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WO1992002444A1 - Amelioration de la resistance a la compression de fibres par contrainte radiale - Google Patents

Amelioration de la resistance a la compression de fibres par contrainte radiale Download PDF

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Publication number
WO1992002444A1
WO1992002444A1 PCT/US1991/005407 US9105407W WO9202444A1 WO 1992002444 A1 WO1992002444 A1 WO 1992002444A1 US 9105407 W US9105407 W US 9105407W WO 9202444 A1 WO9202444 A1 WO 9202444A1
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WO
WIPO (PCT)
Prior art keywords
core
fibers
fiber
resin
percent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US1991/005407
Other languages
English (en)
Inventor
Harvey D. Ledbetter
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dow Chemical Co
Original Assignee
Dow Chemical Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dow Chemical Co filed Critical Dow Chemical Co
Priority to CA002088580A priority Critical patent/CA2088580A1/fr
Publication of WO1992002444A1 publication Critical patent/WO1992002444A1/fr
Priority to KR1019930700354A priority patent/KR930701338A/ko
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65H—HANDLING THIN OR FILAMENTARY MATERIAL, e.g. SHEETS, WEBS, CABLES
    • B65H81/00—Methods, apparatus, or devices for covering or wrapping cores by winding webs, tapes, or filamentary material, not otherwise provided for
    • B65H81/06—Covering or wrapping elongated cores
    • D—TEXTILES; PAPER
    • D07—ROPES; CABLES OTHER THAN ELECTRIC
    • D07B—ROPES OR CABLES IN GENERAL
    • D07B1/00—Constructional features of ropes or cables
    • D07B1/02—Ropes built-up from fibrous or filamentary material, e.g. of vegetable origin, of animal origin, regenerated cellulose, plastics
    • D07B1/04—Ropes built-up from fibrous or filamentary material, e.g. of vegetable origin, of animal origin, regenerated cellulose, plastics with a core of fibres or filaments arranged parallel to the centre line
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/06—Fibrous reinforcements only
    • B29C70/10—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres
    • B29C70/16—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of substantial or continuous length
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/06—Fibrous reinforcements only
    • B29C70/10—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres
    • B29C70/16—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of substantial or continuous length
    • B29C70/20—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of substantial or continuous length oriented in a single direction, e.g. roofing or other parallel fibres
    • B29C70/202—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of substantial or continuous length oriented in a single direction, e.g. roofing or other parallel fibres arranged in parallel planes or structures of fibres crossing at substantial angles, e.g. cross-moulding compound [XMC]
    • 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
    • D02G3/36—Cored or coated yarns or threads
    • 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
    • D—TEXTILES; PAPER
    • D07—ROPES; CABLES OTHER THAN ELECTRIC
    • D07B—ROPES OR CABLES IN GENERAL
    • D07B1/00—Constructional features of ropes or cables
    • D07B1/02—Ropes built-up from fibrous or filamentary material, e.g. of vegetable origin, of animal origin, regenerated cellulose, plastics
    • D07B1/025—Ropes built-up from fibrous or filamentary material, e.g. of vegetable origin, of animal origin, regenerated cellulose, plastics comprising high modulus, or high tenacity, polymer filaments or fibres, e.g. liquid-crystal polymers
    • D—TEXTILES; PAPER
    • D07—ROPES; CABLES OTHER THAN ELECTRIC
    • D07B—ROPES OR CABLES IN GENERAL
    • D07B5/00—Making ropes or cables from special materials or of particular form
    • D07B5/06—Making ropes or cables from special materials or of particular form from natural or artificial staple fibres
    • D07B5/08—Making ropes or cables from special materials or of particular form from natural or artificial staple fibres agglutinated by adhesives
    • D—TEXTILES; PAPER
    • D07—ROPES; CABLES OTHER THAN ELECTRIC
    • D07B—ROPES OR CABLES IN GENERAL
    • D07B2205/00—Rope or cable materials
    • D07B2205/20—Organic high polymers
    • D07B2205/201—Polyolefins
    • D07B2205/2014—High performance polyolefins, e.g. Dyneema or Spectra
    • D—TEXTILES; PAPER
    • D07—ROPES; CABLES OTHER THAN ELECTRIC
    • D07B—ROPES OR CABLES IN GENERAL
    • D07B2205/00—Rope or cable materials
    • D07B2205/20—Organic high polymers
    • D07B2205/2046—Polyamides, e.g. nylons
    • D07B2205/205—Aramides
    • D—TEXTILES; PAPER
    • D07—ROPES; CABLES OTHER THAN ELECTRIC
    • D07B—ROPES OR CABLES IN GENERAL
    • D07B2205/00—Rope or cable materials
    • D07B2205/20—Organic high polymers
    • D07B2205/2096—Poly-p-phenylenebenzo-bisoxazole [PBO]

Definitions

  • the present invention relates to fibers and matrix composites which contain them.
  • Composites contain a matrix resin that contains and is supported by a reinforcing fiber.
  • reinforcing fiber is usually one with a high tensile strength and/or tensile modulus.
  • reinforcing fibers include some carbon fibers, aramid fibers (commercially available under the trademark KevlarTM from E.I. DuPont de Nemours & Co.): highlyoriented polyethylene fibers (commercially available under trademark SpectraTM from Allied-Signal Corp.); and polybenzazole fibers.
  • Fibers that have a high tensile strength typically have a relatively low compressive strength, and vice-versa.
  • the compressive strength of fibers with high tensile strength is seldom more than 30 percent of tensile strength, and is frequently much less. They also frequently have a very low compressive strain-tofailure ratio, requiring little work to cause
  • U.S. Patent 4,499,716 (February 19, 1985) teaches that compressive strength may be improved by wrapping a thick core of high tenacity fiber, which is. typically solidified into a bar by impregnating with epoxy resin and curing prior to wrapping, with a helical wrapping of high tenacity yarn under very high tension. such that the core is under at least C.1 percent radial compression.
  • the structures taught in the patent are stiff and inflexible. Flexibility is
  • the fiber may be wrapped on a spool and shaped to conform to a desired shape before curing in a composite.
  • What is needed is a means to increase the compressive strength of a fiber or a matrix composite containing the fiber and/or increase the amount of work needed to cause compressive failure of a fiber or a matrix composite containing the fiber, while leaving the the fiber sufficiently flexible enough to be drapable and handleable prior to curing in a composite.
  • One aspect of the present invention is a filiform article containing: (a) a core containing one or more essentially parallel core fibers; (b) a sheath containing one or more wrap fibers surrounding the core and covering at least 50 percent of the outer surface of the core; and (c) a hardenable resin that is flowable before it is hardened and is hardenable to provide a hardened resin having a compressive modulus of at least 50,000 psi, characterized in that;
  • the core has an average diameter of no more than 0.8 mm and contains fibers whose compressive strength that is no more than 30 percent of their tensile strength;
  • a second aspect of the present invention is a matrix composite containing (a) a plurality of
  • the supporting fibers are organized into cores of essentially parallel fibers wrapped by a wrap fiber, wherein each core has an average diameter of no more than 0.8 mm, and the structure of wrap and core fibers together have an average diameter of no more than 1.3 mm;
  • the matrix composite has a compressive strength of at least 20 MPa.
  • a third aspect of the present invention is a process comprising the steps of:
  • the process of the present invention can be used to make filiform articles and prepregs of the present invention.
  • Those filiform articles and prepregs are flexible enough to be drapable.
  • the prepregs are useful for making composites, which can be shaped before curing to form useful structural materials.
  • composites preferably have a compressive strength at least 10 percent higher than the compressive strength of a similar composite made using the core fibers alone. They also preferably require substantially higher work to cause compressive failure than do composites
  • the present invention uses a core containing a reinforcing fiber.
  • the reinforcing fiber preferably has a tensile strength of at least 2 GPa, more preferably at least 3 GPa and most preferably at least 4 GPa. It preferably has a tensile modulus of at least 100 GPa and more preferably at least 200 GPa.
  • the compressive strength of the reinforcing fiber is no more than 30 percent of its tensile
  • the polymer is preferably an aramid, a highly oriented polyethylene or a polybenzazole. It is more preferably an aramid or a polybenzazole and most preferably a polybenzazole.
  • Suitable fibers are discussed more fully hereinafter.
  • Aramid fibers are known and commercially available. Exemplary suitable fibers are commercially available under the trademarks KevlarTM, TwaronTM and
  • the polymers in the fibers preferably contain primarily p-phenylene moieties linked by amice groups. Certain preferred polymers contain a mixture of m- and p-phenylene moieties linked by amide groups, but the most preferred polymers contain essentially no m-phenylene moieties.
  • Aramid fibers are discussed in greater detail in 3 Kirk-Othmer Ency. Chem. Tech. (3rd Ed.), Aramid Fibers, 213 (J. Wiley & Sons 1978).
  • Oriented polyethylene fibers are also known and commercially available. Oriented polyethylene fibers are typically gel-spun, ultra-high molecular weight polyethylene. Exemplary suitable fiber is commercially available under the trademark SpectraTM from AlliedSignal Co.
  • Polybenzazole polymers and processes to make fibers from them are also known.
  • Polybenzazole polymers contain a plurality of mer units that comprise:
  • DM divalent organic moiety
  • Polybenzazole mer units are preferably represented by one of Formulae 1(a) or (b), and more preferably by Formula 1(b):
  • each Ar represents an aromatic group
  • each Z represents -O-, -S- or -NR-, wherein each R is a hydrogen atom, a lower alkyl group or a phenylene moiety
  • each DM represents a bond or divalent organic moiety as previously defined.
  • Each aromatic group (Ar) is preferably a carbocyclic group containing no more than 12 carbon atoms, and more preferably either a 1,3,4-phenylene moiety in the case of AB-polybenzazole (AB-PBZ: Formula 1(a)) or a 1,2,4,5-phenylene moiety in the case of AA/BB-polybenzazole (AA/BB-PBZ; Formula 1(b)).
  • Each DM is preferably an aromatic grout and more preferably a 1,4-phenylene moiety.
  • moieties are preferably chosen such that resulting polymer is a rigid rod polymer or a semi-rigid polymer and are more preferably chosen such that the resulting polymer is a rigid rod polymer.
  • Examples of highly preferred mer units are represented by Formulae 2(a)-(e):
  • the polybenzazole polymer may be a polybenzazole "homopolymer,” consisting essentially of a single repeated of mer unit as described in U.S. Patent
  • the polymer is preferably a
  • homopolymer It more preferably forms a liquid crystalline solution when dissolved at a suitable concentration in a solvent acid, such as polyphosphoric acid and/or methanesulfonic acid, and/or coagulates from solvent acid to form a crystalline or semicrystalline coagulated fiber.
  • a solvent acid such as polyphosphoric acid and/or methanesulfonic acid
  • the polybenzazole polymer preferably should have sufficient molecular weight to form a spinnable dope solution. Its molecular weight is preferably at least 5000; more preferably at least 10,000; and most preferably at least 25,000.
  • the intrinsic viscosity of the polymer in methanesulfonic acid at 25°C and 0.05 g/dL concentration is preferably at least 10 dL/g, more preferably at least 20 dL/g and most preferably at least 30 dL/g. It is preferably no more than 50 dL/g.
  • the polybenzazole polymers may be synthesized by reaction of suitable monomers in dehydrating acid solutions, such as polyphosphoric acid and/or a mixture of methanesulfonic acid and P 2 O 5 , with vigorous
  • the spun polybenzazole fiber may be exposed to brief high temperature under tension ("heat treatment” or "heat setting") to improve tensile strength and/or modulus, such as is described in U.S. Patent 4,544,119, which is incorporated herein by reference.
  • heat treatment or "heat setting” to improve tensile strength and/or modulus, such as is described in U.S. Patent 4,544,119, which is incorporated herein by reference.
  • treatment may be for any period of time from a few seconds to 30 minutes, and at a temperature between 300°C and 700°C, inclusive.
  • longer residence time is ordinarily desirable at lower temperatures and shorter residence time at higher temperatures.
  • the reinforcing fibers in the present invention are organized into cores that contain at least one reinforcing fiber.
  • the core may contain a single fiber, but preferably contains a plurality of fibers.
  • the core fibers are preferably parallel with each other. More preferably, at least some of the fibers in the core are not substantially twisted but extend essentially
  • the core may contain two or more types of fiber, such as a mixture of aramid fibers and polybenzazole fibers.
  • the maximum and minimum size of the core are governed primarily by practical considerations.
  • a core having too small an average diameter is undesirable for at least two reasons.
  • First, a core containing only one fiber is so thin that it is difficult to sheath by wrapping with a wrap fiber unless the wrap fiber is very flexible.
  • Second, a very thin core is more likely to have a high ratio of sheath to core fiber. It is desirable to minimize the ratio of sheath to core fiber in order to obtain the best composite properties.
  • a core having too large an average diameter is also undesirable because a thicker core is ordinarily substantially less flexible than a thin core.
  • the core has an average diameter of no more than 0.8 mm.
  • the average diameter is preferably no more than 0.6 mm, more preferably no more than 0.5 mm and most preferably no more than 0.4 mm.
  • the average diameter of the core is preferably at least 0.05 mm and more preferably at least 0.1 mm.
  • the core preferably has a denier no higher than 3000, more preferably no higher than 2500 and most preferably no higher than 1500; and it preferably has a denier of at least 200, more preferably at least 500 and most
  • the core is surrounded by a sheath containing a wrapping fiber that surrounds the core.
  • the wrapping fiber should be flexible enough to wrap securely around the core without substantial damage.
  • the wrapping fiber preferably has a high glass transition temperature and sufficient thermal stability to permit its use
  • Suitable wrapping fibers may contain, for example, polybenzazole, aramid, nylon. polyester, polypropylene, or polyethylene. Preferred wrapping materials are polybenzazole fiber and aramid fiber.
  • the polybenzazole is preferably not a rigid rod polybenzazole, but is preferably an AB-polybenzazole or a flexible coil AA/BB-polybenzazole polymer.
  • the wrapping fiber may be wrapped around the core using a number of known devices. Examples of processes for wrapping fibers around fibers, and the products of those processes, are described in numerous references, such as U.S. Patents 3,495.646; 3.556,922: 3,644,866; 4,269,024; 4,272,950: 4,299,884; 4,384,449: 4,499,716; and 4,861,575, which are incorporated herein by reference.
  • the core may be wrapped with a fiber made of flowable and hardenable material, such as wrapping a strand of polybenzazole-containing acid dope or an aramid-containing acid dope or a molten nylon around the core.
  • the flowable wrapping is then solidified, by coagulating in the case of a dope or by cooling in the case of a molten polymer.
  • the flowable wrapping should be viscous enough to substantially hold its shape until coagulated.
  • the flowable wrapping is preferably a polybenzazole dope.
  • the sheath should be thick enough to provide radially restraining pressure without breaking.
  • the sheath is preferably as thin as possible for two reasons.
  • thicker sheaths add to the overall thickness of the filiform article.
  • Thicker filiform articles are less flexible, and have- poorer drapability and handleability.
  • Second, higher composite compressive and tensile strengths are realized when the filiform article contains a high ratio of core fiber to sheath. It is theorized that the axial strength of the filiform article, both in tension and in compression, comes primarily from the core, rather than from the sheath. If the sheath occupies a large part of the volume allowed for the filiform article in a composite, then the volume must contain an equivalently smaller amount of core fiber.
  • the sheath is preferably no more than 0.2 mm thick, more preferably no more than 0.15 mm and most preferably no more than 0.1 mm thick.
  • containing a wrapping fiber may have one. two or more layers of wrapping, but preferably contains no more than two layers and more preferably no more than one layer.
  • the wrap fiber need not cover 100 percent of the outer surface of the core.
  • the wrapping fiber preferably covers at least 70 percent of the core surface, more preferably at least 90 percent of the core surface, and most preferably 100 percent of the core surface.
  • the wrapping fiber is preferably wrapped around the core with tension.
  • the wrapping fiber is preferably wrapped around the core with tension.
  • tension producing means such as a brake or clutch for the wrapping fiber. If it does not, some tension may be generated by
  • the speed of wrapping when the wrapping equipment does not contain a tensioning device is preferably at least 15,000 wraps per minute and more preferably at least 30,000 wraps per minute.
  • the tension on the wrapping fiber is preferably at least 20 grams, more preferably at least 50 grams and most preferably at least 75 grams. Very high tension is neither necessary nor desirable. Wrapping the core under high tension twists and deforms the core unless the core is itself under high tension, and a core under high tension must be undesirably thick to avoid
  • the tension of the wrapping is preferably no more than 1000 grams, more preferably no more than 500 grams and most preferably no more than 260 grams.
  • the foregoing tensions are suitable for wrapping fibers having a diameter about equivalent to that of a 200 denier KevlarTM 49 aramid fiber. Persons of ordinary skill can adjust those tensions appropriately for other fibers to obtain an essentially equivalent radial restraining pressure. Tensions sufficient to compress the radial diameter of the core by 0.1 percent are undesirable and should be avoided.
  • the core is impregnated with a flowable, hardenable resin prior to wrapping and subsequently hardening the matrix resin.
  • the resin is preferably impregnated into the core after the core is wrapped.
  • the flowable, hardenable resin may be a molten
  • thermoplastic polymer such as poly(aromatic ether ketone), poly(aromatic ether sulfone) and poly(etherimide).
  • the flowable, hardenable resin is preferably a thermosetting resin, such as epoxy resins, polycyanate resins, phenolic resins, butadiene resins, vinyl ester resins and polyimides.
  • the thermosetting resin is preferably an epoxy resin or a polycyanate resin.
  • the flowable, hardenable resin preferably has a compressive modulus after curing of at least 50,000 psi. more preferably at least 100,000 psi, and most
  • the flowable, hardenable resin should not be fully cured prior to wrapping, but may be partially cured as long as the filiform article remains flexible.
  • the wrapped filiform article is much stiffer and less handleable after the resin is cured. Therefore, the resin should not be fully cured until after the sheath is applied to the core, and preferably not until a matrix composite containing the filiform article is cured.
  • the diameter of the filiform article is the diameter of the filiform article.
  • the diameter containing both sheath and core is preferably small enough that the filiform article remains flexible, sc that it is drapable and handleable.
  • the diameter is preferably no more than 1.5 mm, more preferably no more than 0.8 mm and most preferably no more than 0.6 mm.
  • the minimum diameter of the filiform article is governed primarily by practical considerations, such as the size of core fibers and the flexibility of wrapping fibers.
  • the filiform article preferably has a diameter of at least 0.1 mm and more preferably at least 0.3 mm.
  • the filiform article may be prepregged according to known practices by impregnating the sheath. and the core if it is not previously impregnated, with a flowable, hardenable resin.
  • the flowable, hardenable resin has the same definition and preferred embodiments as the resin discussed for impregnating the core and is preferably similar to the resin which impregnates the core.
  • the core is preferably impregnated before it is sheathed, and the sheath of the filiform article is preferably impregnated with resin in a separate step while the sheath is added to the core or afterwards. If no resin is added to the core before it is sheathed, subsequent prepregging may not completely impregnate the core, and the resulting composite may have lower
  • the resulting prepreg should contain sufficient flowable and hardenable matrix resin to bend the fibers together and so that the prepreg is curable with a plurality of other prepregs to form a matrix composite.
  • the prepreg preferably contains enough matrix resin to minimize voids in the filiform article. In the present invention, it is desirable to maximize the volume percent of the prepreg and composite that is occupied by core fibers, while adequately filling voids and
  • Prepregs and the resulting matrix composites typically contain 25 to 60 volume percent matrix resin and 40 to 75 volume percent fibers or filiform articles.
  • the prepreg or composite more preferably contains at least 60 volume percent filiform articles. It preferably contains no more than 20 volume percent void, more preferably no more than 10 volume percent, more highly preferably no more than 5 percent and most preferably no more than 2 volume percent.
  • Prepregging and formation of matrix composites are described in numerous general references, such as Kirk-Othmer Ency. Chem. Tech. - Supplement, Composites. High Performance, 260-80 (J. Wiley & Sons 1984), which is incorporated herein by reference.
  • the uncured prepregs may then be laminated, draped over molds and otherwise shaped.
  • the shaped prepregs are hardened by curing a thermosetting hardenable resin or cooling a thermoplastic one, in order to form a shaped article.
  • the shaped article may be further machined, and is useful as a structural or electronics material.
  • An improvement in compressive strength in the filiform article does not necessarily translate directly into a proportional improvement in composite properties.
  • the core fibers do not make up 100 percent of a
  • the matrix composite made using the filiform article preferably has a compressive strength at least 10 percent higher than that using an unsheathed fiber.
  • the improvement in compressive strength is more preferably at least 20 percent, mere highly preferably at least 50 percent, and most
  • the compressive strength of a composite containing the filiform article is preferably at least 22 kpsi (151 MPa), more preferably at least 30 kpsi (200 MPa) and most preferably at least 35 kpsi (240 MPa).
  • the compressive strength of a composite containing the filiform article is preferably at least 30 kpsi (207 MPa), more preferably at least 35 kpsi (240 MPa), and most preferably at least 40 kpsi (275 MPa).
  • the core fiber is an oriented
  • the compressive strength of a composite containing the filiform article is preferably at least 16 kpsi (110 MPa) and more preferably at least 20 kpsi (138 MPa).
  • the filiform articles, and composites that contain them can preferably withstand much greater compressive strain before compressive failure occurs than can unsheathed core fibers, so that the work required to cause compressive failure is increased.
  • the strain to compressive failure in a composite containing filiform articles having an aramid core or polybenzazole is preferably at least 10 percent, more preferably at least 15 percent and most preferably at least 19
  • fiber and composite compressive strength is measured by a minicomposite measuring technique, which is a small scale adaptation of ASTM D-3410-82 and, in our experimente, provides generally equivalent results with that ASTM test.
  • a bundle of parallel fibers or filiform articles is impregnated with Tactix ® 123 epoxy resin and Tactix ® Hardener H31 curing agent in a weight ratio of 100: 17 and laid up in uniaxial fashion in a TeflonTM coated mold. The mold is filled with the same epoxy resin and hardener in the same proportions. The epoxy resin is cure to provide a minicomposite.
  • the mold provides a test section containing the bundles and cured epoxy resin, said test section having a cross-sectional area of 0.062 inches by 0.125 inches and a length in the axial direction of 0.19 inches.
  • the fiber bundles extend beyond each end of the test section into epoxy tabs located at each end of the test section.
  • the ends of the tabs are cut planar, parallel to each other and perpendicular to the test section, using a diamond saw.
  • the specimen is mounted on an InstronTM testing machine and compressed until failure occurs. The stress and strain to failure is recorded.
  • compressive strength is derived by dividing the stress at failure by the cross-sectional area of the test section.
  • a wrapping mechanism is constructed naving a wrapping element from an American Volkmann Model No. VTS-05-0 twister mounted in a centrifuge case and driven by a centrifuge motor.
  • the wrapping mechanism has an
  • a core containing parallel fibers of KevlarTM 49 aramid fiber having the denier set out in Table 1 (Core Denier) is wrapped with fibers of KevlarTM 49 having the denier set out in Table 1 (Wrap Denier, to form a filiform article having a total denier as set out in Table 1 (Total Denier).
  • the wrapping speed is 7000 wraps per minute, and the wrapping coverage is 100 percent.
  • the wrapped fiber is impregnated again with the epoxy resin and hardener and tested for compressive strength as previously described.
  • the testing results are set out in Table 1.
  • Composite refers to the total number of prepregged filiform articles in the test section of each specimen.
  • Total Test Denier refers to the total denier of wrapped filiform articles contained in the minicomposite.
  • Total Core Denier refers to the total denier of core fibers contained in the minicomposite.
  • Load to Break refers to the compressive load on the minicomposite when compressive failure occurs.
  • strain to Break refers to the compressive strain of the minicomposite when compressive failure occurs.
  • Compress. Strength refers to the average compressive strength calculated for this portion in the
  • Example 2 The process of Example 1 is repeated, except that the core is impregnated with Tactix ® 123 epoxy resin and Tactix ® Hardener H31 curing agent prior to wrapping.
  • the variables and results are set out in Table 2.
  • the clutch mechanism is calibrated to determine the approximate tension at the wrap, in grams, of the wrap fiber which is generated by placing a particular DC voltage across the clutch and reading the tension with a ChecklineTM tensiometer (1) just after the line leaves the clutch while the wrapping equipment is operating, and (2) just past the wrapping point while the wrapping equipment is stationary.
  • the first measurement does not include friction from the equipment and is lower than the actual wrap tension.
  • the second measurement include friction from equipment which is not in contact with the fiber when the wrapping equipment is in motion, and is higher than the actual wrap tension. Actual wrap tension is taken as being between the two.
  • Table 3(A) The results are set out in Table 3(A):
  • Example 2 The process of Example 2 is repeated using SpectraTM polyethylene fibers as the core and either 66 denier monofilament nylon or 10 strand 7 denier
  • Example 3 The process of Example 3 is repeated using a
  • KevlarTM 49 aramid f i ber wrap The wrap f i ber clutch i s set at 14 volts. The tension on the core is 140-158 g.
  • the average denier of the wrapped fiber is 2680 denier.
  • a composite sample is prepared having 12 bundles of wrapped fiber.
  • the core denier in the composite is 15,600 and the total denier of wrapped fiber in the composite is 32,300.
  • a comparative composite that contains 25 bundles of unwrapped 130C denier PBO (total denier 32,500) is prepared.
  • the wrapped PBO composite has a compressive strength of 25 kpsi (240 MPa) and a strain-to-break of 22 percent.
  • the unwrapped PBO composite has a compressive strength of 18 kpsi (125 MPa) and a strain-to-break of 5.7 percent.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Composite Materials (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Reinforced Plastic Materials (AREA)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)

Abstract

Un article filiforme comprend une âme en fibre imprégnée de résine et enveloppée par une fibre. Des fibres de renforcement sont organisées en âmes contenant au moins une fibre de renforcement, mais contenant de préférence une pluralité desdites fibres. L'âme est entourée par une gaine contenant une fibre d'enveloppement. Ladite fibre d'enveloppement est de préférence entourée autour de l'âme avec une tension. L'âme est imprégnée d'une résine coulable, durcissable, de préférence une fois l'âme enveloppée. Le diamètre de l'article filiforme ne dépasse de préférence pas 1,5 mm. Les articles filiformes peuvent être préimprégnés selon des techniques connues.
PCT/US1991/005407 1990-08-08 1991-07-30 Amelioration de la resistance a la compression de fibres par contrainte radiale Ceased WO1992002444A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CA002088580A CA2088580A1 (fr) 1990-08-08 1991-07-30 Amelioration de la resistance a la compression des fibres par contrainte radiale
KR1019930700354A KR930701338A (ko) 1990-08-08 1993-02-06 방사상으로 억제하여 섬유의 압축 강도를 증진시키는 방법

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US564,480 1983-12-21
US56448090A 1990-08-08 1990-08-08

Publications (1)

Publication Number Publication Date
WO1992002444A1 true WO1992002444A1 (fr) 1992-02-20

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Application Number Title Priority Date Filing Date
PCT/US1991/005407 Ceased WO1992002444A1 (fr) 1990-08-08 1991-07-30 Amelioration de la resistance a la compression de fibres par contrainte radiale

Country Status (7)

Country Link
EP (1) EP0546111A1 (fr)
JP (1) JP3125222B2 (fr)
KR (1) KR930701338A (fr)
CA (1) CA2088580A1 (fr)
IE (1) IE912792A1 (fr)
TW (1) TW206263B (fr)
WO (1) WO1992002444A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5700823A (en) * 1994-01-07 1997-12-23 Sugen, Inc. Treatment of platelet derived growth factor related disorders such as cancers
US5773476A (en) * 1994-03-07 1998-06-30 Sugen, Inc. Methods and compositions for inhibiting cell proliferative disorders
US6316479B1 (en) 1997-05-19 2001-11-13 Sugen, Inc. Isoxazole-4-carboxamide compounds active against protein tryosine kinase related disorders
US6331555B1 (en) 1995-06-01 2001-12-18 University Of California Treatment of platelet derived growth factor related disorders such as cancers
EP1743964A1 (fr) * 2005-07-15 2007-01-17 Teijin Twaron B.V. Corde
EP2252731A4 (fr) * 2008-02-28 2013-09-18 Bell Helicopter Textron Inc Corde composite non durcie comprenant plusieurs différentes matières fibreuses

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2015264789B2 (en) * 2008-01-18 2017-05-25 Kone Corporation Rope for a hoisting machine, elevator and use

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4265981A (en) * 1977-05-17 1981-05-05 Commonwealth Scientific And Industrial Research Organization Impact-resisting composites
US4272950A (en) * 1978-12-07 1981-06-16 Commissariat A L'energie Atomique Filiform textile material
US4499716A (en) * 1983-06-13 1985-02-19 E. I. Du Pont De Nemours And Company Reinforcement structure

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4265981A (en) * 1977-05-17 1981-05-05 Commonwealth Scientific And Industrial Research Organization Impact-resisting composites
US4272950A (en) * 1978-12-07 1981-06-16 Commissariat A L'energie Atomique Filiform textile material
US4499716A (en) * 1983-06-13 1985-02-19 E. I. Du Pont De Nemours And Company Reinforcement structure

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5700823A (en) * 1994-01-07 1997-12-23 Sugen, Inc. Treatment of platelet derived growth factor related disorders such as cancers
US5773476A (en) * 1994-03-07 1998-06-30 Sugen, Inc. Methods and compositions for inhibiting cell proliferative disorders
US5789427A (en) * 1994-03-07 1998-08-04 Sugen, Inc. Methods and compositions for inhibiting cell proliferative disorders
US6596878B2 (en) 1994-03-07 2003-07-22 Yissum Research & Development Company Of The Hebrew University Methods and compositions for inhibiting cell proliferative disorders
US7217737B2 (en) 1994-03-07 2007-05-15 Yissum Research And Development Company Of The Hebrew University Of Jerusalem Method and compositions for inhibiting cell proliferative disorders
US6331555B1 (en) 1995-06-01 2001-12-18 University Of California Treatment of platelet derived growth factor related disorders such as cancers
US6316479B1 (en) 1997-05-19 2001-11-13 Sugen, Inc. Isoxazole-4-carboxamide compounds active against protein tryosine kinase related disorders
US6649635B2 (en) 1997-05-19 2003-11-18 Sugen, Inc. Heteroarylcarboxamide compounds active against protein tyrosine kinase related disorders
EP1743964A1 (fr) * 2005-07-15 2007-01-17 Teijin Twaron B.V. Corde
EP2252731A4 (fr) * 2008-02-28 2013-09-18 Bell Helicopter Textron Inc Corde composite non durcie comprenant plusieurs différentes matières fibreuses

Also Published As

Publication number Publication date
JPH06500356A (ja) 1994-01-13
TW206263B (fr) 1993-05-21
EP0546111A1 (fr) 1993-06-16
JP3125222B2 (ja) 2001-01-15
EP0546111A4 (fr) 1993-04-29
KR930701338A (ko) 1993-06-11
IE912792A1 (en) 1992-02-12
CA2088580A1 (fr) 1992-02-09

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