1.

11
Polyamide and Polyester Fibers
XUE-CHAO HU
China Textile University, Shanghai, China
and
H. H. YANG
Richmond, VA, USA

1.11.1 INTRODUCTION 2

1.11.2 POLYAMIDE 6 FIBER 2

1.11.2.1 Introduction 2
1.11.2.2 Polymerization 3
1.11.2.2.1 Batch process 3
1.11.2.2.2 Continuous process 3
1.11.2.2.3 Polymer purification 4
1.11.2.3 Fiber Spinning 4
1.11.2.4 Fiber Properties 4
1.11.2.4.1 General properties 5
1.11.2.4.2 Tensile properties 5
1.11.2.4.3 Elastic recovery 6
1.11.2.4.4 Flame resistance 6
1.11.2.4.5 Light stability 6
1.11.2.4.6 Chemical resistance 6
1.11.2.4.7 Thermal stability 6
1.11.2.4.8 Electric properties 7
1.11.2.4.9 Toxicity 7
1.11.2.4.10 Dyeability 7
1.11.2.4.11 Fatigue resistance 7
1.11.2.4.12 Dimensional stability 7
1.11.3 POLYAMIDE 6,6 FIBER 7
1.11.3.1 Polycondensation 7
1.11.3.1.1 Batch process 7
1.11.3.1.2 Continuous process 7
1.11.3.2 Fiber Spinning 8
1.11.3.2.1 Extrusion and spinning 8
1.11.3.2.2 Drawing 8
1.11.3.3 Fiber Properties 8
1.11.3.3.1 General properties 9
1.11.3.3.2 Tensile properties 9
1.11.3.3.3 Elastic recovery 9
1.11.3.3.4 Moisture regain 9
1.11.3.3.5 Light stability 9
1.11.3.3.6 Electrical properties 10
1.11.3.3.7 Chemical resistance 10
1.11.3.3.8 Optical properties 10
1.11.3.3.9 Identification of nylon 66 vs. nylon 6 10

1
2 Polyamide and Polyester Fibers
1.11.4 POLY(ETHYLENE TEREPHTHALATE) FIBER
1.11.4.1 Polycondensation
1.11.4.1.1 Batch polymerization
1.11.4.1.2 Continuous polymerization
1.11.4.1.3 Solid-phase polymerization
1.11.4.2 Fiber Spinning
1.11.4.2.1 Spinning
1.11.4.2.2 Drawing
1.11.4.2.3 Process modifications
1.11.4.3 Fiber Properties
1.11.4.3.1 General properties
1.11.4.3.2 HM/LS fiber
1.11.5 COPOLYESTER AND OTHER POLYESTER FIBERS
1.11.5.1 Synthesis of Copolyesters
1.11.5.2 Spinning and Fiber Properties
1.11.5.3 Cationic Dyeable Polyesters
1.11.5.4 Poly(ethylene-2,6-naphthalene dicarboxylate)
1.11.5.4.1 Polycondensation
1.11.5.4.2 Fiber spinning and drawing
1.11.5.4.3 Fiber properties
1.11.5.5 Poly(trimethylene terephthalate)
1.11.5.5.1 Synthesis of PTT
1.11.5.5.2 Fiber spinning
1.11.5.5.3 Typical PTT fiber properties
1.11.6 REFERENCES
1.11.1 INTRODUCTION
Aliphatic polyamide (nylon) and polyester
fibers are well known as textile fibers. They
have also been used as reinforcing fibers for
composite materials. In recent years, high-
strength nylon and polyester fibers have been
developed and increasingly used in industrial
applications such as tires, hoses, or belts. This
chapter will cover the general methods of poly-
mer and fiber preparation, and typical fiber
properties of commercially available poly-
amides and polyesters. The fiber products
include nylon 6, nylon 66, poly(ethylene ter-
ephthalate), poly(ethylene-2,6-naphthalene di-
carboxylate), cationic dyeable polyester, and
poly(trimethylene terephthalate).
1.11.2 POLYAMIDE 6 FIBER
1.11.2.1 Introduction
Polyamides are polymers containing charac-
teristic amide linkages of ÐNHÐCOÐ in the
polymer main chain (Hill, 1953). These poly-
mers are generally divided into two groups. One
group is formed from the polycondensation of
difunctional monomers utilizing amino acids or
pairs of dicarboxylic acids and diamines, and
the other group from the ring-opening polymer-
ization of lactams. The polyamides formed
from diacids and diamines are often referred
to as AABB type, whereas those derived from
either amino acids or lactams are AB type,
10
11
11
11
12
12
12
13
13
13
14
14
14
14
14
15
15
16
16
16
17
17
18
18
18
where A and B represent two different func-
tional groups.
Aliphatic polyamides are commonly named
either as nylon X, Y, or Z, where X, Y, and Z
are the number of carbon atoms in the respec-
tive monomer. The pair X, Y refers to the
AABB-type nylons, where the first number X
is equal to the number of carbon atoms in the
diamine unit and the second number Y repre-
sents the number of carbon atoms in the diacid
unit. The number Z refers to the AB-type ny-
lons and is equal to the number of carbon
atoms in the amino acid unit. Thus, nylon 6,6
is the polyamide produced from hexamethylene
diamine and adipic acid, whereas nylon 11 is
made from aminoundecanoic acid, and nylon 6
is made from caprolactam. In addition, poly-
amide structures are represented by a single
letter or a combination of letters to identify
ring-containing units. For example, nylon 6,T
refers to a polyamide produced from hexam-
ethylene diamine and terephthalic acid. Copo-
lymer compositions are represented by listing
the components in order of decreasing percen-
tages and adding the mole percentages in par-
entheses. Thus, nylon 6,6-6 (60/40) refers to a
product obtained by copolymerizing hexam-
ethylene diamine, adipic acid, and caprolactam
in such quantities that a copolyamide contain-
ing 60% 6,6 units and 40% 6 units is obtained.
Nylon 6,6 was pioneered and commercialized
by E. I. duPont de Nemours & Company in the
United States. I. G. Farben introduced nylon 6
at almost the same time in Germany. The word
ªnylonº has become a household term today
 Polyamide 6 Fiber 3

in the world. The application spectrum of

both nylon fibers is very broad as textile yarns,
tire cord, and industrial cord (Hesselberth,
1994). The manufacture of nylon fiber involves
two basic steps: polymer preparation and fiber
spinning.

1.11.2.2 Polymerization
Nylon 6 polymer is prepared from the poly-
condensation of caprolactam. The basic synth-
esis is represented by the following reaction:

CH2-CH2-CO
CH2 --NH(CH2)5-CO- -

CH2-CH2-NH Polycaprolactam
(Nylon 6)
Caprolactam

Caprolactam has a ring structure and its ring-

opening reaction can induce polymerization.
For this reason, the polymerization of capro-
lactam is called ring-opening polymerization.
The reaction can be initiated by either water
or a strong base. The water-initiated process is
known as hydrolytic polymerization whereas
initiation by a strong base pertains to an anio-
nic polymerization that requires anhydrous
conditions. The latter process is therefore not
practiced commercially. The hydrolytic poly-
merization is performed commercially either
batchwise or in a continuous operation.

1.11.2.2.1 Batch process

In a batch process, ring-opening polymeriza-
tion occurs in a batch reactor at the desired
temperature and pressure. When the desired
polymer molecular weight is reached, the poly-
mer melt is discharged from the reactor. It is
extruded and cut into chips.
1.11.2.2.2 Continuous process
The continuous polymerization of nylon 6
compared with batch polymerization is charac-
terized by high output, consistent product qual-
ity, and process controllability. A typical
example is the VK tube process (Dong et al.,
1996). The VK tube can be divided into three
zones as shown in Figure 1. Caprolactam is first
melted by heating to about 100 8C. The mono-
mer, water (initiator), acids (molecular weight
regulator), pigments, delustrants, and other
additives are then carefully measured and
pumped to the top of a vertical VK tube reac-
Figure 1 VK tube process (after Dong et al.,
1996).
tor. All compositions are homogeneously
blended at the tube top which is heated to
about 220±230 8C. The ring-opening reaction
is initiated and most of the water is distilled
off. The reaction mixture flows downward to a
second zone of the tube. The temperature of
this zone is kept at around 260 8C and polymer-
ization is accelerated very quickly. In order to
achieve high conversion of monomer and high
polymer molecular weight, a relatively low tem-
perature is favorable in a third zone. The total
process takes about 14±20 h. At the bottom of
the VK tube, nylon 6 melt can be either made
into chips or converted directly to fibers.
Thus, the continuous polymerization process
is characterized by heating caprolactam in the
presence of water in the range of 230±260 8C for
4 Polyamide and Polyester Fibers
about 12 h to more than 24 h under the protec-
tion of carbon dioxide or nitrogen. The total
reaction time depends on the particular process,
reactor design, and requirements of the final
polymer. Most of the water used to initiate the
reaction is removed during the process, usually
after about 92% of the caprolactam has been
converted to polymer.
1.11.2.2.3 Polymer purification
The polymerization does not result in a com-
plete conversion of caprolactam, but in equili-
brium. The quantity of the residual monomer
depends on the reaction temperature. In addi-
tion, there is about 3% of low molecular weight
oligomers, which are mostly cyclic. Since sub-
sequent processing as well as performance char-
acteristics in many applications are affected by
both the residual monomer and the oligomers,
it is necessary to remove them from the poly-
mer. This can be accomplished by water extrac-
tion and partly by vacuum evaporation.
Hot water extraction is required if the poly-
mer purification process does not include a
vacuum stage. In this case, the molten polymer
is extruded in the form of rods of about 3 mm in
diameter. The rods are quenched in water and
cut into chips of about 3 mm length. These
chips are then extracted with water at tempera-
tures slightly below 100 8C. The extraction
process can be carried out batchwise or con-
tinuously in a countercurrent operation. The
residence time for this process is about 8±12 h.
The extracted chips are then dried batchwise or
continuously. Vacuum tumble dryers are most
commonly used at temperatures of 100±120 8C
and final pressures of 0.1 torr. Rotary dryers or
towers are used in a continuous processes in
which the chips are dried countercurrently with
circulating hot nitrogen. Depending on the
dryer design, polymer molecular weight, and
type of end groups, residence times in the
range of 20±50 h may be required to reduce
the water content of chips. The residual water
content of chips used in most commercial pro-
cesses ranges from 0.02% to 0.1%.
Vacuum evaporation for polymer purifica-
tion is usually a part of a continuous operation.
In this case, the molten polymer is fed into a
suitable apparatus, such as a thin-film evapora-
tor, where most of the monomer and part of the
cyclic oligomers are distilled from the melt
under vacuum. The efficiency of this operation
depends on the vacuum applied, the residence
time, and the processing temperature. Along
with the vacuum distillation of monomer and
oligomers, the polymer molecular weight is usu-
ally increased. The polymer melt emerging from
the vacuum stage can then be converted directly
to fibers, films, or chips. Nylon 6 produced with
vacuum evaporation usually contains a higher
concentration of oligomers when compared
with water extraction. Whereas the residual
water-soluble compounds in extracted commer-
cial nylon 6 are generally below 1%, concentra-
tions of 2.8±3.8% are characteristic for products
from vacuum evaporation.
1.11.2.3 Fiber Spinning
There are two kinds of spinning operation:
one is a direct spinning process, the other is a
remelting process as shown in Figure 2. In the
direct spinning process, polyamide melt is
directly pumped to spin blocks. In the remelt
process, an extruder is usually used to remelt
polyamide chips. Except for remelting the
chips, the melt spinning operation is essentially
the same for both processes. In either case, the
polymer melt is pumped through a filter pack
and a spinning manifold to various spinning
blocks. The filter pack contains a filtration unit
composed of different layers of special sand or
layers of stainless steel screens and sintered
stainless steel plates. Each spinning block con-
tains a metering pump, filter, and spinneret.
The filtration step removes foreign particles,
gel particles, or precipitated additives. It also
improves the melt homogeneity and provides a
rather high shear which affects the melt rheo-
logical and viscoelastic behavior by virtue of
molecular orientation.
The molten polymer is accurately metered to
the spinneret by means of a meter pump. Fila-
ments emerging from the spinneret are cooled
in quench ducts usually by a cross-blast of
conditioned air and while passing through a
spinning duct are wetted with an aqueous spin-
ning finish containing antistatic and lubricating
agents, and are wound on to bobbins at take-up
speeds ranging from 400 to 6000 m min71. The
next most significant step is the drawing of the
filaments to 1.5±6 times their undrawn length.
This drawing process is done in either one or
two stages. Newer developments are concerned
with combining both spinning and drawing into
one process stage. Such processes are charac-
terized by take-up speeds of more than 4000 m
min71. Both spinning and drawing are complex
processes and require generally sophisticated
technologies.
1.11.2.4 Fiber Properties
Nylon 6 fiber is produced in two general
product types: the regular type for textile uses
 Polyamide 6 Fiber 5

Figure 2 Fiber spinning process.

and the high-strength type for industrial uses.
Most nylon 6 is produced in the form of fila-
ment yarns and staple fiber yarns for the man-
ufacture of carpets, tire cords, apparel, hosiery,
upholstery, seat belts, parachutes, ropes, and
industrial cords. This wide spectrum of applica-
tion can be attributed to the particular combi-
nation of fiber properties (Lim et al., 1989;
Moncreff, 1975) as shown in Table 1 (Cook,
1984).
1.11.2.4.1 General properties
Nylon 6 typically exhibits a glass transition
temperature of 48 8C and a melt temperature of
214 8C. It has a density of 1.14 g cm73. Nylon 6
filaments have a smooth surface and are as
featureless as glass rods. Nylon 6 has an out-
standing resistance to abrasion.
1.11.2.4.2 Tensile properties
The tensile strength of nylon 6 may be varied
by adjustment of the manufacturing conditions.
In general, the greater the degree of stretch
during drawing, the higher the tenacity and
the lower the elongation. Regular nylon 6
fiber has a tenacity of 4.4±5.7 cN dtex71 and
initial modulus of 1.96±4.41 GN m72. These
tensile properties are quite adequate for
textile applications. High-strength nylon fiber
for industrial application has a tenacity of
6 Polyamide and Polyester Fibers

Table 1 Typical properties of nylon 6 fiber.

Product type Staple Regular High strength

Molecular weight 20 000

Degree of polymerization 200
Glass transition temperature (8C) 75
Melt temperature (8C) 214
Density (g cm73) 1.14
Tenacity (cN dex71)
Dry 4.2±5.9 4.4±5.7 5.7±7.7
Wet 3.5±5.0 3.7±5.2 5.2±6.5
Wet/dry tenacity ratio (%) 83±90 84±92 84±92
Elongation at break (%)
Dry 38±50 28±42 16±25
Wet 40±53 36±52 20±30
Recovery at 3% elongation (%) 95±100 98±100 98±100
Initial modulus (GN m72) 0.98±2.45 1.96±4.41 2.75±5.00

Source: Dong et al., 1996.

5.7±7.7 cN dtex71 and initial modulus of 2.75± 1.11.2.4.5 Light stability

5.00 GN m72. Relatively high fiber strength
and initial modulus are necessary for reinfor-
cing applications such as tires and composites.
At low temperatures nylon 6 retains its
strength well. There is, in fact, a slight gain in
tensile strength after exposure of nylon 6 to low
temperatures. The fiber regains its original
strength when returned to room temperature.
On the other hand, nylon 6 loses strength with
increasing temperature. The tensile strength is
regained when the fiber is returned to room
temperature. However, prolonged exposure of
nylon 6 to air at elevated temperatures can
cause permanent loss in breaking strength,
elongation, and toughness. The fiber discolors
with yellowing to some extent.
1.11.2.4.3 Elastic recovery
Nylon 6 is a highly elastic fiber in that it will
recover its original dimensions after being de-
formed by the application of a stress. A typical
filament has an elastic recovery of 100% up to
an extension of 6±8%. Recovery from 10%
extension is about 85%, only part of it being
instantaneous and the remainder taking place
over several hours.
On prolonged exposure to light, nylon 6
suffers some loss of strength, with superficial
yellowing and a general deterioration of other
fiber properties. The degree of deterioration
due to light is affected by many factors, of
which the following are important: (i) transpar-
ency of fiber; bright nylon 6 is more resistant
than dull nylon 6; (ii) yarn count: yarns of
higher count are more resistant than those of
lower count.
1.11.2.4.6 Chemical resistance
Some materials have a permanent effect on
nylon 6 fiber, e.g., 3% solution of oxalic acid in
water at 99 8C for 3 h causes a loss of almost
30% strength and elongation in nylon 6 yarn.
There are some solvents for nylon 6 such as (i)
concentrated formic acid, e.g., 50% formic acid
solution at 80 8C, (ii) concentrated hydrochlo-
ric, nitric, and sulfuric acids, (iii) 25% solution
of zinc chloride in methanol at 50 8C, and (iv)
phenol and phenolic compounds. Most of the
common bleaches cause some degradation in
nylon 6.

1.11.2.4.7 Thermal stability

1.11.2.4.4 Flame resistance Nylon 6 yarns heated in dry air for 5 h at

Nylon 6 melts when heated above 215 8C and
the molten polymer tends to drip. Fabrics of
nylon 6 do not normally support combustion
on their own, but their flammability may be
increased by the presence of certain chemical
finishes and dyes.
150 8C undergo deterioration, losing brightness
and becoming yellow. The relatively low melt-
ing point of nylon 6 means that it may not be
used at elevated temperatures. At temperatures
below its melting point, on the other hand,
nylon 6 has a somewhat better resistance to
prolonged heating. This can be an important
 Polyamide 6,6 Fiber
factor in some applications, e.g., tires, where the
fibers must withstand elevated temperatures.
1.11.2.4.8 Electric properties
The capacity of nylon 6 to undergo static
electrification is due to its low moisture regain
and high electrical resistivity. The dielectric
constant of dry nylon 6 is 3.7 at 105 Hz and
20 8C. The surface resistance is 2.0 6 1012 MO
and the specific resistance 2.6 6 108 MO.
1.11.2.4.9 Toxicity
Nylon 6 is absolutely free of all toxic proper-
ties, and is chemically inert. It will not cause
irritation to the skin.
1.11.2.4.10 Dyeability
The increased affinity of nylon 6 for some
types of dyestuff makes for greater versatility in
dyeing, with the possibility of producing
brighter, deeper prints.
1.11.2.4.11 Fatigue resistance
Nylon 6 has a better fatigue resistance than
nylon 6,6, and this is important in applications
such as tires, where the fiber is subjected to
repeated stresses.
1.11.2.4.12 Dimensional stability
Nylon 6 fiber tends to shrink more in boiling
water than similar types of nylon 6,6. There is
a slight amount of lateral swelling of nylon 6
fiber in water, but the length remains almost
unaffected.
1.11.3 POLYAMIDE 6,6 FIBER
The commercial production of nylon 6,6
began in 1939 (Cook, 1984). The largest market
for the fiber is in stockings where natural silk
has been completely replaced by nylon. Nylon
blends with wool and cotton also command a
large market segment. Other uses for the fiber
include rope production and tire cords (Malikv,
1991), especially for airplanes.
7
1.11.3.1 Polycondensation
Nylon 6,6 is synthesized from the reaction of
hexamethylene diamine and adipic acid to form
hexamethylene diammonium adipate, or
ªnylon salt.º This is performed by reacting a
70% methanolic solution of the diamine and a
20% methanolic solution of the diacid. The
nylon salt precipitates as it is formed. After
isolation, a 60% aqueous solution of nylon
salt is polymerized to form poly(hexamethylene
adipamide) or nylon 6,6. The overall polycon-
densation is represented by the following
reaction:
NH2-(CH2)6-NH2 + HOOC-(CH2)4-COOH
Hexamethylene Adipic acid
diamine
NH(CH2)6-NH-CO-(CH2)4-CO
Poly(hexamethylene adipamide) (nylon 6,6)
The polycondensation of nylon 6,6 may be
performed by a batch or continuous process.
1.11.3.1.1 Batch process
For the batch process, a 50±60% aqueous
solution of the nylon salt and a small amount
of viscosity stabilizer (0.5% acetic acid) is
pumped into an autoclave and heated to 260±
280 8C. Before the condensation starts, the
autoclave is purged with very pure nitrogen
(less than 0.0050% oxygen) to avoid polymer
discoloration. During heating, a pressure of 15±
16 atm is built up. At this point, the pressure is
released and heating is continued until all water
has been distilled off. Towards the end of dis-
tillation, the autoclave is evacuated. The result-
ing polymer is a clear, viscous melt and is
removed from the autoclave by nitrogen pres-
sure. The polymer melt is immediately con-
ducted through an electrically heated slot at
the bottom of the autoclave into a bath of
cold water, where it solidifies to a ribbon. The
ribbon is then cut into small chips. The polymer
product contains a small amount of oligomers.
1.11.3.1.2 Continuous process
In continuous process as shown in Figure 3,
three or four specially designed tubular reactors
are connected. An aqueous solution of nylon
6,6 salt containing 0.5% adipic acid and 2%
caprolactam is pumped into a tube where the
solution is heated to 210±215 8C. It is then
pumped to a second high-pressure tubular
8 Polyamide and Polyester Fibers
Figure 3 Continuous polycondensation of nylon 6,6.
reactor in which the temperature is increased
further. Water is distilled off and the concen-
tration of nylon salt is increased. At the end, the
second vessel may eventually reach 250 8C. The
reaction mixture is pumped into a flasher where
the pressure is decreased from 1.766106 Pa to
normal by a vacuum pump. Its residence time in
the flasher is only a few seconds at very high
throughput. The flasher temperature is con-
trolled in the range of 280±285 8C and water
continues to be distilled off. The reaction mix-
ture then flows into the deaerator where most
of the water is to be distilled off. The prepoly-
mer, which has been formed in the preceding
steps, is put into a polycondensation reactor at
270±285 8C near vacuum pressure. The reaction
is completed after about 30 min. The polymer
molecular weight ranges from 12 000 to 20 000,
and is typically 14 500.
1.11.3.2 Fiber Spinning
Nylon 6,6 fiber is produced primarily by the
melt-spinning process. Because of its melt sta-
bility and low viscosity, nylon 6,6 can be spun
in the molten state at speeds of up to 6000 m
min71. As with nylon 6, a new process which
combines spinning and drawing has been devel-
oped recently. The windup speed can be as high
as 5000±6000 m min71. This makes nylon spin-
ning very economical.
1.11.3.2.1 Extrusion and spinning
Nylon chips are first fed into an extruder and
extrusion melted. The molten polymer is then
pumped by a meter pump through a series of
sand filters to a spinneret. The spinneret nor-
mally has 24±120 capillary holes for multifila-
ment yarns. Filaments exiting the spinneret
solidify immediately on contact with air. A
cross air blast is normally applied in order to
assist solidification of the filaments. Since these
filaments are completely free of water, they are
treated with steam in a chamber and then with a
formulated finish oil before being wound on to
a bobbin as as-spun fibers.
1.11.3.2.2 Drawing
The drawing process causes a parallel orien-
tation of polymer molecules which enhances the
fiber properties. It increases fiber strength and
modulus while decreasing fiber elongation.
These fiber properties are needed for the pro-
duction of tire cords. The as-spun fiber is
stretched 100±400% at ambient temperature,
depending on the spinning speed. Higher tem-
peratures allow additional stretching after cold
stretching. For improved heat stability, the
stretched fiber is treated with steam. Deluster-
ing of the fibers is normally accomplished by
adding titanium dioxide during polycondensa-
tion or before extrusion.
1.11.3.3 Fiber Properties
Nylon 6,6 can be used as fibers for textiles or
resins for a wide range of industrial applica-
tions. In fact, nylon 6,6 gives fibers of high
tensile strength, great flexibility, and abrasion
resistance. It is superior in this respect to nearly
 Polyamide 6,6 Fiber 9

Table 2 Typical properties of nylon 6,6 fiber.

Product type Regular High strength

Molecular weight 12 000±20 000

Glass transition temperature (8C) 60
Melt temperature (8C) 260
Ignition temperature (8C) 530
Density (g cm73) 1.14
Dry 4.9±5.7 5.7±7.7
Wet 4.0±5.3 4.9±6.9
Wet/dry tenacity ratio (%) 90±95 85±90
Elongation at break (%)
Dry 26±40 16±24
Wet 30±52 21±28
Recovery at 3% elongation (%) 95±100 98±100
Initial modulus (GN m72) 3.66±4.38 2.30±3.11

Source: Dong et al., 1996.

all other kinds of fibers. Table 2 (Lim et al., reduces modulus. Increasing molecular orienta-
1989) presents the typical properties of nylon tion by the stretching process increases modu-
6,6 fiber. lus. A 10% increase in drawing will increase the
modulus by about 20%.

1.11.3.3.1 General properties

Nylon 6,6 has the same density as nylon 6,
1.14 g cm73. It exhibits slightly higher transi-
tion temperatures than nylon 6: 50 vs. 48 8C
glass transition temperature and 260 vs. 214 8C
melt temperature.
1.11.3.3.2 Tensile properties
Nylon 6,6 offers almost the same fiber
strength as nylon 6. It is generally affected by
the conditions and time of loading, degree of
molecular orientation, temperature, and rela-
tive humidity (Moore, 1989). The effect of hu-
midity on the breaking extension is greater than
on the breaking load, and the effect of tempera-
ture is greater at high humidity than at low
humidity. Cold drawing increases the tensile
strength considerably. A 10% increase in cold
draw may increase the tensile strength by 25%.
The resistance to deformation of nylon 6,6 is
generally defined by its modulus. It is affected
by the type of stress, load±extension±time con-
ditions, and ambient temperature and humid-
ity. It decreases with loading time because the
contribution of primary and secondary creep to
the observed deformation is greater at longer
loading times. Moisture has less influence on
the mechanical properties of nylon 6,6 than
other fibers due to its high crystallinity and
relatively hydrophobic character. Disorienta-
tion decreases modulus. Therefore, relaxation
by water or heat treatment below 150 8C
1.11.3.3.3 Elastic recovery
Elastic recovery is important for reinforcing
fibers, particularly for applications in tires and
mechanical rubber goods. Generally, fibers
under stress undergo a delayed extension. The
immediate extension of a fiber is immediately
recoverable due to elasticity. Nylon 6,6 fiber
shows an almost complete recovery even at high
loads. The extent of recovery depends on the
duration of load and the time allowed for
recovery.
1.11.3.3.4 Moisture regain
The moisture regain of nylon 6,6 is typically
affected by the ambient temperature and rela-
tive humidity. It decreases with increasing mo-
lecular orientation and temperature.
1.11.3.3.5 Light stability
When nylon 6,6 is exposed to sunlight, it
undergoes degradation that causes a loss of
strength. The photodegradation is oxidative,
because the fiber is much more stable in nitro-
gen. Increasing the temperature increases the
photodegradation, while moisture has no great
influence. Delustrant increases degradation,
especially with titanium oxide. Many dyestuffs
have a positive or negative influence on the rate
of light degradation.
10 Polyamide and Polyester Fibers
1.11.3.3.6 Electrical properties
The current conductivity of nylon 6,6 is low.
For a 30 denier nylon 6,6 yarn, the value is
5 6 1014 O cm71. The conductivity increases
with increasing moisture regain, which in-
creases the surface-absorbed water. Increasing
the temperature increases the current conduc-
tivity of polyamides exponentially. The insulat-
ing properties give rise to the accumulation of
static electrical charges. Positive or negative
charges can be generated by yarns during
their passage over various surfaces. Humidity
and the application of conducting finishes will
dissipate the static charges.
1.11.3.3.7 Chemical resistance
The resistance of polyamides to chemicals
depends on the end groups and the amide
groups, while the hydrocarbon residues are
very stable. Water under pressure at tempera-
tures above 150 8C will cause complete hydro-
lysis, which is promoted by caustic alkalis.
Mineral acids will cause slow hydrolysis in di-
lute solutions, and stronger organic acids, such
as aqueous oxalic or lactic acids, have the same
effect. The fiber will be destroyed by strong
oxidizing agents such as nitric acid, potassium
permanganate solutions, hydrogen peroxide,
and hypochlorites. Nylon 6,6 will swell in
some polar compounds, such as phenols and
lower aliphatic acids, especially formic acid,
and will dissolve in concentrated solutions. Mo-
lecular orientation influences the rate of uptake
of the swelling agent by polyamide fibers.
1.11.3.3.8 Optical properties
Molecular orientation during drawing results
in positive changes in birefringence. Fully
drawn fibers have a refractive index of about
1.58 along the fiber axis and 1.52 laterally.
Birefringence increases more rapidly at lower
draws.
1.11.3.3.9 Identification of nylon 6,6 vs. nylon 6
The following test is used to distinguish be-
tween nylon 6,6 and nylon 6. A 50% formic
acid solution is heated carefully to 80 8C. Sev-
eral pieces of yarn or individual filaments are
dropped into the solution. Nylon 6 will coil up
and dissolve almost immediately with very little
agitation. Nylon 6,6 will float in the solution
and appear not to be affected.
1.11.4 POLY(ETHYLENE
TEREPHTHALATE) FIBER
Polyesters are polymers containing charac-
teristic ester groups, ÐOÐCOÐ, in the poly-
mer main chain. They are commonly prepared
by reacting a dibasic acid with a dihydric alco-
hol, as shown below:
HOOC-X-COOH + HO-Y-OH
Dibasic acid Dihydric alcohol
--OC-X-COO-Y-O --- + H2O
Polyester
where X and Y are aromatic or alkyl units. In
the case of poly(ethylene terephthalate) (PET),
X is a 1,4-phenylene ring and Y is ethylene. The
polycondensation reaction takes place between
terephthalic acid and ethylene glycol according
to the following overall equation:
HOOC COOH + HO-CH2CH2-OH
Terephthalic acid Ethylene glycol
OC COO-CH2CH2-O + H2O
Poly(ethylene terephthalate) (PET)
PET is one of the most popular polymers. It
is widely used in the production of fibers and
films, and as a matrix material for moldings and
composites. Today, PET fiber products of var-
ious forms are manufactured in many coun-
tries. In the years since World War II, PET
fiber products bearing the trademarks of ICI
Terylene DuPont and ICI Dacron DuPont have
established dominant positions in the polyester
fiber market. Other types of polyester have,
however, been spun into fibers with varying
degrees of practical success. A few of these
have become of commercial importance.
PET fiber offers attractive mechanical and
thermal properties not only as a textile fiber,
but also as an industrial fiber. It is used in the
manufacture of tire cords, V-belts, conveyor
belts, and hoses. In particular, high molecular
weight PET fiber takes the largest share as a
rubber-reinforcing material where high
strength and excellent durability balanced
with heat shrinkage and modulus are required.
In addition, high molecular weight PET resin is
increasingly being used in vast quantities in
beverage bottles (Cohn, 1988; Isao et al.,
1985, 1991; Kumakawa and Yamamoto, 1987;
Rim and Nelson, 1991; Saitoi et al., 1985; S.
Ahmed and A. Hadi, 1983; Toshiro et al., 1988;
Nelson et al., 1990).
 Poly(Ethylene Terephthalate) Fiber
1.11.4.1 Polycondensation
The synthetic process of PET can be divided
into two stages. The first stage is ester inter-
change or esterification, depending on the start-
ing material. If dimethyl terephthalate and
ethylene glycol are used, the first stage is an
ester interchange, where methanol is distilled
and a linear oligomer, bis(hydroxyethyl)ter-
ephthalate, is formed. If terephthalate acid
and ethylene glycol are used, the first stage is
an esterification process which yields a linear
oligomer directly with the release of water. The
second stage is a polycondensation process.
A catalyst is added to the mixture of linear
oligomers. Free glycol is distilled out as poly-
merization is carried out at about 285 8C and at
a pressure below 25 Pa until the required mole-
cular weight is obtained. The most popular
catalyst for this stage is antimony trioxide,
but antimony pentoxide and germanium diox-
ide have also been employed.
The polycondensation reaction of PET is
reversible. It is therefore important to remove
the glycol produced from the system as quickly
as possible. As with most polymerization pro-
cesses, the rate of achieving high molecular
weight is diffusion controlled rather than che-
mically controlled. It is useful to minimize the
diffusion path by maximizing the surface/vo-
lume ratio of the reaction mixture.
The processes for producing PET can be
batch, continuous, and solid-state polymeriza-
tion. Continuous polymerization, particularly
when integrated with the spinning process, is
employed in most large-scale production. Batch
production is mostly confined to fine filament
yarns, specialties, and nonfiber end uses. Both
the batch and the continuous polymerization
processes, however, have disadvantages in that
a long reaction time is needed, and it is quite
difficult to produce PET having an intrinsic
viscosity (IV) [Z] of at least 0.8 dL g71 on a
commercial scale. Solid-state polymerization is
employed to produce PET resins of 0.8 dL g71
or higher (Chen and Chen, 1987; Ravindranath
and Mashelkar, 1990).
1.11.4.1.1 Batch polymerization
Batch systems usually comprise two reaction
vessels: an ester interchange vessel or an esteri-
fier, and a polymerization vessel. The ester
interchange vessel is equipped with heating fa-
cilities and an agitator. Auxiliary vessels are
provided for metering in ethylene glycol, mol-
ten dimethyl terephthalate, and catalyst. A frac-
tionation column is employed from which the
distillate, mainly methanol, is collected and sent
11
for purification. Terephthalic acid may be
charged as a solid, or more probably as a dis-
persion in glycol, along with additives, to the
esterifier. Water produced from the polymeri-
zation reaction is removed by way of a column
so that glycol is returned to the batch system.
The product from the esterifier is then trans-
ferred to the polymerization vessel. Additives
such as stabilizers, catalysts, and delustrants
can be added at this stage. The polymerization
vessel is equipped with heating facilities, a
heavy-duty agitator and a short column for
glycol vapor removal. An evacuation system is
connected to the glycol column to reduce its
pressure. During polymerization, the electrical
input to the agitator motor increases as the
reaction mixture becomes more viscous. It can
be calibrated as an indicator for polymer melt
viscosity. At the completion of polymerization,
the vessel is pressurized with nitrogen and the
polymer is extruded through a slot into a cold-
water quench system and cut to chips.
1.11.4.1.2 Continuous polymerization
Figure 4 (Pontara, in press) shows the pro-
cess flow diagram of PET continuous polymer-
ization. The system typically consists of at
least three vessels, one for the ester interchange
or direct esterification stage, one for reducing
the excess glycol and producing a prepolymer,
and one for completing polymerization. The
first stage employs a cascade reactor or a series
of reactors arranged as a cascade. Methanol or
water is produced and removed from the
esterifier. The second stage consists of a stirred
vessel and the molecular weight of products
from the first stage is raised to an intermediate
value under slightly reduced pressure. The
third stage employs one or more reactors
that provide a high surface/volume ratio and
frequent renewal of surface to facilitate the
step-growth reaction. Various designs, such
as the Zimmer disc-ring reactor and the Wer-
ner and Pfleiderer twin-screw reactor, have
been developed. Polymerization is carried out
in this stage at a pressure that will ultimately
fall to about 25 Pa. The polymer product is
extracted from the final reactor by a screw and
delivered either directly to melt spinning or to
a polymer extrusion and chip cutting unit. The
melt viscosity of prepolymer entering the final
stage and that of the exiting polymer can be
monitored with an on-line capillary rheometer.
Such information is fed to a process control
system. For textile fibers, the IV of PET resin
is typically about 0.6 dL g71 on a commercial
scale.
12 Polyamide and Polyester Fibers
Figure 4 Continuous polymerization of PET (after Pontara, in press).
1.11.4.1.3 Solid-phase polymerization
The production of PET by solid-phase poly-
condensation is practiced commercially. To this
end, a preliminary melt polycondensation is
carried out to attain an IV of 0.1±0.4. This
prepolymer is cast into a solid form. The parti-
culate polymer is first precrystallized by heating
with forced agitation to prevent sintering, then
heated in flowing nitrogen or under reduced
pressure at a temperature above 200 8C until
the desired molecular weight is obtained (Isao
et al., 1985).
At temperatures below 200 8C, the reaction
rate is chemically controlled. As the tempera-
ture is raised above 200 8C, it becomes progres-
sively controlled by the diffusion of glycol out
of the polymer particles. Consequently, the rate
is affected by particle size. Large particles, such
as standard polymer chips, polymerize slowly
and the product exhibits a relatively wide mo-
lecular weight distribution due to the difference
in degree of polymerization between the center
and surface of the particle. Particle diameters
below 0.8 mm are reported to restore rapid
polymerization rates (Isao et al., 1985).
Progressively increasing the reaction tem-
perature is useful. Very high molecular weight
PET with an IV about 1.0 dL g71 or higher can
be obtained in this way (Isao et al., 1985). A
combination of progressive temperature in-
crease and using waste PET filaments with a
diameter less than 0.05 mm has made it possible
to obtain PET resins with an IV as high as 2.5
dL g71 (Hu and Shao, 1997).
1.11.4.2 Fiber Spinning
In general, the process for producing PET
fibers consists of melt spinning and drawing the
as-spun fiber at 90 8C either immediately or at a
later time. Polyester melt-spinning processes
fall into two distinct classes: (i) relatively low
windup speed processes to produce a spun yarn
with little or no orientation, and (ii) relatively
high windup speed processes to produce a
partly oriented spun yarn. Windup speeds for
the former type of process range up to about
1500 m min71, and for the latter exceed 3200 m
min71. A further division may be made into (i)
processes where spinning and drawing are se-
parated, and (ii) integrated spin/draw pro-
cesses. In the integrated type of process,
ultimate windup speeds may be as high as
6000 m min71.
1.11.4.2.1 Spinning
The pack assembly for melt spinning typi-
cally comprises a meter pump, pack filter,
and spinneret. Graded fine sand, alumina, or
 Poly(Ethylene Terephthalate) Fiber 13

Table 3 Typical properties of PET fibers.

Property MT HT LS HM/LS (DSP)

Tenacity (cN tex71) 35±44 56±70 50±70 70

Initial modulus (cN tex71) 265±530 533±545 330±354 632
Elongation (%) 15±30 8±11 20±28 9±10
LASE-5a (cN tex71) / 54 53 54
e 4.5b (%) / 5±7 13±18 5±6
SARc / 50.8 50.7 50.85
FSd (%) 9±14 58 53 54
FS+e 4.5e (%) 13±15 14±21 9±10

a
LASE-5 (L-5) = load at a specified elongation at 5%. be 4.5 = Elongation at a load of 4.5 g den71. cSAR =
stress±amplification ratio. dFS = free shrinkage. eFS + e 4.5 = free shrinkage at e 4.5, a parameter for HM/
LS PET fiber.

sintered metal disks are employed for
filtration. The filter pressure may range from
2 to 50 MPa. Spinnerets are made of stainless
steel, 5±30 mm thick, and contain capillary
holes of 100±400 mm diameter. Many different
arrangements of holes, such as concentric cir-
cles, parallel rows, and scatter patterns, are
available. The extrusion temperature for regu-
lar PET with number-average molecular weight
of 15 000±20 000 is about 285 8C. The low shear
viscosity is about 1000±3000 poise at this tem-
perature. Filaments ejecting from the spinneret
pass downward through a cooling zone where a
cross-flow of cool, clean air is applied. This is
followed by further cooling inside a cabinet.
The threadline then converges at a guide, passes
through a spin finish applicator, and is wound
as spun yarn.
1.11.4.2.2 Drawing
The as-spun fiber has a microstructure of low
crystal orientation. It is subjected to stretching
to convert it into a commercially useful yarn of
high orientation. The process involves passing
the yarn around driven rollers with successively
higher surface speeds to attain the degree of
stretch or draw ratio required. Although poly-
ester fiber can be drawn at room temperature,
the stress required to initiate drawing is high
and the process unstable. To obtain a uniform
fiber product, it is necessary to draw at a tem-
perature above the glass transition temperature
of the as-spun fiber. In practice, the draw tem-
perature is often in the range of 90±100 8C. It is
also important to locate the draw point as
precisely as possible by using either a heated
pin between the driven rollers or a heated feed
roller. The total draw ratios usually lie between
1.5:1 and 6:1. Higher draw ratios are applied in
the production of high-tenacity yarns and often
involve a two-stage drawing process wherein
the second stage applies a draw ratio of up to
about 6:1 at a somewhat higher temperature.
The process of drawing imparts some crystal-
linity into the fiber structure, but it is insuffi-
cient to stabilize the fiber against thermal
shrinkage. It is often necessary in filament
yarn production to crystallize the yarn further
by heat setting over a hot plate or a heated
draw roller at 140±220 8C during the drawing
process.
1.11.4.2.3 Process modifications
PET resin used to produce HM/LS (high
modulus/low shrinkage) fiber has an IV of
0.9±1.1 dL g71. Fiber spinning is carried out
at high speeds via a two-step spin-windup and
draw process or one-step spin-draw process (Ito
et al., 1990; Murasa et al., 1995). A further
refinement is to provide a higher tension on
the spinning line than in a normal process
(Cook, 1984; Moncreff, 1975; Rim and Nelson,
1991, 1992).
1.11.4.3 Fiber Properties
PET polyester fiber has a number of excellent
properties such as high breaking tenacity and
elastic modulus, moderate elastic resilience,
good heat setting properties, good thermal
and light resistance. Fabrics of PET fiber have
good esthetics, wrinkle resistance, and wash
and wear properties.. Regular PET fiber pro-
ducts are used as textile materials. Industrial
PET fibers include medium tenacity (MT), high
tenacity (HT), high modulus (HM), low shrink-
age (LS) and the newly developed high modu-
lus/low shrinkage (HM/LS) or dimensionally
stable (DSP) types. The typical properties of
different types of PET fibers are illustrated in
Table 3.
14 Polyamide and Polyester Fibers
1.11.4.3.1 General properties
The softening point of PET fibers is approxi-
mately 260 8C and its sticking temperature
230±240 8C. At about 180 8C, PET fiber tena-
city is about half its value at ambient tempera-
ture. PET fiber has excellent oxidation and
reduction resistance. It will withstand severe
bleaching better than other textile fibers. PET
fiber is highly resistant to most of the common
organic solvents and hydrocarbon oils. The
range of chemicals that will dissolve PET fiber
at normal or moderate temperatures is limited.
PET fiber has exceedingly high resistivity at
high humidity due to its low moisture regain.
The volume resistivity of PET remains high at
high temperatures.
1.11.4.3.2 HM/LS fiber
Many PET fiber products are used in fiber-
reinforced composite materials. Among them,
HM/LS PET is a newly developed fiber widely
used in tires, V-belts, transmission belts, and
other mechanical rubber goods. High dimen-
sional stability makes HM/LS or DSP polyester
fiber one of the most advanced tire reinforce-
ments available today (Ito and Takahashi,
1990; Murasa et al., 1995; Rim, 1996). HM/
LS fiber offers about the same tenacity as high-
strength nylon fibers. Its boiling shrinkage is
typically 6% vs. 8±12% for nylon 6,6. Hot air
shrinkage is 54% at 100 8C and 14% at 200 8C
vs. 7 and 9%, respectively, for nylon 6,6. For
tire reinforcement, PET fiber has better fatigue
resistance and about 30% resistance to ªflat
spotting of tiresº than nylon fiber. Thus, this
kind of PET yarn is indeed suitable for incor-
porating as tire cord into rubber tires to provide
an important improvement in fatigue life and
retained fatigue strength.
1.11.5 COPOLYESTER AND OTHER
POLYESTER FIBERS
PET fiber products were first introduced to
the world market in the early 1950s and gained
rapid acceptance due to their durability, wash
and wear properties, and excellent perfor-
mance. However, subsequent efforts have
been continued at producing a polyester fiber
with better properties than PET. The intro-
duction of copolyesters has resulted from
these investigations. These copolyesters have
been aimed primarily at obtaining new types
of polyester fibers with improved dyeability
and mechanical properties. To improve the
dyeability of PET fibers, many additives such
as alkali metal salts of the dimethyl ester of
5-sulfoisophthalic acid, alkyl sulfonic acid,
2-napthol-5-sulfonic acid, hydroquinone sulfo-
nic acid, and 2-bromoethane phosphoric acid
are introduced into the PET molecular
structure. The most common method is poly-
merization in the presence of a dimethyl ester of
5-sulfoisophthalic acid sodium salt (DMS salt)
(Kothari et al., 1996).
PET fiber has been widely used as tire cord,
but its modulus, dimensional stability, and
fatigue properties are not good enough. In
order to improve these properties, several new
polymers have been developed. Among them,
poly(ethylene 2,6-naphthalene dicarboxylate)
(PEN) and poly(trimethylene terephthalate)
(PTT) are the most successful. They provide
alternatives to HM/LS PET fiber with high
strength and dimensional stability, as discussed
in Section 1.11.4 (Jager et al., 1995; Brown and
Chuali, 1997; Buyalos et al., 1989; Chuali and
Corterra, 1996; Ito et al., 1996; Rim, 1996; Rim
et al., 1995; Schauhoff, 1996; Traub et al.,
1995).
1.11.5.1 Synthesis of Copolyesters
The desire to provide copolyesters with high
melting point and high chemical resistance led
to the development of aromatic copolyesters. A
remarkable success in this field by Eastman
Kodak Company resulted in the preparation
of copolyesters with a 4,4-sulfonyl dibenzoic
acid component. Solid-state polycondensation
has also been utilized to prepare high molecular
weight copolyesters. The polycondensation
process of copolyesters is almost the same as
the PET polyester processes.
Most copolyesters used in industrial products
contain at least 90 mol.% PET. The copolymer
may contain minor amounts of one or more
ester-forming ingredients other than ethylene
glycol, terephthalic acid, or its derivatives. Il-
lustrative examples of ester-forming com-
pounds include glycols such as diethylene
glycol, triethylene glycol, teramethylene glycol,
hexamethylene glycol, and dicarboxylic acids
such as isophthalic acid, hexahydroterephthalic
acid, bibenzoic acid, adipic acid, and azelaic
acid (Buyalos et al., 1989).
1.11.5.2 Spinning and Fiber Properties
As with PET fibers, copolyester fibers can be
produced either by a two-step spin-windup and
draw process or a one-step spin-draw process.
 Copolyester and Other Polyester Fibers
For use as tire cords, PET or copolyester
filament yarns are required to have the proper
combination of low work loss and a high degree
of toughness. It has been observed that such
yarn, when incorporated as tire cord into a
rubber tire for reinforcement, will retain its
fatigue strength. This kind of polyester yarn is
characterized as follows (Buyalos et al., 1989):
(i) load at 5% elongation (LASE-5) of at
least 3.7 g den71 at 25 8C;
(ii) tenacity of at least 7.5 g den71 at 25 8C;
(iii) shrinkage of less than 8% in air at
177 8C;
(iv) work loss of less than 0.04 in-lb when
cycled between a stress of 0.6 and 0.5 g den71 at
150 8C measured at a constant strain rate of 0.5
in min71 in a 10 in length of yarn normalized to
that of a multifilament yarn of 1000 total
denier; and
(v) toughness of at least 0.40 g den71.
Such a yarn undergoes a relatively low degree
of shrinkage for a high-strength fibrous mater-
ial due to less oriented amorphous regions. It
exhibits a low degree of hysteresis or work loss
during cyclic extension and contraction. These
effects, in addition to higher yarn toughness
and smaller morphological repeat units,
enhance the fatigue resistance (Buyalos et al.,
1989). The fatigue resistance of a tire cord is not
a property which can be related to any single
parameter, but depends on a combination of
variables such as IV, work loss, toughness, and
undoubtedly fine morphological characteristics
such as crystallite and amorphous sizes and
orientation and amorphous region mobility
(Buyalos et al., 1989).
1.11.5.3 Cationic Dyeable Polyesters
Dyeing of polyester fibers with nonionic
disperse dyes has limitations such as lack of
brightness. For many apparel applications,
consumers often prefer silklike, soft, light-
weight, and drapeable fabrics. This has led to
the development of a new generation of poly-
ester fibers among which cationic dyeable
polyester is a successful commercially exploited
example. Cationic dyeable polyester fiber is
produced by incorporating an additive contain-
ing sulfonic acid groups. The most commonly
used additives is the dimethyl ester of the
5-sulfoisophthalic acid sodium salt.
The manufacture of cationic dyeable poly-
ester involves the polymerization of dimethyl
terephthalate, ethylene glycol, and the dimethyl
ester of 5-sulfoisophthalic acid sodium salt. The
reaction is carried out by the conventional
15
polycondensation process. The spinning and
drawing processes are the same as for PET
fiber.
The addition of a compound containing an
organic group disturbs the regularity of the
polymer chain molecules. Therefore, the struc-
ture of cationic dyeable polyester fiber is less
compact and the mechanical properties are
poorer than those of normal PET fiber. The
large side group ÐSO3 Na in cationic dyeable
polyester molecular chains causes an increase in
chain rigidity and melt viscosity, and a decrease
in crystallinity and orientation. Incorporation
of bulky sulfonate groups increases the intra-
and intermolecular interactions in the polyester,
and results in an increase in glass transition
temperature. Cationic dyeable polyester differs
greatly in chemical properties from regular
polyester fiber. It is more sensitive to alkaline
and acidic conditions (Kothari et al., 1996).
Anionically modified PET is increasingly
used with regular polyesters to achieve attrac-
tive multicolored effects. Cationic dyeable
polyester can also be used where bright and
deep shades are required.
1.11.5.4 Poly(ethylene-2,6-naphthalene
dicarboxylate)
Poly(ethylene-2,6-naphthalene dicarboxy-
late) (PEN) is a typical example of polyester
in which terephthalic acid is not involved. It is
prepared from dimethyl-2,6-naphthalene dicar-
boxylate and ethylene glycol according to the
well-known transesterification/polycondensa-
tion method. High-performance PEN film has
been commercialized and marketed for use in
magnetic recording tapes, flexible printed cir-
cuit board, motor insulation, and photographic
film for miniature cameras. PEN also has po-
tential application in packaging such as hot-fill
bottles. The use of PEN has been driven by its
dimensional stability, high modulus, chemical
resistance, UV stability, and barrier properties
relative to currently used materials like PET.
Extensive research in fiber reinforcement has
made a major contribution to advancing the
design and performance of the modern auto-
mobile tire. The environmental, performance,
and economic requirements have brought PEN
fiber to the verge of commercial viability for
high-performance tire reinforcement.
PEN fiber is intended for industrial yarn
application. It is prepared by melt spinning
and drawing high molecular weight PEN. The
naphthalene moiety in PEN provides stiffness
to the linear polymer backbone, leading to im-
proved thermal resistance, excellent mechanical
16 Polyamide and Polyester Fibers
Table 4 Typical properties of PEN yarns.
Drawn condition
Draw ratio
Roll 1 (8C)
Roll 2 (8C)
Roll 3 (8C)
Dna
Tenacity (g den71)
Modulus (g den71)
Modulus (g den71)
Shrinkage (%)
Tmb (8C)
EASL +c (%)
Source: Rim et al., 1995.
a
Dn = birefringence. bTm = melt temperature. cEASL + = elongation at specified load.
properties, such as tensile properties and di-
mensional stability, and outstanding gas barrier
characteristics.
1.11.5.4.1 Polycondensation
It is very difficult to obtain high molecular
weight PEN through a one-step polycondensa-
tion process because of high viscosity. Solid-
state polycondensation of low molecular weight
polymer is employed instead.
PEN polymer can be produced in an auto-
clave. A mixture of dimethyl-2,6-naphthalene
dicarboxylate and ethylene glycol is transester-
ified with manganese diacetate catalyst at about
230 8C to give PEN oligomer. When transester-
ification is completed, a phosphorous stabilizer
and an antimony trioxide catalyst are added.
The oligomer is polymerized at 290 8C to yield a
PEN prepolymer with relatively low solution
viscosity. Postcondensation of the chips to high
molecular weight PEN is carried out in the solid
state by means of a tumble dryer for 14 h under
high vacuum at a chip temperature of 227 8C
(Jager et al., 1995).
1.11.5.4.2 Fiber spinning and drawing
PEN chips are extruded at 310 8C and 100
bar pressure. The spinning assembly is main-
tained at 310 8C. A spin tube is mounted di-
rectly under the spinneret and is heated to
354 8C. PEN filament yarn is thus produced
by either separate spin and draw processes or
a coupled spin±draw process. The yarn bundle
is cooled with ambient air. A standard PET tire
yarn finish is applied to the yarn. The winding
speed is varied between 500 and 4000 m min71
(Jager et al., 1995).
Undrawn yarn Drawn yarn
6.3
140
157
RT
0.004 0.462
0.6 6.2
18.6 176
18.6 176
5.7
268 272
8.3
The drawing of PEN as-spun yarn is carried
out in two stages using conventional heated
rolls. The first stage is cold drawing. The yarn
is preheated to 115±120 8C on a hot plate or on
a hot roll, it is then drawn on a hot metal pin
wrapped once or twice. The second stage is hot
drawing. The yarn is invariably drawn in hot
steam at a temperature of 260 8C in a long box.
This gives a yarn with an elongation at break of
6±8% (Jager et al., 1995; Ito et al., 1992).
1.11.5.4.3 Fiber properties
The typical properties of PEN undrawn and
drawn yarns are illustrated in Table 4. As ex-
pected, birefrigence (Dn), tenacity, and modulus
of drawn yarn are much higher than those of
undrawn yarn. The melt temperature, Tm, of
drawn yarn is also slightly higher than that of
undrawn yarn. Spinning speed has a great effect
on fiber properties. Table 5 and 6 exemplify the
properties of undrawn and drawn PEN yarns
produced at different spinning speeds. It can be
seen that the yarn tenacity and modulus in-
crease with increasing spinning speed and
draw ratio. Increasing the spinning speed to
greater than 5000 m min71 would result in
further development of molecular orientation,
producing a PEN fiber with high tenacity, low
elongation, and low shrinkage. Yarn tenacity
reaches the maximum value of 0.92 GPa at
7000 m min71. This value seems to be the high-
est obtained by a simple high-speed spinning of
commercially available polymers. However, the
tenacity decreases when the spinning speed ex-
ceeds 7000, probably due to the formation of a
skin-core structure (Jager et al., 1995; Rim et al.,
1995).
By and large, PEN multifilament yarns ex-
hibit better physical properties than PET. They
 Copolyester and Other Polyester Fibers 17

Table 5 Typical properties of PEN undrawn yarn at various windup speeds.

Windup speed 770 2000 3000 4000 5000

(m min71)

Dn 0.043 0.279 0.273 0.267 0.270

Tenacity (g den71) 1.5 3.6 4.1 5.1 7.8
Modulus (g den71) 24 86 122 151 190
Tm (8C) 265 272 281 298 294

Source: Rim et al., 1995

Table 6 Typical properties of PEN drawn yarn at various windup speeds.

Windup speed 770 770 2000 2000 3000 3000 4000 4000
(m min71)

Draw ratio 3.0 3.6 1.4 1.5 1.2 1.3 1.3 1.3
Roll 1 (8C) 125 125 125 125 125 125 4000 125
Roll 2 (8C) RT RT RT RT RT RT RT RT
Heading plate (8C) 230 230 235 230 240 230 240 230
Dn 0.404 0.404 0.420 0.402 0.402 0.406 0.369
Tenacity (g den71) 5.8 6.6 5.8 6.6 5.6 6.8 6.4 6.7
Modulus (g den) 174 257 222 295 255 295 262 323
LASE-5 (g den71) 3.2 5.0 4.8 5.9 4.8 5.9 6.2 5.4
LTa 12 37 61 72 73 61 102 46
Tm (8C) 274 257 276 276 281 281 286
DTm 9 10 11 11 16 16 21

Source: Rim et al., 1995

a
LT = [(L±5)4/T5.16]*1000, where L-5 is LSAE-5 and T = tenacity.

have very high modulus, good tenacity, and low
shrinkage, and are particularly useful for the
reinforcement of tires. The initial modulus of
drawn PEN yarn is about twice as high as that
of PET yarn. The thermal shrinkage of PEN
yarn is only half or even less than that of
commercial PET yarn spun at the same speed.
The dimensional stability of PEN yarn exceeds
that of PET yarn as a consequence of the much
higher initial modulus and lower thermal
shrinkage of PEN yarn (Jager et al., 1995;
Buyalos et al., 1989; Ito et al., 1996; Rim,
1996; Rim et al., 1995).
1.11.5.5 Poly(trimethylene terephthalate)
Poly(trimethylene terephthalate) (PTT) is a
promising new polyester which combines many
of the advantages of nylon and PET. PTT fiber
has high resilience and excellent dyeability. It is
a semicrystalline thermoplastic polyester like
PET and poly(butylene terephthalate) (PBT).
In particular, it can be used as a carpet fiber.
PTT has remained an obscure polymer for a
long time not because of its lack of good phy-
sical and chemical properties and potential
applications, but due to economical reasons.
One of the raw materials, trimethylene glycol,
or 1,3-propanediol, is very expensive (Brown
and Chuali, 1997; Chuali, 1996; Schauhoff,
1996; Traub et al., 1995).
1.11.5.5.1 Synthesis of PTT
In the synthesis of PTT resin, trimethylene
glycol is used to take the place of ethylene
glycol. Compared with the physical properties
of ethylene glycol and 1,4-butanediol, the prop-
erties of trimethylene glycol fall between the
C-2 and C-4 compounds. However, like other
odd-numbered members of a homologue series,
the melting point is much lower than that of its
neighbors (Schauhoff, 1996).
PTT can be produced from dimethyl tere-
phthalate (DMT) or terephthalic acid (TPA).
Although TPA is cheaper than DMT, it has
been mainly used for industrial PET production
to date. Using TPA for the preparation of PBT,
a certain amount of tetrahydrofuran is formed
from 1,4-butanediol. In the process of prepara-
tion of PTT from TPA, no ether is formed
(Schauhoff, 1996; Traub et al., 1995). The direct
esterification of TPA with trimethylene glycol
comprises three steps: esterification, precon-
densation of oligomers under vacuum, and
polycondensation for chain growth under full
vacuum. The general features of the process are
more similar to the PBT than to the PET
process. The main reason is that the melting
18 Polyamide and Polyester Fibers
points of PTT and PBT are nearly identical.
Their crystallite melting points are 233 and
232 8C, respectively. The esterification can be
carried out under elevated or atmospheric pres-
sure. If atmospheric pressure is applied, a cat-
alyst is necessary. In the PTT process, a
titanium catalyst is used for the esterification
step. The polycondensation step is catalyzed by
titanium as well as antimony compounds
(Schauhoff, 1996).
With DMT, transesterification occurs at tem-
peratures of 140±220 8C, using 261074 mole
titanium tetrabutylate per mole of DMT as a
catalyst. After the removal of methanol, poly-
condensation is carried out by increasing the
temperature to 270 8C while reducing the pres-
sure to 0.05 mbar. Since the titanium com-
pound is also active in the polycondensation
step, no deactivation and no addition of an-
other catalyst is necessary (Traub et al., 1995).
1.11.5.5.2 Fiber spinning
PTT fiber can be prepared by the same melt
spinning and drawing processes as PET. It is
generally possible to produce a filament yarn
on standard PET spinning equipment from
PTT polymer with an intrinsic viscosity of 0.9.
The ideal spinning temperature was found to be
255 8C. Windup speeds above 4000 m min71
could be easily handled. Its textile properties
are closer to PBT than to PET (Brown and
Chuali, 1997; Chuali and Corterra, 1996;
Schauhoff, 1996).
1.11.5.5.3 Typical PTT fiber properties
At low spinning speeds up to about 3000 m
min71, there are no significant differences in
mechanical properties between as-spun fibers of
PTT and PET. As the spinning speed increases,
the maximum tenacity of PET fiber increases.
In comparison, spinning speed does not have
any perceptible influence on the maximum te-
nacity of PTT. Furthermore, the modulus of
PTT as-spun fiber does not depend on the
spinning speed.
The maximum tenacity of PTT drawn yarn is
somewhat lower than that of PET drawn yarn.
The initial module of PTT drawn yarn is in-
dependent of the draw ratio. The break elonga-
tion of PTT drawn yarn decreases with
increasing draw ratio, but the minimum break
elongation of PTT drawn yarn is about 20%.
Consequently, it is impossible to produce PTT
yarns with a high modulus and a low break
elongation as with PET fiber by increasing the
draw ratio (Brown and Chuali, 1997; Chuali,
1996; Schauhoff, 1996; Traub et al., 1995).
Copyright # 2000 Elsevier Science Ltd.
All rights reserved. No part of this publication may be reproduced, stored in any
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electrostatic, magnetic tape, mechanical, photocopying, recording or otherwise,
without permission in writing from the publishers.
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Comprehensive Composite Materials
ISBN (set): 0-08 0429939
Volume 1; (ISBN: 0-080437192); pp. 327±344