EP0156600A1 - Mélanges de différentes fibres - Google Patents

Mélanges de différentes fibres Download PDF

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Publication number
EP0156600A1
EP0156600A1 EP85301792A EP85301792A EP0156600A1 EP 0156600 A1 EP0156600 A1 EP 0156600A1 EP 85301792 A EP85301792 A EP 85301792A EP 85301792 A EP85301792 A EP 85301792A EP 0156600 A1 EP0156600 A1 EP 0156600A1
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Prior art keywords
fiber
tow
fibers
thermoplastic
intermixing
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German (de)
English (en)
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EP0156600B1 (fr
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Paul E. Mc Mahon
Tai-Shung Chung
Lincoln Ying
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Celanese Corp
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Celanese Corp
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    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/44—Yarns or threads characterised by the purpose for which they are designed
    • D02G3/446—Yarns or threads for use in automotive applications
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/22—Yarns or threads characterised by constructional features, e.g. blending, filament/fibre
    • D02G3/40—Yarns in which fibres are united by adhesives; Impregnated yarns or threads
    • D02G3/402—Yarns in which fibres are united by adhesives; Impregnated yarns or threads the adhesive being one component of the yarn, i.e. thermoplastic yarn

Definitions

  • This invention relates to a fiber tow and to a process for preparing it. Such tows are useful in forming composite articles. More particularly, this invention involves the use of fiber blends containing strong reinforcing fibers which are useful in preparing composite articles.
  • Fiber-reinforced products have been known for several years; see, for example, U.S. Patents Nos.3,914,499 3,969,171 and 4,214,931, as well as U.S. Patent No. 4,341,835.
  • U.S. Patent No. 4,226,079 discloses the combining of two different types of fibers in order to produce a bulk yarn.
  • the fibers are intermixed in a jet intermixing zone.
  • the fibers disclosed in the patent are polyester and poly- amid fibers. There is no indication of combining carbon and thermoplastic fibers.
  • U.S. Patent No. 3,175,351 discloses a method of bulking continuous filament yarns.
  • the two yarns which are combined may be of different compositions.
  • any of the yarns might be a carbon fiber yarn.
  • U.S. Patent No. 3,859,158 discloses the preparation of carbon fiber reinforced composite articles by forming an open weave of a carbon fiber and coating with a carbonaceous material.
  • U.S. Patent No. 4,368,234 discloses complex woven materials used for reinforcement which are formed from alternating bands of graphite fibers and low modulus fibers. The woven materials disclosed in this c patent are subsequently impregnated with a thermosetting resin and cured.
  • the invention provides a continuous fiber tow useful in forming composite articles which comprises an intimate blend of 90 to 30% by volume, based on the total fiber content, of a spun thermoplastic fiber having a melting point of at least 50°C. and 10 to 70% by volume, based on the total fiber content, of a non-thermoplastic reinforcing fiber.
  • the tows of the invention are capable of being formed into articles having a radius of curvature of at least 0.002 inch (0.05 mm).
  • the invention also provides a process of preparing a fiber tow which comprises:
  • the process of this invention involves (a) forming a fiber tow from a multitude of strong filamentary reinforcement materials; (b) forming a thermoplastic polymeric fiber tow;(c) intermixing the two tows; and (d) withdrawing the intermixed tows for use.
  • the filamentary reinforcing material is non-thermoplastic.
  • the intermixed tows may then be employed in forming various fiber-reinforced composites.
  • the fiber blends prepared according to the invention are flexible and handleable and have good draping properties, so that they can be used to form intricately shaped articles.
  • good wetting of the reinforcing fiber by the thermoplastic material is obtained when appropriate heat and pressure are applied to the mold.
  • Good wetting is obtained in large measure because of the substantially uniform distribution of the thermoplastic fiber and the reinforcing fiber within the fiber blend.
  • the products of the invention find particular utility in end-use applications where a small radius of curvature in the final product is desired. For example, using the prior art tapes, it was not possible in many instances to prepare articles which had 90° bend, because tapes would crack or deform at the bend line. However, the tows of the invention may be employed with radii or curvature as low as 0.002 in (0.05 mm).
  • thermoplastic polymers which are useful in carrying out the invention may belong to 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), polyether ether ketones, polybutylene terephthalate and the like.
  • the melting point of the polymer should generally be at least 50°F (28°C), preferably at least 200°F (111°C) above ambient temperature. Higher melting temperatures ensure that there will be no undue sticking or binding of the spun fibers prior to use.
  • mixtures of various thermoplastic polymers may also be employed to advantage where specific combinations of properties are desired.
  • liquid crystal polymers or LCP's- Examples of these polymers include the wholly aromatic polyester resins which are discussed in the following publications : (a) Polyesters of Hydroxybenzoic Acids, by Russell Gilkey and John R. Caldwell, J. of Applied Polymer Sci., Vol. II, Pages 198 to 202 (1959); (b) Polyarylates (Polyesters From Aromatic Dicarboxylic Acids and Bisphenols), by G.Bier, Polymer, Vo1.15, Pages 527 to 535 (March 1974): (c) Aromatic Polyester Plastics, by S.G.
  • polyesters and copolyesters which are preferred consist essentially of structural units having recurring groups of the formula and and/or wherein units I and II, if present, are present in substantially equimolar amounts;
  • R 1 ,R 2 and R 3 are radicals selected from (1) single and fused six-membered aromatic carbocyclic ring systems wherein the chain-extending bonds of the ring system, if attached to the same ring, are positioned 1,3- or 1,4- (preferably 1,4-) to each other,and if attached to different rings, are preferably in positions parallel and oppositely directed, and (2) multiple six-membered aromatic carboxcyclic ring systems in which the individual rings are joined by a chemical bond or a trans- vinylene group and in which the chain extending bonds of each ring are in the 1,3- or 1,4- (preferably 1,4-) positions;
  • R 2 may also be wherein A is a divalent radical containing one or two bicyclic in-chain atoms; and
  • R 3 may also be wherein the
  • R 2 is also intended to include one or more substituents, e.g., chloro, bromo, fluoro, or lower alkyl (1-4 carbon atoms) on the ring or rings.
  • the R 2 aromatic ring systems should preferably be unsubstituted when only one kind of unit I and one kind of unit II are used, i.e., when a homopolymer is formed to ensure obtaining oriented fibers. In the case of copolymers, it is preferred that the R 2 aromatic ring systems be unsubstituted because of thermal or hydrolytic instability and/or cost of the R 2 -ring substituted copolymers.
  • aromatic polymer-forming units i.e., units wherein the chain extending functional groups are attached to aromatic rings
  • a non-limiting list of these units includes and
  • the (co)polyesters may comprise units I and II in substantially equimolar 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 for use in the invention consist essentially of units I and II.
  • R 1 is selected from 1,4-phenyl-ene; chloro-, dichloro-,bromo-,dibromo-, methyl-,dimethyl- and fluoro-1,4-phenylene; 4,4'-biphenylene, 3,3',5,5' - tetra - methyl-4,4'-biphenylene and
  • R 2 is selected from trans-1,4-cyclohexylene; trans-2,5-dimethyl-1,4-cyclo- hexylene; trans-vinylenebis(l, 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.
  • the polymers consist essentially of the recurring units(x) wherein X is selected from chloro-,bromo-, fluoro-, and methyl radicals; n is 1 or 2; and Y is selected from 4,4'-biphenylene and 2,6-naphthylene, the ratio of units being within the range of 4:1 to 1:4.
  • the polymers consist essentially of the recurring units wherein Z is selected from 4,4'-biphenylene, 2,6-naphthylene, and 1,4-phenylene, the ratio of units being within the range of 4:1 to 3:2. With each type of polymer, up to 25 mol percent of non-conforming units may be present as described above.
  • a list of useful dicarboxylic acids includes,for example, terephthalic acid, 4,4'-bibenzoic acid, 4,4' - oxydibenzoic acid, 4,4' - thiodibenzoic acid, 4-carboxyphen- oxyacetic acid, 4,4'-trans-tilbenedicarboxylic acid, 2,6-naphthalene- dicarboxylic acid, ethyleneoxy-4,4'-dibenzoic acid, isophthalic acid, the halogen and methyl substituted derivatives of the foregoing dicarboxylic acids, 1,4-trans- cyclohexane- dicarboxylic acid, and 2,5-dimethyl-1, 4-trans- cyclohexanedi- carboxylic acid.
  • phenolic carboxylic acids includes 6-hydroxy-2-naphthoic acid, 4-hydroxy-4' carboxy azobenzene, ferulic acid, 4-hydroxybenzoic acid, 4-(4'hydro- xyphenoxy)- benzoic acid and 4-hydroxycinnamic acid and the alkyl, alkoxy and halogen substituted versions of these compounds.
  • the (co) polyesters are prepared preferably by melt polycondensation of derivatives of dihydric phenols and aromatic-aliphatic, aromatic and cycloaliphatic dicarboxylic acids or their derivatives.
  • a convenient preparative method is the melt polycondensation of the diacetate of a dihydric phenol with a dicarboxylic acid.
  • phenolic carboxylic acids or their derivatives may_be used as co-reactants in the preparation of polyesters and copolyesters.
  • a list of useful dihydric phenols preferably used in the form of their diacetate derivatives, includes, for example, hydroquinone, chlorhydroquinone, bromohydroquinone, methylhydroquinone, dimethylhydroquinone,dichlorohydroquinone, dibromohydroquinone,4,4'- oxydiphenol, 4,4'isopropylidenediphenol,4,4'-thiodiphenol,4,4'-biphenol,3,5,3',5'-tetramethyl-4,4'-bisphenol, 3,5,3'5'-tetrachloro-4,4'-biphenol,2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, and 4,4'-methylenediphenol,
  • anisotropic polymers by polymerizing methylacryloxy benzoic acid utilizing an alkali metal hydroxide and free radical initiators as described in U.S. Patents Nos. 4,112,212, 4,130,702,and 4,160,755.
  • Useful phenolic-carboxylic acid derivatives include, for example, p-acetoxybenzoic acid and p-acetoxy- cinnamic acid.
  • polyesters and copolymers includes : poly(methyl-1,4-phenylene, 2,5-demethyl- trans- hexahydroterephthalate); copoly(methyl-1-4-phenylene trans-hexahydroterephthalate/terephthalate) (8/2);copoly (chloro-1,4-phenylene trans-hexahydroterephthalate/isophthalate) (9/1) and (8/2); copoly(ethyl-1,4-phenylene terephthalate/-2,6-naphthalate) (7/3); copoly(tert.butyl-1,4-phenylene/-3,3',5,5'- tetramethyl-4,4'-biphenylene/terephthalate)(7/3); 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 involving reacting organic monomer compounds possessing functional groups which, upon condensation, form the requisite recurring moieties.
  • 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 compounds may be reacted in the absence of a heat exchange fluid via a melt acidolysis procedure. They accordingly may be heated initially to form a melt solution of the reactants with the reaction continuing as said polymer particles are suspended therein.
  • a vacuum may be applied to facilitate removal of volatiles formed during the final state of the condensation (e.g., acetic acid or water).
  • the organic monomer reactants from which the wholly aromatic polyesters are derived may be initially provided in a modified form 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 two to four carbon atoms.
  • the acetate esters of organic monomer reactants are provided.
  • an amine group may be provided as a lower acyl amide.
  • Representative catalysts which optionally may be employed in either the melt acidolysis procedure 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 dixoide, antimony trioxide, alkoxy titanium silicates, titanium alkoxides,alkali and alkaline earth metal salts of carboxylic acids (e.g. zinc acetate), the gaseous acid catalysts such as Lewis acids (e.g. BF 3 ), hydrogen halides (e.g. HC1), etc.
  • the quantity of catalyst utilized typically is 0.001 to 1 percent by weight based upon the total monomer weight, and most commonly 0.01 to 0.2 percent by weight.
  • the wholly aromatic polyesters and poly(ester-amide)s suitable for use in the present invention tend to be substantially insoluble in common polyester solvents and accordingly are not susceptible to solution processing. As discussed previously, they can be readily processed by common melt processing techniques. Most suitable wholly aromatic polymers are soluble in pentafluorophenol to a limited extent.
  • the wholly aromatic polyesters which are preferred for use in the present invention commonly exhibit a weight average molecular weight of 2,000 to 200,000,and preferably 10,000 to 50,000, and most preferably 20,000 to 25,000.
  • the wholly aromatic poly(ester-amide)s which are preferred for use in the present invention commonly exhibit a molecular weight of 5,000 to 50,000, and preferably 10,000 to 30,000; e.g., 15,000 to 17,000.
  • Such molecular weight may be deter- minded by gel permeation chromatography and other standard techniques not involving the dissolving of the polymer,e.g. by end group determination via infrared spectroscopy on compression molded films.
  • light scattering techniques in a pentafluorophenol solution may be employed to determine the molecular weight.
  • the wholly aromatic polyesters and poly(ester- amide)s commonly exhibit an inherent viscosity (I.V.) of at least 2.0 dl./g.,e.g.,2.0 to 10.0 dl./g.,when dissolved at a concentration of 0.1 percent by weight in pentafluorophenol at 600C.
  • I.V. inherent viscosity
  • the aromatic 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.
  • substituents 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.
  • Preferred 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 suitable for inclusion as a possible substituent on the aromatic rings.
  • thermoplastic materials with non-thermoplastic materials or materials having a sufficiently high melting temperature, whereupon effective bonding and integration can be achieved by application of heat and pressure sufficient to melt the thermoplastic material but not sufficient to melt the reinforcing material.
  • relatively high melting thermoplastic materials as reinforcing fibers is contemplated in the present invention, and such materials are referred to as "non-thermoplastic" throughout the specification and claims for the sake of brevity.
  • the reinforcing fibers useful herein are metallic or ceramic, amorphous, polycrystalline or single-crystal reinforcing fibers of filaments. Common examples are carbon, glass, boron and boron nitride, ceramic fibers, such as silicon carbide, silicon nitride and alumina,aramides, and ordered polymers.
  • the glass fibers utilized are manufactured and marketed commercially.
  • the fibers are drawn from a molten supply of glass contained in a platinum container having a large plurality of very fine holes in the bottom thereof from which the molten glass is drawn at high rates of speed which attenuate the glass into extremely fine diameter.
  • the glass filaments are pretreated as drawn from the platinum container, usually called a "bushing" with a size serving to enhance the compatability of the ultimate glass yarn with the thermoplastic fiber which is utilized.
  • glass fibers contemplated are continuous glass fibers in the form of unstranded filaments,stranded glass filaments,untwisted bundles of stranded glass filaments including twistless roving all hereinafter referred to as glass fibers.
  • Size compositions are contemplated herein and those preferred for use in the practice of the present invention are those conventionally used in the treatment of glass fibers.
  • Such size compositions contain, as the essential component, a glass fiber anchoring agent such as an organo silicon compound or a Werner complex compound.
  • Preferred anchoring agents are the amino silanes, such as gamma-aminopropyltriethoxy silane or N-(betaamino- ethyl)- gamma-aminopropyltriethoxy silane.
  • amino silanes such as gamma-aminopropyltriethoxy silane or N-(betaamino- ethyl)- gamma-aminopropyltriethoxy silane.
  • suitable anchoring agents which can be used in the practice of this invention are the organo silicons and their hydrolysis products and polymerization products (polysiloxane).
  • Suitable Werner complex compounds include stearato chromic chloride,metha- crylato chromic chloride, aminopropylato chromic chloride, glycine chromic complex or glyclato chromic chloride.
  • Ceramic fibers contemplated for use herein include silicon carbide (composed of ultrafine beta-SiC crystals), silicon nitride (Si 3 N 4 ) and alumina (A1 2 0 3 ) fibers.
  • any silicon carbide fiber system with the requisite strength can be used, although a multi-filament silicon carbide yarn with an average filament diameter up to 50 microns is preferred and yarn with average filament diameter of 5 to 15 microns is especially preferred. If a silicon carbide monofilament is used, a typical silicon carbide monofilament of approximately 140 microns diameter is available from AVCO Systems Divisions, Lowell, Mass. This fiber exhibits an average tensile strength of up to 3450 MPa, has a temperature capability of over 1300°C. and is stable in oxidizing environments.
  • Alumina fibers have been available for several years. They have been of particular interest for application in metal matrix composites because of their excellent strength and modulus, especially at high temperature.
  • the two principal types of alumina fiber were the large diameter (>350 ⁇ ) single crystal rods or alumina whiskers.
  • the problems of handling and processing whiskers and the very high cost of the single crystal fiber dampened the enthusiasm for their use in composites.
  • these fibers are produced by E.I. DuPont de Nemours, Inc. and 3M Corporation in the USA and Sumitomo Chemicals Co.in Japan.
  • the DuPont fiber is a round cross section, 20 ⁇ m diameter, continuous length yarn having 210 fibers per tow. It is available in two forms. Type I is pure alpha alumina while Type II is similar but coated with a thin layer of glass. Type II was originally intended for resin matrix composites and Type I for metal matrix composites; however, it is found by this invention that both are suitable for ceramic composites. Although the initial fiber strength is not particularly high, of the order of 1380 MPA (200,000 psi), it is very important to note that this strength is stable and not affected by handling and is not very different from that realized in composites reinforced with alumina rods of initially higher unhandled "pristine" strength.
  • the Sumitomo Chemicals fiber is also produced in yarn form; however, there the similarity with fiber FP ends.
  • This fiber is not pure alumina and, in fact, it is the presence of some SiO 2 and a very fine structure which permit a claimed use temperature to be 1350°C.
  • this fiber On the basis of specific mechanical properties this fiber is attractive. Its low density and high tensile strength provide a specific strength nearly twice that of fiber FP while the specific modulus approximately equals the FP property. The Sumitomo fiber appears to have superior handleability.
  • boron nitride properties such as exceptionally high heat resistance (1800°F. in oxidizing 5000°F. in reducing atmospheres),dielectric strength (950 v./mil), high surface and volume resistivity and low dissipation factor over a wide temperature range, make it potentially attractive high temperature reinforcing fiber candidate.
  • the fibers may vary in diameter, although those preferred are about 10 microns in diameter and fibers having diameters up to 30 microns may be used.
  • Continuous boron nitride fibers (99+% boron nitride) are available commercially from the Carborundum Corporation.
  • the reinforcing fibers which are particularly useful herein have bundle or tow deniers in the range of from 1 to 100,000 and filament counts of from 300 to 300,000, preferably deniers of 1000 to 16,000 and filament counts of 3,000 to 24,000.
  • the fibers also should exhibit a tensile strength of at least 100,000 psi (689 000 kPa) and a tensile modulus of 10 to 120 x 10 6 psi (68.9 to 826.8 x 10 6 kPa).
  • thermoplastic fibers which are particularly useful herein have bundle cross-sectional areas ranging from twice that of the reinforcing fiber tows to half that of the reinforcing fiber tow.
  • Bundle or tow denier will be in the range of 1 to 50 and the fiber count will depend upon single filament denier (higher counts are required with lower denier filaments). However, in general, from 10 to 150,000 filaments, preferably 100 to 10,000 filaments, are employed.
  • the modulus of the fiber should be in the range of 50,000 to 500,000 psi (344500 to 3445000 kPa).
  • the thermoplastic fiber should also exhibit a melting point which is at least 50°F (28°C), preferably at least 200°F (111°C), above ambient temperatures. And of course, the fiber should melt and fuse at temperatures no higher than 1,000°F (538°C), preferably no higher than 800°F (427°C), in order to be useful herein.
  • the weight ratio of the two fibers which are intermixed can vary widely. However, in order to prepare satisfactory composites, it is necessary that sufficient thermoplastic polymer fiber be employed to obtain complete wetting of the reinforcing fibers. Generally, no less than 30 percent, by volume, of the thermoplastic polymer fibers may be employed. The maximum amount of thermoplastic polymer depends upon the strength properties which are required. In general, when less than ten percent, by volume of the reinforcing fiber is present, the resulting composite products have strength and stiffness properties which are poor in relation-tc products containing higher amounts of reinforcing fibers and exhibit little or no improvement over unreinforced matrices. Preferably 20 to 60 percent, by volume, of the reinforcing fiber materials should be present in the combined tow.
  • the reinforcing fiber and the thermoplastic fibers which are used herein it is contemplated to add carbon fibers to the fiber blends of the invention as reinforcing fibers. In the event additional carbon fibers are added, it is possible to reduce the amount of the reinforcing fiber which is used to as low as 10 volume percent. However, the maximum combined amount of the added carbon fiber plus the amount of the reinforcing fiber which is employed should not exceed the upper limit specified above for the reinforcing fiber alone.
  • a reinforcing fiber tow (1) is obtained having the properties specified above.
  • the fibers from the reinforcing fiber tow are passed through a fiber gales (3) and onto a first Godet roll (4).
  • the first Godet roll is synchronized with a second Godet roll(ll) at rates of speed such that the second Godet roll revolves slightly slower than the first Godet roll.
  • the fibers between the two Godet rolls, which are subsequently spread and intermixed during the process of the invention remain in a low tensioned (approaching tension-free) state which provides for effective fiber intermixing.
  • thermoplastic polymer fibers such as polybutylene terephthalate fibers
  • a tension comb may be employed after the fibers leave the bobbin and before they are brought into contact with the Godet roll. This tension comb serves to improve the contact of the fiber with the Godet roll and to increase the width of the fiber tow.
  • the gas banding jets showing In FIGS. 3 and 4 is used to uniformly spread the fiber tows.
  • a gas "banding" jet can also be used as an intermixing means whereby the gas jet serves to uniformly intermix the two fiber tows.
  • the banding jet consists of a gas box (40) into which compressed air or another gas is fed through a conventional adjustable gas metering means (41).
  • the preferred pressure of gas flow into the gas jet is in the range of 0.5 to 10 psi (3.45 to 68.9 kPa).
  • One or more than one, gas exit ports (44) are provided to cause gas from within the gas box to impinge in a generally perpendicular fashion upon the fiber tow which passes across the exit ports.
  • the exit ports are V-shape-d and pointed in the direction of movement of the fiber tow across the box.
  • the gas banding jet is provided with shims (46) or other means to allow a gas box cover (48) to be attached,so that a flow channel for the fibers is provided.
  • the gas box cover is held in place by convenient attachment means, such as clamps (49).
  • both the thermoplastic fiber and the reinforcing fiber are subject to gas banding jet treatment (26) and (27).
  • gas banding jet treatment 26) and (27).
  • a fiber comb having a plurality of spaced-apart fingers as described above, may be employed in place of the banding jet.
  • the intermixing means is a pair of stationary rods or bars.
  • the fibers from the spread reinforcement fiber tow and the fibers from the spread thermoplastic tow or yarns both initially come into contact together on the bottom of the first stationary rod or bar.
  • the fibers then are deflected across the top of the second stationary bar or rod and, as a result, are intermixed.
  • both fibers be uniformly spread across their entire width and that the area within which both fibers are spread be virtually identical.
  • intermixing be undertaken in a relatively tension-free state. If high tension is imparted to either of the fiber tows,full (or optimal)intermixing may not occur.
  • the combined fiber tow may be further intermixed using an air entanglement jet as described above.
  • the fibers After intermixing, the fibers pass through a comb (9) to maintain dimensional stability and through twist guides (10) to impart a slight twist to the intermixed fibers.
  • the twist is imparted in order to maintain the intermixing of the fibers.
  • false-twisting of the fibers using methods well known in the art may be employed.
  • a fiber wrap may be used to hold the intermixed fibers together.
  • the overwrap may be of any convenient type of fiber. However,it is preferred that the overwrap consist of a relatively small quantity of thermoplastic fibers.
  • the mixed fibers are then wrapped around a second Godet roll (11) which, as pointed out above, serves in conjunction with the first Godet roll to provide a relatively tension-free zone to allow fiber intermixing.
  • the fibers are then taken up by a take-up roll (12) for storage.
  • a take-up roll (12) for storage.
  • the intermixed fibers may be made stable by application of an appropriate fiber finish which serves to hold the intermixed fibers together and enable easier handling in subsequent operations, such as weaving.
  • FIG.2 is similar to FIG.1 but is the process most preferred when a liquid crystal type of polymer or other higher melting point polymer is used.
  • a roll of reinforcing filamentary material (21) feeds fiber through tension comb (22) and onto Godet roll (25).
  • Liquid crystal fibers from a roll (23) are fed through a guide (24) and onto the same Godet roll (25). Separation is maintained between both fibers on the Godet roll.
  • the first Godet roll (25) when used in combination with the optional second Godet roll (35), serves to maintain the fibers in a relatively tension-free state during the intermixing process. High tension during intermixing must be avoided to assure that complete intermixing occurs.
  • the reinforcing fibers and the liquid crystal fibers leave the first Godet roll they are both fed into gas banding jets (26) and-(-27) through guides (28) and_(29), respectively.
  • the fibers are spread to a uniform width.
  • the fibers then pass through a second set of fiber guides (30) and (31) and are intermixed using stationary,longitudinally extended bars shown at (32).
  • intermixing occurs as the thermoplastic bundle is fed onto the same bar in the same areas as is the reinforcement fiber.
  • the width of both tows is the same, and as they are brought simultaneously into contact with the same area of the bar, intimate intermixing occurs.
  • the two fiber tows are fed simultaneously into a gas jet or other gaseous intermixing device in a relatively tension-free state.
  • the fibers may be fed into a gas jet for further intermixing after they have been treated on the stationary bars.
  • the gas intermixing means a jet of air impinges on the fibers, preferably perpendicular to their direction of flow.
  • the fibers are fed through twist guides (33) to add at least a half-twist per yard to the fiber to ensure dimensional stability. Fibers then pass through a guide (34) onto a second Godet roll (35) and from there onto a take-up roll (36).
  • the intermixed fibers may be filament wound, or otherwise assembled and placed on a mold, and heated under pressure to the flow temperature of the thermoplastic polymer to form composite articles which are useful in a variety of end-uses where high strength, high stiffness and low weight are essential.
  • the composites formed from products prepared according to this invention may be used in forming spacecraft, airplane or automobile structural components.
  • the reinforced fiber blends of the instant invention find particular utility in those end-uses where complex, three-dimensional shapes are involved.
  • the compositions of the instar.t invention are particularly useful where there is a small radius of curvature requiring substantial bending and shaping cf the compositions of the instant invention.
  • the only limiting factor in forming reinforced fiber shaped articles using the compositions of the instant invention is the"bendability" of the reinforcing fiber itself.
  • compositions of the invention it is possible to prepare materials having a minimum radius of curvature of 0.002 in (0.05 mm), preferably as low as 0.003 in.(0.08 mm).
  • the minimum radius of curvature is about 0.005 in. (0.13 mm).
  • fiber directionality or alignment is distorted.
  • structural elements formed from the fiber tows of this invention are heated under pressure above the melting point of the thermoplastic fiber, these fibers melt and fuse the fibers together forming a consolidated composite product containing well-dispersed reinforcing fibers.
  • recreational articles such as tennis racquet frames, racquetball racquet frames, hockey sticks, ski poles, fishing rods and golf club shafts.
  • the fibers of the invention find particular utility in filament winding applications.
  • the prior art employed the filament winding process with success this process was limited to use of reinforcing fibers in combination with thermosetting resins if long, thin rods were to be prepared.
  • the reinforcing fiber was wound onto a mold after applying a thermosetting coating or coated with the thermosetting material after winding. As a result, however, it was often difficult for the thermosetting material actually to penetrate and/or achieve good wetting of closely wound products.
  • thermoplastic polymers in conjunction with fiber reinforcements.
  • This modified filament winding process begins with the use of the intermixed tows of the invention. These tows may be fed directly to a filament winder. As the filament winder moves around or up and down the mandrel or form, the reinforcement fiber/thermoplastic fiber tow is applied directly to the mold and heated using a radiant heater or other suitable means for immediately melting and fusing the thermoplastic polymeric fibers within the reinforcing fiber tow.
  • the reinforcing fiber/thermoplastic fiber tow should be heated under pressure as soon as or soon after it meets the mandrel.
  • the mandrel either may be dissolved using a suitable solvent, may be pulled from the product, or the mandrel may actually become a part of the product.
  • the fiber blends prepared according to the invention is in forming woven fabrics utilizing standard techniques.
  • the tow of the instant invention is used either alone or in combination with other tows or fibers to form a woven mat.
  • the woven fabrics prepared according to the process of this invention may be applied to the desired mold or otherwise used in forming a composite.
  • the previous method of choice of forming such materials involved laying down a layer of reinforcing fibers, e.g. glass fibers, followed by a layer of thermcplastic film, followed by another layer of glass, etc. Now the materials can be combined in a solid woven layer and much more readily applied to a mold.
  • the strength and stiffness enhancement can occur in one or more directions, i.e., those directions along which reinforcement fiber is aligned parallel to the defining vector.
  • a liquid crystal polymeric (LCP) fiber tow based upon a copolymer prepared from 6-hydroxy-2-naphthoic acid and p-hydroxy benzoic acid is obtained.
  • the LCP has a density of 1.4 g/cc, and the tow itself is formed of 660 filaments (2.25 denier per filament).
  • the tow had an initial modulus of 5670 gms, a tenacity of 10.5 g/denier, and an elongation of 2%.
  • the second fiber to be used for intermixing with the LCP fiber is E-glass fiber (204 filament count designated as ECG 150 1/0), having a density of 2.55 g/cc, a tensile strength of 300,000 psi (2067000 kPa), a tensile modulus of 10,500,000 psi (72345000 kPa) and an ultimate elongation of 2.8%.
  • the glass fiber is available from both PPG Industries and OCF.
  • Bobbins containing the LCP polymeric fiber tow and the glass fiber tow are spaced apart on a bobbin rack. Fibers from both bobbins are fed onto and separately wrapped around a Godet roll, so that upon mixing the mixed tow contains approximately 50% by volume of liquid crystal poly- n.er and approximately 50% by volume of glass.
  • the LCP polymeric fiber is subject to a 50 gram weight on a tensioning device prior to being wrapped around the Godet roll, in order to maintain smooth tracking on the roll.
  • both fibers are separately subjected to air jet banding treatments utilizing an air jet which impinges air approximately perpendicular to the fiber through V-shaped nozzles.
  • the jet for the liquid crystal polymer is operated at 5 psi (34.45 kPa), while the glass fiber jet was operated at 4 psi (27.56 kPa).
  • the fibers are brought together over the top and underneath of two parallel, longitudinally extended, staggered stationary bars and are fed through fiber guides into an entanglement jet, which is similar in design to the gas banding jet and operated at a gas pressure of 7 psi (48.23 kPa).
  • the fibers are taken up on a take-up roll at a take-up speed of 7-8 m/min.
  • the composite panels (3.5" x 10")(90 x 250 mm) are prepared using 20 layers of the intermixed fiber tow. Each layer is prepared by first wrapping a heated drum with a Kapton film and then filament winding parallel rows on the fiber blend prepared above onto the Kapton wrapped drum. A layer of Kapton film is then placed over the drum, and the entire wrapped drum is heated so as to temporarily fuse the fibers together.
  • the composite containing the 20 fused layers is placed in a pressure mold, heated to about 315°C. and held at this temperature for five minutes without application of significant mold pressure.
  • the mold pressure is then increased to 500 psi (3445 kPa) and held at about 315c temperature and under such increased pressure for thirty minutes.
  • the material is then cooled at 70°C. and removed from the mold.
  • the resulting material contains about 50% by volume of E-glass fiber and has a panel thickness of about 0.103" (2.62 mm).
  • a six-ply 3.5" x 10" (90 x 250 mm) composite panel is prepared having a glass fiber volume of about 60%, a panel thickness of about 0.035" (0.89 mm).
  • the composites are evaluated and exhibit excellent tensile, flexural and compression properties.
  • polybutylene terephthalate (PBT) glass fiber blend Utilizing the same glass fiber as described in Example 1, an approximate 50% by volume polybutylene terephthalate (PBT) glass fiber blend is prepared.
  • the polybutylene terephthalate material has a density of 1.34 g/cc and a denier of 1520 g/9000m.
  • the polybutylene terephthalate has a draw ratio of 2.25-1, an initial modulus of 24 g, a tenacity of 5.3 g/denier, an elgonation of 28%, a melting point of 227°C. and a denier per filament of 2.7.
  • Ten packages of 33 filament count yarn are employed on a creel, and all packages are merged into a single polybutylene terephthalate fiber tow on a Godet roll. Maintained separately, but on the same Godet roll, ten packages of 408 filament count glass fiber(Type ECK 75 2/1) to provide a total approximate blend of 50/50 by volume glass fiber/PBT.
  • the polybutylene terephthalate tow is fed through a fiber comb having approximately 30 teeth, while the glass fiber tow is fed through a gas banding jet operating as described in Example 1, at a pressure of 2.5 to 3.5 psi (17.23 to 24.12 kPa).
  • the two tows are then intermixed over and under parallel extending rods by feeding both tows into the same area on the bars. Intermixing is aided by the use of a second gas banding jet of the type described in Example 1, operating at 2.5 to 3.5 psi (17.23 to 24.12 kPa).
  • the fibers After leaving the banding jet, the fibers are fed through a second fiber comb which was arranged parallel to the direction of flow of the fiber, so as to provide a tensioning path to aid in intermixing. After leaving the comb, the fibers are fed through twist guides to provide approximately a half twist per yard (per 0.9 m), so as to maintain the fibers in their intermixed state. The fibers are then wrapped around a second Godet roll and taken up at a speed of 7-8 m/min. In order to minimize tension during the intermixing process, the second Godet roll is operated at a slightly lower speed than the first Godet roll.
  • a sample of the PBT/glass fiber blend prepared above is wrapped with 90 denier polybutylene terephthalate yarn as described above at four wraps per in (per 2.5 cm) to form a compact yarn suitable for fabric weaving.
  • the PBT fabric wrap is chosen, so that it would form a part of the matrix upon composite fabrication.
  • the resulting wrapped yarn is then divided into 96 different yarn segments and placed on spools mounted on a special creel.
  • a 6" (152 mm) wide fabric is then woven on a modified Draper XD loom, using a plain weave pattern.
  • the resulting woven product has dimensions of 16 ends per inch (per 25.4 mm) x 15 picks per inch (per 25.4 mm) and weighs ca.
  • the fabric is ca.10 mils (0.25 mm) in thickness, is soft but compact, and exhibits good dimensional stability. Satisfactory fiber composites having irregular shapes are prepared from the resulting fabric.
  • An approximate 50/50% by volume blend is prepared based upon the glass fiber described in Example 1 and a polyether ether ketone (PEEK) thermoplastic polymer.
  • the fiber prepared from the PEEK has a density of 1.3 g/cc, a melting point of 338°C., an initial modulus of 53 grams, a tenacity of 2.7 g/denier, an elongation of 65%, and in 10 filaments per package tows a dpf of 367 (g/9000m).
  • Four (10 filaments per package) tows are placed on a creel and the fibers are blended together on a Godet roll, but maintained separately from the glass fiber which is also wrapped around the Godet roll.
  • the PEEK fiber is then directed through a fiber comb as described in Example 2 and into a gas banding jet.
  • the glass fiber after leaving the Godet roll also enters a gas banding jet. Both jets are operating at a pressure of about 3 psi (20.7 kPa). After leaving the jets the fibers are intermixed above and below two parallel, longitudinally extended rods and are fed through a second parallel fiber comb, twisted to maintain dimensional stability, fed over a second Godet . roll and taken up at a speed of 7-10 m/min. A satisfactory composition results.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Textile Engineering (AREA)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
EP19850301792 1984-03-15 1985-03-14 Mélanges de différentes fibres Expired EP0156600B1 (fr)

Applications Claiming Priority (6)

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US58992984A 1984-03-15 1984-03-15
US58993084A 1984-03-15 1984-03-15
US58992884A 1984-03-15 1984-03-15
US589929 1984-03-15
US589930 1984-03-15
US589928 1990-10-01

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EP0156600B1 EP0156600B1 (fr) 1988-05-11

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Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0351201A2 (fr) * 1988-07-13 1990-01-17 Hoechst Celanese Corporation Fil mixte non rétrécissable
FR2634790A1 (fr) * 1988-07-29 1990-02-02 Schappe Sa Fils hybrides pour materiaux composites a matrice thermoplastique et leur procede d'obtention
EP0383953A1 (fr) * 1988-09-02 1990-08-29 Gunze Limited Procédé pour le façonnement thermique et tricot à utiliser dans un tel procédé
FR2653142A1 (fr) * 1989-10-16 1991-04-19 Chaignaud Ind Materiau composite et son procede de realisation.
US5076872A (en) * 1985-12-09 1991-12-31 Fuji Standard Research, Inc. Process for preparing a flexible composite material
EP0466618A1 (fr) * 1990-07-13 1992-01-15 Sa Schappe Fil hybride pour matériaux composites à matrice thermoplastique et procédé pour son obtention
EP0486884A1 (fr) * 1990-11-20 1992-05-27 Cytec Technology Corp. Procédé pour la production de fil hybride
EP0542070A1 (fr) * 1991-11-14 1993-05-19 Cytec Technology Corp. Fil hybride de fibres en polyamide et de fibres de renforcement
EP0717133A2 (fr) 1994-12-16 1996-06-19 Hoechst Aktiengesellschaft Fabrication et utilisation d'un matériau textile retrécissable et retréci, mis en forme de manière permanente et réalisé à partir d'un fil hybride
US5792555A (en) * 1995-04-10 1998-08-11 Hoechst Aktiengesellschaft Hybrid yarn and permanent deformation capable textile material produced therefrom, its production and use
WO2003002798A1 (fr) * 2001-06-28 2003-01-09 Owens Corning Co-texturation de fibres renforcees et de fibres thermoplastiques
US6820406B2 (en) 2001-05-14 2004-11-23 Cargill, Incorporated Hybrid yarns which include plant bast fiber and thermoplastic fiber, reinforcement fabrics made with such yarns and thermoformable composites made with such yarns and reinforcement fabrics
US6833399B2 (en) 2001-09-21 2004-12-21 Cargill, Limited Flowable flax bast fiber and flax shive blend useful as reinforcing agent
WO2005090662A2 (fr) * 2004-03-18 2005-09-29 Diolen Industrial Fibers B.V. Procede de melange de fils continus
US20140335355A1 (en) * 2006-05-22 2014-11-13 Innegra Technologies, Llc Hybrid Composite Yarn

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DE2166629A1 (de) * 1970-03-13 1974-12-12 Brunswick Corp Verfahren zum herstellen eines stapelfasergarns mit antistatischen eigenschaften
JPS5149948A (en) * 1974-10-23 1976-04-30 Kuraray Co Fukugoshino seizoho
US3978267A (en) * 1970-05-20 1976-08-31 Imperial Chemical Industries Limited Compact twistless textile yarn comprising discontinuous fiber bonded by potentially adhesive composite fibers
US4051660A (en) * 1974-07-15 1977-10-04 Akzona Incorported Yarns and their method of manufacture
GB2090882A (en) * 1980-12-31 1982-07-21 Valeo Glass fibre yarns
BE894875A (nl) * 1982-10-29 1983-02-14 Luxilon Ind Co Thermoplastisch textielmateriaal

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Publication number Priority date Publication date Assignee Title
DE2166629A1 (de) * 1970-03-13 1974-12-12 Brunswick Corp Verfahren zum herstellen eines stapelfasergarns mit antistatischen eigenschaften
US3978267A (en) * 1970-05-20 1976-08-31 Imperial Chemical Industries Limited Compact twistless textile yarn comprising discontinuous fiber bonded by potentially adhesive composite fibers
US4051660A (en) * 1974-07-15 1977-10-04 Akzona Incorported Yarns and their method of manufacture
JPS5149948A (en) * 1974-10-23 1976-04-30 Kuraray Co Fukugoshino seizoho
GB2090882A (en) * 1980-12-31 1982-07-21 Valeo Glass fibre yarns
BE894875A (nl) * 1982-10-29 1983-02-14 Luxilon Ind Co Thermoplastisch textielmateriaal

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5076872A (en) * 1985-12-09 1991-12-31 Fuji Standard Research, Inc. Process for preparing a flexible composite material
EP0351201A3 (fr) * 1988-07-13 1991-01-09 Hoechst Celanese Corporation Fil mixte non rétrécissable
EP0351201A2 (fr) * 1988-07-13 1990-01-17 Hoechst Celanese Corporation Fil mixte non rétrécissable
FR2634790A1 (fr) * 1988-07-29 1990-02-02 Schappe Sa Fils hybrides pour materiaux composites a matrice thermoplastique et leur procede d'obtention
EP0354139A1 (fr) * 1988-07-29 1990-02-07 Sa Schappe Fils hybrides pour matériaux composites à matrice thermoplastique et leur procédé d'obtention
EP0383953A1 (fr) * 1988-09-02 1990-08-29 Gunze Limited Procédé pour le façonnement thermique et tricot à utiliser dans un tel procédé
EP0383953A4 (en) * 1988-09-02 1991-03-13 Teijin Limited Sheet for reinforcing material
FR2653142A1 (fr) * 1989-10-16 1991-04-19 Chaignaud Ind Materiau composite et son procede de realisation.
EP0424215A1 (fr) * 1989-10-16 1991-04-24 Société Industrielle des Ets L.A. CHAIGNAUD-S.I.L.A.C. Matériau composite, son procédé de réalisation et utilisation dudit matériau
EP0466618A1 (fr) * 1990-07-13 1992-01-15 Sa Schappe Fil hybride pour matériaux composites à matrice thermoplastique et procédé pour son obtention
FR2664621A1 (fr) * 1990-07-13 1992-01-17 Schappe Sa Fil hybride pour materiaux composites a matrice thermoplastique et procede pour son obtention.
US5910361A (en) * 1990-07-13 1999-06-08 Sa Schappe Hybrid yarn for composite materials with thermoplastic matrix and method for obtaining same
EP0486884A1 (fr) * 1990-11-20 1992-05-27 Cytec Technology Corp. Procédé pour la production de fil hybride
EP0542070A1 (fr) * 1991-11-14 1993-05-19 Cytec Technology Corp. Fil hybride de fibres en polyamide et de fibres de renforcement
US5688594A (en) * 1994-12-16 1997-11-18 Hoechst Aktiengesellschaft Hybrid yarn
EP0717133A2 (fr) 1994-12-16 1996-06-19 Hoechst Aktiengesellschaft Fabrication et utilisation d'un matériau textile retrécissable et retréci, mis en forme de manière permanente et réalisé à partir d'un fil hybride
US5792555A (en) * 1995-04-10 1998-08-11 Hoechst Aktiengesellschaft Hybrid yarn and permanent deformation capable textile material produced therefrom, its production and use
US6820406B2 (en) 2001-05-14 2004-11-23 Cargill, Incorporated Hybrid yarns which include plant bast fiber and thermoplastic fiber, reinforcement fabrics made with such yarns and thermoformable composites made with such yarns and reinforcement fabrics
WO2003002798A1 (fr) * 2001-06-28 2003-01-09 Owens Corning Co-texturation de fibres renforcees et de fibres thermoplastiques
US6715191B2 (en) 2001-06-28 2004-04-06 Owens Corning Fiberglass Technology, Inc. Co-texturization of glass fibers and thermoplastic fibers
US6833399B2 (en) 2001-09-21 2004-12-21 Cargill, Limited Flowable flax bast fiber and flax shive blend useful as reinforcing agent
WO2005090662A2 (fr) * 2004-03-18 2005-09-29 Diolen Industrial Fibers B.V. Procede de melange de fils continus
WO2005090662A3 (fr) * 2004-03-18 2005-11-24 Diolen Ind Fibers Bv Procede de melange de fils continus
US20140335355A1 (en) * 2006-05-22 2014-11-13 Innegra Technologies, Llc Hybrid Composite Yarn

Also Published As

Publication number Publication date
DE3562637D1 (en) 1988-06-16
EP0156600B1 (fr) 1988-05-11
CA1294772C (fr) 1992-01-28

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