Fibre Chemistry. Vol. 29, No 2.

1997

RHEOLOGICAL PROPERTIES OF LIQUID-CRYSTALLINE

SOLUTIONS OF POLY(p-PItENYLENE TEREPHTHALAMIDE)

AND B E H A V I O R O F T H E J E T IN S P I N N I N G T H R O U G H
AN A I R S P A C E

V. N. Kiya-Oglu, T. A. Rozhdestvenskaya, and L. D. Serova UDC [677.494.675:536.495].021.125.2

LC solutions of PPTA behave like liquids with a power law of flow and n = 0.65-0. 78 for flow through the
channels of standard spinnerets with small diameters and q = O.88-0. 95for longitudinal flow in jets. Spinneret
expansion of a freely falling jet in channels with small diameters is equal to 1.70-1.75 and is not a function
of the shear rate on the wall. Spinneret expansion is preserved in conditions of repeated drawing of the jets
in the air space until very small air spaces at 1.5-2.5 mm are used. In spinning PPTA fibres through an air
space with a lu'gh jet draw ratio, only a small fraction of this drawing in the spinning bath is possible.

Liquid-crystalline (LC) sulfuric acid solutions of poly(p-phenylene terephthalamide) (PPTA) with a concentration of
19-20% heated to 80-95"C are used to fabricate high-strength fibres by spinning through an air space [1]. In optimum
conditions, the air space is usually small, 4-20 ram, and the diameter of the spinneret chapels is 0.05-0.08 ram. Orientational
drawing of the jet in the space with a ratio of 4-8 is used (calculated as the ratio of the fibre take-up rate to the rate of extrusion
of the solution through the channel without consideration of spinneret expansion of the jets). The fibre take-up rate is 70-400
m/min and its range can be wider. Water and aqueous solutions of sulfuric acid in low and moderate concentrations with
preferred temperatures of O-10*C are used as the spinning bath (SB). These are "harsh" polymer precipitators, since the liminal
concentration of PPTA corresponds to a solvent composition with an approximately 10% concentration of water in the sulfuric
acid [2]. The possibility of conducting high-speed spinning indicates formation of the structure of the high-strength fibre directly
in the SB.
It was interesting to study the rheological properties of the solutions and the behavior of the jets in conditions of real
spinning of high-strength fibres.
We used 19% LC solutions of PPTA in 99.6% H2SO4 at 82"C with a viscosity of 120-200 Pa-see, determined on a
Hoeppler rheoviscometer with shear stress of 200 Pa. The intrinsic viscosity [77] of the polymer, determined in 96 % H2SO4
at 25~ was 6.0-6.5 dl/g. Standard cup spinnerets made of a precious metal with a 12.5 mm cup diameter and 0.3 mm wall
thickness were used. The spinneret channels had a capillary with diameter D from 0.06 to 0.17 and 1.0 mm, ratio of length
to diameter L/D equal to 1.0 (0.3 for D = 1.0 mm), and an entry conical part with an angle at the apex of 22"C (except for
the channel with D = 1.0 mm). The number of channels in the spinnerets ranged from 18 to 40 and was 1 for the spinneret
with D = 1.0 mm. Mono- and .complex filaments were spun through an air space up to 20 mm in size, heated by hot air feed
or unheated, into a water SB with a temperature of 10*C, as described in [3]. The flow curve of a LC solution of PPTA with
a viscosity of 120 Pa-sec through channels 0.08 mm in diameter is shown in Fig. 1. The shear stress a was calculated as

a = DPI4L,

where P is the pressure of the solution in the spinneret, and the real shear rate on the wall of the channel 5',o was calculated
with the Weissenberg Rabinovich equation:

Terlon Industrial Association, Mytishchi. Translated from Khimicheskie Volokna, No. 2, pp. 3-7, March-April, 1997.

0015-0541/97/2902-0081518.00 o1997 Plenum Publishing Corporation 81

 ~-. sec
w

~dJ[ /
./
J~ " , , /

./
/
/
/
10' /
/
/
5 "7
4
,.z-o.$$
.J r
q

Z i i i i i i

tO1 2 J ~ $ fO 6
a. Pa

Fig. 1. Flow curve of a LC solution of

PPTA through the channels of spinnerets
with D = 0.08 mm.

B@

t,6 --r--2.?.--""
.,t 2 9
.>.,.I
/.---~1 ~
I i
J
,fEte:-!,]
Fig. 2. Spinneret expansion of freely falling
jets of LC PPTA solution Bo vs. apparent
shear rate on the wall of the channel 5'.
Number/spinneret channel diameter, ram:
I) 1/1.0; 2) 40/0.17; 3) 40/0.10; 4)401
0.08; 5) 40/0.06.

dlnof

where ~ is the apparent shear rate on the wall of the channel.

y--- 32 Q/(nD3m),
where Q/m is the volume flow rate of solution through the channel; m is the number of spinneret channels.
It is necessary to note that these existing equations in capillary rheometry hold for steady shear flow in long channels.
For this reason, the estimation of o, -~, and the rheological properties in the short channels of standard spinnerets are somewhat
formal and reflect the real reaction of the polymer system undergoing spinning only in the well-known approximation.
The values of 5'w and q are close. The limits of the change in q in Fig. 1 correspond to the spinning speeds (fibre take-
up) in the 7.5-600 m/rain range (for 5-fold drawing of the jets). According to the data in Fig. 1, flow of the solution obeys
the power law o = KS'nwfor n = 0.65-0.78, increasing as the shear rate increases and, correspondingly, as the residence time
of the solution in the channel decreases. We know that exponent n increases with a decrease in the length of the channel, i.e.,
ratio L/D. This effect indicates attenuation of the viscosity anomaly with a decrease in the duration of deformation (time in the
channel) and the umteady character of flow of solutions in short channels. Due to the unsteady character of the flow, a
difference was obtained in the values of n. The lowest values of n coincided with the value for 19% solutions of PPTA (n =
0.65-0.71) obtained by capillary and rotary rheometry [4].

82
 D 9

.Z.
"~ 0 0

v I / "5

/o//
8-I0

/
I
I
/| 8-$.5
i

$ I I i

$ rO I$ /z. ITIITI

Fig. 3. Draw ratio of jets with consideration of spinneret

expansion D* for different spaces h if the values of h are
constant and equal to 10 without consideration of spinneret
expansion D.
Curve D, mm v0, m/min
1 0.08 8
2,4,5 0.10 8
3 0.10 20

The viscosity of the LC solution is 150 Pa.see (1-3). Broken

lines 4 and 5 (without points) correspond to the similar
curve for an LC solution with a viscosity of 90 Pa-sec and
D = 6.5 and 10.

A/Ar . , wx, m/min

g f75
I
/I
o,a s../ is j f~o
/ I
/ I
/ .4_~
o,s / I ~o5

/ /
J,o
; 0.8 0.91,0

o.z - i I .j~

'1 /' ? '

_ -.,%,,1

0
0 Z 4' 6 8 X, m m

Fig. 4. Relative area of jet cross section A/A x =0 (I, 2) and

flow rate vx (3, 4) vs. distance from spinneret surface x.

Curve h, mm Dt
1, 3 10 8.3
2, 4 5.6 38.2

Viscosity of LC solution of 160 Pa-sec, D = 1.0 ttm, vo =

3.9 m/rain. See explanations in the text for the fine lines in
curves 1 and 2 and lines 5 and 6.

83
 TABLE 1. Conditions of Repeated Drawing of Jets of PPTA LC SoLution in Spinning of Monofilaments through an
Air Space Using Spinnerets with a 1.0 mm Channel Diameter

~fl ~ ~ 0 IP LU B h , B! q
I monofilament, [ m/min mm
No I te x
1 !

I , 26 9 0 0 3.90 4.26 40.4 10.4 10,0 8.3 0,88

2 i
9
5.208 I
1
3.94 4.52 210.0 53.5 6,0 33,3 0.92
93
I
i -;, 788 [ 0.82 0.91 61.0 74.0 5,6 43,0 0,89 --0.92
i I 5,6 38,2 0.95
4 3.802 3,93 4.60 288.O 73,5
5 - I 3.93 4.60 288.0 73.5 5,0 Breakage

9 "~ ,r r. (I
Note: ,,-o = ,',,
4 , -~o
0 s, = .4,_,, : where x = 0 means reading from the spinneret surface, Vtu is the take-up speed of the

monofilament on the spool.

As the data in Fig. 1 indicate, the viscosity of the solution, like the ratio a/qw for 5'2 of 2.104-2 9105 sec - l , is 12-20
times lower than the viscosity determined with the Hoeppler rheoviscometer for stress of 200 Pa (5' -~ 2 sec-t). A sharp
decrease in the viscosity of such solutions in spinneret channels with D = 0.05 and 0.08 mm was noted previously [5].
Spinneret expansion of the jets of PPTA solutions is only described for model channels with large diameters
(determined as the ratio of the diameter of the jets at maximum expansion to the channel diameter). It is usually small. For
an isotropic solution of PPTA, spinneret expansion of freely falling jets B0 is 1.1-1.4 (D = 1.32 mm, L/D = 5, 10, and 20)
[6], and for a 19% LC solution of PPTA, B0 = 1.2-1.3 for q = 102"8-103"2 see - I (D = 0.4 mm, L/D = 2) [4]. This is much
lower than for solutions of flexible-chain polymers [6]. Spinneret expansion of jets is usually correlated with elastic recoil after
shear flow of viscoelastic liquids stops, i.e., with return of the rnaeromolecules from a forced deformed to an equilibrium
conformational state. As observed in many studies, all of this indicates the low elastic properties of the solutions, probably due
to the limited deformability of stiff-chain maeromoleeules. This is probably why the perturbations in jet flow caused by the
phenomenon of elastic turbulence of flow in spinneret channels are not observed.
As Fig. 2 shows, the degree of spinneret expansion of freely falling jets of LC solution of PPTA with a viscosity of
200 Pa-see is virtually independent of the apparent shear rate on the wall 5' and channel diameter D if D = 0.06-0.08 mm and
5' --- 103"6-105 see-t- 130 = 1.70-1.75 were obtained for these channels. For channels of larger diameter, with D = 0.17 and
1.0 ram, Bo increases with an increase in 5', by analogy with the published data for PPTA [4].
For freely falling jets, their diameter in the channels are scarcely larger than the spinneret chanrtel diameter. This can
be the cause of sticking of the solution to the outer surface of the spinneret in prolonged free flow of the jets and subsequent
formation of a fibre with small lumps of polymer in it.
-Drawing of; the jets ensures a decrease in the degree of spinneret expansion. We know that spinneret expansion
decreases with an increase in the degree of drawing of the PPTA LC solution jets as a result of a decrease in the air space h
and totally disappears for spaces with h < 15-20 mm for jets in model channels with D = 0.40 mm and L/D _< 1 [7]. In
contrast to this, spinneret expansion of jets is significant even for small spaces if they are obtained in the channels of small
diameter used in the technology for spinning high-strength fibres from PPTA. This can be seen from the data in Fig. 3, which
shows the change in the real jet draw ratio D* for different air spaces h with constant formal D, calculated with and without
consideration of spinneret expansion of the jets B. According to the determination, D* = B2D. For channels 0.08 and 0.10
mm in diameter, spinneret expansion is correspondingly absent only for spaces of 1-1.5 and 2-2.5 mm. For h < 2.5 mm, the
diameter of the jet coming out of a channel with D = 0.10 mm is smaller than the diameter of the channel itself. The solution
is "pulled out" of the channel due to drawing of the jets. If h > 2.5 mm, the real draw ratio will increase sharply with an
increase in h due to expansion of the jets, and it will be approximately two times larger than the formal ratio for spaces in 15-
20 mm.
As an example, we cite the data obtained for h = 10 ram: if D = 6.5 and 10, then D* = 11.5 and 15.6, and B = 1.32
and 1.24, respectively (D = 0.10 mm, ~'0 = 8 m/min). Spinneret expansion in the same conditions of jet drawing is slightly
greater in channels with D = 0.08 mm than in those with D = 0. I0 mm. The degree of spinneret jet expansion is close for
solution flow rates of ;'o = 8 and 20 m/min (Fig. 3). The presence of spinneret expansion thus requires an important correction
for determining the real jet draw ratio in spinning of high-strength fibres if h > 2.5 mm and channel diameters equal to 0.08-
0.10 ram, which can be done with the graphs in Fig. 3. Increasing the air space in fibre spinning conditions to 15-20 mm can

84
negatively affect the stability of their drawing, since it causes an increase in the real draw ratio and possible entry into the
region of resonance in drawing and breaking of the jets.
Jets were photographed in channels with a diameter of 1.0 mm in different conditions of isothermal drawing in an air
space to study the kinematics of longitudinal flow of LC solutions of PPTA. Monofilaments were spun from a LC solution of
PPTA with a viscosity of 160 Pa.sec. The flow rate of the solution in the channel, calculated with the bulk flow rate, was %
= 3.9 m/min. Due to drawing of the jets in small spaces, their diameter at the level of the face of the spinneret was less than
1.0 mm and J'0 > 3 9 m/min. This is seen from the data in Table 1. The area of the cross section of the jets began to be read
from the level of the face of the spinneret (x = 0) to the level of the SB (x = h). The change in the relative area of the cross
section of jets of the solution A/A x__o and flow rate ~, as a function of the distance from the surface of the spinneret x is shown
in Fig. 4. For the steady-state process, A~, = Q is constant in time in different sections of the jets.
A model of a viscous liquid with a power law of longitudinal flow (power-law liquid) was used as a model of
comparison for describing steady-state isothermal spinning. For this model [18]

A/A~. = 0 = [! + ~X( B (q- I)lq _ l) l ~(,-~. (1)

where q is an exponent in the equation of the law of flow; ~- = K(dv/dx)q.

The f'me lines on curves 1 and 2 in Fig. 4 correspond to the profiles of liquid jets obeying the power law of flow with
q = 0.8 and 0.9 and of a Newtonian liquid for which q = 1.0. For a Newtonian liquid, A / A x = 0 = B -x/h. A comparison of
the experimentally obtained jet profiles with the model profiles indicates the satisfactory correspondence of longitudinal flow
of LC solutions of PPTA to the power law with q = 0.88-0.55 (quasi-Newtonian liquid). An increase in q in the range
indicated above is observed for jets with more intense extension due to an increase in D from 8.3 to 38.2 with a simultaneous
decrease in h from 10 to 5.6 mm; and this could be due to the appearance of a highly elastic reaction of the polymer material
in the jets for high take-up rates and rate gradients in small spaces. This hypothesis is based on the fact that the rate profiles
of jets of highly elastic Newtonian liquids or liquids with a power law of flow change as the degree of extension increases,
approaching the linear [9], and the rate profiles of model, only viscous liquids with a power law of flow and a set of
increasingly high values of q, approaching the linear for q = oo [8], approximately correspond to them. The longitudinal rate
gradient characterizing the degree of extension of the jets increases from 114 to 1615 s e e - l in the final segments of the jets
(calculated for simplicity in the approximation of a Newtonian model) with the equation

_ /t"'h InB
d," _ vo for x = h. (2)
dx h

We know that steady-state drawing of jets in space takes place in a process with pulsation of the diameter of the jets
if their draw ratio is greater than a critical value Dcrit, equal to 1517 for LC solutions of PPTA [7]. This phenomenon is
known in the mechanics of jet formation as draw resonance. We also know that Derit changes little with a change in air space
h. However, for very small h, beginning with a certain value, Dcrit increases sharply (the shape of the curves is reported in
[3, 7]). For a solution with a viscosity of 160 Pa.sec, this takes place for h < 14 mm (D = 10 mm, ~'o = 3.9 m/min). The
observed increase in Dcrit is in agreement with the theoretical predictions for model viscoelastic liquids and is due to the
stabilizing effect of the elastic reaction of the polymer material with a brief duration of jet drawing commensurate with the
relaxation time of the material [9]. For this reason, steady-state spinning with a jet draw ratio of 38.2 occurs in conditions of
the appearance of highly elastic properties in the polymer material according to the data on jet draw resonance. On the contrary,
drawing of jets with a ratio of 8.3 in a space with h = 10 mm (where q = 0.88) occurs in conditions of primarily viscous flow.
This follows from the existence of a less stressed state (dv/dx h = 114 see - t ) than in jets in the region of the effect of a highly
elastic reaction (dv/dx h) _ 190 see - l (the rate gradient was calculated with Eq. (2) for x = h and h = 14 mm, P0 = 3.9
m/min, Dcrit = 15, in the region of the inflection of the curve of Dcrit vs. h). For this reason, q = 0.88 is constant, is not a
function of the effect of the highly elastic reaction, and the values of q and n do not agree for the given material. A detailed
analysis of jet flow of viscoelastic media requires using more complex Maxwellian models of liquids as models for comparison
[9-11].
As Table 1 shows, the overall draw ratio D, calculated from the take-up rate or linear density T of the monofilaments,
is significantly higher than the value obtained with data from photographing the jets in the space D t. This indicates their
additional drawing in SB (water with a temperature of 10~ in conditions of precipitation of the polymer from the solution.
Drawing by 1.2-1.4 times is observed in photography of jets in SB in the first I-3 mm below the level of the bath. Only slight

85
drawing was thus detected in the SB, since the jet falling in it is rapidly cooled and the polymer is precipitated from the solution
on contact of the jets with the SB. Breaking of the jets (monofilaments) in the SB for D -- 73.5 (D l = 38.2) is perhaps
observed as a result of this drawing if the space decreased from 5.6 to 5.0 mm (Example 5), while the rate profile of the jets
in the air space in these conditions is far from the theoretically maximum possible profiles for Maxwellian liquids in which
the jets should break, namely from the Fisher-Denn linear profile in a cohesive mechanism of breaking (Example 5, Fig. 4),
or the profile with d v / d x -.-, oo (Example 6) in the final Nama-Bogue segment [10] in breaking according to a mechanism of
extreme rheological thinning. Breaks in jets were observed at a different depth in their vertical movement in the SB, usually
beginning from the surface layers and up to a depth of 5-10 cm.
For thinner jets obtained in conditions of spinning high-strength fibres through channels with D = 0.6-0. I0 mm, their
slight drawing in the SB is probably also not excluded, especially for the high-speed process. We know that the strength of
PPTA fibres begins to decrease with an increase in the spinning speed if it is greater than 300-400 m/min. This decrease could
be due to slight drawing of the jets in the SB, resulting in breaks in the precipitated polymer shell.

REFERENCES

1. H. Blades, US Patent 3,767,756 (1973).

2. T. Hayshi, T. Hiraj, and A. Nakajima, Am. Chem. Soc. Polym. Prepr., 20, No. 1, 53-56 (1979).
3. V . N . Kiya-Oglu, G. A. Belinskii, et al., Khim. Volokna, No. 4, 20-22 (1992).
4. G . A . Belinskii, Candidate Dissertation, All-Russian Scientific-Research of Synthetic Fibres-Planning, Mytishclhi
(1988).
5~ T. Kaneda, S. Ishikawa, et al., Makromol. Chem., 183, 417-457 (1981).
6. C. H. Kao and D. G. Baird, Polym. Eng. Sei., 22, No. 9, 521-526 (1982).
7. G. A. Belinskii, V. N. Kiya-Oglu, and V. G. Kulichikhin, Khim. Volokna, No. 1, 32-34 (1991).
8. J. C. Hyun and R. L. Ballman, J. Rheol., 22, No. 4, 349-380 (1978).
9. R.J. Fisher and M. M. Denn, AICHE J., 22, No. 2, 236-346 (1976).
10. J. Tsou and D. C. Bogue, J. Non-Newtonian Fluid Mech., 17, 331-347 (1985).
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86