CN101407637B - Fiber reinforced composite material and preparation thereof - Google Patents
Fiber reinforced composite material and preparation thereof Download PDFInfo
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- CN101407637B CN101407637B CN2008102031066A CN200810203106A CN101407637B CN 101407637 B CN101407637 B CN 101407637B CN 2008102031066 A CN2008102031066 A CN 2008102031066A CN 200810203106 A CN200810203106 A CN 200810203106A CN 101407637 B CN101407637 B CN 101407637B
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Abstract
The invention discloses a fiber reinforced composite material and a preparation method thereof. The fiber reinforced composite material comprises polymeric matrix and fibers and also comprises a solder which leads the fibers which are dispersed in the polymeric matrix to connect together so as to essentially form a three-dimensional network skeleton structure which is formed by the solder and the fibers and is independent in the polymeric matrix. The fiber reinforced composite material can use the fiber characteristics effectively, reduces the fiber usage, supplies higher heat resistance, electric conductivity or heat conductivity and has wide application prospect in the fields of transportation, electronic information and residential construction and the like.
Description
Technical field
The invention belongs to field of compound material, particularly fiber reinforced composite material and preparation method thereof.
Background technology
Matrix material is to be matrix with a kind of material, and another kind of material is for strengthening the material that body combines.Various materials make up for each other's deficiencies and learn from each other on performance, produce synergistic effect, make the over-all properties of matrix material be better than former composition material and satisfy various requirement.
Most widely used in the matrix material with fiber reinforced material, consumption is maximum.Fibre reinforced composites are various fibre reinforcements to be placed in the body material be composited.The fibre-reinforced high molecular matrix material becomes the ideal material of alternative metals with characteristics such as its light weight, intensity height, corrosion-resistant, easy processing, obtains to use widely in fields such as aerospace, communications and transportation, electronic information and building dwelling houses.
Along with improving constantly that structure-function integration requires, how giving characteristics such as high temperature resistant, the high heat conduction of matrix material, anti-electromagnetic wave interference cheaply is the important topic of fibre-reinforced high molecular matrix material research.It is generally acknowledged that the maximum operation (service) temperature of fibre-reinforced high molecular matrix material depends on second-order transition temperature of polymeric matrix (Tg) or fusing point (Tm), irrelevant with length-to-diameter ratio, dispersion state and the physical properties of fiber.Polymeric matrix is a heat insulator, and its thermal conductivity is generally between 0.15～0.3W/mK.In order to realize high heat conduction, prior art requires to fill 50% volume fraction above heat conduction powder or fiber, not only mobile poor, be difficult to process, and than great, cost is high.In order to improve effectiveness, reduce the volume specific resistance of material as far as possible, existing polymer-based electromagnetic shielding material mainly is to get by adding a large amount of conductive filler material (as steel fiber or metallized fibre) preparation.But the addition of conductive filler material is subjected to the forming process requirement of material and the restriction of mechanical strength thereof, is limited to 0.1 Ω cm under the volume specific resistance of existing steel fiber enhancing thermal plastic high polymer goods, has hindered the further raising of effectiveness.In addition, along with the passing of duration of service, oxidation takes place in the metallic surface, and effectiveness is constantly degenerated.Therefore, in order further to improve the performance of fibre reinforced composites, it is to be solved to also have a lot of problems to have.
Summary of the invention
Therefore, the technical problem to be solved in the present invention is exactly at existing fibre reinforced composites above shortcomings, and new fibre reinforced composites of a class and preparation method thereof are provided.These fibre reinforced composites can effectively utilize fiber properties, reduce fiber consumption, and performances such as it is heat-resisting, conduction or heat conduction are significantly strengthened.
The inventor is through discovering: for existing high strength and high-temperature fibre (as glass fibre, carbon fiber etc.) enhanced polymer composite, when temperature is higher than the softening temperature of polymeric matrix, do not pretend firmly owing to do not exist between fiber and the fiber, relative displacement takes place with the slippage of fractionated polymer subchain in fiber under external force, thereby causes matrix material generation deformation; And,, must add a large amount of conduction or heat conducting fiber in order to obtain sufficiently high conduction or heat conductivility for the conduction or the fibre reinforced composites of heat conduction, the forming process of material requires and the restriction of mechanical strength but its addition is subjected to again; There are contact resistance or thermal contact resistance between conduction or heat conducting fiber, further hindered the raising of composite material conductive or heat conductivility.
The inventor finds again through a large amount of tests, in fibre reinforced composites, add a spot of welding compound, the fiber that is dispersed in the polymeric matrix is coupled together, thereby substantially form the three-dimensional network skeleton structure of welding certainly that is independent of polymeric matrix, such fibre-reinforced high molecular performance of composites has obtained significant enhancing.As when fiber and welding compound have high strength and thermotolerance, this three-dimensional network skeleton structure from welding becomes the high temperature resistant skeleton of matrix material, thereby breaks through the limitation that resistance toheat depends on polymeric matrix; When fiber and welding compound have conduction or thermal conductivity, this three-dimensional network skeleton structure from welding can be eliminated interfibrous contact resistance or thermal contact resistance, reduce effectively and fill content, thereby obtain low-cost but high performance electromagnetic shielding material and thermally conductive material.Fibre reinforced composites with this three-dimensional network skeleton structure can effectively utilize fiber properties, under less fiber consumption, give higher heat resistance, conductivity or heat conductivility, thereby finish the present invention.
Therefore, the present invention solves the problems of the technologies described above the technical scheme that is adopted: a kind of fibre reinforced composites, comprise polymeric matrix and fiber, wherein, also comprise welding compound, this welding compound couples together the fiber that is dispersed in the polymeric matrix, has substantially formed a kind of three-dimensional network skeleton structure that is independent of polymeric matrix that is made of welding compound and fiber.
Among the present invention, the mode of connection of welding compound and fiber is preferable in the described three-dimensional network skeleton structure can be selected from any or multiple in following three kinds of modes: (1) welding compound is coated on fiber surface; (2) welding compound is coated on the end of fiber; (3) welding compound is coated on the infall of fiber and fiber.Fibre reinforced composites of the present invention can form the three-dimensional network skeleton structure by above one or more mode of connection.The structural representation of described three-dimensional network skeleton structure as shown in Figure 1.
Among the present invention, described welding compound can be various metal alloys, thermoplastic polymer or melting organic-inorganic composition.Polymeric matrix of the present invention is the polymkeric substance of this area routine, comprises thermoplastic polymer and thermosetting polymer.Described fiber can be selected from as the carbon series fiber, glass fibre, metal and alloy fiber thereof, organic fibre, the aforementioned all fibres of plating metal on surface, and above-mentioned each fiber of process surface grafting or surperficial coupling agent treatment.Wherein, described carbon series fiber can be selected from carbon nanotube, carbon nano fiber, carbon fiber and graphite fibre; Metal and alloy fiber thereof can be selected from copper fiber, Stainless Steel Fibre, aluminum fiber and nickel fiber; Organic fibre can be the fiber that polymer forms after the drawing-off spinning, more as being selected from Kevlar fiber and nylon fiber etc.; The fiber of plating metal on surface can be selected from metallized glass fiber, copper facing Stainless Steel Fibre, metallizing carbon fiber and metallizing organic fibre.Through above-mentioned each fiber of surface grafting or surperficial coupling agent treatment, and the interfacial interaction Li Gengjia between the welding compound.The diameter of described fiber is this area routine, is generally 1nm～100 μ m.Elaborate it below.
Fibre reinforced composites of the present invention comprise polymeric matrix and fiber, also comprise welding compound.Preferable, described fibre reinforced composites are a kind of fibre reinforced composites of high conduction, wherein said fiber is high electro-conductive fiber, and described polymeric matrix is selected from thermoplastic polymer and thermosetting polymer, and described welding compound is a fusing point at 100 ℃～400 ℃ metal alloy.Wherein, described high electro-conductive fiber is this area routine, the preferable fiber that is selected from copper fiber, nickel fiber, copper coating and nickel plating.That the diameter of described high electro-conductive fiber is preferable is 1 μ m～100 μ m.The fibre reinforced composites of high conduction of the present invention are better comprises the high electro-conductive fiber of 1～60wt% and 30～90wt% polymeric matrix, and 1～30wt% fusing point is at the welding compound of 100 ℃～400 ℃ metal alloy.Formed the three-dimensional network skeleton structure that metal alloy welds high electro-conductive fiber in this novel high conductive material, eliminated the contact resistance between high electro-conductive fiber, reduced the loading level of high electro-conductive fiber effectively, the volume specific resistance of this high conductive material is 1 * 10 under low high electro-conductive fiber loading level
1Ohm.cm～1 * 10
-5Ohm.cm, preferable can be 1 * 10
-1Ohm.cm～1 * 10
-3Ohm.cm.In addition, described three-dimensional network skeleton structure has also been eliminated because of high conductive fiber surfaces oxidation causes the influence that matrix material volume resistivity rises, and can give matrix material stable specific conductivity, thereby has obtained low-cost but high performance high conductive material.
Fibre reinforced composites of the present invention comprise polymeric matrix and fiber, also comprise welding compound.Another kind of preferable mode is, described fibre reinforced composites are a kind of resistant to elevated temperatures fibre reinforced composites, wherein said fiber is glass fibre or carbon fiber, and described polymeric matrix is selected from thermoplastic polymer, and described welding compound is a thermoplastic polymer.Wherein, described glass fibre is the glass fibre of this area routine, can be selected from successive glass fiber bundle and short glass fiber, and that its length is preferable is 3mm～10mm, and that its diameter is preferable is 10 μ m～30 μ m.Described carbon fiber is the carbon fiber of this area routine, and that its diameter is preferable is 5 μ m～20 μ m.
Especially, for low-cost but high performance high temperature material, polymeric matrix and welding compound all are selected from thermoplastic polymer, the mode of choosing that it is preferable can for: (1) if polymeric matrix be selected from unbodied polymkeric substance, welding compound is selected from crystalline polymkeric substance, and then the fusing point of welding compound (Tm) should be higher than the second-order transition temperature (Tg) of polymeric matrix more than 50 ℃; (2) if polymeric matrix and welding compound all are selected from unbodied polymkeric substance, then the Tg of welding compound should be higher than more than Tg50 ℃ of polymeric matrix; (3) if polymeric matrix and welding compound all are selected from crystalline polymkeric substance, then the Tm of welding compound should be higher than more than Tm50 ℃ of polymeric matrix; (4) if polymeric matrix is selected from crystalline polymkeric substance, welding compound is selected from unbodied polymkeric substance, and then the Tg of welding compound should be higher than more than Tm50 ℃ of polymeric matrix.
Resistant to elevated temperatures fibre reinforced composites of the present invention are better comprises 5～45wt% glass fibre or carbon fiber, the welding compound of 50～90wt% polymeric matrix and 5～30wt% thermoplastic polymer.Glass fibre or carbon fiber that resistant to elevated temperatures thermoplastic polymer will be scattered in the polymeric matrix couple together, and form the three-dimensional network skeleton structure, can provide high temperature resistant skeleton for matrix material, thereby have obtained low-cost but high performance high temperature material.
Fibre reinforced composites of the present invention comprise polymeric matrix and fiber, also comprise welding compound.Another preferable mode is, described fibre reinforced composites are a kind of fibre reinforced composites of semiconduction type, and wherein said fiber is the carbon series fiber, and described polymeric matrix is a polar polymer, and described welding compound is a non-polar polymer.Wherein, described carbon series fiber is this area routine, preferable carbon nanotube, carbon nano fiber, carbon fiber and the graphite fibre of being selected from.That the diameter of described carbon series fiber is preferable is 1nm～30 μ m.Described polar polymer is preferable is selected from acrylonitrile-butadiene-styrene copolymer, polystyrene, polyvinyl chloride, various polymeric amide, various polymethacrylate, polyacrylic ester, polyvinyl acetate (PVA), polyvinylidene difluoride (PVDF), polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyoxymethylene, polyphenylene oxide, polyphenylene sulfide, PPSS, polyaryletherketone, polyetherketone, polyether-ether-ketone, polysulfones, polyethersulfone, various liquid crystalline resins, polyimide, urethane, polydimethylsiloxane, polyphenyl methyl siloxane, rubber and elastomericss such as polyhutadiene, polyoxyethylene glycol, polyvinyl alcohol, polyoxyethylene, lactide in poly-, poly-glycollide, poly-ε-own lactide and poly(lactic acid).Described non-polar polymer is preferable is selected from polyethylene and polypropylene.Fibre reinforced composites of the present invention are better comprises 0.5～10wt% carbon series fiber, the welding compound of 80～97wt% polar polymer matrix and 1～10wt% non-polar polymer.The non-polar polymer selectivity is coated on the end of carbon series fiber, and the carbon series fiber that will be scattered in the polymeric matrix couples together, and forms the three-dimensional network skeleton structure, thereby has obtained the high performance semiconduction section bar material of low-carbon (LC) series fiber content.
Fibre reinforced composites of the present invention comprise polymeric matrix and fiber, also comprise welding compound.Also have a kind of preferable mode to be, described fibre reinforced composites are a kind of fibre reinforced composites of high heat conduction, wherein said fiber is high heat conducting fiber, and described polymeric matrix is selected from thermoplastic polymer and thermosetting polymer, and described welding compound is compound welding compound.Wherein, described high heat conducting fiber is this area routine, the preferable fiber that is selected from carbon series fiber, metal and alloy fiber thereof and plating metal on surface.That the diameter of described high heat conducting fiber is preferable is 1nm～100 μ m.Described compound welding compound is preferable comprises 10～90wt% fusing point at 100 ℃～400 ℃ metal alloy and 10～90wt% auxiliary agent, and wherein, described auxiliary agent is to be selected from copper powder, silver powder, aluminium powder, nickel powder and the graphite etc. one or more.The fibre reinforced composites of high heat conduction of the present invention are better comprises the high heat conducting fiber of 10～30wt%, the compound welding compound of 40～60wt% polymeric matrix and 10～30wt%.
Among the present invention, what described " fusing point 100 ℃ to 400 ℃ metal alloy " was preferable comprises tin and is selected from one or more metal alloy in antimony, silver, copper, nickel, zinc, aluminium, lead and the magnesium for being selected from.Wherein, preferable, the content of described tin is 5～99.3wt%, and described one or more the content that is selected from antimony, silver, copper, nickel, zinc, aluminium, lead and the magnesium is 0.7～95wt%.
Among the present invention, described " thermoplastic polymer " preferable for being selected from acrylonitrile-butadiene-styrene copolymer, polystyrene, polyethylene, polypropylene, polyvinyl chloride, various polymeric amide, various polymethacrylate, polyacrylic ester, polyvinyl acetate (PVA), polyvinylidene difluoride (PVDF), polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyoxymethylene, polyphenylene oxide, polyphenylene sulfide, PPSS, polyaryletherketone, polyetherketone, polyether-ether-ketone, polysulfones, polyethersulfone, various liquid crystalline resins, polyimide, polyisobutene, polyisoprene, urethane, polydimethylsiloxane, polyphenyl methyl siloxane, rubber and elastomericss such as polyhutadiene, polyoxyethylene glycol, polyvinyl alcohol, polyoxyethylene, lactide in poly-, poly-glycollide, poly-ε-own lactide, poly(lactic acid), and in above-mentioned high molecular grafts and the multipolymer one or more.Wherein, described polymeric amide is preferable is selected from nylon 6, Ni Long11, nylon 12, nylon 66, nylon 1010, nylon 46, nylon 69, NYLON610, nylon 612 and nylon 1212.Among the present invention, described " thermosetting polymer " is preferable is selected from various Resins, epoxy and bismaleimides.
The present invention also provides the preparation method of described fibre reinforced composites, can be selected from any in following method (1), (2) and (3):
(1) admixture of powder method 10～30 ℃ of mechanically mixing, then at polymeric matrix with more than all flowable temperature of welding compound, is utilized polymer powder matrix, fiber and Powdered welding compound hot pressing, is extruded or injection moulding process prepares moulding;
(2) melt-blending process, utilize double roll mill, Banbury mixer, single screw rod or twin screw extruder and various dispersing and mixing instrument with dispersion blend function, at least more than the yield temperature of polymeric matrix with polymeric matrix, fiber and Powdered welding compound dispersing and mixing, then at polymeric matrix with more than all flowable temperature of welding compound, utilize hot pressing, extrude or injection moulding process prepares moulding;
(3) masterbatch dispersion method, utilize double roll mill, Banbury mixer, single screw rod or twin screw extruder and various dispersing and mixing instrument with dispersion blend function, more than the yield temperature of polymeric matrix, polymeric matrix and fiber dispersion are mixed, get the masterbatch of 40～60wt% fibre content; And then with polymeric matrix, welding compound and masterbatch utilize double roll mill, Banbury mixer, single screw rod or twin screw extruder and various have disperse the blend function the dispersing and mixing instrument in polymeric matrix and the above dispersing and mixing of all flowable temperature of welding compound; At last at polymeric matrix with more than all flowable temperature of welding compound, utilize hot pressing, extrude or injection moulding process prepares moulding; Perhaps with masterbatch and polymeric matrix and welding compound 10～30 ℃ be mixed after, at polymeric matrix with more than all flowable temperature of welding compound, utilize and extrude or injection moulding process prepares moulding.
Especially, for the copper fibre reinforced composites, the masterbatch dispersion method of the preferred described method of its preparation method (3).Wherein, the Continuous Copper fibrous bundle that described fiber is preferable for hubbing production, preferable as follows of the preparation process of its masterbatch: the head position at single screw extrusion machine is equipped with Thead off-set die head, successive copper fibrous bundle draws perpendicular to extruding direction by the Thead off-set die head edge, polymeric matrix melt extrudes more than yield temperature and evenly is coated on the copper fiber surface, obtains the masterbatch of 40～90wt% copper fibre content after the dry pelletizing of water-cooled.
Above-mentioned three kinds of equipment that the preparation method adopted of the present invention are conventional in this area.Among the described preparation method, preferable, can be by the viscosity ratio between telomerized polymer matrix and the welding compound, melt elasticity ratio and interfacial tension, change the kind and the concentration of fiber surface grafting or coupling agent treatment, perhaps control temperature in the dispersing and mixing process, time, shearing resistance etc., to improve the performance of made fibre reinforced composites.Also can suitably prolong hot pressing time or improve injection temperature, so that Han Jie three-dimensional network skeleton structure is more firm certainly.Also can add expanding material, with effective interfacial tension of improving between polymeric matrix and the welding compound.Expanding material is of a great variety, can be selected according to relevant professional book and paper.
Among the present invention, described " dispersing and mixing " is meant and passes through shear-mixed under yield temperature, impel welding compound to the orientation coating of fiber and the dispersion between polymkeric substance and the welding compound.Described " yield temperature " is meant for the crystal type polymer and is higher than Tc, be lower than decomposition temperature, is meant to be higher than second-order transition temperature for armorphous polymer, is lower than decomposition temperature.Under some reason, such as in order to regulate and control viscosity ratio, can add selectivity polymer or low molecule-type softening agent to reduce viscosity, to promote to flow, yield temperature at this moment is meant and is higher than plasticization temperature, is lower than decomposition temperature.The yield temperature of performed polymer can be decided according to the polymerization degree and reaction extrusion characteristics.
Preparation method of the present invention, at polymeric matrix with more than all flowable temperature of welding compound, utilize polymeric matrix and welding compound viscosity, polarity and with the difference of functional group, perhaps by changing feeding sequence, perhaps fiber surface is carried out grafting or coupling agent treatment, impel soldered dose of most fibers to couple together with physisorption or chemical reaction effect, substantially form a kind of three-dimensional network skeleton structure that is independent of polymeric matrix that constitutes by welding compound and fiber, thereby obtained fibre reinforced composites of the present invention.
Raw material that the present invention is used or reagent except that specifying, all commercially available getting.
Than prior art, beneficial effect of the present invention is as follows: the present invention adds a spot of welding compound in fibre reinforced composites, the fiber that is dispersed in the polymeric matrix is coupled together, thereby substantially form the three-dimensional network skeleton structure that is independent of polymeric matrix, fibre reinforced composites with such structure can effectively utilize fiber properties, reduce fiber consumption, have higher heat resistance, conductivity or heat conductivility, have broad application prospects in fields such as aerospace, communications and transportation, electronic information and building dwelling houses.Particularly: high temperature material: because irrelevant with the heatproof characteristic of matrix, can prepare various low-cost high temperature materials, at household electrical appliance such as electronic printing system, communication system, automotive upholstery and electric iron, electric cooker, showers, and aerospace ablator, aspects such as high-performance brake facing and technics of reclaim of plastic waste and regeneration are used.Highly heat-conductive material: can have widely at the aspects such as thermal conductive shell that anticorrosion heat exchanger, heat pipe, solar water heater, dwelling house floor heating system and electronic information equipment need because of miniaturization and slimming and use.Electro-conductive material: can be in the anti-electrostatic in fields such as military project, medicine equipment, electronics and IT products and residential houses, antistatic and electromagnetic wave shielding application.
Description of drawings
Fig. 1 is the structural representation of three-dimensional network skeleton structure.1, polymeric matrix; 2, welding compound; 3, fiber.
Fig. 2 is the light micrograph of three-dimensional network skeleton structure.1, glass fibre; 2, nylon 6.
Embodiment
Further specify the present invention with embodiment below, but the present invention is not limited.The experimental technique of unreceipted actual conditions in the following example, usually according to normal condition, or the condition of advising according to manufacturer.Described room temperature is the temperature of operation room, is 10～30 ℃.
Embodiment 1
Acrylonitrile-butadiene-styrene copolymer is melt extruded under 220 ℃ in the single screw extrusion machine of head position outfit Thead off-set die head, diameter is that 30 μ m successive copper fibrous bundles draw perpendicular to extruding direction by the Thead off-set die head edge, obtain containing the master batch of 85wt% copper fibre content after the dry pelletizing of water-cooled, again with acrylonitrile-butadiene-styrene copolymer, above-mentioned copper fiber master batch and particle diameter are tinsel powder (the lead content 35wt% of 35 μ m, fusing point is 183 ℃) after 74/20/6 weighing, adding twin screw extruder melt extrudes under 220 ℃, after the extrudate granulated and dried, 230 ℃ of following injection moldings.The volume specific resistance of gained material is 8.36 * 10
-1Ohm.cm.
Embodiment 2
With acrylonitrile-butadiene-styrene copolymer, diameter is the copper fiber of 30 μ m and tinsel powder (the lead content 35wt% that mean diameter is 35 μ m, fusing point is 183 ℃) press mass ratio 61/11/28 weighing after, add in the twin screw extruder and under 220 ℃, melt extrude, after the extrudate granulated and dried, 230 ℃ of following injection moldings.The volume specific resistance of gained material is 4.55 * 10
-2Ohm.cm.
Embodiment 3
With the method for embodiment 1, prepare the fibre-reinforced polypropylene masterbatch of 85wt% copper down at 220 ℃.
The gun-metal powder (copper content 0.7wt%, 227 ℃ of fusing points) that with polypropylene, masterbatch and particle diameter is 35 μ m again prepares matrix material by weight 64/30/6 with embodiment 1, and wherein extrusion temperature is 220 ℃, and injection temperature is 240 ℃.The volume specific resistance of gained material is 6.35 * 10
-2Ohm.cm.
Embodiment 4
With the method for embodiment 1, prepare the fibre-reinforced polycarbonate masterbatch of 85wt% copper down at 280 ℃.The gun-metal powder (copper content 0.7wt%, 227 ℃ of fusing points) that with polycarbonate, polycarbonate masterbatch and particle diameter is 35 μ m again prepares matrix material by weight 50/25/25 with embodiment 1, and wherein extrusion temperature is 280 ℃, and injection temperature is 300 ℃.The volume specific resistance of gained material is 8.94 * 10
-4Ohm.cm.
Embodiment 5
With polyphenylene sulfide powder, diameter is that 30 μ m copper fibers and particle diameter are tinsel powder (the lead content 95wt% of 35 μ m, 300 ℃ of fusing points) after 80/15/5 weighing, at room temperature place high-speed mixer to mix after 10 minutes, hot pressing is 10 minutes on the inherent thermocompressor of immigration mould, temperature is 320 ℃, pressure is 10MPa, obtains goods after the air cooling.The volume specific resistance of gained material is 1.2 * 10
-2Ohm.cm, thermal conductivity are 17W/m.K.
Embodiment 6
With the method for embodiment 1, prepare 85wt% copper carbon fiber enhanced polyether-ether-ketone masterbatch down at 380 ℃.The tinsel powder (lead content 95wt%, about 300 ℃ of fusing point) that with polyether-ether-ketone, masterbatch and particle diameter is 35 μ m again prepares matrix material by weight 45/35/20 with embodiment 1, and wherein extrusion temperature is 380 ℃, and injection temperature is 390 ℃.The volume specific resistance of gained material is 8.94 * 10
-5Ohm.cm, thermal conductivity are 26W/m.K.
Embodiment 7
With high density polyethylene(HDPE), diameter is that 60 μ m copper fibers and particle diameter are tinsel powder (the lead content 35wt% of 35 μ m, fusing point is 183 ℃) after 65/20/15 weighing, add blend in two roller mills, blending temperature is 190 ℃, and the time is 10 minutes.With blend hot pressing 10 minutes on thermocompressor, temperature is 220 ℃, and pressure is 10MPa.Gained material volume resistivity is 5.6 * 10
-3Ohm.cm.
Embodiment 8
With acrylonitrile-butadiene-styrene copolymer and nylon 6 after 80/20 weighing, add blend in the twin screw extruder, successive glass fiber bundle (the individual glass fibers diameter is 10 μ m) adds by the side spout near extruder head, the about 30wt% of the content of glass fibre, extrusion temperature is 240 ℃, after the extrudate granulated and dried, 260 ℃ of following injection moldings.Gained materials hot deformation temperature (0.45MPa) is 161 ℃.The gained material is thinly sliced, adopted tetrahydrofuran (THF) as solvent, etching is removed the acrylonitrile-butadiene-styrene copolymer matrix, stays glass fibre and nylon 6 welding compounds, observes under opticmicroscope and takes pictures, and the gained light micrograph is seen Fig. 2.Can be clearly seen that from Fig. 2 nylon 6 links together glass fibre, has substantially formed a kind of three-dimensional network skeleton structure that is independent of acrylonitrile-butadiene-styrene copolymer that is made of nylon 6 and glass fibre.
Embodiment 9
Polystyrene, nylon 66 and carbon black by weight 80/15/5 method with embodiment 8, are prepared the matrix material of about 40wt% content of glass fiber, and wherein extrusion temperature is 290 ℃, and injection temperature is 310 ℃.Gained materials hot deformation temperature (0.45MPa) is 214 ℃.
Embodiment 10
With polypropylene and nylon 66 by weight 85/15 method with embodiment 8, the matrix material of the about 20wt% content of glass fiber of preparation, wherein extrusion temperature is 290 ℃, injection temperature is 310 ℃.Gained materials hot deformation temperature (0.45MPa) is 226 ℃.
Embodiment 11
With high density polyethylene(HDPE) and nylon 6 after 85/15 weighing, add blend in the twin screw extruder, short glass fiber (the individual glass fibers diameter is 10 μ m) adds by the side spout near extruder head, the about 25wt% of the content of glass fibre, extrusion temperature is 240 ℃, after the extrudate granulated and dried, 260 ℃ of following injection moldings.Gained materials hot deformation temperature (0.45MPa) is 158 ℃.
Embodiment 12
With polystyrene powder, polyphenylene sulfide powder and diameter be the carbon fiber of 8 μ m after 75/10/15 weighing, place high-speed mixer to mix 10 minutes, moved on the inherent thermocompressor of mould hot pressing 10 minutes, hot pressing temperature is 320 ℃, pressure is 10MPa.Gained materials hot deformation temperature (0.45MPa) is 256 ℃.
Embodiment 13
With polycarbonate (PC), high density polyethylene(HDPE) (HDPE), diameter be the Nano carbon fibers peacekeeping graphitized carbon black of 0.2 μ m after 88/7/3/2 weighing, earlier PC and HDPE are added blend in the Banbury mixer, blending temperature is 280 ℃, the time is 5 minutes; Add carbon fiber again and continue blend discharging after 5 minutes.With injection molding after the blend granulated and dried, injection temperature is 300 ℃.The volume specific resistance of gained material is 5.21 * 10
5Ohm.cm.
Embodiment 14
With polyphenylene sulfide powder, diameter is that carbon fiber, the particle diameter of 10 μ m is gun-metal powder (the copper content 0.7wt% of 35 μ m, 227 ℃ of fusing points), copper powder and graphite are after 50/19/7/4/20 weighing, place high-speed mixer to mix after 10 minutes, hot pressing is 10 minutes on the inherent thermocompressor of immigration mould, temperature is 320 ℃, pressure is 10MPa, obtains goods after the air cooling.The thermal conductivity of gained material is 21W/mK.
Comparative example 1
Except that not adding the tinsel powder,, make matrix material with embodiment 1.Gained material volume resistivity is 1.75 * 10
13Ohm.cm.
Comparative example 2
Except that not adding nylon 6,, make matrix material with embodiment 8.Gained materials hot deformation temperature (0.45MPa) is 102 ℃.
Comparative example 3
Except that not adding the HDPE, make matrix material with embodiment 13.The volume specific resistance of gained material is 8.62 * 10
11Ohm.cm.
Comparative example 4
Except that not adding the gun-metal powder,, make matrix material with embodiment 14.The thermal conductivity of gained material is 1.87W/mK.
Claims (21)
1. fibre reinforced composites, comprise polymeric matrix and fiber, it is characterized in that, also comprise welding compound, this welding compound couples together the fiber that is dispersed in the polymeric matrix, has substantially formed a kind of three-dimensional network skeleton structure that is independent of polymeric matrix that is made of welding compound and fiber;
Wherein, described fiber is high electro-conductive fiber, and described polymeric matrix is selected from thermoplastic polymer and thermosetting polymer, and described welding compound is a fusing point at 100 ℃～400 ℃ metal alloy; Or
Described fiber is glass fibre or carbon fiber, and described polymeric matrix is selected from thermoplastic polymer, and described welding compound is a thermoplastic polymer; Or
Described fiber is the carbon series fiber, and described polymeric matrix is a polar polymer, and described welding compound is a non-polar polymer; Or
Described fiber is high heat conducting fiber, described polymeric matrix is selected from thermoplastic polymer and thermosetting polymer, described welding compound is compound welding compound, described compound welding compound comprises 10～90wt% fusing point at 100 ℃～400 ℃ metal alloy and 10～90wt% auxiliary agent, wherein, described auxiliary agent is to be selected from copper powder, silver powder, aluminium powder, nickel powder and the graphite one or more.
2. fibre reinforced composites as claimed in claim 1 is characterized in that, the mode of connection of welding compound and fiber is selected from any or multiple in following three kinds of modes in the described three-dimensional network skeleton structure: (1) welding compound is coated on fiber surface; (2) welding compound is coated on the end of fiber; (3) welding compound is coated on the infall of fiber and fiber.
3. fibre reinforced composites as claimed in claim 1 is characterized in that, described high electro-conductive fiber is selected from the fiber of copper fiber, nickel fiber, copper coating and nickel plating.
4. fibre reinforced composites as claimed in claim 1 is characterized in that, comprise the high electro-conductive fiber of 1～60wt%, and 30～90wt% polymeric matrix and 1～30wt% fusing point are at 100 ℃～400 ℃ metal alloy.
5. fibre reinforced composites as claimed in claim 1, it is characterized in that, when described fiber is glass fibre or carbon fiber, the mode of choosing of polymeric matrix and welding compound is: (1) is if polymeric matrix is selected from unbodied polymkeric substance, welding compound is selected from crystalline polymkeric substance, and then the fusing point of welding compound (Tm) should be higher than the second-order transition temperature (Tg) of polymeric matrix more than 50 ℃; (2) if polymeric matrix and welding compound all are selected from unbodied polymkeric substance, then the Tg of welding compound should be higher than the Tg of polymeric matrix more than 50 ℃; (3) if polymeric matrix and welding compound all are selected from crystalline polymkeric substance, then the Tm of welding compound should be higher than the Tm of polymeric matrix more than 50 ℃; (4) if polymeric matrix is selected from crystalline polymkeric substance, welding compound is selected from unbodied polymkeric substance, and then the Tg of welding compound should be higher than the Tm of polymeric matrix more than 50 ℃.
6. fibre reinforced composites as claimed in claim 1 is characterized in that, comprise 5～45wt% glass fibre or carbon fiber, the welding compound of 50～90wt% polymeric matrix and 5～30wt% thermoplastic polymer.
7. fibre reinforced composites as claimed in claim 1 is characterized in that, described carbon series fiber is selected from carbon nanotube, carbon fiber and graphite fibre.
8. fibre reinforced composites as claimed in claim 7 is characterized in that, described carbon fiber is a carbon nano fiber.
9. fibre reinforced composites as claimed in claim 1, it is characterized in that described polar polymer is selected from acrylonitrile-butadiene-styrene copolymer, polystyrene, polyvinyl chloride, polymeric amide, polymethacrylate, polyacrylic ester, polyvinyl acetate (PVA), polyvinylidene difluoride (PVDF), polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyoxymethylene, polyphenylene oxide, polyphenylene sulfide, PPSS, polyaryletherketone, polysulfones, polyimide, urethane, polydimethylsiloxane, polyphenyl methyl siloxane, polybutadiene rubber and elastomerics, polyoxyethylene glycol, polyvinyl alcohol, poly-glycollide, poly-ε-own lactide and poly(lactic acid).
10. fibre reinforced composites as claimed in claim 9 is characterized in that, described polyaryletherketone is polyetherketone or polyether-ether-ketone, and described polysulfones is a polyethersulfone.
11. fibre reinforced composites as claimed in claim 1 is characterized in that, described non-polar polymer is selected from polyethylene and polypropylene.
12. fibre reinforced composites as claimed in claim 1 is characterized in that, comprise 0.5～10wt% carbon series fiber, the welding compound of 80～97wt% polar polymer matrix and 1～10wt% non-polar polymer.
13. fibre reinforced composites as claimed in claim 1 is characterized in that, described high heat conducting fiber is selected from the fiber of carbon series fiber, metal and alloy fiber thereof and plating metal on surface.
14. fibre reinforced composites as claimed in claim 1 is characterized in that, comprise the high heat conducting fiber of 10～30wt%, the compound welding compound of 40～60wt% polymeric matrix and 10～30wt%.
15., it is characterized in that described fusing point is to be selected to comprise tin and be selected from one or more metal alloy in antimony, silver, copper, nickel, zinc, aluminium, lead and the magnesium at 100 ℃ to 400 ℃ metal alloy as claim 1 or 4 described fibre reinforced composites.
16. fibre reinforced composites as claimed in claim 15 is characterized in that, the content of described tin is 5～99.3wt%, and described one or more the content that is selected from antimony, silver, copper, nickel, zinc, aluminium, lead and the magnesium is 0.7～95wt%.
17. as claim 1 or 6 described fibre reinforced composites, it is characterized in that, described thermoplastic polymer is for being selected from acrylonitrile-butadiene-styrene copolymer, polystyrene, polyethylene, polypropylene, polyvinyl chloride, polymeric amide, polymethacrylate, polyacrylic ester, polyvinyl acetate (PVA), polyvinylidene difluoride (PVDF), polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyoxymethylene, polyphenylene oxide, polyphenylene sulfide, PPSS, polyaryletherketone, polysulfones, polyimide, polyisobutene, polyisoprene, urethane, polydimethylsiloxane, polyphenyl methyl siloxane, polybutadiene rubber and elastomerics, polyoxyethylene glycol, polyvinyl alcohol, poly-glycollide, poly-ε-own lactide, poly(lactic acid), and in above-mentioned high molecular grafts and the multipolymer one or more.
18. fibre reinforced composites as claimed in claim 17 is characterized in that, described polyaryletherketone is polyetherketone or polyether-ether-ketone, and described polysulfones is a polyethersulfone.
19. fibre reinforced composites as claimed in claim 1 is characterized in that, described thermosetting polymer is selected from Resins, epoxy and bismaleimides.
20. the preparation method of fibre reinforced composites, it is characterized in that, described fibre reinforced composites comprise polymeric matrix and fiber, it also comprises welding compound, this welding compound couples together the fiber that is dispersed in the polymeric matrix, substantially formed a kind of three-dimensional network skeleton structure that is independent of polymeric matrix that is made of welding compound and fiber, this preparation method is selected from any in following method (1), (2) and (3):
(1) admixture of powder method 10～30 ℃ of mechanically mixing, then at polymeric matrix with more than all flowable temperature of welding compound, is utilized polymer powder matrix, fiber and Powdered welding compound hot pressing, is extruded or injection moulding process prepares moulding;
(2) melt-blending process, utilize double roll mill, Banbury mixer, single screw rod or twin screw extruder and various dispersing and mixing instrument with dispersion blend function, at least more than the yield temperature of polymeric matrix with polymeric matrix, fiber and Powdered welding compound dispersing and mixing, then at polymeric matrix with more than all flowable temperature of welding compound, utilize hot pressing, extrude or injection moulding process prepares moulding;
(3) masterbatch dispersion method, utilize double roll mill, Banbury mixer, single screw rod or twin screw extruder and various dispersing and mixing instrument with dispersion blend function, more than the yield temperature of polymeric matrix, polymeric matrix and fiber dispersion are mixed, get the masterbatch of 40～60wt% fibre content; And then with polymeric matrix, welding compound and masterbatch utilize double roll mill, Banbury mixer, single screw rod or twin screw extruder and various have disperse the blend function the dispersing and mixing instrument in polymeric matrix and the above dispersing and mixing of all flowable temperature of welding compound; At last at polymeric matrix with more than all flowable temperature of welding compound, utilize hot pressing, extrude or injection moulding process prepares moulding; Perhaps with masterbatch and polymeric matrix and welding compound 10～30 ℃ be mixed after, at polymeric matrix with more than all flowable temperature of welding compound, utilize hot pressing, extrude or injection moulding process prepares moulding.
21. fibre reinforced composites according to claim 20, it is characterized in that, fiber described in method (3) the masterbatch dispersion method is the Continuous Copper fibrous bundle that hubbing is produced, the step of the preparation of its masterbatch is as follows: the head position at single screw extrusion machine is equipped with Thead off-set die head, successive copper fibrous bundle draws perpendicular to extruding direction by the Thead off-set die head edge, polymeric matrix melt extrudes more than yield temperature and evenly is coated on the copper fiber surface, obtains the masterbatch of 40～90wt% copper fibre content after the dry pelletizing of water-cooled.
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