CN103160826A - 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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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 material technology field, 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 zero thermal expansivity, high Young's modulus and excellent mechanical property make its research and attention of being subject to more and more people, have high specific tenacity, specific rigidity, low excellent properties such as thermal expansivity with its carbon fiber reinforced aluminum matrix composite of preparing as reinforcement.But smooth because of carbon fiber surface, surperficial 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 occur, cause easily when surface reaction is too much that aluminium alloy formed strong interface and is combined between carbon fiber, make the matrix material of preparing be subject to tension load and do used time generation brittle rupture, cause the mechanical property of matrix material lower, restrict its research and extension and use.Carry out coating modified processing at carbon fiber surface and can effectively improve wettability between carbon fiber and matrix alloy, improve the infiltration effect of matrix material, and stop the generation of bad surface reaction, rationally control the interface binding power between carbon fiber and aluminium alloy, thereby 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 methods preparations such as chemical vapor deposition (CVD), sol-gel method, electroless plating.
China Patent Publication No. CN101705456B has announced a kind of method for preparing carbon fiber reinforced magnesium-base composite material in the Electroless Nickel Plating on Carbon Fiber coating, the method can enhanced carbon fiber and matrix between wettability, improve the infiltration effect of matrix material and improve its mechanical property.
Find through literature search, and document " Ceng 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 the interface thermal stresses of bringing due to the thermal expansivity difference between carbon fiber, aluminium alloy, promote both consistencies, simultaneously TiO
2The surface can be higher, and the wetting angle of aluminium liquid is better than between carbon, aluminium, this just can improve wettability and interfacial bonding property between carbon fiber and aluminium alloy, and has controlled to a certain extent the generation of the hole defect of matrix material.
Yet, 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 fragility phase during separately as coating in matrix material, literature survey also shows, it is limited to the surface reaction effect of controlling between carbon fiber and aluminium alloy, is suitable for being TiO transition layer and that can improve wettability though sol-gel method can be prepared
2Coating, but generally, whole sol-gel process required time is more, cycle is longer, and efficient is lower, and has a large amount of micropores in gel, will overflow again in drying process many gases and organism, and produce contraction, and also can have a negative impact to coating structure, affect the successful preparation of desirable carbon fiber reinforced metal based composites.
Summary of the invention
Longer for overcoming the cycle that exists in prior art, efficient is lower, and there are a large amount of micropores in gel, evolving gas and organism have a negative impact to coating structure in drying process, affect the deficiency of the preparation of carbon fiber reinforced metal based composites, the present invention proposes the surperficial RESEARCH OF PYROCARBON of a kind of continuous carbon fibre/nickel composite coat preparation method.
Detailed process of the present invention is:
Step 1 is at carbon fiber surface deposition pyrocarbon coating.Adopt conventional chemical Vapor deposition process deposition pyrocarbon coating.The 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 ℃, and depositing time is 1～3 hour, after chemical vapor deposition stove is cooled to room temperature, takes out carbon fiber, obtains the carbon fiber that the surface is prepared with pyrocarbon coating.
Step 2, the chemical nickel plating on surface pre-treatment.The carbon fiber that deposited pyrocarbon coating is carried out the chemical nickel plating on surface pre-treatment, specifically:
The first step, the carbon fiber that the surface that obtains is prepared with pyrocarbon coating carries out roughening treatment.Carbon fiber is put into H
2SO
4: HNO
3In the mixed acid solution of=3:1, roughening treatment is 1～2 hour; Described H
2SO
4With HNO
3Ratio be volume ratio.
Second step carries out neutralizing treatment to the carbon fiber after alligatoring.It is that 10～20% NaOH solution soaks 10～20min that carbon fiber after alligatoring is put into mass ratio, and constantly stirs with glass stick, to remove the nitration mixture of carbon fiber surface; Clean carbon fiber to neutral with distilled water.
In the 3rd step, the carbon fiber after neutralization is carried out sensitization process.With SnCl
2Solution is 10～20g/L with distilled water diluting to concentration, is mixed with sensitizing solution, then will at room temperature put into this solution through the carbon fiber of neutralizing treatment and soak 20～30min.
The 4th step to carrying out activation treatment through the sensitization Treatment of Carbon, was dissolved in 2～5g Silver Nitrate in the distilled water of 100ml, obtained silver nitrate solution.With described silver nitrate solution with distilled water diluting to 1L, be mixed with activated solution.At room temperature will put into the activated solution that obtains through the sensitization Treatment of Carbon and activate 10～30min, obtain the carbon fiber through activation treatment.
In the 5th step, the carbon fiber after activation is reduced processing, with SnCl
2Solution is 10～20g/L with distilled water diluting to concentration, obtains sensitizing solution; To immerse through the carbon fiber of activation treatment in the solution of sodium hypophosphite, at room temperature mechanical stirring 1～5min, obtain the surface through the pretreated carbon fiber of chemical nickel plating, takes out standby.
Step 3, the preparation chemical nickel-plating solution
After described chemical nickel-plating solution is mixed by A solution and B solution and stirs, form through overregulating pH value.
Wherein A solution is that 30～50g/L nickel sulfate solution, 18～30g/L sodium acetate soln and 30～40g/L ammoniumsulphate soln are mixed successively respectively and stir formulated.B solution is that 36～50g/L ortho phosphorous acid sodium solution and 10～20g/L citric acid three sodium solution are mixed and stir formulated.A solution and B solution are mixed; Adjusting obtains chemical nickel-plating solution by the pH value to 4.5 of the mixing solutions of A solution and B solution preparation～6.5.
Preparation is during mixed solution A, after first nickel sulfate solution being mixed with sodium acetate soln and stirring, then adds ammoniumsulphate soln to mix and stirs.
Step 4, the Electroless Nickel Plating on Carbon Fiber coating.
It is in 85～95 ℃ of thermostatic bath water tanks that the carbon fiber chemical nickel-plating solution that obtains is put bath temperature, the surface is placed in plating solution through the pretreated carbon fiber of chemical nickel plating, carry out chemical plating and oven dry through 5～18min, obtain being prepared with the carbon fiber of RESEARCH OF PYROCARBON/nickel composite coat.
The present invention adopts chemical Vapor deposition process (CVD) preparing pyrocarbon coating without the carbon fiber surface in the latitude carbon cloth, pyrocarbon coating thickness is between 0.03-0.1 μ m, adopt again electroless plating method to prepare nickel coating at the carbon fiber surface that is prepared with pyrocarbon coating, by controlling the reaction times of carbon fiber in chemical nickel-plating solution (plating solution), make nickel coating thickness between 0.02-0.1 μ m, thereby obtain to contain the carbon fiber of RESEARCH OF PYROCARBON/nickel composite coat, the thickness of compound coating is between 0.05-0.2 μ m.
The present invention uses separately nickel coating easily to generate bad fragility phase in matrix material for solving, and the interface is in conjunction with being difficult to effective control, use sol-gel method to prepare coating cycle long, easily produce the problem of micropore in coating, and realize that carbon fiber and matrix wettability improve, and making has transition layer to exist between the two, to avoid not mating due to thermal expansivity the generation of the matrix material hole defect that brings, effectively improves matrix material and prepares effect.The pyrocarbon coating of specifically first preparing 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 prepare thickness by electroless plating method again on this basis controlled, nickel coating, can improve the wettability between carbon fiber and aluminium alloy uniformly, greatly improves 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, can reduce both interface thermal stresses, when controlling composite material solidification because thermal expansivity does not mate the defectives such as hole of bringing, given play to the comprehensive advantage of pyrocarbon coating and nickel coating, carried out prerequisite for the successful preparation of desirable carbon fiber reinforced aluminum matrix composite and prepare.
The pyrocarbon coating that at first the present invention prepares with the CVD method at carbon fiber surface; this coating is a kind of good oxidation resistant coating; oxidation easily occurs in time more than 300 ℃ in carbon fiber; there has been the existence of this coating can prevent preferably that fiber is oxidized; 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, more serious surface reaction easily occurs in itself, the existence of pyrocarbon coating is arranged between carbon fiber and aluminium alloy, because the microtexture of RESEARCH OF PYROCARBON more is tending towards greying, graphitized fibre generally is difficult for and 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.
Prepare uniform nickel coating by electroless plating method, the deficiency that overcome that the common coating production cycle such as traditional collosol and gel is long and efficient is low, there is micropore the coating centre etc., common 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 can even just can be completed in several hours at one day.Simultaneously, because the wettability between nickel and aluminium alloy obviously is better than wettability between carbon fiber and aluminium alloy, the nickel coating of carbon fiber surface just can improve the wetting effect between carbon fiber and aluminium alloy like this, under equal processing condition, can improve the homogenizing infiltration effect of carbon fiber reinforced aluminum matrix composite.In addition, the thermal expansivity of nickel coating is between carbon fiber and aluminium alloy, the shock absorption of can between bringing into play well stress, thereby can reduce both interface thermal stresses, do not mate the appearance of the defectives such as hole of bringing when controlling composite material solidification due to thermal expansivity, be suitable for the preparation of desirable carbon fiber reinforced aluminum matrix composite.
Provide the EDS analytical results of the carbon fiber surface coating that is prepared with compound coating in accompanying drawing 2, can find out from elemental distribution, prepared the compound coating that contains RESEARCH OF PYROCARBON/nickel at carbon fiber surface.Through experimental examination and checking, adopt pressure infiltration method, use the prepared carbon fiber reinforced aluminum matrix composite of compound coating in the present invention, infiltrate respond well, there is no obvious hole defect, the tensile strength of matrix material is compared with aluminum matrix alloy and has been improved more than 60%.
Description of drawings
Fig. 1 is schema of the present invention.
Fig. 2 is the EDS analytical results of the prepared RESEARCH OF PYROCARBON/nickel composite coat of the present invention, shows to have prepared at carbon fiber surface to contain RESEARCH OF PYROCARBON/nickel composite coat.
Embodiment
Embodiment 1
The present embodiment is the surperficial RESEARCH OF PYROCARBON of a kind of continuous carbon fibre/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 is 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 process deposition pyrocarbon coating.The 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 ℃, and depositing time is 1～3 hour, after chemical vapor deposition stove is cooled to room temperature, takes out carbon fiber, obtains the carbon fiber that the surface is prepared with pyrocarbon coating.In the present embodiment, N
2Intake is 0.1m
3/ h, CH
4Intake is 18L/h, and depositing temperature is 1000 ℃, and depositing time is 1 hour.
Step 2, the carbon fiber that deposited pyrocarbon coating is carried out the chemical nickel plating on surface pre-treatment specifically:
The first step, the carbon fiber that the surface that obtains is prepared with pyrocarbon coating carries out roughening treatment.Carbon fiber is put into H
2SO
4: HNO
3In the mixed acid solution of=3:1, roughening treatment is 1～2 hour; 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.It is that 10～20% NaOH solution soaks 10～20min that carbon fiber after alligatoring is put into mass ratio, and constantly stirs with glass stick, to remove the nitration mixture of carbon fiber surface, then is 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.
In the 3rd step, the carbon fiber after neutralization is carried out sensitization process.The SnCl of coming will be bought
2Solution is 10～20g/L with distilled water diluting to concentration, in dilution will with glass stick constantly mechanical stirring make it even, thereby be mixed with sensitizing solution, then will at room temperature put into this solution through the carbon fiber of neutralizing treatment and soak 20～30min.In the present embodiment, SnCl
2The concentration of solution after with distilled water diluting is 10g/L, and the time that sensitization is processed is 20min.
The 4th step to carrying out activation treatment through the sensitization Treatment of Carbon, was dissolved in load weighted Silver Nitrate 2～5g in the distilled water of 100ml, obtained the silver nitrate solution of high density.With the silver nitrate solution of the high density that configures with distilled water diluting to 1L, be mixed with activated solution.At room temperature will put into the activated solution that obtains through the sensitization Treatment of Carbon and activate 10～30min, obtain the carbon fiber through activation treatment.In the present embodiment, the consumption of Silver Nitrate is 3g, and the time that the carbon fiber of processing through sensitization is activated is 15min.
In the 5th step, the carbon fiber after activation is reduced processings, the SnCl that will buy
2Solution is 10～20g/L with distilled water diluting to concentration, will constantly stir with glass stick in dilution makes it even, thereby preparation sensitizing solution, to immerse through the carbon fiber of activation treatment in the solution of sodium hypophosphite, mechanical stirring 1～5min at room temperature, obtain the surface through the pretreated carbon fiber of chemical nickel plating, take out standby.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 are to be mixed and machinery stirs by A solution and B solution, and form through overregulating pH value.
Wherein A solution is to mix successively respectively 30～50g/L nickel sulfate solution, 18～30g/L sodium acetate soln and 30～40g/L ammoniumsulphate soln formulated.B solution is to be mixed and machinery stirs formulated by 36～50g/L ortho phosphorous acid sodium solution and 10～20g/L citric acid three sodium solution.A solution and B solution are mixed.The pH value that hydrochloric acid is regulated by the mixing solutions of A solution and B solution is 4.5～6.5, obtains chemical nickel-plating solution.When preparing again A solution, after first nickel sulfate solution being mixed with sodium acetate soln and stirring, then add ammoniumsulphate soln to 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, the Electroless Nickel Plating on Carbon Fiber coating.
The carbon fiber chemical nickel-plating solution that obtains is placed on the thermostatic bath water tank, and the temperature that makes described thermostatic bath water tank remains on 85～95 ℃, the surface is placed in plating solution through the pretreated carbon fiber of chemical nickel plating, carry out chemical plating through 5～18min, after plating is completed, take out from solution and dry, obtaining being prepared with the carbon fiber of RESEARCH OF PYROCARBON/nickel composite coat.In the present embodiment, the temperature of thermostatic bath water tank is 85 ℃; The time of chemistry plating is 15min.
Embodiment 2
The present embodiment is the surperficial RESEARCH OF PYROCARBON of a kind of continuous carbon fibre/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 is 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 process deposition pyrocarbon coating.The 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 ℃, and depositing time is 1～3 hour, after chemical vapor deposition stove is cooled to room temperature, takes out carbon fiber, obtains the carbon fiber that the surface is prepared with pyrocarbon coating.In the present embodiment, N
2Intake is 0.3m
3/ h, CH
4Intake is 20L/h, and depositing temperature is 1050 ℃, and depositing time is 1.5 hours.
Step 2 is carried out the chemical nickel plating on surface pre-treatment specifically to the carbon fiber that deposited pyrocarbon coating,
The first step, the carbon fiber that the surface that obtains is prepared with pyrocarbon coating carries out roughening treatment.Carbon fiber is put into H
2SO
4: HNO
3In the mixed acid solution of=3:1, roughening treatment is 1～2 hour; 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.It is to soak 10～20min in 10～20% NaOH solution that carbon fiber after alligatoring is placed on mass ratio, and constantly stirs with glass stick, to remove the nitration mixture of carbon fiber surface, then is 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.
In the 3rd step, the carbon fiber after neutralization is carried out sensitization process.The SnCl of coming will be bought
2Solution is 10～20g/L with distilled water diluting to concentration, in dilution will with glass stick constantly mechanical stirring make it even, thereby be mixed with sensitizing solution, then will at room temperature put into this solution 20～30min through the carbon fiber of neutralizing treatment.In the present embodiment, SnCl
2The concentration of solution after with distilled water diluting is 15g/L, and the time that sensitization is processed is 25min.
The 4th step to carrying out activation treatment through the sensitization Treatment of Carbon, was dissolved in load weighted Silver Nitrate 2～5g in the distilled water of 100ml, obtained the silver nitrate solution of high density.With the silver nitrate solution of the high density that configures with distilled water diluting to 1L, be mixed with activated solution.At room temperature will put into the activated solution that obtains through the sensitization Treatment of Carbon and activate 10～30min, obtain the carbon fiber through activation treatment.In the present embodiment, the consumption of Silver Nitrate is 4g, and the time that the carbon fiber of processing through sensitization is activated is 20min.
In the 5th step, the carbon fiber after activation is reduced processings, the SnCl that will buy
2Solution is 10～20g/L with distilled water diluting to concentration, will constantly stir with glass stick in dilution makes it even, thereby preparation sensitizing solution, to immerse through the carbon fiber of activation treatment in the solution of sodium hypophosphite, mechanical stirring 1～5min at room temperature, obtain the surface through the pretreated carbon fiber of chemical nickel plating, take out standby.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 are to be mixed and machinery stirs by A solution and B solution, and form through overregulating pH value.
Wherein A solution is to mix successively respectively 30～50g/L nickel sulfate solution, 18～30g/L sodium acetate soln and 30～40g/L ammoniumsulphate soln formulated.B solution is to be mixed and machinery stirs formulated by 36～50g/L ortho phosphorous acid sodium solution and 10～20g/L citric acid three sodium solution.A solution and B solution are mixed.The pH value that hydrochloric acid is regulated by the mixing solutions of A solution and B solution is 4.5～6.5, obtains chemical nickel-plating solution.When preparing again A solution, after first nickel sulfate solution being mixed with sodium acetate soln and stirring, then add ammoniumsulphate soln to 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, the Electroless Nickel Plating on Carbon Fiber coating.
The carbon fiber chemical nickel-plating solution that obtains is placed on the thermostatic bath water tank, and the temperature that makes described thermostatic bath water tank remains on 85～95 ℃, the surface is placed in plating solution through the pretreated carbon fiber of chemical nickel plating, carry out chemical plating through 5～18min, after plating is completed, take out from solution and dry, obtaining being prepared with the carbon fiber of RESEARCH OF PYROCARBON/nickel composite coat.In the present embodiment, the temperature of thermostatic bath water tank is 85 ℃; The time of chemistry plating is 10min.
Embodiment 3
The present embodiment is the surperficial RESEARCH OF PYROCARBON of a kind of continuous carbon fibre/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 is 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 process deposition pyrocarbon coating.The 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 ℃, and depositing time is 1～3 hour, after chemical vapor deposition stove is cooled to room temperature, takes out carbon fiber, obtains the carbon fiber that the surface is prepared with pyrocarbon coating.In the present embodiment, N
2Intake is 0.5m
3/ h, CH
4Intake is 24L/h, and depositing temperature is 1100 ℃, and depositing time is 2 hours.
Step 2, the carbon fiber that deposited pyrocarbon coating is carried out the chemical nickel plating on surface pre-treatment specifically:
The first step, the carbon fiber that the surface that obtains is prepared with pyrocarbon coating carries out roughening treatment.Carbon fiber is put into H
2SO
4: HNO
3In the mixed acid solution of=3:1, roughening treatment is 1～2 hour; 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.It is to soak 10～20min in 10～20% NaOH solution that carbon fiber after alligatoring is placed on mass ratio, and constantly stirs with glass stick, to remove the nitration mixture of carbon fiber surface, then is 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.
In the 3rd step, the carbon fiber after neutralization is carried out sensitization process.The SnCl of coming will be bought
2Solution is 10～20g/L with distilled water diluting to concentration, in dilution will with glass stick constantly mechanical stirring make it even, thereby be mixed with sensitizing solution, then will at room temperature put into this solution 20～30min through the carbon fiber of neutralizing treatment.In the present embodiment, SnCl
2The concentration of solution after with distilled water diluting is 20g/L, and the time that sensitization is processed is 30min.
The 4th step to carrying out activation treatment through the sensitization Treatment of Carbon, was dissolved in load weighted Silver Nitrate 2～5g in the distilled water of 100ml, obtained the silver nitrate solution of high density.With the silver nitrate solution of the high density that configures with distilled water diluting to 1L, be mixed with activated solution.At room temperature will put into the activated solution that obtains through the sensitization Treatment of Carbon and activate 10～30min, obtain the carbon fiber through activation treatment.In the present embodiment, the consumption of Silver Nitrate is 5g, and the time that the carbon fiber of processing through sensitization is activated is 25min.
In the 5th step, the carbon fiber after activation is reduced processings, the SnCl that will buy
2Solution is 10～20g/L with distilled water diluting to concentration, will constantly stir with glass stick in dilution makes it even, thereby preparation sensitizing solution, to immerse through the carbon fiber of activation treatment in the solution of sodium hypophosphite, mechanical stirring 1～5min at room temperature, obtain the surface through the pretreated carbon fiber of chemical nickel plating, take out standby.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 are to be mixed and machinery stirs by A solution and B solution, and form through overregulating pH value.
Wherein A solution is to mix successively respectively 30～50g/L nickel sulfate solution, 18～30g/L sodium acetate soln and 30～40g/L ammoniumsulphate soln formulated.B solution is to be mixed and machinery stirs formulated by 36～50g/L ortho phosphorous acid sodium solution and 10～20g/L citric acid three sodium solution.A solution and B solution are mixed.The pH value that hydrochloric acid is regulated by the mixing solutions of A solution and B solution is 4.5～6.5, obtains chemical nickel-plating solution.When preparing again A solution, after first nickel sulfate solution being mixed with sodium acetate soln and stirring, then add ammoniumsulphate soln to 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, the Electroless Nickel Plating on Carbon Fiber coating.
The carbon fiber chemical nickel-plating solution that obtains is placed on the thermostatic bath water tank, and the temperature that makes described thermostatic bath water tank remains on 85～95 ℃, the surface is placed in plating solution through the pretreated carbon fiber of chemical nickel plating, carry out chemical plating through 5～18min, after plating is completed, take out from solution and dry, obtaining being prepared with the carbon fiber of RESEARCH OF PYROCARBON/nickel composite coat.In the present embodiment, the temperature of thermostatic bath water tank is 95 ℃; The time of chemistry plating is 5min.
Claims (2)
1. the surperficial RESEARCH OF PYROCARBON of continuous carbon fibre/nickel composite coat preparation method, is characterized in that, detailed process is:
Step 1 is at carbon fiber surface deposition pyrocarbon coating; Adopt conventional chemical Vapor deposition process deposition pyrocarbon coating; The 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 ℃, and depositing time is 1～3 hour, after chemical vapor deposition stove is cooled to room temperature, takes out carbon fiber, obtains the carbon fiber that the surface is prepared with pyrocarbon coating;
Step 2, the chemical nickel plating on surface pre-treatment; The carbon fiber that deposited pyrocarbon coating is carried out the chemical nickel plating on surface pre-treatment, specifically:
The first step, the carbon fiber that the surface that obtains is prepared with pyrocarbon coating carries out roughening treatment; Carbon fiber is put into H
2SO
4: HNO
3In the mixed acid solution of=3:1, roughening treatment is 1～2 hour; Described H
2SO
4With HNO
3Ratio be volume ratio;
Second step carries out neutralizing treatment to the carbon fiber after alligatoring; It is that 10～20% NaOH solution soaks 10～20min that carbon fiber after alligatoring is put into mass ratio, and constantly stirs with glass stick, to remove the nitration mixture of carbon fiber surface; Clean carbon fiber to neutral with distilled water;
In the 3rd step, the carbon fiber after neutralization is carried out sensitization process; With SnCl
2Solution is 10～20g/L with distilled water diluting to concentration, is mixed with sensitizing solution, then will at room temperature put into this solution through the carbon fiber of neutralizing treatment and soak 20～30min;
The 4th step to carrying out activation treatment through the sensitization Treatment of Carbon, was dissolved in 2～5g Silver Nitrate in the distilled water of 100ml, obtained silver nitrate solution; With described silver nitrate solution with distilled water diluting to 1L, be mixed with activated solution; At room temperature will put into the activated solution that obtains through the sensitization Treatment of Carbon and activate 10～30min, obtain the carbon fiber through activation treatment;
The 5th step, the carbon fiber after activation is reduced processing, be 10～20g/L with SnCl2 solution with distilled water diluting to concentration, obtain sensitizing solution; To immerse through the carbon fiber of activation treatment in the solution of sodium hypophosphite, at room temperature mechanical stirring 1～5min, obtain the surface through the pretreated carbon fiber of chemical nickel plating, takes out standby;
Step 3, the preparation chemical nickel-plating solution
After described chemical nickel-plating solution is mixed by A solution and B solution and stirs, form through overregulating pH value;
Wherein A solution is that 30～50g/L nickel sulfate solution, 18～30g/L sodium acetate soln and 30～40g/L ammoniumsulphate soln are mixed successively respectively and stir formulated; B solution is that 36～50g/L ortho phosphorous acid sodium solution and 10～20g/L citric acid three sodium solution are mixed and stir formulated; A solution and B solution are mixed;
Adjusting obtains chemical nickel-plating solution by the pH value to 4.5 of the mixing solutions of A solution and B solution preparation～6.5;
Step 4, the Electroless Nickel Plating on Carbon Fiber coating;
It is in 85～95 ℃ of thermostatic bath water tanks that the carbon fiber chemical nickel-plating solution that obtains is put bath temperature, the surface is placed in plating solution through the pretreated carbon fiber of chemical nickel plating, carry out chemical plating and oven dry through 5～18min, obtain being prepared with the carbon fiber of RESEARCH OF PYROCARBON/nickel composite coat.
2. a kind of continuous carbon fibre surface RESEARCH OF PYROCARBON/nickel composite coat preparation method as claimed in claim 1, it is characterized in that, during described preparation mixed solution A, after first nickel sulfate solution being mixed with sodium acetate soln and stirring, then add ammoniumsulphate soln to mix and stir.
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