705

Effects of Molecular Weight Spinning and Mechanical Properties of

on Melt
High-Performance Poly(ethylene Terephthalate) Fibers
ANDRZEJ ZIABICKI
Polish Academy of Sciences, Institute of Fundamental Technological Research, Warsaw, Poland

ABSTRACT
Effects of the molecular weight (intrinsic viscosity) of poly(ethylene terephthalate)
on the formation of fibers and their properties are analyzed. Correlations between
molecular weight and various viscosity characteristics are compared. Because of high
melt viscosity, effective melt spinning is limited to polymers with intrinsic viscosities
[η] not higher than 0.8-0.9 dl/g. High molecular weight polymers ([η] 2.0-4.9 dl/
=

g) have been used for solution (gel) spinning. Molecular weight is not a primary
characteristic responsible for mechanical properties, but it may affect tenacity and
modulus indirectly. The tenacity of industrial PET fibers manufactured by a variety
of processes exhibits positive correlation with intrinsic viscosity; the correlation of the
modulus is less evident. Melt spun and drawn fibers exhibit tenacities of up to 12 g/
den and moduli of up to 220 g/den, while fibers solution spun from high molecular
weight PET ([η] 2.6 dl/g) subjected to deep drawing (total draw ratio 16.4) reach
= =

a tenacity of 18.5 g/den and a modulus of 313.2 g/den. A new zone drawing and
annealing process, apparently insensitive to molecular weight, yields PET fibers with
a tenacity of 14 g/den and a modulus of 246 g/den. The role of molecular weight in
obtaining high mechanical performance is discussed.

Molecular weight plays an important role in the for- Correlation of Molecular Weight
mation and mechanical performance of fibers from Characteristics
flexible chain polymers. Higher molecular weights are
chosen for industrial fibers when high tenacity is re- In the patent literature, the molecular weight of
is described by many dinerent
quired, but molecular weights that are too high make polymer molecules
melt spinning difficult or impossible. Questions arise: characteristics, which leads to confusion when data
Is it justified to increase the molecular weight of in- from various sources are compared. Avenge motecuhr
dustrial PET fibers infinitely, or should an optimum weight is characterized by intrinsic viscosity I ~1 ~ defined
molecular weight be sought? A new class of high per- as a limit (at infinite dilution) of one of the following
formance fibers has been developed based on gel spin- expressions:
ning and deep drawing of ultra-high molecular weight
polyethylene. For gel spun polyethylene with an ultra-
high molecular weight ( Mw > 106 ), the maximum
draw ratio, modulus, and tenacity increase with mo-
lecular weight [ 51 ] . Is this true also for PET? Can high
tenacity, high modulus PET fibers be produced from
moderate molecular weights? Based on an analysis of
literature data, we discuss the range of intrinsic vis-
cosities appropriate for industrial PET fibers. We begin where q denotes the viscosity of a polymer solution,
by correlating various molecular weight characteristics; with concentration c, ’1o is the viscosity of a pum solvent
we then discuss the effects of intrinsic viscosity on melt ( c 0), and c is the polymer concentration expressed
=

viscosity, and compare the maximum tenacity and in w / v percent, or grams of polymers in a docilittr of
maximum tensile modulus of PET fibers manufactured the solution. Therefore, intrinsic viscosity is usually
by a variety of industrial processes. expressed in dl / g units.

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706

A simplified characteristic is relative viscosity of an

x-percent polymer solution ( R Vx ) :

We will intrinsic viscosity [ill to be a basic

assume
characteristic, and seek correlations with other Mew
characteristics used in the literature on PET fibers.
Sometimes the correlations lack precision when based
on limited data, but they are indispensable for com-
paring information from different sources.
The most popular molecular weight correlation for
linear polymers has been proposed by Mark and Hou-
FIGURE 1. Viscosity-average molecular weight versus intrinsic vis-
wink in the form cosity for polyethylene terephthalate: Ravens & Ward [ 52 ] , Koepp
& Wemer [311, Conix [111.

ml hexafluoro-isopropanol containing 80 ppm H2S04,

yield
where Mw is the viscosity-average molecular weight,
and K, a, and k are material constants dependent on
the solvent and temperature. Three sets of constants
for PET are listed in Table I.
Figure 2 presents correlations for R V, , R VIO, and HR V
Figure 1 presents Mw versus [17] calculated from plotted versus intrinsic viscosity [ n] .
Equation 5 with constants from Table I. The first and
third correlations yield similar results. For a compar-
ison of literature data, we will use the constants of Ra-
ven and Ward [ 52 ] .
The data on I % PET solutions in o-chlorophenol [ 22 ]
have been used to produce linear correlations for rel-
ative viscosity R V, :

Experimental data given in the patents by Chantry and

Molini [ 10 ] and Vail [60] ] have been used to correlate
10% relative viscosity with intrinsic viscosity:

FIGURE 2. Relative viscosity characteristics, R V, , R V,o, and tfRV

, and two points indicated in the DuPont patent [ 9 to versus intrinsic viscosity for polyethylene terephthalate solutions. Solid
relate another molecular weight measure HR V, defined lines, are linear correlations; points taken from references 22 ( RV, ),
viscosity of a solution of 0.8 g PET in
’

as the relative 10 10, 60 ( R V,o ), and 9 ( HR V ).

.
..

0
TABLE I. Viscosity-molecular weight constants for poly(ethylene terephthtalate).
’

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INTRINSIC VISCOSITY AND MELT VISCOSITY
The viscoelastic behavior of polymer melts is con-
trolled by average molecular weight, molecular weight
distribution, and other characteristics, like chemical
composition, chain branching, etc. For PET used for
melt spinning, elastic effects are of secondary impor-
tance, and the main rheological characteristic is melt
viscosity, controlled by average molecular weight (in-
trinsic viscosity). Melt viscosity determines the range
of conditions in which fibers can be melt spun. Dutta
and Nadkarni [ 15 proposed the following relation:
where &dquo;melt is expressed in poise units ( 1 P 0.1 Pa. 5),
=
[n] in dl/g, and temperature T in °C. This relation,
.
converted to molecular weight using Equation 4 with
parameters K and a from reference 52, yields
Figure 3 presents the melt viscosity of PET calculated
.
from Equation 9 for T 280°C and T 320’C, and
= =
plotted versus intrinsic viscosity [ n] . Solid lines cor- Substituting the Dutta-Nadkarni equation for
respond to the Dutta and Nadkarni equation; experi- viscosity, we obtain
mental data for T =
280°C have been taken from ref-
erences 8, 17, 22, 39, 40, 47, 49, 56.
FIGURE 3. Melt viscosity of polyethylene terephthalate. Solid lines
calculated from the formula of Dutta & Nadkarni [ 15for T 280°C
=
and T 320°C Eaperimental points for T 280°C from references
=
=
8, I5, 17, 22, 39, 40, 47, 49, 56.
INTRINSIC VISCOSITY AND MELT EXTRUSION
Extruding PET with high intrinsic viscosity is limited
by viscous resistance to aow offered by the filter pack
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707
and spinneret channels. When [ ~] does not exceed 0.8-
0.9 dl / g, the viscosity of the melt at usual spinning
temperatures ( 280-320°C ) lies bdow 1000 Pae,
(10,000 P), and the pressure required for extrusion
below 15 MPa ( 150 atm or 2 l 00 psi).
The melt viscosity correlation (Equation 9) makes
it possible to estimate the pressure drop AP required
for extruding PET melt through spinneret hoks. For
steady-state flow in the capillary (Poixuile flow),
where Q denotes flow rate per spinneret hole (in CM3/
s / hole ) ,1~ and Ro are, respoctively, the kngth and ra-
dius of the spinneret channel (in cm), and &dquo;mdt is melt
viscosity in poise units (P). Assuming typical values
for tire cord melt spinning of
we obtain
mdt
This equation is evaluated for temperatures 280-
320°C, representing the range recommended for meh
spinning. The results are plotted in Figure 4 as a func-
’
tion of intrinsic viscosity.
Extrusion of high molecular weight PET (tv] 0.9- =
1.4 dl / g, melt viscosity 10,000-70,000 P) crates many
problems. The outflow of highly viscous meh from the
spinneret channel may become discontinuous and ir-
regular (melt fracture insZobility) [ 59,63 ]. The pt~ne
required for extrusion in standard spinning tempera-
tures may reach, or exceed, 1000 atm ( 14,000 psi ) .
Spinning of such melts requires special provisions.
Raising melt temperature reduces viscosity and elim-
inates melt fracture, but may kad to degradation of
the polymer and dripping of the melt at the spinneret
due to capillary instability [ 59, 63 ] . For high molecular
weight PET, spinning temperatures as high as 335°C
have been recommended [20]. Application of intrimic
viscosities above 0.85 dl/g may require special design
of the spinning pack [50] and delayed quenching by
application of hot air blow [ 10 or heated shroud [20].
708
FIGURE 4. Pressure drop, OP in atmospheres ( 1 atm = 0. 1 MPa),
required for extrusion of PET melt through spinneret holes versus
intrinsic viscosity.
For regular melt spinning without special modifi-
cations, recommended intrinsic viscosity seems to be
limited to 0.7-0.9 dl/g; this can yield fibers with te-
nacities up to 10 g/den (see Figure 5). With appro-
priate mechanical and thermal treatment of such fibers,
moduli of 200 g/den can be obtained (Figure 6).
FIGURE 5. Maximum tenacity of polyethylene terephthalate fibers
versusintrinsic viscosity. Data for melt-spun fibers from references
l-7, 9, 10, 12, -13, 16, 18, 20, 21, 23, 29, 30, 38, 4l-46, 50, 53, 60,
62; ZDA zone drawing and annealing [ 36 ] ; squares == fibers spun
=
from solutions or plasticized melts [ 19, 25-28, 57, 58 ] .
Intrinsic viscosity reported for commercial melt
spinning of PET fibers rarely exceeds 1.0 dl/g. Some
Hoechst-Celanese patents [ 12, 13, 38 ] claim intrinsic
viscosity as high as 2.0 dl/g, but examples in these
patents do not exceed the 0.9 dl/g limit. The DuPont
patent by Chantry & Molini [10], involving special
spinning relative viscosity 7!~o
conditions, mentions
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FIGURE 6. Maximum initial modulus of polyethylene terephthalate
fibers versus intrinsic viscosity. Data for melt spun fibers from ref-
erences 1-7, 9, 10, 12, 13, 16, 18, 20, 21, 23, 29, 30, 38, 41-46, 50,
53, 60, 62; ZDA zone drawing & annealing [ 36 ]; squares fibers
=
spun from solutions or plasticized melts [ 19, 25-28, 57, 58].
= 90, which, according to our correlations, corresponds
to [ n] 1.37. The highest molecular weight of com-
=
mercial melt spun PET fibers ( M,, 54,000) has been
=
reported by Berg [ 6 ] . Using correlations listed in Table
I, this would correspond to [n] in the range of 1.32-
&dquo;
1.60 dl / g. It is possible that the molecular weight re-
ported ~y Berg is based on correlations different from
ours and, in our terms, would correspond to lower [ r~]
values.
An alternative to reducing melt viscosity by raising
the temperature is mixing the polymer with solvents
or plasticizers. Using solvents, PET fibers can be spun
from polymers with higher molecular weights. High
molecular weight PET fibers can be obtained by solid-
state polymerization in the fiber form [ 37 ] or by spin-
ning separately polymerized PET from solutions or
plasticized melts [ 19, 24-28, 57, 58 ] . Huang, Ito, and
Kanamoto [ 24, 25, 28 ] obtained PET films and fibers
with intrinsic viscosity in the range of 2.2-4.9 dl/g.
The tenacity of highly drawn fibers with [r~] 2.6 dl/ =
g reached 18.5 g/den (2.3 GPa), and the initial mod-
ulus 313.2 g/den (39 GPa) [ 25 ] . The molecular
weights involved ( 100,000-150,000 ) are considerably
smaller than those used in gel spinning of uHMw poly-
ethylene.
MOLECULAR WEIGHT AND MELT SPINNING
CONDITIONS
Workers have known [ 63, 64 ] that molecular weight
and related rheological properties affect the dynamics
of the spinning process, the structure of as-spun fibers,
and their processability (drawing). This is strongly ev-
ident at high spinning speeds [48, 54, 55, 61 ] . The
 709

molecular weight of melt spun polymer affects the From Figures 5, it is evident that a monotonic cor-
spinning tension [ 14, 54], molecular orientation, and relation exists between the maximum tenacity and the
crystallinity of as-spun fibers [ 48, 55, 61 ], and reduces intrinsic visoosity of PET fibers; 17-18.5 g/den tenacity
maximum draw ratio [ 48, 61 ] . Some patents [ 12, 13, can be obtained from high molecular weight material
38 recommend melt spinning of industrial PET fibers ( [ n] = 2.4-2.6 dill) processed by solution spinning
at high take-up speeds and high spinline tension, fol- and deep drawing. The tenacity of 14 g/den has been
lowed by low ratio drawing. Here, intrinsic viscosity produced by intensive zone treatment [36]. The
plays an important role, because spinning stress is mechanism of structure formation in zone drawing and
known to increase with molecular weight of the poly- annealing is not clear, but the data indicate that high
mer [ 14, 63 ] . Other technologies [ e.g., 2, 53 ] base their tenacities and moduli can be obtained without high ,
e

high performance PET fibers on low speed (and low molecular weights.
tension) spinning, followed by drawing and heat treat- In contrast to tenacity, a correlation of the initial
ment. High tenacities and high moduli can be obtained modulus with intrinsic viscosity is less evident (Figure
in both groups of conditions. 6). Mechanical and thermal treatments seem to be
more important than the effects of molecular weight.

INTRINSIC VISCOSITY AND MECHANICAL Fibers obtained with regular melt spinning, drawing.
’

PROPERTIES .
and heat treatment of a PET with [ill 0.7-0.8 dl/g
=

.
exhibit moduli in the range of 50-230 g/den; 250 g/
.

Figures 5 and 6 present the maximum tenacity and den has been obtained with zone treatment [ 36 ] , white
maximum initial tensile moduli of PET fibers plotted 270-313 g/den was observed for solution spun and
versus intrinsic viscosity [ ~] . The fibers differ in pro- drawn, high molecular weight fibers [25-28].
cessing conditions (spinning, drawing, heat treatment).
We have selected experimental data from references Discussion
1-7, 9, 10, 12, 13, 16, 18-21, 23, 26-30, 36-38, 41-
46, 50, 53, 57, 58, 60, 62, so that fibers with the highest For linear polymers, molecular weight (intrinsic vis-
tenacities and moduli, prepared in optimum conditions, cosity) is the main factor responsible for melt viscosity
are considered. In the case of patent sources, only data and processability Therefore intrinsic viscosity deter-
presented as examples have been used, while claims mines the limits of individual industrial processes. Meh
have been neglected. spinning of PET with [q] above 0.9 dill crcates prob-
In addition to data related to melt spinning [ 1-7, 9, lems resulting from high melt viscosity and pressure
10, 12, 13, 16, 18, 20, 21, 23, 29, 30, 38, 41-46, 50, in the spinneret pack. An alternative to melt spinni~-
5 3, 60, 62 ] , or solution ( plasticized melt) spinning [ 19, solution spinning-has been successfully applied to PET
24-28, 57, 58], Figures 5 and 6 also include the me- with [ ~j as high as 4.9 dl / g [24]. No upper limit of
chanical characteristics of PET fibers obtained by zone intrinsic viscosity can be expected, since optimum via-
drawing and annealing [ 36 ] . The technique consists cosity of the spinning dope can be controlled by poly-
of slowly moving a heated ring over stressed fibers, mer concentration.
followed by hot-ring local annealing of drawn fibers rheological properties, molecular
In contrast to
using high temperatures and high tensions [ 33-36 ] . weight does not provide a primary mokcular charac-
Zone drawn and annealed PET fibers reach tenacities teristic directly controlling mechanical . of
of 14 g/den and initial moduli of 246 g/den [36]. solid fibers. The observed correlation between intrinsic
Since intrinsic viscosity (or other molecular weight, viscosity on one hand and tenacity and modulus on
characteristics) of the material have not been indicated the other seems to reflect an indirert effect of molecular
in the published sources [ 33-36 ], tenacity and modulus weight on the drawing process. The primary Structural
levels in Figures 5 and 6 have been indicated as a hor- characteristic responsible for mechanical properties is
izontal series of stars. Dr. Kunugi assured me [ 32 ] that the degree of molecular orientation, no matter how ori-
&dquo;regular, commercial undrawn PET fibers&dquo; were used entation has been created in the fiber. In many cases,
for his zone drawing and annealing experiments. We high molecular weight favors formation of highly on-
can assume that this corresponds to [ ~] in the range ented fibers.
. of 0.6-0.9 dl/g. The properties of zone drawn and an- Theoretical analysis of orientation mechanisms in
nealed fibers with (supposedly) moderate molecular polymer processing [65-67] indicates that in contrast
weight are comparable with those for solution spun to rigid suuctures (Keviar, perr), which can be oriented
fibers with intrinsic viscosities in the range of 1.5-2.5 in flow, in flexible-chain polymers (like PE or PET), a
dl/g [19, 26-28, 57, 58]. high degree of molecular orientation requires mlii8mO

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 710
deformation. In an ideal case of zero molecular
bility, the degree of orientation is a function of defor-
mation ( draw ratio ) and asymptotically reaches unity
(full orientation) when draw ratio approaches infinity.
With increasing molecular mobility, drawing is less and
less effective.
The maximum draw ratio in melt spun PET fibers
(with moderate intrinsic viscosities) is limited to 4-5.
Above this level, the material breaks. This is also true
for other melt spun polymers. Extensive studies of high
molecular weight polyethylene have shown [ 51 ] that
solution spun fibers can be extended to draw ratios as
high as 100 or 200. The maximum draw ratio increases
with molecular weight (intrinsic viscosity), while the
tenacity and modulus of such fibers linearly increase
with total draw ratio. Studies by Huang, Ito, and Ka-
namoto [ 24-28 ] on solution spun PET films and fibers
show that similar effects also occur in high molecular
weight PET. Maximum (total) draw ratio increases with
intrinsic viscosity in the range of [il] = 1.5-4.9; tenacity
and modulus increase with draw ratio and, implicitly,
with molecular weight of the polymer [ 24 ] . The total
draw ratio of 16.4 is obtained for PET fibers with [ n]
=
2.6, and their tenacity and modulus are considerably
higher than those of fibers with lower viscosities [ 25 ] .
The mechanical performance of solution spun and
drawn, high molecular weight PET fibers resembles the
behavior of gel spun polyethylene.
Different rules seem to govern zone drawing and
annealing. The published sources [ 33-36] do not pre-
sent data on the effective draw ratios produced in the
zone treatment. Personal information
[ 32 suggests
that draw ratios do not considerably exceed the values
obtained in regular drawing. The degree of molecular
orientation obtained in intensive zone treatment (lam
=
0.854) [36] ] was even higher than that for fibers ob-
tained from high molecular weight PET ([Ill
2.46,
lam 0.76), [ 25 ] . This confirms the governing role of
=
molecular orientation. At the same time, zone drawing
and annealing demonstrate that strong and stiff PET
fibers can be produced without high intrinsic viscosity
or high draw ratios. The mechanism of structure for-
mation in conventional drawing and, the more so, in
zone drawing and annealing is not clear. More exper-
imental data and theoretical studies are needed.
Summing up, our experience shows that reasonably
high tenacities and moduli can be obtained by regular
melt spinning, drawing, and heat treatment of PET fi-
bers with intrinsic viscosities below 0.9 dl/g. Research
on new techniques involving solution
spinning of high
molecular weight PET followed by deep drawing and
zone drawing and annealing techniques is on the way.
Downloaded from trj.sagepub.com at NORTH CAROLINA STATE UNIV on January 1, 2015
mo- The present record (tenacity 18.5 g/den, modulus
313.2 g / den ) is yet to be surpassed.
.
Literature Cited
1.Andrews, E. D. (Fiber Industries), Low thermal shrink-
age polymer yarns, Canadian patent 925, 275, 1973.
2. Asada, Y., and Tsujii, O. (Teijin), Method of making
polyester materials for use in reinforcing rubber struc-
ture materials, Japanese patent 74-21,260, 1974.
3. Barbe, G. M., Curtillat, P. G., and Lequay, C. (Societe
Rhodiaceta ), Process for the production of orientated
synthetic filaments, U.S. patent 3,840,633, 1974.
4. Barker, I., and Marshall, G. (ICI), Polymeric filaments
and process for forming such material, U.S. patent
4,359,441, 1982.
5. Bauer, G., and Jacob, I. (Hoechst), Process for preheating
and drawing filaments of synthetic linear polyesters,
U.S. patent 3,551,550, 1970.
6. Berg, H. (Hoechst), Struktur und Eigenschaften von
Polyesterfasern, Chemiefasern, (3) 215 (1972).
7. Boone, J. D., and Knight, D. V. (DuPont), Process for
making high-tenacity, low-elongation industrial yarn,
U.S. patent 3,400,194, 1968.
8. Bragato, G., and Gianotti, G., High Speed Spinning of
Polyethylene Terephthalate, I : Steady State Equations
Fundamental Analysis, Structural Property Measure-
ments Along the Spinning Path, Eur. Polym. J. 19, 795
(1983).
9. Chantry, W. A., and Conrad, R. M. (DuPont), Contin-
uous spin drawing process for preparing PET yarns,
U.S. patent 4,003,974, 1977.
10. Chantry, W. A., and Molini, A. E. (DuPont), High
strength polyethylene terephthalate yarn, U.S. patent
3,216,187, 1965.
11. Conix, A., Intrinsic Viscosity of Polyethylene Tere-
phthalate, Makromol. Chem. 26, 226, 1958.
12. Davis, H. L., Jaffee, M. L., LaNieve, H. L., and Powers,
E. J. (Celanese), Polyester yarn of high strength pos-
sessing an unusually stable internal structure, U.S. pat-
=
ent 4,101,525, 1978.
13. Davis, H. L., Jaffee, M. L., LaNieve, H. L., and Powers,
E. J. (Celanese), Production of improved polyester fil-
aments of high strength possessing an unusually stable
internal structure, U.S. patent 4,195,052, 1980.
14. Dumbleton, J. H., Spin Orientation Measurement in
Polyethylene Terephthalate, Textile Res. J. 40, 1035
(1970).
15. Dutta, A., and Nadkarni, V. M., Process Variables in
Polyethylene Terephthalate Melt Spinning, Textile Res.
J. 54
, 35 (1984).
16.
Fukui, J., Yoshida, K., Kamata, T., and Takemura, T.
(Mitsubishi Rayon), High tenacity polyester fibers,
Japanese patent 88-135516, 1988.
17. Gregory, D. R., Rheological Properties of Molten Poly-
ethylene Terephthalate, J. Appl. Polym. Sci. 16, 1479
( 1972).

18. Gupta, V. B., and Kumar, S., The Effect of Heat Setting
on the Structure and Mechanical Properties of
Poly(ethylene Terephthalate) Fiber, IV: Tensile Prop-
erties Other than Modulus and their Dependence on
Structure, J. Appl. Polym. Sci. 26, 1897 (1981).
19. Hagura, S., Fukui, J., and Ito, H. (Mitsubishi Rayon),
Polyester fibers with high strength and modulus, Jap-
anese patent 92-073212, 1992.
20. Harris, E. F., Roberts, J. F. L. (ICI), Process for spinning
high tenacity fibers, U.S. patent 3,832,436, 1974.
21. Hashikura, T.,et al. (Asahi Kasei), Method of making
polyester fiber having excellent dimensional stability,
Japanese patent 75-25,819, 1975.
22. Hillier, K. W., Homopolymers, in "Man-Made Fibers,
Science and Technology," vol. III, H. Mark, S. Atlas,
and E. Cernia, Eds., Interscience, NY, 1968, pp. 1-20.
23. Hoechst AG, Process for the manufacture of polyester
filaments having a low degree of shrinkage, British pat-
ent 1,325,297, 1973.
24. Huang, B., Ito, M., Kanamoto, T., Deformation Mech-
anism of Amorphous Polyethylene Terephthalate as a
Function of Molecular Weight and Entanglements,
Polymer 35, 1210-1215 (1994).
25. Huang, B., Ito, M., and Kanamoto, T., Effects of Draw
Conditions on Deformability and Draw Efficiency of
High Molecular Weight Polyethylene Terephthalate
Fibers, Polymer 35, 1329-1331 (1994).
26. Ito, M., Takahashi, K., and Kanamoto, T., Preparation
of High Modulus and High Strength PET Fibers from
Solution-Spun Fibers, Polym. Preprints Jpn. 38, 4352
(1989).
27. Ito, M., Takahashi, K., and Kanamoto, T., Effects of
Sample Geometry and Draw Conditions on the Me-
chanical Properties of Drawn Poly(ethylene Tere-
, 58 (1990).
phthalate ) Fibres, Polymer 31
28. Ito, M., Wakayama, Y., and Kanamoto, T. (Rikkyo
Daigaku), Preparation and Properties of Ultra-High-
Molecular-Weight Polyethylene Terephthalate Fibers,
Sen-I Gakkaishi 48, 569 ( 1992).
29. Hayashi, S., Tani, K., Ishihara, H., and Yasuda, H.,
Fundamental Analysis of Hot Drawing in Spinline and
Introduction of Basic Equations for Simulation, Sen-I
Gakkaishi 48, 541 (1992).
30. Kawashima, H., Nakamura, Y. (Teijin), Method of
making high strength polyester yarn, Japanese patent
77-121,529 1977.
31. Koepp, H. M., and Wemer, H., Molecular Weight and
Intrinsic Viscosity of Polyethylene Terephthalate,
Makromol. Chem. 32, 79 (1959).
32. Kunugi, T., Yamanashi University, private communi-
cation, October 1994.
33. Kunugi, T., Preparation of Highly Oriented Fibers or
Films with Excellent Mechanical Properties by Zone
Drawing/ Zone Annealing Method, in "Oriented Poly-
mer Materials," S. Fakirov, Ed., Huthig Verlag (in
press).
34. Kunugi, T., Ichinose, C., and Suzuki, A., Preparation of 51. Prevorsek, D., Preparation, Structure, Properties and
Downloaded from trj.sagepub.com at NORTH CAROLINA STATE UNIV on January 1, 2015
711
High Modulus and High Strength Polyethylene Tere-
phthalate Film by Zone Annealing Method, J. Appl
.
Polym. Sci. 31
, 429 (1986).
35. Kunugi, T., Suzuki, A., and Hashimoto, M., Mechanical
Properties and Superstructure of High Modulus and
High Strength PET Fibers Prepared by Zone Annealing,
J. Appl. Polym. Sci. 26, 1951-1960 (1981).
36. Kunugi, T., Suzuki, A., and Tsuiki, T., Mechanical
Properties and Superstructure of Poly(ethylene Tere-
phthalate) (PET) Fibers Annealed under Extremely
High Tension, Kobunshi Ronbunshu 7038, (1991).
4
et al. (Toyobo), Polyester fibers having high
37. Kurita, K.,
high strength and high modulus and process for pro-
ducing the same, European patent 251313, 1988.
38. McClary, E. (Fiber Ind.), Production of polyester fila-
ments of high strength possessing an unusually stable
internal structure employing improved processing con-
ditions, U.S. patent 4,414,169, 1983.
39. Manaresi, P., Giachetti. E., and De Fornasari, E., Re-
lation entre Indice de Fluidite a Chaud, Viscosite a l’Etat
Fondu, Viscosite Intrinseque et Temperature pour le
Poly(ethylene Terephthalate) et pour un Poly(ethylene
Terephthalate) Partiellement Modifie, J. Polym. Sci.
1
-
,C 3133-3144 6 (1968).
40. Martin, E. V., Kibler, C. J., in "Man-Made Fibers, Sci-
ence and Technology," vol. III, H. Mark, S. Atlas, and
E. Cernia, Eds., Interscience, NY, 1968.
41. Martin, H. G., Glutz, B., and Linz, H. (Soc. Viscose
Suisse), Process for the preparation of polyethylene
terephthalate filaments, U.S. patent 3,715,421, 1973.
42. Munting, J. P. (Akzona Inc.), Manufacture of unique
PET fiber, U.S. patent 3,966,867, 1976.
43. Nelson, (Allied-Signal),
C.
et Dimensionally
J.,
al. stable
polyester yam for high tenacity treaty cords, U.S. patent
5,234,764, 1993.
44. Onuma, Fujiwara Y., Manufacturing of polyester fibers,
Japanese patent 76-53,019, 1976.
45. Pajgrt,
et
, "Polyesterova
O., Reichstadter,
al. Vlakna"
B.,
(in Czech), SNTL, Prague, 1973.
46. Pajgrt, O., Reichstadter,
et
., al B., "Processing of Polyester
Fibers,"’ Elsevier, Amsterdam, 1979.
47. Perez, G., Some Effects of the Rheological Properties of
Polyethylene Terephthalate on Spinning Line Profile
and Structure Developed in High Speed Spinning.
Rhone Poulenc internal report, July 30, 1982.
48. Perez, G., Some Effects of the Rheological Properties of
Polyethylene Terephthalate on Spinning Line Profile
and Structure Developed in High Speed Spinning, in
"High Speed Fiber Spinning," A. Ziabicki and H. Ka-
wai, Eds., Interscience, NY, 1985, p. 333.
49. Petukhov, B.V., "Polyfirnye volokna" (Polyester Fibers,
in Russian), ch. 5, Khimiya, Moscow, 1976, p. 101
(English ed.: "Technology of Polyester Fibres," Per-
gamon Press, 1983.
50. Pierce, M. L. (DuPont), Mdt spinning apparatus and
method, U.S. patent 3,437,725, 1969.
712
Applications of Gel-spun Ultrastrong Polyethylene Fi-
bers, TRIP 1, 4 (1995).
52. Ravens, D. A. S., and Ward, I. M., Intrinsic Viscosity of
Polyethylene Terephthalate, Trans. Faraday Soc. 57,
150(1961).
53. Russell, W. N., Bruton, J.I., Twilley, I. C. (Allied Chem-
ical ), Process for preparing high strength polyamide
and polyester filamentary yarn, U.S. patent 4,113,821,
1978.
54. Shimizu, J., Okui, N., Kaneko, A., and Toriumi, K.,
High Speed Spinning of Polyethylene Terephthalate
(PET), Effect of Molecular Weight, Sen-I Gakkaishi
34, T93-98 (1978).
55. Shimizu, J., Okui, N., and Kikutani, K., Fine Structure
and Physical Properties of Fibers Melt Spun at High
Speeds from Various Polymers, in "High Speed Fiber
Spinning," A. Ziabicki and H. Kawai, Eds., Interscience,
NY, 1985, p. 429.
56. Schulken, R. M. (Eastman Tennessee), unpublished data
cited after Gregory, ref. 17.
57. Tani, K., et al. (Toyobo), Polyester fibers with high
strength and modulus, Japanese patent 91-294539,
1991.
58. Tani, K., Yabuki, K., et al. (Toyobo), Manufacture of
polyester fibers with high strength and modulus, Jap-
anese patent 90-92917, 1990.
59. Thompson, A. B., Fibres from Condensation Polymers,
in "Fibre Structure," A. Hearle and R. Peters, Eds.,
Butterworth, Manchester, U.K., 1963.
Downloaded from trj.sagepub.com at NORTH CAROLINA STATE UNIV on January 1, 2015
60. Vail, O. R. (DuPont), Two-stage drawn and relaxed sta-
ple fiber, U.S. patent 3,816,486, 1974.
61. Vassilatos, G., Knox, B. H., Frankfort, H. R. E., Dy-
namics, Structure Development and Fiber Properties
in High Speed Spinning of Polyethylene Terephthalate,
in "High Speed Fiber Spinning," A. Ziabicki and H.
Kawai, Eds., Interscience, NY, 1985, p. 383.
62. Yoon, K. J., et al., Crystallization in Oriented Polyeth-
ylene Terephthalate Fibers, II, J. Polym. Sci. A-2, 24,
1665 (1986).
63. Ziabicki, A., "Fundamentals of Fibre Formation," Wiley,
London, 1976.
64. Ziabicki, A., Theoretical Aspects of High Speed Spinning,
Sen-I Gakkaishi 38, 409 (1992).
65. Ziabicki, A., Development of Structure in Processing
Polymers Composed of Rigid vs. Flexible-Chain Poly-
mers, in "Polymers for Advanced Structures," M.
Lewin, Ed., VCH, NY, 1988, pp. 580-601.
66. Ziabicki, A., Orientation-Stress Relations of Polymer
Fluids, Networks and Liquid Crystals, in "Polymer
Networks ’91," A. Kuchanov and K. Dusek, Eds., VSP,
Zeist, 1992, pp. 147-157.
67. Ziabicki, A., Orientation Mechanisms in the Develop-
ment of High-Performance Fibers, Prog. Colloid Polym.
Sci. 92, 1-7 (1993).
i
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~OMMN-npt feMfM/ September 11. 1995; accepted January 22. 1996.