CN105239207A - Graphitized compound carbon fibers and preparation method thereof - Google Patents
Graphitized compound carbon fibers and preparation method thereof Download PDFInfo
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- CN105239207A CN105239207A CN201510796076.4A CN201510796076A CN105239207A CN 105239207 A CN105239207 A CN 105239207A CN 201510796076 A CN201510796076 A CN 201510796076A CN 105239207 A CN105239207 A CN 105239207A
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Abstract
The invention discloses a preparation method of graphitized compound carbon fibers. The method comprises the following steps: charging materials by steps and mixing, centrifuging and spinning, spraying hot airflow, curing, carbonizing and graphitizing. The prepared graphitized compound carbon fibers have the characteristics that the average diameter is 0.5-4 microns, the average length is 0.1mm-120mm, the tensile strength is 0.7GPa-1.8GPa, the tensile modulus is 30GPa-80GPa, the heat conductivity is 1W/m.k-5W/m.k (radial) and the initial oxidization temperature is 500-650 DEG C. The graphitized compound carbon fibers have low manufacturing cost and can be widely applied to technical fields of heat preservation and heat insulation, activated adsorption, friction and the like.
Description
Technical field
The present invention relates to a kind of carbon fiber reinforce plastic technical field, particularly relate to the preparation method of the difficult graphitization carbon fiber reinforce plastic of a kind of Novel super-thin.
Background technology
Along with the development of society, the raising of people's living standard and the renewal of industrial technology, the environmental consciousness of people constantly strengthens, and energy-saving and emission-reduction are concerned day by day.
No matter soak material, be reduce discharging material as space industry anti-yaw damper material or industrial energy saving, be proposed harsher requirement to the performance of material.Phenolic aldehyde base carbon fibre is the carbon fiber adopting difficult graphitization resin phenolic aldehyde to prepare, it has the incomparable thermal insulation of other carbon fiber systems and ablation resistance, be the best carbon fiber being applied to field of thermal insulation, the preparation key of phenolic aldehyde base carbon fibre is preparation and the solidification of phenolic fibre.
At present, prepare phenolic aldehyde base carbon fibre and usually can adopt novolac resin or thermosetting phenolic resin two kinds of modes.
Adopt novolac resin to prepare phenolic aldehyde base carbon fibre, need to shape with formaldehyde and hydrochloric acid, the shortcoming preparation technology of this preparation method is loaded down with trivial details, and uses formaldehyde to be unfavorable for environmental protection, cannot meet Environment protection and safety demand.Can also adopt the method for disc centrifuge spinning or adopt novolac resin and polyethylene mixing to prepare phenolic aldehyde base carbon fibre through melt spinning again, but the curing process of these two kinds of preparation methods is loaded down with trivial details equally, still cannot meet Environment protection and safety demand.
Thermosetting phenolic resin is adopted to prepare phenolic aldehyde base carbon fibre, because thermosetting phenolic resin is difficult to spinning moulding because of easy heat cure.Prior art carries out electrostatic spinning by polyvinyl alcohol and phenolic aldehyde raw material are mixed with low viscosity spinning solution, then solves the difficult shaping problem of thermosetting phenolic resin by the mode of heated polymerizable.High molecular weight linear, novolac resin, thermosetting phenolic resin can also be adopted, be mixed with electrostatic spinning liquid and make fiber, again through curing molding, but the difficult point of this preparation method is the requirement of spinning solution high, current electrostatic spinning technique is also immature, causes its reappearance poor.
In order to overcome above-mentioned difficulties, high speed centrifugation method can be adopted to prepare carbon nano-fiber, centrifugal spinning technology is a kind of spinning process of low cost, but low viscosity solution or melt also can only be processed into sub-micron fibers by this spinning mode, for high viscosity liquid, because centrifugal force is limited, be difficult to reach less than 2 microns, and centrifugal spinning technology is generally the preparation process being applied to novolac resin, fatal problem such as centrifugal spinning technology being applied to the preparation process of thermosetting resin, easily causing thermosetting resin easily to solidify, equipment cleaning is difficult.
Therefore, for the defect of above prior art, to the fine centrifugal spinning of high viscosity liquid, a kind of new carbon fiber reinforce plastic preparation method is proposed.
Summary of the invention
For solving the problems of the technologies described above, the invention provides a kind of graphitization composite fibre and preparation method thereof, the present invention by the spinning asphalt after visbreaking, then coordinates the thermosetting phenolic resin of dissolving, the viscosity of spinning material is significantly reduced, is beneficial to the refinement of fiber; And by the use to the low-temperature heat of thermosetting resin, the blended and releasing agent of non-thermosettable pitch, significantly reduce the coking of material fiber and the probability etc. of resin solidification, in preparation process, without the need to using caustic acid, toxic formaldehyde, technical process Environmental Safety, cheap for manufacturing cost.
According to an aspect of the present invention, provide a kind of preparation method of carbon fiber reinforce plastic, described method comprises: step S1, Multistep feeding mixes: in mass ratio, get the solubility thermosetting phenolic resin solvent of 5-300 part spinning asphalt, 2-30 part aromatic hydrocarbons viscosity reductant, 0.5-10 part high-temperature mold lubricant, 100 parts of solubility thermosetting phenolic resins, 3-120 part, be mixed to get spinning material; Step S2, centrifugal spinning: described spinning material is put into centrifugal spinning equipment, through heating centrifugal spinning, obtains a drawn fiber; Step S3, thermal current is jetted: a described drawn fiber is put into thermal current and jets, obtain secondary drawn fiber, thermal current is air, water vapor mixture body, and mixing quality is than being 100:10-150, temperature 120-250 DEG C, injection rate is 10-100m/s, by described secondary drawn fiber by negative-pressure adsorption on guipure, obtain primary solidification fiber, roofing density <1kg/m
2; Step S4, solidification, charing and graphitization: by described primary solidification fiber successively through overcuring, charing and graphitization processing, obtain graphitization carbon fiber reinforce plastic.
Wherein, described step S1 comprises further: in mass ratio, gets 5-300 part spinning asphalt, 2-30 part aromatic hydrocarbons viscosity reductant, 0.5-10 part high-temperature mold lubricant, add screw extruder, be heated to 160-340 DEG C of melting, and extrude from the die orifice of diameter 1-3mm, obtain the first melting material; In mass ratio, get the solubility thermosetting phenolic resin solvent of 100 parts of solubility thermosetting phenolic resins, 3-120 part, add screw extruder, be heated to 50-150 DEG C and obtain the second melting material; First, second melting material is extruded from die orifice respectively and obtains first, second strip fused raw material, first, second strip fused raw material described is added screw extruder, be heated to 120-300 DEG C, time of staying <20s, is mixed to get spinning material.
Wherein, in described step S2, described centrifugal spinning equipment is disc centrifuge spinning equipment, and spinning temperature is 180-320 DEG C, and centrifugal pan diameter is more than or equal to 300mm, and centrifugal rotational speed is 7000-15000rpm.
Wherein, in described step S2, the average diameter of a described drawn fiber is 8-15 μm, and length is 205-480mm; In described step S3, the average diameter of described secondary drawn fiber is 1.8-1.6 μm, and length is 100-230mm.
Wherein, quinoline insolubles content QI<40%, the ash content <300ppm of described spinning asphalt, softening point are 180-300 DEG C.
Wherein, described aromatic hydrocarbons viscosity reductant is the mixture of one or more in naphthalene, anthracene, methyl naphthalene.
Wherein, described high-temperature mold lubricant is the mixture of one or more in methyl-silicone oil, perfluoro polyether oil, triethanolamine, the two hard acid amides of ethylene.
Wherein, described step S4 comprises further: step S41, and it is 150-350 DEG C that described primary solidification fiber is put into oxidizing temperature, and under air penetrates fibrolaminar environment with 0.1-3m/min speed, oxidation 5-50h, obtains cured fiber;
Step S42, by described cured fiber under inert atmosphere nitrogen protection, is heated to 600-1400 DEG C, constant temperature 0.25-2h, obtains carbon fiber; Step S43, puts into graphitizing furnace by described carbon fiber, under inert atmosphere argon shield, is heated to 1800-2800 DEG C, constant temperature 0.25-2h, obtains graphitized fibre.
Wherein, in the step of described solidification, the gas of described inert atmosphere is nitrogen; In the step of described charing, the gas of described inert atmosphere is argon gas.
Wherein, the average diameter of described graphitization carbon fiber reinforce plastic is 0.5-4 μm, average length is 0.1-120mm, tensile strength is 0.7-1.8GPa, tensile modulus is 30-80GPa, thermal conductivity is 1-5W/mk (radial direction), and oxidation onset temperature is 500-650 DEG C.
According to another aspect of the present invention, a kind of graphitization composite fibre prepared by above-mentioned preparation method is provided.
The present invention has following beneficial effect:
1. adopt the spinning asphalt after visbreaking, then coordinate the thermosetting phenolic resin of dissolving, the viscosity of spinning material is significantly reduced, is beneficial to the refinement of fibre diameter;
2. adopt the use of the low-temperature heat of thermosetting resin, the blended and releasing agent of non-thermosettable pitch, significantly reduce the coking of material fiber and the probability of resin solidification;
3. adopt disc centrifuge spinning equipment, avoid spinning blockage problem, be conducive to continuous seepage;
4. gained material fiber is by centrifugal, thermal current drawing-off, and while drawing-off, in material, volatile component (as viscosity reductant, solvent) obtains effectively removing and being unlikely to leave defect fast;
5. the drafting force of pair material fiber is provided by centrifugal pan and air flow blowing, is conducive to the fine of fiber;
6. in preparation process, without the need to using caustic acid, toxic formaldehyde, technical process Environmental Safety.
7. cheap for manufacturing cost.
Detailed description of the invention
For making the object, technical solutions and advantages of the present invention clearly understand, below in conjunction with detailed description of the invention, the present invention is described in more detail.Should be appreciated that, these describe just exemplary, and do not really want to limit the scope of the invention.In addition, in the following description, the description to known features and technology is eliminated, to avoid unnecessarily obscuring concept of the present invention.
Graphitization carbon fiber reinforce plastic preparation method of the present invention, comprises the steps:
Step S1, Multistep feeding mixes: in mass ratio, get the solubility thermosetting phenolic resin solvent of 5-300 part spinning asphalt, 2-30 part aromatic hydrocarbons viscosity reductant, 0.5-10 part high-temperature mold lubricant, 100 parts of solubility thermosetting phenolic resins, 3-120 part, be mixed to get spinning material.
Here, to the Property requirements of solubility thermosetting phenolic resin be, when the heating-up temperature of described solubility thermosetting phenolic resin is 180 DEG C, hardening time >20s.
Optionally, quinoline insolubles content QI<40%, the ash content <300ppm of described spinning asphalt, softening point are 180-300 DEG C.Optionally, described solubility thermosetting phenolic resin is oil-soluble phenolic resin.Optionally, described aromatic hydrocarbons viscosity reductant is the mixture of one or more in naphthalene, anthracene, methyl naphthalene.Optionally, described high-temperature mold lubricant is the mixture of one or more in methyl-silicone oil, perfluoro polyether oil, triethanolamine, the two hard acid amides of ethylene.
Step S2, centrifugal spinning: described spinning material is put into centrifugal spinning equipment, through heating centrifugal spinning, obtains a drawn fiber.
Step S3, thermal current is jetted: a described drawn fiber is put into thermal current and jets, and obtains secondary drawn fiber, by described secondary drawn fiber by negative-pressure adsorption on guipure, obtain primary solidification fiber, roofing density <1kg/m
2.
Step S4, solidification, charing and graphitization: by described primary solidification fiber successively through overcuring, charing and graphitization processing, obtain graphitization carbon fiber reinforce plastic.
Aforementioned described step S1 comprises further:
In mass ratio, get 5-300 part spinning asphalt, 2-30 part aromatic hydrocarbons viscosity reductant, 0.5-10 part high-temperature mold lubricant, add screw extruder, heating obtains the first melting material.Wherein, the heating-up temperature of described first screw extruder is 160-340 DEG C.
In mass ratio, get the solubility thermosetting phenolic resin solvent of 100 parts of solubility thermosetting phenolic resins, 3-120 part, add screw extruder, heating obtains the second melting material.Wherein, the heating-up temperature of described second screw extruder is 50-150 DEG C.
First, second melting material extruded from die orifice respectively and obtain first, second strip fused raw material, first, second strip fused raw material described is added screw extruder, heating is mixed to get spinning material.Wherein, the heating-up temperature of described three-screw extruder is 120-300 DEG C, time of staying <20s.
Optionally, the diameter of described die orifice is 1-3mm.
In abovementioned steps S2, the temperature of described thermal current is 120-250 DEG C, and injecting velocity is 10-100m/s.
In abovementioned steps S2, described centrifugal spinning equipment is disc centrifuge spinning equipment, and centrifugal pan diameter is greater than 300mm.
In abovementioned steps S2, the average diameter of a described drawn fiber is 8-15 μm, and length is 205-480mm.In abovementioned steps S3, the average diameter of described secondary drawn fiber is 1.8-1.6 μm, and length is 100-230mm.
Wherein, the spinning temperature of described centrifugal spinning equipment is 180-320 DEG C, and centrifugal rotational speed is 7000-15000rpm.
In an Alternate embodiments, described thermal current, in mass ratio, air, water mixed proportion are 100:10-150.
In a preferred embodiment, described solubility thermosetting phenolic resin solvent is 100# solvent naphtha.
In the present invention, abovementioned steps S4 comprises further:
Step S41, it is 150-350 DEG C that described primary solidification fiber is put into oxidizing temperature, and under air penetrates fibrolaminar environment with 0.1-3m/min speed, oxidation 5-50h, obtains cured fiber.
Step S42, by described cured fiber under inert atmosphere protection, is heated to 600-1400 DEG C, constant temperature 0.25-2h, obtains carbon fiber.
Step S43, puts into graphitizing furnace by described carbon fiber, under inert atmosphere protection, is heated to 1800-2800 DEG C, constant temperature 0.25-2h, obtains graphitized fibre.
Preferably, in the step of described solidification, the gas of described inert atmosphere is nitrogen.
Preferably, in the step of described charing, the gas of described inert atmosphere is argon gas.
Wherein, the average diameter of described graphitization carbon fiber reinforce plastic is 0.5-4 μm, average length is 0.1-120mm, tensile strength is 0.7-1.8GPa, tensile modulus is 30-80GPa, thermal conductivity is 1-5W/mk (radial direction), and oxidation onset temperature is 500-650 DEG C.
[embodiment 1]
A kind of graphitization carbon fiber reinforce plastic preparation method, comprises the steps:
Multistep feeding mixes: the quinoline insolubles content QI of spinning asphalt is 38%, ash content is 280ppm, softening point is 285 DEG C.Solubility thermosetting phenolic resin is the hardening time that commercially available oil-soluble thermosetting phenolic is set 180 DEG C time is 45s.
Adopt three screw extruders, added material is calculated in mass ratio, get 100 parts of spinning asphalts, 20 parts of naphthalenes, 5 parts of perfluoro polyether oils add the first screw extruder, be heated to 340 DEG C of thawings, the 100# solvent naphtha getting 10 parts of solubility thermosetting phenolic resins and 6 parts adds the second screw extruder, be heated to 140 DEG C, the die orifice being 1mm from diameter respectively by the melting material of first, second screw extruder melt extrudes and obtains strip fused raw material, gained fused raw material is added three-screw extruder jointly, be heated to 280 DEG C, the time of staying is 15s.
Centrifugal spinning: spinning material is extruded through three-screw extruder, directly enters centrifugal spinning equipment, spinning temperature 300 DEG C, centrifugal rotational speed 7000rpm, obtains average diameter 15 μm, a drawn fiber of length 480mm.
Thermal current winding-up secondary drawing-off: a described drawn fiber is directly got rid of in the hot blast pass of mist composition of air and steam, in hot blast pass, in mass ratio, air, steam mixed proportion are 100:100, blowing air temperature 150 DEG C, injecting velocity 15m/s, obtain average diameter 1.4 μm, length 100mm bis-drawn fiber, by gained secondary drawn fiber by the continuous guipure of negative-pressure adsorption bottom spinning equipment, obtain primary solidification fiber, roofing density is 0.5kg/m2.
Solidification: described primary solidification fiber is entered net belt type oxidation furnace by transporting reticulation belt, oxidizing temperature 250 DEG C, air penetrates fibrage with 1m/min speed, oxidation 8h, obtains cured fiber.
Charing: described cured fiber is sent to net belt type continuous carbonization furnace, under nitrogen atmosphere protection, is heated to 1000 DEG C, constant temperature 1h, obtains carbon fiber.
Graphitization: described carbon fiber is loaded graphitizing furnace, under argon gas atmosphere protection, is heated to 1800 DEG C, constant temperature 1h, obtains graphitized fibre.
Gained graphitized carbon composite fibre average diameter is 1.1 μm, average length is 100mm, tensile strength is 1.2GPa, tensile modulus is 50GPa, thermal conductivity is 2.4W/mk (radial direction), and oxidation onset temperature is 520 DEG C.
[embodiment 2]
The preparation of graphitization carbon fiber reinforce plastic, comprises the steps:
Multistep feeding mixes: the quinoline insolubles content QI of spinning asphalt is 5%, ash content is 250ppm, softening point is 240 DEG C.Solubility thermosetting phenolic resin is the hardening time that commercially available oil-soluble thermosetting phenolic is set 180 DEG C time is 25s.
Adopt three screw extruders, added material is calculated in mass ratio, get 10 parts of spinning asphalts, 2 parts of naphthalenes, 1 part of methyl-silicone oil add the first screw extruder, be heated to 260 DEG C of thawings, the 100# solvent naphtha getting 100 parts of solubility thermosetting phenolic resins and 80 parts adds the second screw extruder, be heated to 50 DEG C, the die orifice being 3mm from diameter respectively by the melting material of first, second screw extruder melt extrudes and obtains strip fused raw material, gained fused raw material is added three-screw extruder jointly, be heated to 150 DEG C, the time of staying is 15s.
(2) centrifugal spinning: spinning material is extruded through three-screw extruder, directly enters centrifugal spinning equipment, spinning temperature 180 DEG C, centrifugal rotational speed 9000rpm, obtains average diameter 12 μm, a drawn fiber of length 550mm.
(3) thermal current winding-up secondary drawing-off: a described drawn fiber is directly got rid of in the hot blast pass of mist composition of air and steam, in hot blast pass, in mass ratio, air, steam mixed proportion are 100:80, blowing air temperature 120 DEG C, injecting velocity 10m/s, obtain average diameter 0.8 μm, the secondary drawn fiber of length 100mm, by gained secondary drawn fiber by the continuous guipure of negative-pressure adsorption bottom spinning equipment, obtain primary solidification fiber, roofing density is 0.5kg/m
2.
(4) solidify: described primary solidification fiber is entered net belt type oxidation furnace by transporting reticulation belt, oxidizing temperature 250 DEG C, air penetrates fibrage with 0.5m/min speed, oxidation 20h, obtains cured fiber.
(5) carbonize: described cured fiber is sent to net belt type continuous carbonization furnace, under nitrogen atmosphere protection, be heated to 1000 DEG C, constant temperature 1h, obtain carbon fiber.
(6) graphitization: described carbon fiber is loaded graphitizing furnace, under argon gas atmosphere protection, is heated to 2200 DEG C, constant temperature 1h, obtains graphitized fibre.
Gained carbon fiber average diameter is 0.6 μm, average length is 100mm, tensile strength is 0.7GPa, tensile modulus is 40GPa, thermal conductivity is 2.8W/mk (radial direction), and oxidation onset temperature is 550 DEG C.
[embodiment 3]
The difficult graphitization carbon fiber reinforce plastic preparation of Novel super-thin, comprises the steps:
Multistep feeding mixes: the quinoline insolubles content QI of spinning asphalt is 25%, ash content is 200ppm, softening point is 240 DEG C.Solubility thermosetting phenolic resin is commercially available oil-soluble thermosetting phenolic resin (hardening time when 180 DEG C is 45s). adopt three screw extruders, added material is calculated in mass ratio, get 100 parts of spinning asphalts, 10 parts of naphthalenes, 3 parts of triethanolamines add the first screw extruder, be heated to 280 DEG C of thawings, the 100# solvent naphtha getting 100 parts of solubility thermosetting phenolic resins and 40 parts adds the second screw extruder, be heated to 120 DEG C, by first, the die orifice that the melting material of the second screw extruder is 2mm from diameter respectively melt extrudes and obtains strip fused raw material, gained fused raw material is added three-screw extruder jointly, be heated to 180 DEG C, the time of staying is 15s.
Centrifugal spinning: spinning material is extruded through three-screw extruder, directly enters centrifugal spinning equipment, spinning temperature 240 DEG C, centrifugal rotational speed 10000rpm, obtains average diameter 8 μm, a drawn fiber of length 250mm.
Thermal current winding-up secondary drawing-off: a described drawn fiber is directly got rid of in the hot blast pass of mist composition of air and steam, in hot blast pass, in mass ratio, air, steam mixed proportion are 100:100, blowing air temperature 150 DEG C, injecting velocity 15m/s, obtain average diameter 1.6 μm, length 230mm bis-drawn fiber, by gained secondary drawn fiber by the continuous guipure of negative-pressure adsorption bottom spinning equipment, obtain primary solidification fiber, roofing density is 0.5kg/m
2.
Solidification: described primary solidification fiber is entered net belt type oxidation furnace by transporting reticulation belt, oxidizing temperature 250 DEG C, air penetrates fibrage with 1m/min speed, oxidation 10h, obtains cured fiber.
Charing: described cured fiber is sent to net belt type continuous carbonization furnace, under nitrogen atmosphere protection, is heated to 900 DEG C, constant temperature 1h, obtains carbon fiber.
Graphitization: described carbon fiber is loaded graphitizing furnace, under argon gas atmosphere protection, is heated to 2400 DEG C, constant temperature 1h, obtains graphitized fibre.
Gained carbon fiber average diameter is 1.2 μm, average length is 220mm, tensile strength is 1.0GPa, tensile modulus is 35GPa, thermal conductivity is 3.8W/mk (radial direction), and oxidation onset temperature is 630 DEG C.
According to a further aspect in the invention, a kind of graphitization carbon fiber reinforce plastic utilizing above-mentioned preparation method to prepare is additionally provided.
As mentioned above, the invention provides a kind of graphitization carbon fiber reinforce plastic and preparation method thereof, present invention optimizes preparation technology, the present invention has following advantage:
1. adopt the spinning asphalt after visbreaking, then coordinate the thermosetting phenolic resin of dissolving, the viscosity of spinning material is significantly reduced, is beneficial to the refinement of fiber;
2. adopt the use of the low-temperature heat of thermosetting resin, the blended and releasing agent of non-thermosettable pitch, significantly reduce the coking of material fiber and the probability of resin solidification;
3. adopt disc centrifuge spinning equipment, avoid spinning blockage problem, be conducive to continuous seepage;
4. gained material fiber is by centrifugal, thermal current drawing-off, and while drawing-off, in material, volatile component (as viscosity reductant, solvent) obtains effectively removing and being unlikely to leave defect fast;
5. the drafting force of pair material fiber is provided by centrifugal pan and air flow blowing, is conducive to the fine of fiber;
6. in preparation process, without the need to using caustic acid, toxic formaldehyde, technical process Environmental Safety.
7. cheap for manufacturing cost.
Should be understood that, above-mentioned detailed description of the invention of the present invention only for exemplary illustration or explain principle of the present invention, and is not construed as limiting the invention.Therefore, any amendment made when without departing from the spirit and scope of the present invention, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.In addition, claims of the present invention be intended to contain fall into claims scope and border or this scope and border equivalents in whole change and modification.
Claims (11)
1. a graphitization carbon fiber reinforce plastic preparation method, is characterized in that, comprises the steps:
Step S1, Multistep feeding mixes: in mass ratio, get the solubility thermosetting phenolic resin solvent of 5-300 part spinning asphalt, 2-30 part aromatic hydrocarbons viscosity reductant, 0.5-10 part high-temperature mold lubricant, 100 parts of solubility thermosetting phenolic resins, 3-120 part, be mixed to get spinning material;
Step S2, centrifugal spinning: described spinning material is put into centrifugal spinning equipment, through heating centrifugal spinning, obtains a drawn fiber;
Step S3, thermal current is jetted: a described drawn fiber is put into thermal current and jets, obtain secondary drawn fiber, thermal current is air, water vapor mixture body, and mixing quality is than being 100:10-150, temperature 120-250 DEG C, injection rate is 10-100m/s, by described secondary drawn fiber by negative-pressure adsorption on guipure, obtain primary solidification fiber, roofing density <1kg/m
2;
Step S4, solidification, charing and graphitization: by described primary solidification fiber successively through overcuring, charing and graphitization processing, obtain graphitization carbon fiber reinforce plastic.
2. preparation method according to claim 1, is characterized in that, described step S1 comprises further:
In mass ratio, get 5-300 part spinning asphalt, 2-30 part aromatic hydrocarbons viscosity reductant, 0.5-10 part high-temperature mold lubricant, add screw extruder, be heated to 160-340 DEG C of melting, and extrude from the die orifice of diameter 1-3mm, obtain the first melting material; In mass ratio, get the solubility thermosetting phenolic resin solvent of 100 parts of solubility thermosetting phenolic resins, 3-120 part, add screw extruder, be heated to 50-150 DEG C and obtain the second melting material;
First, second melting material is extruded from die orifice respectively and obtains first, second strip fused raw material, first, second strip fused raw material described is added screw extruder, be heated to 120-300 DEG C, time of staying <20s, is mixed to get spinning material.
3. preparation method according to claim 1, is characterized in that, in described step S2, described centrifugal spinning equipment is disc centrifuge spinning equipment, and spinning temperature is 180-320 DEG C, and centrifugal pan diameter is more than or equal to 300mm, and centrifugal rotational speed is 7000-15000rpm.
4. preparation method according to claim 1, is characterized in that, in described step S2, the average diameter of a described drawn fiber is 8-15 μm, and length is 205-480mm;
In described step S3, the average diameter of described secondary drawn fiber is 1.8-1.6 μm, and length is 100-230mm.
5. preparation method according to claim 1 and 2, is characterized in that, the quinoline insolubles content QI<40% of described spinning asphalt, ash content <300ppm, softening point are 180-300 DEG C.
6. preparation method according to claim 1 and 2, is characterized in that, described aromatic hydrocarbons viscosity reductant is the mixture of one or more in naphthalene, anthracene, methyl naphthalene.
7. preparation method according to claim 1 and 2, is characterized in that, described high-temperature mold lubricant is the mixture of one or more in methyl-silicone oil, perfluoro polyether oil, triethanolamine, the two hard acid amides of ethylene.
8. preparation method according to claim 1, is characterized in that, described step S4 comprises further:
Step S41, it is 150-350 DEG C that described primary solidification fiber is put into oxidizing temperature, and under air penetrates fibrolaminar environment with 0.1-3m/min speed, oxidation 5-50h, obtains cured fiber;
Step S42, by described cured fiber under inert atmosphere protection, is heated to 600-1400 DEG C, constant temperature 0.25-2h, obtains carbon fiber;
Step S43, puts into graphitizing furnace by described carbon fiber, under inert atmosphere protection, is heated to 1800-2800 DEG C, constant temperature 0.25-2h, obtains graphitization composite fibre.
9. preparation method according to claim 8, is characterized in that, in the step of described solidification, the gas of described inert atmosphere is nitrogen; In the step of described charing, the gas of described inert atmosphere is argon gas.
10. the preparation method according to claim 1 or 8, it is characterized in that, the average diameter of described graphitized carbon composite fibre is 0.5-4 μm, average length is 0.1-120mm, tensile strength is 0.7-1.8GPa, tensile modulus is 30-80GPa, thermal conductivity is 1-5W/mk (radial direction), and oxidation onset temperature is 500-650 DEG C.
11. 1 kinds of graphitization composite fibres that preparation method prepares any one of above-mentioned 1-10.
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| CN107417244A (en) * | 2017-08-22 | 2017-12-01 | 安徽艾米伦特建材科技有限公司 | Insulation material and preparation method thereof |
| CN107502997A (en) * | 2017-08-22 | 2017-12-22 | 安徽艾米伦特建材科技有限公司 | Asphalt base carbon fiber material and preparation method thereof |
| CN107540339A (en) * | 2017-08-22 | 2018-01-05 | 安徽艾米伦特建材科技有限公司 | Antistatic warming plate and preparation method thereof |
| CN107540275A (en) * | 2017-08-22 | 2018-01-05 | 安徽艾米伦特建材科技有限公司 | Insulation material and preparation method thereof |
| CN111621858A (en) * | 2020-05-22 | 2020-09-04 | 清华大学 | Spinning method for preparing micro-nanofiber by using negative pressure and micro-nanofiber |
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| CN107540339A (en) * | 2017-08-22 | 2018-01-05 | 安徽艾米伦特建材科技有限公司 | Antistatic warming plate and preparation method thereof |
| CN107540275A (en) * | 2017-08-22 | 2018-01-05 | 安徽艾米伦特建材科技有限公司 | Insulation material and preparation method thereof |
| CN111621858A (en) * | 2020-05-22 | 2020-09-04 | 清华大学 | Spinning method for preparing micro-nanofiber by using negative pressure and micro-nanofiber |
| CN111676530A (en) * | 2020-05-22 | 2020-09-18 | 清华大学 | Spinning device for preparing micro-nanofibers by utilizing negative pressure |
| CN111676530B (en) * | 2020-05-22 | 2021-08-10 | 清华大学 | Spinning device for preparing micro-nanofibers by utilizing negative pressure |
| CN111621858B (en) * | 2020-05-22 | 2021-08-10 | 清华大学 | Spinning method for preparing micro-nanofiber by using negative pressure and micro-nanofiber |
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