percent and
return to its original dimensions rapidly and forcibly.
o Where a rapid retraction is not needed, elastic polymer formulations
often outperform rubber. Such materials are derived from vinyl
polymers and copolymers, polystyrene and acrylates.

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Refer: Dryden’s OCT, p- 615 #Back
Natural Rubber
Latex is obtained by tapping the tree, collected frequently to avoid
contamination. The collection is carried processing area where its
strained to remove foreign particles & a preservative (NH3) is added.
• The rubber is separated by a process known as coagulation, which
occurs when various acids or salts are added & the rubber separates
from the liquid as a white, dough-like mass, which is then milled &
sheeted to remove excess liquid present and to allow even drying.
• Today, a newer method is used, in which the formed coagulated
latex is granulated by cutting with rotary knives or by shear between
two rollers running at different speeds. The granules are dried in
mechanical dryer in hours, instead of days in earlier process.
• The dried sheet or granules are then compressed into bales of
certain weight

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Natural Rubber - Manufacturing overview
Natural rubber is collected in ready
polymerized form. Thus, the manufacturing
process of natural rubber starts by
mastication (Mastication of natural rubber is a
process in which the rubber is ground and mixed with
various additives to improve its properties. This process
helps to break down the rubber into smaller particles,
making it easier to process and mix with other
materials). During the mastication process, the
viscosity is decreased by breaking the crosslinks
and branches mechanically by shear forces on a
two-roll mill.
Mastication can also help to improve the elasticity,
strength, and overall quality of the rubber, making
it more suitable for various industrial and
commercial applications.
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Synthetic Rubber
A synthetic rubber is an artificial elastomer. They are polymers
synthesized from petroleum by-products.
• Synthetic rubber, similar to natural rubber, has many uses in
the automotive industry for tires, door and window profiles, seals such
as O-rings and gaskets, hoses, belts, matting, and flooring.
• They offer a different range of physical and chemical properties
which can improve the reliability of a given product or application.
• Synthetic rubbers are superior to natural rubbers in two major
respects: thermal stability, and resistance to oils and related
compounds.
• They are more resistant to oxidizing
agents, such as oxygen and ozone
which can reduce the life of products
like tires.
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Synthetic Rubber
The most prevalent synthetic rubber is styrene-butadiene rubbers (SBR)
derived from the copolymerization of styrene and 1,3-butadiene. Other
synthetic rubbers include:
• Polyisoprene, prepared by polymerization of isoprene
• Neoprene, prepared by polymerization of 2-chlorobutadiene
• Nitrile rubber made from cyano-butadiene or 2-propenenitrile and
butadiene
Silicone rubber is also a synthetic elastomer composed of silicone
polymers. Silicone rubber is generally non-reactive, stable, and resistant
to extreme environments and temperatures.
• Natural rubber, coming from latex of Hevea brasiliensis, is mainly
poly-cis-isoprene.
• Synthetic rubber, like other polymers, is made from various
petroleum-based monomers.
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Synthetic Rubber
o Synthetic rubbers have been classified into vulcanizable & non-
vulcanizable & also by the chemical composition of the polymer
chain.
o The most widely used synthetic rubber is SBR as per table below.

o Other commonly used elastomers are polybutadiene, polyethylene-

propylene, butyl rubber, neoprene, nitrile rubber & polyisoprene.
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Rubber
o SBR is a general purpose rubber widely used for tires either by itself or
as a high percentage blend with natural rubber. It is superior to
natural rubber in all properties except tensile strength, resistance and
heat build-up under heavy loading. SBR is also used for mechanical
goods and electrical insulation.
o Butadiene and styrene are copolymerized by emulsion polymerization
in about 3:1 weight ratio.
o Properties of SBR rubber can be modified by the temperature of
polymerization.
• "Hot" rubber is prepared at 50°C.
• Superior quality "cold" rubber is made at 5°C by refrigeration
techniques with slightly higher operating costs. The development
of improved catalysts of the redox type more than offset the
decrease in reaction rate with temperature, thus allowing
successful commercialization of a continuous cold rubber process.
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Refer: Dryden’s OCT, p- 614
Production of SBR
o The process involves 20% aqueous caustic purification of the fresh plus
recycle monomers, followed by consecutive passage through 6 to 12
glass-lined or stainless steel reactors. The total residence time ranges
from 5-15 hours and reactors are equipped for steam heating, water
cooling, and refrigeration. The reactors can thus produce cold SBR (5°C,
1 atm. gage) or hot SBR (50°C, 3-4 atms. gage).
o Latex from the reactors is collected in blow-down tanks after stripping
the polymerization with chemical inhibitors and then fed to a falling
film stripper to remove butadiene, The bottoms are passed to a
perforated plate column to strip out styrene.

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SBR
Production of SBR
o The monomer-free emulsion is pumped to blend tanks for addition of
certain compounding ingredients.
o The latex is coagulated to rubber "crumbs" which float onto shaker
screens where wash water removes catalyst, emulsifiers and other
solubles.
o The crumbs are
dried with hot air
in continuous-belt
dryers, then
pressed into bales
for shipping to
compounding and
fabricating plants.

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Refer: Dryden’s OCT, p- 615 SBR #Back
Rubber Products
Physical properties important for rubber products are: Tensile strength,
Repeated stress failure, Hardness, Permanent set, Tear resistance, Aging,
Resilience, Ozone and oxygen reactivity, Flex failure, Oil and solvent
resistance, Abrasion, Thermal and electrical
Such properties are dependent, not only on the original polymer
molecular structure out on additional processing which includes:
o Compounding: addition of fillers, coloring agents, plasticizers,
antioxidants, vulcanizing agents
o Mixing: homogeneous distribution of compounding ingredients into
solid elastomeric polymer; rubber mill is used which has one of the
two rolls running at slower speed, giving kneading action
o Vulcanization: optical cross-linking process at C = C in polymer units
of Table VB-7; sulfur is common vulcanizing agent with accelerators
(catalysts) of the organic or inorganic type
o Forming: production of final shapes by molding, calendering,
extrusion 26
Refer: Dryden’s OCT, p- 614 SBR
Rubber Compounding
Pure rubber (natural or synthetic) is usually not suitable for use. The desired
properties of plasticity, toughness, hardness, or softness, abrasive resistance,
impermeability, etc. are achieved by compounding of rubber. The processing
of rubbers starts by mixing elastomers and additives. A typical rubber
compound is shown below.

Ref Shreve’s CPI page: 706

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SBR #Back
Rubber Processing Chemicals
Rubber processing chemicals are additives added to rubber to improve
product end property, processibility during manufacturing phase, etc.

SBR
28
Ref Shreve’s CPI page: 707 #Back
Rubber Processing Chemicals
• The vulcanizing agents are usually sulfur compounds which react with
the polymer to produce a cross-linked material in which the linkages
are –C-Sx-C-
• The cross links may be mono-, di-, or poly-sulfidic. The type of linkage
determined by the concentration of sulfur, accelerators, retarders, &
curing temperature.
• The accelerators reduce the time required for the vulcanization of
rubber from several hours to a few minutes. In addition, less sulfur is
needed & a uniform product is obtained. Most accelerators contains
nitrogen & sulfur.
• Age resistors, or antioxidants, protects rubber goods from attack by
oxygen & ozone in the atmosphere.
• Catalytic plasticizer, or peptizer, serve to reduce the viscosity of rubber
to permit easier processing.
• Inert filler or reinforcement filler may be added to rubber as required.
29SBR
Ref Shreve’s CPI page: 707-708 for full text #Back
Rubber Fabrication
As a plastic material, rubber may be spread, cemented, calendered,
molded, extruded, or wrapped into virtually any shape: coated on
cloth, plastic, or metals; & sandwiched or forced into cracks. Rubber
being extremely tough material, heavy machinery is required for
handling/processing. After compounding rubbers are shaped by using
different kinds of processing methods, such as;
• Calendering or Coating
• Mouding
• Extruding

Calendering or Coating
Earliest use of rubber was for coating fabric
to make it waterproof. Rubber compounds
are applied to fabric by calendaring, i.e,
rolling the rubber compound into the fabric
on multi-roll calender machines.
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Ref Shreve’s CPI page: 708 #Back
Rubber Fabrication
Molding
Doughlike rubber compounds may be moulded into virtually any
shape, which is retained by curing the compound in the mold. A
tennis ball is a good example, a very high grade resilient rubber
compound is moulded in muffin tins shaped as halves of the ball.
These are cemented together (with a pill of a gas-releasing chemical
enclosed) and vulcanized to form the core of a ball, to which the
fabric cover & proper nap fiber are cemented.

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 Ref Shreve’s CPI page: 708

Rubber Fabrication
Extruding
Weather-strip, hose, inner tubes, tyre
treads, gaskets, channels, and many
other rubber articles are produced by
extrusion of the plastic compound,
which may be cured during this
operation or later.

After shaping, the rubber product is vulcanized, so that mechanical

properties and dimensional stability appear.

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Vulcanization
Vulcanization is a chemical process used to harden rubber. Vulcanization
can therefore be defined as the curing of elastomers. It works by forming
cross-links between sections of polymer chain which results in increased rigidity
and durability.
Vulcanisation generally applied to rubbery or elastomeric materials
where crosslinks are inserted between polymer chains through the use
of vulcanizing agents. The crosslink may be a group of sulfur atoms in a short
chain, a single sulfur atom, a carbon to carbon bond, a polyvalent organic
radical, an ionic cluster, or a polyvalent metal ion (Coran, 2005).
Vulcanization traditionally referred to the treatment of natural
rubber with sulfur and this remains the most common example, however the
term has also grown to include the hardening of other (synthetic) rubbers via
various means.
Examples include silicone rubber via room temperature vulcanizing
and chloroprene rubber (neoprene) using metal oxides.
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Vulcanization by use of Sulfur
The main polymers subjected to sulfur vulcanization
are polyisoprene (natural rubber) & styrene-
butadiene rubber (SBR), which are used for most
street-vehicle tires.
The most common vulcanizing methods for rubber depend on
sulfur. The number of sulfur atoms in the crosslink strongly
influences the physical properties of the final rubber article.
Sulfur does not vulcanize synthetic poly-olefins ( alkene with the general formula
CnH2n) i.e. Polypropylene, polyethylene

Vulcanization of polychloroprene
The vulcanization of neoprene or polychloroprene rubber (CR rubber) is carried
out using metal oxides (specifically MgO and ZnO, sometimes PbO) rather than
sulfur compounds which are presently used with many natural and synthetic
rubbers.
Vulcanization of silicones
Room-temperature vulcanizing (RTV) silicone is constructed of reactive oil-
based polymers combined with strengthening mineral fillers. 34
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 Ref Shreve’s CPI page: 711

Latex Compound
Natural latex concentrated after stabilization with ammonia (to inhibit the
bacterial growth which will otherwise cause spontaneous coagulation) &
centrifugation to about 60% rubber (from 30%). Concentrated latices
permits the use of rubber as a liquid which may be spread, painted,
dipped or whipped into foam. Suspensions of compounding ingredients
provide cure, but reinforcement is not nearly as effective.

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Classifications, different types of rubber
A common classification of different types of rubber is:
Ø General purpose elastomers
Ø Special purpose elastomers
Ø Speciality elastomers
General purpose elastomers
General purpose types constitute the largest volume of polymer used.
The category comprise:
• Natural rubber (NR)
• Polyisoprene rubber (IR)
• Butadiene rubber (BR)
• Styrene-butadiene rubber (SBR)
These types have good physical properties, good process ability and
compatibility, are generally economical and are typical polymers used in tyres
and mechanical rubber goods with demand for good abrasion resistance and
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tensile properties. #Back
Special purpose elastomers
The category comprise:
• Ethylene-propylene rubber (EPM and EPDM)
• Butyl rubber (IIR)
• Chloroprene rubber (CR)
• Acrylonitrile-butadiene rubber or Nitrile rubber (NBR)
They have all unique properties which cannot be matched by the general
purpose types and are very important for manufacturing of industrial and
automotive rubber products.
Speciality elastomers
The Specialty elastomers are a great number of polymers with very special
properties, in many cases of great importance for the automotive-,
aircraft-, space- and offshore industries.
Some of these polymers are: Ø Floursilicone Rubber (FPQ)
Ø Chlorosulfonated Polyethylene (CSM) Ø Fluor elastomers (FPM/FFKM/FEPM)
Ø Acrylic Rubber (ACM) Ø Urethane Rubber (AU/EU)
Ø Silicone Rubber (PMQ/PV/MQ/VMQ) Ø Epichlorohydrine Rubber (CO/ECO/GECO) 37
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