CN110396816A - A kind of carbon fiber surface HfB2The preparation method of-SiBNC composite coating - Google Patents
A kind of carbon fiber surface HfB2The preparation method of-SiBNC composite coating Download PDFInfo
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Abstract
The invention discloses a kind of carbon fiber surface HfB2The preparation method of-SiBNC composite coating, the method are low temperature precursor solution infiltration pyrolysis method, which is characterized in that successively include: the preparation of coating solution, carbon fiber surface activation processing, coating, dry and heat treatment；Up to the HfB of fire-resistant oxidation resistant2- SiBNC carbon fiber coating layer.Present invention process is simple, equipment and operating environment require simply, to be not necessarily to special equipment, and exploitativeness is strong, the prices of raw materials are cheap, and it is easily obtained, easy to accomplish, energy conservation and environmental protection, it can be in the fire-resistant oxidation resistant coating that even compact is made in carbon fiber surface and adhesive force is good, thickness is within 2 μm, the original mechanical property of carbon fiber is not only remained, the high-temperature oxidation resistance of carbon fiber is improved, further improves the interface compatibility problem of fiber and matrix.
Description
Technical field
The invention belongs to technical field of inorganic nonmetallic materials, and in particular to a kind of carbon fiber surface HfB2- SiBNC is compound
The preparation method of coating.
Background technique
Carbon fiber have high-modulus, high intensity, low-density, low thermal expansion, high temperature resistant, it is anti-oxidant, without creep, high thermal conductivity,
The excellent performance such as corrosion-resistant, can be used as the reinforcement of composite material, so that carbon fiber is in materials such as ceramics, resin, metal, carbon
Expect to be used widely in the composite material for matrix.But carbon fiber has just aoxidized in 400 DEG C or more of air, antioxygen
It is poor to change performance, causes the performance of material to decline, and lower without the carbon fiber surface activity of surface treatment, with certain bases
The wellability of body is bad, and binding ability is poor, also results in the reduced performance of composite material.Moreover, composite wood is being prepared
At a temperature of expecting Pintsch process, carbon fiber is easy to react with certain matrixes, to damage fiber, seriously reduces composite wood
The performance of material.
Carrying out surface covering to carbon fiber can be with the effective solution above problem.Coating can not only improve the antioxygen of carbon fiber
Change performance, and it can prevent carbon fiber and matrix from interfacial reaction, energy occurs as the barrier layer between carbon fiber and matrix
Enough improve the interface compatibility problem of Fiber In Composite Material and matrix.Hafnium boride (HfB2) it is that a kind of grey has metallic luster
Crystal, crystal structure belong to hexagonal crystal system, and fusing point is up to 3380 DEG C, have good high-temperature stability, inoxidizability and with
Carbon fiber has good chemical compatibility, can preferably meet the requirement under hyperthermal environments, these advantages make its at
For a kind of fire-resistant oxidation resistant coating with development potential.SiBNC has good high-temperature stability, inoxidizability and and carbon
Fiber has good chemical compatibility, without thermal weight loss and split-phase when being lower than 1700 DEG C under inert gas protection, at 2000 DEG C
Just having crystalline transition is SiC and Si3N4And a small amount of amorphous BN, and the antioxygenic property at 1700 DEG C in air is much better than
SiC and Si3N4, these advantages also become a kind of fire-resistant oxidation resistant coating with development potential.2017, middle promulgated by the State Council
Bright 107523778 A of patent CN discloses the preparation method of hafnium boride composite coating, it is compound with hafnium oxide/boron carbide/aluminum
Powder relates generally to boride using in thermal spraying in-situ reactive synthesis hafnium boride composite coating according to certain proportion for raw material
To the plating of the base materials such as metal, ceramics, it is unsuitable for preparing fine and close interface phase coating in fiber surface.2015, China
104609892 A of patent of invention CN disclose appearance deposition SiBNC coating mullite fiber and preparation method thereof, it be with
Boron azine (BZ) and liquid Polycarbosilane (LPCS) are that raw material is prepared by chemical vapor deposition process.The preparation of CVD technique
SiBNC, needs to find suitable SiBNC precursor, and condition is harsh, needs special equipment, expensive, complicated for operation, is difficult
Realize industrialized production, and the reactant of this method is mostly toxic gas, tests and greatly increases in the environment of high temperature and pressure
Risk.The present invention is the low temperature of use using polyvinyl alcohol, boric acid, inorganic hafnium salt, SiBNC nano ceramic powder as raw material
Precursor solution infiltration pyrolysis method is suitable for the carbon fiber surface coating of variform, and the preparation method is not only in carbon fiber surface
The HfB of uniformly continuous densification is prepared2- SiBNC coating, and entire coating solution preparation process, simple process, without special
Equipment, energy saving, the prices of raw materials are cheap, nontoxic and pollution-free, and are easily obtained, easy to accomplish, by lower heat treatment
The coating formed after temperature not only improves the antioxygenic property of fiber and the interface problem of fiber and matrix, also overcomes
Drawbacks described above.
Summary of the invention
It is an object of the invention to overcome above-mentioned the deficiencies in the prior art, a kind of carbon fiber surface HfB is provided2-SiBNC
The preparation method of composite coating.
The present invention is achieved by the following technical solutions: first with polyvinyl alcohol, boric acid, inorganic hafnium salt, SiBNC nanometers
Ceramic powders are precursor prepared coating liquid, then by the impregnated carbon fiber after surface activation process in coating solution, are obtained
There are the carbon fiber of coating solution, the carbon fiber after being coated after dry, finally by the carbon fiber after coating in nitrogen protection in surface
Lower heat treatment, obtaining has HfB2The carbon fiber of-SiBNC composite coating.
The present invention the following steps are included:
1) preparation of coating solution:
A) using polyvinyl alcohol, boric acid as solute, deionized water is solvent, prepares boric acid solution respectively and polyvinyl alcohol is molten
Liquid；
B) inorganic hafnium salt is dissolved in deionized water and uniformly mixed, addition ammonium hydroxide adjusting pH value to 9.5, generation is stirred at room temperature
White precipitate will be dissolved in nitric acid with the white precipitate after deionized water eccentric cleaning, is controlled solution ph less than 2, is obtained
Hafnium oxide colloidal sol；
C) ethyl alcohol is added in boric acid solution and is stirred at room temperature to it and is uniformly mixed, obtain boric acid alcohol solution；
D) by poly-vinyl alcohol solution be quickly poured into it is above-mentioned c) in and be stirred at room temperature to its be uniformly mixed；
E) above-mentioned colloidal sol b) is mixed with above-mentioned solution d), it is finally that SiBNC nano ceramic powder is equal by magnetic agitation
Even is dispersed in above-mentioned mixed solution, and the coating solution is obtained after being stirred at room temperature 2~3 hours.
2) carbon fiber surface coating:
A) carbon fiber surface is activated: carbon fiber being placed in tube furnace keeps the temperature 30~40 minutes at 450 DEG C and take off
Glue processing will impregnate etching 60~100 minutes except the carbon fiber after glue is placed in concentrated nitric acid, then be washed with deionized water carbon fiber
Drying for standby after the Liquid Residue of dimension table face.
B) coat and be dried: by carbon fiber ultrasonic immersing in above-mentioned steps 1) 10~100 points in obtained coating solution
Carbon fiber after coating is stood 12~15 hours by clock at room temperature, is then placed in baking oven and is kept the temperature 40~60 in 60~70 DEG C
Minute.
C) carbon fiber coating layer is heat-treated: carbon fiber being placed in tube furnace, under inert gas protection with 2~3 DEG C/min
Heating rate be heated to 300 DEG C and keep the temperature 10~15 minutes, then be heated to 550 DEG C with the heating rate of 5 DEG C/min, heat preservation 30~
60 minutes, then 800 DEG C are heated to the heating rate of 8~10 DEG C/min, 30~60 minutes are kept the temperature, then with 6~8 DEG C/min's
Heating rate is heated to 1300~1500 DEG C of Pintsch process temperature, keeps the temperature 2~3 hours, obtains and is coated with HfB2- SiBNC coating
Carbon fiber.
Preferably, above-mentioned steps 1) described in boric acid solution concentration be 0.4~0.8mol/L.
Preferably, above-mentioned steps 1) described in poly-vinyl alcohol solution concentration be 0.8~1.2mol/L.
Preferably, above-mentioned steps 1) described in inorganic hafnium salt be HfOCl2·8H2O、Hf(NO3)4·xH2O、
HfO(NO3)2·xH2O、HfCl4、Hf(SO4)2One of aqueous inorganic salt, hafnium ion concentration can in the hafnium oxide colloidal sol
Amount by the way that deionized water is added is adjusted between 0.3~0.6mol/L.
Preferably, above-mentioned steps 1) described in ethyl alcohol and boric acid solution volume ratio be (1.2~2.8): 1.
Preferably, above-mentioned steps 1) described in coating solution in polyvinyl alcohol, boric acid, hafnium ion molar ratio be
(3.5~3.7): (0.9~1.1): (0.20~0.43).
Preferably, above-mentioned steps 1) described in SiBNC nano ceramic powder particle size be 40~80nm,
The volume content of SiBNC nano ceramic powder is 10~20% in the coating solution.
Preferably, above-mentioned steps 2) described in coating and be dried and can at most be repeated 3 times, then
Subsequent coating heat treatment is carried out again, can control the thickness of coating.
Preferably, the fire-resistant oxidation resistant composite coating is HfB2- SiBNC coating.
Preferably, the thickness of the coating is within 2 μm.
Preferably, the carbon fiber is one in carbon fiber bundle, carbon cloth and three-dimensional carbon fiber precast body
Kind is a variety of.
Due to containing various ingredients in the preparation system of coating solution, the hydrolysising condition of every kind of component is all respectively different, so that
The stability of solution is difficult to control, for example boric acid solution is mixed under room temperature, low temperature and hot conditions with poly-vinyl alcohol solution and stood
There is viscous flocculent deposit and escape (boric anhydride of boric acid and generation in solution has biggish volatility) with a large amount of bubbles,
And the colloidal sol being added in coating solution how to be enable to be stabilized, how to be prepared in room temperature and clarifies uniform and stable coating
Liquid makes HfB2Precursor solution, so that it is not had flocculate, be a difficult thing.
In the method for the invention, previous preparation HfB is changed2With the main method of SiBNC: HfB will be synthesized2With SiBNC institute
The powder raw material needed is mixed in a certain ratio, and reaction generates HfB at high temperature2With SiBNC, this method is not suitable in carbon
Fiber surface prepares coating, and synthesis reaction temperature is high, impurity is high；CVD technique prepares HfB2With SiBNC, suitable HfB is found2
With SiBNC precursor and presoma is more toxic, and synthesis reaction temperature is high, and complex process needs special equipment, and is unsuitable for more
Tie up the uniform coating of fiber surface；Using organic polymer cracking process, need first to prepare precursor polymer, then Pintsch process
HfB out2With SiBNC, this method is complicated for operation, and is unsuitable for preparing fine and close interface phase coating in fiber surface.
Appropriate modifier ethyl alcohol is added at room temperature, matches for entire coating solution preparation process in the present invention in boric acid group water solution
Addition sequence and the content control for closing various reagents, overcome the problem that boric acid solution mixes i.e. precipitating with poly-vinyl alcohol solution,
It can make at room temperature and clarify uniform and stable HfB2Precursor solution, and in process for preparation ethyl alcohol be added boric acid solution
In, polyvinyl alcohol be required to directly be quickly poured into when being added in boric acid alcohol solution, and in the past when preparing solution, adding manner
It being often slowly dropped in other solution, this process of the invention has not only been saved the time, and it is also easy to operate, without special
Equipment is added directly into HfB in the form of SiBNC nano ceramic powder in the present invention2In precursor solution, due to SiBNC
With good high-temperature stability, HfB can be generated2With SiBNC, and side reaction is avoided, simple process, without specially setting
Standby, energy saving, pollution-free, the prices of raw materials are cheap, and are easily obtained, easy to accomplish, and the present invention can be in fiber surface system
The coating of standby uniformly continuous densification out.
Compared with prior art, the beneficial effects of the present invention are:
(1) present invention uses low temperature precursor solution infiltration pyrolysis method, with polyvinyl alcohol, boric acid, inorganic hafnium salt, SiBNC
Nano ceramic powder be raw material can mixed preparing precursor coating solution at room temperature, the prices of raw materials are cheap, are easily obtained, and are easy
It realizes, and preparation process is simple, no especial equipment requirements, energy conservation and environmental protection, strong operability, is suitble to industrialized production.
(2) in the present invention, fire-resistant oxidation resistant HfB2- SiBNC coating generates the required more previous powder of heat treatment temperature
Synthesis technology (1500 DEG C or more) is low, and HfB can be obtained at 1300 DEG C2- SiBNC composite coating, to reduce to equipment
It is required that energy saving.
(3) in the present invention, the HfB of obtained carbon fiber surface2- SiBNC composite coating is uniformly complete fine and close, no fine fisssure
Line, fire-resistant oxidation resistant are had excellent performance.
(4) in the present invention, small to Carbon Fiber Damage, obtained coating can improve between fiber and matrices of composite material
Interface compatibility problem.
(5) in the present invention, film thickness can be kept adjustable by changing coating liquid concentration, coating and drying process number,
Meet different demands.
Detailed description of the invention
Fig. 1 is the carbon fiber scanning electron microscope (SEM) photograph of non-coating.
Fig. 2 is carbon fiber surface HfB2The scanning electron microscope (SEM) photograph of-SiBNC composite coating.
Specific embodiment
To be more clear the objectives, technical solutions, and advantages of the present invention, the present invention is made below by specific embodiment
It further illustrates.
Embodiment 1
A kind of carbon fiber surface HfB2The preparation method of-SiBNC composite coating, it the following steps are included:
Using polyvinyl alcohol, deionized water as solvent, it is 1mol/L's that concentration is configured under conditions of 85 DEG C of heating stirrings
Poly-vinyl alcohol solution；It is 0.6mol/L's that boric acid, which is dissolved in deionized water to be configured to concentration under conditions of 60 DEG C of heating stirrings,
Boric acid solution；Chlorine hydrate hafnium oxide precursor material is completely dissolved in deionized water, at room temperature while stirring upwards
It states and ammonium hydroxide generation white flock precipitate (pH=9.5) is added dropwise in solution, by above-mentioned white precipitate deionized water centrifuge washing 4
It is secondary, white precipitate is then dissolved in nitric acid (pH=1.5), obtains the hafnium oxide colloidal sol that hafnium ion concentration is 0.5mol/L；
The ethyl alcohol of 33.97 deals is added in the boric acid solution of 16.19 deals according to volume fraction, it is mixed in room temperature with magnetic stirring apparatus
It closes uniformly (about 30 minutes), obtains precursor solution A；The poly-vinyl alcohol solution of 34.00 deals is quickly poured into above-mentioned solution A
(about 2~13 seconds), and it is stirred at room temperature uniformly mixed, obtain precursor solution B；Take the hafnium oxide colloidal sol of 5.84 deals with it is above-mentioned
Solution B mixing, obtains precursor solution C；The SiBNC nano ceramic powder of 10.00 deals is uniformly divided by magnetic agitation
It is dispersed in solution C, the coating solution is obtained after being stirred at room temperature 2~3 hours；Carbon fiber is placed in tube furnace in 450 DEG C
40 minutes progress degumming process of lower heat preservation will be impregnated etching 60 minutes except the carbon fiber after glue is placed in concentrated nitric acid, then be spent
Ionized water cleans carbon fiber surface Liquid Residue, obtains the carbon fiber of surface active；By the carbon fiber ultrasound after surface activation process
It is impregnated in above-mentioned coating solution 10 minutes, is put into baking oven after the carbon fiber after coating is stood 12 hours at room temperature in 60 DEG C
Carbon fiber, is then placed in tube furnace, is heated to 300 under nitrogen protection with the heating rate of 3 DEG C/min by heat preservation 60 minutes
DEG C heat preservation 10 minutes, then 550 DEG C are heated to the heating rate of 5 DEG C/min, 40 minutes are kept the temperature, then with the heating speed of 8 DEG C/min
Degree is heated to 800 DEG C, keeps the temperature 30 minutes, then is heated to 1300 DEG C of Pintsch process temperature with the heating rate of 6 DEG C/min, heat preservation
It 3 hours, obtains and is coated with HfB2The carbon fiber of-SiBNC coating, the thickness of coating are about 0.15 μm.
Embodiment 2
Carbon fiber is immersed in coating liquid, ultrasonic immersing 50 minutes, the carbon fiber after being coated, remaining processing step
And process conditions are same as Example 1.
It is obtained through above-mentioned steps and is coated with HfB2The carbon fiber of-SiBNC coating, the thickness of coating are about 0.81 μm.
Embodiment 3
By treated, carbon fiber is immersed in coating liquid, and ultrasonic immersing 100 minutes, the carbon fiber after being coated,
Remaining processing step and process conditions are same as Example 1.
It is obtained through above-mentioned steps and is coated with HfB2The carbon fiber of-SiBNC coating, the thickness of coating are about 1.68 μm.
Embodiment 4
A kind of carbon fiber surface HfB2The preparation method of-SiBNC composite coating, it the following steps are included:
Using polyvinyl alcohol, deionized water as solvent, it is 0.8mol/L that concentration is configured under conditions of 85 DEG C of heating stirrings
Poly-vinyl alcohol solution；It is 0.4mol/L that boric acid, which is dissolved in deionized water to be configured to concentration under conditions of 60 DEG C of heating stirrings,
Boric acid solution；Chlorine hydrate hafnium oxide precursor material is completely dissolved in deionized water, at room temperature while stirring to
Ammonium hydroxide is added dropwise in above-mentioned solution and generates white flock precipitate (pH=9.5), by above-mentioned white precipitate deionized water centrifuge washing 4
It is secondary, white precipitate is then dissolved in nitric acid (pH=1.8), obtains the hafnium oxide colloidal sol that hafnium ion concentration is 0.3mol/L；
The ethyl alcohol of 37.73 deals is added in the boric acid solution of 13.00 deals according to volume fraction, it is mixed in room temperature with magnetic stirring apparatus
It closes uniformly (about 30 minutes), obtains precursor solution A；The poly-vinyl alcohol solution of 24.06 deals is quickly poured into above-mentioned solution A
(about 2~13 seconds), and it is stirred at room temperature uniformly mixed, obtain precursor solution B；Take the hafnium oxide colloidal sol of 5.21 deals with it is above-mentioned
Solution B mixing, obtains precursor solution C；The SiBNC nano ceramic powder of 20.00 deals is uniformly divided by magnetic agitation
It is dispersed in solution C, the coating solution is obtained after being stirred at room temperature 2~3 hours；Carbon fiber is placed in tube furnace in 450 DEG C
30 minutes progress degumming process of lower heat preservation will be impregnated etching 90 minutes except the carbon fiber after glue is placed in concentrated nitric acid, then be spent
Ionized water cleans carbon fiber surface Liquid Residue, obtains the carbon fiber of surface active；By the carbon fiber ultrasound after surface activation process
It is impregnated in above-mentioned coating solution 40 minutes, is put into baking oven after the carbon fiber after coating is stood 12 hours at room temperature in 70 DEG C
Carbon fiber, is then placed in tube furnace, is heated to 300 under nitrogen protection with the heating rate of 3 DEG C/min by heat preservation 50 minutes
DEG C heat preservation 10 minutes, then 550 DEG C are heated to the heating rate of 5 DEG C/min, 40 minutes are kept the temperature, then with the heating speed of 10 DEG C/min
Degree is heated to 800 DEG C, keeps the temperature 30 minutes, then is heated to 1400 DEG C of Pintsch process temperature with the heating rate of 8 DEG C/min, heat preservation
It 3 hours, obtains and is coated with HfB2The carbon fiber of-SiBNC coating, the thickness of coating are about 0.42 μm.
Embodiment 5
Will treated that carbon fiber is immersed in colloidal sol, ultrasonic immersing 40 minutes, carbon fiber repeatedly by coating twice and
It is dried, furnace cooling in 2 hours is kept the temperature at 1350 DEG C, remaining processing step and process conditions are same as Example 4.
The thickness of the coating obtained through above-mentioned steps is about 0.89 μm.
Embodiment 6
A kind of carbon fiber surface HfB2The preparation method of-SiBNC composite coating, it the following steps are included:
Using polyvinyl alcohol, deionized water as solvent, it is 1.2mol/L that concentration is configured under conditions of 85 DEG C of heating stirrings
Poly-vinyl alcohol solution；It is 0.8mol/L that boric acid, which is dissolved in deionized water to be configured to concentration under conditions of 60 DEG C of heating stirrings,
Boric acid solution；Chlorine hydrate hafnium oxide precursor material is completely dissolved in deionized water, at room temperature while stirring to
Ammonium hydroxide is added dropwise in above-mentioned solution and generates white flock precipitate (pH=9.5), by above-mentioned white precipitate deionized water centrifuge washing 4
It is secondary, white precipitate is then dissolved in nitric acid (pH=1.6), obtains the hafnium oxide colloidal sol that hafnium ion concentration is 0.6mol/L；
The ethyl alcohol of 24.08 deals is added in the boric acid solution of 16.03 deals according to volume fraction, it is mixed in room temperature with magnetic stirring apparatus
It closes uniformly (about 30 minutes), obtains precursor solution A；The poly-vinyl alcohol solution of 38.48 deals is quickly poured into above-mentioned solution A
(about 2~13 seconds), and it is stirred at room temperature uniformly mixed, obtain precursor solution B；Take the solution oxide hafnium colloidal sol of 6.41 deals with
Above-mentioned solution B mixing, obtains precursor solution C；The SiBNC nano ceramic powder of 15.00 deals is uniform by magnetic agitation
Be dispersed in solution C, the coating solution is obtained after being stirred at room temperature 2~3 hours；By carbon fiber be placed in tube furnace in
35 minutes progress degumming process are kept the temperature at 450 DEG C, will be placed in immersion etching 70 minutes in concentrated nitric acid except the carbon fiber after glue, then
It is washed with deionized water carbon fiber surface Liquid Residue, obtains the carbon fiber of surface active；By the carbon fiber after surface activation process
Ultrasonic immersing 20 minutes in above-mentioned coating solution, be put into baking oven after the carbon fiber after coating is stood 12 hours at room temperature in
70 DEG C keep the temperature 50 minutes, and then carbon fiber is placed in tube furnace, is heated under nitrogen protection with the heating rate of 3 DEG C/min
300 DEG C keep the temperature 10 minutes, then are heated to 550 DEG C with the heating rate of 5 DEG C/min, keep the temperature 40 minutes, then with the heating of 9 DEG C/min
Speed is heated to 800 DEG C, keeps the temperature 30 minutes, then is heated to 1500 DEG C of Pintsch process temperature with the heating rate of 7 DEG C/min, protects
Temperature 3 hours obtains and is coated with HfB2The carbon fiber of-SiBNC coating, the thickness of coating are about 0.52 μm.
It needs to illustrate, the above is only part preferred embodiments of the invention, it should be appreciated that there are also other real by the present invention
Example is applied, specific example described herein for explaining only the invention, is not intended to limit the scope of the present invention, the skill of this field
Art personnel above content according to the present invention is made some nonessential modifications and adaptations and is all belonged to the scope of protection of the present invention.
Claims (7)
1. a kind of carbon fiber surface HfB2The preparation method of-SiBNC composite coating, the method are low temperature precursor solution dipping
Cracking process, comprising: the preparation of coating solution, carbon fiber surface activation processing, coating, dry and heat treatment；It is characterized in that, described
The preparation of coating solution includes the following steps:
A) using polyvinyl alcohol, boric acid as solute, deionized water is solvent, prepares boric acid solution and poly-vinyl alcohol solution respectively；
B) inorganic hafnium salt is dissolved in deionized water and uniformly mixed, addition ammonium hydroxide adjusting pH value to 9.5, generation white is stirred at room temperature
Precipitating, will be dissolved in nitric acid with the white precipitate after deionized water eccentric cleaning, is controlled solution ph less than 2, is aoxidized
Hafnium colloidal sol；
C) ethyl alcohol is added in boric acid solution and is stirred at room temperature to it and is uniformly mixed, obtain boric acid alcohol solution；
D) by poly-vinyl alcohol solution be quickly poured into it is above-mentioned c) in and be stirred at room temperature to its be uniformly mixed；
E) above-mentioned colloidal sol b) is mixed with above-mentioned solution d), it is finally that SiBNC nano ceramic powder is uniform by magnetic agitation
It is dispersed in above-mentioned mixed solution, the coating solution is obtained after being stirred at room temperature 2~3 hours.
2. a kind of carbon fiber surface HfB as described in claim 12The preparation method of-SiBNC composite coating, which is characterized in that
Boric acid solution concentration described in above-mentioned steps a) is 0.4~0.8mol/L, and poly-vinyl alcohol solution concentration is 0.8~1.2mol/
L；Inorganic hafnium salt described in step b) is HfOCl2·8H2O、Hf(NO3)4·xH2O、HfO(NO3)2·xH2O、HfCl4、Hf
(SO4)2One of aqueous inorganic salt, hafnium ion concentration can be existed by the way that the amount of deionized water is added in the hafnium oxide colloidal sol
It is adjusted between 0.3~0.6mol/L；The volume ratio of ethyl alcohol described in step c) and boric acid solution is (1.2~2.8): 1；Step
E) polyvinyl alcohol in the coating solution described in, boric acid, hafnium ion molar ratio be (3.5~3.7): (0.9~1.1): (0.20~
0.43)。
3. a kind of carbon fiber surface HfB as described in claim 12The preparation method of-SiBNC composite coating, which is characterized in that
Above-mentioned steps 1) described in the particle size of SiBNC nano ceramic powder be 40~80nm, SiBNC nanometers in the coating solution
The volume content of ceramic powders is 10~20%.
4. a kind of carbon fiber surface HfB as described in claim 12The preparation method of-SiBNC composite coating, which is characterized in that
The carbon fiber surface activation processing refers to that carbon fiber is placed in tube furnace keeps the temperature progress degumming in 30~40 minutes at 450 DEG C
Processing will impregnate etching 60~100 minutes except the carbon fiber after glue is placed in concentrated nitric acid, then be washed with deionized water carbon fiber
Drying for standby after remained on surface liquid.
5. a kind of carbon fiber surface HfB as described in claim 12The preparation method of-SiBNC composite coating, which is characterized in that
The coating refers to carbon fiber ultrasonic immersing 10~100 minutes in coating solution；The drying refers to will be after coating
Carbon fiber stands 12~15 hours at room temperature, is finally putting into baking oven and keeps the temperature 40~60 minutes in 60~70 DEG C.
6. a kind of carbon fiber surface HfB as described in claim 12The preparation method of-SiBNC composite coating, which is characterized in that
The heat treatment, which refers to, is placed in carbon fiber in tube furnace, is added under inert gas protection with the heating rate of 2~3 DEG C/min
Heat keeps the temperature 10~15 minutes to 300 DEG C, then is heated to 550 DEG C with the heating rate of 5 DEG C/min, keeps the temperature 30~60 minutes, then with 8
The heating rate of~10 DEG C/min is heated to 800 DEG C, keeps the temperature 30~60 minutes, then is heated with the heating rate of 6~8 DEG C/min
To 1300~1500 DEG C of Pintsch process temperature, 2~3 hours are kept the temperature, obtains and is coated with HfB2The carbon fiber of-SiBNC coating.
7. a kind of carbon fiber surface HfB as described in claim 12The preparation method of-SiBNC composite coating, which is characterized in that
The coating and drying process can at most be repeated 3 times, can be used to control the thickness of film, obtained coating
Thickness is within 2 μm.
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| CN201910737169.8A Withdrawn CN110396816A (en) | 2019-08-11 | 2019-08-11 | A kind of carbon fiber surface HfB2The preparation method of-SiBNC composite coating |
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