US20080020193A1 - Hybrid fiber tows containning both nano-fillers and continuous fibers, hybrid composites, and their production processes - Google Patents
Hybrid fiber tows containning both nano-fillers and continuous fibers, hybrid composites, and their production processes Download PDFInfo
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- US20080020193A1 US20080020193A1 US11/491,657 US49165706A US2008020193A1 US 20080020193 A1 US20080020193 A1 US 20080020193A1 US 49165706 A US49165706 A US 49165706A US 2008020193 A1 US2008020193 A1 US 2008020193A1
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- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02J—FINISHING OR DRESSING OF FILAMENTS, YARNS, THREADS, CORDS, ROPES OR THE LIKE
- D02J1/00—Modifying the structure or properties resulting from a particular structure; Modifying, retaining, or restoring the physical form or cross-sectional shape, e.g. by use of dies or squeeze rollers
- D02J1/18—Separating or spreading
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- 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
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- 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
- B29B15/122—Coating or impregnating independently of the moulding or shaping step of reinforcements of indefinite length with a matrix in liquid form, e.g. as melt, solution or latex
- B29B15/125—Coating or impregnating independently of the moulding or shaping step of reinforcements of indefinite length with a matrix in liquid form, e.g. as melt, solution or latex by dipping
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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
- B29C70/02—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising combinations of reinforcements, e.g. non-specified reinforcements, fibrous reinforcing inserts and fillers, e.g. particulate fillers, incorporated in matrix material, forming one or more layers and with or without non-reinforced or non-filled layers
- B29C70/021—Combinations of fibrous reinforcement and non-fibrous material
- B29C70/025—Combinations of fibrous reinforcement and non-fibrous material with particular filler
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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
- B29C70/06—Fibrous reinforcements only
- B29C70/10—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres
- B29C70/16—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of substantial or continuous length
- B29C70/20—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of substantial or continuous length oriented in a single direction, e.g. roofing or other parallel fibres
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04C—BRAIDING OR MANUFACTURE OF LACE, INCLUDING BOBBIN-NET OR CARBONISED LACE; BRAIDING MACHINES; BRAID; LACE
- D04C1/00—Braid or lace, e.g. pillow-lace; Processes for the manufacture thereof
- D04C1/06—Braid or lace serving particular purposes
- D04C1/12—Cords, lines, or tows
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
- D04H3/02—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of forming fleeces or layers, e.g. reorientation of yarns or filaments
- D04H3/04—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of forming fleeces or layers, e.g. reorientation of yarns or filaments in rectilinear paths, e.g. crossing at right angles
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
- D04H3/08—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating
- D04H3/12—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with filaments or yarns secured together by chemical or thermo-activatable bonding agents, e.g. adhesives, applied or incorporated in liquid or solid form
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
- D06B1/00—Applying liquids, gases or vapours onto textile materials to effect treatment, e.g. washing, dyeing, bleaching, sizing or impregnating
- D06B1/04—Applying liquids, gases or vapours onto textile materials to effect treatment, e.g. washing, dyeing, bleaching, sizing or impregnating by pouring or allowing to flow on to the surface of the textile material
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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
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
- B29K2105/16—Fillers
- B29K2105/162—Nanoparticles
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- 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
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249924—Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity
Definitions
- the present invention is related to a hybrid composite containing both a nano-filler and a continuous fiber dispersed in a matrix material.
- the nano-filler comprises nano-scaled graphene plates (NGPs), carbon nano-tubes (CNTs), carbon nano-fibers (CNFs), nano-clay platelets, nano-rods, or any other nanoscale reinforcement with at least an elongate axis.
- the matrix material comprises a polymer, organic, metal, ceramic, glass, carbon material, or a combination thereof.
- the nano-filler can be made to be substantially oriented in a preferred direction (e.g., with an elongate axis perpendicular to the continuous fiber).
- Advanced composites containing continuous fibers dispersed in a matrix material
- polymer matrices and carbon or graphite fibers are examples, continuous carbon fiber reinforced polymer composites exhibit these good properties only in the directions parallel to the fiber axial directions. In other words, these composites have excellent in-plane properties and relatively poor thickness-direction and shear properties.
- the thickness-direction and shear strengths and moduli of continuous carbon fiber reinforced polymer composite laminates are relatively poor. Poor interlaminar shear strengths in turn lead to poor delamination resistance. Incorporation of reinforcements that are oriented in a direction perpendicular to the continuous fiber axis can significantly improve these mechanical properties.
- the longitudinal conductivities (both thermal and electrical) of a carbon fiber are orders of magnitude greater than its corresponding transverse conductivities.
- the transverse conductivities of a composite laminate are also much lower than the longitudinal properties.
- the transverse conductivities of a continuous fiber composite can be significantly improved by incorporating a reinforcement phase perpendicular to the continuous fiber axis.
- the addition of transverse reinforcements such as short (chopped) fibers is known to create processing difficulties.
- nanoscale fillers like carbon nano-tubes (CNTs) and carbon nano-fibers (CNFs)
- a small amount of these nano-fillers could dramatically alter the flow properties (e.g., increased viscosity) of a matrix resin.
- the resulting matrix material, a nano-filler/resin mixture is typically so viscous that it becomes extremely difficult to disperse continuous fibers in this matrix.
- the loading of conductive nano-fillers increases the viscosity of the matrix resin to a level that is not conducive to filament winding and other automated composite manufacturing techniques.
- a low percentage ( ⁇ 5% by wt.) of nano-fillers normally does not provide adequate through-thickness thermal or electrical conductivity to a composite structure for certain engineering applications.
- nanoscale fillers are finely dispersed in the matrix, the tremendous surface area developed could contribute to both polymer chain confinement and load transfer effects, leading to higher glass transition temperature, stiffness, and strength; (2) nanoscale fillers provide an extraordinarily zigzagging, tortuous path that leads to enhanced resistance to micro-cracking; (3) nanoscale fillers can also enhance the electrical and thermal conductivities; and (4) carbon-based nanoscale fillers have excellent thermal protection properties and, when incorporated in a matrix material, could eliminate the need for a thermal protective layer—for instance, in missile and rocket applications.
- Nanodia carbon nanotubes
- An NGP is a nanoscale platelet composed of one or more layers of graphene plane.
- carbon atoms occupy a 2-D hexagonal lattice. These carbon atoms are bonded together through strong covalent bonds lying on this plane.
- several graphene planes may be weakly bonded together primarily through van der Waals forces.
- An NGP may be viewed as a flattened sheet of a CNT.
- NGP-reinforced composites are also expected to exhibit similar properties compared to CNT-reinforced composites.
- the NGP-resin mixture a nanocomposite
- the resulting hybrid composite (containing both the NGP and the continuous fiber as reinforcement phases) is expected to have improved mechanical and physical properties compared to the conventional fiber composite (containing only continuous fiber, no NGP).
- the loading of nano-fillers e.g., CNTs and CNFs
- such a process can be automated.
- the present invention provides a process that is capable of producing a hybrid composite that contains both nano-fillers (e.g., NGPs, CNTs, CNFs, or a combination thereof) and continuous fibers as reinforcement phases dispersed in a matrix material.
- the nano-fillers can be oriented in a direction that is non-parallel to the longitudinal axis direction of the continuous fiber (e.g., preferably perpendicular to the continuous fiber axis).
- the process begins with spreading a continuous fiber tow separate continuous filaments from each other and then incorporating nano-fillers in a continuous fiber tow with individual nano-fillers embedded in the interstitial spaces between continuous filaments.
- hybrid fiber tow is then impregnated with a resin to produce a resin-pre-impregnated hybrid tow or hybrid towpreg.
- This wet hybrid towpreg can then go through a filament winding, fiber placement, prepregging, or pultrusion process for making a composite structure.
- the hybrid fiber tow can be woven, braided, knitted, or stitched into a textile-structured preform, which is then impregnated with a resin.
- the process may involve incorporating continuous fibers, nano-fillers, and a matrix-making material in a powder form concurrently to form a matrix-forming powder-impregnated hybrid fiber tow, a dry hybrid towpreg.
- the dry hybrid towpreg can then go through a filament winding, fiber placement, weaving, braiding, knitting, or stitching to form a structured preform, which is then converted to become a hybrid composite structure by heating and consolidating the matrix-forming material to become the solid matrix material.
- the present invention also provides hybrid fiber tows, hybrid fiber towpregs, and resulting hybrid fiber composites that can be composed of a wide range of fibers, fillers, and matrix materials.
- the versatility of the invented process opens up a window of many application opportunities for hybrid composites containing continuous fibers and nano-fillers such as NGPs, CNTs, and CNFs.
- FIG. 1 ( a ) Schematic of a hybrid fiber tow containing nano-fillers 16 , 18 embedded in the interstitial spaces 14 between continuous filaments 12 and ( b ) schematic of a hybrid fiber towpreg containing both nano-fillers and a matrix-forming material (e.g., thermoplastic powder particles 20 ) embedded in the interstitial spaces between continuous filaments.
- a matrix-forming material e.g., thermoplastic powder particles 20
- FIG. 2 Schematic of a roll-to-roll process for continuous production of hybrid fiber tows or towpregs.
- FIG. 3 Schematic of a process for continuously producing a towpreg and fabricating a composite structure.
- FIG. 4 Schematic of another version of the roll-to-roll process for the continuous production of hybrid fiber tows or towpregs.
- FIG. 5 Transverse thermal conductivity of hybrid composites containing continuous carbon fibers and NGPs (7 compositions) and CNTs (2 compositions).
- the conventional approach to fabricating composite materials containing both continuous fibers and fillers typically involves mixing the fillers with a resin first, followed by impregnating the continuous fiber tows with the resin/filler mixture.
- a small amount of nano-fillers like carbon nano-tubes (CNTs) and carbon nano-fibers (CNFs) could dramatically increase the viscosity of a matrix resin.
- the resulting nano-filler/resin mixture is typically so viscous that it becomes extremely difficult to disperse continuous fibers in this matrix.
- nano-fillers can be incorporated in a hybrid composite.
- the prior-art sequence of mixing nano-fillers with a resin and then impregnating continuous fibers with the nano-filler/resin mixture tends to produce a hybrid composite with fillers oriented along the continuous fiber axis. Such an orientation does not improve thickness-direction properties and shear properties of a composite laminate with continuous fibers lying on a laminar plane.
- This process also enables impregnation of continuous fiber/nano-filler preform shape with a ceramic, glass, or carbon matrix via a specialized technique like chemical vapor infiltration to produce corresponding hybrid composites, which otherwise would be difficult to obtain.
- a fluidized-bed powder impregnation or coating process ( FIG. 2 ) has been successfully adapted for incorporating a controlled percentage of nano-fillers (e.g., NGPs, CNFs, and/or CNTs) in a continuous fiber tow (consisting of multiple filaments) to produce a hybrid fiber tow containing nano-fillers residing in the interstices between individual filaments.
- the process begins with continuously feeding a fiber tow into a fiber tow spreader to separate individual carbon filaments from one another, opening up interstitial spaces between filaments to accommodate nano-fillers.
- the separated filaments are fed into a fluidized bed chamber in which nano-fillers are driven by an air flow to move around like a fluid.
- the nano-fillers are trapped in the interstitial spaces with an elongate axis of the filler typically oriented in the fluid flow direction. This direction can be controlled to ensure that a majority of the fillers are oriented perpendicular to the longitudinal axis of the continuous fibers.
- the resulting structure is a continuous hybrid fiber tow, as schematically shown in FIG. 1( a ).
- Electrostatic charges may be imparted to nano-fillers to facilitate attraction of nano-fillers to the carbon fiber tow.
- This is analogous to the conventional towpreg production operation by which micron-scaled thermoplastic powder particles, serving as a precursor to the composite matrix, are incorporated into a continuous fiber tow [e.g., J. D. Muzzy, et al., U.S. Pat. No. 5,094,883, Mar. 10, 1992].
- No nanoscale filler was involved in this earlier process.
- a matrix-forming material e.g., thermoplastic powder particles 20 in FIG. 1( b )
- a matrix-forming material in addition to nano-fillers, is also suspended in the fluidized medium.
- the resulting structure composed of continuous fibers, nano-fillers, and a matrix-forming material, is hereinafter referred to as a hybrid towpreg.
- the hybrid towpreg may then be subjected to a weaving, winding, or any other textile structure-forming procedure to produce a composite preform, which is heated (to melt out the thermoplastic powder) and consolidated to obtain a composite structure.
- the continuous hybrid fiber tow may be directed to enter a resin bath for impregnation with a matrix resin in a filament-winding, prepreg-forming, pultrusion, or fiber placing operation ( FIG. 3 ).
- This resin can be a thermosetting, cyclic, or thermoplastic resin. This is an automated process that is suitable for mass production of hybrid composites.
- the hybrid fiber tow may be subjected to weaving, winding, braiding, stitching, knitting, freeform fabrication, and/or other textile-forming procedures to produce a dry composite preform, which is then impregnated with a matrix material to obtain a composite structure.
- the preform With a polymer matrix, the preform can be impregnated through resin transfer molding, reaction injection molding, vacuum-assisted transfer molding, pressure-assisted liquid resin impregnation, etc.
- the preform can be impregnated through microwave-assisted infiltration, liquid metal impregnation, etc.
- the preform can be impregnated through chemical vapor deposition or chemical vapor infiltration.
- a resin-impregnated preform can be subjected to a heat treatment (pyrolization) that converts a polymer into a carbonaceous matrix.
- the nanoscale filler that can be used in the presently invented hybrid fiber tow, towpreg, or composite can be a nanoscale graphene plate, non-graphite platelet, carbon nano-tube, nano-rod, carbon nano-fiber, non-carbon nano-fiber, or a combination thereof.
- These entities all have one thing in common—they have at least on elongate axis.
- CNTs have one elongate axis (in the tube axial direction) and platelets have two elongate axes (in the length and width direction).
- the resulting hybrid composite can easily have nano-fillers that are present at a loading of greater than 5% by weight based on the total weight of nano-fillers plus the matrix material.
- the nano-fillers in many cases exceed 15% by weight.
- a majority of these nano-fillers have an elongate axis oriented at an angle of at least 45 degrees with respect to the continuous fiber axis. If improved transverse thermal or electrical conductivities are desired, carbon-based nano-
- the NGPs obtained in our facilities typically have a platelet thickness of 1-100 nm and length and width of 0.1-10 ⁇ m. These rigid two-dimensional platelets appear to be conducive to fitting into inter-filament interstices.
- the nanoscale graphene plate or non-graphite platelet that has a length or width smaller than 500 nm is particularly well-suited to the present application.
- the flexibility of both the CNT and the CNF afforded to by their large length-to-diameter ratios makes these one-dimensional structures tend to assume curved or coiled shapes and should make it more difficult to be incorporated in a hybrid composite.
- the presently invented process is capable of incorporating CNTs and CNFs into the inter-filament spaces.
- a fluidized-bed powder impregnation apparatus schematically shown in FIG. 2 , was designed and constructed for incorporating a controlled percentage of nano-fillers in a continuous fiber tow to produce a hybrid fiber tow.
- the apparatus is mainly composed of a feeder roller, a fiber tow spreader, a fluidized bed chamber, and an optional fiber tow consolidator.
- the fiber tow (or strands of fibers or filaments) is reeled from a fiber spool or feeder roller and directed to go through a tow spreader in which individual filaments are separated from each other.
- the separated fibers are fed into the fluidized bed chamber in which the nano-fillers, “fluidized” by an air flow, are introduced to impinge upon the fibers.
- the nano-fillers may be electrostatically charged and the fiber tow grounded to promote nano-filler impregnation of the fiber tow, with nano-fillers residing in interstices between fibers while being re-merged or compacted.
- the fluidized bed powder coating apparatus are well-known in the art. For instance, these apparatus were successfully used to prepare a towpreg that is composed of reinforcing filaments coated with matrix-forming resin powder as a precursor to a plastic matrix composite [J. Lamanche, et al., U.S. Pat. No. 3,703,396 (Nov. 21, 1972)].
- a key component in the system is a tow spreader. Spreading of the filaments can be achieved by vibrating the graphite fiber tow in air pulsating at a frequency and intensity sufficient to couple the energy of the pulsating medium to the graphite tow [e.g., S. Iyer, et al., U.S. Pat. No. 5,042,122 (Aug. 27, 1991)]. Spreading may also be facilitated or promoted by using air currents or electrostatic charges of the same polarity.
- An optional filament re-merger or compactor may be used to facilitate the merging of separated filaments, along with the embedded nano-fillers, into a more compact fiber tow.
- This filament re-merging step can occur before, during, and after the resin impregnation step.
- Resin impregnation can be part of a filament-winding, prepreg-forming, fiber-placing, or pultrusion process.
- the continuous filament can be a polymer fiber, ceramic fiber, carbon fiber, graphite fiber, glass fiber, or a combination thereof.
- the nano-fillers are preferably oriented in a direction substantially non-parallel to the continuous filament axial direction and further preferably perpendicular to the filament axis.
- the process for producing a hybrid fiber tow comprises (a) spreading a continuous fiber tow into multiple, separated filaments that define interstitial spaces between the filaments; (b) exposing the separated filaments to a fluid medium or fluidized medium containing nanoscale fillers under a flow condition for a duration of time sufficient to cause the nanoscale fillers to stay in the interstitial spaces; and (c) moving the separated filaments with the interstitial nanoscale fillers away from the medium to produce the hybrid fiber tow.
- the step of exposing can comprise moving the separated filaments through a fluidized bed comprising a fluidized medium that contains the nanoscale particles suspended in the medium, as illustrated in FIG. 2 .
- the fluidized bed may be provisioned with electrostatic charging means to facilitate attraction of the nanoscale fillers to the filaments.
- the step of exposing comprises moving the separated filaments through a fluid medium that contains the nanoscale particles suspended in a liquid or solution.
- the fluidized-bed powder coater device shown in FIG. 2 is now replaced by a tank of liquid with nano-fillers suspended in the liquid which is driven (e.g., pumped) to flow around in the tank with a desired flow pattern that enables impingement of nano-fillers with the continuous filaments at a desired direction.
- the step of exposing can comprise moving the separated filaments at a desired speed in a desired direction while directing a stream of a liquid medium (or gaseous medium such as air) containing the nanoscale fillers to impinge upon the filaments in such a manner that the fillers are trapped in the interstitial spaces to form a hybrid fiber tow.
- the process begins with reeling a continuous fiber tow 54 from a fiber spool 32 , feeding the tow into a tow spreader 56 to obtain separated filaments 58 , which are impinged upon by a fluid (liquid or air) suspending nano-fillers 60 therein.
- the nano-fillers are trapped between filaments, allowing the liquid or air to filter through the gaps between filaments.
- the hybrid tow 62 can be optionally compacted by a compactor or consolidator 64 to become consolidated hybrid fiber tow which is then collected on a take-up roller 46 . Again, such a roll-to-roll process is suitable for mass production of composites.
- the fluid medium e.g., in FIG. 4
- fluidized medium e.g., in FIG. 2 or 3
- the step of exposing then comprises causing both the nanoscale fillers and the matrix-forming material to stay in the interstitial spaces to form a matrix-forming material-impregnated hybrid tow, referred to as a hybrid fiber towpreg.
- the matrix-forming material may also be coated onto the surface of continuous filaments.
- the process further comprises (d) reeling the continuous fiber tow from a roller or spool prior to the fiber tow spreading step; (e) impregnating the hybrid fiber tow with a matrix material to form a matrix-impregnated hybrid fiber tow; (f) subjecting the matrix-impregnated hybrid tow to a shape-forming operation to form a composite shape; and (g) consolidating the composite shape through heating, curing, and/or cooling the matrix material to form a hybrid composite structure.
- the shape-forming operation can comprise a filament winding, fiber placement, prepreg-forming, pultrusion, freeform fabrication step, or a combination thereof. Freeform fabrication involved computerized deposition of a material point-by-point and layer-by-layer. The process is also commonly referred to as rapid prototyping.
- the process comprises, in addition to aforementioned steps (a), (b), and (c), the following steps: (d) reeling the continuous fiber tow from a roller or spool prior to the fiber tow spreading step; (e) subjecting the hybrid fiber tow to a shape-forming operation to form a composite preform; (f) impregnating the preform with a matrix material; and (g) consolidating the matrix-impregnated preform through heating, curing, and/or cooling the matrix material to form a hybrid composite structure.
- the shape-forming operation can comprise a step of filament winding, fiber placement, freeform fabrication, weaving, braiding, stitching, knitting, or a combination thereof.
- the process comprises, in addition to the aforementioned steps (a), (b), and (c), the following steps: (d) reeling the continuous fiber tow from a roller or spool prior to the fiber tow spreading step; (e) subjecting the hybrid fiber towpreg to a shape-forming operation to form a composite shape; and (f) consolidating the composite shape through heating, curing, and/or cooling the matrix-forming material to form a hybrid composite structure.
- the shape-forming operation can include a step of filament winding, fiber placement, prepreg-forming, freeform fabrication, weaving, braiding, stitching, knitting, or a combination thereof.
- the step of consolidating can comprise melting a matrix material, cooling or solidifying a matrix material, curing a resin, polymerizing or cross-linking a resin precursor, converting an organic or polymeric material to a carbonaceous material, chemical vapor infiltration, or a combination thereof.
- the thermal conductivity values of a series of hybrid composites containing continuous graphite fibers (approximately 60% by volume of the total composite) and NGP/epoxy matrix materials (with several NGP weight fractions based on the total NGP/epoxy weight) or CNT/epoxy matrices As shown in FIG. 5 , the transverse thermal conductivity values of hybrid composites (with NGPs substantially perpendicular to the continuous graphite fiber direction) can be improved from approximately 9.1 Wm ⁇ 1 K ⁇ 1 for a continuous graphite fiber/epoxy composite (0% NGP) to 193 Wm ⁇ 1 K ⁇ 1 for a hybrid composite (15% NGP).
- the longitudinal thermal conductivity values, parallel to the continuous graphite fiber direction, for all these composites are in the range of 125-180 Wm ⁇ 1 K ⁇ 1 , relatively independent of the NGP content in the matrix. Addition of CNTs has also significantly improved the transverse thermal conductivity of the hybrid composite, albeit to a smaller extent.
- the high transverse as well as longitudinal thermal conductivity for these composites is a highly significant result since thermally conductive composites can be used as thermal management materials for microelectronic devices and rocket motor cases, just to cite two of many examples.
Abstract
Description
- This invention is based on the research results of a project supported by the U.S. Department of Energy (DOE) SBIR-STTR Program. The US Government has certain rights on this invention.
- The present invention is related to a hybrid composite containing both a nano-filler and a continuous fiber dispersed in a matrix material. The nano-filler comprises nano-scaled graphene plates (NGPs), carbon nano-tubes (CNTs), carbon nano-fibers (CNFs), nano-clay platelets, nano-rods, or any other nanoscale reinforcement with at least an elongate axis. The matrix material comprises a polymer, organic, metal, ceramic, glass, carbon material, or a combination thereof. The nano-filler can be made to be substantially oriented in a preferred direction (e.g., with an elongate axis perpendicular to the continuous fiber).
- Advanced composites, containing continuous fibers dispersed in a matrix material, are widely used in aerospace, sports equipment, infrastructure, automotive, and other transportation industries, as both primary and secondary load-bearing structures. These composite materials derive their excellent mechanical strength, stiffness, electrical conductivity, and thermal conductivity from the reinforcement fibers. However, using polymer matrices and carbon or graphite fibers are examples, continuous carbon fiber reinforced polymer composites exhibit these good properties only in the directions parallel to the fiber axial directions. In other words, these composites have excellent in-plane properties and relatively poor thickness-direction and shear properties.
- Specifically, the thickness-direction and shear strengths and moduli of continuous carbon fiber reinforced polymer composite laminates are relatively poor. Poor interlaminar shear strengths in turn lead to poor delamination resistance. Incorporation of reinforcements that are oriented in a direction perpendicular to the continuous fiber axis can significantly improve these mechanical properties.
- In addition, the longitudinal conductivities (both thermal and electrical) of a carbon fiber are orders of magnitude greater than its corresponding transverse conductivities. Hence, the transverse conductivities of a composite laminate are also much lower than the longitudinal properties. The transverse conductivities of a continuous fiber composite can be significantly improved by incorporating a reinforcement phase perpendicular to the continuous fiber axis. However, the addition of transverse reinforcements such as short (chopped) fibers is known to create processing difficulties. Even with nanoscale fillers like carbon nano-tubes (CNTs) and carbon nano-fibers (CNFs), a small amount of these nano-fillers could dramatically alter the flow properties (e.g., increased viscosity) of a matrix resin. The resulting matrix material, a nano-filler/resin mixture, is typically so viscous that it becomes extremely difficult to disperse continuous fibers in this matrix.
- Further specifically, on the one hand, the loading of conductive nano-fillers (e.g., >5 wt. % of CNTs or CNFs) increases the viscosity of the matrix resin to a level that is not conducive to filament winding and other automated composite manufacturing techniques. On the other hand, a low percentage (<5% by wt.) of nano-fillers normally does not provide adequate through-thickness thermal or electrical conductivity to a composite structure for certain engineering applications. A need exists to develop an approach that can resolve these conflicting issues; i.e. a process capable of combining continuous fibers with a matrix that features an adequate proportion of nano-fillers dispersed in a resin or other material with these fillers preferentially oriented along a desired direction for improved transverse or shear properties.
- Generally, the advantages of nanoscale reinforcements in polymer matrices are fourfold: (1) when nanoscale fillers are finely dispersed in the matrix, the tremendous surface area developed could contribute to both polymer chain confinement and load transfer effects, leading to higher glass transition temperature, stiffness, and strength; (2) nanoscale fillers provide an extraordinarily zigzagging, tortuous path that leads to enhanced resistance to micro-cracking; (3) nanoscale fillers can also enhance the electrical and thermal conductivities; and (4) carbon-based nanoscale fillers have excellent thermal protection properties and, when incorporated in a matrix material, could eliminate the need for a thermal protective layer—for instance, in missile and rocket applications.
- Fabrication of carbon nanotubes (CNTs) is expensive, particularly for the purifying process required to make them useful in applications. Instead of trying to discover lower cost processes for CNTs, we have been seeking to develop an alternative nanoscale carbon material with comparable properties that can be produced cost-effectively and in larger quantities. This development work has led to the discovery of processes for producing a new class of nano material herein referred to as nanoscale graphene plates (NGP) [Jang, et al., “Nano-scaled Graphene Plates,” U.S. Pat. No. 7,071,258 (Jul. 4, 2006) and “Process for Producing Nano-scaled Graphene Plates,” U.S. patent pending, Ser. No. 10/858,814 (Jun. 3, 2004)]. An NGP is a nanoscale platelet composed of one or more layers of graphene plane. In a graphene plane, carbon atoms occupy a 2-D hexagonal lattice. These carbon atoms are bonded together through strong covalent bonds lying on this plane. In the c-axis direction, several graphene planes may be weakly bonded together primarily through van der Waals forces. An NGP may be viewed as a flattened sheet of a CNT. Although NGP and CNT are geometrically different in architecture, preliminary calculations have indicated very similar mechanical properties (in-plane stiffness and strength) and thermal and electrical conductivities (Table 1).
-
TABLE 1 Estimated physical constants of CNTs and NGPs. Property Single-Walled CNTs NGP Specific Gravity 0.8 g/cm3 1.8–2.2 g/cm3 Elastic modulus ~1 TPa ~1 TPa (in-plane) Strength 50–500 GPa ~100–400 GPa Resistivity 5–50 μΩ cm 50 μΩ cm (in plane) Thermal Up to 1,500 W m−1 K−1 3,000 W m−1 K−1 (in-plane) Conductivity (estimated) 6–30 W m−1 K−1 (c-axis) Magnetic 22 × 106 EMU/g (⊥ to 22 × 106 EMU/g (⊥ to the Susceptibility the plane) plane) 0.5 × 106 EMU/g (|| to 0.5 × 106 EMU/g (|| to the the plane) plane) Thermal Negligible (theoretical) −1 × 10−6 K−1 (in-plane) expansion 29 × 10−6 K−1 (c-axis) Thermal stability >700° C. (in air); 450–650° C. (in air) 2800° C. (in vacuum) Specific surface Typically 100–500 m2/g Up to 1,500 m2/g area - NGP-reinforced composites are also expected to exhibit similar properties compared to CNT-reinforced composites. When the NGP-resin mixture, a nanocomposite, is incorporated as a matrix for forming a continuous fiber reinforced composite, the resulting hybrid composite (containing both the NGP and the continuous fiber as reinforcement phases) is expected to have improved mechanical and physical properties compared to the conventional fiber composite (containing only continuous fiber, no NGP). A need exists for incorporating both NGPs and continuous fibers in a matrix material to make a hybrid composite. Further, as indicated earlier, the loading of nano-fillers (e.g., CNTs and CNFs) increases the viscosity of the matrix resin to a level that is not conducive to subsequent filament winding and other automated composite manufacturing techniques. A need exists to develop a process that is capable of combining both continuous fibers and CNTs, CNFs, other nano-rods, or nano-platelets with a matrix material to make a hybrid composite. Preferably, such a process can be automated.
- The present invention provides a process that is capable of producing a hybrid composite that contains both nano-fillers (e.g., NGPs, CNTs, CNFs, or a combination thereof) and continuous fibers as reinforcement phases dispersed in a matrix material. The nano-fillers can be oriented in a direction that is non-parallel to the longitudinal axis direction of the continuous fiber (e.g., preferably perpendicular to the continuous fiber axis). The process begins with spreading a continuous fiber tow separate continuous filaments from each other and then incorporating nano-fillers in a continuous fiber tow with individual nano-fillers embedded in the interstitial spaces between continuous filaments. The resulting hybrid fiber tow is then impregnated with a resin to produce a resin-pre-impregnated hybrid tow or hybrid towpreg. This wet hybrid towpreg can then go through a filament winding, fiber placement, prepregging, or pultrusion process for making a composite structure.
- Alternatively, the hybrid fiber tow can be woven, braided, knitted, or stitched into a textile-structured preform, which is then impregnated with a resin.
- The process may involve incorporating continuous fibers, nano-fillers, and a matrix-making material in a powder form concurrently to form a matrix-forming powder-impregnated hybrid fiber tow, a dry hybrid towpreg. The dry hybrid towpreg can then go through a filament winding, fiber placement, weaving, braiding, knitting, or stitching to form a structured preform, which is then converted to become a hybrid composite structure by heating and consolidating the matrix-forming material to become the solid matrix material.
- The present invention also provides hybrid fiber tows, hybrid fiber towpregs, and resulting hybrid fiber composites that can be composed of a wide range of fibers, fillers, and matrix materials.
- The versatility of the invented process opens up a window of many application opportunities for hybrid composites containing continuous fibers and nano-fillers such as NGPs, CNTs, and CNFs.
-
FIG. 1 (a) Schematic of a hybrid fiber tow containing nano-fillers interstitial spaces 14 betweencontinuous filaments 12 and (b) schematic of a hybrid fiber towpreg containing both nano-fillers and a matrix-forming material (e.g., thermoplastic powder particles 20) embedded in the interstitial spaces between continuous filaments. -
FIG. 2 Schematic of a roll-to-roll process for continuous production of hybrid fiber tows or towpregs. -
FIG. 3 Schematic of a process for continuously producing a towpreg and fabricating a composite structure. -
FIG. 4 Schematic of another version of the roll-to-roll process for the continuous production of hybrid fiber tows or towpregs. -
FIG. 5 Transverse thermal conductivity of hybrid composites containing continuous carbon fibers and NGPs (7 compositions) and CNTs (2 compositions). - The conventional approach to fabricating composite materials containing both continuous fibers and fillers (such as nanoscale fillers, short fibers, etc.) typically involves mixing the fillers with a resin first, followed by impregnating the continuous fiber tows with the resin/filler mixture. It is now well-recognized that a small amount of nano-fillers like carbon nano-tubes (CNTs) and carbon nano-fibers (CNFs) could dramatically increase the viscosity of a matrix resin. The resulting nano-filler/resin mixture is typically so viscous that it becomes extremely difficult to disperse continuous fibers in this matrix. Hence, it is also commonly believed that only a small amount of nano-fillers can be incorporated in a hybrid composite.
- Furthermore, the prior-art sequence of mixing nano-fillers with a resin and then impregnating continuous fibers with the nano-filler/resin mixture tends to produce a hybrid composite with fillers oriented along the continuous fiber axis. Such an orientation does not improve thickness-direction properties and shear properties of a composite laminate with continuous fibers lying on a laminar plane.
- Contrary to what composite materials experts would or might expect, we have developed an approach that enables the fabrication of hybrid composites containing a high proportion of nano-fillers with a preferential orientation that is substantially perpendicular to the continuous fiber axis (
FIG. 1( a)). Instead of mixing the nano-fillers with a matrix resin first and then impregnating continuous fibers with the nano-filler/resin mixture, we took a novel and innovative approach that involved mixing the nano-fillers with continuous fibers first to produce a hybrid fiber tow (with nano-fillers such as NGPs 16 and/orCNTs 18 embedded in theinterstitial spaces 14 between continuous fibers 12) and then impregnating the hybrid fiber tow with a resin. An important step was to spread a continuous fiber tow into separated, individual continuous filaments prior to nano-filler mixing or addition. It turns out that, with this sequence, the resin can readily penetrate into the interstitial spaces and wet out both the continuous fibers and nano-fillers. Any resin that is commonly used in a filament winding, prepregging, fiber placement, or pultrusion operation can be used in the invented process. This process surprisingly but elegantly accomplishes the task of fabricating advanced composites containing both continuous filaments (fibers) and nano-fillers as reinforcement phases. - This process also enables impregnation of continuous fiber/nano-filler preform shape with a ceramic, glass, or carbon matrix via a specialized technique like chemical vapor infiltration to produce corresponding hybrid composites, which otherwise would be difficult to obtain.
- As an example to illustrate this process, a fluidized-bed powder impregnation or coating process (
FIG. 2 ) has been successfully adapted for incorporating a controlled percentage of nano-fillers (e.g., NGPs, CNFs, and/or CNTs) in a continuous fiber tow (consisting of multiple filaments) to produce a hybrid fiber tow containing nano-fillers residing in the interstices between individual filaments. The process begins with continuously feeding a fiber tow into a fiber tow spreader to separate individual carbon filaments from one another, opening up interstitial spaces between filaments to accommodate nano-fillers. The separated filaments are fed into a fluidized bed chamber in which nano-fillers are driven by an air flow to move around like a fluid. When the air-suspended fillers impinge upon the filaments with desired interstitial space sizes the nano-fillers are trapped in the interstitial spaces with an elongate axis of the filler typically oriented in the fluid flow direction. This direction can be controlled to ensure that a majority of the fillers are oriented perpendicular to the longitudinal axis of the continuous fibers. The resulting structure is a continuous hybrid fiber tow, as schematically shown inFIG. 1( a). - Electrostatic charges may be imparted to nano-fillers to facilitate attraction of nano-fillers to the carbon fiber tow. This is analogous to the conventional towpreg production operation by which micron-scaled thermoplastic powder particles, serving as a precursor to the composite matrix, are incorporated into a continuous fiber tow [e.g., J. D. Muzzy, et al., U.S. Pat. No. 5,094,883, Mar. 10, 1992]. No nanoscale filler was involved in this earlier process.
- In one embodiment of the present invention, a matrix-forming material (e.g.,
thermoplastic powder particles 20 inFIG. 1( b)), in addition to nano-fillers, is also suspended in the fluidized medium. The resulting structure, composed of continuous fibers, nano-fillers, and a matrix-forming material, is hereinafter referred to as a hybrid towpreg. The hybrid towpreg may then be subjected to a weaving, winding, or any other textile structure-forming procedure to produce a composite preform, which is heated (to melt out the thermoplastic powder) and consolidated to obtain a composite structure. - In the presently invented hybridfiber tow approach, the continuous hybrid fiber tow may be directed to enter a resin bath for impregnation with a matrix resin in a filament-winding, prepreg-forming, pultrusion, or fiber placing operation (
FIG. 3 ). This resin can be a thermosetting, cyclic, or thermoplastic resin. This is an automated process that is suitable for mass production of hybrid composites. - Alternatively, the hybrid fiber tow may be subjected to weaving, winding, braiding, stitching, knitting, freeform fabrication, and/or other textile-forming procedures to produce a dry composite preform, which is then impregnated with a matrix material to obtain a composite structure. With a polymer matrix, the preform can be impregnated through resin transfer molding, reaction injection molding, vacuum-assisted transfer molding, pressure-assisted liquid resin impregnation, etc. For a metal matrix, the preform can be impregnated through microwave-assisted infiltration, liquid metal impregnation, etc. For a glass or ceramic matrix, the preform can be impregnated through chemical vapor deposition or chemical vapor infiltration. A resin-impregnated preform can be subjected to a heat treatment (pyrolization) that converts a polymer into a carbonaceous matrix.
- The nanoscale filler that can be used in the presently invented hybrid fiber tow, towpreg, or composite can be a nanoscale graphene plate, non-graphite platelet, carbon nano-tube, nano-rod, carbon nano-fiber, non-carbon nano-fiber, or a combination thereof. These entities all have one thing in common—they have at least on elongate axis. For instance, CNTs have one elongate axis (in the tube axial direction) and platelets have two elongate axes (in the length and width direction). The resulting hybrid composite can easily have nano-fillers that are present at a loading of greater than 5% by weight based on the total weight of nano-fillers plus the matrix material. The nano-fillers in many cases exceed 15% by weight. A majority of these nano-fillers have an elongate axis oriented at an angle of at least 45 degrees with respect to the continuous fiber axis. If improved transverse thermal or electrical conductivities are desired, carbon-based nano-fillers are preferred.
- The NGPs obtained in our facilities typically have a platelet thickness of 1-100 nm and length and width of 0.1-10 μm. These rigid two-dimensional platelets appear to be conducive to fitting into inter-filament interstices. The nanoscale graphene plate or non-graphite platelet that has a length or width smaller than 500 nm is particularly well-suited to the present application. The flexibility of both the CNT and the CNF afforded to by their large length-to-diameter ratios makes these one-dimensional structures tend to assume curved or coiled shapes and should make it more difficult to be incorporated in a hybrid composite. However, surprisingly, the presently invented process is capable of incorporating CNTs and CNFs into the inter-filament spaces.
- A fluidized-bed powder impregnation apparatus, schematically shown in
FIG. 2 , was designed and constructed for incorporating a controlled percentage of nano-fillers in a continuous fiber tow to produce a hybrid fiber tow. The apparatus is mainly composed of a feeder roller, a fiber tow spreader, a fluidized bed chamber, and an optional fiber tow consolidator. The fiber tow (or strands of fibers or filaments) is reeled from a fiber spool or feeder roller and directed to go through a tow spreader in which individual filaments are separated from each other. The separated fibers are fed into the fluidized bed chamber in which the nano-fillers, “fluidized” by an air flow, are introduced to impinge upon the fibers. The nano-fillers may be electrostatically charged and the fiber tow grounded to promote nano-filler impregnation of the fiber tow, with nano-fillers residing in interstices between fibers while being re-merged or compacted. - The fluidized bed powder coating apparatus are well-known in the art. For instance, these apparatus were successfully used to prepare a towpreg that is composed of reinforcing filaments coated with matrix-forming resin powder as a precursor to a plastic matrix composite [J. Lamanche, et al., U.S. Pat. No. 3,703,396 (Nov. 21, 1972)]. A key component in the system is a tow spreader. Spreading of the filaments can be achieved by vibrating the graphite fiber tow in air pulsating at a frequency and intensity sufficient to couple the energy of the pulsating medium to the graphite tow [e.g., S. Iyer, et al., U.S. Pat. No. 5,042,122 (Aug. 27, 1991)]. Spreading may also be facilitated or promoted by using air currents or electrostatic charges of the same polarity.
- An optional filament re-merger or compactor may be used to facilitate the merging of separated filaments, along with the embedded nano-fillers, into a more compact fiber tow. This filament re-merging step can occur before, during, and after the resin impregnation step. Resin impregnation can be part of a filament-winding, prepreg-forming, fiber-placing, or pultrusion process.
- The continuous filament can be a polymer fiber, ceramic fiber, carbon fiber, graphite fiber, glass fiber, or a combination thereof. In the hybrid fiber tow, the nano-fillers are preferably oriented in a direction substantially non-parallel to the continuous filament axial direction and further preferably perpendicular to the filament axis.
- In summary, the process for producing a hybrid fiber tow comprises (a) spreading a continuous fiber tow into multiple, separated filaments that define interstitial spaces between the filaments; (b) exposing the separated filaments to a fluid medium or fluidized medium containing nanoscale fillers under a flow condition for a duration of time sufficient to cause the nanoscale fillers to stay in the interstitial spaces; and (c) moving the separated filaments with the interstitial nanoscale fillers away from the medium to produce the hybrid fiber tow. The step of exposing can comprise moving the separated filaments through a fluidized bed comprising a fluidized medium that contains the nanoscale particles suspended in the medium, as illustrated in
FIG. 2 . The fluidized bed may be provisioned with electrostatic charging means to facilitate attraction of the nanoscale fillers to the filaments. - Alternatively, the step of exposing comprises moving the separated filaments through a fluid medium that contains the nanoscale particles suspended in a liquid or solution. In other words, the fluidized-bed powder coater device shown in
FIG. 2 is now replaced by a tank of liquid with nano-fillers suspended in the liquid which is driven (e.g., pumped) to flow around in the tank with a desired flow pattern that enables impingement of nano-fillers with the continuous filaments at a desired direction. - Further alternatively, as schematically shown in
FIG. 4 , the step of exposing can comprise moving the separated filaments at a desired speed in a desired direction while directing a stream of a liquid medium (or gaseous medium such as air) containing the nanoscale fillers to impinge upon the filaments in such a manner that the fillers are trapped in the interstitial spaces to form a hybrid fiber tow. Again, the process begins with reeling acontinuous fiber tow 54 from afiber spool 32, feeding the tow into atow spreader 56 to obtain separatedfilaments 58, which are impinged upon by a fluid (liquid or air) suspending nano-fillers 60 therein. The nano-fillers are trapped between filaments, allowing the liquid or air to filter through the gaps between filaments. Thehybrid tow 62 can be optionally compacted by a compactor orconsolidator 64 to become consolidated hybrid fiber tow which is then collected on a take-uproller 46. Again, such a roll-to-roll process is suitable for mass production of composites. - The fluid medium (e.g., in
FIG. 4 ) or fluidized medium (e.g., inFIG. 2 or 3) can further contain a matrix-forming material. The step of exposing then comprises causing both the nanoscale fillers and the matrix-forming material to stay in the interstitial spaces to form a matrix-forming material-impregnated hybrid tow, referred to as a hybrid fiber towpreg. The matrix-forming material may also be coated onto the surface of continuous filaments. - In another embodiment of the present invention, in addition to the aforementioned steps (a), (b), and (c), the process further comprises (d) reeling the continuous fiber tow from a roller or spool prior to the fiber tow spreading step; (e) impregnating the hybrid fiber tow with a matrix material to form a matrix-impregnated hybrid fiber tow; (f) subjecting the matrix-impregnated hybrid tow to a shape-forming operation to form a composite shape; and (g) consolidating the composite shape through heating, curing, and/or cooling the matrix material to form a hybrid composite structure. The shape-forming operation can comprise a filament winding, fiber placement, prepreg-forming, pultrusion, freeform fabrication step, or a combination thereof. Freeform fabrication involved computerized deposition of a material point-by-point and layer-by-layer. The process is also commonly referred to as rapid prototyping.
- In yet another embodiment of the present invention, the process comprises, in addition to aforementioned steps (a), (b), and (c), the following steps: (d) reeling the continuous fiber tow from a roller or spool prior to the fiber tow spreading step; (e) subjecting the hybrid fiber tow to a shape-forming operation to form a composite preform; (f) impregnating the preform with a matrix material; and (g) consolidating the matrix-impregnated preform through heating, curing, and/or cooling the matrix material to form a hybrid composite structure. The shape-forming operation can comprise a step of filament winding, fiber placement, freeform fabrication, weaving, braiding, stitching, knitting, or a combination thereof.
- In still another embodiment of the present invention, the process comprises, in addition to the aforementioned steps (a), (b), and (c), the following steps: (d) reeling the continuous fiber tow from a roller or spool prior to the fiber tow spreading step; (e) subjecting the hybrid fiber towpreg to a shape-forming operation to form a composite shape; and (f) consolidating the composite shape through heating, curing, and/or cooling the matrix-forming material to form a hybrid composite structure. The shape-forming operation can include a step of filament winding, fiber placement, prepreg-forming, freeform fabrication, weaving, braiding, stitching, knitting, or a combination thereof.
- In all of the aforementioned versions of the invented process, the step of consolidating can comprise melting a matrix material, cooling or solidifying a matrix material, curing a resin, polymerizing or cross-linking a resin precursor, converting an organic or polymeric material to a carbonaceous material, chemical vapor infiltration, or a combination thereof.
- As examples to illustrate the utility value of the developed hybrid composites, we obtained the thermal conductivity values of a series of hybrid composites containing continuous graphite fibers (approximately 60% by volume of the total composite) and NGP/epoxy matrix materials (with several NGP weight fractions based on the total NGP/epoxy weight) or CNT/epoxy matrices. As shown in
FIG. 5 , the transverse thermal conductivity values of hybrid composites (with NGPs substantially perpendicular to the continuous graphite fiber direction) can be improved from approximately 9.1 Wm−1K−1 for a continuous graphite fiber/epoxy composite (0% NGP) to 193 Wm−1K−1 for a hybrid composite (15% NGP). The longitudinal thermal conductivity values, parallel to the continuous graphite fiber direction, for all these composites are in the range of 125-180 Wm−1K−1, relatively independent of the NGP content in the matrix. Addition of CNTs has also significantly improved the transverse thermal conductivity of the hybrid composite, albeit to a smaller extent. The high transverse as well as longitudinal thermal conductivity for these composites is a highly significant result since thermally conductive composites can be used as thermal management materials for microelectronic devices and rocket motor cases, just to cite two of many examples.
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