US20020187346A1 - Powder coated roving for making structural composite - Google Patents
Powder coated roving for making structural composite Download PDFInfo
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- US20020187346A1 US20020187346A1 US09/935,267 US93526701A US2002187346A1 US 20020187346 A1 US20020187346 A1 US 20020187346A1 US 93526701 A US93526701 A US 93526701A US 2002187346 A1 US2002187346 A1 US 2002187346A1
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Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B15/00—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00
- B29B15/08—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00 of reinforcements or fillers
- B29B15/10—Coating or impregnating independently of the moulding or shaping step
- B29B15/12—Coating or impregnating independently of the moulding or shaping step of reinforcements of indefinite 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
- B29C70/28—Shaping operations therefor
- B29C70/40—Shaping or impregnating by compression not applied
- B29C70/42—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles
- B29C70/46—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles using matched moulds, e.g. for deforming sheet moulding compounds [SMC] or prepregs
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2933—Coated or with bond, impregnation or core
Definitions
- the present invention relates generally to structural composites and more specifically to powder coated rovings for making structural composites.
- Structural composites are well known and are used in a wide variety of applications that require plastic parts having a minimum threshold of mechanical properties such as strength and impact resistance while imparting cost savings in terms of manufacturing techniques and in terms of weight reduction.
- structural composites include sheet molding compound (SMC) and structural reaction injection molding (SRIM).
- Structural composites are typically made by introducing glass fiber or other reinforcing material to a thermoplastic or thermosetting polymer material.
- the glass fiber and polymer material may be mixed together and formed into a composite part in a wide variety of methods, including compression molding and injection molding.
- structural composites include sheet molding compound (SMC) and structural reaction injection molding (SRIM).
- thermoplastic or thermosetting polymer materials commonly used in these processes are typically solvent-based systems. As such, volatile organic content (VOC) may be released to the atmosphere as the part is cured.
- VOC volatile organic content
- the process used to make the material is very complicated, thus adding to the manufacturing costs. For example, in a typical SRIM process, the reinforcement materials and polymer resin are introduced individually to the molding equipment and the part is molded, which adds to the cost of manufacture. Third, in these types of equipment, composite parts having an inadequately dispersed reinforcement material in the part is possible if the machine is calibrated inappropriately.
- injection molding processes the amount of fiber content that may be loaded within the composite part is limited due to the process itself as is well known in the art. As polymer resins are typically more expensive than the reinforcement material, the cost of the composite part is correspondingly increased.
- Powder coating system use aqueous slurries of polymer powder and water to introduce coatings to a part.
- Organic emissions are limited to additives that may help the polymer remain dispersed in the slurry and to help the resin flow during the curing step.
- a unique feature of the present invention is that the composite roving material is formed by introducing a powder coating to the outside fibers of a high integrity bundle of inorganic or organic fibers held together with a sizing composition. The powder coating is attached and partially melts around the outside fibers, leaving the internal fibers bundled together with the sizing composition.
- the fiber reinforced composite parts have higher fiber content than is generally found in other fiber-reinforced composites due to the fact that the part may be formed from one source, as compared with traditional techniques such as injection molding which involve introducing the reinforcement material and polymer resin separately. Further, the mechanical properties are improved due to higher reinforcement content in the composite part. Further, raw material costs are reduced by introducing higher amounts of reinforcement material in the composite part. Finally, molding costs are lessened due to simplified molding techniques involving only the chopped powder-coated composite material as compared with separate introduction of the reinforcement fibers and polymer resin to an injection mold.
- FIG. 1 is an end view of one strand of a composite roving material used to make a composite part according to a preferred embodiment of the present invention
- FIG. 2 is a schematic diagram for making the composite roving of FIG. 1;
- FIG. 3 is a schematic diagram of one preferred way for making a composite part from the composite roving of FIG. 1;
- FIG. 4 is a schematic diagram of another preferred way for making a composite part from the composite roving material of FIG. 1;
- FIG. 5 is a schematic diagram of another preferred way for making a composite part from the composite roving material of FIG. 1;
- FIG. 6 is a schematic diagram for making moldable chop to be used to make a composite part from the composite roving of FIG. 1;
- FIGS. 7A, 7B, and 7 C illustrate weaving patterns that can be formed from the composite roving material of FIG. 1 that may be subsequently molded into a composite part;
- FIG. 8 depicts a table comparing various mechanical properties of composite parts having varying fiber contents according to the present invention with other traditionally available reinforced composite parts.
- the roving 10 is comprised of bundle of fibers 12 .
- the bundle of fibers 12 is comprised of a plurality of inner fibers 14 and a plurality of outer fibers 16 held together by a high integrity sizing composition 18 .
- the high integrity sizing composition comprises approximately 0.5 to 5% by weight of the total weight of the bundle of fibers 12 .
- the bundle 12 contains between approximately 500 and 1100 filaments of inner fibers 14 and outer fibers 16 comprised of filaments that are approximately 8-16 microns in diameter.
- a powder coating polymer material 20 is introduced to the outer surfaces 22 of the outer fibers 16 such that the powder coating material substantially surrounds the bundle 12 . Of course, some of the powder coating polymer material 20 enters within the bundle 12 during this introduction step.
- the powder coating material 20 is approximately 10-80% of the weight of the multiend composite roving 10 weight.
- the powder coating material 10 powder is appoximately 1-100 microns in diameter, with preferred ranges equaling 5-10 microns in diameter.
- the process for making the multiend roving material 10 is shown below in FIG. 2.
- the multiend composite roving material 10 may then be processed further to form a molded composite part 80 as shown in FIG. 3 below.
- the sizing composition 18 is approximately 1% by weight of the total weight of the bundle 12 of fibers and the fiber bundle 12 is approximately 12 microns in diameter and contains approximately 800 individual filament fibers 14 , 16 .
- the powder-coating polymer material 20 preferably comprises approximately 20-30% of the weight of the composite roving 10 .
- Suitable fibers 14 , 16 that may be used in the present invention should be thermally stable at the temperatures involved in the consolidation step to make the composite structure.
- the fibers 14 , 16 must have glass transition and melting temperature greater than room temperature.
- These fibers 14 , 16 that are used may thus be of many different types, including glass fibers, carbon and graphite fibers, organic fibers, aramid fibers, natural fibers, synthetic fibers, hybrid fibers and combinations thereof that are well known in the art.
- e-type glass, s-type glass, or carbon fibers are used as the reinforcing material.
- a high integrity sizing composition 18 maintains the individual fibers 14 , 16 in a bundle 12 during processing. It therefore is not easy to filamentize the bundle 12 during processing.
- a low integrity sizing composition allows the bundle strands to easily filamentize.
- the bundle 12 is flattened out when wound on a tube that makes a forming cake (shown as 30 in FIG. 2). Accordingly, an end view of the flattened bundle 12 provides a generally elliptical cross section.
- the elliptical cross section provides for greater surface area of the bundle 12 that is exposed to the powder coating material 20 .
- the cross sectional shape may be round or irregularly shaped as opposed to generally elliptical.
- the powder coating 20 that is used is made of a slurry or emulsion coating having a powdered polymer material.
- the powdered polymer material is a good wetting matrix resin that is capable of being applied as a dip coating at room temperature.
- the polymer powder coating material 20 should also be capable of melting, flowing, and curing when it is molded into a final composite part.
- powdered polymers including polyesters, bisphenol type epoxies, novalac type epoxies, phenolics, acrylics, polyurethanes, hybrid polymers (for example, an epoxy polyester copolymer or a polyester triglycidylisocyanurate copolymer) and other thermoplastic or thermosetting polymers that exhibit good wetting and processability for making a structural composite part.
- the powder coating 20 may contain film formers that aid in attaching the powdered polymer material to the bundles 12 .
- polyurethanes may be used as film formers.
- the powder coating 20 typically contains additives that aid in dispersing the powdered polymer material in the film former and water and in thickening the slurry to a desired thickness.
- One preferred powder coating slurry is shown below in Table 1.
- Table 1 above shows one preferred composition of a powder coating 20 that is used to coat the bundle 12 .
- the slurry is made by first mixing together the polyurethane, polyacrylamide, thickener, and water under agitation to form a premix.
- the powdered polymer material is then added slowly to premix material under agitation to produce the slurry bath having approximately 40% solids.
- the slurry bath is maintained under agitation during the application process to ensure that the powder polymer material remains evenly dispersed within the slurry bath.
- FIG. 2 shows a schematic diagram for making the multiend composite roving 10 of FIG. 1.
- Individual sized bundled fibers 12 are unrolled from a plurality of forming cakes 30 and introduced through a slurry bath containing the powder coating polymer material 20 dispersed in a slurry or emulsion.
- the aqueous powder coated slurry is approximately 40% solids and is adhered mostly to the outer fibers 16 of the bundle 12 to form the composite roving material 10 .
- a stripper die 34 is used the meter the amount of powder coating 20 on the coated bundle 12 .
- the amount of powder coating material 20 metered onto the bundle 12 is controlled by varying the size of the orifice (not shown) in the stripper die 34 .
- the coated bundle 12 is then sent through a drying oven 36 to remove water from the powder coating material 20 .
- the drying oven 36 should be maintained at a temperature hot enough to remove the water from the powder coating 20 but cool enough to prevent the powder coating material 20 from significant melting.
- the dried composite roving 10 is then cooled and wound up onto a multiend roving package 38 for further processing.
- a squeegee (not shown) may be used instead of or in conjunction with the stripper die 34 to meter the amount of powder coating 20 applied to the bundle 12 .
- coated bundle 12 may simply be air dried as opposed to dried using a drying oven 36 as shown in FIG. 2.
- FIG. 3 a schematic diagram for making a composite part 80 from the composite roving material 10 is shown.
- the dried composite roving material 10 is unwound from the creel 38 and introduced to a chopper 39 .
- the chopper 39 chops the composite roving material 10 onto a preform screen 37 , thereby forming a preform 40 from the chopped composite roving material 41 .
- a vacuum (not shown) may be used to ensure that the chopped roving material 41 falls onto the preform screen 39 in a manner consistent with the design of the composite part 80 .
- the preform 40 is then heat consolidated to form a handleable preform.
- the handleable preform 40 containing the chopped roving material 41 is then placed in a heated press 42 and compression molded at a chosen pressure, preferably 300-1200 pounds per square inch, to form a composite part 80 .
- the upper mold section 44 of the heated press 42 is maintained at an elevated temperature high enough to cause the powdered polymer coating 20 on the bundle 12 to melt, flow, and cure.
- this elevated temperature is between 300 and 450 degrees Fahrenheit.
- the fiber bundles 12 flatten out as the high integrity sizing composition 18 melts slightly. This allows seepage of some of the powder coating material 20 within the inner fibers 14 and allows air removal from the composite part 80 to prevent the formation of voids, thereby giving the composite part 80 enhanced structural integrity.
- the upper mold section 44 and lower mold section 46 of the press 42 are held together a sufficient amount of time to ensure that the powder coated material 20 has completely reacted and to ensure that the fiber bundle 12 has compressed to its required thickness.
- the composite part 80 is then released from the mold 42 and cooled.
- the composite roving material 10 is chopped in the presence of a hot air source device 54 which impacts the chopped composite roving material 41 as it leaves the chopping head of the chopper 39 .
- the hot air source device 54 melts a portion of the powder coating material 20 on the powder coated roving material 10 to make them tacky without cure occuring.
- the tacky strands then impact a mold 52 with enough force and at sufficiently high temperature to keep the powder coating 20 warm without reversibly curing the powder coating material 20 .
- this is between 300 and 360 degrees Fahrenheit.
- the chopper 39 is then removed and the mold 52 containing the chopped roving material 41 is placed in a press 60 and compression molded at a chosen pressure to form a composite part 80 as in FIG. 3.
- the upper mold section 56 of the press 60 is maintained at an elevated temperature high enough to cause the powdered polymer coating 20 on the bundle 12 to melt, flow, and cure.
- this elevated temperature is between 300 and 450 degrees Fahrenheit.
- the fiber bundles 12 flatten out as the high integrity sizing composition 18 melts slightly. This allows seepage of some of the powder coating material 20 within the inner fibers 14 and allows air movement within the composite part 80 , thereby giving the composite part 80 better flow characteristics and enhanced structural integrity.
- the upper mold section 56 and lower mold section 58 of the press 60 are held together a sufficient amount of time to ensure that the powder coated material 20 has completely reacted and to ensure that the fiber bundle 12 has compressed to its required thickness.
- the composite part 80 is then released from the mold 52 and press 60 and cooled.
- FIG. 5 another preferred method for making a composite part 80 from the composite roving material 10 is shown.
- the dried composite roving material 10 is unwound from the creel 38 and introduced to a chopper 39 .
- the chopper 39 chops the composite roving material 10 and drops it onto a moving belt 70 .
- the chopped roving material 41 is then compacted and heated in a press 74 to form a sheet 76 .
- the sheet 76 is then cut to an appropriate size and shape using a chopping blade 78 .
- One or more layers of the sheet 76 may then be placed into a press 86 and compression molded at a chosen pressure to form a composite part 80 .
- the upper mold section 84 of the press 86 is maintained at an elevated temperature high enough to cause the powdered polymer coating 20 on the bundle 12 to melt, flow, and cure.
- this elevated temperature is between 300 and 450 degrees Fahrenheit.
- the fiber bundles 12 flatten out as the high integrity sizing composition 18 melts slightly. This allows seepage of some of the powder coating material 20 within the inner fibers 14 and allows air movement within the composite part 80 , thereby giving the composite part 80 better flow characteristics and enhanced structural integrity.
- the upper mold section 84 and lower mold section 82 of the press 86 are held together a sufficient amount of time to ensure that the powder coated material 20 has completely reacted and to ensure that the fiber bundle 12 has compressed to its required thickness.
- the composite part 80 is then released from the press 86 and cooled.
- FIG. 6 a schematic diagram for making a moldable chop 110 is shown.
- Individual sized bundled fibers 12 are unrolled from a plurality of forming cakes 30 and introduced through a slurry bath containing the powder coating polymer material 20 dispersed in a slurry or emulsion.
- the aqueous powder coated slurry is approximately 40% solids and is adhered mostly to the outer fibers 16 of the bundle 12 to form the composite roving material 10 .
- a stripper die 34 is used the meter the amount of powder coating 20 on the coated bundle 12 .
- the amount of powder coating material 20 metered onto the bundle 12 is controlled by varying the size of the orifice (not shown) in the stripper die 34 .
- the coated bundle 12 is then sent through a drying oven 36 to remove water from the powder coating material 20 that forms the composite roving material 10 .
- the drying oven 36 should be maintained at a temperature hot enough to remove the water from the powder coating 20 but cool enough to prevent the powder coating material 20 from significant melting.
- the composite roving material 10 is then chopped to approximately one-half inch moldable chop 110 in length using a chopper 39 and stored in a container (not shown).
- the moldable chop 110 is similar to or smaller in size than the chopped composite roving material 41 of FIGS. 3 - 5 . This allows the chop 110 to be easily poured from the container into a mold for compression molding. This forms a composite part 80 (not shown) having good reinforcing characteristics. Alternatively, the chop 110 could be layered onto the preform 40 as in FIG. 3 to form a molded composite part 80 having different lengthed fibers for different reinforcing applications.
- the composite roving material 10 of FIG. 1 may be alternatively processed prior to a chopping steps as in FIGS. 3 - 6 .
- the composite roving material 10 may be woven, as shown in FIG. 7A, knitted, as described in FIG. 7B, or braided, as described in FIG. 7C, in a manner similar to what known in the fiberglass industry to form a fabric 120 .
- One or more layers of the fabric 120 may then be placed in a mold and compression molded as described above in FIG. 3 to form composite parts 80 having unique reinforcing characteristics.
- FIG. 8 compares and contrasts mechanical properties of structural reaction injection molding (“SRIM”), sheet molding compound (“SMC”), 70% fiber composite part, and 75% fiber composite part according to the present invention.
- the composite parts 80 of the present invention had improved tensile strength, tensile modulus, flex stress, and impact resistance (both notched and unnotched Izod) as compared with similar size and shaped SRIM and SMC composite parts.
- the higher fiber content in the composite part improved tensile modulus, flex stress, and impact resistance as compared with the lower fiber content composite parts.
- the present invention offers many advantages over typical structural composite materials in terms of mechanical properties, cost and processing. Many problems exist with the technologies used to make structural composites and inherent in the structural composites themselves. For example, the volatile organic content (VOC) that may be released to the atmosphere during the processing steps for the present invention is minimal.
- VOC volatile organic content
- the composite parts 80 of the present invention offer good mechanical properties due to their high fiber 14 , 16 content.
- the process used to make the composite parts 80 is simple, thus minimizing the manufacturing costs as compared with other structural composites.
- the reinforcement materials and polymer resin are introduced individually to the molding equipment and the part is molded, which adds to the cost of manufacture.
- the composition of the final composite parts 80 is precisely controlled as compared with other structural composite systems, wherein the polymer resin material and fiber content are separately introduced into an injection mold or similar apparatus. This is important because the structural and mechanical properties of the composite parts 80 may be more precisely controlled from part to part.
- aesthetic properties of the composite parts 80 of the present invention may be more precisely controlled and enhanced.
- dyes or colored powders may be added to the powder coating material 20 that may then be molded into the final composite part 80 .
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Abstract
A polymer composite multiend roving material used to make structural composite parts is comprised bundle of fibers held together by a high integrity sizing composition and surrounded by a powder coating polymer material. The powder coating material is approximately 10-80% of the dry weight of the multiend composite roving weight. The multiend composite roving material may then be easily processed further to form a molded composite part having good mechanical properties and high fiber content.
Description
- The present application claims priority from provisional application Serial No. 60/295,707, filed Jun. 4, 2001.
- The present invention relates generally to structural composites and more specifically to powder coated rovings for making structural composites.
- Structural composites are well known and are used in a wide variety of applications that require plastic parts having a minimum threshold of mechanical properties such as strength and impact resistance while imparting cost savings in terms of manufacturing techniques and in terms of weight reduction. Examples of structural composites include sheet molding compound (SMC) and structural reaction injection molding (SRIM).
- Structural composites are typically made by introducing glass fiber or other reinforcing material to a thermoplastic or thermosetting polymer material. The glass fiber and polymer material may be mixed together and formed into a composite part in a wide variety of methods, including compression molding and injection molding. Examples of structural composites include sheet molding compound (SMC) and structural reaction injection molding (SRIM).
- Many problems exist with the technologies used to make structural composites and are inherent in the structural composites themselves. First, the thermoplastic or thermosetting polymer materials commonly used in these processes are typically solvent-based systems. As such, volatile organic content (VOC) may be released to the atmosphere as the part is cured. Second, the process used to make the material is very complicated, thus adding to the manufacturing costs. For example, in a typical SRIM process, the reinforcement materials and polymer resin are introduced individually to the molding equipment and the part is molded, which adds to the cost of manufacture. Third, in these types of equipment, composite parts having an inadequately dispersed reinforcement material in the part is possible if the machine is calibrated inappropriately. Finally, in injection molding processes, the amount of fiber content that may be loaded within the composite part is limited due to the process itself as is well known in the art. As polymer resins are typically more expensive than the reinforcement material, the cost of the composite part is correspondingly increased.
- With regard to the VOC problem, one potential polymer system that may be used is a powder coating system. Powder coating system use aqueous slurries of polymer powder and water to introduce coatings to a part. Organic emissions are limited to additives that may help the polymer remain dispersed in the slurry and to help the resin flow during the curing step.
- It is therefore highly desirable to provide a method for combining the powder coating industry and glass fiber industry for making structural composite parts. It is also desirable to increase the fiber content in structural composite parts to improve or maintain mechanical properties such as strength or impact resistance. It is also desirable to simplify the manufacturing of structural composite parts by introducing the polymer resin and fiber reinforcement material in one step to be molded to a desired shape.
- It is thus an object of the present invention to combine the technologies of the powder coating and glass fiber industry to make a structural composite material having good mechanical properties, increased reinforcement content and simplified manufacturing techniques.
- The above objects are accomplished by producing a unique powder coated composite roving material that is subsequently chopped, preformed, and introduced to a compression mold to form reinforced composite parts. A unique feature of the present invention is that the composite roving material is formed by introducing a powder coating to the outside fibers of a high integrity bundle of inorganic or organic fibers held together with a sizing composition. The powder coating is attached and partially melts around the outside fibers, leaving the internal fibers bundled together with the sizing composition.
- The fiber reinforced composite parts have higher fiber content than is generally found in other fiber-reinforced composites due to the fact that the part may be formed from one source, as compared with traditional techniques such as injection molding which involve introducing the reinforcement material and polymer resin separately. Further, the mechanical properties are improved due to higher reinforcement content in the composite part. Further, raw material costs are reduced by introducing higher amounts of reinforcement material in the composite part. Finally, molding costs are lessened due to simplified molding techniques involving only the chopped powder-coated composite material as compared with separate introduction of the reinforcement fibers and polymer resin to an injection mold.
- Other objects and advantages of the present invention will become apparent upon considering the following detailed description and appended claims, and upon reference to the accompanying drawings.
- FIG. 1 is an end view of one strand of a composite roving material used to make a composite part according to a preferred embodiment of the present invention;
- FIG. 2 is a schematic diagram for making the composite roving of FIG. 1;
- FIG. 3 is a schematic diagram of one preferred way for making a composite part from the composite roving of FIG. 1;
- FIG. 4 is a schematic diagram of another preferred way for making a composite part from the composite roving material of FIG. 1;
- FIG. 5 is a schematic diagram of another preferred way for making a composite part from the composite roving material of FIG. 1;
- FIG. 6 is a schematic diagram for making moldable chop to be used to make a composite part from the composite roving of FIG. 1;
- FIGS. 7A, 7B, and7C illustrate weaving patterns that can be formed from the composite roving material of FIG. 1 that may be subsequently molded into a composite part; and
- FIG. 8 depicts a table comparing various mechanical properties of composite parts having varying fiber contents according to the present invention with other traditionally available reinforced composite parts.
- Referring now to FIG. 1, a powder coated composite multiend roving used for making a structural composite according to a preferred embodiment of the present invention is depicted as10. The
roving 10 is comprised of bundle offibers 12. The bundle offibers 12 is comprised of a plurality ofinner fibers 14 and a plurality ofouter fibers 16 held together by a highintegrity sizing composition 18. Preferably, the high integrity sizing composition comprises approximately 0.5 to 5% by weight of the total weight of the bundle offibers 12. In addition, thebundle 12 contains between approximately 500 and 1100 filaments ofinner fibers 14 andouter fibers 16 comprised of filaments that are approximately 8-16 microns in diameter. A powdercoating polymer material 20 is introduced to theouter surfaces 22 of theouter fibers 16 such that the powder coating material substantially surrounds thebundle 12. Of course, some of the powdercoating polymer material 20 enters within thebundle 12 during this introduction step. Thepowder coating material 20 is approximately 10-80% of the weight of the multiend composite roving 10 weight. Thepowder coating material 10 powder is appoximately 1-100 microns in diameter, with preferred ranges equaling 5-10 microns in diameter. The process for making themultiend roving material 10 is shown below in FIG. 2. The multiendcomposite roving material 10 may then be processed further to form a moldedcomposite part 80 as shown in FIG. 3 below. - In a preferred embodiment of the present invention, as shown in FIG. 1, the
sizing composition 18 is approximately 1% by weight of the total weight of thebundle 12 of fibers and thefiber bundle 12 is approximately 12 microns in diameter and contains approximately 800individual filament fibers coating polymer material 20 preferably comprises approximately 20-30% of the weight of thecomposite roving 10. -
Suitable fibers fibers fibers - A high
integrity sizing composition 18, by definition, maintains theindividual fibers bundle 12 during processing. It therefore is not easy to filamentize thebundle 12 during processing. A low integrity sizing composition, by contrast, allows the bundle strands to easily filamentize. In the present invention, it is necessary to maintain thefibers bundle 12, thereby allowing only anouter surface 22 of the plurality ofouter fibers 16 to be coated with thepowder coating 20. During formation of the bundle, thebundle 12 is flattened out when wound on a tube that makes a forming cake (shown as 30 in FIG. 2). Accordingly, an end view of the flattenedbundle 12 provides a generally elliptical cross section. The elliptical cross section provides for greater surface area of thebundle 12 that is exposed to thepowder coating material 20. Of course, in other embodiments, the cross sectional shape may be round or irregularly shaped as opposed to generally elliptical. - The
powder coating 20 that is used is made of a slurry or emulsion coating having a powdered polymer material. The powdered polymer material is a good wetting matrix resin that is capable of being applied as a dip coating at room temperature. The polymerpowder coating material 20 should also be capable of melting, flowing, and curing when it is molded into a final composite part. Many different powdered polymers may be used, including polyesters, bisphenol type epoxies, novalac type epoxies, phenolics, acrylics, polyurethanes, hybrid polymers (for example, an epoxy polyester copolymer or a polyester triglycidylisocyanurate copolymer) and other thermoplastic or thermosetting polymers that exhibit good wetting and processability for making a structural composite part. In addition, thepowder coating 20 may contain film formers that aid in attaching the powdered polymer material to thebundles 12. For example, polyurethanes may be used as film formers. Also, thepowder coating 20 typically contains additives that aid in dispersing the powdered polymer material in the film former and water and in thickening the slurry to a desired thickness. One preferred powder coating slurry is shown below in Table 1.TABLE 1 NAME DESCRIPTION WEIGHT SOLIDS Blue 49/00340 Polyester- 500 100% (Tiger Drylac USA, triglycidyl Inc.) isocyanurate powder coating Bayer Baybond Polyurethane resin 107 40% PU403 film former Igepal CA-630 Polyacrylamide 12 100% (Rhone-Poulenc) Resin DrewFloc (1%) Thickener 100 1% (Ashland Chemical/Drew Industrial) Water 669 TOTALS 1388 40% - Table 1 above shows one preferred composition of a
powder coating 20 that is used to coat thebundle 12. The slurry is made by first mixing together the polyurethane, polyacrylamide, thickener, and water under agitation to form a premix. The powdered polymer material is then added slowly to premix material under agitation to produce the slurry bath having approximately 40% solids. The slurry bath is maintained under agitation during the application process to ensure that the powder polymer material remains evenly dispersed within the slurry bath. - FIG. 2 shows a schematic diagram for making the multiend composite roving10 of FIG. 1. Individual sized bundled
fibers 12 are unrolled from a plurality of formingcakes 30 and introduced through a slurry bath containing the powdercoating polymer material 20 dispersed in a slurry or emulsion. The aqueous powder coated slurry is approximately 40% solids and is adhered mostly to theouter fibers 16 of thebundle 12 to form the compositeroving material 10. A stripper die 34, is used the meter the amount ofpowder coating 20 on thecoated bundle 12. The amount ofpowder coating material 20 metered onto thebundle 12 is controlled by varying the size of the orifice (not shown) in the stripper die 34. Thecoated bundle 12 is then sent through a dryingoven 36 to remove water from thepowder coating material 20. The dryingoven 36 should be maintained at a temperature hot enough to remove the water from thepowder coating 20 but cool enough to prevent thepowder coating material 20 from significant melting. The dried composite roving 10 is then cooled and wound up onto a multiendroving package 38 for further processing. - In alternative embodiments, a squeegee (not shown) may be used instead of or in conjunction with the stripper die34 to meter the amount of
powder coating 20 applied to thebundle 12. In addition,coated bundle 12 may simply be air dried as opposed to dried using a dryingoven 36 as shown in FIG. 2. - Referring now to FIG. 3, a schematic diagram for making a
composite part 80 from the compositeroving material 10 is shown. The dried compositeroving material 10 is unwound from thecreel 38 and introduced to achopper 39. Thechopper 39 chops the compositeroving material 10 onto a preform screen 37, thereby forming apreform 40 from the chopped compositeroving material 41. A vacuum (not shown) may be used to ensure that the choppedroving material 41 falls onto thepreform screen 39 in a manner consistent with the design of thecomposite part 80. Thepreform 40 is then heat consolidated to form a handleable preform. Thehandleable preform 40 containing the choppedroving material 41 is then placed in aheated press 42 and compression molded at a chosen pressure, preferably 300-1200 pounds per square inch, to form acomposite part 80. Theupper mold section 44 of theheated press 42 is maintained at an elevated temperature high enough to cause thepowdered polymer coating 20 on thebundle 12 to melt, flow, and cure. Preferably, this elevated temperature is between 300 and 450 degrees Fahrenheit. During the curing process, the fiber bundles 12 flatten out as the highintegrity sizing composition 18 melts slightly. This allows seepage of some of thepowder coating material 20 within theinner fibers 14 and allows air removal from thecomposite part 80 to prevent the formation of voids, thereby giving thecomposite part 80 enhanced structural integrity. Theupper mold section 44 andlower mold section 46 of thepress 42 are held together a sufficient amount of time to ensure that the powder coatedmaterial 20 has completely reacted and to ensure that thefiber bundle 12 has compressed to its required thickness. Thecomposite part 80 is then released from themold 42 and cooled. - In an alternate preferred process, as depicted in FIG. 4, the composite
roving material 10 is chopped in the presence of a hotair source device 54 which impacts the chopped compositeroving material 41 as it leaves the chopping head of thechopper 39. The hotair source device 54 melts a portion of thepowder coating material 20 on the powder coatedroving material 10 to make them tacky without cure occuring. The tacky strands then impact amold 52 with enough force and at sufficiently high temperature to keep thepowder coating 20 warm without reversibly curing thepowder coating material 20. Preferably, this is between 300 and 360 degrees Fahrenheit. - The
chopper 39 is then removed and themold 52 containing the choppedroving material 41 is placed in apress 60 and compression molded at a chosen pressure to form acomposite part 80 as in FIG. 3. Theupper mold section 56 of thepress 60 is maintained at an elevated temperature high enough to cause thepowdered polymer coating 20 on thebundle 12 to melt, flow, and cure. Preferably, this elevated temperature is between 300 and 450 degrees Fahrenheit. During the curing process, the fiber bundles 12 flatten out as the highintegrity sizing composition 18 melts slightly. This allows seepage of some of thepowder coating material 20 within theinner fibers 14 and allows air movement within thecomposite part 80, thereby giving thecomposite part 80 better flow characteristics and enhanced structural integrity. Theupper mold section 56 andlower mold section 58 of thepress 60 are held together a sufficient amount of time to ensure that the powder coatedmaterial 20 has completely reacted and to ensure that thefiber bundle 12 has compressed to its required thickness. Thecomposite part 80 is then released from themold 52 andpress 60 and cooled. - Referring now to FIG. 5, another preferred method for making a
composite part 80 from the compositeroving material 10 is shown. The dried compositeroving material 10 is unwound from thecreel 38 and introduced to achopper 39. Thechopper 39 chops the compositeroving material 10 and drops it onto a movingbelt 70. The choppedroving material 41 is then compacted and heated in a press 74 to form asheet 76. Thesheet 76 is then cut to an appropriate size and shape using achopping blade 78. - One or more layers of the
sheet 76 may then be placed into apress 86 and compression molded at a chosen pressure to form acomposite part 80. Theupper mold section 84 of thepress 86 is maintained at an elevated temperature high enough to cause thepowdered polymer coating 20 on thebundle 12 to melt, flow, and cure. Preferably, this elevated temperature is between 300 and 450 degrees Fahrenheit. During the curing process, the fiber bundles 12 flatten out as the highintegrity sizing composition 18 melts slightly. This allows seepage of some of thepowder coating material 20 within theinner fibers 14 and allows air movement within thecomposite part 80, thereby giving thecomposite part 80 better flow characteristics and enhanced structural integrity. Theupper mold section 84 andlower mold section 82 of thepress 86 are held together a sufficient amount of time to ensure that the powder coatedmaterial 20 has completely reacted and to ensure that thefiber bundle 12 has compressed to its required thickness. Thecomposite part 80 is then released from thepress 86 and cooled. - Referring now to FIG. 6, a schematic diagram for making a
moldable chop 110 is shown. Individual sized bundledfibers 12 are unrolled from a plurality of formingcakes 30 and introduced through a slurry bath containing the powdercoating polymer material 20 dispersed in a slurry or emulsion. The aqueous powder coated slurry is approximately 40% solids and is adhered mostly to theouter fibers 16 of thebundle 12 to form the compositeroving material 10. A stripper die 34, is used the meter the amount ofpowder coating 20 on thecoated bundle 12. The amount ofpowder coating material 20 metered onto thebundle 12 is controlled by varying the size of the orifice (not shown) in the stripper die 34. Thecoated bundle 12 is then sent through a dryingoven 36 to remove water from thepowder coating material 20 that forms the compositeroving material 10. The dryingoven 36 should be maintained at a temperature hot enough to remove the water from thepowder coating 20 but cool enough to prevent thepowder coating material 20 from significant melting. The compositeroving material 10 is then chopped to approximately one-half inchmoldable chop 110 in length using achopper 39 and stored in a container (not shown). - The
moldable chop 110, at approximately one-half inch, is similar to or smaller in size than the chopped compositeroving material 41 of FIGS. 3-5. This allows thechop 110 to be easily poured from the container into a mold for compression molding. This forms a composite part 80 (not shown) having good reinforcing characteristics. Alternatively, thechop 110 could be layered onto thepreform 40 as in FIG. 3 to form a moldedcomposite part 80 having different lengthed fibers for different reinforcing applications. - Referring now to FIGS. 7A, 7B, and7C, the composite
roving material 10 of FIG. 1 may be alternatively processed prior to a chopping steps as in FIGS. 3-6. Here, the compositeroving material 10 may be woven, as shown in FIG. 7A, knitted, as described in FIG. 7B, or braided, as described in FIG. 7C, in a manner similar to what known in the fiberglass industry to form afabric 120. One or more layers of thefabric 120 may then be placed in a mold and compression molded as described above in FIG. 3 to formcomposite parts 80 having unique reinforcing characteristics. - While some seepage of the
powder coating material 20 into the plurality ofinner fibers 14 may occur when compression molding thecomposite part 80 as in FIGS. 3-6, 7A-7C, most of thepowder coating material 20 is maintained along theouter surface 22 of theouter fibers 16 around thebundle 12. This is an important aspect of the present invention, as this arrangement producescomposite parts 80 having good mechanical properties including impact resistance. - FIG. 8 compares and contrasts mechanical properties of structural reaction injection molding (“SRIM”), sheet molding compound (“SMC”), 70% fiber composite part, and 75% fiber composite part according to the present invention. As seen in FIG. 8, the
composite parts 80 of the present invention had improved tensile strength, tensile modulus, flex stress, and impact resistance (both notched and unnotched Izod) as compared with similar size and shaped SRIM and SMC composite parts. Further, the higher fiber content in the composite part improved tensile modulus, flex stress, and impact resistance as compared with the lower fiber content composite parts. - The present invention offers many advantages over typical structural composite materials in terms of mechanical properties, cost and processing. Many problems exist with the technologies used to make structural composites and inherent in the structural composites themselves. For example, the volatile organic content (VOC) that may be released to the atmosphere during the processing steps for the present invention is minimal.
- Also, the
composite parts 80 of the present invention offer good mechanical properties due to theirhigh fiber - In addition, the process used to make the
composite parts 80 is simple, thus minimizing the manufacturing costs as compared with other structural composites. For example, in a typical SRIM process, the reinforcement materials and polymer resin are introduced individually to the molding equipment and the part is molded, which adds to the cost of manufacture. - Also, because the
powdered polymer material 20 is added in metered amounts to the outside of the fiber bundles 12, the composition of the finalcomposite parts 80 is precisely controlled as compared with other structural composite systems, wherein the polymer resin material and fiber content are separately introduced into an injection mold or similar apparatus. This is important because the structural and mechanical properties of thecomposite parts 80 may be more precisely controlled from part to part. - Similarly, aesthetic properties of the
composite parts 80 of the present invention may be more precisely controlled and enhanced. For example, dyes or colored powders may be added to thepowder coating material 20 that may then be molded into the finalcomposite part 80. - Additionally, problems inherent with processing and manufacturing composite parts with high fiber content are eliminated in the present invention. For example, as described above, it is difficult to introduce a high fiber content into an injection molding process. Therefore, the amount of fiber content that may be loaded within the composite part is controlled by the mechanical properties desired, not by the inherent problems with the process itself As polymer resins are typically more expensive than the fiber reinforcement material, the cost of the composite part is correspondingly decreased as more fiber is introduced. Therefore, composite parts having fiber contents surpassing 70% or more may be realized.
- Finally, cost savings both in terms of manufacturing costs and raw material costs are realized by the present invention.
- While the invention has been described in terms of preferred embodiments, it will be understood, of course, that the invention is not limited thereto since modifications may be made by those skilled in the art, particularly in light of the foregoing teachings.
Claims (26)
1. A composite roving used for making structural composites comprising:
a continuous fiber bundle of a first fiber type, said continuous fiber bundle having a plurality of inner fibers and a plurality of outer fibers coupled together with a high integrity sizing material; and
a powder coating applied to an outer portion of said plurality of outer fibers.
2. The composite roving of claim 1 , wherein said first fiber type is selected from the group consisting of e-type glass, s-type glass, carbon fiber, aramid fibers, synthetic fibers, and natural fibers.
3. The composite roving of claim 1 , wherein said powder coating comprises between approximately ten and eighty percent by weight of the dry total weight the composite roving.
4. The composite roving of claim 1 , wherein said powder coating comprises between approximately twenty and thirty percent by weight of the dry total weight the composite roving.
5. The composite roving of claim 1 , wherein said powder coating is selected from the group consisting of a polyester powder coating, a bisphenol-type epoxy powder coating, a novalac epoxy powder coating, a phenolic powder coating, a hybrid epoxy and polyester powder coating, a polyurethane powder coating, and an acrylic powder coating.
6. The composite roving of claim 1 , wherein said powder coating is a thermoplastic powder coating.
7. A method for forming a composite roving for use in structural composites comprising the steps of:
forming a sized fiber bundle of a first type having high structural integrity;
applying a first amount of an aqueous powder coating to an outer portion of said sized fiber bundle form a coated fiber bundle; and
drying said coated fiber bundle to remove water from said aqueous powder coating.
8. The method of claim 7 , wherein the step of applying a first amount of an aqueous powder coating comprises the steps of:
dipping said sized fiber bundle into an aqueous slurry of a powder coating material; and
metering the amount of said aqueous slurry applied to said sized fiber bundle to a first amount.
9. The method of claim 8 , wherein the step of metering the amount of said aqueous slurry applied to said sized fiber bundle to a first amount comprises the step of metering the amount of said aqueous slurry applied to said sized fiber bundle to a first amount using a stripper die.
10. The method of claim 8 , wherein the step of metering the amount of said aqueous slurry applied to said sized fiber bundle to a first amount comprises the step of metering the amount of said aqueous slurry applied to said sized fiber bundle to a first amount using a squeegee.
11. A method for forming a structural composite part comprising the steps of:
forming a sized fiber bundle of a first type having high structural integrity, said sized fiber bundle comprising a plurality of inner fibers and a plurality of outer fibers and a high integrity sizing composition;
applying a first amount of an aqueous powder coating to an outer portion of said plurality of outer fibers to form a coated fiber bundle; and
drying said coated fiber bundle to form a composite roving, wherein the weight of said plurality of inner fibers and said plurality of outer fibers within said composite roving comprises between approximately ten and eighty percent of the dry total weight of said coated fiber bundle;
chopping said composite roving into a plurality of chopped strands having a first length; and
compression molding said plurality of chopped strands to a desired shape to form the structural composite part.
12. The method of claim 11 , wherein the step of applying a first amount of an aqueous powder coating comprises the steps of:
dipping said sized fiber bundle into an aqueous slurry of a powder coating material; and
metering the amount of said aqueous slurry applied to said sized fiber bundle to a first amount.
13. The method of claim 11 , wherein the step of metering the amount of said aqueous slurry applied to said sized fiber bundle to a first amount comprises the step of metering the amount of said aqueous slurry applied to said sized fiber bundle to a first amount using a stripper die.
14. The method of claim 11 , wherein the step of metering the amount of said aqueous slurry applied to said sized fiber bundle to a first amount comprises the step of metering the amount of said aqueous slurry applied to said sized fiber bundle to a first amount using a squeegee.
15. The method of claim 11 , wherein the step of drying said coated fiber bundle to form a composite roving comprises the step of air-drying said coated fiber bundle to form a composite roving, wherein the weight of said plurality of inner fibers and said plurality of outer fibers within said composite roving after the drying step comprises between approximately ten and eighty percent of the total dry weight of said coated fiber bundle.
16. The method of claim 11 , wherein the step of drying said coated fiber bundle to form a composite roving comprises the step of heating said coated fiber bundle in a drying oven to remove a quantity of water from said aqueous powder coating to form a composite roving, wherein the weight of said plurality of inner fibers and said plurality of outer fibers within said composite roving after the drying step comprises between approximately ten and eighty percent of the total dry weight of said coated fiber bundle.
17. The method of claim 11 , wherein the step of drying said coated fiber bundle to form a composite roving comprises the step of air-drying said coated fiber bundle to remove a quantity of water from said aqueous powder coating to form a composite roving, wherein the weight of said plurality of inner fibers and said plurality of outer fibers within said composite roving after the air-drying step comprises between approximately ten and eighty percent of the total weight of said coated fiber bundle.
18. The method of claim 1 1, wherein the step of chopping said composite roving into a plurality of chopped strands comprising the steps of
chopping said composite roving in the presence of a hot air source device, wherein said hot air source device partially melts and tackifies said powder coating material on said composite roving; and
impacting said composite roving on a mold surface with sufficiently high temperature to keep said powder coating material tackified without reversibly curing said powder coating material.
19. The method of claim 11 , wherein the step compression molding said plurality of chopped strands to a desired shape to form the structural composite part comprises the steps of:
placing said plurality of chopped stands onto a preforming screen to form a preform;
heat consolidating said preform to form a handleable preform;
placing said handleable preform between a lower mold section and an upper mold section of a press;
compressing said handleable preform between said lower mold section and said upper mold section of said press for a predetermined amount of time at a predetermined pressure and at a predetermined elevated temperature of said upper mold section sufficient to melt, flow and cure a powder coating material contained within said composite roving to form the structural composite part; and
releasing the structural composite part from said press.
20. The method of claim 19 , wherein said predetermined elevated temperature is between approximately 300 and 450 degrees Fahrenheit and said predetermined pressure is between approximately 300 and 1200 pounds per square inch.
21. The method of claim 11 , wherein the step compression molding said plurality of chopped strands to a desired shape to form the structural composite part comprises the steps of:
placing said plurality of chopped stands onto a moving belt;
compacting and heating said plurality of chopped strands to form a preform;
cutting said preform to a desired size and shape;
placing at least one layer of said preform between a lower mold section and an upper mold section of a press;
compressing said preform between said lower mold section and said upper mold section of said press for a predetermined amount of time at a predetermined pressure and at a predetermined elevated temperature of said upper mold section sufficient to melt, flow and cure a powder coating material contained within said composite roving to form the structural composite part; and
releasing the structural composite part from said press.
22. The method of claim 21 , wherein said predetermined elevated temperature is between approximately 300 and 450 degrees Fahrenheit and said predetermined pressure is between approximately 300 and 1200 pounds per square inch.
23. A method for forming a structural composite part comprising the steps of:
forming a sized fiber bundle of a first type having high structural integrity, said sized fiber bundle comprising a plurality of inner fibers and a plurality of outer fibers and a high integrity sizing composition;
applying a first amount of an aqueous powder coating to an outer portion of said plurality of outer fibers to form a coated fiber bundle; and
drying said coated fiber bundle to form a composite roving, wherein the weight of said plurality of inner fibers and said plurality of outer fibers within said composite roving comprises between approximately ten and eighty percent of the dry total weight of said coated fiber bundle;
coupling a plurality of strands of said composite roving to form a fabric;
placing at least one layer of said fabric in a mold; and
compression molding said at least one layer of fabric at a predetermined temperature and a predetermined pressure to form the structural composite part.
24. The method of claim 23 , wherein the step of coupling a plurality of strands of said composite roving to form a fabric comprises the step of weaving a plurality of strands of said composite roving to form a fabric.
25. The method of claim 23 , wherein the step of coupling a plurality of strands of said composite roving to form a fabric comprises the step of knitting a plurality of strands of said composite roving to form a fabric.
26. The method of claim 23 , wherein the step of coupling a plurality of strands of said composite roving to form a fabric comprises the step of braiding a plurality of strands of said composite roving to form a fabric.
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US12/688,165 US8802232B2 (en) | 2001-06-04 | 2010-01-15 | Powder coated roving for making structural composites |
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WO1999064216A1 (en) * | 1998-06-08 | 1999-12-16 | Complastik Corporation | Composite articles including prepregs, preforms, laminates and sandwich moldings, and methods of making the same |
US6630231B2 (en) * | 1999-02-05 | 2003-10-07 | 3M Innovative Properties Company | Composite articles reinforced with highly oriented microfibers |
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2001
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2002
- 2002-05-28 WO PCT/US2002/016431 patent/WO2002098961A1/en not_active Application Discontinuation
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2004
- 2004-06-02 US US10/858,692 patent/US7648733B2/en not_active Expired - Fee Related
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US5296064A (en) * | 1989-04-17 | 1994-03-22 | Georgia Tech Research Corp. | Flexible multiply towpreg tape from powder fusion coated towpreg and method for production thereof |
US5302419A (en) * | 1989-04-17 | 1994-04-12 | Georgia Tech Research Corporation | Towpregs from recycled plastics by powder fusion coating and method of production therefor |
US5360661A (en) * | 1989-04-17 | 1994-11-01 | Georgia Tech Research Corp. | Towpregs from recycled plastics by powder fusion coating |
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8802232B2 (en) | 2001-06-04 | 2014-08-12 | Ocv Intellectual Capital, Llc | Powder coated roving for making structural composites |
KR100983531B1 (en) | 2009-04-30 | 2010-09-30 | 조연호 | Method of manufacturing carbon fiber sheet |
US20110129608A1 (en) * | 2009-11-30 | 2011-06-02 | Adzima Leonard J | Methods of applying matrix resins to glass fibers |
WO2013017434A1 (en) * | 2011-07-29 | 2013-02-07 | Toho Tenax Europe Gmbh | Flexible reinforcement fiber yarn pre-impregnated with resin |
AU2012292259B2 (en) * | 2011-07-29 | 2014-11-06 | Toho Tenax Europe Gmbh | Flexible reinforcement fiber yarn pre-impregnated with resin |
TWI565844B (en) * | 2011-07-29 | 2017-01-11 | 東邦特耐克絲歐洲股份有限公司 | Flexible reinforcing fiber yarn pre-impregnated with resin |
Also Published As
Publication number | Publication date |
---|---|
US20040241441A1 (en) | 2004-12-02 |
WO2002098961A1 (en) | 2002-12-12 |
US7648733B2 (en) | 2010-01-19 |
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