CN110451969A - Carbon fiber-zirconium carbide composite material and preparation method - Google Patents
Carbon fiber-zirconium carbide composite material and preparation method Download PDFInfo
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Abstract
The present invention provides a kind of carbon fiber-zirconium carbide composite material and preparation method, and the preparation method includes the following steps: raw material preparation process, provides zirconium carbide nano-powder and zirconium carbide precursor sol；The zirconium carbide nano-powder, dispersing agent and deionized water are configured to the zirconium carbide slurry that solid volume content is 50~57vol.% by the preparation step of zirconium carbide slurry；The zirconium carbide slurry is coated on carbon fiber knitted body so that its density, and dries in a vacuum drying oven by zirconium carbide coating step, obtains the carbon fiber knitted body coated with zirconium carbide；The carbon fiber knitted body coated with zirconium carbide is immersed in 10~60min in the zirconium carbide precursor sol by impregnation steps；Cleavage step, carbon fiber knitted body taking-up after the dipping is dried in a vacuum drying oven, hereafter it is put into and cracks and keep the temperature 0.5~2h in sintering furnace at 1400~1600 DEG C in an inert gas atmosphere, then cool to room temperature with the furnace, obtain the carbon fiber-carbonization zirconium composite material.
Description
Technical field
The invention belongs to new material technology fields, and in particular to carbon fiber-zirconium carbide composite material and preparation method.
Background technique
New high-tech material is the important symbol for measuring the development such as national economy, technology, a national defence.Since 21 century, the world
Each state all using have at high speed, high-intensitive and high reliability hypersonic vehicle as main direction of studying, and it is this with
Space shuttle, strategic missile and carrier rocket are that the development of the hypersonic vehicle of representative will play certainly nation's security
Qualitative effect, while also to the high temperature resistant of hyperthermal material, mechanical property and Burning corrosion resistance can more stringent requirements are proposed.
Hyperthermal material is the material for referring to work normally in 2000 DEG C or more high temperature, mainly includes refractory metal material
(zirconium, hafnium, tantalum, tungsten, molybdenum etc.), graphite material, carbon carbon composite and superhigh temperature ceramics and its composite material etc..But due to infusibility
Metal material density is big, oxidizable under high temperature, and graphite material intensity is gradually reduced in 2500 DEG C or more high temperature, carbon carbon composite
Too poor etc. reasons of inoxidizability cannot be all used widely.
Superhigh temperature ceramics mainly include the carbide, nitride and boride of refractory metal, modulus height high with intensity,
Various advantages such as Burning corrosion resistance is good, the deficiency in terms of making up fracture toughness by the way that fiber is added, availability are excellent
Ultra-temperature ceramic-based composite material.Fiber largely determines the final performance of ultra-temperature ceramic-based composite material, mesh
Before the fiber commercially produced mainly have glass fibre (Gf), quartz fibre, silicon carbide fibre and carbon fiber etc., but due to glass
The structure of glass fiber, quartz fibre and silicon carbide fibre is easy to happen variation in hyperthermal environments, cause its performance sharply under
It drops and cannot use.And carbon fiber has the characteristics that density is low, intensity is high, fracture toughness is good, can protect in hyperthermal environments
It is fixed to keep steady, and is the currently the only commercialization fiber used in hyperthermal environments.Therefore, using fibre reinforced superhigh temperature ceramics
It can make its mutual supplement with each other's advantages, not only have the advantages that carbon fiber density is low, fracture toughness is high, and there is superhigh temperature ceramics power
Performance height and the good feature of erosion are learned, to meet the requirement in hyperthermal environments.
Meanwhile superhigh temperature ceramics are again because the significant difference of physics and chemical property causes it to make pottery in fiber reinforcement superhigh temperature
Application in porcelain based composites exists apparent different.Tantalum compound density is bigger, and anti-burning in an oxidizing environment
Corrosion can be poorer than hafnium compound and zirconium compounds.Although the property of hafnium compound and zirconium compounds is very close, due to it
The reasons such as content is few, expensive, density is big limit application range.
The matrix research of fibre reinforced ultra-temperature ceramic-based composite material is mainly zirconium compounds at present, is especially carbonized
Zirconium (ZrC).It is few about report in this respect but due to the relevant technologies concerning security matters of fibre reinforced ZrC composite material
Road.
Preparation method is to influence another key factor of ultra-temperature ceramic-based composite material performance, determines the equal of matrix
Interface cohesion situation between even property and consistency, the distribution of fiber and matrix and fiber.Currently, ultra-temperature ceramic-based
Composite material and preparation method thereof mainly has chemical vapor infiltration (Chemical vapor infiltration, CVI), metal molten
Melt method of impregnation (Reactive melting infiltration, RMI) etc..Chemical vapor infiltration can be at a lower temperature
Complex-shaped and dead size superhigh temperature ceramics matrix material is prepared, but that there are consistency is low, the production cycle is long and preparation
Disadvantage at high cost.Metal melting method of impregnation be by molten metal penetrate into porous preform in, then with prefabricated component or atmosphere ring
Border reaction generate ceramic matrix, have it is with short production cycle, can prepare complex-shaped, dead size superhigh temperature ceramics matrix material excellent
Point, but its preparation temperature is high, metal bath easily reduces fibre property with fiber-reactive and causes metal residual.
Summary of the invention
In view of this, a kind of the purpose of the present invention is to provide consistency high, with short production cycle, at low cost, bending strength
With fracture toughness height, the good carbon fiber of erosion performance-carbonization zirconium composite material preparation method.
It is another object of the present invention to provide a kind of carbon fiber-carbonization zirconium composite materials.
In order to achieve the above object, the present inventor is for by repeatedly the study found that polymer infiltration and pyrolysis method is true
So that superhigh temperature ceramics presoma is penetrated into prefabricated component under empty or pressure state, successively converts presoma by crosslinking and cracking technology
For ceramic matrix, repeats its dipping-crosslinking-cracking process and finally obtain the ultra-temperature ceramic-based composite material haveing excellent performance.
This method simple process, preparation temperature are low, can prepare complex-shaped and dead size component excellent characteristics necessarily to lead to it
In the extensive use of ultra-temperature ceramic-based composite material.
In addition, the inventors of the present invention also found, success prepares the key of high-performance ultra-temperature ceramic-based composite material
Can place be obtain suitable superhigh temperature ceramics presoma, and has carried out depth to superhigh temperature ceramics presoma on this basis
Enter research.The research of superhigh temperature ceramics presoma is broadly divided into two methods.A kind of method is by chemical reactive synthesis infusibility
Organometallic polymer presoma, the presoma contain the chemical bonds such as M-C or M-B (M:Zr, Hf, Ta etc.), can be straight after cracking
It connects to form MC or MB superhigh temperature ceramics；Another method is the presoma that multicomponent mixing is prepared using sol-gel method, before this
Drive body by sol-gel, be crosslinked, cracking obtains the mixture containing elements such as refractory metal, carbon, boron or nitrogen, then through high temperature
Reaction, obtains required superhigh temperature ceramics.Organic polymer using first method synthesis refractory metal is relatively difficult.It is another
Aspect, sol-gel method can be with the uniform presomas of synthetic molecules rank, and durings sol-gel, crosslinking and cracking etc.
Not phenomena such as not generating split-phase and crystallization, therefore carbon fiber/carbonization zirconium composite material is prepared using the method, it can have excellent
Performance.But at present using sol-gel method prepare zirconium carbide presoma exist using raw material is various, production technology is complicated,
The disadvantage and use polymer infiltration and pyrolysis method of experiment condition harshness prepare carbon fiber/carbonization zirconium composite material, and there are PIP weights
Again the deficiencies of number is too many, composite material consistency is not high, capability of heat etching resistance is poor, it would be highly desirable to simplify production technology, improve composite wood
Expect performance.
On the basis of above-mentioned discovery, the present invention completes the present invention by deeply studying repeatedly.
According to a first aspect of the present invention, a kind of preparation method of carbon fiber-carbonization zirconium composite material is provided, including is walked as follows
It is rapid:
Raw material preparation process provides zirconium carbide nano-powder and zirconium carbide precursor sol；
The zirconium carbide nano-powder, dispersing agent and deionized water are configured to solid by the preparation step of zirconium carbide slurry
Phase volume content is the zirconium carbide slurry of 50~57vol.%；
The zirconium carbide slurry is coated on carbon fiber knitted body so that its density by zirconium carbide coating step, and true
It is dry in empty drying box, obtain the carbon fiber knitted body coated with zirconium carbide；
The carbon fiber knitted body coated with zirconium carbide is immersed in the zirconium carbide precursor sol by impregnation steps
10~60min；
Carbon fiber knitted body taking-up after the dipping is dried in a vacuum drying oven, is hereafter put into burning by cleavage step
It cracks and keeps the temperature 0.5~2h in freezing of a furnace at 1400~1600 DEG C in an inert gas atmosphere, then cool to room temperature with the furnace, obtain
To the carbon fiber-carbonization zirconium composite material.
Further, which can also include the following steps:
Densification steps, impregnation steps described in repetitive operation and cleavage step 3~4 times are multiple to improve carbon fiber-zirconium carbide
The consistency of condensation material.
Wherein, the zirconium carbide precursor sol can be prepared by following preparation methods:
It is put into conical flask after zirconium compounds and carbon compound are weighed in an inert gas atmosphere, is configured to mix molten
Liquid；
After oil bath heating 2~5 hours, be added deionized water, and 80~120 DEG C at a temperature of continue stirring 2~5 hours
Obtain the zirconium carbide precursor sol.
Further, the zirconium carbide nano-powder can be prepared by the zirconium carbide precursor sol, preparation
Method may include:
The zirconium carbide precursor sol is placed in sintering furnace, in an inert gas atmosphere in 200~400 DEG C of temperature
1~3h of chemical crosslinking is carried out under degree；
Hereafter, continuation is warming up to 1400~1600 DEG C with the rate of 5~10 DEG C/min and is cracked and kept the temperature 0.5~2h,
Subsequent natural cooling obtains the zirconium carbide nano-powder.
Wherein, the molar ratio of the zirconium compounds and the carbon compound is 1:2~4, the deionized water and the zirconium
The molar ratio of compound is 1~3:1.
Preferably, the zirconium compounds is or mixtures thereof tetrabutyl zirconate or zirconium oxychloride, and the carbon compound is second
Or mixtures thereof acyl acetone, benzoyl acetone, 1,3- diphenyl -1,3- propanedione.
Preferably, the dispersing agent is or mixtures thereof polyacrylic acid, polyethylene glycol, polyetherimide, the dispersing agent
Content in the zirconium carbide slurry is 0.1~1.0wt%.
Preferably, in the zirconium carbide coating step, the carbon fiber knitted body passes through chemical vapor infiltration before the use
Saturating method carries out density, and used carbon source gas is CH4, carrier gas H2And N2。
Preferably, in the zirconium carbide coating step and the cleavage step, drying time is 1~3h, drying temperature
It is 40~80 DEG C.
Preferably, in the cleavage step, the heating rate of cracking is 5~10 DEG C/min.
According to a second aspect of the present invention, a kind of carbon fiber-carbonization zirconium composite material is provided, by described in any of the above embodiments
Preparation method is made.
Above-mentioned technical proposal of the invention one of at least has the advantages that:
1, the raw material type involved in the present invention is few, and zirconium carbide precursor sol can be synthesized under low-temperature atmosphere-pressure, and
And the collosol stability is good, can store 3 months or more under room temperature, is conducive to the progress of subsequent polymer infiltration and pyrolysis technique；
2, the present invention uses the zirconium carbide slurry of superelevation volume content to be coated on carbon fiber knitted body to fill gross blow hole,
Reduce polymer infiltration and pyrolysis technique number, improves production efficiency；
3, carbon fiber prepared by the present invention/zirconium carbide composite property is stablized, and bending strength and fracture toughness are high, heat resistanceheat resistant
Corrosion can be good, and zirconium carbide of the crystal grain less than 100nm fills uniformly in carbon fiber hole；
4, low production cost of the present invention, preparation process is simple, is easily industrialized production, therefore has wide city
Field space.
Detailed description of the invention
Fig. 1 is the carbon fiber-according to made from the carbon fiber of the embodiment of the present invention 1-carbonization zirconium composite material preparation method
The SEM photograph of carbonization zirconium composite material；
Fig. 2 is the photo according to the zirconium carbide precursor sol in the embodiment of the present invention 1；
Fig. 3 a is the SEM photograph of the Zirconium carbide powder obtained after Pintsch process according to the zirconium carbide precursor sol of Fig. 2；
Fig. 3 b is the TEM photo of the Zirconium carbide powder obtained after Pintsch process according to the zirconium carbide precursor sol of Fig. 2.
Fig. 3 c is the XRD diagram of the Zirconium carbide powder obtained after Pintsch process according to the zirconium carbide precursor sol of Fig. 2
Spectrum.
Specific embodiment
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention,
The technical solution of the embodiment of the present invention is clearly and completely described.Obviously, described embodiment is of the invention one
Divide embodiment, instead of all the embodiments.Based on described the embodiment of the present invention, those of ordinary skill in the art are obtained
The every other embodiment obtained, shall fall within the protection scope of the present invention.
Carbon fiber according to an embodiment of the present invention-carbonization zirconium composite material preparation method is specifically described first below.
Carbon fiber according to an embodiment of the present invention-carbonization zirconium composite material preparation method, includes the following steps:
One) raw material preparation process
Zirconium carbide nano-powder and zirconium carbide precursor sol are provided.
Wherein, commercially available material can be used in zirconium carbide nano-powder and zirconium carbide precursor sol, it is preferable that by such as
It is prepared by lower preparation method.
The preparation of zirconium carbide precursor sol:
It is put into conical flask after zirconium compounds and carbon compound are weighed in an inert gas atmosphere, is configured to mix molten
Liquid；
Then, after oil bath heating 2~5 hours, be added deionized water, and 80~120 DEG C at a temperature of continue stirring 2~
Obtain within 5 hours the zirconium carbide precursor sol.
Herein on basis, zirconium carbide nano-powder can also be prepared using the zirconium carbide precursor sol, it is specific to prepare
Method is as follows:
The zirconium carbide precursor sol is placed in sintering furnace, in an inert gas atmosphere in 200~400 DEG C of temperature
1~3h of chemical crosslinking is carried out under degree；
Hereafter, continuation is warming up to 1400~1600 DEG C with the rate of 5~10 DEG C/min and is cracked and kept the temperature 0.5~2h,
Subsequent natural cooling obtains the zirconium carbide nano-powder.
Wherein, the zirconium compounds can for tetrabutyl zirconate or zirconium oxychloride, or mixtures thereof.
The carbon compound can be acetylacetone,2,4-pentanedione, benzoyl acetone, 1,3- diphenyl -1,3- propanedione or its mixing
Object.
Wherein, if containing zirconium oxide in the zirconium carbide nano-powder that carbon compound is prepared very little, on the contrary, if carbon compound
Contain carbon in the zirconium carbide nano-powder that object is then prepared too much.In addition, it is heavy that colloidal sol can generate when deionized water additive amount is excessive
It forms sediment, the excessively few colloidal sol then prepared of additive amount is unstable.It is therefore preferred that mole of the zirconium compounds and the carbon compound
Than for 1:2~4, the molar ratio of the deionized water and the zirconium compounds is 1~3:1.
By above-mentioned it is found that raw material type involved in the present invention is few, and under low-temperature atmosphere-pressure as starting material
Zirconium carbide precursor sol is synthesized, and the collosol stability is good, can store 3 months or more under room temperature, is conducive to subsequent forerunner
The progress of body impregnating cracking technology.
Two) preparation step of zirconium carbide slurry
Specifically, such as the zirconium carbide nano-powder, dispersing agent and deionized water can be configured to solid volume
Content is the zirconium carbide slurry of 50~57vol.%.
Wherein, the dispersing agent is or mixtures thereof polyacrylic acid, polyethylene glycol, polyetherimide.
Specific address, the usage amount of the dispersing agent, such as content in the zirconium carbide slurry can for 0.1~
1.0wt%.
Using these dispersing agents, the zirconium carbide slurry that solid volume content is up to 50~57vol.% can be configured, by this
The zirconium carbide slurry of superelevation volume content, which is coated on carbon fiber knitted body, can fill gross blow hole, reduce polymer infiltration and pyrolysis
Technique number, greatly improves production efficiency.
Three) zirconium carbide coating step
The zirconium carbide slurry is coated on carbon fiber knitted body so that its density, and is dried in a vacuum drying oven,
Obtain the carbon fiber knitted body coated with zirconium carbide.
In some embodiments of the invention, in order to improve the consistency of carbon fiber knitted body, the carbon fiber knitted body
Density can be carried out by the method for chemical vapor infiltration before the use.Specifically, used carbon source gas can be CH4,
Carrier gas can be H2And N2。
In addition, specific condition does not have special limitation when dry, from the point of view of the viewpoints such as improving efficiency, it is preferable that dry
The dry time is 1~3h, and drying temperature is 40~80 DEG C.
Four) impregnation steps
The carbon fiber knitted body coated with zirconium carbide is immersed in 10 in the zirconium carbide precursor sol~
60min。
Zirconium carbide precursor sol can be filled in the gap of carbon fiber knitted body as a result, and be coated on carbon fiber
Knitted body surface, by following cleavage steps, zirconium carbide precursor sol is formed as zirconium carbide nano particle and is coated on carbon fiber
It ties up the surface of knitted body and is filled in its gap.
Five) cleavage step
Carbon fiber knitted body taking-up after the dipping is dried in a vacuum drying oven, is hereafter put into sintering furnace lazy
0.5~2h is cracked and kept the temperature at 1400~1600 DEG C in property gas atmosphere, is then cooled to room temperature with the furnace, is obtained the carbon fiber
Dimension-carbonization zirconium composite material.
Specifically, in cleavage step, the heating rate of cracking can be 5~10 DEG C/min.
Six) densification steps
It, can be multiple with impregnation steps described in repetitive operation and cleavage step in order to further increase the consistency of composite material
(for example, 3~4 times).
Carbon fiber/carbonization zirconium composite material is prepared by above-mentioned preparation method, the carbon fiber/carbonization zirconium composite material
Performance is stablized, and bending strength and fracture toughness are high, and erosion performance is good, and zirconium carbide of the crystal grain less than 100nm fills uniformly with
In carbon fiber hole.
In the following, being described in further detail by specific embodiment
In the above embodiment of the present invention, material used is not limited in the present invention, can be directly commercially available, or
It is prepared using conventional method.
The present invention is further understood combined with specific embodiments below.
Embodiment 1
It is put into conical flask, prepares after tetrabutyl zirconate and acetylacetone,2,4-pentanedione are weighed in argon atmosphere with molar ratio 1:2
At mixed solution.
In oil bath, after being heated 2 hours in argon atmosphere, be added deionized water (deionized water and tetrabutyl zirconate
Molar ratio is 3:1), and 120 DEG C at a temperature of continue stirring and obtain zirconium carbide presoma in 2 hours.Fig. 2 shows the zirconium carbides
The photo of presoma, it is stable liquid condition as seen from the figure.
Zirconium carbide presoma is placed in multifunctional sintering furnace, in argon atmosphere 400 DEG C at a temperature of
Crosslinking 1h is learned, continuation is warming up to 1600 DEG C with the rate of 5 DEG C/min and is cracked and kept the temperature 0.5h, and subsequent natural cooling obtains
Zirconium carbide nano-powder.Fig. 3 a shows the carbonization zirconium powder that zirconium carbide precursor sol according to fig. 2 obtains after Pintsch process
The SEM photograph of body, Fig. 3 b show the Zirconium carbide powder that zirconium carbide precursor sol according to fig. 2 obtains after Pintsch process
TEM photo, Fig. 3 c show the Zirconium carbide powder that zirconium carbide precursor sol according to fig. 2 obtains after Pintsch process
XRD spectrum.The powder obtained known to Fig. 3 c is close to pure Zirconium carbide powder (peak of zirconium oxide can almost be ignored).Figure
3a and Fig. 3 b shows that obtained powder is the consistent spheric granules of general uniform, and crystallite dimension is less than 100nm.
Carbon fiber knitted body is subjected to density by the method for chemical vapor infiltration, carbon source gas is CH4, carrier gas H2And N2。
Hereafter, by the above-mentioned zirconium carbide nano-powder being prepared, deionized water and as the polypropylene of dispersing agent
Acid is configured to the zirconium carbide slurry that volume content is 57vol.%, dispersing agent 0.8wt% is wherein contained in the zirconium carbide slurry.
The zirconium carbide slurry is coated on the carbon fiber knitted body after above-mentioned density to fill gross blow hole to further density, then
In a vacuum drying oven, 3 hours dry at 40 DEG C.
Carbon fiber knitted body after coating zirconium carbide slurry is placed in vacuum impregnation kettle, is equipped in the vacuum impregnation kettle upper
The zirconium carbide precursor sol for stating synthesis makes the zirconium carbide precursor sol of above-mentioned synthesis penetrate into carbon fiber braiding by vacuumizing
Body intrinsic silicon, dip time 10min.
After dipping, takes out and dry in a vacuum drying oven, it is 3 hours dry at 40 DEG C.By the sample dress after drying
Enter in multifunctional sintering furnace, under an argon atmosphere, be warming up to 5 DEG C/min of heating rate and 0.5h is cracked and kept the temperature at 1600 DEG C,
Then room temperature is cooled to the furnace.
Above-mentioned dipping and cleavage step 3 times are repeated, carbon fiber-carbonization zirconium composite material is obtained.
The carbon fiber-carbonization zirconium composite material consistency is 90%, bending strength 250MP, and fracture toughness is
13MPa·m1/2。
In addition, Fig. 1 shows the carbon fiber-carbonization zirconium composite material SEM photograph, it should be by the SEM photograph it is found that crystal grain
Zirconium carbide less than 100nm fills uniformly in carbon fiber hole.
Embodiment 2
It is put into conical flask, prepares after tetrabutyl zirconate and acetylacetone,2,4-pentanedione are weighed in argon atmosphere with molar ratio 1:4
At mixed solution.
In oil bath, after being heated 4 hours in argon atmosphere, be added deionized water (deionized water and tetrabutyl zirconate
Molar ratio is 2:1), and 100 DEG C at a temperature of continue stirring and obtain zirconium carbide presoma in 4 hours.
Zirconium carbide presoma is placed in multifunctional sintering furnace, in argon atmosphere 300 DEG C at a temperature of
Crosslinking 2h is learned, continuation is warming up to 1500 DEG C with the rate of 10 DEG C/min and is cracked and kept the temperature 1h, and subsequent natural cooling obtains carbon
Change zirconium nano-powder.
Carbon fiber knitted body is subjected to density by the method for chemical vapor infiltration, carbon source gas is CH4, carrier gas H2And N2。
Hereafter, the above-mentioned zirconium carbide nano-powder being prepared, deionized water and the polyacrylic acid as dispersing agent,
It is configured to the zirconium carbide slurry that volume content is 53vol.%, dispersing agent 0.6wt% is wherein contained in the zirconium carbide slurry.It should
Zirconium carbide slurry is coated on the carbon fiber knitted body after above-mentioned density to fill gross blow hole to further density, then true
It is 2 hours dry at 60 DEG C in empty drying box.
Carbon fiber knitted body after coating zirconium carbide slurry is placed in vacuum impregnation kettle, is equipped in the vacuum impregnation kettle upper
The zirconium carbide precursor sol for stating synthesis makes the zirconium carbide precursor sol of above-mentioned synthesis penetrate into carbon fiber braiding by vacuumizing
Body intrinsic silicon, dip time 30min.
After dipping, takes out and dry in a vacuum drying oven, it is 2 hours dry at 60 DEG C.By the sample dress after drying
Enter in multifunctional sintering furnace, under an argon atmosphere, is warming up to 10 DEG C/min of heating rate and 1h is cracked and kept the temperature at 1500 DEG C, so
After cool to room temperature with the furnace.
Above-mentioned dipping and cleavage step 4 times are repeated, carbon fiber-carbonization zirconium composite material is obtained.
The carbon fiber-carbonization zirconium composite material consistency is 91%, bending strength 270MPa, and fracture toughness is
16MPa·m1/2。
Embodiment 3
It is put into conical flask, prepares after tetrabutyl zirconate and acetylacetone,2,4-pentanedione are weighed in argon atmosphere with molar ratio 1:3
At mixed solution.
In oil bath, after being heated 5 hours in argon atmosphere, be added deionized water (deionized water and tetrabutyl zirconate
Molar ratio is 1:1), and 80 DEG C at a temperature of continue stirring and obtain zirconium carbide presoma in 5 hours.
Zirconium carbide presoma is placed in multifunctional sintering furnace, in argon atmosphere 200 DEG C at a temperature of
Crosslinking 3h is learned, continuation is warming up to 1400 DEG C with the rate of 5 DEG C/min and is cracked and kept the temperature 2h, and subsequent natural cooling obtains carbon
Change zirconium nano-powder.
Carbon fiber knitted body is subjected to density by the method for chemical vapor infiltration, carbon source gas is CH4, carrier gas H2And N2。
Hereafter, the above-mentioned zirconium carbide nano-powder being prepared, deionized water and the polyacrylic acid as dispersing agent,
It is configured to the zirconium carbide slurry that volume content is 51vol.%, dispersing agent 0.4wt% is wherein contained in the zirconium carbide slurry.It should
Zirconium carbide slurry is coated on the carbon fiber knitted body after above-mentioned density to fill gross blow hole to further density, then true
It is 1 hour dry at 80 DEG C in empty drying box.
Carbon fiber knitted body after coating zirconium carbide slurry is placed in vacuum impregnation kettle, is equipped in the vacuum impregnation kettle upper
The zirconium carbide precursor sol for stating synthesis makes the zirconium carbide precursor sol of above-mentioned synthesis penetrate into carbon fiber braiding by vacuumizing
Body intrinsic silicon, dip time 20min.
After dipping, takes out and dry in a vacuum drying oven, it is 1 hour dry at 80 DEG C.By the sample dress after drying
Enter in multifunctional sintering furnace, under an argon atmosphere, is warming up to 5 DEG C/min of heating rate and 2h is cracked and kept the temperature at 1400 DEG C, so
After cool to room temperature with the furnace.
Above-mentioned dipping and cleavage step 4 times are repeated, carbon fiber-carbonization zirconium composite material is obtained.
The carbon fiber-carbonization zirconium composite material consistency is 90%, bending strength 260MPa, and fracture toughness is
15MPa·m1/2。
The above is a preferred embodiment of the present invention, it is noted that for those skilled in the art
For, without departing from the principles of the present invention, it can also make several improvements and retouch, these improvements and modifications
It should be regarded as protection scope of the present invention.
Claims (10)
1. a kind of carbon fiber-carbonization zirconium composite material preparation method, which comprises the steps of:
Raw material preparation process provides zirconium carbide nano-powder and zirconium carbide precursor sol；
The zirconium carbide nano-powder, dispersing agent and deionized water are configured to solid phase body by the preparation step of zirconium carbide slurry
The zirconium carbide slurry that product content is 50~57vol.%；
The zirconium carbide slurry is coated on carbon fiber knitted body so that its density by zirconium carbide coating step, and dry in vacuum
It is dry in dry case, obtain the carbon fiber knitted body coated with zirconium carbide；
Impregnation steps, the carbon fiber knitted body coated with zirconium carbide is immersed in 10 in the zirconium carbide precursor sol~
60min；
Carbon fiber knitted body after the impregnation steps is taken out, dries in a vacuum drying oven, be hereafter put into burning by cleavage step
It cracks and keeps the temperature 0.5~2h in freezing of a furnace at 1400~1600 DEG C in an inert gas atmosphere, then cool to room temperature with the furnace, obtain
To the carbon fiber-carbonization zirconium composite material.
2. preparation method according to claim 1, which is characterized in that further include following steps:
Densification steps, impregnation steps described in repetitive operation and cleavage step 3~4 times, to improve carbon fiber-zirconium carbide composite wood
The consistency of material.
3. preparation method according to claim 1, which is characterized in that the preparation method packet of the zirconium carbide precursor sol
It includes:
It is put into conical flask after zirconium compounds and carbon compound are weighed in an inert gas atmosphere, is configured to mixed solution；
After oil bath heating 2~5 hours, be added deionized water, and 80~120 DEG C at a temperature of continue to obtain for stirring 2~5 hours
The zirconium carbide precursor sol.
4. preparation method according to claim 3, which is characterized in that before the zirconium carbide nano-powder is by the zirconium carbide
It drives body colloidal sol to be prepared, preparation method includes:
The zirconium carbide precursor sol is placed in sintering furnace, in an inert gas atmosphere 200~400 DEG C at a temperature of
Carry out 1~3h of chemical crosslinking；
Hereafter, continuation is warming up to 1400~1600 DEG C with the rate of 5~10 DEG C/min and is cracked and kept the temperature 0.5~2h, then
Natural cooling obtains the zirconium carbide nano-powder.
5. preparation method according to claim 3, which is characterized in that mole of the zirconium compounds and the carbon compound
Than for 1:2~4, the molar ratio of the deionized water and the zirconium compounds is 1~3:1, the zirconium compounds is four fourth of zirconic acid
Or mixtures thereof ester or zirconium oxychloride, the carbon compound are acetylacetone,2,4-pentanedione, benzoyl acetone, 1,3- diphenyl -1,3- the third two
Or mixtures thereof ketone.
6. preparation method according to claim 1, which is characterized in that the dispersing agent is polyacrylic acid, polyethylene glycol, gathers
Or mixtures thereof etherimide, content of the dispersing agent in the zirconium carbide slurry are 0.1~1.0wt%.
7. preparation method according to claim 1, which is characterized in that in the zirconium carbide coating step, the carbon fiber
The method that knitted body passes through chemical vapor infiltration before the use carries out density, and used carbon source gas is CH4, carrier gas H2With
N2。
8. preparation method according to claim 1, which is characterized in that the zirconium carbide coating step and cracking step
In rapid, drying time is 1~3h, and drying temperature is 40~80 DEG C.
9. preparation method according to claim 1, which is characterized in that in the cleavage step, the heating rate of cracking is 5
~10 DEG C/min.
10. a kind of carbon fiber-carbonization zirconium composite material, which is characterized in that by according to claim 1 to 9 any preparation methods
It is made.
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| CN115385704A (en) * | 2022-08-23 | 2022-11-25 | 广西三元华鑫特种陶瓷有限公司 | Method for reducing drying stress deformation of micro-nano fiber reinforced silicon carbide material semi-finished product |
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