CN1103449A - Method and apparatus for electrochemical surface treatment of viscose base carbon cloth - Google Patents
Method and apparatus for electrochemical surface treatment of viscose base carbon cloth Download PDFInfo
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- CN1103449A CN1103449A CN 94101828 CN94101828A CN1103449A CN 1103449 A CN1103449 A CN 1103449A CN 94101828 CN94101828 CN 94101828 CN 94101828 A CN94101828 A CN 94101828A CN 1103449 A CN1103449 A CN 1103449A
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Abstract
The viscose-base carbon cloth as anode is continuously put in electrolyzer that has graphite plate as cathode and contains acids or ammonium salts as electrolyte, so as to electrolyze in it for 2-30 min with current density of 0.2-20 ma/sq.cm. After treatment, the carbon/phenolic compound material has shear strength between layers increased by 20-100%, bend and tension strengthes improved to a certain extent and a unchanged ablation property.
Description
The present invention relates to viscose base carbon cloth surface treatment method and device, particularly relate to surface treatment method that uses electrochemical oxidation process and the device that is used for this method.
Carbon fiber has many premium properties, is a kind of rare high performance material, obtains application more and more widely in spaceship, space shuttle, guided missile and general industry department.When but carbon fiber uses separately, can not bring into play its excellent properties, it could embody its value after will making composite with other materials such as resins.So just requiring has good cementitiousness between fiber and the resin, yet because the surperficial smoother of carbon fiber, specific area is little, the surface lack can and the polar group that works of resin, cause between it and the resin good bonding taking place, showing in composite is exactly that interlaminar shear strength (ILSS) is lower.In order to give full play to the excellent properties of carbon fiber, we handle the surface of carbon fiber with regard to being necessary, improve its surface nature.
The method of surface treatment of carbon fibers is a lot, and wherein electrochemical oxidation method is the electric conductivity that utilizes carbon fiber, and as anode, under certain current condition, fiber is continuously by electrolyte it, and the electrochemical oxidation reactions of dependence anode is finished.Its basic process is: under the effect of electric current, and the close anode of the anion in the electrolyte, and near anode, discharge, producing nascent oxygen, nascent oxygen further forms various oxygen containing polar groups at fiber surface.These groups can and resin between bonding takes place, simultaneously, the introducing of these groups has also improved the specific surface energy of fiber, makes resin and to obtain excellent contact at the fiber surface drawout.In addition, specific area that can also increased fiber after the processing with the contact-making surface between increased fiber and the resin, thereby improves the ILSS of composite.
Domestic and international many researchers [Kozlowski, C. et al, Carbon, 24,357(1986)] by repeatedly studies show that, the character of electrolyte has very significant effects to electrolytic process.They make electrolyte with acids, bases and salts substances respectively, and the result of oxidation can both introduce oxygen containing functional group at fiber surface, but what of functional group content then have tangible relation with electrolytical kind.When making electrolyte with acid, the acidic functionality of handling the back carbon fiber surface is more, when making electrolyte with ammonium salt, handles the back and can also introduce nitrogenous functional group at fiber surface.Current condition also has suitable influence, people such as Fizter (16th Bienn.Conf.Carbon, 1983, extended abstracts and program, p494) research indicates, carry out oxidation when electrode voltage is higher than 1.9V, carbon fiber is easy to degrade, when being lower than 1.9V, increase along with voltage, electric current is strengthened, and the polar functional group of fiber surface can increase, and the ILSS that handles the back composite also is improved; General electrolysis is to carry out at normal temperatures, handles a few minutes to dozens of minutes.When electrolysis just began, along with the prolongation of time, the polar functional group of fiber surface can be along with increase, but continue time expand, the increase trend of the polar functional group of fiber surface slows down, and can cause fibre damage on the contrary, also is very important so rationally control the processing time.
Be used for the report (JP 61,174,470 and JP58,115,123) of suitability for industrialized production though abroad have as surface treatment of carbon fibers, but concrete technology and equipment all belongs to business secret, does not see detailed report with electrochemical oxidation process.
The object of the present invention is to provide a kind ofly with the method for electrochemical oxidation process surface treatment viscose base carbon cloth and the isolated plant of this method, viscose base carbon cloth of handling with this method and apparatus and the cohesive force between the resinous substrates are significantly improved.
The invention provides a kind of viscose base carbon cloth electrochemical surface processing method that is used for composite, carbon cloth enters electrolytic cell continuously by graphite roller, in groove, pass through up and down and leave electrolytic cell after several are immersed in graphite cathode in the electrolyte, electrolyte in the electrolytic cell is acids, as sulfuric acid, nitric acid, phosphoric acid, acetic acid, also can be the ammonium salt class, as ammonium acetate, cellulose acetate hydrogen ammonium, ammonium carbonate etc., the concentration of electrolyte is the 0.1-5.0 mol, carbon cloth the 0.2-20 milliampere/centimetre
2Current density under handled 2-30 minute.
Electrolysis unit of the present invention comprises several graphite cathodes 10 of be arrangeding in parallel in electrolytic cell 9, voltage-stabilized power supply 12, transmission device, graphite roller 5 and brush 6, the electrolytic cell 9, enters the carbon cloth anode of electrolytic cell 9 by graphite roller 5 and plastics fabric guide roll 11, can be under speed governing in electrolytic cell 9 the continuous surface electrochemical treatments.
Carbon cloth all has no adverse effects to its every physical property after electrochemical oxidation is handled, and the warp-wise fracture strength obtains obviously to improve, and this is verified from table 1.
Table 1 surface treatment is to the influence of carbon cloth physical property
| The carbon cloth performance | Be untreated | Handle |
| Thickness (millimeter) surface density (gram/rice 2) phosphorus content (%) alkali and alkaline earth metal content (ppM) warp-wise fracture strength (newton/25 millimeter) broadwise fracture strength (newton/25 millimeter) | 1.01 363 95.97 62 248.8 180.8 | 1.072 372 95.64 82 462.8 188.2 |
The Mechanics Performance Testing of carbon/phenolic composite the results are shown in Table 2.The carbon cloth of handling through electrochemical oxidation of the present invention can improve 20-100% with the interlaminar shear strength of the composite (carbon/phenolic composite) of phenolic resins composition, bending strength, TENSILE STRENGTH, stretch modulus all have improvement in various degree, have elongation at break only and descend, but this is the inevitable outcome that carbon fiber and the raising of resinous substrates cohesive force are brought.
Table 2 surface treatment is to the influence of carbon/phenolic composite mechanical property
* QSES is the professional standard of 703 of first research institutes of the Ministry of Aerospace Industry.
Other useful performance (as ablation property) of carbon/phenolic composite after electrochemical oxidation of the present invention is handled is unaffected.Test condition to the ablation property of carbon/phenolic composite is:
Time: 15 seconds
Chamber pressure: 1.4MPa
Distance: 110mm/105mm
Angle: 30 °
Its result is:
The ablation velocity of untreated carbon/phenolic composite is: 0.183mm/s;
The ablation velocity of carbon/phenolic composite of having handled is: 0.189mm/s,
Experimental result shows that electrochemical oxidation method for treating of the present invention does not influence the ablation property of carbon/phenolic composite.
Carbon cloth after electrochemical oxidation of the present invention is handled can also be formed composite with epoxy resin.
But apparatus of the present invention compare with general electrolysis unit have continued operation, can be according to the processing time governing speed, and features simple structure, advantage such as with low cost.
Accompanying drawing is used to describe main flow process proposed by the invention, untreated carbon cloth 4 enters the electrolytic cell 9 that is fixed on the frame 3 through pressure roller 7, graphite roller 5, brush 6, pressure roller 7 and drive roll 8, in groove, pass through graphite cake electrode group 10 along plastics fabric guide roll group 11, provide constant voltage dc source by electric control box 12, carbon cloth 4 in electrolytic cell through the electrochemical oxidation surface treatment, the carbon cloth of handling 13 leaves electrolytic cell 9 through roller 14, finishes processing procedure.
Embodiment 1: with 1MHAc solution is electrolyte, and current density is 1.8mA/cm
2, electrolysis time is 5min.On the said equipment viscose base carbon cloth being carried out electrochemical oxidation handles.Gained carbon cloth and phenolic resins are made composite (the resin solid content is 60-65, resin: carbon cloth=1.5: the 1(weight ratio)), record interlaminar shear strength by the GB1450.1-83 method and carry 105%, but bending strength, TENSILE STRENGTH etc. have obvious decline.
Embodiment 2: with 0.5MH
2SO
4Solution is electrolyte, and current density is 1.0mA/cm
2, electrolysis time is 3min, and the interlaminar shear strength of treated carbon/phenolic composite improves 71%, and TENSILE STRENGTH, stretch modulus, bending strength have raising in various degree, and elongation at break reduces about 30%.
Embodiment 3: with 0.1MH
3PO
4Solution is electrolyte, and current density is 1.8mA/cm
2, electrolysis time is 5min, the interlaminar shear strength of treated carbon/phenolic composite improves 77%.
Embodiment 4: with 1M(NH
4)
2CO
3Solution is electrolyte, and current density is 1.8mA/cm
2, electrolysis time is 5min, the interlaminar shear strength of treated carbon/phenolic composite improves 38%.
Claims (3)
1, a kind of electrochemical oxidation surface-treated method that is used for viscose base carbon cloth.The invention is characterized in that carbon cloth enters electrolytic cell as anode continuously by graphite roller, in groove, pass through up and down and leave electrolytic cell after several are immersed in negative electrode in the electrolyte, electrolyte in the electrolytic cell can be acids, also can be the ammonium salt class, the concentration of electrolyte is the 0.5-5 mol, carbon cloth the 0.2-20 milliampere/centimetre
2Current density under handled 2-30 minute.
2, according to the method for claim 1, it is characterized in that the acids that electrolyte adopts can be sulfuric acid, nitric acid, phosphoric acid and acetic acid, the ammonium salt class that is adopted can be ammonium acetate, carbonic hydroammonium and ammonium carbonate.
3, a kind of electrolysis unit that is applicable to the method for claim 1 comprises electrolytic cell 9 and voltage-stabilized power supply 12.The invention is characterized in and also comprise transmission device, graphite roller 5 and brush 6, several graphite cathodes 10 that be arranged in parallel in the electrolytic cell 9, enter the carbon cloth anode of electrolytic cell by graphite rod 5 and plastics selvage guide rod 11, can be under speed governing in electrolytic cell 9 continuous surface handle.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 94101828 CN1103449A (en) | 1994-04-09 | 1994-04-09 | Method and apparatus for electrochemical surface treatment of viscose base carbon cloth |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 94101828 CN1103449A (en) | 1994-04-09 | 1994-04-09 | Method and apparatus for electrochemical surface treatment of viscose base carbon cloth |
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| CN1103449A true CN1103449A (en) | 1995-06-07 |
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| CN 94101828 Pending CN1103449A (en) | 1994-04-09 | 1994-04-09 | Method and apparatus for electrochemical surface treatment of viscose base carbon cloth |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101440193B (en) * | 2007-11-23 | 2010-12-22 | 航天材料及工艺研究所 | Carbon / phenolic heat insulating composite material and manufacturing process thereof |
| CN105038110A (en) * | 2015-07-06 | 2015-11-11 | 陕西科技大学 | Electrochemically modified carbon cloth reinforced friction material and preparation method thereof |
| CN105449226A (en) * | 2015-11-18 | 2016-03-30 | 广西师范大学 | Novel three-dimensional electrode material for lithium air battery and preparation method for novel three-dimensional electrode material |
| CN110997264A (en) * | 2017-08-01 | 2020-04-10 | 沙特基础工业全球技术有限公司 | Method and system for producing unidirectional carbon fiber tape and method for surface treating carbon fibers |
-
1994
- 1994-04-09 CN CN 94101828 patent/CN1103449A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101440193B (en) * | 2007-11-23 | 2010-12-22 | 航天材料及工艺研究所 | Carbon / phenolic heat insulating composite material and manufacturing process thereof |
| CN105038110A (en) * | 2015-07-06 | 2015-11-11 | 陕西科技大学 | Electrochemically modified carbon cloth reinforced friction material and preparation method thereof |
| CN105449226A (en) * | 2015-11-18 | 2016-03-30 | 广西师范大学 | Novel three-dimensional electrode material for lithium air battery and preparation method for novel three-dimensional electrode material |
| CN110997264A (en) * | 2017-08-01 | 2020-04-10 | 沙特基础工业全球技术有限公司 | Method and system for producing unidirectional carbon fiber tape and method for surface treating carbon fibers |
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