CN1316555A - Process for preparing high-strength viscose carbon fibres - Google Patents
Process for preparing high-strength viscose carbon fibres Download PDFInfo
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- CN1316555A CN1316555A CN 00113268 CN00113268A CN1316555A CN 1316555 A CN1316555 A CN 1316555A CN 00113268 CN00113268 CN 00113268 CN 00113268 A CN00113268 A CN 00113268A CN 1316555 A CN1316555 A CN 1316555A
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Abstract
A process for preparing high strength uiscose based carbon fibre uses viscose rayon as a raw materials. The viscose rayon fibre is processed by the mixed solution of amine catalyst. At first pre-oxidized under low temperature air, then high temperature carbonized progressively. The produced viscose based carbon fibre containing 95% of carbon content is black and bright with the tensile strength of 1.6-1.8 Gpa, average diameter of 4-7 um, density of 1.55-1.60 g Lcm3 and no inclusion of metal impurities.
Description
The present invention relates to can be applicable to the preparation method of high-strength viscose carbon fibres in the fields such as active carbon fibre peacekeeping active carbon cloth of high-tech ablator, the functional carbon fiber of special electromagnetic, biocompatibility composite, biocompatibility.
In the preparation method of existing viscose carbon fibres, as do not pass through the superhigh temperature graphitizing process, the tensile strength of the carbon fiber of gained is lower, is generally about 1.2GPa, and this has limited its application in general structural composite.
The object of the present invention is to provide a kind of tensile strength of viscose carbon fibres can the raising greatly, can enlarge the preparation method of the high-strength viscose carbon fibres of its Application Areas.
This method may further comprise the steps: 1. pretreatment of raw material (pickling, washing, drying); 2. catalyst solution floods; 3. 100-280 ℃ of Cryogenic air pre-oxidation; 4. warm charing in 300-1000 ℃; 5. at 1300 ℃ of high temperature carbonizations.It is characterized in that the mixing amine that consists of 5-30% of catalyst solution and the aqueous solution of 0.1-2.0% non-ionic surface active agent, dip time is 0.5-4 minute.
Described mixed amine catalyst comprises ammonium chloride, diethylentriamine, ethylenediamine, hexa, pyridine, N, a kind of to several in the compounds such as N-dimethyl-p-phenylenediamine.
Described ionic surfactant pack is drawn together: TX-100, OP, polyethylene glycol, polyvinyl alcohol are a kind of to several.
The air pre-oxidation furnace is divided into 2 to 3 warm areas, and maximum temperature is 280 ℃.Above-mentioned catalyst solution stain and air pre-oxidation are the continuous process of a series connection.The fiber that obtains like this is the soft and loose pre-oxygen silk of dark brown.Above-mentioned pre-oxygen silk enters the charing processing procedure.Warm charing and high temperature carbonization during charing is divided into, middle temperature charing are divided into 3 to 4 warm areas, and its maximum temperature is respectively 1000 ℃; The high temperature carbonization temperature is 1300 ℃.Each step carbonization process all is connected with flowing nitrogen and adopts strict nitrogen sealing gland.
As pre-oxidation mid-term by coating, introduce the preceramic organosilicon polymer body at fiber surface, as the toluene solution of Polycarbosilane, behind pre-oxidation and middle temperature, high temperature carbonization, finally can obtain having the functional composite coating carbon fiber of special electromagnetic.
The present invention can make viscose generate pre-oxygen silk under lower temperature, and it is soft and loose that fiber is remained in high temperature carbonization processing procedure subsequently.Through the viscose carbon fibres softness of this method preparation, shiny black, phosphorus content is about 95%, does not introduce any metal impurities, and tensile strength is 1.6-1.8GPa, and average fibre diameter is 4-7 μ m, and density is 1.55-1.60g/cm
3Every stable performance of fiber, good process repeatability.
Embodiment 1:
With ammonium chloride and ethylenediamine (1: 0.5) as mixed amine; Be mixed with the mixed catalyst aqueous solution with OP and polyethylene glycol (1: 1) as surfactant.The amine total concentration is 20%; The surfactant total concentration is 0.2%.With high-strength viscose is initiation material, through the pickling drying of removing photoresist, enters above-mentioned catalyst solution dipping 0.5 minute in multi beam plying mode, and air pre-oxidation furnace warm area is respectively 100 ℃ and 260 ℃, obtains pre-oxygen silk.Warm charing processing procedure during above-mentioned pre-oxygen silk enters, warm area is respectively 350 ℃, and 600 ℃, 1000 ℃.Carry out high temperature carbonization at 1300 ℃ subsequently.Obtain soft shiny black viscose carbon fibres.The tensile strength of this carbon fiber is 1.6GPa, and average diameter is 5.1 μ m.
Embodiment 2:
With iodate amine and diethylentriamine (1: 0.3) as mixed amine; Be mixed with the mixed catalyst aqueous solution with OP and TX-100 (1: 1) as surfactant.The amine total concentration is 5%; The surfactant total concentration is 1%.With high-strength viscose is initiation material, through the pickling drying of removing photoresist, under the stepper motor traction, enters above-mentioned catalyst solution dipping 2 minutes in multi beam plying mode then.Obtain pre-oxygen silk through air pre-oxidation furnace (warm area is respectively 100 ℃ and 170 ℃).Above-mentioned pre-oxygen silk enters the charing processing procedure.Be respectively 300 ℃ at warm area, 450 ℃, 600 ℃, 1000 ℃ carry out in warm charing; Carry out high temperature carbonization at 1300 ℃.Obtain soft shiny black viscose carbon fibres.The tensile strength of this carbon fiber is 1.8GPa, and average diameter is 6.1 μ m.
Embodiment 3:
With 28%N, the N-dimethyl-p-phenylenediamine aqueous solution and OP and TX-100 (1: 1) surfactant is mixed with the mixed catalyst aqueous solution.The surfactant total concentration is 1.8%.With high-strength viscose is initiation material, through the pickling drying of removing photoresist, enters above-mentioned catalyst solution dipping 4 minutes in multi beam plying mode continuously.Enter warm area and be respectively 100 ℃, 160 ℃, 230 ℃ air pre-oxidation furnace carries out pre-oxidation, obtains pre-oxygen silk.300 ℃ respectively of warm areas, 450 ℃, 1000 ℃ middle temperature retort carries out charing, carries out high temperature carbonization under 1300 ℃.Obtain soft shiny black viscose carbon fibres.The tensile strength of this carbon fiber is 1.6GPa, and average diameter is 4.5 μ m.
Embodiment 4:
Be mixed with the mixed catalyst aqueous solution with the aqueous solution of 10% pyridine and 2% hexa and polyvinyl alcohol and TX-100 (1: 1) surfactant.The surfactant total concentration is 0.8%.With high-strength viscose is initiation material, through the pickling drying of removing photoresist, enters above-mentioned catalyst solution dipping 4 minutes in multi beam plying mode continuously, after 150 ℃ of air pre-oxidation, enter the toluene solution groove of Polycarbosilane continuously, after the drying, every fiber surface evenly is coated with the last layer Polycarbosilane.Continue to enter 200 ℃ and 260 ℃ of pre-oxidation subsequently, obtain the pre-oxygen silk of coating.Warm charing in being undertaken by tubular type retort (300 ℃, 450 ℃, 1000 ℃ respectively of warm areas) continuously is at 1300 ℃ of high temperature carbonizations.Obtain the viscose carbon fibres of soft shiny black coat of silicon carbide.This carbon fiber contains 5% carborundum and small amounts silicon, penetrates into fibrous inside with being distributed in fiber surface and gradient shape.The tensile strength of fiber is 1.5GPa, and average diameter is 6.5 μ m, and resistivity is never through 10 of Polycarbosilane processing
-4It is 10 that Ω M increases
-2Ω M, and demonstrate good microwave (X-band) absorbent properties.
Claims (4)
1, the preparation method of high-strength viscose carbon fibres may further comprise the steps: 1. pretreatment of raw material (pickling, washing, drying); 2. catalyst solution floods; 3. 100-280 ℃ of Cryogenic air pre-oxidation; 4. warm charing in 300-1000 ℃; 5. at 1300 ℃ of high temperature carbonizations, it is characterized in that the mixing amine that consists of 5-30% of catalyst solution and the aqueous solution of 0.1-2.0% non-ionic surface active agent, dip time is 0.5-4 minute.
2, the preparation method of high-strength viscose carbon fibres according to claim 1, it is characterized in that described mixed amine catalyst comprises ammonium chloride, diethylentriamine, ethylenediamine, hexa, pyridine, N, a kind of in the compounds such as N-dimethyl-p-phenylenediamine to several.
3, the preparation method of high-strength viscose carbon fibres according to claim 1 is characterized in that described ionic surfactant pack draws together: TX-100, OP, polyethylene glycol, polyvinyl alcohol are a kind of to several.
4, the preparation method of high-strength viscose carbon fibres according to claim 1 is characterized in that passing through coating mid-term in pre-oxidation, introduces the preceramic organosilicon polymer body at fiber surface.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00113268 CN1116454C (en) | 2000-02-02 | 2000-02-02 | Process for preparing high-strength viscose carbon fibres |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00113268 CN1116454C (en) | 2000-02-02 | 2000-02-02 | Process for preparing high-strength viscose carbon fibres |
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| CN1316555A true CN1316555A (en) | 2001-10-10 |
| CN1116454C CN1116454C (en) | 2003-07-30 |
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| CN 00113268 Expired - Fee Related CN1116454C (en) | 2000-02-02 | 2000-02-02 | Process for preparing high-strength viscose carbon fibres |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1314725C (en) * | 2005-09-05 | 2007-05-09 | 天津大学 | Novel light-wave absorbing carbon fiber composite material preparation method |
| CN101864635A (en) * | 2010-05-25 | 2010-10-20 | 大连理工大学 | Method for manufacturing high-strength viscose-based active carbon fiber fabrics |
| CN101560701B (en) * | 2009-05-13 | 2010-12-08 | 北京化工大学 | Method for preparing high-strength carbon fibers |
| CN101550616B (en) * | 2009-05-08 | 2011-05-11 | 北京化工大学 | Method of preparing high strength carbon fibre |
| CN105544022A (en) * | 2016-01-29 | 2016-05-04 | 合肥天玾环保科技有限公司 | Production device of mucilage glue based active carbon fibers and energy-saving and environment-protection method |
| CN115182154A (en) * | 2022-07-22 | 2022-10-14 | 江苏米格新材料有限公司 | Ultra-pure viscose-based graphite felt and preparation method and application thereof |
-
2000
- 2000-02-02 CN CN 00113268 patent/CN1116454C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1314725C (en) * | 2005-09-05 | 2007-05-09 | 天津大学 | Novel light-wave absorbing carbon fiber composite material preparation method |
| CN101550616B (en) * | 2009-05-08 | 2011-05-11 | 北京化工大学 | Method of preparing high strength carbon fibre |
| CN101560701B (en) * | 2009-05-13 | 2010-12-08 | 北京化工大学 | Method for preparing high-strength carbon fibers |
| CN101864635A (en) * | 2010-05-25 | 2010-10-20 | 大连理工大学 | Method for manufacturing high-strength viscose-based active carbon fiber fabrics |
| CN105544022A (en) * | 2016-01-29 | 2016-05-04 | 合肥天玾环保科技有限公司 | Production device of mucilage glue based active carbon fibers and energy-saving and environment-protection method |
| CN115182154A (en) * | 2022-07-22 | 2022-10-14 | 江苏米格新材料有限公司 | Ultra-pure viscose-based graphite felt and preparation method and application thereof |
| CN115182154B (en) * | 2022-07-22 | 2024-01-26 | 江苏米格新材料股份有限公司 | Ultra-high-purity viscose-based graphite felt and preparation method and application thereof |
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| Publication number | Publication date |
|---|---|
| CN1116454C (en) | 2003-07-30 |
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