US3844822A - Production of uniformly resin impregnated carbon fiber ribbon - Google Patents
Production of uniformly resin impregnated carbon fiber ribbon Download PDFInfo
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- US3844822A US3844822A US00211339A US21133971A US3844822A US 3844822 A US3844822 A US 3844822A US 00211339 A US00211339 A US 00211339A US 21133971 A US21133971 A US 21133971A US 3844822 A US3844822 A US 3844822A
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- ribbon
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
- D01F11/10—Chemical after-treatment of artificial filaments or the like during manufacture of carbon
- D01F11/14—Chemical after-treatment of artificial filaments or the like during manufacture of carbon with organic compounds, e.g. macromolecular compounds
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2307/00—Use of elements other than metals as reinforcement
Definitions
- the fibrous ribbon undergoing treatment is resin impregnated with a neat liquid resin system of relatively high viscosity containing an A-stage thermosetting resin through the application of a force sufficient to bring the resin into intimate association with the individual fibers of the ribbon.
- the resin impregnated ribbon is next partially cured while continuously passing through a heating zone as described while interposed between a pair of flexible endless belts.
- the resulting ribbon is uniformly impregnated with a thermosetting resin of a tacky B-stage consistency and may be utilized in the formation of carbon fiber reinforced composite structures by filament winding or other suitable techniques.
- carbon fibers or carbonaceous fibers are used herein in the generic sense and include graphite fibers which consist substantially of carbon and have a predominant X-ray diffraction pattern characteristic of graphite.
- Amorphous carbon fibers are defined as fibers in which the bulk of the fiber weight can be attributed to carbon and which exhibit a predominantly amorphous X-ray diffraction pattern.
- Graphite fibers generally have a higher Youngs modulus than do amorphous carbon fibers and in addition are more highly electrically and thermally conductive.
- Carbon fiber reinforced composites are commonly formed by coating or impregnating carbon fibers with an uncured or partially cured liquid thermosetting resinous material which is ultimately to serve as the matrix or continuous phase in the composite article, converting the resinous material present on the carbon fibers to a tacky consistency through partial curing and/or evaporation of solvent, molding or otherwise shaping the same into the desired configuration, and fully curing the same to form a rigid monolithic structure.
- a thermosetting resinous material has commonly been applied to the carbon fibers from a solvent system which has necessitated volatilization of the solvent during the composite formation prior to complete curing. Additionally, techniques have been proposed wherein the thermosetting resin is applied from a liquid solventless system.
- the resin impregnated carbon fibers bearing a partially cured resin must by necessity be provided in an appreciable length.
- the efficient uniform resin impregnation, handling, and partial curing of continuous lengths of carbon fibers particularly in ribbon form has been an elusive goal when employing prior art technology.
- Arch ovens have been employed wherein the resin impregnated ribbon is passed through a highly elongated heating zone while supported upon one surface and the solvent evaporated. The exposed surface accordingly tends to cure at a different rate than the surface in contact with the support. If the resin impregnated ribbon is unsupported over an appreciable span, roping and/or splitting of the 5 same commonly occurs.
- a non-uniformly resin impregnated or nonuniformly partially cured carbon fiber ribbon is incapable of yielding a carbon fiber reinforced composite structure consistently exhibiting the required tensile properties for many end use applications.
- thermosetting resin impregnated carbon fiber ribbon wherein the necessity to volatilize a solvent from the resin system in contact with the ribbon is eliminated.
- the carbonaceous fibrous ribbon which serves as the starting material in the present process contains at least about 90 percent carbon by weight.
- the carbon fibers of the ribbon may exhibit either an amorphous carbon or a predominantly graphitic carbon X-ray diffraction pattern.
- the carbon fibers contain at least about 95 percent carbon by weight and exhibit a predominantly graphitic X-ray diffraction pattern.
- the width of the carbonaceous fibrous ribbon may conveniently vary from about 0.5 to 12 inches, or more.
- the carbonaceous fibrous ribbon may comprise a single flat tow of continuous carbon filaments or a plurality of substantially parallel multifilament fiber bundles which are substantially coextensive with the length of the ribbon.
- the carbonaceous fiber bundles of the ribbon may be provided in a variety of physical configurations.
- the bundles of the ribbon may assume the configuration of continuous lengths of multifilament yarns, tows, strands, cables, or similar fibrous assemblages.
- the multifilament bundles are preferably lengths of a continuous multifilament yarn.
- the fiber bundles within the ribbon optionally may be provided with a twist which tends to improve their handling characteristics. For instance, a twist of about 0.1 to 5 tpi, and preferably about 0.3 to l tpi, may be imparted to each fiber bundle. Also, a false twist may be used instead of or in addition to a real twist. Alternatively, the fiber bundles may possess substantially no twist.
- Multifilament fiber bundles may be provided within the ribbon in a substantially parallel manner in the sub stantial absence of bundle crossovers to produce a flat ribbon.
- the number of parallel multifilament bundles present within the carbonaceous ribbon may be varied widely, e.g., from 6 to 1,000, or more.
- a ribbon precursor is selected having a weft pick interlaced with substantially parallel fiber bundles in accordance with the teachings of commonly assigned U.S. Ser. No. 1 12,189, filed Feb. 3, 1971 of K. S. Burns, G. R. Ferment, and R. C. Waugh which is herein incorporated by reference. It is not essential, however, that the parallel fiber bundles or the filaments of a flat tow be bound by any form of weft interlacement when constructing carbon fiber tapes for resin impregnation in accordance with the present invention.
- the carbonaceous ribbon which serves as the starting material in the present process may be produced in accordance with a variety of techniques as will be apparent to those skilled in the art.
- organic polymeric fibrous materials which are capable of undergoing thermal stabilization may be initially stabilized by treatment in an appropriate atmosphere at a moderate temperature (e.g., 200 to 400 C. and subsequently heated in an inert atmosphere at a more highly elevated temperature, e.g., 900 to 1.000 C., or more, until a carbonaceous fibrous material is formed.
- a moderate temperature e.g., 200 to 400 C.
- an inert atmosphere e.g., 900 to 1.000 C., or more
- substantial amounts of graphitic carbon are commonly detected in the resulting carbon fiber, otherwise the carbon fiber will commonly exhibit a substantially amorphous x-ray diffraction pattern.
- Suitable organic polymeric fibrous materials from which the carbonaceous ribbon may be derived include an'acrylic polymer, a cellulosic polymer, a polyamide, a polybenzimidazole, polyvinyl alchol, etc. Acrylic polymeric materials are particularly suited for use as precursors in the formation of the carbonaceous ribbon.
- suitable cellulosic materials include the natural and regenerated forms of cellulose, e.g., rayon.
- suitable polyamide materials include the aromatic polyamides, such as nylon 6T, which is formed by the condensation of hexamethylenediamine and terephthalic acid.
- An illustrative example of a suitable polybenzimidazole is poly-2,2-mphenylene-5,5' bibenzimidazole.
- Preferred carbonization and graphitization techniques for use in forming the carbonaceous ribbon are described in commonly assigned U.S. Ser. Nos. 777,275, filed Nov. 20, 1968 of Charles M. Clarke (now abandoned); 17,780, filed Mar. 9, 1970 of Charles M. Clarke, Michael J. Ram, and John P. Riggs (now U.S. Pat. No. 3,677,705); and 17,832, filed Mar. 9, 1970 of Charles M. Clarke, Michael .1. Ram, and Arnold J. Rosenthal.
- Each of these disclosures is herein incorporated by reference.
- the carbonaceous ribbon optionally may be surface treated in order to improve its ability to bond to a thermosetting resinous material.
- Conventional surface modification techniques may be selected. Preferred surface modification treatments are disclosed in commonly assigned U.S. Ser. Nos. 65,454 and 65,456, (now U.S. Pat. No. 3,723,150) filed Aug. 20, 1970 of M. L. Druin, G. R. Ferment. and N.V.P. Rao.
- the carbonaceous ribbon is continuously conveyed to the impregnation zone while in a flat configuration.
- the ribbon may be conveyed in accordance with conventional fiber advancing techniques, and is preferably under a uniform tension across its width when it arrives at the impregnation zone.
- a liquid solventless system of a relatively high viscosity comprising an A-stage thermosetting resin is forced into intimate association with the individual fibers of the ribbon.
- the solventless system exhibits a viscosity of about 500 to 10,000 cps. and preferably a viscosity of about 1,000 to 3,000 cps, during impregnation. It has been found that such resin systems of relatively high viscosity are capable of producing a more uniformly resin impregnated ribbon.
- the solventless system comprising an A-stage thermosetting resin is a flowable liquid and is substantially uncured during the impregnation step.
- a material when exposed to heat hardens or sets to a rigid solid consistency designated as a C-stage thermoset resin, and may not subsequently be rendered plastic or flowable upon the reapplication of heat.
- the curing or hardening of the thermosetting resin is brought about by heat-promoted chemical changes which result in the formation of a compact, often crossl inked systen i lt is for use in the process of the invention.
- the epoxy resins utilized in the present invention are most commonly prepared by the condensation of bisphenol A (4.4 isoproplidene diphenol) and epichlorohydrin.
- thermosetting resins may be molded to the desired configuration prior to the point in time when the curing reaction has progressed to the C-stage.
- a B-stage thermosetting resin is defined as a partially cured thermosetting resin which has neither the consistency of a flowable liquid, nor the consistency of a rigid solid.
- a B-stage thermosetting resin is accordingly soft and tacky in its consistency and may be readily molded. Upon the passage of time even at room temperature, a B-stage thermosetting resin will assume a C-stage consistency.
- the solventless system applied in the impregnation zone may comprise the A-stage thermosetting resin, one or more curing agents for the thermosetting resin, one or more accelerators and one or more solid particulate inert fillers.
- Conventional solvents such as acetone which may dissolve the A-stage thermosetting resin are to be avoided, since upon evaporation such solvents tend to produce strength-reducing voids, and also lengthen the period of time required for the A- stage thermosetting resin to assume a B-stage consistency within the heating zone (described in detail hereafter).
- various modifiers or diluents of the reactive type may be present within the solventless system since such components form a permanent portion of the hardened thermoset resin, and it is not essential to evaporate the same during the curing reaction.
- the resin employed in the solventless system may generally be selected from those thermosetting resins utilized in the production of fiber reinforced composites by prior art techniques. It is, of course, necessary that a substantially uncured thermosetting resin be selected which inherently possesses the required viscosity at the impregnation temperature or which may be modified to possess the required viscosity at the impregnation temperature by the addition of a reactive modifier or diluent.
- suitable thermosetting resins for use in the present process include epoxy resins, phenolic resins, polyester resins, polyimides, etc.
- An epoxy resin is the preferred thermosettingresin where n varies between zero and a small number less than about 10.
- the resin is a very fluid light-colored material which is substantially the diglycidyl ether of bisphenol A.
- the particularly preferred liquid epoxy resins generally possess an n value averaging less than about 1.0.
- illustrative examples by standard trade designations of particularly useful commercially available epoxy resins include: Epi-Rez 508 and Epi-Rez 510 (Celanese Coatings) ERLA 2256 (Union Carbide), ERLA 4617 (Union Carbide), and Epon (Shell) epoxy resins.
- Epoxy novolac resins formed by the reacting of epichlorohydrin with phenol-formaldehyde resins are also particularly preferred thermosetting resins.
- An illustrative example of a highly useful resin is Epi-Rez 5155 epoxy novolac resin (Celanese Coatings).
- a variety of epoxy resin curing agents may be em- ,ployed in conjunction with the epoxy resin.
- the curing or hardening of the epoxy resin typically involves fur- .ther reaction of the epoxy or hydroxyl groups to cause molecular chain growth and cross-linking.
- the term Ycuring agent as used herein is accordingly defined to include the various hardeners of the co-reactant type.
- Illustrative classes of known epoxy curing agents which may be utilized include aliphatic and aromatic amines,
- the preferred epoxy curing agents for use with the epoxy resin are acid anhydrides (e.g. hexahydrophthalic acid and methylbicyclo[2.2. l ]heptenel l -dicarboxylic anhydride isomers marketed under the designation Nadic Methyl Anhydride by the Allied Chemical Company), and aromatic amines (e.g., meta-phenylene diamine and dimethylaniline).
- acid anhydrides e.g. hexahydrophthalic acid and methylbicyclo[2.2. l ]heptenel l -dicarboxylic anhydride isomers marketed under the designation Nadic Methyl Anhydride by the Allied Chemical Company
- aromatic amines e.g., meta-phenylene diamine and dimethylaniline
- the solventless system comprising an A-stage thermosetting may be provided at a moderately elevated temperature during the impregnation step of the process in order to impart the required viscosity to the same.
- the exact temperature selected will vary with the specific system selected as will be apparent to those skilled in the art. Resin system temperatures commonly range from about 25 to 100 C. at the time of impregnation. Those resin systems which exhibit a substantial pot life at the impregnation temperature are preferred.
- the technique utilized to force the resin system into intimate association with multifilament fiber bundles of the ribbon may be varied. It is essential, however, that the impregnation technique selected results in no substantial diminution of the tensile properties of the carbonaceous bundles.
- the resin system is initially applied to the ribbon by briefly passing the ribbon through a vessel containing the same, and the ribbon bearing the resin system adhering to its surface is next passed between a pair of parallel nip rollers.
- the resin initially may be satisfactorily applied by spraying, extruding, etc., prior to passage between a pair of nip rollers.
- One of the nip rollers optionally may be provided with a flat groove corresponding in width to the width of the ribbon, and the other nip roller provided with a substantially matching raised surface which in combination with the grooved roller provides a rectangular gap for the ribbon.
- the force exerted by such nip rolls causes the resin system to flow throughout the ribbon.
- the impregnation step may be accomplished through the use of poltrusion or other application technique capable of bringing out the desired impregnation.
- the carbonaceous ribbon while in intimate association with the solventless system is next interposed between the outer surfaces of a pair of flexible endless belts.
- the belts preferably have smooth nonporous surfaces, are relatively thin so as to permit efficient heat transfer therethrough in the heating zone as described hereafter, and are capable of being readily stripped from a ribbon impregnated with a tacky thermosetting resin.
- the belts are capable of withstanding the temperatures employed in the subsequent heating zone, are capable of withstanding wash solvents, and may be formed from a variety of materials.
- Preferred endless belts are formed from fiberglass reinforced polytetrafluoroethylene sheets having a thickness of about 0.005 to 0.030 inch.
- Flexible endless belts alternatively may be formed from flexible metallic strips or other fiber reinforced flexible resinous materials.
- the width of the endless belts is greater than the width of the ribbon interposed therebetween (e.g., 0.5 to 2 inches or wider), so that the ribbon has each of its surfaces completely covered by the endless belts.
- the ribbon is preferably interposed substantially at the center of each belt and is aligned in parallel with the edges of the belts.
- the resin impregnated ribbon While interposed between the flexible belts, the resin impregnated ribbon is continuously passed in the direction of its length through a substantially enclosed heating zone provided with a heated gaseous atmosphere wherein the belts and the ribbon are looped in a single wrap about each of a multiplicity of rotating spaced parallel rollers wherein the inner surfaces of the belts are in alternating contact with the rollers as the belts and the ribbon progress through the heating zone.
- the heating zone may be relatively compact and provided with a plurality of pairs of spaced parallel rollers.
- the impregnated ribbon remains between the belts at a fixed location in the absence of slidaas ntac mtissq sta t ly saspsn wi mnthc.
- heated gaseous atmosphere within the heating zone may be varied. For instance, ordinary air may be employed. Alternatively, inert gases such as nitrogen may serve as the gaseous atmosphere.
- the gas is preferably preheated prior to introduction into the heating zone such as by passing over electrical resistance heaters. Additionally, the gas is preferably circulated within the heating zone by continuously introducing and withdrawing a portion of the same.
- thermosetting resin in intimate association with the ribbon is converted to a tacky B-stage consistency.
- the temperature of the gaseous atmosphere of the heating zone, as well as the residence time during which the ribbon is within the heating zone will vary depending upon the specific thermosetting resin undergoing partial curing. Heating zone temperatures of about 75 to 175 C. are commonly selected, and preferably the temperature of the gaseous atmosphere within the heating zone is maintained at about 100 to 150 C. Satisfactory residence times in which to accomplish the desired partial curing within the heating zone commonly range from about 2 to 30 minutes, an preferably about 10 to 15 minutes.
- the ribbon is positioned between the endless belts as it passes through the heating zone, no splitting of roping of the ribbon occurs as is common in the prior art when a resin impregnated ribbon is passed across an unsupported span.
- the overall dimensious of the heating zone may be substantially reduced.
- any volatile components of the resin system e.g., curing agents, are retained within the ribbon by the adjoining belts, thereby making possible uniform curing of the thermosetting resin to the desired tacky consistency. Since the endless belts have a width greater than that of the ribbon, the resin system never contacts the rotating rollers present within the heating zone.
- the resulting ribbon is continuously withdrawn from the heating zone while interposed between the flexible belts prior to a point in time when the thermosetting resin is advanced to a hard non-tacky C-stage consistency.
- the resin in intimate association with the ribbon remains in a tacky B-stage consistency at the time of its withdrawl from the heating zone.
- the resin impregnated carbonaceous ribbon is next separated from the flexible endless belts and may be collected or directly utilized in the formation of carbon fiber reinforced composite structures.
- the endless belts following separation from the resin impregnated ribbon may be washed with an appropriate solvent (e.g., acetone or methylene chloride) to remove any adhering resin and returned for further use.
- an appropriate solvent e.g., acetone or methylene chloride
- the uniformly resin impregnated carbon fiber ribbons formed in the present process preferably contain about to 55 percent partially cured thermosetting resin by volume (preferably about to percent by volume) and about 45 to 65 percent carbon fiber by volume (preferably about to percent by volume).
- the resin impregnated ribbon following its separation from the endless flexible belts may be positioned 1291 releasable int rla sa hass l c n oat e a
- the resin impregnated ribbons produced in the present process find particular utility in the production of high performance composite structures which are highly useful in the aerospace industry. For instance, impellers, turbine blades, and similar lightweight structural componentsmay be formed by conventional filament winding, molding, or shaping techniques.
- Carbonaceous ribbon having a width of 2.75 inches is continuously unwound from flanged bobbin 2 which is free to rotate about its central axis.
- the carbonaceous ribbon consists of 300 continuous multifilament yarn bundles which are arranged in parallel with each yarn bundle containing about 400 filaments, having a twist of about 0.5 tpi, exhibiting a total denier of about 400, and a predominantly graphitic X-ray diffraction pattern.
- the yarn bundles are derived from an acrylonitrile homopolymer and contain in excess of 99 percent carbon by weight.
- An interlay 4 of Kraft paper is also continuously unwound from flanged bobbin 2 and is received by interlay takeup 6 which is rotated about its axis by a driven constant speed AC motor (not shown) having a spring-tensioned friction plate.
- the unwinding of carbonaceous ribbon 1 from flanged bobbin 2 is accordingly assisted by the rotation of interlay takeup 6 which exerts a pulling force on interlay 4.
- the carbonaceous ribbon 1 following unwinding from flanged bobbin 1 passes over three grooved idler rolls 8, 10, and 12 which serve to center the ribbon, eliminate splits, and equalize yarn density across the web.
- Each of the grooved idler rolls 8, l0, and 12 has groove width of 2.75 inches, a groove depth of 0.25 inch, and a diameter within the groove of 3 inches.
- the carbonaceous ribbon is wrapped about a series of four tensioning rollers l4, l6, l8, and each having a 6 inch diameter, which apply a uniform tension to the ribbon.
- the tension is adjusted by varying the weight 22 on dancer arm 24 as the ribbon passes about idler rolls 26, 28, and 30 each having a diameter of 6 inches.
- Dancer arm 24 controls the speed of tensioning rollers l4, 16, 18, and 20 as well as the speed of upper nip roller 35 with all five of these rollers being driven by the same variable speed motor (not shown) by means of a chain drive (not shown).
- the carbonaceous ribbon passes about a driven grooved dip roller 34 which is partially immersed in vessel 36 which contains a liquid solventless system containing an A-stage thermosetting resin and a curing agent for the resin.
- the driven grooved dip roller 34 has groove width of 2.75 inches, a groove depth of 0. l inch, and a diameter within the groove of 3 inches.
- the carbonaceous ribbon bearing a coating of the solventless system next passes between a pair of driven parallel nip rollers 35 and 38.
- the nip rollers 35 and 38 serve to force the resin system comprising an A-stage thermosetting resin into intimate association with the multifllament fiber bundles of the ribbon.
- Dip roller 34, vessel 36, and nip rollers 35, and 38 are internally heated by a recirculating ethylene glycol-water solution which aids in maintaining the solventless resin system at the desired viscosity.
- the carbonaceous ribbon 40 in intimate association with the resin system comprising an A-stage thermosetting resin is next interposed between a pair flexible endless belts 44 and 45.
- the endless belts 44 and 45 are non-porous, have widths of 4 inches, and are composed of polytetrafluoroethylene coated fiberglass.
- Spring mounted idler rollers 46 and 48 facilitate the interpositioning of the ribbon 40 between belts 44 and 45.
- the impregnated carbonaceous ribbon interposed between the belts passes as a flat unitary structure 50 over compression plate 52 and into heating zone 54.
- the heating zone 54 is provided in a forced air convection oven measuring 3 X 3 X 2 feet having a top to bottom air flow. Cantilevered within the heating zone 54 are eight oven rollers 56, 58, 60, 62, 64, 66, 68, and '70 having diameters of 6 inches which are driven by a common motor (not shown) at a constant speed. The resin impregnated ribbon while interposed been the belts and present in heating zone 54 is successively wrapped about each of oven rollers 56, 58, 60, 62, 64', 66, 68, and 70.
- the driven rollers 56, 58, 60, 62, 64, 66, 68 and 70 within the heating zone 54 are rotated at the same rate as grooved dip roller 34 and lower nip roller 38. While passing through heating zone 54 the thermosetting resin in intimate association with the carbonaceous ribbon is advanced to a tacky B-stage consistency, and it is in this state when it exits from heating zone 54 at opening 72.
- the resulting carbonaceous ribbon 78 is separated from the endless flexible belts 42 and 44.
- the exit nip rollers 74 and 76 serve to isolate the tension exerted upon the ribbon within the oven from the takeup winding tension.
- the belts 42 and 44 pass through belt washing pans 80 and 82'containing a solvent for the resin system where any adhering resin is removed by the aid of rotating brushes. Uniform tension is maintained upon endless belts 42 and 44 by dancer arm assemblies 84 and 86.
- a releasable paper interlay 88 is continuously unwound from reel 90 and contacts the surface of idler roller 92 prior to the arrival of the resulting thermosetting resin impregnated carbonaceous ribbon 78.
- the interlay 88 hearing the tacky thennosetting resin impregnated carbonaceous ribbon 78 next passes about tensioning arm 94 and is wound upon flanged bobbin 96.
- the solventless system provided in dip pan 36 contained parts by weight of epoxy novolac resin formed by reacting epichlorohydrin with a phenolformaldehyde resin, and 88 parts by weight of an anhydride curing agent.
- the solventless system at room temperature i.e., 25 C.
- Internally heated dip roller 34, vessel 36, and nip rollers 35 and 38 were maintained at 50 C. during the resin impregnation step at which temperature the resin system exhibited a viscosity of about 1,000 cps.
- the gap between nip rollers 35 and 38 was 0.008 inch.
- the carbonaceous ribbon was passed through apparatus at a rate of 20 inches per minute, and was present in heating zone 54 for a residence time of 13.5 minutes which was maintained at a uniform temperature of 132 C.
- the resulting carbonaceous ribbon was uniformly impregnated with the tacky B-stage epoxy resin and consisted of about 42.6 percent of volume resin, and about 57.4 percent by volume carbon fiber.
- the solventless system provided in dip pan 36 contained 100 parts by weight of epoxy resin formed by reacting bisphenol A with epichlorohydrin, and 35 parts by weight of an amine curing agent.
- the solventless system at room temperature i.e., 25 C.
- room temperature i.e. 25 C.
- Internally heated dip' roller 34, vessel 36, and nip rollers 35 and 38 were maintained at 78 C. during the resin impregnation step at which temperature the resin system exhibited a viscosity of about 2,000 cps.
- the gap between nip rollers 35 and 38 was 0.0l inch.
- the carbonaceous ribbon was passed through the apparatus at a rate of 20 inches per minute, and was present in heating zone 54 for a residence time of 13.5 minutes which was maintained at a uniform temperature of 125 C.
- the resulting carbonaceous ribbon was uniformly impregnated with the tacky B-stage epoxy resin and consisted of about 45 percent by volume resin, and 55 percent by volume carbon fiber.
- An improved process for the production of a uniformly resin impregnated ribbon of a carbonaceous fibrous material which is suitable for use in the manufacture of carbon fiber reinforced composite structures comprising:
- liquid solventless system comprising an A-stage thermosetting resin has a viscosity of about 1,000 to 3,000 cps.
- said solventless system comprises an A-stage epoxy resin and a curing agent for said resin.
- said epoxy resin is an epoxy novolac resin formed by the reacting of epichlorohydrin with a phenolformaldehyde resin.
- An improved process for the production of a uniformly resin impregnated ribbon of a carbonaceous fibrous material which is suitable for use in the manufacture of carbon fiber reinforced composite structures comprising:
- a liquid solventless system having a viscosity of about 1,000 to 3,000 cps. comprising an A- stage thermosetting epoxy resin and a curing agent for said resin into intimate association with said carbonaceous fibrous ribbon while present in said impregnation zone,
- said epoxy resin is an epoxy novolac resin fonned by the reacting of epichlorohydrin with a phenol-formaldehyde resin.
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US00211339A US3844822A (en) | 1971-12-23 | 1971-12-23 | Production of uniformly resin impregnated carbon fiber ribbon |
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US00211339A US3844822A (en) | 1971-12-23 | 1971-12-23 | Production of uniformly resin impregnated carbon fiber ribbon |
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Cited By (34)
Publication number | Priority date | Publication date | Assignee | Title |
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US3914504A (en) * | 1973-10-01 | 1975-10-21 | Hercules Inc | Sized carbon fibers |
WO1981003305A1 (en) * | 1980-05-16 | 1981-11-26 | Budd Co | A compound and method of repairing surface defects |
US4529757A (en) * | 1980-05-16 | 1985-07-16 | The Budd Company | Thermosetting resin patching compound |
US4534919A (en) * | 1983-08-30 | 1985-08-13 | Celanese Corporation | Production of a carbon fiber multifilamentary tow which is particularly suited for resin impregnation |
US4714642A (en) * | 1983-08-30 | 1987-12-22 | Basf Aktiengesellschaft | Carbon fiber multifilamentary tow which is particularly suited for weaving and/or resin impregnation |
US4781223A (en) * | 1985-06-27 | 1988-11-01 | Basf Aktiengesellschaft | Weaving process utilizing multifilamentary carbonaceous yarn bundles |
US4804509A (en) * | 1986-12-17 | 1989-02-14 | Amoco Corporation | Hot-melt prepreg tow process |
US5160400A (en) * | 1990-05-24 | 1992-11-03 | United Container Machinery Group, Inc. | Corrugating apparatus having a liquid filled seal roll |
US5266139A (en) * | 1992-10-02 | 1993-11-30 | General Dynamics Corporation, Space Systems Division | Continuous processing/in-situ curing of incrementally applied resin matrix composite materials |
US5273602A (en) * | 1990-12-19 | 1993-12-28 | Hercules Incorporated | Ribbonizing method for selectively heating a respective one of a plurality of fiber tows |
US5445701A (en) * | 1987-05-08 | 1995-08-29 | Research Association For New Technology Development Of High Performance Polymer | Apparatus of manufacturing a sheet-prepreg reinforced with fibers |
US5518568A (en) * | 1992-09-09 | 1996-05-21 | Fawley; Norman C. | High tensile strength composite reinforcing bands and methods for making same |
US5618367A (en) * | 1995-04-10 | 1997-04-08 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Dry powder process for preparing uni-tape prepreg from polymer powder coated filamentary towpregs |
WO1997019226A1 (en) * | 1995-11-19 | 1997-05-29 | Clark-Schwebel, Inc. | Structural reinforcement member and method of utilizing the same to reinforce a product |
US5801074A (en) * | 1996-02-20 | 1998-09-01 | Kim; Jong Tae | Method of making an air tight cavity in an assembly package |
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US5836715A (en) * | 1995-11-19 | 1998-11-17 | Clark-Schwebel, Inc. | Structural reinforcement member and method of utilizing the same to reinforce a product |
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US6468625B1 (en) | 1997-05-07 | 2002-10-22 | Hexcel Cs Corporation | Laminate configuration for reinforcing glulam beams |
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US7513965B2 (en) | 2004-04-21 | 2009-04-07 | Ingersoll Machine Tools, Inc. | Performing high-speed events “on-the-fly” during fabrication of a composite structure by automated fiber placement |
US20100043982A1 (en) * | 2005-08-25 | 2010-02-25 | Ingersoll Machine Tools, Inc. | Add Roller for a Fiber Placement Machine |
US8464773B2 (en) | 2007-07-27 | 2013-06-18 | The Boeing Company | Tape removal apparatus and process |
US8345269B2 (en) | 2007-09-22 | 2013-01-01 | The Boeing Company | Method and apparatus for measuring the width of composite tape |
US20090079998A1 (en) * | 2007-09-22 | 2009-03-26 | The Boeing Company | Method and apparatus for measuring the width of composite tape |
US20110114265A1 (en) * | 2008-01-02 | 2011-05-19 | The Boeing Company | Graphite Tape Supply and Backing Paper Take-Up Apparatus |
US8272419B2 (en) * | 2008-01-02 | 2012-09-25 | The Boeing Company | Graphite tape supply and backing paper take-up apparatus |
US20090211698A1 (en) * | 2008-02-27 | 2009-08-27 | The Boeing Company | Reduced complexity automatic fiber placement apparatus and method |
US9884472B2 (en) | 2008-02-27 | 2018-02-06 | The Boeing Company | Reduced complexity automatic fiber placement apparatus and method |
US8557074B2 (en) | 2008-02-27 | 2013-10-15 | The Boeing Company | Reduced complexity automatic fiber placement apparatus and method |
US8986482B2 (en) | 2008-07-08 | 2015-03-24 | The Boeing Company | Method and apparatus for producing composite structures |
US20100006205A1 (en) * | 2008-07-08 | 2010-01-14 | The Boeing Company | Method and apparatus for producing composite structures |
US20100193103A1 (en) * | 2009-01-31 | 2010-08-05 | The Boeing Company | Automated fiber placement using networked autonomous vehicles |
US8308101B2 (en) | 2009-03-09 | 2012-11-13 | The Boeing Company | Simplified fiber tensioning for automated fiber placement machines |
US8490910B2 (en) | 2009-03-09 | 2013-07-23 | The Boeing Company | Simplified fiber tensioning for automated fiber placement machines |
US20100224716A1 (en) * | 2009-03-09 | 2010-09-09 | The Boeing Company | Simplified fiber tensioning for automated fiber placement machines |
US8454788B2 (en) | 2009-03-13 | 2013-06-04 | The Boeing Company | Method and apparatus for placing short courses of composite tape |
US20100230043A1 (en) * | 2009-03-13 | 2010-09-16 | The Boeing Company | Method and Apparatus for Placing Short Courses of Composite Tape |
DE102010016946A1 (en) * | 2010-05-14 | 2011-11-17 | Andritz Küsters Gmbh | Method for finishing material web, involves transporting material web on rotating application roller immersed in liquor bowl containing liquor, in order to apply liquor on material web |
US11518120B2 (en) | 2018-07-23 | 2022-12-06 | Crompton Technology Group Limited | Fibre coating apparatus |
US11794423B2 (en) | 2018-07-23 | 2023-10-24 | Crompton Technology Group Limited | Fibre coating apparatus |
US20220288872A1 (en) * | 2019-08-26 | 2022-09-15 | Graphite Design Inc. | Method for manufacturing structure and structure |
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