Ramaiah Kotra and Xiao Gao
In 1996, 24.1 million metric tons of manmade fibers were
produced worldwide. This was 4% more than in the previous year. The main
volume gain took place in production of PET fibers (PET filament 9%, PET
staple 4%) . The primary drive for this growth is demand for fiber and
container resin. Seventy five percent of the entire PET production is
directed toward fiber manufacturing. Hoechst, DuPont and Eastman are the
three world largest polyester producers. Additional current U.S. Polyester
Fiber Producers are: Acordis Industrial Fibers, Inc.; AlliedSignal Inc;
Cookson Fibers, Inc.; Kg5A; Intercontinental Polymers, Inc., Martin Color-Fi.
Nan Ya Plastics Corp., Wellman, Inc.  Dramatic growth in PET fiber
production is foreseen in Asia in the near future .
The cost of polyester, with the combination of its
superior strength and resilience, is lower than that of rayon. Polyester
fibers are hydrophobic, which is desirable for lightweight facing fabrics
used in the disposable industry. They provide a perceptible dry feel on the
facing, even when the inner absorbent media is saturated. As new methods of
processing and bonding of PET are developed, rayon is being replaced by
polyester on the market. According to David Harrison , 49% of the total
nonwovens market share in the USA belongs to polyester staple, reaching 291
million pounds in 1996 and ranking number one among all kind of fiber
supplies. If one were to assume that the filament fiber consumption is half
of that of staple, the total PET consumption in the USA nonwovens industry
alone would be over 450 million pounds. Even if the estimate is not be
completely accurate, polyester has become the most widely used polymer in
the nonwovens industry since 1995. The next most popular was
polypropylene . But in 1996, poly-olefins and particularly
polypropylene(PP) moved ahead of PET fibers. They had 46% market shares in
fibers used for nonwovens, whereas, PET had a 45% share. By the end of 1998,
olefin fibers increased their share to 49% and PET dropped to 42%.
Mechanical properties of nonwoven fabrics depend on many
parameters, including fiber properties, web structure and processing. It is,
therefore, useful to review some of the elementary knowledge of fiber
properties and other factors like web processing techniques and structure.
What follows is a brief review of PET fiber properties, which should serve
as background information for better understanding the subject.
Polyester fiber is a " manufactured fiber in which the
fiber forming substance is any long chain synthetic polymer composed at
least 85% by weight of an ester of a dihydric alcohol (HOROH) and
terephthalic acid (p-HOOC-C6H4COOH)" . The most
widely used polyester fiber is made from the linear polymer poly (ethylene
terephtalate), and this polyester class is generally referred to simply as
PET. High strength, high modulus, low _shrinkage, heat set stability, light
fastness and chemical resistance account for the great versatility of PET.
Polyethylene Teraphthalate (PET) is a condensation
polymer and is industrially produced by either terephthalic acid or
dimethyl terephthalate with ethylene glycol.  Other polyester fibers
of interest to the nonwovens field include:
( a ) Terephthalic Acid (PTA), produced directly from
p-xylene with bromide-controlled oxidation.
( b ) Dimethyl Terephthalate (DMT), made in the early
stages by esterification of terephthalic acid. However, a different
process involving two oxidation and esterification stages now accounts for
( c ) Ethylene Glycol ( EG ), initially generated as an
intermediate product by oxidation of ethylene. Further ethylene glycol is
obtained by reaction of ethylene oxide with water.
Equation 4 - PolyesterA
SYNTHESIS OF POLYMER
( 1 ) Linear Polyesters
A representative linear polyester, PET is polymerized by
one of the following two ways: Ester Interchange: Monomers are dimethyl
terephthalate and ethylene glycol. Direct Esterification: Monomers are
terephthalic acid and ethylene glycol. Both ester interchange and direct
esterification processes are combined with polycondensation steps either
batch-wise or continuously. Batch-wise systems need two reaction vessels-
one for esterification or ester interchange, the other for polymerization.
Continuous systems need at least three vessels - one for esterification or
shear interchange, another for reducing excess glycols, the other for
Another way to produce PET is solid-phase
polycondensation. In the process, a melt polycondensation is continued until
the pre-polymer has an Intrinsic Viscosity of 1.0-1.4, at which point the
polymer is cast into a solid firm. The pre-crystallization is carried out by
heating (above 200oC) until the desirable molecular weight is
obtained. Later the particulate polymer is melted for spinning. This process
is not popular for textile PET fibers but is used for some industrial
( 2 ) Branched and Crosslinked Polyesters
If glycerol is allowed to react with a diacid or its anhydride each glycerol
will generate one branch point. Such molecules can grow to very high
molecular weight. If internal coupling occurs ( reaction of a hydroxyl group
and an acid function from branches of the same or different molecule), the
polymer will become crosslinked. Rigidly crosslinked polymers are totally
unaffected by solvents.
3. FIBER FORMATION
The sequences for production of PET fibers and yarns
depend on the different ways of polymerization (continuous, batch-wise, and
solid-phase) and spinning (low or high windup speed) processes.
( 1 ) Spinning Process
The degree of polymerization of PET is controlled, depending on its
end-uses. PET for industrial fibers has a higher degree of polymerization,
higher molecular weight and higher viscosity. The normal molecular weight
range lies between 15,000 and 20,000. With the normal extrusion temperature
(280-290oC), it has a low shear viscosity is 1000-3000 poise. Low
molecular weight PET is spun at 265oC, whereas ultrahigh
molecular weigh PET is spun at 300oC or above. The degree of
orientation is generally proportional to the wind-up speeds in the spinning
process. Theoretically, the maximum orientation along with increase in
productivity is obtained at a wind-up speed of 10,000m/min. Although due to
a voided skin, adverse effects may appear at wind-up speeds above 7000m/min.
( 2 ) Drawing Process
To produce uniform PET, the drawing process is carried out at temperature
above the glass transition temperature (80-90oC). Since the
drawing process gives additional orientation to products, the draw ratios
(3:1-6:1) vary according to the final end-uses. For higher tenacities, the
higher draw ratios are required. In addition to orientation, crystallinity
may be developed during the drawing at the temperature range of 140-220oC.
(3) Polyester Fiber Flow Chart
(4) The latest Polyester production (Research Method)
Dr Boncella and Dr Wagner at The University of Florida
are two scientists involved with the study to reveal a method for
manufacturing polyester from two inexpensive gases: carbon monoxide and
The polyester most commonly used today is referred to as
PET or polyethylene terepthalate. Scientists have been successful in
producing low molecular weight polyester using carbon monoxide and ethylene
oxide, but researchers still lack the catalyst - a substance that speeds up
chemical reactions - needed to make the reaction work more efficiently. They
are looking for the chemical compound that will take molecules of low DP and
create 1arger ones. Although they have had success in the research so far,
they have yet to produce a commercially useable polyester from the
inexpensive gases. If this is successful, then these research findings can
be used to replace the current polyester product, getting the same
performance for a lower price. Finally, we all know that research requires
patience and a long-term effort.
STRUCTURAL COMPOSITION OF PET
The one of the distinguishing characteristics of PET is
attributed to the benzene rings in the polymer chain. The aromatic character
leads to chain stiffness, preventing the deformation of disordered regions,
which results in weak van der Waals interaction forces between chains. Due
to this, PET is difficult to be crystallized. Polyester fibers may be
considered to be composed of crystalline, oriented semicrystalline and
noncrystalline (amorphous) regions. The aromatic, carboxyl and aliphatic
molecular groups are nearly planar in configuration and exist in a
side-by-side arrangement. Stabilization distances between atoms in
neighboring molecules are usually van der Waals contact distances, and there
is no structural evidence of any abnormally strong forces among the
molecules. The unusually high melting point of PET (compared to aliphatic
polyesters) is not the result of any unusual intermolecular forces, but is
attributed to ester linkages. The cohesion of PET chains is a result of
hydrogen bonds and van der Waals interactions, caused by dipole interaction,
induction and dispersion forces among the chains. The capacity to form
useful fibers and the tendency to crystallize depend on these forces of
The interactive forces create inflexible tight packing
among macromolecules, showing high modulus, strength, and resistance to
moisture, dyestuffs and solvents. The limited flexibility in the
macromolecule is mainly due to the ethylene group. The extended quenched
fiber does not show any early development of crystallinity; the growth of
crystals starts to occur upon drawing. A number of basic structural models
are required to represent the different states of the fiber: amorphous (no
orientation) after extrusion, amorphous (no orientation) after cold drawing,
crystalline orientation after thermal treatment and after hot drawing,
stretching and annealing. The crystalline oriented form can also be obtained
by high stress (high-speed) spinning.
Crystallinity and molecular orientation within the fibers
can be measured by Differential Scanning Calorimetry (DSC). This type of
analysis is based on distinctly different values of the heats of fusion for
crystalline and noncrystalline forms of the polymer. The heat of fusion of
the sample is compared with a calibration standard. The crystallinity is
determined by the following relationship
% Crystallinity =
where ) Hf*
is the heat of fusion of a 100% crystalline polymer, reported in the
literature to be about 33.45 cal/g (equal to 140 J/g) . The Tg
(glass transition temperature) and Tm (melting point) of the
fibers can also be determined by DSC analysis. The results of the density
and DSC measurements are shown in Table 1.
|Fiber Type Base Fibers
||?? H3 (Cal/g)
1Glass transition temperature.
3?H?--heat of fusion.
4Cold Crystallization range.
The rapid quenched PET without drawing is amorphous. The
temperature range of crystallization for PET is from 10oC below
the melting point to the temperature a little higher than the glass
transition temperature, 250-100oC. Typical PET has a 50%
crystallinity. The repeat unit of PET is 1.075 nm and is slightly shorter
than the length of a fully extended chain (1.09 nm). Therefore, the chains
are nearly planar. The crystal unit cell is triclinic with dimensions a =
0.456nm, b = 0.594nm, c = 1.075nm , ( = 98.5o,
and ( = 112o. PET crystal structure is illustrated in Fig. 1.
Another factor for crystallization is the position of the benzene rings. If
benzene rings are placed on the chain axis (c), then close packing of the
molecular chains eases polymer crystallization.
General Polyester Fiber Characteristics:
- Resistant to stretching and shrinking
- Resistant to most chemicals
- Quick drying
- Crisp and resilient
- Wrinkle resistant
- Mildew resistant
- Abrasion resistant
- Retains heat-set pleats and crease
- Easily washed
MELT-BLOWN PROCESS OF POLYESTER
The IV (intrinsic viscosity) and crystallinity levels of
a melt-blown polyester determine the performance of the finished product. A
higher IV leads to an increased level of crystallinity, which improves the
barrier properties of the polyester melt-blown structure. However, it
significantly reduces modulus, toughness and elongation. The advantage of
using polyester over such polymers as polyolefins is its heat resistance and
greater chemical resistance. Polyesters also offer a moderate oxygen
RELATIONSHIP BETWEEN STRUCTURE, PROPERTIES
AND PROCESSING PARAMETERS OF PET FIBERS
Properties of polyester fibers are strongly affected by
fiber structure. The fiber structure, which has a strong influence on the
applicability of the fiber, depends heavily on the process parameters of
fiber formation such as spinning speed (threadline stress), hot drawing
(stretching), stress relaxation and heat setting (stabilization) speed.
As the stress in the spinning threadline is increased by
higher wind-up speed, the PET molecules are extended, resulting in better
as-spun uniformity, lower elongation and higher strength, greater
orientation and high crystallinity. Hot drawing accomplishes the same effect
and allows even higher degrees of orientation and crystallinity. Relaxation
is the releasing of strains and stresses of the extended molecules, which
results in reduced shrinkage in drawn fibers. Heat stabilization is the
treatment to "set" the molecular structure, enabling the fibers to resist
further dimensional changes. Final fiber structure depends considerably on
the temperature, rate of stretching, draw ratio (degree of stretch),
relaxation ratio and heat setting condition. The crystalline and
noncrystalline orientation and the percentage of crystallinity can be
adjusted significantly in response to these process parameters.
As the degree of fiber stretch is increased (yielding
higher crystallinity and molecular orientation), so are properties such as
tensile strength and initial Young's modulus. At the same time, ultimate
extensibility, i.e., elongation, is usually reduced. An increase of
molecular weight further increases the tensile properties, modulus, and
elongation. Typical physical and mechanical properties of PET fibers are
given in Table 2. and stress-strain curves in Fig. 2. It can be seen that
the filament represented by curve C has a much higher initial modulus than
the regular tenacity staple shown in curve D. On the other hand, The latter
exhibits a greater tenacity and elongation. High tenacity filament and
staple (curve A and B) have very high breaking strengths and moduli, but
relatively low elongations. Partially oriented yarn (POY) and spun filament
yarns, exhibit low strength but very high elongation (curve E). When
exposing PET fiber to repeated compression (for example, repeated bending),
so-called kink bands start to form, finally resulting in breakage of the
kink band into a crack. It has been shown in  that the compressibility
stability of PET is superior to that of nylons.
||Staple and tow
breaking tenacity,e N/tex
|elastic recovery at 5% elongation, %
initial modulus, N/texf
|moisture regian, %
melting temperature, oC
aTextile-filament yarns for woven and knit fabrics.
bTire cord and high strength, high modulus industrial yarns.
cRegular staple for 100% polyester fabrics, carpet yarn,
fiberfill, and blends with cellulosic blends or wool.
dHigh strength, high modulus staple for industrial
applications, sewing thread, and cellulosic blends.
eStandard measurements are conducted in air at 65% rh and 22oC.
fTo convert N/text to ge/den, multiply by 11.33.
gThe equilibrim moisure content of the fibers at 21oC
and 65% rh.
Shrinkage varies with the mode of treatment. If
relaxation of stress and strain in the oriented fiber is allowed to occur
through shrinkage during fiber manufacture, then shrinkage at the textile
processing stage is reduced and initial modulus is lowered. Polyester yarns
held to a fixed length under tension during heat treatment are less affected
with change in modulus, and reduced shrinkage values can still be obtained.
This is very important in fiber stabilization.
PET shows nonlinear and time-dependent elastic behavior.
It recovers well from stretch, compression, bending, and shear because of
its relatively high initial modulus. Extensional creep occurs under load,
with subsequent delay in recovery upon removal of the load. But compared
with other melt-spun fibers, the creep is small.
The formation of small fuzz balls of entangled fibers
(pills) on the fabric surface can be a serious problem. Fuzz formation may
be affected by friction, stiffness, breaking strength and abrasion
resistance. Shape, fineness, stiffness, recovery, friction and elongation
influence entanglement of fibers. After the pills have been formed, their
rate of wear-off can affect the fabric appearance. Wear-off is a function of
fiber breaking strength and flex life. Reducing the molecular weight which
affects the abrasion resistance, flex life, and breaking strength, results
in a decrease in pilling tendency of PET fiber. However, spinning low
molecular weight linear PET fiber is difficult. As the molecular weight is
reduced, the melt viscosity decreases and a uniform fiber with satisfactory
continuity of spinning cannot be produced. Melt viscosity can be raised by
the addition of a cross-linking compound, which is prone to hydroxyl groups.
Another property, important especially to the apparel industry, is crimp
stability or crimp compression. Generally, the tighter the packing of
molecular chains, the stiffer and more mechanically resistant the fiber is.
Crimp stability of the fiber can be improved with an increase in heating
temperature. In addition, crimp compression of the fiber can be decreased by
increasing draw ratio when the fiber is produced .
Polyester fibers have good resistance to weak mineral
acids, even at boiling temperature, and to most strong acids at room
temperature, but are dissolved with partial decomposition by concentrated
sulfuric acid. Hydrolysis is highly dependent on temperature. Thus
conventional PET fibers soaked in water at 70oC for several weeks
do not show a measurable loss in strength, but after one week at 100oC,
the strength is reduced by approximately 20%.
Polyesters are highly sensitive to bases such as sodium
hydroxide and methylamine, which serve as catalysts in the hydrolysis
reaction. Methylamine penetrates the structure initially through
noncrystalline regions, causing the degradation of the ester linkages and,
thereby, loss in physical properties. This susceptibility to alkaline attack
is sometimes used to modify the fabric aesthetics during the finishing
process. The porous structures produced on the fiber surface by this
technique contribute to higher wettability and better wear properties .
Polyester displays excellent resistance to oxidizing
agents, such as conventional textile bleaches, and is resistant to cleaning
solvents and surfactants. Also, PET is insoluble in most solvents except for
some polyhalogenated acetic acids and phenols. Concentrated solutions of
benzoic acid and o-phenylphenol have a swelling effect.
PET is both hydrophobic and oleophilic. The hydrophobic
nature imparts water repellency and rapid drying. But because of the
oleophilic property, removal of oil stains is difficult. Under normal
conditions, polyester fibers have a low moisture regain of around 0.4%,
which contributes to good electrical insulating properties even at high
temperatures. The tensile properties of the wet fiber are similar to those
of dry fiber. The low moisture content, however, can lead to static problems
that affect fabric processing and soiling.
PET has optical
Figure 2 characteristics of many thermoplastics, providing bright, shiny
effects desirable for some end uses, such as silk-like apparel. Recently
developed polyester microfiber with a linear density of less than 1.0 denier
per filament (dpf), achieves the feel and luster of natural silk .
The thermal properties of PET fibers depend on the method
of manufacture. The DTA (Fig. 3.) and TMA (Fig. 4) data for fibers spun at
different speeds show peaks corresponding to glass transition,
crystallization, and melting regions. Their contours depend on the amorphous
and crystalline content. The curves shown for 600 m/min and above are
characteristic of drawn fiber. The glass transition range is usually in the
range of 75oC; crystallization and melting ranges are around 130oC
and 260oC, respectively.
The thermal degradation of PET proceeds by a molecular
mechanism with random chain scission at ester linkages, although a radical
mechanism has also been proposed. A chain-scission scheme is shown below:
The degradation products can undergo further changes, but
at ordinary processing temperatures a certain proportion of carboxyl groups
is introduced into the polymer structure. Color formation upon degradation
has been attributed to the formation of polyenaldehydes from acetaldehyde
and from a further breakdown of poly(vinyl ester)s.
Because of its rigid structure, well-developed
crystallinity and lack of reactive dyesites, PET absorbs very little dye in
conventional dye systems. This is particularly true for the highly
crystalline (highly drawn), high tenacity-high modulus fibers. Polyester
fibers are therefore dyed almost exclusively with disperse dyes.
A considerable amount of research work has been done to
improve the dyeability of PET fibers. Polymerizing a third monomer, such as
dimethyl ester, has successfully produced a cationic dyeable polyester fiber
into the macro-molecular chain. This third monomer has introduced functional
groups as the sites to which the cationic dyes can be attached . The
third monomer also contributes to disturbing the regularity of PET polymer
chains, so as to make the structure of cationic dyeable polyester less
compact than that of normal PET fibers. The disturbed structure is good for
the penetration of dyes into the fiber. The disadvantage of adding a third
monomer is the decrease of the tensile strength.
A new dyeing process for polyester fiber at low
temperature (40(C and below) has been reported . This method employs a
disperse dye in a microemulsion of a small proportion of alkyl halogen and
phosphoglyceride. The main advantage of this method is low temperature
processing, but there remains the environmental problem that is produced by
using toxic carriers.
Another approach has been introduced by Saus et al .
The textile industry uses large amounts of water in dyeing processes
emitting organic compounds into the environment. Due to this problem a dying
process for polyester fiber was developed , in which supercritical CO2
is used as a transfer medium . This gives an option avoiding water
discharge. It is low in cost, non-toxic, non-flammable and recyclable. When
dyed in an aqueous medium, reduction clearing is to be carried out to
stabilize color intensity, which produces more waste water. Reduction
clearing is not carried out following supercritical dyeing. Other advantages
are better control of the dying process and better quality of application
Spunbond PET nonwoven webs have been treated by (SO2+O2)
plasma and (N2+H2+He) plasma at the University of
Tennesse, Knoxville. The research results show that spunbond PET nonwovens
web can be colored by conventional water soluble acid dyes . Plasma
techniques open new avenues for coloring PET fabrics and are sure to be more
evident in the coloring of polyester fibers in the future.
Polyester fibers display good resistance to sunlight but
long-term degradation appears to be initiated by ultraviolet radiation.
However, if protected from daylight by glass, PET fiber gives excellent
performance, when enhanced by an UV stabilizer, in curtains and automobile
interiors.Although PET is flammable, the fabric usually melts and drops away
instead of spreading the flame. PET fiber will burn, however, in blends with
cotton, which supports combustion.
Polyester has good oxidative and thermal resistance.
Color forming species are produced and carboxyl end groups are increased.
The resistance to both oxidative and thermal degradation may be improved by
antioxidants. Mechanical properties are not affected by moderate doses of
high-energy radiation. At doses of more than 0.5Mgy (Mrad), the tensile
strength and ultimate elongation decrease, and deteriorate rapidly at 1-5
Mgy(100-500Mrad). Finally the resistance of polyester fibers to mildew,
aging and abrasion is excellent. Molds, mildew and fungus may grow on some
of the lubricants or finishes, but do not attack the fiber.
Consumption of PET fibers for nonwovens/fiberfill(in
The first U.S. commercial polyester fiber was produced by
DuPont Company in 1953. Since polyester fiber has a lot of special
characteristics, most of them are used in the following three major
||Every form of clothing
||Carpets, curtains, draperies, sheets and
pillow cases, wall coverings, and upholstery
||Hoses, power belting, ropes and nets,
thread, tire cord, auto upholstery, sails, floppy disk liners, and
fiberfill for various products including pillows and furniture
Surgeon's gowns ,for example, were once woven linen but
are now for the most part repellant treated entangled polyester fiber pulp
composites on spunbond melt blown laminates. These new gowns are far
superior to the older material in providing a breathable barrier between the
surgeon and the patient, which serves to significantly reduce hospital
infections. Spunlace mattress pad facing of 100% polyester continues to be
the replacement of spunbond material because of the textile-like character
of entangled fiber fabrics. PET has become the most important polymer type
of fibrous prostheses. It is reasonably inert, bio-compatible, flexible,
resilient and has an appropriate level of tissue acceptance. But,
polymerization initiators, antioxidants, titanium dioxide and other
impurities should be minimized to improve its bio-compatability.
Thermoplastics such as polyester are usually considered
less flammable than cellulosic fibers because they melt and shrink of drip
away from the flame. Polyester resin such as Crystar, a DuPont trade name,
is used to produce spunbonded polyester in a variety of applications: a
nonwoven sheet fabric, fabric softener dryer sheets filtration media,
apparel interlining, carpet backing, furniture and bedding, automotive seats
and agricultural crop covers.
One of the important applications of PET is in the form of bicomponent
fibers. To increase the strength of the nonwoven fabric, in while
maintaining the soft hand of LLDPE, PET is used in continuous bicomponent
filaments having a sheath component made of LLDPE and a core component made
of PET. The tensile strength of the fabrics is improved remarkably by the
bicomponent filaments and depends on the LLDPE/PET ratio. The ultrasonically
bonded polyester/polypropylene blend like Matarh's Ultraskin, the protective
clothing, is said to protect wearers from rain while offering the
breathability needed to provide comfort.
Dry and wet laid nonwovens made from a range of synthetic
and inorganic fibers are used in various insulation and industrial
applications. A series of nonwoven polyester fiber mats are used in class
F(155 c)DMD flexible electrical insulation laminates and electrical tape
backing applications. Nonwoven mats made of polyester fibers and high
temperature resistant m-aramid are used as a cost effective replacement for
aramid paper in class H(180 C) flexible electrical insulation
Composites made of 100% polyester fibers are widely used
as filtration media. Its layered structure gives excellent tear strength, a
smooth, fiber free surface and edge stability. These products provide higher
filtration efficiencies than spunbonded media that has not been calendered.
The main advantage of these products is that they have no short fibers to be
carried downstream and contaminate the filtrate.
In Fiberfill applications polyester fibers are used
inside seat cushions, back pillows, mattresses and waterbeds, decorative and
throw pillows, outdoor furniture and even hand-stuffed custom
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