Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
3~
BACKGROUND OF INVENTION
This rnvention relates to processes for forming fiber
rein.orced tz~es. ~ore particularly, this invention relates to
processes for forming impregnated carbon fiber tapes using a
crosshead type die.
The use or crosshead dies for coating metallic wires OL
~-arious types wi.h plastic materials is well known. See, e.g.,
. S. Pa~en~ `~o. 4,341,509, U. S. Patent No. 4,247,5D4, and U. S.
Fa-ent No. 4,150,929. Crosshead dies have also been used to
coa. .ire cord, with, for example, an acrilonitrile/butadienne
co?ol~eric rubber. See, U. S. Patent No. 4,328,133 and U. S.
Patent No. 4,300,878. Other patents disclosing the use of
c-osshead dies include U. S. Patent No. 4,171,195, U. S. Patent
I;o. 4,172,106 and U. S. Patent ~o. 4,274,821.
U. S. Patent No. 3,485,912 discloses that "high tensile
strength ele~ents, such as tapes" may be formed by
manufacturing a plurality of synthetic
resinous oriented strands or filaments
and subsequently encapsulating such
~aterials within a relatively soft low
tensile strength matrix or casing.
~owever, this patent does not disclose the composition of the
~atrix. Likewise, U. S. Patent No. 3,461,197, discloses a
si~ilar article which consists of
a first thermoplastic or thermosetting plastic
material having dispo~ed therein a plurality
of reinforcing filaments such as ~ibers or
filaments of glass.
U. S. Patent No. 3,758,247 refers to a crosshead die
~hich is used for coating flat cables utilizing a~melt consisting
of rubber or plastics including polyethylene or polypropylene.
~inelly, U. S. Patent No. 3,993,?26, diseloses the use of "a
crosshead extruder to impregnate the rovings with a thermoplastic
po'ymer under high pressure".
The use of air to spread a carbon fiber prior to impreg-
notion is disclosed in several patents. In U. S. Patent No.
3,704,485, an apparatus for spreading a graphite fiber tow is
disclosed which involves the use of a pulsating, gaseous medium.
U. S. Patent Nos. 3,873,389 and 3,795,944 both disclose the use
of a counter air flow means for spreading graphite fiber tows
which are to be impregnated with thermosetting materials.
The cooling of impregnated carbon fiber bundles follow-
ing crosshead die extrusion is also known. For example, in U.S.
Patent No. 3,993,726, cooling sprays or a cooling bath are used,
and in U.S. Patent No. 3,728,424, electrical cables impregnated
with a polyester in a crosshead die are cooled by passing through
cooling tank.
However, none of the above-identified patents discloses
either the inventors' specific gas jet spreading system, their
crosshead die design or their air cooling means as disclosed
hereafter.
In the prior art, carbon fiber-based, prepreg tapes were
normally prepared using thermoset resins, with the thermoset
resin itself literally painted onto the tapes in an uncured
condition. However, care had to be taken to insure that the
temperature of the tape remained low during storage, so that
autocuring did not occur. When the tape was to be used in
forming an article, layers of the tape with the desired orienta-
tion were placed on an appropriate form, heated to the curing
temperature in a controlled manner and normally under vacuum
and/or externally applied pressure baked for the period of time
necessary to insure a complete sure. But a major problem with
this system was that after curing, it was impossible to reform
-3-
~213~34~
629~7-20~
the article if errors in forming had occurred. Therefore, large
amounts oE wasted material often resulted. Finally, using this
method, it was difficult to obtain thick, uniform coatings and
the adhesion of the thermoset polymer to the carbon fiber was
often poor.
Thus, it is an object of the instant invention to
prepare a simple and inexpensive, but readily usable, crosshead
die.
It is another object of this invention to prepare such
a die for use in impregnating fibers with thermoplastic, resi-
nous, materials.
It is another object of this invention to prepare
tapes which are based upon a thermoplastic resinous, fibrous
matrix.
These and other objectives are obtained by utilizing
the process of the instant invention.
5UMMARY OF THE INVENTION
The instant invention involves a process for preparing
tapes from thermoplastic polymers and carbon fibers which com-
prises: (a) spreading a tow of carbon fibers to provide sub-
stantia:Lly complete wetting of the carbon fibers when impregna-
ted in a crosshead die; (b) feeding a carbon fiber tow into a
crosshead die; (c) impregnating the tow in the crosshead die
under pressure with a thermoplastic polymer to form a tape, (d)
withdrawing the tape from the die; and immediately thereafter
(e) cooling the tape with a jet of gas. The process of the
instant invention allows the application of high molecular
weight, high melting, thermoplastic polymers under controlled
conditions without the use of a solvent. The tapes of the
instant invention may be employed to form shaped articles, such
as airplane wing skins and/or other wing
" 62957-2~4
8~
components, and may be reused even after shaping by simply
heating to slightly above the polymer melting point and
reshaping or reforming.
; - 4a -
' `
~ 8~3~
DESCRIPTION OF THE DRAWINGS
Fig. 1 is a diagramatic view of the various devices used
in carrying out the process of the instant invention.
Fig. 2 is a perspective view of the gas jet carbon fiber
spreader used in carrying out the process of the instant in-
vention.
Fig. 2-A is a perspective view of the same devise with
the tO~ removed.
- Fig. 3 is a cutaway side view of the polymer entry port
of the crosshead die of the instant invention.
Fig. 4 is a cutaway end view of the crosshead die of the
instant invention.
Fig. 5 is another version of the bottom half of Fig. 4.
SUMMARY OF PROCESS
In Fig. l, several graphite fiber bundles ~1) are shown.
The tow or bundles are conveyed to the crosshead die by a
suitable drive roll (~). In order to insure uniform spreading of
each of the graphite fiber bundles, they are passed over a gas
spreading mealls (5). After uniform spreading, the fibers enter
the crosshead die (6). The thermoplas'tic polymer which is used
to impregnate the fiber tow is added in pellet or other dry form
to the extruder, melted and conveyed to the crosshead die through
a barrel (7). After impregnating the fiber tow to form a tape
(8), the tape is with~rawn from the die and passed through the
gas cooling means (9), using suitable drive rollers (10).
The polymers which are useful in carrying out the
procPss of the instant invention for impregnating carbon fibers
constitute virtually any type of relatively high molecular weight
thermoplastic polymer, including polyethylene, polypropylene,-
polyester, the various polyamides, polyimides, polyamidimides,
polyetherimides, polysulfones, e.g., polyether sulfones,
_5 _
3 ~ ~
polyether ether ketones, polybutylene terephthalate and the like
T:~e melting point OI the polymer must be at least S0~ F. and
p-e erably at least 2009 F. above ambient conditions. Higher
melting temperatures insure that there will be no undue sticking
or bindlng of the extruded polymer tapes prior to use. In
Gaci.ion to one component pol~er systems, mixtures of ~arious
ther~oplastic polymers may also be employed to advantege where
spec fic combinations o, properties are desired.
Of particular importance are the liquid crystal polymers
or LCPs. Examples of these polymers include the wholly aromatic
p~lyester resins which are discùssed in the following publi-
ca.ions: ~a) Polyesters of Hydroxybenzoic Acids, by Russell
Gi'key and John R. Caldewellt J. of Applied Polymer Sci., Vol.
II, Pages 198 to 202 (1959), (b) Polyarylates ~Polyesters From
Aromatic Dicarboxyllc Acids and Bisphenols), by G~ Bier, Polymer,
ol. 15, Pages 527 to 535 (August 1974), (c) Aromatic Pol~ster
Pl2stics, by S.- G. Cottis, Modern Plastics, Pages 62 to 63 (July
1975); and (d) Poly(p-Oxybenæoyl Systems): Homopolymer for
Coatings Copolymers for Compression and Iniectlon Molding, by
Roger S. Storm and Steven G. Cottis, Coatings Plast. Preprint,
Vol. 34, No. 1, Pages 194 to 197 (April 1974). See also, U. S.
Patent Nos. 3,039,994; 3,169,121; 3,321,437, 3,5539167;
3,637,595; 3,651,014; 3,723,388; 3,759,870; 3,767,621; 3,778,410;
3,787,370; 3,790,528; 3,829,406; 3,890,256; and 3,975,487.
Other polyesters are disclosed, for instance, ~a~
Polyester X7~-A Self Reinforced Thermoplastic, by W. J. Jackson,
3r., H. F. Kuhfuss, and T. F. Gray, Jr., 30th Anniversary Techni-
c21 Conference, 1975 Reinforced PlasticslComposites Institute~
The Socie~y of the Plastics Industry, Inc~, Section 17-~, Pages 1
3 ~ ~
to 4, (b) Belgian PG~ CS. 838,935 and 828,936, (c) Dutch Pat.
~o. 7505551, (d) ~est G_~man Pat. Nos. 2520819, 2520820,
27~22120, 2834535, ~8~4 36 and 2834537, (e) Japanese Pat. Nos.
43-223; 2132-116; ar.d 3321-293, and (f) U. S. Pat. Nos.
3,C91,083; 4,9gl,C lL; 4, O~ 7,597; 4,066,620; 4,067,852; 4,075,262;
4,C83,829; 4,093, g5; 4,1~2,212; ~,118,372; 4,130,545; 4,130,702;
4,146,702; 4,153,/7,; 4 ! 1~ 6,070; 4,159,365; 4,160,755; 4,161,470;
4,-~69,933; 4,181,/9~; 4,183,895; 4,184,996; 4,188,476; 4,191,6~1;
4,201,856; 4,219,~6 ; 4,224,433; 4,226,970, 4,230,817; 4,232,143;
4,~38,598; 4,238,~0C; 4,239,913; 4,~42,496; 4,245,082; 4 9 245,804;
4,247,514; 4,256,62~; 4,265,802; 4,267,289; 4,269,965; 4,27~ t ~3;
anc 4,299,756.
The polyes~e~s and copolyes~ers which are pre~erred
consist essentially o structur~l units having recurring groups
of the formula
(I) ~ O - R7 - O t and
~ OC ~ ~2 ~ CO~ and/or
(II~) ~ O - R3 - CO ~
wherein units I ard Il, if present, are present in substantially
eq~i~olar amounts; Rl, ~2 and R3 are radicals selected from the
group of 1) single and used six-membered aromatic carbocyclic
rir.g systems wher~ir. _he chain-extending bonds of the ring system
i~ attached to the sa3e ring, are positioned 1,3- or 1,4- (pre-
ferably 1,4-) to each o,her, and if attached ~o dif~erent rings,
are preferably in po~itlons parallel and oppositely directed, and
2) multiple si~-mem~e-ed aromatic carboxcyclic ring systems in
wh.ch the individ~a~ ri~.gs are 3Oined by a chemical bond or a
~r2ns-vinylene grou? cn~ in which the chain extending bonds of
~ 8~ 3~ ~
each ring are in the 1,3- or 1,4- (preferably 1,4-) positions; R2
-.ay also be
~ or ~ A-
wherein A is a divalent radical containing one or two bycyclic
in-chain atoms; and R3 may also be
H H
~'C= 1-
~;herein the aliphatic portion is attached to the carbonyl group.
P-eferred group 1) radicals are phenylene and naphthylene.
P.eferred group 2) radicals are two-ring systems. Illustrative
ol 1) are
~J
and of 2) are
H H
and ~ C = C ~
~he foregoing ring systems, except ~or R2~ as indicated below are
also .ntended to include one or more substituents, e.g., chloro~
, ~2 8~ 3 ~ i
bromo, fluoro, or lower alkyl (1-4 carbon atoms) on the ring or
rings. The R2 aromatic ring systems should preferably be unsub-
stituted when only one kind of unit I and one kind o~ unit II are
used, i.e., when a homopoly~er is formed to insure obtaining
oriented fibers. In the case of copolymers, it is preferred that
the R2 aromatic ring systems be unsubstituted becausé of thermal
or hydrolytic inst~bility and/or cost of the R~-ring substituted
copolymers.
Also included are those (co)polyesters wherein up to 25
mol %, preferably up to 5 mol %, based on the total I, II and III
units, are aromatic polymer-iorming units (i.e., units wherein
the chain extending functional groups are attached to aromatic
rings) not conforming to those described above and which do not
interfere with the anisotropic melt forming capability of the
polymers. A non-limiting list of these units includes
O
G- Cl
~ O O I O ~ O
. I .
Cl Cl
C8 ~ H
j CH3
Cl Cl
_9_
~ 80 3
and
_o~ O--
~J
The (co~polyesters, as mentioned above, ~ay comprise
units I and II in sub s tantially equimoler amounts or may comprise
unit III or may comprise a combination of units I, II, and III
and, of course, more than one kind of unit (I, II and/or III) can
be present in the polymer.
Preferred (co)polyesters of the invention consist essentially
of units I and II. In such polymers, it is preferred that Rl is
selected from the group of 1,4-phenylene; chloro-, dichloro-,
bromo-, dibromo-, methyl-, dimethyl- and fluoro-1,4-phenylene;
4,4'-biphenylene; 3,3',5,5'-tetramethyl-4,4'-biphenyle~e and R2
is selected from the group of trans-1,4-cyclohexylene; trans-2,5-
dimethyl-1,4-oyclohexylene; trans-vinylenebis(1,4-phenylene);
4,4'-biphenylene; 2,6-naphthylene; and 1,4-phenylene and with the
proviso that more than one kind of unit I or II are present. Of
such copolyesters, two types axe par~icularly preferred because
of properties and cost. In the first type, the pol~mers consist
essentially of the recurring units
n
O O O O
- O ~ O- , - C- ~ C- , and - C- y_ tl
wherein X is selected from the group of chloro-, bromo-, fluoro-,
and methyl radicals; n is 1 or 2; and Y is seleeted from the
~roup of 4,4'-biphenylene and 2,6-naphthylen~, the ratio of
O O O O
- C ~ C~ to -C ~ Y C-
-10-
.
3~
..
units being within the range of 4:1 to 1:4. In the second type,
the poly~ers consist essentially of the recurring units
CH3 CH3 CH3
~ ~ ~ . - ~ O- and
CH3 CH3 CH3
O O
--C--Z--C--
wherein Z is selected from the group of 4,4'biphenylene, 2,6-
naphthylene, and 1,4-phenylene, the ratio of
CH3 C\3 f H3
-O ~ O- to - O ~ o-
CH3 CH3 H3
units being within the range of 4:1 to 3:2. With each type of
polymer, up to 25 mol percen~ of non- onfor,ming units may be
present as described above.
Of the (co)'polyesters containing only type III units,
the polyme~s consisting essentially of the recurring units
O H H O
-C ~ O~ and -O- ~ - C= C C-- are preferred.
(1,4-benzoate unit) ~1,4-cinnamate unit) .
- 1 1 -
1~8~3~1~Ll
The (co)polyesters are prepared prererably by melt
polycondensatlon of derivatlves of dihydric phenols and aromatic-
aliphatic, aromatic and cycloaliphatic dicarboxylic acids or
their d~rivatives. A convenient preparative method is the melt
polyco~densation of the diacetate of a dihydric phenol with a
dicarboxylic acid. Alternatively, phenolic carboxylic acids or
.heir deriva.ives may be used âS coreactants in the preparation
of polyesters and copolyesters.
A list of useful dihydric phenols preferably in the form
of th~lr diacetate derivatives includes hydroquinone, chlorohydro-
.quinor.e, bromohydroquinone, methylhydroquinone, dimethylhydro-
quinone, dichlorohydroquinone, dibromohydroquinone, 4,4'-oxydi-
phenol, 4,4'-isopropylidenediphenol, 4,4'-thiodiphenoi,
4,4'-biphenol, 3,5,3',5'-tetramethyl-4,4'-bisphenol, 3,5,3',5'-
tetrachloro-4,4'-biphenol, 2,6-dihydroxynaphthalene, 2,7-dihy-
droxynaphthalene, and 4,4'-methylenediphenol and the like.
A list of useful dicarboxylic acids includes tere-
phthalic acid, 4,4'-bibenzoic acid, 4,4'-oxydibenzoic acid,
4,4'-thiodibenzoic acid, 4-carboxyphenoxyacetic acid, 4,4'-trans~
stilbenedicarbo~ylic acid, 2,6-naphthalenedicarboxylic acid,
ethylenedioxy-4,4'-dibenzoic acid, isophthalic acid, the halogen
and methyl substituted derivatives of the foregoing dicarboxylic
acids, 1,4-trans-cyclohexanedicarboxylic acid, 2,5-dimethyl-1,4-
trans-cyclohexanedicarboxylic.acid, and the like-.
A nonlimiting list of phenolic carboxylic acids includes
6-nydroxy-2-naphthoic acid, 4-hydroxy-4'carboxy azobenzene,
-12-
~'~ 8~ 3~ ~
~e~ulic acid, 4-hydroxybenzoic acid, 4~(4'-hydroxyphenoxy)-
benzoic acid and 4-hydroxycinnamic acid and the alkyl, alkoxy and
.alogen substituted versions of these compounds.
In addition, it is possible to prepare anisotropic
?l~ers by polymerizing methylacryloxy benzoic acid utilizing an
clkali metal hydroxide and free radical initiators as described
in U. S. Patent Nos. 4,112,212, 4,130,702 and 4,150,755.
Useful phenolic-carboxylic acid derivatives include
p-acetoxybenzoic acid and p-acetoxycinnamic acid ar.d the like.
A nonlimiting list of various polyesters and copoly-
es.ers includes: poly(methyl-1~4-phenylene 2,5-dimethyl-trans-
hexahydroterephthalate); copoly(methyl-1,4-phenylene trans-hexa-
hydroterephthalate/terephthalate) (8/2); copoly(chloro-1,4-pheny-
lene trans-hexahydroterephthalate/isophthalate~ (9/1) and (8/2);
copoly(ethyl-1,4-phenylene terephthalate/2,6-naphthalate) (7/3);
copoly(~ert. butyl-1,4-phenylene/3,3',5,5'-tetramethyl-4,4'-bi-
phenylene/terephthalate) (713j; copoly(chloro-1,4-phenylene/-
3,3',5,5'-tetrachloro-4,4'-biphenylene terephthalate) (7/3),
The liquid crystal polymers including wholly aromatic
polyesters and poly(ester-amide)s which are suitable for use in
the present invention may be formed by a variety of ester forming
techniques whereby organic monomer compounds possessing
functional groups which, upon condensation, form the requisite
recurring moieties are reacted. For instance, the functional
groups of the organic monomer compounds may be carboxylic acid
groups, hydroxyl groups, ester groups, acryoxy groups, acid
halides, amine groups, etc. The organic monomer compoundc may be
reacted in the absence of a heat exchange fluid via a melt
acidolysis procedure. They, accordingly, may be heated initially
~ 3~ ~
to form a melt solution of the reactants with the reaction
cont~nuing as said polymer particles are suspended therein. A
~-acuum may be applied to facilitate removal o~ volatiles formed
curing the final state of the condensation ~e.g., acetic acid or
~-ater).
Com~only-assigned U. S. Patent No. 4,083,829, entitled
"~elt Processable Thermotropic Wholly Aromatic Polyester,"
cescribes 2 slurry polymerization process which may be employed
.o form the wholly aromatic polyesters which are preferred for
use in the present invention. According to such a process, the
solid product is suspended in a heat exchange medium. The
cisclosure of this patent has previously been incorporated herein
by reference in its entirety. Although that patent is directed
to the preparation of wholly aromatic polyesters, the process may
also be employed to form poly(ester-amide)s.
~ en employing either the melt acidolysus procedure or
the slurry procedure of U. S. Patent No. 4,083,829, the organic
~onomer reactants from which the wholly aromatic polyesters are
derived may be initially provided in a modified ~orm whereby the
usual hydroxy groups of such monomers are esterified (i.e.~ they
are provided as lower acyl esters). The lower acyl groups
preferably have from about two to about four carbon atoms.
Preferably, the acetate esters of organic monomer reactants are
provided. When poly(ester-amide)s are to be formed, an amine
group may be provided as a lower acyl amide.
Representative catalysts which optionally may be e~-
ployed in either the melt acidolysis proeedure or in the slurry
procedure of U. S. Patent No. 4,083,829 include dialkyl tin oxide
(e.g., dibutyl tin oxide), diaryl tin oxide, titanium dioxide,
entimony trioxide, alkoxy titanium sili~ates, titanium alkoxides,
~ 4 ~ .
alkali and alkaline earth metal salts of carboxylic acids (e.g.,
zinc acetate), the gaseous acid catalysts such as l,ewis acids
(e.g., BF3) ! hydrogen halides (e.g., HCl), etc. The quantity of
catalyst utilized typically is about 0.001 to 1 percent by weight
based upon the total monomer weight, and most comm,only about 0.01
ro 0.2 percent by weight.
The wholly aromatic polyesters and poly(ester-amide)s
suitable for use in the present invention tend to be substanti-
211y insoluble in common polyester solvents and accordingly are
not susceptible to solution processing. As discussed previously,
.hey can be readily processed by common melt processing tech-
niques. Most suitable wholly aromatic polymers are soluble in
pentafluorophenol to a limited extent.
The wholly aromatic polyesters which are pre~erred for
use in the present invention commonly exhibit a weight average
molecular weight of about 2,000 to 200,Q00, and preferably about
lO,000 to 50,000, and most preferably about 2Q,000 to 25,0Q0.
~he wholly aromatic poly(ester-amide)s which are preferred for
use in the present invention commonly exhibit a molecular weight
of about 5,~0Q to 50,0Q0, and preferably about lO,OOQ to 30,0Q0;
e.g., 15,000 to 17,0Q0. Such molecular weight may be determined
by gel permeation chromatography and other standard techni~ues
not involving the solutioning of the polymer, e.g., by end group
determination via infrared spectroscopy on compression molded
films. Alternatively, light scattering techniques in a penta-
fluoropherol solution may be employed to determine the molecular
weight.
The wholly aromatic polyesters and poly~ester-ami~e)s
additionally co,mmonly exhibit an inherent viscosity (I.V.) of at
~a~3~
62957-20~
least approximately 2.0 dl./g., e.g., approximately 2.0 to 10.0
dl./g., when dissolved at a concentration of 0.1 percent b~
weight in pentafluorophenol at 60 C.
For the purposes of the present invention, the aroma-
tic rings which are included in the polymer backbones of the
polymer components may include substitution of at least some of
the hydrogen atoms present upon an aromatic ring. Such substi-
tuents include alkyl groups of up to four carbon atoms; alkoxy
groups having up to four carbon atoms; halogens; and additional
aromatic rings, such as phenyl and substituted phenyl. Prefer-
red halogens include fluorine, chlorine and bromine. Although
bromine atoms tend to be released from organic compounds at high
temperatures, bromine is more stable on aromatic rings than on
aliphatic chains, and therefore is suitable for inclusion as a
possible substituent on the aromatic rings.
The fibers useful herein are basically carbon fibers
which may be prepared by a variety of methods. Virtually any of
the prior art methods of carbon fiber preparation may be employ-
ed in this invention~
The preparation of carbon fibers has been well known
in the art for many years. Basically, there are two methods for
preparing these fibers, which differ with respect to the start-
ing materials employed. One method starts with a natural or
synthetic fiber, which is then carbonized. In the other process
petroleum pitch or coal tar pitch is used as the starting
material.
Typical of the patents involving the use of pitch is
U.S. Patent NoO 4,317,809. Generally, using the pitch process,
3~
62957-204
the pitch is heated under hiyh pressure and then under
atomospheric pressure with sparging to form a mesophase pitch.
Following this step, the pitch is converted into a fiber,
thermoset, and carbonized.
Included among the Eibers which may be formed into
graphite or carbon fibers an~ are useful in this invention are
those materials where the polymeric precursor is, for exarnple,
cellulose, acrylic derivatives, and, in particular,
polyacrylonitriles. Specifically, the acrylic polymer may
contain not less than about 85 mol percent of acrylonitrile
units, with not more than about 15 mol percent of a monovinyl
compound which ls copolymerizable with acrylonitrile~ such as
styrene, methylacrylate, methylmethacrylate, vinyl acetate,
vinyl chloride, vinylidene chloride, vinyl pyridine and the
like. Other copolymerizable monomers include styrene sulfonic
acid, allyl sulfonic acid, alkyl acrylates and methacrylates,
vinyl acetate, vinyl proprionate, vinyl chloriner vinylidine
chloride, and the like.
There are numerous procedures for carbonizing the
precursor fibers of the instant invention. In general, they
involve a first heating step in the range of about 200-400 C.,
followed by a second heating step in a non-oxidizing atmosphere
at temperatures ranging from 800-3000 C. For examples of these
processes, see U.S. Patent No. 4,197,282, U.S. Patent No.
4,079,122, as well as U.S. Patent No. 4,131,644.
Fig. 1 is a drawiny of the overall process of the
instant invention. A fiber roll frame (2) is shown which
contains numerous rolls of graphite fiber tows. The individual
fiber tows are pulled from the fiber bundles onto a roll (3~ and
from the roll directed into a gas jet spreading means (5), which
acts to spread the fibers to provide better wetability in the
- 17 -
~ C~3 ~
crosshead die (6). After impregnation of the ribers, the high
temperature, semi-molten t~pe which results is pulled from the
die by dr2wing rolls (10), while being cooled ~y gas cooling
~eans ~9).
The purpose of the gas jet spreading means shown in Fig.
2 is to insure that the bundles or tows of individual carbon
Iibers, which may each contain up to as many as ~4,000 flbers,
2ze unifor~ly spread out across the entire width of the merged
to~ nless unilorm distribution of the fibers is obtained, the
strength properties of the resulting tape will not be uniform and
the tape will have a tendency to split along its lengthwise
direction. The gas jet spreading means consists of a gas box
(30) into which compressed air or another gas is fed through a
conventional adjustable gas metering means (31). The preferred
pressure of gas flow into the gas jet spreading means is in the
range of approximately 40-90 psi. One~ or more than one, gas
exit ports ~34) are provided to cause gas from within the gas box
to impinge in a generally perpendicular fashion on the moving
fiber tows that pass across the exit ports. Preferably the exit
ports are "V" shaped and pointed in the direction of movement of `
the fiber tow. After exiting from the air spreading means, the
tow demonstrates a relatively uniform appearance across its
entire width. The gas spreading means, as shown in Fig. 2-A, is
provided with shims (36) or other means to allow an air box cover
(38) to be attached, so that a flow channel for the carbon fiber
tow is provided. The gas box is held in place by convenient
attached means, such as clamps ~39).
The fiber bundles which are introduced into the cross-
head die generally perpendicular to the direction of flow of the
~ 8~
polymer melt, are fed into the crosshead die through a horizon-
tally extended fiber entry window (25) shown in Fig. 4. As ~he
fiber moves through the crosshead die and reaches the point where
the polymer exits from the lower and upper exit ports (23) and
(22), the polymer is forced into contact with the ~ibers actually
surrounding each individual fiber. The resulting i~?regnated
-iber tape exits rrom the die through a horizontally extended
exit window (26). Within the crosshead die itself, entrance
w ndow adjus-ment means (27) and exit window adjus~ment means
(28) are provided. In a preferred embodiment, the adjustment
means comprise threaded screws which cause the leading edge of
the entrance die lips (29) and the exit die lips (30) to deflect
do~wardly as pressure from the screw is increased upon the die
lips. In order to facilitate adjustment of the width of the die
lips, hollow spaces are provided at A and B within the die. The
die may also be equipped with a pressure transducer means and
various thermocouples or heating elements to monitor and control
conditions within the die.
The extruder which is used ~or extruding the thermo-
plastic polymer disclosed herein may be of any conventional
design, although the preferred types are the-so-c211ed screw
extruders (preferably ~win screw). Polymeric flake or chip is
added to the extruder, melted and then forced out from the
extruder and in through the entry barrel (13~ of the crosshead
die, as shown in Fig. 3. The molten polymer enters the barrel at
the entry port (14) and is conducted along a main polymer flow
chznnel (15) to the division chamber (16). where the ~low of ~he
polymer is divided into an upper flow ch~nnel (17) and a lower
flow channel (18).
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~ 3 ~
The temperature at which the extruder operates is of
course ~ependent on the melting point of the thenmoplastic
polyner which is to be used or fiber impregnation. In general,
it is preferred that the extruder be operated approximately
3C-55 C. higher than the melting point of the polymer. For
exc~ple, with the liquid crystal type polymers disclosed above,
t~e melting point is in the range of 270-300 C. It is important
t~at extrusion temperatures not greatly exceed the polymer's
~elting point because of the possibility of polymer heat degrad-
alion. The pressure within the crosshead die is relatively low,
usually no more than about 2 or 3 atmospheres, but is above
a~bient pressure, in order to assure that there is complete
wetting of the carbon fiber with the thermoplastic pol~mer.
After the polymer is forced from the extruder and enters
the barrel through entry port ~14), it is maintained at or above
the desired temperature by means of variable heaters (l9) which
surround the barrel. In order more accurately to control the
flow of poly~er through the barrel from the extruder to the
crosshead die, a metering pump may be attached within the barrel.
T~is pump adjustably controls the rate of flow of the extruded
polymer into the crosshead die.
The entry barrel is attached to the extruder and the
crosshead die by the use of attachment means ~11). Preferably
these devices are simply bolted together. The flow rate of the
poly~er through the barrel is controlled by the rate at which the
polymer is added to the extruder, the rate at which the extr~der
is operating, and by flow control valves ~12) which control the
ficw to t'ne upper and lo-~er flow channels (17) and (18)
respectively.
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~ 8~
Fig. 4 is a cutaway end view of the crosshead die of the
instant inventlon. An end view of the upper polymer flow channel
is shown at (20), while at (21) an end view o~ the lower polymer
flow channel is shown. The polymer which flows into these areas
of the die, exits through upper and lower exit ports (22) and
(23? and impregnates the fiber bundles (26) which are moving in
the direction of flow through the crosshead die as shown. The
rate of flow of the polymer through the crosshead die is deter-
mined by the rate at which it is fed to the die by the extruder.
The rate of tape formation may vary from 0.1 to 10 feet per
~inute. Usin~ the crosshead die and process of this invention,
tapes having widths of up to about 6" and thicknesses of from
about 2 to about 20 mils may be prepared.
A partial cutaway end view of a modification of the
crosshead die of the instant invention is sho~n in Fig. 5. In
order to increase tension on the incoming fibers, a fiber
diversion path is provided. In this modification, instead of
providing a straight path for the fibers to follow through the
crosshead die, a diversion around a stationary spindle (50) is
provided. This diversion increases the tension on the fibers,
thereby increasing the adhesion of the polymer to the fiber. The
modified crosshead die is also provided with a drain opening (72)
to allow escape of excess impregnation plastic as it builds up
within the die.
After impregnation, the resulting tape is pulled from
the exit die by the drive rolls 10, and i~mediately cooled in a
gas cooling means (6~, as shown at Fig. 1. The purpose of
-mmediate ~as cooling (i.e., a,r cooling) is to insure that the
tape which leaves the erosshead die in a semimolten, and
Lherefore, weakened state, does not pull apart transversely prior
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lZ ~ 3 ~ ~
tO cooling. The gas cooler, as shown in Fig. 1, includes an air
regu~ator (60), an air regulation guage, and a tube (64J for
providing co~pressed air or another gas to the co~ler. The
cooler is designed in such a fashion that gas is provided both
above and below the plane of the exiting tapes. In a preferred
device a longitudinally extended, cylindrical tube (64) is
provided with 2 uniform flow of air. The tube itself may be
equipped with a filter/diffusion screen, so as to insure that a
relatively uniform flow of air appears across the entire
crosssectional area of thP air cooler. In order to allow passage
of the tape through the device, openings commensurate with the
width and height with the tape (66) are provided. The openings
should be at least wide enou~h to allow ready passage of the tape
without any obstruction or contact between the tape and the gas
cooler itself. A closure cap (68) may optionally be provided to
maintain gas pressure within the tube. Preferably the gas is air
which is provided to the tube at about the 20 psi level.
A~ter the tapes of the instant invention have been
prepared, they may be formed into the desired shapes. In pract-
ice, the tapes are placed on a mold and arranged in an
orientation order dictated by the structural requirements of the
article being formulated. Usually some layers will be placed at
cross angles to each other in order to improve transverse
strength. The tapes are then heated to the desired temperature,
which is slightly above the melting point of the polymer material
which has been employed and pressure is applied to form a
consolidated article. The tapes or ar~icles prepared from ~he
crosshead die of t~.e instant invention may be reused after
formation by simply remelting the tapes and then reorienting
and/or reforming them.
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34
Example 1
A copolymer based upon LCP4060, manufactured by CelaneseSpecialty Operations, having a melting point of about 275 C.
and an average I.V. of about 4.0, was prepared in a reactor and
rendered in chip form. The polymer is a reaction product of 2,6-
hydroxy naphthanoic acid, terephthalic acid, and para-amino-
phenol. The polymer chip was then added to a ZSK model twin-
blade extruder operating at a temperature of about 300 C. The
~elted polymer from the extruder was fed into the barrel of a
crosshead die at the rate of 10 gms per second. The barrel
itself had ~een heated to and was maintained at approximately
310 C. throughout, as monitored by thermocouples attached to the
barrel. Within the barrel, the polymer was forced into upper and
lower flow channels and ultimately into the crosshead die itself,
entering the die at a 90 angle to the flow of the polymer was a
carbon fiber tow.
A carbon fiber tow was prepared by assembling on a grid
fifteen individual, small-sized fiber tows o~ carbon fiber having
an approximate fiber count of 6000 per bundle for a total of
90,000 individual fibers. The carbon fibers themselves were
prepared based upon acryloni~rile copolymers having a percent
elongatlon of 1.3 percent at room temperature and are known under
. the trade ~ of Celion. The 15 bundles were merged onto a
drive roll and fed through an air je~ spreading device which
uniformly spread the individual fiber tows into a single fiber
tow having a width of approximately 3 1/2i'. The air jet
spreading device contained a pair of V-shaped air impingement
slots, and air wa~ fed into. the devire at a pressure of 60 psi.
(The pressure inside the box was about 5 psi.) After air jet
spreading, the combined tow was fed into the crosshead die at the
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~2 ~
rate of approximately 0.3 meters per minute. Upon entering the
crosshead die, the fiber was deflected from its n~rmal path by a
stationary deflection bar located within the crosshe~d die. The
bar served to increase the tension of the fiber. Within the die
the fiber was forced into contact with the polymer coming from
~he extruder through the barrel. The polymer within the die was
maintained at approximately 315-320D CO The polymer was forced
into contact with the carbon fiber, from both above and below the
plane of the fiber. The resulting tape exited from the die
through compressed die lips to produce an impregnated fiber tape
having a width of approximately 3" and a thickness of about 3-5
mil.
Immediately after extrusion from the die, the tape was
air cooled in an air quench device which provided a flow of air
above ant below the tape. The air quench device was operated at
an internal air pressure of 1 atmosphere. The tape itself was
pulled from the die by a pair of rubber dri~en rolls and wound up
between sheets of paper onto a large roll. The resulting tape
was useful in preparing composite structures.
Example 2
Example 1 was repeated except that in place of ~he
Celion fiber a Hercules Co., Inte~mide Modulus CF,IM-6 carbon
fibers having an epoxy size was employed on 20 bsbbins. A
satisfactory tape useful in preparing composite s~ructures
resulted.
Example 3
Example 1 was repeated except that a high-strength
carbon fiber having a 1.7Z elongation at room temperature was
employed on 15 bobbins. The fiber is available from the Celanese
-2~- .
8~ 3 ~
Specialty Operations under the trade name of Celion. A satis-
factory tape resulted.
Example 4
Example 1 was repeated except that a copolymer
(LCP2000), a~ailable from the Celanese Specialty Operations,
based upon hydroxy benzoic acid and hydroxy naphthoic acid, was
obtained having a melting point of about 250 C. and an I.V. of
about 2.5 and rendered in chip form. The polymer was then added
to a ZSK model twin-blade extruder operating at a temperature of
about 260 C. The extruder was fed into the barrel of a
crosshead die. The barrel of the crosshead die was also hea~ed
to 26~ C. A tow was prepared as in Example 1, using a bobbin
rack and ten individual, small-sized fiber tows. The polymer in
the crosshead die itself was maintained at approximately 275 C.
Otherwise processing was the same as in Example 1. A
satisfactory tape was preparing using this process.
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