CN103160826B - Preparation method of continuous carbon fiber surface pyrolytic carbon/nickel composite coating - Google Patents
Preparation method of continuous carbon fiber surface pyrolytic carbon/nickel composite coating Download PDFInfo
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- CN103160826B CN103160826B CN201310093388.XA CN201310093388A CN103160826B CN 103160826 B CN103160826 B CN 103160826B CN 201310093388 A CN201310093388 A CN 201310093388A CN 103160826 B CN103160826 B CN 103160826B
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Abstract
The invention discloses a preparation method of a continuous carbon fiber surface pyrolytic carbon/nickel composite coating. According to the invention, a pyrolytic carbon coating is prepared on the surface of a carbon fiber in weftless carbon fiber cloth through a chemical vapor deposition method, and the thickness of the pyrolytic carbon coating is 0.03-0.1 micrometer. A nickel coating is prepared on the surface of the carbon fiber with the pyrolytic carbon coating through a chemical plating method. By controlling the reaction time of the carbon fiber in a chemical nickel-plating solution, the thickness of the nickel coating is controlled to 0.02-0.1 micrometer, so that the carbon fiber containing a pyrolytic carbon/nickel composite coating which is 0.05-0.2 micrometers in thickness is acquired. According to the preparation method, the carbon fiber can be well prevented from being oxidized and is effectively prevented from being damaged and destroyed; and the occurrence of too many interfacial reactions between the carbon fiber and aluminum alloy can be reduced because the microstructure of pyrolytic carbon tends to be graphitized so that the interface combinability between the carbon fiber and the aluminum alloy can be adjusted.
Description
Technical field
The present invention relates to a kind of field of material technology, specifically a kind of continuous carbon fibre surface RESEARCH OF PYROCARBON/nickel composite coat preparation method.
Background technology
Carbon fiber is with its low density, be bordering on the thermal expansivity of zero, high Young's modulus and excellent mechanical property make its research being subject to more and more people and attention, have the excellent properties such as high specific tenacity, specific rigidity, low thermal expansivity with it as the carbon fiber reinforced aluminum matrix composite that reinforcement is prepared.But because carbon fiber surface is smooth, surface energy is low, reactive behavior is low, when preparing aluminum matrix composite as reinforcement and the wettability of matrix poor, also be easy to during comparatively high temps, with matrix, bad surface reaction occurs, easily cause when surface reaction is too much between aluminium alloy and carbon fiber and formed strong interface cohesion, brittle rupture is produced when making the matrix material prepared be subject to tension load effect, cause the mechanical property of matrix material lower, restrict its research and extension application.Carry out coating modified process at carbon fiber surface and effectively can improve wettability between carbon fiber and matrix alloy, improve the infiltration effect of matrix material, and stop the generation of bad surface reaction, interface binding power between conservative control carbon fiber and aluminium alloy, thus make the mechanical property of carbon fiber reinforced aluminum matrix composite reach perfect condition.The coated material of existing carbon fiber surface mainly contains RESEARCH OF PYROCARBON (PyC), silicon-dioxide (SiO
2), silicon carbide (SiC), nickel (Ni) coating etc., usually adopt the preparation of the method such as chemical vapor deposition (CVD), sol-gel method, electroless plating.
China Patent Publication No. CN101705456B disclose a kind of in Electroless Nickel Plating on Carbon Fiber coating to prepare the method for carbon fiber reinforced magnesium-base composite material, the method can wettability between enhanced carbon fiber and matrix, improves the infiltration effect of matrix material and improves its mechanical property.
Find through literature search, and document " Zeng Qingbing. sol-gel method TiO
2coat carbon fiber reinforced aluminum matrix composites [J]. Acta Metallurgica Sinica, 1997,33(9): 1003-1009 " adopt sol-gel method to prepare TiO at carbon fiber surface
2coating, and then prepare aluminum matrix composite, TiO
2thermal expansivity between carbon fiber and aluminium alloy, use it as transition layer, can reduce due to the interfacial thermal stress that brings of thermal expansivity difference between carbon fiber, aluminium alloy, the consistency of both enhancements, simultaneously TiO
2surface energy higher, and the wetting angle of aluminium liquid is better than between carbon, aluminium, and this just can improve wettability between carbon fiber and aluminium alloy and interfacial bonding property, and controls the generation of the hole defect of matrix material to a certain extent.
But, based on own characteristic, above-mentioned prepared coating has himself range of application, though nickel coating can improve the wettability of carbon fiber and matrix alloy, but easily generate bad brittlement phase in the composite as during coating separately, literature survey also shows, it is to the surface reaction limited efficiency controlled between carbon fiber and aluminium alloy, though sol-gel method can prepare the TiO that also can improve wettability being suitable for doing transition layer
2coating, but under normal circumstances, whole sol-gel process required time is more, cycle is longer, and efficiency is lower, and there is a large amount of micropore in gel, will to overflow again in drying process much gas and organism, and produce contraction, also can have a negative impact to coating structure, affect the successful preparation of desirable Carbon Fibre Reinforced Metal Matrix Composites.
Summary of the invention
Longer for overcoming the cycle existed in prior art, efficiency is lower, and in gel, there is a large amount of micropore, in drying process, evolving gas and organism have a negative impact to coating structure, affect the deficiency of the preparation of Carbon Fibre Reinforced Metal Matrix Composites, the present invention proposes a kind of continuous carbon fibre surface RESEARCH OF PYROCARBON/nickel composite coat preparation method.
Detailed process of the present invention is:
Step 1, at carbon fiber surface deposition pyrocarbon coating.Adopt conventional chemical vapor deposition pyrocarbon coating.Coating process parameter is: N
2intake is 0.1 ~ 0.5m
3/ h, CH
4intake is 16-24L/h, and depositing temperature is 1000 ~ 1200 DEG C, and depositing time is 1 ~ 3 hour, is cooled to after room temperature until chemical vapor deposition stove, takes out carbon fiber, obtains the carbon fiber that surface preparation has pyrocarbon coating.
Step 2, chemical nickel plating on surface pre-treatment.Chemical nickel plating on surface pre-treatment is carried out to the carbon fiber depositing pyrocarbon coating, specifically:
The first step, has the carbon fiber of pyrocarbon coating to carry out roughening treatment to the surface preparation obtained.Carbon fiber is put into H
2sO
4: HNO
3roughening treatment 1 ~ 2 hour in the mixed acid solution of=3:1; Described H
2sO
4with HNO
3ratio be volume ratio.
Second step, carries out neutralizing treatment to the carbon fiber after alligatoring.Carbon fiber after alligatoring is put into NaOH solution immersion 10 ~ 20min that mass ratio is 10 ~ 20%, and constantly stir, to remove the nitration mixture of carbon fiber surface with glass stick; With distilled water cleaning carbon fiber to neutral.
3rd step, carries out sensitized treatment to the carbon fiber after neutralization.By SnCl
2solution distilled water diluting is 10 ~ 20g/L to concentration, is mixed with sensitizing solution, then the carbon fiber through neutralizing treatment is at room temperature put into this solution immersion 20 ~ 30min.
4th step, carries out activation treatment to through sensitized treatment carbon fiber, is dissolved in the distilled water of 100ml, obtains silver nitrate solution by 2 ~ 5g Silver Nitrate.By described silver nitrate solution distilled water diluting to 1L, be mixed with activated solution.At room temperature will put into the activated solution activation 10 ~ 30min obtained through sensitized treatment carbon fiber, obtain the carbon fiber through activation treatment.
5th step, carries out reduction treatment, by SnCl to the carbon fiber after activation
2solution distilled water diluting is 10 ~ 20g/L to concentration, obtains sensitizing solution; Carbon fiber through activation treatment is immersed in the solution of sodium hypophosphite, at room temperature mechanical stirring 1 ~ 5min, obtain surface through the pretreated carbon fiber of chemical nickel plating, take out for subsequent use.
Step 3, preparative chemistry nickel plating solution
Described chemical nickel-plating solution is mixed by solution A and B solution and after stirring, forms through overregulating pH value.
Wherein solution A 30 ~ 50g/L nickel sulfate solution, 18 ~ 30g/L sodium acetate soln and 30 ~ 40g/L ammoniumsulphate soln is mixed successively respectively and stirs formulated.B solution 36 ~ 50g/L ortho phosphorous acid sodium solution and 10 ~ 20g/L citric acid three sodium solution is mixed and stirs formulated.Solution A is mixed with B solution; Regulate pH value to 4.5 ~ 6.5 of the mixing solutions prepared by solution A and B solution, obtain chemical nickel-plating solution.
During preparation mixed solution A, first nickel sulfate solution to be mixed with sodium acetate soln and after stirring, then add ammoniumsulphate soln and mix and stir.
Step 4, Electroless Nickel Plating on Carbon Fiber coating.
The carbon fiber chemical nickel-plating solution obtained being put bath temperature is in 85 ~ 95 DEG C of thermostatic bath water tanks, surface is placed in plating solution through the pretreated carbon fiber of chemical nickel plating, carry out chemical plating through 5 ~ 18min and dry, obtaining preparing the carbon fiber having RESEARCH OF PYROCARBON/nickel composite coat.
The present invention adopts chemical Vapor deposition process (CVD) preparing pyrocarbon coating without the carbon fiber surface in latitude carbon cloth, pyrocarbon coating thickness is between 0.03-0.1 μm, electroless plating method is adopted to have the carbon fiber surface of pyrocarbon coating to prepare nickel coating in preparation again, by controlling the reaction times of carbon fiber in chemical nickel-plating solution (plating solution), make nickel coating thickness between 0.02-0.1 μm, thus the carbon fiber obtained containing RESEARCH OF PYROCARBON/nickel composite coat, the thickness of compound coating is between 0.05-0.2 μm.
The present invention solves to be used alone nickel coating and easily to generate bad brittlement phase in the composite, and interface cohesion is difficult to effective control, sol-gel method is used to prepare coating cycle long, the problem of micropore is easily produced in coating, and realize carbon fiber and matrix wettability improves, and make have transition layer to exist between the two, to avoid the generation of the matrix material hole defect brought because thermal expansivity does not mate, effectively improve matrix material and prepare effect.The pyrocarbon coating specifically first prepared by chemical Vapor deposition process (CVD) at carbon fiber surface can protect carbon fiber not to be damaged destruction, and can control the interfacial bonding property between carbon fiber and matrix alloy.Can thickness be prepared by electroless plating method again on this basis controlled, uniform nickel coating, the wettability between carbon fiber and aluminium alloy can be improved, greatly improve the homogenizing infiltration effect of carbon fiber reinforced aluminum matrix composite.And the thermal expansivity of nickel coating is between carbon fiber and aluminium alloy, both interfacial thermal stress can be reduced, the defects such as the hole brought are not mated due to thermal expansivity when controlling composite material solidification, given play to the comprehensive advantage of pyrocarbon coating and nickel coating, the successful preparation for desirable carbon fiber reinforced aluminum matrix composite is carried out prerequisite and is prepared.
The present invention is first at the pyrocarbon coating that carbon fiber surface CVD is prepared; this coating is a kind of good oxidation resistant coating; easily be oxidized when carbon fiber is more than 300 DEG C; the existence of this coating has been had to prevent fiber oxidized preferably; coating is coated on the surface of carbon fiber simultaneously; play the effect of transmitted load, can effectively protect carbon fiber not to be damaged destruction.Simultaneously, between carbon fiber and aluminium alloy easily there is more serious surface reaction in itself, the existence of pyrocarbon coating is had between carbon fiber and aluminium alloy, because the microtexture of RESEARCH OF PYROCARBON is more tending towards greying, graphitized fibre general not easily with aluminium alloy generation surface reaction, this just can reduce the generation of the too much bad surface reaction between carbon fiber and aluminium alloy to a certain extent, regulates interfacial bonding property between carbon fiber and aluminium alloy.
Uniform nickel coating is prepared by electroless plating method, overcome the deficiency that the common coating production cycles such as conventional sol gel are grown and efficiency is low, there is micropore etc. coating centre, usual whole sol-gel process required time particularly digestion time needs several days even a few weeks, and the nickel process in the present invention generally just can be able to complete in one day even several hours.Simultaneously, because the wettability between nickel and aluminium alloy is obviously better than the wettability between carbon fiber and aluminium alloy, the nickel coating of such carbon fiber surface just can improve the wetting effect between carbon fiber and aluminium alloy, under equal processing condition, the homogenizing infiltration effect of carbon fiber reinforced aluminum matrix composite can be improved.In addition, the thermal expansivity of nickel coating is between carbon fiber and aluminium alloy, the shock absorption of stress can be played between well, thus both interfacial thermal stress can be reduced, do not mate the appearance of the defects such as the hole brought during control composite material solidification due to thermal expansivity, be suitable for the preparation of desirable carbon fiber reinforced aluminum matrix composite.
Give the EDS analytical results that preparation has the carbon fiber surface coating of compound coating in accompanying drawing 2, as can be seen from elemental distribution, prepare the compound coating containing RESEARCH OF PYROCARBON/nickel at carbon fiber surface.Through experimental examination and checking, adopt pressure infiltration method, use the carbon fiber reinforced aluminum matrix composite prepared by compound coating in the present invention, infiltrate respond well, do not have obvious hole defect, the tensile strength of matrix material improves more than 60% compared with aluminum matrix alloy.
Accompanying drawing explanation
Fig. 1 is schema of the present invention.
The EDS analytical results of the RESEARCH OF PYROCARBON/nickel composite coat of Fig. 2 prepared by the present invention, shows to have prepared containing RESEARCH OF PYROCARBON/nickel composite coat at carbon fiber surface.
Embodiment
Embodiment 1
The present embodiment is a kind of continuous carbon fibre surface RESEARCH OF PYROCARBON/nickel composite coat preparation method, and in embodiment, carbon fiber used is the T700 carbon fiber of 12K.
The concrete steps of the present embodiment are:
Step 1, at carbon fiber surface deposition pyrocarbon coating.The T700 carbon fiber of 12K is placed in chemical vapor deposition stove, adopts conventional chemical vapor deposition pyrocarbon coating.Coating process parameter is: N
2intake is 0.1 ~ 0.5m
3/ h, CH
4intake is 16-24L/h, and depositing temperature is 1000 ~ 1200 DEG C, and depositing time is 1 ~ 3 hour, is cooled to after room temperature until chemical vapor deposition stove, takes out carbon fiber, obtains the carbon fiber that surface preparation has pyrocarbon coating.In the present embodiment, N
2intake is 0.1m
3/ h, CH
4intake is 18L/h, and depositing temperature is 1000 DEG C, and depositing time is 1 hour.
Step 2, chemical nickel plating on surface pre-treatment is carried out specifically to the carbon fiber depositing pyrocarbon coating:
The first step, has the carbon fiber of pyrocarbon coating to carry out roughening treatment to the surface preparation obtained.Carbon fiber is put into H
2sO
4: HNO
3roughening treatment 1 ~ 2 hour in the mixed acid solution of=3:1; Described H
2sO
4with HNO
3ratio be volume ratio.In the present embodiment, the time of roughening treatment is 1 hour.
Second step, carries out neutralizing treatment to the carbon fiber after alligatoring.Carbon fiber after alligatoring is put into NaOH solution immersion 10 ~ 20min that mass ratio is 10 ~ 20%, and constantly stir with glass stick, to remove the nitration mixture of carbon fiber surface, be then washed till neutrality with distilled water.In the present embodiment, the concentration of NaOH solution is 15%, and carbon fiber soak time in NaOH solution is 10min.
3rd step, carries out sensitized treatment to the carbon fiber after neutralization.The SnCl of coming will be bought
2solution distilled water diluting is 10 ~ 20g/L to concentration, in dilution with glass stick constantly mechanical stirring make it even, thus be mixed with sensitizing solution, then the carbon fiber through neutralizing treatment at room temperature put into this solution and soak 20 ~ 30min.In the present embodiment, SnCl
2concentration after solution distilled water diluting is 10g/L, and the time of sensitized treatment is 20min.
4th step, carries out activation treatment to through sensitized treatment carbon fiber, is dissolved in the distilled water of 100ml, obtains the silver nitrate solution of high density by load weighted Silver Nitrate 2 ~ 5g.By the silver nitrate solution distilled water diluting of high density that configures to 1L, be mixed with activated solution.At room temperature will put into the activated solution activation 10 ~ 30min obtained through sensitized treatment carbon fiber, obtain the carbon fiber through activation treatment.In the present embodiment, the consumption of Silver Nitrate is 3g, and the time activated the carbon fiber through sensitized treatment is 15min.
5th step, carries out reduction treatment to the carbon fiber after activation, will buy the SnCl of coming
2solution distilled water diluting to concentration is 10 ~ 20g/L, constantly stirring with glass stick in dilution makes it even, thus preparation sensitizing solution, carbon fiber through activation treatment is immersed in the solution of sodium hypophosphite, at room temperature mechanical stirring 1 ~ 5min, obtain surface through the pretreated carbon fiber of chemical nickel plating, take out for subsequent use.In the present embodiment, SnCl
2the concentration of solution is 10g/L, and the churned mechanically time is 5min.
Step 3, chemical nickel-plating solution mixes also machinery by solution A and B solution to stir, and form through overregulating pH value.
Wherein solution A mixes formulated respectively successively by 30 ~ 50g/L nickel sulfate solution, 18 ~ 30g/L sodium acetate soln and 30 ~ 40g/L ammoniumsulphate soln.B solution mixes also machinery by 36 ~ 50g/L ortho phosphorous acid sodium solution and 10 ~ 20g/L citric acid three sodium solution to stir formulated.Solution A and B solution are mixed.It is 4.5 ~ 6.5 that hydrochloric acid regulates by the pH value of the mixing solutions of solution A and B solution, obtains chemical nickel-plating solution.When preparing solution A again, first nickel sulfate solution to be mixed with sodium acetate soln and after stirring, then add ammoniumsulphate soln and mix and stir.
In the present embodiment, described single nickel salt is 30g/L, and sodium-acetate is 18g/L, and ammonium sulfate is 30g/L; Described inferior sodium phosphate is 36g/L, and trisodium citrate is 15g/L; The pH value of carbon fiber chemical nickel-plating solution is 4.8.
Step 4, Electroless Nickel Plating on Carbon Fiber coating.
The carbon fiber chemical nickel-plating solution obtained is placed on thermostatic bath water tank, and make the temperature of described thermostatic bath water tank remain on 85 ~ 95 DEG C, surface is placed in plating solution through the pretreated carbon fiber of chemical nickel plating, chemical plating is carried out through 5 ~ 18min, after plating completes, take out from solution and dry, obtaining preparing the carbon fiber having RESEARCH OF PYROCARBON/nickel composite coat.In the present embodiment, the temperature of thermostatic bath water tank is 85 DEG C; The time of chemistry plating is 15min.
Embodiment 2
The present embodiment is a kind of continuous carbon fibre surface RESEARCH OF PYROCARBON/nickel composite coat preparation method, and in embodiment, carbon fiber used is the T300 carbon fiber of 3K.
The concrete steps of the present embodiment are:
Step 1, at carbon fiber surface deposition pyrocarbon coating.The T300 carbon fiber of 3K is placed in chemical vapor deposition stove, adopts conventional chemical vapor deposition pyrocarbon coating.Coating process parameter is: N
2intake is 0.1 ~ 0.5m
3/ h, CH
4intake is 16-24L/h, and depositing temperature is 1000 ~ 1200 DEG C, and depositing time is 1 ~ 3 hour, is cooled to after room temperature until chemical vapor deposition stove, takes out carbon fiber, obtains the carbon fiber that surface preparation has pyrocarbon coating.In the present embodiment, N
2intake is 0.3m
3/ h, CH
4intake is 20L/h, and depositing temperature is 1050 DEG C, and depositing time is 1.5 hours.
Step 2, carries out chemical nickel plating on surface pre-treatment specifically to the carbon fiber depositing pyrocarbon coating,
The first step, has the carbon fiber of pyrocarbon coating to carry out roughening treatment to the surface preparation obtained.Carbon fiber is put into H
2sO
4: HNO
3roughening treatment 1 ~ 2 hour in the mixed acid solution of=3:1; Described H
2sO
4with HNO
3ratio be volume ratio.In the present embodiment, the time of roughening treatment is 1.5 hours.
Second step, carries out neutralizing treatment to the carbon fiber after alligatoring.Carbon fiber after alligatoring being placed on mass ratio is soak 10 ~ 20min in the NaOH solution of 10 ~ 20%, and constantly stirs with glass stick, to remove the nitration mixture of carbon fiber surface, is then washed till neutrality with distilled water.In the present embodiment, the concentration of NaOH solution is 15%, and carbon fiber soak time in NaOH solution is 15min.
3rd step, carries out sensitized treatment to the carbon fiber after neutralization.The SnCl of coming will be bought
2solution distilled water diluting is 10 ~ 20g/L to concentration, in dilution with glass stick constantly mechanical stirring make it even, thus be mixed with sensitizing solution, then the carbon fiber through neutralizing treatment at room temperature put into this solution 20 ~ 30min.In the present embodiment, SnCl
2concentration after solution distilled water diluting is 15g/L, and the time of sensitized treatment is 25min.
4th step, carries out activation treatment to through sensitized treatment carbon fiber, is dissolved in the distilled water of 100ml, obtains the silver nitrate solution of high density by load weighted Silver Nitrate 2 ~ 5g.By the silver nitrate solution distilled water diluting of high density that configures to 1L, be mixed with activated solution.At room temperature will put into the activated solution activation 10 ~ 30min obtained through sensitized treatment carbon fiber, obtain the carbon fiber through activation treatment.In the present embodiment, the consumption of Silver Nitrate is 4g, and the time activated the carbon fiber through sensitized treatment is 20min.
5th step, carries out reduction treatment to the carbon fiber after activation, will buy the SnCl of coming
2solution distilled water diluting to concentration is 10 ~ 20g/L, constantly stirring with glass stick in dilution makes it even, thus preparation sensitizing solution, carbon fiber through activation treatment is immersed in the solution of sodium hypophosphite, at room temperature mechanical stirring 1 ~ 5min, obtain surface through the pretreated carbon fiber of chemical nickel plating, take out for subsequent use.In the present embodiment, SnCl
2the concentration of solution is 15g/L, and the churned mechanically time is 5min.
Step 3, chemical nickel-plating solution mixes also machinery by solution A and B solution to stir, and form through overregulating pH value.
Wherein solution A mixes formulated respectively successively by 30 ~ 50g/L nickel sulfate solution, 18 ~ 30g/L sodium acetate soln and 30 ~ 40g/L ammoniumsulphate soln.B solution mixes also machinery by 36 ~ 50g/L ortho phosphorous acid sodium solution and 10 ~ 20g/L citric acid three sodium solution to stir formulated.Solution A and B solution are mixed.It is 4.5 ~ 6.5 that hydrochloric acid regulates by the pH value of the mixing solutions of solution A and B solution, obtains chemical nickel-plating solution.When preparing solution A again, first nickel sulfate solution to be mixed with sodium acetate soln and after stirring, then add ammoniumsulphate soln and mix and stir.
In the present embodiment, described single nickel salt is 40g/L, and sodium-acetate is 25g/L, and ammonium sulfate is 35g/L; Described inferior sodium phosphate is 40g/L, and trisodium citrate is 15g/L; The pH value of carbon fiber chemical nickel-plating solution is 5.
Step 4, Electroless Nickel Plating on Carbon Fiber coating.
The carbon fiber chemical nickel-plating solution obtained is placed on thermostatic bath water tank, and make the temperature of described thermostatic bath water tank remain on 85 ~ 95 DEG C, surface is placed in plating solution through the pretreated carbon fiber of chemical nickel plating, chemical plating is carried out through 5 ~ 18min, after plating completes, take out from solution and dry, obtaining preparing the carbon fiber having RESEARCH OF PYROCARBON/nickel composite coat.In the present embodiment, the temperature of thermostatic bath water tank is 85 DEG C; The time of chemistry plating is 10min.
Embodiment 3
The present embodiment is a kind of continuous carbon fibre surface RESEARCH OF PYROCARBON/nickel composite coat preparation method, and in embodiment, carbon fiber used is the T700 carbon fiber of 6K.
The concrete steps of the present embodiment are:
Step 1, at carbon fiber surface deposition pyrocarbon coating.The T700 carbon fiber of 6K is placed in chemical vapor deposition stove, adopts conventional chemical vapor deposition pyrocarbon coating.Coating process parameter is: N
2intake is 0.1 ~ 0.5m
3/ h, CH
4intake is 16-24L/h, and depositing temperature is 1000 ~ 1200 DEG C, and depositing time is 1 ~ 3 hour, is cooled to after room temperature until chemical vapor deposition stove, takes out carbon fiber, obtains the carbon fiber that surface preparation has pyrocarbon coating.In the present embodiment, N
2intake is 0.5m
3/ h, CH
4intake is 24L/h, and depositing temperature is 1100 DEG C, and depositing time is 2 hours.
Step 2, chemical nickel plating on surface pre-treatment is carried out specifically to the carbon fiber depositing pyrocarbon coating:
The first step, has the carbon fiber of pyrocarbon coating to carry out roughening treatment to the surface preparation obtained.Carbon fiber is put into H
2sO
4: HNO
3roughening treatment 1 ~ 2 hour in the mixed acid solution of=3:1; Described H
2sO
4with HNO
3ratio be volume ratio.In the present embodiment, the time of roughening treatment is 2 hours.
Second step, carries out neutralizing treatment to the carbon fiber after alligatoring.Carbon fiber after alligatoring being placed on mass ratio is soak 10 ~ 20min in the NaOH solution of 10 ~ 20%, and constantly stirs with glass stick, to remove the nitration mixture of carbon fiber surface, is then washed till neutrality with distilled water.In the present embodiment, the concentration of NaOH solution is 20%, and carbon fiber soak time in NaOH solution is 20min.
3rd step, carries out sensitized treatment to the carbon fiber after neutralization.The SnCl of coming will be bought
2solution distilled water diluting is 10 ~ 20g/L to concentration, in dilution with glass stick constantly mechanical stirring make it even, thus be mixed with sensitizing solution, then the carbon fiber through neutralizing treatment at room temperature put into this solution 20 ~ 30min.In the present embodiment, SnCl
2concentration after solution distilled water diluting is 20g/L, and the time of sensitized treatment is 30min.
4th step, carries out activation treatment to through sensitized treatment carbon fiber, is dissolved in the distilled water of 100ml, obtains the silver nitrate solution of high density by load weighted Silver Nitrate 2 ~ 5g.By the silver nitrate solution distilled water diluting of high density that configures to 1L, be mixed with activated solution.At room temperature will put into the activated solution activation 10 ~ 30min obtained through sensitized treatment carbon fiber, obtain the carbon fiber through activation treatment.In the present embodiment, the consumption of Silver Nitrate is 5g, and the time activated the carbon fiber through sensitized treatment is 25min.
5th step, carries out reduction treatment to the carbon fiber after activation, will buy the SnCl of coming
2solution distilled water diluting to concentration is 10 ~ 20g/L, constantly stirring with glass stick in dilution makes it even, thus preparation sensitizing solution, carbon fiber through activation treatment is immersed in the solution of sodium hypophosphite, at room temperature mechanical stirring 1 ~ 5min, obtain surface through the pretreated carbon fiber of chemical nickel plating, take out for subsequent use.In the present embodiment, SnCl
2the concentration of solution is 10g/L, and the churned mechanically time is 2min.
Step 3, chemical nickel-plating solution mixes also machinery by solution A and B solution to stir, and form through overregulating pH value.
Wherein solution A mixes formulated respectively successively by 30 ~ 50g/L nickel sulfate solution, 18 ~ 30g/L sodium acetate soln and 30 ~ 40g/L ammoniumsulphate soln.B solution mixes also machinery by 36 ~ 50g/L ortho phosphorous acid sodium solution and 10 ~ 20g/L citric acid three sodium solution to stir formulated.Solution A and B solution are mixed.It is 4.5 ~ 6.5 that hydrochloric acid regulates by the pH value of the mixing solutions of solution A and B solution, obtains chemical nickel-plating solution.When preparing solution A again, first nickel sulfate solution to be mixed with sodium acetate soln and after stirring, then add ammoniumsulphate soln and mix and stir.
In the present embodiment, described single nickel salt is 50g/L, and sodium-acetate is 30g/L, and ammonium sulfate is 40g/L; Described inferior sodium phosphate is 50g/L, and trisodium citrate is 20g/L; The pH value of carbon fiber chemical nickel-plating solution is 6.
Step 4, Electroless Nickel Plating on Carbon Fiber coating.
The carbon fiber chemical nickel-plating solution obtained is placed on thermostatic bath water tank, and make the temperature of described thermostatic bath water tank remain on 85 ~ 95 DEG C, surface is placed in plating solution through the pretreated carbon fiber of chemical nickel plating, chemical plating is carried out through 5 ~ 18min, after plating completes, take out from solution and dry, obtaining preparing the carbon fiber having RESEARCH OF PYROCARBON/nickel composite coat.In the present embodiment, the temperature of thermostatic bath water tank is 95 DEG C; The time of chemistry plating is 5min.
Claims (1)
1. continuous carbon fibre surface RESEARCH OF PYROCARBON/nickel composite coat preparation method, it is characterized in that, detailed process is:
Step 1, at carbon fiber surface deposition pyrocarbon coating; Adopt conventional chemical vapor deposition pyrocarbon coating; Coating process parameter is: N
2intake is 0.1 ~ 0.5m
3/ h, CH
4intake is 16-24L/h, and depositing temperature is 1000 ~ 1200 DEG C, and depositing time is 1 ~ 3 hour, is cooled to after room temperature until chemical vapor deposition stove, takes out carbon fiber, obtains the carbon fiber that surface preparation has pyrocarbon coating;
Step 2, chemical nickel plating on surface pre-treatment; Chemical nickel plating on surface pre-treatment is carried out to the carbon fiber depositing pyrocarbon coating, specifically:
The first step, has the carbon fiber of pyrocarbon coating to carry out roughening treatment to the surface preparation obtained; Carbon fiber is put into H
2sO
4: HNO
3roughening treatment 1 ~ 2 hour in the mixed acid solution of=3:1; Described H
2sO
4with HNO
3ratio be volume ratio;
Second step, carries out neutralizing treatment to the carbon fiber after alligatoring; Carbon fiber after alligatoring is put into NaOH solution immersion 10 ~ 20min that mass ratio is 10 ~ 20%, and constantly stir, to remove the nitration mixture of carbon fiber surface with glass stick; With distilled water cleaning carbon fiber to neutral;
3rd step, carries out sensitized treatment to the carbon fiber after neutralization; By SnCl
2solution distilled water diluting is 10 ~ 20g/L to concentration, is mixed with sensitizing solution, then the carbon fiber through neutralizing treatment is at room temperature put into this solution immersion 20 ~ 30min;
4th step, carries out activation treatment to through sensitized treatment carbon fiber, is dissolved in the distilled water of 100ml, obtains silver nitrate solution by 2 ~ 5g Silver Nitrate; By described silver nitrate solution distilled water diluting to 1L, be mixed with activated solution; At room temperature will put into the activated solution activation 10 ~ 30min obtained through sensitized treatment carbon fiber, obtain the carbon fiber through activation treatment;
5th step, immerses in the solution of sodium hypophosphite by the carbon fiber through activation treatment, at room temperature mechanical stirring 1 ~ 5min, obtains surface through the pretreated carbon fiber of chemical nickel plating, takes out for subsequent use;
Step 3, preparative chemistry nickel plating solution
Described chemical nickel-plating solution is mixed by solution A and B solution and after stirring, forms through overregulating pH value;
Wherein solution A 30 ~ 50g/L nickel sulfate solution, 18 ~ 30g/L sodium acetate soln and 30 ~ 40g/L ammoniumsulphate soln is mixed successively respectively and stirs formulated; B solution 36 ~ 50g/L ortho phosphorous acid sodium solution and 10 ~ 20g/L citric acid three sodium solution is mixed and stirs formulated; Solution A is mixed with B solution; Regulate pH value to 4.5 ~ 6.5 of the mixing solutions prepared by solution A and B solution, obtain chemical nickel-plating solution; Step 4, Electroless Nickel Plating on Carbon Fiber coating;
During described preparation mixed solution A, first nickel sulfate solution to be mixed with sodium acetate soln and after stirring, then add ammoniumsulphate soln and mix and stir;
The carbon fiber chemical nickel-plating solution obtained being put bath temperature is in 85 ~ 95 DEG C of thermostatic bath water tanks, surface is placed in plating solution through the pretreated carbon fiber of chemical nickel plating, carry out chemical plating through 5 ~ 18min and dry, obtaining preparing the carbon fiber having RESEARCH OF PYROCARBON/nickel composite coat.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310093388.XA CN103160826B (en) | 2013-03-22 | 2013-03-22 | Preparation method of continuous carbon fiber surface pyrolytic carbon/nickel composite coating |
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| CN103745195B (en) * | 2013-12-20 | 2017-02-22 | 西北工业大学 | Pyrocarbon organization structure quantitative characterization method based on polarization image |
| CN104561924B (en) * | 2014-12-05 | 2018-08-14 | 林荣铨 | A kind of preparation method of pyrocarbon coating |
| CN105038110B (en) * | 2015-07-06 | 2017-07-21 | 陕西科技大学 | A kind of electrochemical modification carbon cloth enhancing friction material and preparation method thereof |
| CN105220087B (en) * | 2015-07-20 | 2017-05-03 | 西安科技大学 | High-strength and high-tenacity Ti(C,N)-based metal and ceramic composite material and preparation method thereof |
| CN105200401A (en) * | 2015-10-29 | 2015-12-30 | 无锡桥阳机械制造有限公司 | Carbon fiber surface metallization method |
| CN106930094B (en) * | 2015-12-31 | 2019-11-15 | 中国科学院宁波材料技术与工程研究所 | A kind of preparation method of carbon fibre composite boundary layer |
| CN109627028A (en) * | 2019-01-16 | 2019-04-16 | 苏州宏久航空防热材料科技有限公司 | A kind of 3D printing carbon fiber toughened silicon carbide pottery aluminium composite material and preparation method thereof |
| CN113161738B (en) * | 2021-05-25 | 2021-08-31 | 中国电子科技集团公司第二十九研究所 | Preparation method of low-frequency broadband curved surface circuit |
| CN113522262A (en) * | 2021-07-15 | 2021-10-22 | 陕西科技大学 | Recyclable flexible titanium dioxide/pyrolytic carbon/carbon fiber felt composite photocatalytic material and preparation method and application thereof |
| CN114263036B (en) * | 2021-12-31 | 2023-07-25 | 湖南东映碳材料科技股份有限公司 | Preparation method of carbon fiber |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101319325A (en) * | 2008-07-03 | 2008-12-10 | 西北工业大学 | Method of manufacturing fine helical nickel-carbon alloy material |
| CN101451278A (en) * | 2007-12-03 | 2009-06-10 | 西北工业大学 | Method for preparing helical carbon fiber |
| CN102505101A (en) * | 2011-10-13 | 2012-06-20 | 西北工业大学 | Carbon fiber surface C/Si composite coating and preparation method thereof |
| CN102644069A (en) * | 2012-05-22 | 2012-08-22 | 东北林业大学 | Method for chemically plating nickel on surface of carbon fiber |
-
2013
- 2013-03-22 CN CN201310093388.XA patent/CN103160826B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101451278A (en) * | 2007-12-03 | 2009-06-10 | 西北工业大学 | Method for preparing helical carbon fiber |
| CN101319325A (en) * | 2008-07-03 | 2008-12-10 | 西北工业大学 | Method of manufacturing fine helical nickel-carbon alloy material |
| CN102505101A (en) * | 2011-10-13 | 2012-06-20 | 西北工业大学 | Carbon fiber surface C/Si composite coating and preparation method thereof |
| CN102644069A (en) * | 2012-05-22 | 2012-08-22 | 东北林业大学 | Method for chemically plating nickel on surface of carbon fiber |
Non-Patent Citations (1)
| Title |
|---|
| 碳纤维表面化学镀镍工艺研究;何为;《电镀与涂饰》;20030228;第22卷(第1期);第8-11页 * |
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