CN101660185A - Method of strong effect carbon fiber anodic oxidation surface treatment - Google Patents
Method of strong effect carbon fiber anodic oxidation surface treatment Download PDFInfo
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- CN101660185A CN101660185A CN200910093280A CN200910093280A CN101660185A CN 101660185 A CN101660185 A CN 101660185A CN 200910093280 A CN200910093280 A CN 200910093280A CN 200910093280 A CN200910093280 A CN 200910093280A CN 101660185 A CN101660185 A CN 101660185A
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Abstract
The invention belongs to the field of electrochemistry and fiber materials. The method speeds up oxidation process by conducting anodic oxidation treatment on carbon fiber in an applied magnetic field, and the strength of the applied magnetic field is 5-50mT; electrolyte is one or a mixture of a plurality of ammonium salt, alkali or acid, the concentration of electrolyte ranges from 2-12 percent and the temperature of the electrolyte is minus 60 DEG C of room temperature; the applied current density is 0.1-8A/cm<2>, and the carbon fiber stays in the electrolyte for 25-120s. The method has theadvantages of speeding up the surface oxidation treatment of carbon fiber, reducing the use amount of the electrolyte and cost, relieving environment pollution and the like.
Description
Technical field
The present invention relates to a kind of method that is used for surface treatment of carbon fibers, belong to electrochemistry and filamentary material field.
Technical background
Carbon fiber (CF) is a kind of strongthener that grows up after the 1950's, it has a series of excellent properties such as high specific strength, high ratio modulus, high temperature resistant, corrosion-resistant, conduction and thermal expansivity be little, therefore is widely used in fields such as aerospace, sports equipment.Carbon fiber need use with the compound form with matrix material of resin matrix usually, and the mechanical property of excellences such as the high specific strength of carbon fiber, high ratio modulus will be fully played, and needs between carbon fiber and resin matrix bonding good.Carbon fiber is through after high temperature cabonization or the greying thermal treatment, smooth surface, and active site is few, and chemical reactivity is poor, need introduce active oxygen-containing functional group at fiber surface by surface oxidation treatment technology, improves the bonding strength of itself and resin matrix.The industrial widely used surface treatment method of carbon fiber is an electrochemistry anodic oxidation, and its oxidizing reaction relaxes, and is easy to control, obvious processing effect.But along with the development of CF preoxidation, carbonization technology, the carbonization speed of CF is more and more faster, from original per hour tens meters developed into more than 400 meter, accordingly new requirement has been proposed also for process of surface treatment and equipment.For adapting to the quickening of preoxidation, charing rate, usually adopt following three kinds of measures in the anode oxidation surface processing process: 1) increase the length of electrolyzer, guarantee the residence time of fiber, the shortcoming of this method is that occupation area of equipment is big, need more ionogen, increased cost; 2) improve current density, increase the oxide etch degree, remedy the deficiency of the residence time, the problem that this method exists is the increase along with electric current, and voltage also increases, and causes safety problem; 3) temperature of raising electrolytic solution increases the oxide etch degree, remedies the deficiency of the residence time, because the electrolytic solution that uses is ammonium salt solution mostly at present, temperature raises, and can cause that ammonium salt decomposes, the concentration of electrolyte instability causes the deterioration of Working environment simultaneously on the one hand.
Summary of the invention
The object of the present invention is to provide a kind of simple, consuming time weak point of technology, effective that has, the SURFACE TREATMENT OF CARBON FIBER method of advantage such as can be complementary with the production line of flash carbonization.
A kind of strong effect carbon fiber anodic oxidation surface-treated method provided by the present invention may further comprise the steps: carbon fiber is carried out anodic oxidation treatment in externally-applied magnetic field, the intensity of externally-applied magnetic field is 5-50mT; Ionogen is one or more the mixture in ammonium salt, alkali or the acid, and the concentration range of electrolytic solution is 2～12%, and the temperature of electrolytic solution is a room temperature-60 ℃; The current density that applies is 0.1-8mA/cm
2, the time that carbon fiber stops in electrolytic solution is 25～120 seconds.
Wherein, the negative electrode that uses in the described anodic oxidation reactions is graphite, stainless steel or nickel plate.Described ammonium salt is bicarbonate of ammonia, volatile salt, ammonium phosphate, ammonium sulfate, Secondary ammonium phosphate or primary ammonium phosphate.Described alkali is potassium hydroxide, sodium hydroxide or yellow soda ash.Described acid is sulfuric acid, nitric acid, acetate or phosphoric acid.
The present invention can apply magnetic field, the accelerating anode oxidation by the mode of placing magnet in electrolyzer.The modes of emplacement of magnet can place the bottom (as shown in Figure 1) of electrolyzer, also can be placed on the both sides (as shown in Figure 2) of electrolyzer; And placing the bottom of electrolyzer, the magneticstrength that is produced is more even, helps the uniform and stable of anodic oxidation effect.Described magnet can be selected neodymium iron boron, SmCo, aluminium nickel cobalt or ferrite for use.
Anodized surface treatment process provided by the present invention is applicable to that promptly polyacrylonitrile (PAN) base carbon fibre is applicable to asphaltic base and viscose-based carbon fiber again.
Compared with prior art, the present invention has following beneficial effect:
The present invention makes carbon fiber carry out anodic oxidation treatment in magnetic field, can accelerate carbon fiber surface oxide treatment speed, shorten the length of electrolyzer, reduce the floor space of device, reduce electrolytical usage quantity simultaneously, reduced cost, alleviated the environmental pollution in operation workshop.
Description of drawings
Fig. 1, carbon fiber electrolysis groove synoptic diagram (bottom of electrolytic tank placement magnet): 1. carbon fiber, 2. electrolyzer, 3. magnet, 4. negative electrode.
Fig. 2, carbon fiber electrolysis groove synoptic diagram (magnet is placed in the electrolyzer both sides), figure A is a front view, figure B is a side-view: 1. carbon fiber, 2. electrolyzer, 3. magnet, 4. negative electrode.
The invention will be further described below in conjunction with the drawings and specific embodiments.
Embodiment
All adopt the mode of placing the ferromagnetic iron of neodymium in electrolyzer, to apply magnetic field among the following embodiment, adopt electrolyzer shown in Figure 1 among the embodiment 1; Adopt electrolyzer shown in Figure 2 among the embodiment 2.The interlaminar shear strength of the unidirectional composite laminate by carbon fiber and Resins, epoxy is estimated the SURFACE TREATMENT OF CARBON FIBER effect.
Under room temperature and externally-applied magnetic field condition, the 3K, the PAN base carbon fibre that obtain with 1600 ℃ of thermal treatments are anode, are negative electrode with the stainless steel, are that 5% ammonium dibasic phosphate aqueous solution is an electrolytic solution with mass concentration, carry out anodized surface and handle, current density is 0.5mA/cm
2, magneticstrength is 10mT, the time that carbon fiber stops in electrolytic solution is 40 seconds.Then with carbon fiber with deionized water wash and in 120 ℃ of dryings, silk is received in starching (sizing agent is the bisphenol A type epoxy resin water miscible liquid, and the starching amount is 1.2%).
The gained carbon fiber is carried out synnema tensile strength and tensile modulus test, tensile strength: 3752Mpa, tensile modulus: 231Gpa.Gained carbon fiber and bisphenol A type epoxy resin 6101 are carried out the test of interlaminar shear strength after compound, the volume ratio of fiber and resin is 6: 4, and solidifying agent is a triethylene tetramine, 80 ℃ of solidification values, 2 hours set times, interlaminar shear strength: 84.8Mpa.
Under room temperature and externally-applied magnetic field condition, the 3K, the PAN base carbon fibre that obtain with 2500 ℃ of thermal treatments are anode, are negative electrode with the stainless steel, are that 5% ammonium dibasic phosphate aqueous solution is an electrolytic solution with mass concentration, carry out anodized surface and handle, current density is 1.0mA/cm
2, magneticstrength is 15mT, the time that carbon fiber stops in electrolytic solution is 40 seconds.Then with carbon fiber with deionized water wash and in 120 ℃ of dryings, silk is received in starching (sizing agent is the bisphenol A type epoxy resin water miscible liquid, and the starching amount is 1.2%).
The gained carbon fiber is carried out synnema tensile strength and tensile modulus test, tensile strength: 3286Mpa, tensile modulus: 407Gpa.Gained carbon fiber and novolac epoxy 648 are carried out the test of interlaminar shear strength after compound, the volume ratio of fiber and resin is 6: 4, and solidifying agent is the boron trifluoride mono aminoethane, 80 ℃ of solidification values, 2 hours set times, interlaminar shear strength: 71.3Mpa.
Comparative example 1
Except removing magnetic field, other condition is all identical with embodiment 1.Test result is as follows: tensile strength: 3705Mpa, tensile modulus: 236Gpa, interlaminar shear strength: 73.8Mpa.
Comparative example 2
Except removing magnetic field, other condition is all identical with embodiment 2.Test result is as follows: tensile strength: 3317Mpa, tensile modulus: 406Gpa, interlaminar shear strength: 66.2Mpa.
Claims (5)
1, a kind of strong effect carbon fiber anodic oxidation surface-treated method is characterized in that, carbon fiber is carried out anodic oxidation treatment in externally-applied magnetic field, and the intensity of externally-applied magnetic field is 5-50mT; Ionogen is one or more the mixture in ammonium salt, alkali or the acid, and the concentration range of electrolytic solution is 2～12%, and the temperature of electrolytic solution is a room temperature-60 ℃; The current density that applies is 0.1-8mA/cm
2, the time that carbon fiber stops in electrolytic solution is 25～120 seconds.
2, require 1 described method according to power, it is characterized in that, a kind of as in graphite, stainless steel or the nickel plate of the negative electrode that uses in the described anodic oxidation reactions.
3, require 1 described method according to power, it is characterized in that, described ammonium salt is bicarbonate of ammonia, volatile salt, ammonium phosphate, ammonium sulfate, Secondary ammonium phosphate or primary ammonium phosphate.
4, require 1 described method according to power, it is characterized in that, described alkali is potassium hydroxide, sodium hydroxide or yellow soda ash.
5, require 1 described method according to power, it is characterized in that, described acid is sulfuric acid, nitric acid, acetate or phosphoric acid.
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102002847A (en) * | 2010-11-15 | 2011-04-06 | 四川城际轨道交通材料有限责任公司 | Electrochemical CF (Carbon Fiber) surface modification method |
| CN102505449A (en) * | 2011-11-05 | 2012-06-20 | 中国科学院山西煤炭化学研究所 | Electrochemical modification treatment method of carbon fiber surface |
| CN102660866A (en) * | 2012-05-09 | 2012-09-12 | 北京化工大学 | Method for modifying electrochemical surfaces of carbon fibers |
| WO2014127501A1 (en) * | 2013-02-19 | 2014-08-28 | 中国海洋大学 | Oxygen and nitrogen co-doped polyacrylonitrile-based carbon fiber and preparation method thereof |
| CN104047070A (en) * | 2014-06-27 | 2014-09-17 | 陕西天策新材料科技有限公司 | Preparation method of high-modulus graphite fibers |
| CN104178790A (en) * | 2014-08-19 | 2014-12-03 | 中复神鹰碳纤维有限责任公司 | Carbon fiber surface treatment method and treatment device |
| CN104652131A (en) * | 2015-01-23 | 2015-05-27 | 北京京阳环保工程有限公司 | Bioactive carbon fiber, composite ecological film packing component comprising bioactive carbon fiber and preparation method of bioactive carbon fiber |
| CN105063994A (en) * | 2015-08-20 | 2015-11-18 | 北京化工大学 | Surface treatment method for carbon fibers |
| CN106436274A (en) * | 2016-09-14 | 2017-02-22 | 郑州峰泰纳米材料有限公司 | Method for treating carbon fiber anodic oxidation surfaces |
| CN109020591A (en) * | 2018-08-22 | 2018-12-18 | 至玥腾风科技投资集团有限公司 | A kind of preparation method and tesla's turbine disk of tesla's turbine disk |
| CN109161947A (en) * | 2018-08-30 | 2019-01-08 | 北京化工大学 | High modulus carbon fiber surface treatment method and device and its application |
| CN110010875A (en) * | 2019-04-11 | 2019-07-12 | 陕西科技大学 | A kind of preparation method of flake cobalt sulfide composite and flexible carbon cloth electrode material |
| 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 |
| CN114855304A (en) * | 2022-05-07 | 2022-08-05 | 南通普朗克石墨烯科技有限公司 | Preparation method of high-thermal-conductivity carbon fiber |
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2009
- 2009-09-25 CN CN2009100932804A patent/CN101660185B/en not_active Expired - Fee Related
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102002847A (en) * | 2010-11-15 | 2011-04-06 | 四川城际轨道交通材料有限责任公司 | Electrochemical CF (Carbon Fiber) surface modification method |
| CN102505449A (en) * | 2011-11-05 | 2012-06-20 | 中国科学院山西煤炭化学研究所 | Electrochemical modification treatment method of carbon fiber surface |
| CN102660866A (en) * | 2012-05-09 | 2012-09-12 | 北京化工大学 | Method for modifying electrochemical surfaces of carbon fibers |
| US9683314B2 (en) | 2013-02-19 | 2017-06-20 | Ocean University Of China | Oxygen and nitrogen co-doped polyacrylonitrile-based carbon fiber and preparation method thereof |
| WO2014127501A1 (en) * | 2013-02-19 | 2014-08-28 | 中国海洋大学 | Oxygen and nitrogen co-doped polyacrylonitrile-based carbon fiber and preparation method thereof |
| CN104838051A (en) * | 2013-02-19 | 2015-08-12 | 中国海洋大学 | Oxygen and nitrogen co-doped polyacrylonitrile-based carbon fiber and preparation method thereof |
| CN104047070A (en) * | 2014-06-27 | 2014-09-17 | 陕西天策新材料科技有限公司 | Preparation method of high-modulus graphite fibers |
| CN104047070B (en) * | 2014-06-27 | 2016-05-18 | 陕西天策新材料科技有限公司 | A kind of preparation method of high modulus graphite fiber |
| CN104178790A (en) * | 2014-08-19 | 2014-12-03 | 中复神鹰碳纤维有限责任公司 | Carbon fiber surface treatment method and treatment device |
| CN104652131A (en) * | 2015-01-23 | 2015-05-27 | 北京京阳环保工程有限公司 | Bioactive carbon fiber, composite ecological film packing component comprising bioactive carbon fiber and preparation method of bioactive carbon fiber |
| CN105063994A (en) * | 2015-08-20 | 2015-11-18 | 北京化工大学 | Surface treatment method for carbon fibers |
| CN106436274A (en) * | 2016-09-14 | 2017-02-22 | 郑州峰泰纳米材料有限公司 | Method for treating carbon fiber anodic oxidation surfaces |
| CN109020591A (en) * | 2018-08-22 | 2018-12-18 | 至玥腾风科技投资集团有限公司 | A kind of preparation method and tesla's turbine disk of tesla's turbine disk |
| CN109161947A (en) * | 2018-08-30 | 2019-01-08 | 北京化工大学 | High modulus carbon fiber surface treatment method and device and its application |
| CN110010875A (en) * | 2019-04-11 | 2019-07-12 | 陕西科技大学 | A kind of preparation method of flake cobalt sulfide composite and flexible carbon cloth electrode material |
| 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 |
| CN114855304A (en) * | 2022-05-07 | 2022-08-05 | 南通普朗克石墨烯科技有限公司 | Preparation method of high-thermal-conductivity carbon fiber |
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| CN101660185B (en) | 2011-01-05 |
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