CN105064031A - Method for preparing high-modulus carbon fibers at low temperature - Google Patents
Method for preparing high-modulus carbon fibers at low temperature Download PDFInfo
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- CN105064031A CN105064031A CN201510513788.0A CN201510513788A CN105064031A CN 105064031 A CN105064031 A CN 105064031A CN 201510513788 A CN201510513788 A CN 201510513788A CN 105064031 A CN105064031 A CN 105064031A
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Abstract
The invention discloses a method for preparing high-modulus carbon fibers at low temperature. The method includes the steps that carbon fibers produced from a carbonization furnace are soaked in a water solution of a nitrogen-containing boride or a mixed water solution of boride and nitrogen-containing compounds for 0.50-10 minutes; water on the surfaces of the fibers is removed in air at 105-150 DEG C through drying; the dried fibers are subjected to graphitization treatment at 2000-2500 DEG C under nitrogen protection, and then through electrochemistry anodic oxidation treatment, sizing, drying and other technologies, the high-modulus carbon fibers can be obtained at the low temperature.
Description
Technical field
The present invention relates to a kind of preparation method of carbon fiber, belong to fibrous material field.
Background technology
Carbon fiber is a kind of reinforcing material grown up after the 1950's, it has high specific strength, high ratio modulus, high temperature resistant, corrosion-resistant, conduction and a series of excellent properties such as thermal coefficient of expansion is little, is therefore widely used in the field such as Aero-Space, sports equipment.One of carbon fiber special performance is high-modulus, and material modulus is higher, and rigidity is better, and non-deformability is stronger.High-temperature heat treatment improves the basic skills of modulus during carbon fiber is produced, but rely on intensification to improve modulus to there is a lot of shortcoming.First be the long-term minimizing at high temperature service life of boiler tube of graphitizing furnace, the heat proof material of graphitization annealing device is generally made up of graphite, and the temperature of graphite more than 2000 DEG C starts distillation, is consumed at leisure, therefore need often to change boiler tube, this is very unfavorable to continuous prodution.In addition, the temperature that can reach for graphitization equipment is limited, can not unrestrictedly raised temperature, and temperature is higher, and the energy of consumption is also more, improves the cost of product.For head it off, propose a lot of improvement opportunity, as optimized graphitizing furnace structure, improving graphitizing furnace atmosphere, add CCl4 by original inert atmosphere (N2, Ar), prevent from generating metal carbides, nitride, extend the life-span of graphitization boiler tube.But the most effective or employing catalyzed graphitization method.The catalyst type of catalyzed graphitization is a lot, as metal, metal carbides and metal boride etc.In various catalyst, boron occupies special position, and to be it be uniquely can form the catalyst of solid solution with carbon for boron and the maximum difference of other metallic catalysts, and boron can replace the carbon in graphite lattice, thus graphitization equably.Research shows, the catalytic action that different borides plays in graphitizing process is different.The present invention adopts the method for solution impregnation to introduce containing nitrogen boride at about 1300 DEG C heat treated carbon fiber surfaces, can promote the catalyzed graphitization effect of boron, significantly improve the modulus of carbon fiber, the decline of inhibition strength.
Summary of the invention
The object of the invention is to solve the problems of the prior art, a kind of method of low-temperature growth high modulus carbon fiber is provided, the method can obtain the carbon fiber of higher modulus under lower treatment temperature, drastically increases the service life of graphitizing furnace, reduces production cost.
For achieving the above object, technical scheme of the present invention is as follows:
A method for low-temperature growth high modulus carbon fiber, carries out room temperature immersion from retort carbon fiber out before graphitization processing containing the aqueous solution of nitrogen boride or the mixed aqueous solution of boride and nitrogen-containing compound.
From carbide furnace carbon fiber out room temperature immersion 0.5-10 minute the mixed aqueous solution containing nitrogen boride or boride and nitrogen-containing compound; The moisture of 105-150 DEG C of dry removing carbon fiber surface in air; Dried carbon fiber carries out graphitization processing under nitrogen protection at 2000-2500 DEG C, then through electrochemical anodic oxidation process, starching, drying, obtains high modulus carbon fiber.
The carbon fiber that described carbon fiber is take polyacrylonitrile as raw material, carburizing temperature obtains at 1200-1400 DEG C.
The described aqueous solution containing nitrogen boride is quality is the ammonium pentaborate (NH of 1-10% than concentration
4b
5o
8.4H
2o) aqueous solution.
In the mixed aqueous solution of described boride and nitrogen-containing compound, boride is boric acid, nitrogen-containing compound is ammonium carbonate, ammonium phosphate or diammonium hydrogen phosphate, wherein the quality of nitrogen-containing compound is 4% than concentration, boride quality is 1-30% than concentration, dipping temperature is room temperature to 80 DEG C, and in air, 105-150 DEG C of drying time is 1-4 minute.
Described boride quality is preferably 2-10% than concentration.
The graphitization processing time is 0.5-3 minute, and draw ratio is 1.0-1.2 times.
Described electrochemical anodic oxidation process, starching, drying refer to: with quality than the ammonium bicarbonate soln of concentration 5% for electrolyte, treatment temperature is 50 DEG C, and current density is 2mA/cm
2, then 120 DEG C of dryings 2 minutes, with epoxy resin aqueous emulsion for sizing agent carries out starching, 180 DEG C of dryings 2 minutes, receive silk and obtain high modulus carbon fiber, starching amount controls about 1.2%.
The technique effect that the present invention has is: the use that the present invention proposes is containing after nitrogen boride aqueous impregnation carbon fiber, the carbon fiber of high modulus can be obtained under lower heat treatment temperature, drastically increase the service life of graphitizing furnace, reduce production cost.
Detailed description of the invention
Below by embodiment, the present invention will be further described.
embodiment 1
The 3K that 1300 DEG C of heat treatment obtains, PAN base carbon fibre (intensity 3860MPa, modulus 235GPa) from carbide furnace out after, adopt 10% boric acid (H3B03) and 4% ammonium carbonate ((NH4) 2CO3) mixed aqueous solution in 60 DEG C dipping 5 minutes, then through washing, 120 DEG C of dryings, then graphitizing furnace 2300 DEG C of heat treatments are entered, finally carry out electrochemical anodic oxidation surface treatment, with quality than the ammonium bicarbonate soln of concentration 5% for electrolyte, treatment temperature is 50 DEG C, current density is 2mA/cm2, then 120 DEG C of dryings 2 minutes, with epoxy resin aqueous emulsion for sizing agent carries out starching, 180 DEG C of dryings 2 minutes, receive silk and obtain high modulus carbon fiber.Sizing agent is bisphenol A type epoxy resin aqueous emulsion, and starching amount is 1.2%.Mechanical experimental results is in table 1.
embodiment 2
In embodiment 1, graphite furnace temperature controls at 2500 DEG C, and other condition is identical with embodiment 1.Test result is in table 1.
embodiment 3
In embodiment 1, from carbide furnace carbon fiber out, adopt ammonium pentaborate (NH4B5O8.4H2O) aqueous solution of 4% in 60 DEG C of dippings 5 minutes, other condition is identical with embodiment 1.Test result is in table 1.
embodiment 4
In embodiment 3, graphite furnace temperature controls at 2500 DEG C, and other condition is identical with embodiment 1.Test result is in table 1.
comparative example 1
In embodiment 1, carbon fiber from carbide furnace out after, adopt 10% boric acid (H3BO3) aqueous solution in 60 DEG C dipping 5 minutes, other is identical with embodiment 1.Test result is in table 1.
comparative example 2
In comparative example 1, graphite furnace temperature controls at 2500 DEG C, and other condition is identical with comparative example 1.Test result is in table 1.
comparative example 3
In embodiment 1, carbon fiber from carbide furnace out after, directly enter graphitizing furnace 2300 DEG C of heat treatments, other is identical with embodiment 1.Test result is in table 1.
comparative example 4
In comparative example 3, graphite furnace temperature controls at 2500 DEG C, and other condition is identical with comparative example 3.Test result is in table 1.
table 1 carbon fiber tensile property result
It is emphasized that: be only preferred embodiment of the present invention above, not any pro forma restriction is done to the present invention, every above embodiment is done according to technical spirit of the present invention any simple modification, equivalent variations and modification, all belong in the scope of technical solution of the present invention.
Claims (8)
1. a method for low-temperature growth high modulus carbon fiber, is characterized in that: before graphitization processing, carry out room temperature immersion from retort out carbon fiber containing the aqueous solution of nitrogen boride or the mixed aqueous solution of boride and nitrogen-containing compound.
2. the method for a kind of low-temperature growth high modulus carbon fiber as claimed in claim 1, is characterized in that: from carbide furnace carbon fiber out room temperature immersion 0.5-10 minute the mixed aqueous solution containing nitrogen boride or boride and nitrogen-containing compound; The moisture of 105-150 DEG C of dry removing carbon fiber surface in air; Dried carbon fiber carries out graphitization processing under nitrogen protection at 2000-2500 DEG C, then through electrochemical anodic oxidation process, starching, drying, obtains high modulus carbon fiber.
3. the method for a kind of low-temperature growth high modulus carbon fiber as claimed in claim 2, is characterized in that, the carbon fiber that described carbon fiber is take polyacrylonitrile as raw material, carburizing temperature arrives at 1200-1400 DEG C.
4. the method for a kind of low-temperature growth high modulus carbon fiber as claimed in claim 2, is characterized in that, the described aqueous solution containing nitrogen boride is quality is the ammonium pentaborate (NH of 1-10% than concentration
4b
5o
8.4H
2o) aqueous solution.
5. the method for a kind of low-temperature growth high modulus carbon fiber as claimed in claim 2, it is characterized in that, in the mixed aqueous solution of described boride and nitrogen-containing compound, boride is boric acid, nitrogen-containing compound is ammonium carbonate, ammonium phosphate or diammonium hydrogen phosphate, and wherein the quality of nitrogen-containing compound is 4% than concentration, and boride quality is 1-30% than concentration, dipping temperature is room temperature to 80 DEG C, and in air, 105-150 DEG C of drying time is 1-4 minute.
6. the method for a kind of low-temperature growth high modulus carbon fiber as claimed in claim 5, is characterized in that, described boride quality is 2-10% than concentration.
7. the method for a kind of low-temperature growth high modulus carbon fiber as claimed in claim 2, is characterized in that, the graphitization processing time is 0.5-3 minute, and draw ratio is 1.0-1.2 times.
8. the method for a kind of low-temperature growth high modulus carbon fiber as claimed in claim 2, it is characterized in that, described electrochemical anodic oxidation process, starching, drying refer to: with quality than the ammonium bicarbonate soln of concentration 5% for electrolyte, treatment temperature is 50 DEG C, and current density is 2mA/cm
2, then 120 DEG C of dryings 2 minutes, with epoxy resin aqueous emulsion for sizing agent carries out starching, 180 DEG C of dryings 2 minutes, receive silk and obtain high modulus carbon fiber, starching amount controls about 1.2%.
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Cited By (5)
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| CN109208320A (en) * | 2018-07-12 | 2019-01-15 | 北京化工大学 | A kind of surface treatment method of dry-jet wet-spinning carbon fiber |
| CN110528264A (en) * | 2019-09-11 | 2019-12-03 | 北京化工大学 | A kind of high modulus carbon fiber and preparation method thereof as thermoplastic resin based composite material reinforcement |
| CN113981569A (en) * | 2021-10-27 | 2022-01-28 | 因达孚先进材料(苏州)有限公司 | Method for producing graphite fiber by catalytic graphitization |
| CN114263036A (en) * | 2021-12-31 | 2022-04-01 | 湖南东映碳材料科技有限公司 | Preparation method of carbon fiber |
| CN115726059A (en) * | 2022-11-18 | 2023-03-03 | 深圳市科信通信技术股份有限公司 | Ammonium borate modified carbon-based nanofiber composite material and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109208320A (en) * | 2018-07-12 | 2019-01-15 | 北京化工大学 | A kind of surface treatment method of dry-jet wet-spinning carbon fiber |
| CN110528264A (en) * | 2019-09-11 | 2019-12-03 | 北京化工大学 | A kind of high modulus carbon fiber and preparation method thereof as thermoplastic resin based composite material reinforcement |
| CN113981569A (en) * | 2021-10-27 | 2022-01-28 | 因达孚先进材料(苏州)有限公司 | Method for producing graphite fiber by catalytic graphitization |
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| CN114263036A (en) * | 2021-12-31 | 2022-04-01 | 湖南东映碳材料科技有限公司 | Preparation method of carbon fiber |
| CN115726059A (en) * | 2022-11-18 | 2023-03-03 | 深圳市科信通信技术股份有限公司 | Ammonium borate modified carbon-based nanofiber composite material and preparation method and application thereof |
| CN115726059B (en) * | 2022-11-18 | 2024-05-17 | 深圳市科信通信技术股份有限公司 | Ammonium borate modified carbon-based nanofiber composite material and preparation method and application thereof |
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Application publication date: 20151118 |