CN110396817A - A kind of carbon fiber surface HfZrB2The preparation method of coating - Google Patents
A kind of carbon fiber surface HfZrB2The preparation method of coating Download PDFInfo
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Abstract
The invention discloses a kind of carbon fiber surface HfZrB2The preparation method of 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 is activated, coating, dry and be heat-treated HfZrB to get fire-resistant oxidation resistant2Carbon 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 HfZrB2The system of coating
Preparation Method.
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 material, carbon fiber is easy to react with certain matrixes, to damage fiber, seriously reduces the property of composite material
Energy.
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) and zirconium boride (ZrB2) all have it is good
High-temperature stability well, inoxidizability simultaneously have good chemical compatibility with carbon fiber, can preferably meet hyperthermal environments
Under requirement, these advantages become a kind of fire-resistant oxidation resistant coating with development potential.HfB2With ZrB2Master
Preparation method is wanted to have metal and boron flux synthesis procedure, carbon reduction method, self-propagating high-temperature synthesis, change in inert gas or vacuum
Learn vapor infiltration method.The route that previous hafnium boride is synthesized with zirconium boride is mainly: will synthesize HfB2With ZrB2Required powder former material
Material is mixed in a certain ratio, and reaction generates HfB at high temperature2With ZrB2, this method, which is not suitable for preparing in carbon fiber surface, to be applied
Layer, and synthesis reaction temperature is high, impurity is high；CVD technique prepares HfB2With ZrB2, find suitable HfB2With ZrB2Precursor and
Presoma is more toxic, and synthesis reaction temperature is high, and complex process needs special equipment, and is unsuitable for the equal of multidimensional fiber surface
Even coating；Using organic polymer cracking process, need first to prepare precursor polymer, then Pintsch process goes out HfB2With ZrB2, this
Kind method is complicated for operation, and is unsuitable for preparing fine and close interface phase coating in fiber surface.2009, Chinese invention patent CN
101428812A discloses a kind of preparation method of high-purity hafnium boride powder, it is fixed with hafnium oxide, boron carbide, graphite, nothing
Type boron is raw material, at 1500~1600 DEG C based on a kind of method of carbon heat/boron thermal reduction reaction preparation boronation hafnium powder, this method
Synthesis reaction temperature is high, and energy consumption is high, and is not suitable in carbon fiber surface prepares coating.2014, Chinese invention patent CN
103757603 A disclose a kind of preparation method of zirconium diboride coating, it is with ZrCl4、BCl3And H2As source gas, Ar
Gas or N2As carrier gas and protective gas, zirconium diboride coating is prepared using chemical vapour deposition technique, preparation process is complicated, item
Part is harsh, and temperature is high, and energy consumption is high, needs special equipment, and be unsuitable for the uniform coating of multidimensional fiber surface.2017, China
107523778 A of patent of invention CN discloses the preparation method of hafnium boride composite coating, it is multiple with hafnium oxide/boron carbide/aluminum
It closes powder and relates generally to boronation using in thermal spraying in-situ reactive synthesis hafnium boride composite coating according to certain proportion for raw material
Object is unsuitable for preparing fine and close interface phase coating in fiber surface to the plating of the base materials such as metal, ceramics.2015, in
105331921 A of state patent of invention CN discloses a kind of spraying powder, thermal spraying in-situ synthesis of boride zirconium-carbonization zirconia-based ceramic
Coating and preparation method thereof, it is raw material according to certain proportion that it, which is to include aluminium powder, zirconium powder and boron carbide powder, using in heat
Spray in-situ reactive synthesis zirconium boride composite coating, the preparation method of zirconium boride composite coating, relate generally to boride to metal,
The plating of the base materials such as ceramics is unsuitable for preparing fine and close interface phase coating in fiber surface.The present invention be with polyvinyl alcohol,
Boric acid, inorganic hafnium salt and inorganic zirconium salts are raw material, and the low temperature precursor solution infiltration pyrolysis method of use is suitable for variform
Carbon fiber surface coating, the preparation method have not only prepared the HfZrB of uniformly continuous densification in carbon fiber surface2Coating, and
And a certain amount of zirconium of doping is conducive to the reduction of Pintsch process temperature, it is energy saving, and entire coating liquid preparation process, technique letter
It is single, it is not necessarily to special equipment, the prices of raw materials are cheap, and are easily obtained, and it is easy to accomplish, it is formed after lower heat treatment temperature
Coating, not only improve the antioxygenic property of fiber and the interface problem of fiber and matrix, also overcome 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 HfZrB is provided2Coating
Preparation method.
The present invention is achieved by the following technical solutions: first with polyvinyl alcohol, boric acid, inorganic hafnium salt, inorganic zirconium salts
For precursor, the hafnium oxide colloidal sol adulterated respectively with preparing boric acid group water solution, polyvinyl alcohol group water solution, zirconium is subsequent to prevent
Precipitation reaction occurs for poly-vinyl alcohol solution and boric acid, and modifying agent ethyl alcohol first is added in boric acid solution and is stirred at room temperature to its mixing
Uniformly, boric acid alcohol solution is obtained, is quickly poured into poly-vinyl alcohol solution into above-mentioned solution later, is eventually adding the oxygen of zirconium doping
Change hafnium colloidal sol to be uniformly mixed to obtain coating solution；Again by the impregnated carbon fiber after surface activation process in coating solution, obtain
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 HfZrB2The carbon fiber of 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) using inorganic hafnium salt and inorganic zirconium salts as raw material, wherein the doping concentration of zirconium is 1~50mol%, and raw material is dissolved in
Deionized water is simultaneously stirred at room temperature uniformly mixed, and ammonium hydroxide is added and adjusts pH value to 9.5, generates white precipitate, will with deionized water from
White precipitate after heart cleaning is dissolved in nitric acid, is controlled solution ph less than 2, is obtained the hafnium oxide colloidal sol of zirconium doping；
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 added in above-mentioned solution d), the coating is obtained after being stirred at room temperature 2~3 hours
Liquid.
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 adopt and be washed with deionized water carbon
Drying for standby after fiber surface Liquid Residue.
B) coat and be dried: by the carbon fiber ultrasonic immersing after surface activation process in above-mentioned steps 1) in obtain
Coating solution C in 10~120 minutes, the carbon fiber after coating is stood 12~16 hours at room temperature, is then placed in baking oven
40~60 minutes are kept the temperature in 60~70 DEG C.
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 1200~1400 DEG C of Pintsch process temperature, keeps the temperature 2~3 hours, obtains and is coated with HfZrB2The carbon of coating
Fiber.
Further, above-mentioned steps 1) described in boric acid solution concentration be 0.4~0.8mol/L.
Further, above-mentioned steps 1) described in poly-vinyl alcohol solution concentration be 0.8~1.2mol/L.
Further, 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, the inorganic zirconium salts are ZrOCl2·8H2O、Zr
(NO3)4·xH2O、ZrO(NO3)2·xH2O、ZrCl4、Zr(SO4)2One of aqueous inorganic salt, the zirconium adulterate hafnium oxide
Hafnium and zirconium ion concentration can be adjusted between 0.3~0.6mol/L by the way that the amount of deionized water is added in colloidal sol.
Further, above-mentioned steps 1) described in ethyl alcohol and boric acid solution volume ratio be (1.2~2.8): 1.
Further, above-mentioned steps 1) described in coating solution in polyvinyl alcohol, boric acid, the total ion molar ratio of hafnium zirconium be
(3.5~3.7): (0.9~1.1): (0.20~0.43).
Further, above-mentioned steps 2) described in coating and be dried and can at most be repeated 3 times, then again into
The subsequent coating heat treatment of row, can control the thickness of coating.
Further, the thickness of the coating is within 2 μm.
Further, the coating refers to HfZrB2Coating.
Further, the carbon fiber be one of carbon fiber bundle, carbon cloth and three-dimensional carbon fiber precast body or
It 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 HfZrB2Precursor solution, so that it is not had flocculate, be a difficult thing.
In the method for the invention, previous preparation HfB is changed2With ZrB2Main method: HfB will be synthesized2With ZrB2It is required
Powder raw material be mixed in a certain ratio, at high temperature reaction generate HfB2With ZrB2, this method is not suitable in carbon fiber
Surface prepares coating, and synthesis reaction temperature is high, impurity is high；CVD technique prepares HfB2With ZrB2, find suitable HfB2With
ZrB2Precursor and presoma is more toxic, synthesis reaction temperature is high, and complex process needs special equipment, and is unsuitable for multidimensional
The uniform coating of fiber surface；Using organic polymer cracking process, need first to prepare precursor polymer, then Pintsch process goes out
HfB2With ZrB2, 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 HfZrB2Precursor 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, whole preparation process simple process is energy saving, and pollution-free, the prices of raw materials are cheap, and are easily obtained, easy to accomplish,
And the present invention can prepare the coating of uniformly continuous densification in fiber surface.
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, inorganic zirconium
Salt is raw material, and the prices of raw materials are cheap, pollution-free, is easily obtained, easy to accomplish, and preparation process is simple, and no special installation is wanted
It asks, strong operability, is suitble to industrialized production.
(2) in the present invention, when low temperature precursor solution infiltration pyrolysis method prepares carbon fiber surface coating, needed for coating generates
The more previous technique of heat treatment temperature (1400 DEG C or more) it is low, in HfB2Zirconium is adulterated in coating to be obtained at 1200 DEG C of lower temperature
To HfZrB2Coating, so that the requirement to equipment is reduced, it is energy saving.
(3) in the present invention, carbon fiber surface HfZrB2Coating uniform is completely fine and close, non-microcracked, high-temperature oxidation resistance
It is excellent.
(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 solution 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 HfZrB2The scanning electron microscope (SEM) photograph of 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 HfZrB2The preparation method of 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 and chlorine hydrate zirconium oxide precursor material are completely dissolved in deionized water, in room
Ammonium hydroxide is added dropwise into above-mentioned solution while stirring under temperature and generates white flock precipitate (pH=9.5), above-mentioned white precipitate is spent
Ionized water centrifuge washing 4 times, white precipitate is then dissolved in nitric acid (pH=1.5), obtaining zirconium doping concentration is 50mol%
Ion concentration be 0.5mol/L zirconium adulterate hafnium oxide colloidal sol；The ethyl alcohol of 39.53 deals is added to according to volume fraction
It is uniform (about 30 minutes) in mixed at room temperature with magnetic stirring apparatus in the boric acid solution of 17.48 deals, obtain precursor solution A；It will
The poly-vinyl alcohol solution of 36.70 deals is quickly poured into above-mentioned solution A (about 2~13 seconds), and is stirred at room temperature uniformly mixed, obtains
To precursor solution B；It takes the Sol A of 6.29 deals to mix with above-mentioned solution B, is obtained after being stirred at room temperature 2~3 hours described
Coating solution；Carbon fiber is placed in tube furnace and keeps the temperature 40 minutes progress degumming process at 450 DEG C, will be set except the carbon fiber after glue
It is impregnated in concentrated nitric acid etching 60 minutes, is then washed with deionized water carbon fiber surface Liquid Residue, obtains the carbon of surface active
Fiber；By the carbon fiber ultrasonic immersing after surface activation process 10 minutes in above-mentioned coating solution, the carbon fiber after coating is existed
It is put into baking oven after standing 12 hours at room temperature and keeps the temperature 60 minutes in 60 DEG C, then carbon fiber is placed in tube furnace, in nitrogen
300 DEG C are heated to the heating rate of 3 DEG C/min under protection and keeps the temperature 10 minutes, then are heated to 550 with the heating rate of 5 DEG C/min
DEG C, 40 minutes are kept the temperature, then be heated to 800 DEG C with the heating rate of 8 DEG C/min, keeps the temperature 30 minutes, then with the heating of 6 DEG C/min
Speed is heated to 1200 DEG C of Pintsch process temperature, keeps the temperature 3 hours, obtains and is coated with HfZrB2The carbon fiber of coating, the thickness of coating
About 0.10 μm of degree.
Embodiment 2
Carbon fiber is immersed in coating liquid, ultrasonic immersing 70 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 HfZrB2The carbon fiber of coating, the thickness of coating are about 0.86 μm.
Embodiment 3
By treated, carbon fiber is immersed in coating liquid, and ultrasonic immersing 120 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 HfZrB2The carbon fiber of coating, the thickness of coating are about 1.63 μm.
Embodiment 4
A kind of carbon fiber surface HfZrB2The preparation method of 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 and chlorine hydrate zirconium oxide precursor material are completely dissolved in deionized water, In
Ammonium hydroxide is added dropwise into above-mentioned solution while stirring at room temperature and generates white flock precipitate (pH=9.5), above-mentioned white precipitate is used
Deionized water centrifuge washing 4 times, white precipitate is then dissolved in nitric acid (pH=1.8), obtaining zirconium doping concentration is
The hafnium oxide Sol A that the zirconium that the ion concentration of 17mol% is 0.3mol/L adulterates；According to volume fraction by the second of 46.89 deals
Alcohol is added in the boric acid solution of 16.34 deals, uniform (about 30 minutes) in mixed at room temperature with magnetic stirring apparatus, obtains precursor
Solution B；The poly-vinyl alcohol solution of 30.23 deals is quickly poured into above-mentioned solution B (about 2~13 seconds), and is stirred at room temperature mixed
It closes uniformly, obtains precursor solution C；It takes the Sol A of 6.54 deals to mix with above-mentioned solution C, is stirred at room temperature 2~3 hours
The coating solution is obtained afterwards；Carbon fiber is placed in tube furnace and keeps the temperature 30 minutes progress degumming process at 450 DEG C, it will be except after glue
Carbon fiber be placed in concentrated nitric acid impregnate etching 100 minutes, be then washed with deionized water carbon fiber surface Liquid Residue, obtain table
The carbon fiber of face activation；By the carbon fiber ultrasonic immersing after surface activation process 40 minutes in above-mentioned coating solution, after coating
Carbon fiber stand 12 hours at room temperature after be put into baking oven in 70 DEG C keep the temperature 50 minutes, carbon fiber is then placed in tube furnace
In, 300 DEG C are heated to the heating rate of 3 DEG C/min under nitrogen protection and keeps the temperature 10 minutes, then with the heating rate of 5 DEG C/min
Be heated to 550 DEG C, keep the temperature 40 minutes, then be heated to 800 DEG C with the heating rate of 10 DEG C/min, keep the temperature 30 minutes, then with 8 DEG C/
The heating rate of min is heated to 1400 DEG C of Pintsch process temperature, keeps the temperature 3 hours, obtains and is coated with HfZrB2The carbon fiber of coating
Dimension, the thickness of coating is about 0.34 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 1400 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 0.73 μm.
Embodiment 6
A kind of carbon fiber surface HfZrB2The preparation method of 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 and chlorine hydrate zirconium oxide precursor material are completely dissolved in deionized water, In
Ammonium hydroxide is added dropwise into above-mentioned solution while stirring at room temperature and generates white flock precipitate (pH=9.5), above-mentioned white precipitate is used
Deionized water centrifuge washing 4 times, white precipitate is then dissolved in nitric acid (pH=1.6), obtaining zirconium doping concentration is
The hafnium oxide Sol A that the zirconium that the ion concentration of 25mol% is 0.6mol/L adulterates；According to volume fraction by the second of 28.90 deals
Alcohol is added in the boric acid solution of 18.71 deals, uniform (about 30 minutes) in mixed at room temperature with magnetic stirring apparatus, obtains precursor
Solution B；The poly-vinyl alcohol solution of 44.91 deals is quickly poured into above-mentioned solution B (about 2~13 seconds), and is stirred at room temperature mixed
It closes uniformly, obtains precursor solution C；The solution oxide hafnium of 7.48 deals is taken to mix with zirconium oxide complex sol with above-mentioned solution C,
The coating solution is obtained after being stirred at room temperature 2~3 hours；Carbon fiber is placed in tube furnace at 450 DEG C and keeps the temperature 30 minutes
Degumming process is carried out, will be impregnated etching 80 minutes except the carbon fiber after glue is placed in concentrated nitric acid, be then washed with deionized water carbon
Fiber surface Liquid Residue obtains the carbon fiber of surface active；By the carbon fiber ultrasonic immersing after surface activation process in above-mentioned painting
20 minutes in layer liquid, it is put into baking oven after the carbon fiber after coating is stood 12 hours at room temperature and keeps the temperature 50 minutes in 70 DEG C,
Then carbon fiber is placed in tube furnace, is heated to 300 DEG C under nitrogen protection with the heating rate of 3 DEG C/min and keeps the temperature 10 points
Clock, then 550 DEG C are heated to the heating rate of 5 DEG C/min, 40 minutes are kept the temperature, then be heated to 800 with the heating rate of 9 DEG C/min
DEG C, 30 minutes are kept the temperature, then be heated to 1300 DEG C of Pintsch process temperature with the heating rate of 7 DEG C/min, keep the temperature 3 hours, obtained
Coated with HfZrB2The carbon fiber of coating, the thickness of coating are about 0.46 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 (6)
1. a kind of carbon fiber surface HfZrB2The preparation method of coating, the method are low temperature precursor solution infiltration pyrolysis method, packet
It includes: the preparation of coating solution, carbon fiber surface activation processing, coating, dry and heat treatment；It is characterized in that, the coating solution
Preparation 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) using inorganic hafnium salt and inorganic zirconium salts as raw material, wherein the doping concentration of zirconium be 1~50mol%, by raw material be dissolved in from
Simultaneously uniformly mixed, addition ammonium hydroxide adjusting pH value to 9.5 is stirred at room temperature in sub- water, and generation white precipitate will be centrifuged clear with deionized water
White precipitate after washing is dissolved in nitric acid, is controlled solution ph less than 2, is obtained the hafnium oxide colloidal sol of zirconium doping；
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 added in above-mentioned solution d), the coating solution is obtained after being stirred at room temperature 2~3 hours.
2. a kind of carbon fiber surface HfZrB as described in claim 12The preparation method of coating, which is characterized in that above-mentioned steps
A) the boric acid solution concentration described in is 0.4~0.8mol/L, and poly-vinyl alcohol solution concentration is 0.8~1.2mol/L；Step b)
Described in inorganic hafnium salt be HfOCl2·8H2O、Hf(NO3)4·xH2O、HfO(NO3)2·xH2O、HfCl4、Hf(SO4)2It is aqueous
One of inorganic salts, the inorganic zirconium salts are ZrOCl2·8H2O、Zr(NO3)4·xH2O、ZrO(NO3)2·xH2O、
ZrCl4、Zr(SO4)2One of aqueous inorganic salt, hafnium ion and zirconium ion concentration in the hafnium oxide colloidal sol of the described zirconium doping
It can be adjusted between 0.3~0.6mol/L by the way that the amount of deionized water is added；Ethyl alcohol described in step c) and boric acid solution
Volume ratio is (1.2~2.8): 1；Polyvinyl alcohol, boric acid, the total ion molar ratio of hafnium zirconium are in coating solution described in step e)
(3.5~3.7): (0.9~1.1): (0.20~0.43).
3. a kind of carbon fiber surface HfZrB as described in claim 12The preparation method of 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 30~40 minutes progress degumming process at 450 DEG C, will
It is impregnated etching 60~100 minutes except the carbon fiber after glue is placed in concentrated nitric acid, it is residual to be then washed with deionized water carbon fiber surface
Stay drying for standby after liquid.
4. a kind of carbon fiber surface HfZrB as described in claim 12The preparation method of coating, which is characterized in that the painting
It covers and refers to carbon fiber ultrasonic immersing 10~120 minutes in coating solution；The drying, which refers to, exists the carbon fiber after coating
12~16 hours are stood at room temperature, is finally putting into baking oven and keeps the temperature 40~60 minutes in 60~70 DEG C.
5. a kind of carbon fiber surface HfZrB as described in claim 12The preparation method of coating, which is characterized in that the heat
Processing, which refers to, is placed in carbon fiber in tube furnace, is heated to 300 under inert gas protection with the heating rate of 2~3 DEG C/min
DEG C heat preservation 10~15 minutes, then be heated to 550 DEG C with the heating rate of 5 DEG C/min, keep the temperature 30~60 minutes, then with 8~10 DEG C/
The heating rate of min is heated to 800 DEG C, keeps the temperature 30~60 minutes, then be heated to high temperature with the heating rate of 6~8 DEG C/min
1200~1400 DEG C of cracking temperature, 2~3 hours are kept the temperature, obtains and is coated with HfZrB2The carbon fiber of coating.
6. a kind of carbon fiber surface HfZrB as described in claim 12The preparation method of coating, which is characterized in that the painting
Covering and being dried can at most be repeated 3 times, can be used to control the thickness of film, the thickness of obtained coating is in 2 μ
Within m.
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