CN104177823A - Carbon fiber reinforced nylon 6 resin composite material and preparation method thereof - Google Patents
Carbon fiber reinforced nylon 6 resin composite material and preparation method thereof Download PDFInfo
- Publication number
- CN104177823A CN104177823A CN201410395200.1A CN201410395200A CN104177823A CN 104177823 A CN104177823 A CN 104177823A CN 201410395200 A CN201410395200 A CN 201410395200A CN 104177823 A CN104177823 A CN 104177823A
- Authority
- CN
- China
- Prior art keywords
- carbon fiber
- nylon
- parts
- resin composite
- fiber reinforced
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- 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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
-
- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
-
- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/222—Magnesia, i.e. magnesium oxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/004—Additives being defined by their length
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
Abstract
The invention relates to a carbon fiber reinforced nylon 6 resin composite material with excellent heat conducting performance and a preparation method thereof. The composite material consists of the following materials in parts by weight: 100 parts of nylon 6 resin, 20-80 parts of carbon fiber, 10-20 parts of inorganic filling material, 0.5-5 parts of coupling agent, 0.2-1 part of antioxidant and 0-3 parts of lubricating agent. The preparation method comprises the following steps: weighing each component raw material in proportion; mixing each component raw material except for the carbon fiber at a high speed; adding an obtained mixed material into a double-screw extruder hopper, adding the carbon fiber from a fiber charging opening of the extruder, and then extruding and pelletizing. Compared with the prior art, the composite material provided by the invention is high in rigidity and good in heat conducting performance, is suitable for production and processing of thin-walled and light-weight automobile parts and electronic/electrical products; meanwhile, the composite material is low in raw material cost and simple in manufacturing process, and is suitable for industrial continuous production.
Description
Technical field
The invention belongs to carbon-fibre composite technical field, be specifically related to the good carbon fiber of a kind of heat conductivility and strengthen poly-to nylon 6 composite material and preparation method thereof.
Background technology
Nylon 6 with its good thermotolerance, resistance to chemical reagents, moisten slip, electrical property, processing characteristics, especially good over-all properties and being applied widely in the fields such as electronic apparatus, automotive industry and machinery, instrument and household electrical appliance.Promote the mechanical property of nylon 6 and heat conductivility for the manufacturing of the electric element of light-weighted automobile component and miniaturization, promote its heat radiation, improve precision, prolongs life etc. and there is more and more important effect.
The raising of macromolecular material intensity and thermal conductivity all can adopt composite modifying method.For improving the intensity of Nylon 6, generally can pass through glass fibre, carbon fiber etc. and strengthen compound method, the carbon fiber that wherein strengthens use is mainly PAN-based carbon fiber, and it can significantly improve the strength and modulus of nylon 6 material, but little to improving thermal conductivity effect.For improving the thermal conductivity of nylon 6, conventionally adopt the filler grain of filling high heat conductance, prepare filled-type thermally conductive matrix material.Conventional heat conductive filler comprises: one, metallic stuffing, as powder such as silver, copper, aluminium, magnesium, nickel; Two, inorganic non-metallic filler, as the nitride such as aluminium nitride, boron nitride, magnesium oxide, silicon carbide, oxide compound, carbide etc.; The carbon material three, with graphite-structure, as Graphene, carbon nanotube, carbon nano fiber and asphalt base carbon fiber etc.But metal heat-conducting filler exist density large, be corrosive and bring the shortcomings such as nylon 6 material mechanical properties decrease; It is not to produce effect very much that inorganic non-metallic filler improves Nylon 6 thermal conductivity, often can make Nylon 6 mechanical properties decrease yet.Although and the method for Graphene, carbon nanotube and carbon nano fiber etc. in employing carbon material can significantly improve the thermal conductivity of Nylon 6, but these materials still can not large-scale industrialization be produced, expensive, related technology only rests on the laboratory study stage especially.High-performance asphalt base carbon fiber is the rare carbon material with graphite-structure of having realized large-scale industrial production, Japan Di Ren company (as Chinese patent CN101935919B etc.) has adopted high thermal conductive asphalt base carbon fibre to improve the thermal conductivity of the resins such as polycarbonate, polyphenylene sulfide, polypropylene, poly(lactic acid) and organosilicon, but at present also not by the method for improving the report of nylon 6 thermal conductivity and/or mechanical property.
Summary of the invention
Object of the present invention is exactly in order to overcome the defect that above-mentioned prior art exists, to provide that a kind of mechanical property that can simultaneously significantly improve material and heat conductivility, material cost are low, preparation technology is simply applicable to industrialization quantity-produced carbon fiber reinforced nylon 6 resin composite materials and preparation method.
Object of the present invention can be achieved through the following technical solutions: a kind of carbon fiber reinforced nylon 6 resin composite materials, it is characterized in that, this matrix material is comprised of the material of following weight part: 100 parts of Nylon 6s, 20～80 parts, carbon fiber, 10～20 parts of mineral fillers, 0.5～5 part of coupling agent, 0～3 part of 0.2～1 part, oxidation inhibitor and lubricant.
Described Nylon 6 is selected from a kind of in the pellet of extrusion grade, injection grade, filling level or flame retardant grade or powder.
The content of described carbon fiber is 20～80 parts, when short carbon fiber content is less than 20 parts, cannot in Nylon 6 matrix, form perfect passage of heat, so not remarkable to the raising of Nylon 6 heat conductivility.Carbon fiber content is higher, and mechanical property and the heat conductivility of Nylon 6 are higher.But the mass percent of working as short carbon fiber is too high, when its content is greater than 80 parts, the serious wear to mixing equipment, the work-ing life of shortening screw rod.In addition, too high levels can make that the melt viscosity of matrix material is high, fluidity of molten declines, thereby forming process is brought unfavorable, is especially unfavorable for the moulding of book wall, complex construction goods.
Described carbon fiber is that thermal conductivity is greater than 200W/ (mK), and tensile modulus is greater than the high-performance asphalt base carbon fiber of 700GPa, and its tensile modulus is greater than 700GPa, and thermal conductivity is greater than 200W/ (mK).Can select commercial
k1392U, K13C6U, K13D2U, K63A12 or the Cytec of series
the P-1002K of series, P-100S 2K, P-1202K, the asphalt base carbon fibers such as P-120S 2K, can be also the asphalt base carbon fibers of the suitable modulus of having of other and thermal conductivity.
Described carbon fiber is chopped carbon fiber, and mean length is 10 μ m～2mm.When staple length is less than 10 μ m, be unfavorable for that fiber forms continuous heat conduction via in Nylon 6 matrix, can not effectively improve the heat-conductive characteristic of Nylon 6; So staple length value is more conducive to improve more greatly intensity, modulus and the heat conductivity of material.But when staple length is greater than 2mm, will cause matrix material melt viscosity high, poor fluidity, brings difficulty to the forming process of follow-up goods, is especially unfavorable for the forming process of thin-walled, complex construction goods.
Described mineral filler is selected from one or more in talcum powder, glass microballon, calcium carbonate, barium sulfate, magnesium oxide, calcium sulfate, wollastonite, mica powder, diatomite or polynite, the mixture of the preferred weight ratio talcum powder of 1: 2: 4, magnesium oxide and silicon carbide.
Described coupling agent is selected from one or more in γ-aminopropyl triethoxysilane (KH-550), γ-glycidyl ether oxygen propyl trimethoxy silicane (KH-560), γ-aminopropyltrimethoxysilane, γ-(methacryloxypropyl) propyl trimethoxy silicane (KH-570), positive titanium isopropylate, sec.-propyl three (dioctylphyrophosphoric acid acyloxy) titanic acid ester (KR38S) or Di(dioctylpyrophosphato) ethylene titanate, the mixture of the preferred weight ratio KH-550 of 1: 1 and KR38S.
Described oxidation inhibitor is selected from four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (antioxidant 1010), β-(3.5-di-tert-butyl-hydroxy phenyl) propionic acid octadecanol fat (antioxidant 1076), N, N '-bis--(3-(3,5-di-tert-butyl-hydroxy phenyl) propionyl) one or more in hexanediamine (oxidation inhibitor 1098) or three [2,4-di-tert-butyl-phenyl] phosphorous acid esters (irgasfos 168);
Described lubricant is selected from one or more in ethylene bis-fatty acid amides, ethylene-acrylic acid copolymer or silicone powder.
A preparation method for carbon fiber reinforced nylon 6 resin composite materials, is characterized in that, comprises the following steps:
(1) material carbon fiber, Nylon 6 and mineral filler is fully dry;
(2) according to proportioning, take each component raw material;
(3) by each component raw material high-speed mixing except carbon fiber;
(4) step (3) gained mixture is added to twin screw extruder hopper, carbon fiber is added to fine mouthful in forcing machine and add, extruding pelletization.
Dry condition described in step (1) is forced air drying 4～6 hours at 100～140 ℃, and the water content before processing must be less than 0.02wt%.Carbon fiber has water absorbability, and being dried before processing is very important, otherwise by the degraded causing in Nylon 6 high temperature process process, causes mechanical properties decrease.
Twin screw extruder described in described step (4) is respectively 210,230 ℃, 245 ℃, 245 ℃, 245 ℃, 240 ℃ from spout to extruder die head Liu district Temperature Setting, 20～50 hertz of engine speeds.
Asphalt base carbon fiber is to take the carbon fiber that the condensed-nuclei aromatics compounds such as black petroleum products pitch, coal-tar pitch or naphthalene system are prepared as raw material, according to performance, can be divided into universal pitch-based carbon fiber and high-performance asphalt-based carbon fiber two classes.High-performance asphalt-based carbon fiber has that density is little, modulus is high (the highest 930GPa that reached, reach theoretical value 91%), excellent thermal conductivity (thermal conductivity is up to 600～800W/ (mK), is 1.5～2 times of the best copper of thermal conductivity in metal) and the advantage such as thermal expansivity is little.Utilize the prepared matrix material of asphalt base carbon fiber reinforced nylon 6 resin, can either increase substantially the modulus (rigidity) of Nylon 6, meet electronics/electric product thin-walled property, light-weighted requirement, can increase substantially the heat conductivility of Nylon 6 again simultaneously.In addition, because asphalt base carbon fiber thermal expansivity is extremely low, can also improve the dimensional stability of Nylon 6 goods, be conducive to manufacture the product of high precision size.The mechanical property of matrix material is subject to the factor impacts such as fibre content, interface; And the raising of heat conductivility need to form more Continuous Heat conduction path in polymeric matrix, be subject to the factor impacts such as heat conductivility, content, dispersion of fiber itself, the inventor considers these influence factors, by large quantity research is carried out in the aspects such as apolegamy of the adjustment of recombining process, screw combinations and rotating speed and various auxiliary agents, completed the present invention.
Compared with prior art, the present invention has effectively overcome the shortcoming of filled nylon-6 resin mechanical property, heat conductivility the two conventional art that can not take into account, carbon fiber reinforced nylon 6 thermoplastic composites that a kind of mechanical property and thermal conductivity can be improved have simultaneously been prepared, be applicable to, for manufacturing thin-walled property, light-weighted automobile component and electronics/electric product, can greatly expanding the Application Areas of Nylon 6 material.And the raw materials cost of matrix material is low, preparation technology simple, be suitable for industrial continuous production.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.
The density of the Nylon 6 using in embodiment and comparative example is 1.14g/cm
3, modulus in flexure is 2.5GPa, and flexural strength is 96MPa, and thermal conductivity is 0.30W/ (mK).Carbon fiber is high-performance asphalt base carbon fiber, and density is 2.16g/cm
3, tensile modulus is 760GPa, and tensile strength is 2.6GPa, and thermal conductivity is 440W/ (mK).Before processing, all forced air dryings 4～6 hours at 100～140 ℃ of Nylon 6, carbon fiber and mineral filler, make water content all be less than 0.02wt%.
Mechanical property is measured with universal electrical puller system, and thermal conductivity is measured with the laser method thermal conductivity coefficient measurement instrument that shines.The method of adding up 500～600 length after thermolysis and averaging again for staple length.
Embodiment 1
Take 100 parts of weight part content Nylon 6s, 20 parts, carbon fiber, mineral filler (talcum powder, magnesium oxide and silicon carbide, weight ratio 1: 2: 4) 10 parts, coupling agent (KH-550 and KR38S, weight ratio 1: 1) 0.5 part, (1010) 0.2 parts, oxidation inhibitor and 0 part of batching of lubricant; The input high-speed mixer high speeds such as Nylon 6, maleic anhydride graft Nylon 6, mineral filler, coupling agent, oxidation inhibitor and lubricant are mixed, blanking is to forcing machine hopper, carbon fiber adds fine mouthful in forcing machine and adds, control is respectively 210,230 ℃, 245 ℃, 245 ℃, 245 ℃, 240 ℃ from spout to extruder die head Ge district temperature, 50 hertz of engine speeds, can obtain this matrix material through twin screw extruder extruding pelletization.
In the sample of the present embodiment, the mean length of carbon fiber is 421 μ m, and each performance of matrix material is respectively: flexural strength 223MPa, modulus in flexure 14.1GPa, thermal conductivity 2.2W/ (mK).Flexural strength, modulus and thermal conductivity are respectively 2.3 times, 5.7 times and 6.7 times of pure Nylon 6 material, rigidity and heat conductivility obtain significantly, meet the requirement of thin-walled property, light-weighted automobile component and electronics/electric product forming process, can greatly expand the Application Areas of Nylon 6.And the preparation technology of matrix material is simple, extrusion is continual and steady, be suitable for industrial continuous production.
Embodiment 2
Take 100 parts of weight part content Nylon 6s, 80 parts, carbon fiber, mineral filler (talcum powder, magnesium oxide and silicon carbide, weight ratio 1: 2: 4) 10 parts, coupling agent (KH-550 and KR38S, weight ratio 1: 1) 5 parts, (1010) 1 parts, oxidation inhibitor and 3 parts of batchings of lubricant (silicone powder).Then adopt the method identical with embodiment 1 to prepare matrix material.
In the sample of the present embodiment, the mean length of carbon fiber is 86 μ m, and each performance of matrix material is respectively: flexural strength 523MPa, modulus in flexure 54.2GPa, thermal conductivity 4.6W/ (mK).Flexural strength, modulus and thermal conductivity are respectively 5.4 times, 21.7 times and 15.3 times of pure Nylon 6, rigidity and heat conductivility obtain significantly, meet the requirement of thin-walled property, light-weighted automobile component and electronics/electric product forming process, can greatly expand the Application Areas of Nylon 6.And the preparation technology of matrix material is simple, extrusion is continual and steady, be suitable for industrial continuous production.
Embodiment 3
Take 100 parts of weight part content Nylon 6s, 40 parts, carbon fiber, mineral filler (talcum powder, magnesium oxide and silicon carbide, weight ratio 1: 2: 4) 10 parts, coupling agent (KH-550 and KR38S, weight ratio 1: 1) 2 parts, (1010) 0.6 parts, oxidation inhibitor and 1 part of batching of lubricant (silicone powder).Then adopt the method identical with embodiment 1 to prepare matrix material.
In the sample of the present embodiment, the mean length of carbon fiber is 320 μ m, and each performance of matrix material is respectively: flexural strength 362MPa, modulus in flexure 20.6GPa, thermal conductivity 2.6W/ (mK).Flexural strength, modulus and thermal conductivity are respectively 3.8 times, 8.2 times and 8.7 times of pure Nylon 6, rigidity and heat conductivility obtain significantly, meet the requirement of thin-walled property, light-weighted automobile component and electronics/electric product forming process, can greatly expand the Application Areas of Nylon 6.And the preparation technology of matrix material is simple, extrusion is continual and steady, be suitable for industrial continuous production.
Embodiment 4
Take 100 parts of weight part content Nylon 6s, 40 parts, carbon fiber, mineral filler (talcum powder, magnesium oxide and silicon carbide, weight ratio 1: 2: 4) 20 parts, coupling agent (KH-550 and KR38S, weight ratio 1: 1) 2 parts, (1010) 0.6 parts, oxidation inhibitor and 1 part of batching of lubricant (ethylene bis-fatty acid amides).Then adopt the method identical with embodiment 1 to prepare matrix material.
In the sample of the present embodiment, the mean length of carbon fiber is 268 μ m, and each performance of matrix material is respectively: flexural strength 380MPa, modulus in flexure 23.3GPa, thermal conductivity 3.8W/ (mK).Flexural strength, modulus and thermal conductivity are respectively 4.0 times, 9.3 times and 12.7 times of pure Nylon 6, rigidity and heat conductivility obtain significantly, meet the requirement of thin-walled property, light-weighted automobile component and electronics/electric product forming process, can greatly expand the Application Areas of Nylon 6.And the preparation technology of matrix material is simple, extrusion is continual and steady, be suitable for industrial continuous production.
Embodiment 5
Take 100 parts of weight part content Nylon 6s, 40 parts, carbon fiber, mineral filler (talcum powder, magnesium oxide and silicon carbide, weight ratio 1: 2: 4) 15 parts, coupling agent (KH-550 and KR38S, weight ratio 1: 1) 2 parts, (1010) 0.6 parts, oxidation inhibitor and 1 part of batching of lubricant (ethylene bis-fatty acid amides).Then adopt the method identical with embodiment 1 to prepare matrix material.
In the sample of the present embodiment, the mean length of carbon fiber is 277 μ m, and each performance of matrix material is respectively: flexural strength 371MPa, modulus in flexure 22.7GPa, thermal conductivity 3.7W/ (mK).Flexural strength, modulus and thermal conductivity are respectively 3.9 times, 9.1 times and 12.3 times of pure Nylon 6, rigidity and heat conductivility obtain significantly, meet the requirement of thin-walled property, light-weighted automobile component and electronics/electric product forming process, can greatly expand the Application Areas of Nylon 6.And the preparation technology of matrix material is simple, extrusion is continual and steady, be suitable for industrial continuous production.
Comparative example 1
During matrix material forms, carbon fiber content is 10 parts, and other composition and preparation method are identical with embodiment 1.
In prepared matrix material sample, the mean length of carbon fiber is 549 μ m, and each performance of matrix material is respectively: flexural strength 133MPa, modulus in flexure 5.1GPa, thermal conductivity 1.01W/ (mK).Flexural strength, modulus and thermal conductivity are respectively 1.4 times, 2.0 and 3.4 times of pure Nylon 6.With embodiment 1 relatively, in this ratio, the addition of carbon fiber is too low, cannot play enhancement to Nylon 6, also cannot in Nylon 6 matrix, form heat conduction via, so the rigidity of material and heat conductivility all do not have clear improvement.
Comparative example 2
During matrix material forms, carbon fiber content is 100 parts, and other composition and preparation method are identical with embodiment 1.
In prepared matrix material sample, the mean length of carbon fiber is 68 μ m, and each performance of matrix material is respectively: flexural strength 470MPa, modulus in flexure 55.1GPa, thermal conductivity 2.3W/ (mK).Flexural strength, modulus and thermal conductivity are respectively 4.9 times, 22.0 times and 7.7 times of pure Nylon 6.With embodiment 2 relatively, although improved the addition of carbon fiber in this ratio, modulus is slightly improved, and intensity, thermal conductivity decline on the contrary.This may be that matrix viscosity is too high and carbon fiber bad dispersibility is caused.Because carbon fiber is higher than Nylon 6 price, the increase of carbon fiber consumption also will cause the cost of matrix material to increase.
Comparative example 3
During matrix material forms, the content of mineral filler is 0, and other composition is identical with embodiment 3.Then adopt the method identical with embodiment 1 to prepare matrix material.
In prepared matrix material sample, the mean length of carbon fiber is 370 μ m, and each performance of matrix material is respectively: flexural strength 330MPa, modulus in flexure 18.9GPa, thermal conductivity 1.9W/ (mK).Flexural strength, modulus and thermal conductivity are respectively 3.4 times, 7.6 times and 6.3 times of pure Nylon 6.In this example, there is no mineral filler, and embodiment 3 compares, the strength and modulus of matrix material slightly declines, more but thermal conductivity declines.Magnesium oxide in mineral filler and silicon carbide itself are exactly heat conductive filler, and these fillers coordinate carbon fiber jointly to form the thermal conducting path of composite inner.If do not add mineral filler, thermal conducting path imperfection, so heat conductivility declines.
Comparative example 4
During matrix material forms, coupling agent content is 0, and other composition is identical with embodiment 3.Then adopt the method identical with embodiment 1 to prepare matrix material.
In prepared matrix material sample, the mean length of carbon fiber is 319 μ m, and each performance of matrix material is respectively: flexural strength 163MPa, modulus in flexure 13.5GPa, thermal conductivity 0.99W/ (mK).Flexural strength, modulus and thermal conductivity are respectively 1.7 times, 5.4 times and 3.3 times of pure Nylon 6.Compare with embodiment 3, in this example, do not add coupling agent, so between fiber and resin matrix, interfacial bonding property is very poor, fiber dispersion is also very poor, the intensity of Nylon 6, modulus and heat conductivility be difficult to form thermal conducting path at material internal, so all can not get obvious raising.
The explanation of above embodiment is just for helping to understand method of the present invention and core concept thereof.Be noted that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of the claims in the present invention.
Above-mentioned explanation to the disclosed embodiments, makes professional and technical personnel in the field can realize or use the present invention.To the multiple modification of these embodiment, will be apparent for those skilled in the art, General Principle as defined herein can, in the situation that not departing from the spirit or scope of the present invention, realize in other embodiments.Therefore, the present invention will can not be restricted to these embodiment shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.
Claims (10)
1. carbon fiber reinforced nylon 6 resin composite materials, is characterized in that, this matrix material is comprised of the material of following weight part: 100 parts of Nylon 6s, 20～80 parts, carbon fiber, 10～20 parts of mineral fillers, 0.5～5 part of coupling agent, 0～3 part of 0.2～1 part, oxidation inhibitor and lubricant.
2. a kind of carbon fiber reinforced nylon 6 resin composite materials according to claim 1, is characterized in that, described Nylon 6 is selected from a kind of in the pellet of extrusion grade, injection grade, filling level or flame retardant grade or powder.
3. a kind of carbon fiber reinforced nylon 6 resin composite materials according to claim 1, is characterized in that, described carbon fiber is that thermal conductivity is greater than 200W/ (mK), and tensile modulus is greater than the high-performance asphalt base carbon fiber of 700GPa.
4. a kind of carbon fiber reinforced nylon 6 resin composite materials according to claim 1, is characterized in that, described carbon fiber is chopped carbon fiber, and mean length is 10 μ m～2mm.
5. a kind of carbon fiber reinforced nylon 6 resin composite materials according to claim 1, it is characterized in that, described mineral filler is selected from one or more in talcum powder, glass microballon, calcium carbonate, barium sulfate, magnesium oxide, calcium sulfate, wollastonite, mica powder, diatomite or polynite.
6. a kind of carbon fiber reinforced nylon 6 resin composite materials according to claim 1, it is characterized in that, described coupling agent is selected from one or more in γ-aminopropyl triethoxysilane, γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-aminopropyltrimethoxysilane, γ-(methacryloxypropyl) propyl trimethoxy silicane, positive titanium isopropylate, sec.-propyl three (dioctylphyrophosphoric acid acyloxy) titanic acid ester or Di(dioctylpyrophosphato) ethylene titanate.
7. a kind of carbon fiber reinforced nylon 6 resin composite materials according to claim 1, it is characterized in that, described oxidation inhibitor is selected from four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, β-(3.5-di-tert-butyl-hydroxy phenyl) propionic acid octadecanol fat, N, N '-bis--(3-(3,5-di-tert-butyl-hydroxy phenyl) propionyl) one or more in hexanediamine or three [2,4-di-tert-butyl-phenyl] phosphorous acid ester;
Described lubricant is selected from one or more in ethylene bis-fatty acid amides, ethylene-acrylic acid copolymer or silicone powder.
8. a preparation method for carbon fiber reinforced nylon 6 resin composite materials as claimed in claim 1, is characterized in that, comprises the following steps:
(1) material carbon fiber, Nylon 6 and mineral filler is fully dry;
(2) according to proportioning, take each component raw material;
(3) by each component raw material high-speed mixing except carbon fiber;
(4) step (3) gained mixture is added to twin screw extruder hopper, carbon fiber is added to fine mouthful in forcing machine and add, extruding pelletization.
9. the preparation method of a kind of carbon fiber reinforced nylon 6 resin composite materials according to claim 8, it is characterized in that, dry condition described in step (1) is forced air drying 4～6 hours at 100～140 ℃, and the water content before processing must be less than 0.02wt%.
10. the preparation method of a kind of carbon fiber reinforced nylon 6 resin composite materials according to claim 8, it is characterized in that, twin screw extruder described in described step (4) is respectively 210,230 ℃, 245 ℃, 245 ℃, 245 ℃, 240 ℃ from spout to extruder die head Liu district Temperature Setting, 20～50 hertz of engine speeds.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410395200.1A CN104177823A (en) | 2014-08-12 | 2014-08-12 | Carbon fiber reinforced nylon 6 resin composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410395200.1A CN104177823A (en) | 2014-08-12 | 2014-08-12 | Carbon fiber reinforced nylon 6 resin composite material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104177823A true CN104177823A (en) | 2014-12-03 |
Family
ID=51959184
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410395200.1A Pending CN104177823A (en) | 2014-08-12 | 2014-08-12 | Carbon fiber reinforced nylon 6 resin composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104177823A (en) |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104845289A (en) * | 2015-04-30 | 2015-08-19 | 上海锦湖日丽塑料有限公司 | High-performance carbon-fiber enhancement polymer alloy and preparation method thereof |
| CN104862807A (en) * | 2015-04-09 | 2015-08-26 | 浙江泰索科技有限公司 | High thermal conductivity acrylic fiber and preparation method thereof |
| CN105295368A (en) * | 2015-11-02 | 2016-02-03 | 上海交通大学 | Damp-heat aging resisting carbon fiber-reinforced nylon 66 compound material and preparation thereof |
| CN105482447A (en) * | 2015-12-30 | 2016-04-13 | 中实洛阳工程塑料有限公司 | Highly-wear-resistant plastic sheave liner and preparation method thereof |
| CN105838063A (en) * | 2015-02-02 | 2016-08-10 | 现代自动车株式会社 | Carbon long fiber reinforced thermoplastic resin composition and molded article manufactured using the same |
| CN106009651A (en) * | 2016-07-12 | 2016-10-12 | 蚌埠高华电子股份有限公司 | Silicon carbide-polyamide thermal conductive composite material for LED lamps and preparation method of material |
| CN106046767A (en) * | 2016-07-11 | 2016-10-26 | 铜陵日兴电子有限公司 | Bentonite-nylon heat-conductive composite material for LED lamp and preparation method of material |
| CN106046770A (en) * | 2016-07-12 | 2016-10-26 | 蚌埠高华电子股份有限公司 | Wave-absorbing LED-lamp nylon heat-conduction composite and preparing method thereof |
| CN106147216A (en) * | 2016-07-11 | 2016-11-23 | 铜陵日兴电子有限公司 | A kind of LED is with not carrying out powder nylon heat-conductive composite material and preparation method thereof |
| CN106147215A (en) * | 2016-07-11 | 2016-11-23 | 铜陵日兴电子有限公司 | A kind of LED boron nitride nylon heat-conductive composite material and preparation method thereof |
| CN106167618A (en) * | 2016-07-11 | 2016-11-30 | 铜陵日兴电子有限公司 | A kind of LED Pulvis Talci nylon heat-conductive composite material and preparation method thereof |
| CN106189212A (en) * | 2016-07-11 | 2016-12-07 | 铜陵日兴电子有限公司 | A kind of LED forsterite nylon heat-conductive composite material and preparation method thereof |
| CN106905692A (en) * | 2017-03-14 | 2017-06-30 | 苏州隆芝耀新材料有限公司 | A kind of injection grade heat-resisting chopped carbon fiber nylon composite materials high and its technology of preparing |
| CN108285637A (en) * | 2018-02-01 | 2018-07-17 | 日丰企业（佛山）有限公司 | Polyamide compoiste material and its application |
| CN109627751A (en) * | 2018-11-30 | 2019-04-16 | 上海日之升科技有限公司 | Fire-retardant continuous long glass fiber reinforced PA6 material of one kind and preparation method thereof |
| WO2019074082A1 (en) * | 2017-10-13 | 2019-04-18 | 国立大学法人九州工業大学 | Flame retardant material |
| CN111978718A (en) * | 2020-07-31 | 2020-11-24 | 苏州新华美塑料有限公司 | High-performance nylon hub and preparation method thereof |
| CN113121991A (en) * | 2019-12-30 | 2021-07-16 | 佛山市高明华美塑料有限公司 | Nylon composite material with carbon fiber mixed with molybdenum oxide |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060100368A1 (en) * | 2004-11-08 | 2006-05-11 | Park Edward H | Elastomer gum polymer systems |
| CN102504528A (en) * | 2011-10-21 | 2012-06-20 | 奇瑞汽车股份有限公司 | Hollow glass microsphere-filled fiber-reinforced nylon composite material and preparation method thereof |
| CN102532869A (en) * | 2012-02-17 | 2012-07-04 | 南京聚隆科技股份有限公司 | Heat-conducting antistatic carbon fiber modified polyamide composite material and preparation method thereof |
| CN103059565A (en) * | 2013-01-25 | 2013-04-24 | 本松工程塑料（杭州）有限公司 | Heat-conducting nylon composite material, preparation method and application thereof |
| CN103450668A (en) * | 2013-08-07 | 2013-12-18 | 上海日之升新技术发展有限公司 | High-strength carbon fiber reinforced halogen-free flame-retardant PA6 (Polyamide) composite material and preparation method thereof |
| CN103554904A (en) * | 2013-10-30 | 2014-02-05 | 上海交通大学 | Recovered carbon fiber-reinforced nylon composite material as well as preparation method thereof |
-
2014
- 2014-08-12 CN CN201410395200.1A patent/CN104177823A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060100368A1 (en) * | 2004-11-08 | 2006-05-11 | Park Edward H | Elastomer gum polymer systems |
| CN102504528A (en) * | 2011-10-21 | 2012-06-20 | 奇瑞汽车股份有限公司 | Hollow glass microsphere-filled fiber-reinforced nylon composite material and preparation method thereof |
| CN102532869A (en) * | 2012-02-17 | 2012-07-04 | 南京聚隆科技股份有限公司 | Heat-conducting antistatic carbon fiber modified polyamide composite material and preparation method thereof |
| CN103059565A (en) * | 2013-01-25 | 2013-04-24 | 本松工程塑料（杭州）有限公司 | Heat-conducting nylon composite material, preparation method and application thereof |
| CN103450668A (en) * | 2013-08-07 | 2013-12-18 | 上海日之升新技术发展有限公司 | High-strength carbon fiber reinforced halogen-free flame-retardant PA6 (Polyamide) composite material and preparation method thereof |
| CN103554904A (en) * | 2013-10-30 | 2014-02-05 | 上海交通大学 | Recovered carbon fiber-reinforced nylon composite material as well as preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 杨鸣波等: "《中国材料工程大典.第6卷.高分子材料工程（上）》", 31 March 2006, 化学工业出版社 * |
| 沈曾民: "《新型碳材料》", 31 July 2003, 化学工业出版社 * |
Cited By (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105838063A (en) * | 2015-02-02 | 2016-08-10 | 现代自动车株式会社 | Carbon long fiber reinforced thermoplastic resin composition and molded article manufactured using the same |
| CN105838063B (en) * | 2015-02-02 | 2019-03-22 | 现代自动车株式会社 | The thermoplastic resin composition of fibre reinforced and the mechanograph manufactured using it |
| CN104862807A (en) * | 2015-04-09 | 2015-08-26 | 浙江泰索科技有限公司 | High thermal conductivity acrylic fiber and preparation method thereof |
| CN104845289A (en) * | 2015-04-30 | 2015-08-19 | 上海锦湖日丽塑料有限公司 | High-performance carbon-fiber enhancement polymer alloy and preparation method thereof |
| CN105295368A (en) * | 2015-11-02 | 2016-02-03 | 上海交通大学 | Damp-heat aging resisting carbon fiber-reinforced nylon 66 compound material and preparation thereof |
| CN105482447A (en) * | 2015-12-30 | 2016-04-13 | 中实洛阳工程塑料有限公司 | Highly-wear-resistant plastic sheave liner and preparation method thereof |
| CN106189212A (en) * | 2016-07-11 | 2016-12-07 | 铜陵日兴电子有限公司 | A kind of LED forsterite nylon heat-conductive composite material and preparation method thereof |
| CN106046767A (en) * | 2016-07-11 | 2016-10-26 | 铜陵日兴电子有限公司 | Bentonite-nylon heat-conductive composite material for LED lamp and preparation method of material |
| CN106147216A (en) * | 2016-07-11 | 2016-11-23 | 铜陵日兴电子有限公司 | A kind of LED is with not carrying out powder nylon heat-conductive composite material and preparation method thereof |
| CN106147215A (en) * | 2016-07-11 | 2016-11-23 | 铜陵日兴电子有限公司 | A kind of LED boron nitride nylon heat-conductive composite material and preparation method thereof |
| CN106167618A (en) * | 2016-07-11 | 2016-11-30 | 铜陵日兴电子有限公司 | A kind of LED Pulvis Talci nylon heat-conductive composite material and preparation method thereof |
| CN106009651A (en) * | 2016-07-12 | 2016-10-12 | 蚌埠高华电子股份有限公司 | Silicon carbide-polyamide thermal conductive composite material for LED lamps and preparation method of material |
| CN106046770A (en) * | 2016-07-12 | 2016-10-26 | 蚌埠高华电子股份有限公司 | Wave-absorbing LED-lamp nylon heat-conduction composite and preparing method thereof |
| CN106905692A (en) * | 2017-03-14 | 2017-06-30 | 苏州隆芝耀新材料有限公司 | A kind of injection grade heat-resisting chopped carbon fiber nylon composite materials high and its technology of preparing |
| WO2019074082A1 (en) * | 2017-10-13 | 2019-04-18 | 国立大学法人九州工業大学 | Flame retardant material |
| CN111201269A (en) * | 2017-10-13 | 2020-05-26 | 学校法人东京理科大学 | Flame-retardant material |
| JPWO2019074082A1 (en) * | 2017-10-13 | 2020-11-05 | 学校法人東京理科大学 | Flame-retardant material |
| JP7111311B2 (en) | 2017-10-13 | 2022-08-02 | 学校法人東京理科大学 | flame retardant material |
| US11920076B2 (en) | 2017-10-13 | 2024-03-05 | Tokyo University Of Science Foundation | Fire retardant material |
| CN108285637A (en) * | 2018-02-01 | 2018-07-17 | 日丰企业（佛山）有限公司 | Polyamide compoiste material and its application |
| CN109627751A (en) * | 2018-11-30 | 2019-04-16 | 上海日之升科技有限公司 | Fire-retardant continuous long glass fiber reinforced PA6 material of one kind and preparation method thereof |
| CN113121991A (en) * | 2019-12-30 | 2021-07-16 | 佛山市高明华美塑料有限公司 | Nylon composite material with carbon fiber mixed with molybdenum oxide |
| CN111978718A (en) * | 2020-07-31 | 2020-11-24 | 苏州新华美塑料有限公司 | High-performance nylon hub and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104177823A (en) | Carbon fiber reinforced nylon 6 resin composite material and preparation method thereof | |
| CN104151707B (en) | Carbon fiber reinforced resin composite material with superior heat-conducting property and preparation method thereof | |
| CN104151768A (en) | Carbon fiber reinforced ABS (Acrylonitrile Butadiene Styrene) resin composite material with superior heat conductivity and preparation method | |
| CN104194286A (en) | Carbon fiber reinforced thermoplastic resin composite material and preparation method of carbon fiber reinforced thermoplastic resin composite material | |
| CN103602060B (en) | Heat conduction abrasion-proof insulating nylon 6 composite material and preparation method thereof | |
| CN103044902B (en) | Polyamide compoiste material, its preparation method and application | |
| CN104610714B (en) | A kind of polybutylene terephthalate (PBT)/Merlon insulating heat-conductive composite and preparation method thereof | |
| CN104151805A (en) | Carbon fiber reinforced thermoplastic resin composite material with superior heat dissipation performance and preparation method | |
| CN104559145A (en) | High-toughness and high-thermal-conductivity polymer material and preparation method thereof | |
| CN103435998A (en) | Method for preparing high-tenacity composite material with heat conducting function | |
| CN104559148A (en) | High-thermal-diffusion-coefficient high molecular material and preparation method thereof | |
| CN106519659A (en) | A high-performance heat-conducting nylon composite material, a preparing method thereof and applications of the composite material | |
| CN102070899A (en) | Insulating and heat-conducting polyamide composite material and preparation method thereof | |
| CN106675008B (en) | High-thermal-conductivity nylon 6 composite material and preparation method thereof | |
| CN104559109B (en) | A kind of Merlon heat-conductive composite material and preparation method thereof | |
| CN108250747A (en) | A kind of thermoplastic polyetherimide insulating heat-conductive composite material and preparation method thereof | |
| CN103897241A (en) | Heat conductive plastics and manufacturing method thereof | |
| CN102643480A (en) | Anti-static alloy composite material and preparation method thereof | |
| CN107383615A (en) | A kind of modified polypropylene material and preparation method thereof | |
| CN103289346B (en) | A kind of low-expansion coefficient high-ductility height heat conduction functional composite material and preparation method thereof | |
| CN104292631A (en) | Heat-conducting wear-resisting polypropylene resin and preparation method thereof | |
| CN104072966A (en) | Multi-element composite heat-conducting functional master batch and preparation method thereof | |
| CN105295368A (en) | Damp-heat aging resisting carbon fiber-reinforced nylon 66 compound material and preparation thereof | |
| CN113980459A (en) | High-rigidity glass fiber reinforced nylon composite material and preparation method thereof | |
| CN108929536A (en) | A kind of heat conductive electronic equipment graphene/polyamide compoiste material and preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20141203 |
|
| RJ01 | Rejection of invention patent application after publication |