CN1995531A - Carbon fiber surface silica dioxide coating preparation method - Google Patents
Carbon fiber surface silica dioxide coating preparation method Download PDFInfo
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- CN1995531A CN1995531A CN 200610147644 CN200610147644A CN1995531A CN 1995531 A CN1995531 A CN 1995531A CN 200610147644 CN200610147644 CN 200610147644 CN 200610147644 A CN200610147644 A CN 200610147644A CN 1995531 A CN1995531 A CN 1995531A
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Abstract
The invention relates to a method for preparing silicon dioxide coating on the surface of carbon fiber, belonging to the material technological area. In the invention alcohols is adopted as the solvent. Ethyl orthosilicate generates hydrolysis reaction under the acidic condition to form silicon dioxide precursor solution. The silicon precursor solution dips the pre-treating carbon fiber. It is volatilized by increasing the temperature slowly and then is sintered to generate polycondensation. Silicon dioxide coating is formed on the single-silk surface of carbon fiber and the thickness of coating is less than 1 mum. The coating is smooth and not easy to break off. The carbon fiber maintains the softness and stitchability of original carbon fiber on the one hand. At the same time the oxidative resistance is improved and the infiltrating of compound material with the base in preparing is improved.
Description
Technical field
The present invention relates to the preparation method of the carbon fiber surface coating in a kind of material technology field, specifically is a kind of preparation method of carbon fiber surface silica dioxide coating.
Background technology
Carbon fiber is a kind of reinforcing material of composite commonly used, and it has high specific strength, high ratio modulus, low-density, easily braiding processing and advantages such as heat, electrical property preferably, obtains application widely in Metal Substrate, polymer matrix composite.But the carbon fiber antioxygenic property is relatively poor, promptly occurs significantly weightless in the air more than 400 ℃ and the intensity reduction.And the wettability of carbon fiber and some matrix is bad, is difficult to form the composite of densification, function admirable.Therefore having hindered carbon fiber needs the application in lightweight, high-strength, high mold materials field in Aero-Space etc.Forming fine and close protective coating at carbon fiber surface can address the above problem effectively.The available technology adopting coating production has chemical vapour deposition technique, physical vaporous deposition, electrochemical method and sol-gel infiltration sintering method.Wherein to be equipped with coating simple for sol-gel infiltration sintering legal system, can be applicable to large-scale production, and unique advantages is arranged.
Find through literature search prior art, wide " high temperature oxidation stability of radio frequency method coat carbon fiber " on " fibrous composite " (2005 03 phase 28-31 pages or leaves), delivered that wait of Dong Xing, propose in this article to adopt radio frequency method to prepare the carbon fiber surface ORC, concrete grammar is: carry out chemical vapour deposition (CVD) by radio frequency heating carbon fiber under 700-800 ℃, this method easily causes damage to carbon fiber surface, and control preparation process technological requirement height, the equipment complexity should not be carried out large-scale production.
Summary of the invention
At the deficiency of above technology, the invention provides a kind of preparation method of carbon fiber surface silica dioxide coating.The carbon fiber diameter that the present invention adopts is 5-10 μ m, and the coating layer thickness of acquisition is less than 1 μ m, and controllable thickness, smooth, the difficult drop-off of coating, and preparation technology is simple, satisfies the application requirements of preparation carbon fibre reinforced composite.
The present invention is achieved by the following technical solutions, and the present invention adopts alcohols to make solvent, and silester issues unboiled water at acid condition (pH=1-3) and separates reaction, forms the silica precursor solution; The silica precursor solution infiltration that use obtains slowly heats up then and makes solvent evaporates through pretreated carbon fiber, after polycondensation reaction takes place sintering, makes the carbon fiber monofilament surface form silica dioxide coating.
Described alcohols can adopt a kind of in ethanol, isopropyl alcohol, the n-butanol.
The quality that described silester adds is less than 50% of silica precursor solution gross mass, contains polyvinyl alcohol less than 1% (mass percent) simultaneously in the silica precursor solution, less than the glycerine of 2% (mass percent).Make silica precursor solution pH value be 1-3 by adding hydrochloric acid.
Described infiltration, the time is 10-60 minute, can adopt ultrasonic concussion method to promote infiltration in the infiltration process, reduces the coating short circuit phenomenon between carbon fiber.
Described pre-treatment of carbon fiber comprises that organic solvent removes that glue, high temperature sintering remove photoresist, in the surface oxidation etching one or more.By preliminary treatment, change the functional group of carbon fiber surface, improve the surface-activity of carbon fiber, coating is combined closely with carbon fiber.
Described intensification is warming up to 150-200 ℃, and temperature-rise period carries out under argon shield.
Described sintering, temperature are 450-500 ℃.
Among the present invention, the carbon fiber of process silica precursor solution infiltration is after solvent evaporates, can after being cooled to room temperature, carbon fiber reuse the infiltration of silica precursor solution, and then slowly intensification makes solvent evaporates, this process can repeat repeatedly, rete cracking when reducing primary coating than thick coating and the phenomenon that comes off.
The carbon fiber diameter that the present invention adopts is 6-8 μ m, and the silica dioxide coating thickness for preparing is less than 1 μ m, smooth, the difficult drop-off of coating.
The carbon fiber that the present invention obtains with silica dioxide coating, its oxidate temperature has improved more than 100 ℃ than uncoated carbon fiber, keep compliance that no coat carbon fiber had and stitchability, solved interface wettability and consistency problem between carbon fiber and some matrices of composite material simultaneously.Method at the carbon fiber surface coating silicon dioxide of the present invention, simple and easy to do, can carry out large-scale industrial production.The carbon fiber that adopts this method to produce with silica dioxide coating, its coating layer thickness is less than 1 μ m, and coating is smooth smooth.Use this carbon fiber or its braided fabric can with metal, pottery, the compound acquisition composite of polymer.
The specific embodiment
Below embodiments of the invention are elaborated: present embodiment is being to implement under the prerequisite with the technical solution of the present invention, provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Example 1: get ethyl orthosilicate 208g, water 36g, isopropyl alcohol 244g, glycerine 10g adds hydrochloric acid and makes pH value of solution=3, stirs after 2 hours, and adding 36g mass fraction is 5% PVA (polyvinyl alcohol) aqueous solution, continues to stir 1 hour.Stir and finish back use filter paper filtering, obtain the silica precursor solution.Carbon fiber is produced for the carbon element factory, Jilin, diameter 6-8 μ m, and every bundle carbon fiber has 1000 monofilament.
Carbon fiber bundle is after acetone immersion 2 minutes, rinsed with deionized water and drying, and with above-mentioned silica precursor solution infiltration 10 minutes, infiltration process adopted the ultrasonic concussion of 40kHz.Cellulose bundle took out the back drying at room temperature 10 minutes, be warming up to 200 ℃ with the speed of 4 ℃ of per minutes after constant temperature 30 minutes, be warming up to 500 ℃ with the speed of 4 ℃ of per minutes again after constant temperature 60 minutes, cool off naturally the back, whole process is carried out under argon shield.Resulting carbon fiber with silica dioxide coating, monofilament surface has smooth lubricious, and its thickness is about 0.4 μ m.The coat carbon fiber oxidate temperature that is obtained is 690 ℃.
Example 2: carbon fiber is with example 1.
Get ethyl orthosilicate 208g, water 27g, ethanol 460g, glycerine 15g adds hydrochloric acid and makes pH value of solution=2, stirs after 2 hours, and adding 27g mass fraction is 5% PVA (polyvinyl alcohol) aqueous solution, continues to stir 1 hour.Stir and finish back use filter paper filtering, obtain the silica precursor solution.
Carbon fiber bundle is after acetone immersion 2 minutes, rinsed with deionized water and drying, with above-mentioned silica precursor solution infiltration 60 minutes.Cellulose bundle took out the back drying at room temperature 10 minutes, be warming up to 180 ℃ with the speed of 4 ℃ of per minutes after constant temperature 30 minutes, be warming up to 500 ℃ with the speed of 4 ℃ of per minutes again after constant temperature 60 minutes, cool off naturally the back, whole process is carried out under argon shield.Resulting carbon fiber with silica dioxide coating, monofilament surface has smooth lubricious, and its thickness is about 0.3 μ m.The coat carbon fiber oxidate temperature that is obtained is 650 ℃.
Example 3: the silica precursor solution is with example 2.Carbon fiber is with example 1.
Carbon fiber bundle through high temperature sintering remove photoresist, rinsed with deionized water and dry, after the nitric acid dousing of 10% (volumetric concentration) carried out the surface oxidation etching in 20 minutes, with above-mentioned silica precursor solution infiltration 30 minutes, infiltration process adopted the ultrasonic concussion of 40kHz.Cellulose bundle took out the back drying at room temperature 10 minutes, be warming up to 150 ℃ with the speed of 4 ℃ of per minutes after constant temperature 60 minutes, be warming up to 450 ℃ with the speed of 4 ℃ of per minutes again after constant temperature 60 minutes, cool off naturally the back, whole process is carried out under argon shield.Resulting carbon fiber with silica dioxide coating, monofilament surface has smooth lubricious, and its thickness is about 0.3 μ m.The coat carbon fiber oxidate temperature that is obtained is 660 ℃.
Example 4: get ethyl orthosilicate 208g, water 18g, n-butanol 518g, glycerine 15g adds hydrochloric acid and makes pH value of solution=1, stirs after 2 hours, and adding 36g mass fraction is 5% PVA (polyvinyl alcohol) aqueous solution, continues to stir 1 hour.Stir and finish back use filter paper filtering, obtain the silica precursor solution.Carbon fiber is with example 1.
Carbon fiber bundle is after acetone immersion 2 minutes, rinsed with deionized water and drying, with above-mentioned silica precursor solution infiltration 60 minutes.Cellulose bundle took out the back drying at room temperature 10 minutes; constant temperature is 30 minutes after being warming up to 200 ℃ with the speed of 4 ℃ of per minutes; constant temperature is 60 minutes after being warming up to 480 ℃ with the speed of 4 ℃ of per minutes again; after take out after naturally cooling to 20 ℃; again with repeating above-mentioned temperature-rise period after the infiltration once of silica precursor solution; cool off after 2 hours to 500 ℃ of constant temperature, whole process is carried out under argon shield.Resulting carbon fiber with silica dioxide coating, monofilament surface has smooth lubricious, and its thickness is about 0.5 μ m.The coat carbon fiber oxidate temperature that is obtained is 710 ℃.
Claims (10)
1, a kind of preparation method of carbon fiber surface silica dioxide coating is characterized in that, adopts alcohols to make solvent, and silester issues unboiled water at acid condition and separates reaction, forms the silica precursor solution; The silica precursor solution infiltration that use obtains slowly heats up then and makes solvent evaporates through pretreated carbon fiber, after polycondensation reaction takes place sintering, makes the carbon fiber monofilament surface form silica dioxide coating.
2, the preparation method of carbon fiber surface silica dioxide coating according to claim 1 is characterized in that, described alcohols, a kind of in ethanol, isopropyl alcohol, the n-butanol.
3, the preparation method of carbon fiber surface silica dioxide coating according to claim 1, it is characterized in that, the quality that described silester adds is less than 50% of silica precursor solution gross mass, simultaneously the silica precursor solution contain polyvinyl alcohol less than 1% mass percent, less than the glycerine of 2% mass percent.
4, the preparation method of carbon fiber surface silica dioxide coating according to claim 1 is characterized in that, described acid condition makes silica precursor solution pH value be 1-3 by adding hydrochloric acid.
5, the preparation method of carbon fiber surface silica dioxide coating according to claim 1 is characterized in that, described infiltration, and the time is 5-60 minute, adopts ultrasonic concussion method to promote infiltration in the infiltration process.
6, the preparation method of carbon fiber surface silica dioxide coating according to claim 1 is characterized in that, described pre-treatment of carbon fiber comprises that organic solvent removes that glue, high temperature sintering remove photoresist, in the surface oxidation etching one or more.
7, the preparation method of carbon fiber surface silica dioxide coating according to claim 1 is characterized in that, described intensification is warming up to 150-200 ℃, and temperature-rise period carries out under argon shield.
8, the preparation method of carbon fiber surface silica dioxide coating according to claim 1 is characterized in that, described sintering, and temperature is 450-500 ℃.
9, the preparation method of carbon fiber surface silica dioxide coating according to claim 1, it is characterized in that, the carbon fiber of process silica precursor solution infiltration is after solvent evaporates, after being cooled to room temperature, carbon fiber reuses the infiltration of silica precursor solution, and then slowly intensification makes solvent evaporates, repeats this process repeatedly.
10, the preparation method of carbon fiber surface silica dioxide coating according to claim 1 is characterized in that, described carbon fiber diameter is 6-8 μ m, and the silica dioxide coating thickness for preparing is less than 1 μ m.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2006101476449A CN100516348C (en) | 2006-12-21 | 2006-12-21 | Carbon fiber surface silica dioxide coating preparation method |
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| CNB2006101476449A CN100516348C (en) | 2006-12-21 | 2006-12-21 | Carbon fiber surface silica dioxide coating preparation method |
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| CN1995531A true CN1995531A (en) | 2007-07-11 |
| CN100516348C CN100516348C (en) | 2009-07-22 |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102587123A (en) * | 2011-12-31 | 2012-07-18 | 潘雪峰 | Production method for nanometer SiO2 additive waterproof antistatic cloth |
| CN103266470A (en) * | 2013-05-17 | 2013-08-28 | 东南大学 | Carbon fiber antioxidation coating and preparation method thereof |
| CN103334298A (en) * | 2013-06-08 | 2013-10-02 | 蓝星环境工程有限公司 | Active carbon fiber composite material and preparation method thereof |
| CN103924443A (en) * | 2014-03-21 | 2014-07-16 | 南京航空航天大学 | Preparation method of carbon fiber surface antioxidation coating |
| CN106519301A (en) * | 2016-11-26 | 2017-03-22 | 四川理工学院 | Preparation of SiO2-helical carbon nanofiber double-phase filler and application of double-phase filler in rubber reinforcement |
| CN108130722A (en) * | 2016-11-30 | 2018-06-08 | 比亚迪股份有限公司 | A kind of metallized product and the method for metallization |
| CN108854571A (en) * | 2018-07-11 | 2018-11-23 | 常州大学 | A method of utilizing ultrasonic atomizatio sedimentation preparative separation film |
| CN111484262A (en) * | 2020-05-26 | 2020-08-04 | 深圳大学 | Carbon fiber composite material and preparation method and application thereof |
| CN111742096A (en) * | 2018-02-21 | 2020-10-02 | 日本制纸株式会社 | Fiber composite and method for producing same |
| CN111906142A (en) * | 2020-06-24 | 2020-11-10 | 浙江博星工贸有限公司 | Process for controlling mechanical property of cold-rolled stainless steel strip |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4840762A (en) * | 1984-01-24 | 1989-06-20 | Teijin Ltd. | Process for preparation of high-performance grade carbon fibers |
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2006
- 2006-12-21 CN CNB2006101476449A patent/CN100516348C/en not_active Expired - Fee Related
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102587123A (en) * | 2011-12-31 | 2012-07-18 | 潘雪峰 | Production method for nanometer SiO2 additive waterproof antistatic cloth |
| CN103266470A (en) * | 2013-05-17 | 2013-08-28 | 东南大学 | Carbon fiber antioxidation coating and preparation method thereof |
| CN103266470B (en) * | 2013-05-17 | 2015-03-18 | 东南大学 | Carbon fiber antioxidation coating and preparation method thereof |
| CN103334298A (en) * | 2013-06-08 | 2013-10-02 | 蓝星环境工程有限公司 | Active carbon fiber composite material and preparation method thereof |
| CN103924443A (en) * | 2014-03-21 | 2014-07-16 | 南京航空航天大学 | Preparation method of carbon fiber surface antioxidation coating |
| CN106519301B (en) * | 2016-11-26 | 2018-06-26 | 四川理工学院 | A kind of preparation of SiO2/ spiral nanometer carbon fibers dual phase filler and its application in reinforcing rubber |
| CN106519301A (en) * | 2016-11-26 | 2017-03-22 | 四川理工学院 | Preparation of SiO2-helical carbon nanofiber double-phase filler and application of double-phase filler in rubber reinforcement |
| CN108130722A (en) * | 2016-11-30 | 2018-06-08 | 比亚迪股份有限公司 | A kind of metallized product and the method for metallization |
| CN108130722B (en) * | 2016-11-30 | 2020-03-31 | 比亚迪股份有限公司 | Metallized product and metallization method |
| CN111742096A (en) * | 2018-02-21 | 2020-10-02 | 日本制纸株式会社 | Fiber composite and method for producing same |
| CN108854571A (en) * | 2018-07-11 | 2018-11-23 | 常州大学 | A method of utilizing ultrasonic atomizatio sedimentation preparative separation film |
| CN111484262A (en) * | 2020-05-26 | 2020-08-04 | 深圳大学 | Carbon fiber composite material and preparation method and application thereof |
| CN111484262B (en) * | 2020-05-26 | 2022-01-11 | 深圳大学 | Carbon fiber composite material and preparation method and application thereof |
| CN111906142A (en) * | 2020-06-24 | 2020-11-10 | 浙江博星工贸有限公司 | Process for controlling mechanical property of cold-rolled stainless steel strip |
| CN111906142B (en) * | 2020-06-24 | 2022-08-16 | 浙江博星工贸有限公司 | Process for controlling mechanical property of cold-rolled stainless steel strip |
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