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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.
.
..
0
TABLE I. Viscosity-molecular weight constants for poly(ethylene terephthtalate).
’
INTRINSIC VISCOSITY AND MELT VISCOSITY and spinneret channels. When [ ~] does not exceed 0.8-
0.9 dl / g, the viscosity of the melt at usual spinning
The viscoelastic behavior of polymer melts is con-
temperatures ( 280-320°C ) lies bdow 1000 Pae,
trolled by average molecular weight, molecular weight
(10,000 P), and the pressure required for extrusion
distribution, and other characteristics, like chemical below 15 MPa ( 150 atm or 2 l 00 psi).
composition, chain branching, etc. For PET used for The melt viscosity correlation (Equation 9) makes
melt spinning, elastic effects are of secondary impor-
it possible to estimate the pressure drop AP required
tance, and the main rheological characteristic is melt for extruding PET melt through spinneret hoks. For
viscosity, controlled by average molecular weight (in- steady-state flow in the capillary (Poixuile flow),
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 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
where &dquo;melt is expressed in poise units ( 1 P 0.1 Pa. 5),
=
we obtain
Figure 3 presents the melt viscosity of PET calculated
.
plotted versus intrinsic viscosity [ n] . Solid lines cor- Substituting the Dutta-Nadkarni equation for mdt
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.
For regular melt spinning without special modifi- = 90, which, according to our correlations, corresponds
cations, recommended intrinsic viscosity seems to be to [ n] 1.37. The highest molecular weight of com-
=
limited to 0.7-0.9 dl/g; this can yield fibers with te- mercial melt spun PET fibers ( M,, 54,000) has been
=
moduli of 200 g/den can be obtained (Figure 6). 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/ =
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
deformation. In an ideal case of zero molecular mo- The present record (tenacity 18.5 g/den, modulus
bility, the degree of orientation is a function of defor- 313.2 g / den ) is yet to be surpassed.
mation ( draw ratio ) and asymptotically reaches unity
(full orientation) when draw ratio approaches infinity.
.
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