CN108727049A - A kind of Cf/ SiC-HfC ultra-temperature ceramic-based composite materials and preparation method thereof - Google Patents
A kind of Cf/ SiC-HfC ultra-temperature ceramic-based composite materials and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/38—Non-oxide ceramic constituents or additives
- C04B2235/3817—Carbides
- C04B2235/3826—Silicon carbides
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/38—Non-oxide ceramic constituents or additives
- C04B2235/3817—Carbides
- C04B2235/3839—Refractory metal carbides
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/52—Constituents or additives characterised by their shapes
- C04B2235/5208—Fibers
- C04B2235/5216—Inorganic
- C04B2235/524—Non-oxidic, e.g. borides, carbides, silicides or nitrides
- C04B2235/5248—Carbon, e.g. graphite
Abstract
The present invention relates to a kind of Cf/ SiC-HfC ultra-temperature ceramic-based composite materials and preparation method thereof, including：Using vacuum impregnation technology HfO is introduced in prefabricated carbon fiber body2Powder and carbon source, obtain Cf/HfO2- C preforms；By gained Cf/HfO2- C preforms are placed in inert atmosphere, by carbon thermal reduction 1~2 hour at 1300~1800 DEG C, obtain Cf/ HfC-C preforms；By gained Cf/ HfC-C preforms carry out Si infiltrations at 1400~1700 DEG C, make CfC and Si reaction in-situs generate SiC matrix phase in/HfC-C preforms, obtain the Cf/ SiC-HfC ultra-temperature ceramic-based composite materials.Preparation temperature of the present invention is low, reduces damage of the material preparation process high temperature to carbon fiber；It is simple for process, it is easy to accomplish CfThe quick preparation of/SiC-HfC composite materials.
Description
Technical field
The present invention relates to a kind of Cf/ SiC-HfC ultra-temperature ceramic-based composite material preparation methods, belong to superhigh temperature ceramics system
Standby field.
Background technology
Superelevation velocity of sound vehicle technology is known as " next-generation airmanship ", is in aviation history after invention aircraft, breakthrough sound
The epoch-making milestone of third after barrier flight.Due to superelevation velocity of sound aircraft is round-trip, atmospheric reentry when local surfaces need
Bear the violent scour of 2000 DEG C or more of high temperature and tens of megapascal high pressure draughts, high energy particle.Therefore, it researches and develops high temperature resistant, resist
Oxidation ablation, high intensity high-temperature structural material as one of key technology, in hypersonic aircraft evolution
Play very important effect.
Cf/ SiC ceramic matrix composite material has excellent comprehensive performance, it is considered to be the most thermal structure material of potentiality to be exploited
Material.However, Cf/ SiC ceramic matrix composite material long-time temperature in use the limit is usually no more than 1650 DEG C, and superelevation is introduced into SiC matrix
Warm phase (such as ZrC, ZrB2、HfC、HfB2Deng) C can be effectively improvedfThe service temperature upper limit of/SiC ceramic matrix composite material.HfC is current institute
Know the highest material of fusing point (3890 DEG C), there is extreme high temperature resistance, oxidation product HfO2Fusing point also reaches 2900 DEG C,
Chemical stability is good, the HfO formed in ablation process2It can continue inside protection materials.However, being limited by preparation process, mesh
It is preceding to be also difficult to prepare high-performance Cf/ SiC-HfC ultra-temperature ceramic-based composite materials.
Document " Jinming Jiang, Song Wang, Wei Li, et al.Preparation of 3D Cf/ZrC-
SiC composites by joint processes of PIP and RMI[J].Materials Science and
Engineering:Organic precursor infiltration pyrolysis is taught in A, Volume 607,23June2014, Pages 334-340. "
(PIP) method is difficult to obtain fine and close ceramic matric composite, and there are long preparation period, and ceramic matrix combines weaker lack
Point.And infiltration (Reactive Melt Infiltration, RMI) is reacted although fine and close and base can be prepared by one-pass molding
This flawless matrix is a kind of effective way quickly preparing near-net-shape complex shaped components, has become the country in recent years
One of the hot spot of outer ultra-temperature ceramic-based composite material development.But HfSi2Alloy melting point is higher, if directly infiltration will invade
Fiber and interface are lost, material at high temperature performance is influenced.Comprehensive CfThe present Research of/SiC-HfC ultra-temperature ceramic-based composite materials, urgently
Novel preparation process need to be developed.
Invention content
The present invention is directed to CfThe existing preparation process of/SiC-HfC materials there are the problem of, propose a kind of Cf/ SiC-HfC superelevation
The preparation method of warm ceramic matric composite, including：
Using vacuum impregnation technology HfO is introduced in prefabricated carbon fiber body2Powder and carbon source, obtain Cf/HfO2- C preforms；
By gained Cf/HfO2- C preforms are placed in inert atmosphere, small by carbon thermal reduction 1~2 at 1300~1800 DEG C
When, obtain Cf/ HfC-C preforms；
By gained Cf/ HfC-C preforms carry out Si infiltrations at 1400~1700 DEG C, make CfIn/HfC-C preforms C with
Si reaction in-situs generate SiC matrix phase, obtain the Cf/ SiC-HfC ultra-temperature ceramic-based composite materials.
The present invention selects HfO2Powder utilizes vacuum impregnation technology by raw material (HfO as hafnium source2Powder and carbon source) it introduces
In prefabricated carbon fiber body, C is obtainedf/HfO2- C preforms.Pass through high temperature carbon thermal reduction (1300~1800 DEG C) again so that Cf/
HfO2Hafnium source HfO in-C preforms2HfC+CO is obtained by the reaction with carbon source C, it is final to generate the C with nanoporousf/ HfC-C is pre-
Formed body.Then RMI methods, and the effect of the capillary force using the nanoporous formed are used, is drawn at 1400~1700 DEG C
Enter Si so that Si and CfThe complete carbon source C of unreacted carries out reaction in-situ and generates SiC matrix phase in/HfC-C preforms, most
C is obtained eventuallyfThe ultra-temperature ceramic-based composite woods of/SiC-HfC.The present invention the key reaction being related to include：Carbothermic reduction reaction：
HfO2+C→HfC+CO；Infiltration reacts：Si+C→SiC.Therefore, the ultra-temperature ceramic-based composite material that prepared by the present invention has good
Good mechanical property, and the HfC crystal grain that reaction in-situ generates is tiny, volume content is high, effectively increases the Burning corrosion resistance of material
Energy.
Preferably, the HfO2Powder and the mass ratio of carbon fiber precast body are 1：(0.26~0.52).
Preferably, the carbon source be inorganic carbon source or and organic carbon source, the mass ratio of the carbon source and carbon fiber precast body
It is 1：(1.08~1.78).The carbon source is preferably organic carbon source, and liquid carbon source presoma can be easier to enter material internal
With HfO2Particle reacts completely generates HfC, and can also pass into inside fibre bundle so that during later stage infiltration simple substance Si and
C reactions are cracked, protection fiber C is injury-free；More preferably phenolic resin.The present invention is generated using the cracking reaction of organic carbon source
Gas preferably adjust Cf/HfO2Pore size in-C preforms.
Also, preferably, the inorganic carbon source is at least one of carbon black, graphite powder, carbon dust, the organic carbon source is phenol
At least one of urea formaldehyde, furane resins, silane resin.
Preferably, when the carbon source is organic carbon source or organic carbon source and the mixture of inorganic carbon source, by gained Cf/
HfO2- C preforms are first after drying and cracking, then carry out carbon thermal reduction.
Also, preferably, the drying be keep the temperature 3~6 hours at 80 DEG C~120 DEG C, it is described be cracked into 600 DEG C~
1~2 hour is kept the temperature at 900 DEG C.
Preferably, the vacuum degree of the vacuum impregnation technology is -0.08~-0.10MPa.
Preferably, the structure of the carbon fiber precast body is D refraction statics, two-dimension laminate or 3 D weaving, open pore rate is
30~50vol%.Preferably, it is the pyrolytic carbon of 500~1500nm that fiber surface deposition, which has thickness, in the carbon fiber precast body
PyC or pyrolytic carbon PyC/SiC composite multi-layers interface.Its median surface is excessively thin so that matrix and fiber combine by force, fine in fracture process
Dimension in brittle fracture does not have toughening effect, and interface is blocked up so that fiber and matrix combination be not close, mechanics of materials strength reduction.
Preferably, the atmosphere of the Si infiltrations is vacuum atmosphere, the time is 0.5~3 hour.
On the other hand, the present invention also provides a kind of C prepared according to above-mentioned preparation methodf/ SiC-HfC superhigh temperature ceramics
Based composites, the Cf/ SiC-HfC ultra-temperature ceramic-based composite materials include carbon fiber, SiC phases and HfC phases, wherein carbon fiber
Dimension hplc is that the volume ratio of 25~40vol%, HfC and SiC are 0.10~0.35.
Preferably, the CfThe bending strength of/SiC-HfC ultra-temperature ceramic-based composite materials is 93~125MPa,
Mass ablative rate at 2000 DEG C is 15.32~18.67mg/s.
The beneficial effects of the invention are as follows：This programme realizes infiltration precast body hole by impregnating slurry and carbo-thermal process
Regulation and control synthesize C in conjunction with Si reaction infiltrationsf/ SiC-HfC composite materials solve tradition reaction infiltration process and are difficult to obtain such
The problem of material；Preparation temperature is low, reduces damage of the material preparation process high temperature to carbon fiber；It is simple for process, it is easy to real
Existing CfThe quick preparation of/SiC-HfC composite materials.
Description of the drawings
Fig. 1 is C prepared by embodiment 1fThe X ray diffracting spectrum of/SiC-HfC composite material surfaces；
Fig. 2 is C prepared by embodiment 1fThe low power SEM pictures of/SiC-HfC composite material polishing sections；
Fig. 3 is C prepared by embodiment 1fThe high power SEM pictures of/SiC-HfC composite material polishing sections；
Fig. 4 is C prepared by embodiment 1fThe high power SEM pictures of/SiC-HfC composite material polishing sections.
Specific implementation mode
It is further illustrated the present invention below by way of following embodiments, it should be appreciated that following embodiments are merely to illustrate this
Invention, is not intended to limit the present invention.
The present invention is based on impregnating slurry association response infiltration (RMI) techniques：Respectively with HfO2Powder, inorganic carbon source or/and
Organic carbon source (such as phenolic resin etc.) is used as hafnium source and carbon source, is introduced into carbon fiber precast body by vacuum impregnation, then pass through
It crosses carbon thermal reduction and obtains porous CfThen/HfC-C preforms are penetrated into melt of si under the conditions of certain temperature using infiltration method
Above-mentioned CfIn/HfC-C preforms, SiC matrix phase is generated based on Si-C reaction in-situs, obtains Cf/ SiC-HfC superhigh temperature ceramics
Based composites.
In the present invention, Cf/ SiC-HfC ultra-temperature ceramic-based composite materials include carbon fiber, SiC phases and HfC phases, wherein carbon
Fiber content can be that the volume ratio of 25~40vol%, HfC and SiC are 0.10~0.35.The Cf/ SiC-HfC superhigh temperature ceramics
The bending strength of based composites can be 93~125MPa, and the mass ablative rate at 2000 DEG C can be 15.32~18.67mg/
s。
The present invention solves ceramic matric composite traditional handicraft and is difficult to prepare the difficulty of HfC ultra-temperature ceramic-based composite materials
Topic, and it is simple for process, it is easy to accomplish the quick preparation of material.Illustrate to following exemplary C provided by the inventionf/ SiC-HfC is super
The preparation method of refractory ceramics based composites.
Carbon fiber precast body (Cf) pretreatment.In the present invention, the structure of the carbon fiber precast body can be D refraction statics,
Two-dimension laminate or 3 D weaving.The open pore rate of the carbon fiber precast body can be 30~50vol%, the carbon fiber precast body
Middle fiber surface deposition has the pyrolytic carbon PyC or pyrolytic carbon PyC/SiC composite multi-layers interface that thickness is 500~1500nm.To carbon
Fiber preform is cleaned by ultrasonic, and is put into baking oven is dried later.Ultrasonic cleaning agent used can be alcohol, when cleaning
Between can be 1~3 hour, dry condition is to keep the temperature 6~12 hours at 60~80 DEG C herein.
HfO2It is prepared by slurry.Dispersant PEI is dissolved according to preset ratio in a certain amount of deionized water, ultrasound
Processing is for use.Then the pH value of above-mentioned PEI solution is adjusted to 3~5, so that depositing between particle with HCl and NaOH solution
In larger repulsive force, slurry is in stable state.It finally will advance load weighted HfO2Powder is slowly added to above-mentioned PEI solution
In, ball milling mixing obtains uniform sizing material.Wherein, HfO2HfO in slurry2The mass fraction of powder can be 70.76~86.58wt%.
Dispersant PEI additive amounts can be HfO20~0.2wt% of powder quality, preferably 0.05~0.2wt%.HCl solution and NaOH
The molar concentration of solution can be 0.05~0.2mol/L, and pH value is adjusted to 3~5.The ball milling mixing time can be 12~24 hours.
HfO2The vacuum impregnation of slurry.By HfO obtained2It is pre- that slurry is introduced to processed fiber in a manner of vacuum impregnation
In body processed, taking-up is placed in oven and dried.Wherein, vacuum-impregnated condition is -0.08MPa~-0.10MPa vacuum degrees.
Introduce carbon source.The carbon source can be inorganic carbon source or/and organic carbon source.The grain size of the inorganic carbon source can be 10~
20nm can be at least one of carbon black, graphite powder, carbon dust.The organic carbon source can be phenolic resin, furane resins, silane
At least one of resin.HfO will be impregnated with2The carbon fiber precast body of powder continues vacuum impregnation carbon source.When the carbon source is
It is dry after carbon fiber precast body being directly immersed in the slurry containing inorganic carbon source when inorganic carbon source, obtain Cf/HfO2- C is pre-
Formed body.The content of inorganic carbon source can be 30~40wt% in the slurry for containing inorganic carbon source.When the carbon source is organic carbon
When source or organic carbon source and the mixture of inorganic carbon source, HfO will be impregnated with2The carbon fiber precast body of powder is directly immersed in organic
In carbon source or organic carbon source and the mixed solution of inorganic carbon source, then through dry and cracking.The drying can be 80 DEG C~120
3~6 hours are kept the temperature at DEG C.The cracking can be to keep the temperature 1~2 hour at 600 DEG C~900 DEG C, and the atmosphere of cracking is all inertia
Atmosphere (for example, argon gas etc.).The present invention is in purpose that is dry and cracking, and so that organic carbon source is converted into C, (such as cracking is anti-
It answers：PR (phenolic resin) → C), and more gases are generated in cracking process, preferably regulate and control Cf/HfO2In-C preforms
Pore structure, be more advantageous to the reaction of follow-up Si infiltrations.As an example, HfO will be impregnated with2The carbon fiber precast body of powder
It is directly immersed in phenolic resin, cracking in an inert atmosphere is put into pyrolysis furnace after sample drying and obtains Cf/HfO2- C is preforming
Body.Wherein, vacuum-impregnated condition is -0.08MPa~-0.10MPa vacuum degrees.
Above-mentioned HfO2The vacuum impregnation of slurry and introducing carbon source, the number that can be repeated can be 2~4 times.On it should be noted that
State hafnium source (HfO2Powder) and the vacuum-impregnated number of carbon source it is unrestricted, only need to control HfO2Powder and carbon fiber precast body
Mass ratio is 1：(there are a large amount of HfO in prefabricated carbon fiber body between (0.26~0.52)2Superhigh temperature phase) and the carbon source and carbon
The mass ratio of fiber preform is 1：Between (1.08~1.78) can (ensure carbon source can and HfO2, Si react generation completely
HfC、SiC)。
By Cf/HfO2- C preforms carry out carbothermic reduction reaction under certain condition, during which keep inert atmosphere (such as
Ar atmosphere etc.), C is obtained after carbothermic reduction reactionf/HfC-C(Cf/ HfC-C preforms).Wherein, the condition of carbon-thermal reduction is
1~2 hour is kept the temperature at 1300~1800 DEG C.
React infiltration.Melt of si is penetrated into C in certain temperature, vacuum environmentf/ HfC-C materials (Cf/ HfC-C is preforming
Body), i.e. Si infiltrations, and Si and cracking C or/and the C reaction in-situs of inorganic carbon source generation SiC matrix during Si infiltrations
Phase obtains the Cf/ SiC-HfC ultra-temperature ceramic-based composite materials.Wherein, Si infiltrations condition is to be protected at 1400~1700 DEG C
Temperature 0.5~3 hour, preferably 1~3 hour.
Generally speaking, the present invention prepares C using impregnating slurry association reaction melting Infiltration Technicsf/ SiC-HfC ceramic bases are multiple
Condensation material.With HfO2Powder is hafnium source, organic carbon source or/inorganic carbon source, first with vacuum impregnation technology in carbon fiber precast body
Interior introducing HfO2And carbon source, then obtain porous C through carbon thermal reductionf/ HfC-C preforms finally utilize capillary force action, adopt
With infiltration method in Cf/ HfC-C preforms introduce melt of si, and reaction in-situ obtains Cf/ SiC-HfC is ultra-temperature ceramic-based compound
Material.In the present invention, the key reaction being related to includes：Cracking reaction：Organic carbon source (such as (phenolic resin PR) → C；Carbon heat is also
It is former：HfO2+C→HfC+CO；Infiltration reacts：Si+C→SiC.
The present invention measures C using Instron-5566 type electronic universal testersf/ SiC-HfC is ultra-temperature ceramic-based compound
The three-point bending resistance intensity of material can be 93~125MPa.C is measured using 30kW air plasma material at high temperature testing equipmentsf/
Mass ablative rate of the SiC-HfC ultra-temperature ceramic-based composite materials at 2000 DEG C is 15.32~18.67mg/s.
Embodiment is enumerated further below so that the present invention will be described in detail.It will similarly be understood that following embodiment is served only for this
Invention is further described, and should not be understood as limiting the scope of the invention, those skilled in the art is according to this hair
Some nonessential modifications and adaptations that bright the above is made all belong to the scope of protection of the present invention.Following examples are specific
Technological parameter etc. is also only an example in OK range, i.e. those skilled in the art can be done properly by the explanation of this paper
In the range of select, and do not really want to be defined in hereafter exemplary concrete numerical value.
Embodiment 1
(1) precast body is handled：To open pore rate 30vol% carbon fiber precast bodies, (interface is that the PyC/SiC of thickness 500nm is compound
Three bed boundarys, quality 11.62g) alcohol ultrasonic cleaning is carried out, scavenging period is 1 hour；
(2) prepared by slurry：HfO will be accounted for2The PEI of mass fraction 0.1wt% is dissolved in a certain amount of deionized water, and supersound process waits for
With；Then 0.1molL is used-1HCl and NaOH solution adjust above-mentioned PEI solution to pH=3；It later will be load weighted in advance
HfO2Powder is slowly added in above-mentioned PEI solution, and ball milling mixing for 24 hours, obtains HfO2Powdery pulp (wherein HfO2The quality of powder
86.58%) score is；
(3) vacuum impregnation slurry：By HfO in step (2)2It is processed that slurry is introduced to step (1) in a manner of vacuum-impregnated
In fiber preform, vacuum degree is -0.08MPa, and later in 80 DEG C of dry 8h, its weight is referred to as 53.32, and quality increases part
(41.7g) is HfO2Powder, wherein HfO2Powder and the mass ratio of carbon fiber precast body are 1：0.27；
(4) carbon source is introduced：By in material vacuum impregnated phenolic resin made from step (3), wherein the phenolic resin and carbon that introduce
The mass ratio of fiber preform is 1：1.08.It is put into pyrolysis furnace and cracks after sample drying, it is small respectively to keep the temperature 1 in 600 DEG C, 900 DEG C
When, the Ar throughputs of 10L/min are during which kept, C is obtained after crackingf/HfO2-C；
(5) carbon thermal reduction：(3)~(4) step 2 time is repeated, it will final gained Cf/HfO2- C, which is put into carbon shirt-circuiting furnace, carries out carbon
Thermal reduction reaction obtains C after the carbothermic reduction reaction of 1600 DEG C of heat preservations 1 hourf/HfC-C；
(6) infiltration is reacted：Vacuum, 1500 DEG C/1h infiltration under the conditions of melt of si penetrated into CfIt is in situ in/HfC-C materials
Reaction generates SiC matrix phase, completes the preparation of material.
C prepared by the present embodiment 1fCarbon fiber content is 30vol%, HfC phases and SiC phases in/SiC-HfC composite materials
Volume ratio is 1：2.6, bending strength is 122.57 ± 11.63MPa, and the mass ablative rate of material is 15.32mg/ at 2000 DEG C
s。
Embodiment 2
It is similar with the step in embodiment 1, the difference is that the open pore rate of fiber preform is that 40% (interface is thickness
The PyC/SiC composite multi-layers interface of 1000nm), impregnate HfO2Slurry twice, impregnates a phenolic resin, carbon thermal reduction temperature
1500 DEG C, 1450 DEG C of infiltrating temperature.The prepared C of this experimentfCarbon fiber content is 35vol% in/SiC-HfC composite materials,
The volume ratio of HfC phases and SiC phases is 1：3.2, bending strength is 103.15 ± 14.35MPa, and the quality of material is burnt at 2000 DEG C
Erosion rate is 16.68mg/s.
Embodiment 3
It is similar with the step in embodiment 1, the difference is that the open pore rate of fiber preform is that 50% (interface is thickness
The PyC/SiC composite multi-layers interface of 1500nm, quality 13.3g), impregnate HfO2Slurry (HfO twice2Powder and prefabricated carbon fiber
The mass ratio of body is 1：0.52), (phenolic resin and the mass ratio of carbon fiber precast body are 1 to phenolic resin to dipping twice：1.53),
1550 DEG C of carbon thermal reduction temperature, 1500 DEG C of infiltrating temperature.The prepared C of this experimentfCarbon fiber contains in/SiC-HfC composite materials
It is 30vol% to measure, and the volume ratio of HfC phases and SiC phases is 1：3.6, bending strength is 95.64 ± 12.51MPa, at 2000 DEG C
The mass ablative rate of material is 18.67mg/s.
Embodiment 4
It is similar with the step in embodiment 1, the difference is that dipping HfO2Slurry (HfO twice2Powder and carbon fiber precast body
Mass ratio be 1：0.31), (phenolic resin and the mass ratio of carbon fiber precast body are 1 to phenolic resin to dipping twice：1.65), carbon
Heat-treat 1600 DEG C of temperature, 0.5 hour time, 1500 DEG C of infiltrating temperature, time 2 h.The prepared C of this experimentf/SiC-
Carbon fiber content is 32vol% in HfC composite materials, and the volume ratio of HfC phases and SiC phases is 1：2.8, bending strength is
93.68 ± 10.95MPa, the mass ablative rate of material is 16.21mg/s at 2000 DEG C.
Embodiment 5
It is similar with the step in embodiment 1, the difference is that dipping HfO2Slurry (HfO twice2Powder and carbon fiber precast body
Mass ratio be 1：0.43), (phenolic resin and the mass ratio of carbon fiber precast body are 1 to phenolic resin to dipping twice：1.52), carbon
Heat-treat 1600 DEG C of temperature, 1 hour time, 1500 DEG C of infiltrating temperature, 0.5 hour time.The prepared Cf/SiC- of this experiment
Carbon fiber content is 31ol% in HfC composite materials, and the volume ratio of HfC phases and SiC phases is 1：3.1, bending strength is
106.95 ± 12.84MPa, the mass ablative rate of material is 17.36mg/s at 2000 DEG C.
Embodiment 6
It is similar with the step in embodiment 1, the difference is that dipping HfO2Slurry (HfO twice2Powder and carbon fiber precast body
Mass ratio be 1：0.37), dipping carbon black slurry (10~20nm of particle size carbon black, the mass content of carbon black in carbon black slurry twice
30wt%.Carbon black and the mass ratio of carbon fiber precast body are 1：1.62), 1600 DEG C of carbon thermal reduction temperature, 1 hour time, infiltration
1500 DEG C of temperature, 0.5 hour time.The prepared C of this experimentfCarbon fiber content is 33vol% in/SiC-HfC composite materials,
The volume ratio of HfC phases and SiC phases is 1：4.2, bending strength is 93.51 ± 14.36MPa, and the quality of material is burnt at 2000 DEG C
Erosion rate is 17.62mg/s.
Embodiment 7
It is similar with the step in embodiment 1, the difference is that dipping HfO2Slurry (HfO twice2Powder and carbon fiber precast body
Mass ratio be 1：0.28) carbon black and phenolic resin mixed liquor (wherein 10~20nm of particle size carbon black, carbon black and phenol twice, are impregnated
The mass ratio 1 of urea formaldehyde：1, the mass ratio of total carbon source and carbon fiber precast body is 1：1.57), 1600 DEG C of carbon thermal reduction temperature, when
Between 1 hour, 1500 DEG C of infiltrating temperature, 0.5 hour time.The prepared C of this experimentfCarbon fiber contains in/SiC-HfC composite materials
It is 31vol% to measure, and the volume ratio of HfC phases and SiC phases is 1：2.8, bending strength is 102.84 ± 11.26MPa, at 2000 DEG C
The mass ablative rate of material is 16.24mg/s.
Fig. 1 is C prepared by embodiment 1fThe X ray diffracting spectrum of/SiC-HfC composite material surfaces, schemes as can be known from Fig. 1
There is intensity high in spectrum and sharp HfC and SiC diffraction maximums, shows that HfC, SiC crystallinity are good in material；And material after reacting
A small amount of HfSi is generated in material2Alloy, the HfSi in ablation process2Alloy, which can aoxidize, generates HfO2And SiO2, absorb heat and
Being covered in material surface prevents material to be further destroyed；
Fig. 2 is C prepared by embodiment 1fThe low power SEM pictures of/SiC-HfC composite material polishing sections, in intrinsic silicon brilliant white
Color region is superhigh temperature phase, and black region is fibre bundle.A large amount of superhigh temperature distributed mutuallies are in fiber interfascicular as can be known from Fig. 2, and
It is distributed inside fibre bundle less；
Fig. 3, Fig. 4 are C prepared by embodiment 1fThe high power SEM pictures of/SiC-HfC composite material polishing sections, as we know from the figure
Brilliant white region is HfC and HfSi2Phase, white object are mutually superhigh temperature phase HfC, and gray area is SiC phases.Material internal uniformly divides
A large amount of HfC and SiC are furnished with, and have a small amount of HfSi2It is distributed in island inside HfC.
Claims (11)
1. a kind of CfThe preparation method of/SiC-HfC ultra-temperature ceramic-based composite materials, which is characterized in that including：
Using vacuum impregnation technology HfO is introduced in prefabricated carbon fiber body2Powder and carbon source, obtain Cf/HfO2- C preforms；
By gained Cf/HfO2- C preforms are placed in inert atmosphere, small by carbon thermal reduction 1~2 at 1300~1800 DEG C
When, obtain Cf/ HfC-C preforms；
By gained Cf/ HfC-C preforms carry out Si infiltrations at 1400~1700 DEG C, make CfC and Si in/HfC-C preforms
Reaction in-situ generates SiC matrix phase, obtains the Cf/ SiC-HfC ultra-temperature ceramic-based composite materials.
2. preparation method according to claim 1, which is characterized in that the HfO2The quality of powder and carbon fiber precast body
Than being 1：（0.26~0.52）.
3. the preparation method according to claims 1 or 2, which is characterized in that the carbon source is inorganic carbon source or/and organic
The mass ratio of carbon source, the carbon source and carbon fiber precast body is 1：（1.08~1.78）.
4. according to the preparation method described in claim 3, which is characterized in that the inorganic carbon source is carbon black, carbon dust, graphite powder
At least one of, the organic carbon source is at least one of phenolic resin, furane resins, silane resin.
5. preparation method according to claim 3 or 4, which is characterized in that when the carbon source is organic carbon source or organic carbon
When the mixture of source and inorganic carbon source, by gained Cf/HfO2- C preforms are first after drying and cracking, then carry out carbon thermal reduction.
6. preparation method according to claim 5, which is characterized in that the drying be at 80 DEG C~120 DEG C heat preservation 3~
6 hours, described be cracked into kept the temperature 1~2 hour at 600 DEG C~900 DEG C.
7. according to the preparation method described in any one of claim 1-6, which is characterized in that the vacuum degree of the vacuum impregnation technology
For -0.08~-0.10MPa.
8. according to the preparation method described in any one of claim 1-7, which is characterized in that the structure of the carbon fiber precast body
For D refraction statics, two-dimension laminate or 3 D weaving, open pore rate is 30~50vol%, fiber surface in the carbon fiber precast body
Deposition has the pyrolytic carbon PyC or pyrolytic carbon PyC/SiC composite multi-layers interface that thickness is 500~1500nm.
9. according to the preparation method described in any one of claim 1-8, which is characterized in that the atmosphere of the Si infiltrations is vacuum
Atmosphere, time are 0.5~3 hour.
10. a kind of C prepared according to any one of the claim 1-9 preparation methodsf/ SiC-HfC is ultra-temperature ceramic-based compound
Material, which is characterized in that the Cf/ SiC-HfC ultra-temperature ceramic-based composite materials include carbon fiber, SiC phases and HfC phases,
Middle carbon fiber content is 25~40vol%, and the volume ratio of HfC phases and SiC phases is 0.10~0.35.
11. C according to claim 10f/ SiC-HfC ultra-temperature ceramic-based composite materials, which is characterized in that the Cf/
The bending strength of SiC-HfC ultra-temperature ceramic-based composite materials is 93~125MPa, and the mass ablative rate at 2000 DEG C is
15.32~18.67mg/s.
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| CN110002890A (en) * | 2019-04-18 | 2019-07-12 | 中国科学院上海硅酸盐研究所 | A kind of Cf/ HfC-SiC ultra-temperature ceramic-based composite material and preparation method thereof |
| CN112457035A (en) * | 2020-11-23 | 2021-03-09 | 航天特种材料及工艺技术研究所 | Preparation method of Hf-Ta-C reinforced C/SiC ceramic matrix composite |
| CN114349539A (en) * | 2021-11-30 | 2022-04-15 | 西安鑫垚陶瓷复合材料有限公司 | Preparation method of C/SiC-HfC composite material part transition phase coating, transition phase coating slurry and component thermal protection method |
| CN116120095A (en) * | 2022-12-13 | 2023-05-16 | 西北工业大学 | Method for preparing gradient superhigh temperature ceramic modified C/C composite material by selective reaction infiltration method |
| CN116120095B (en) * | 2022-12-13 | 2024-04-19 | 西北工业大学 | Method for preparing gradient superhigh temperature ceramic modified C/C composite material by selective reaction infiltration method |
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| CN116120095A (en) * | 2022-12-13 | 2023-05-16 | 西北工业大学 | Method for preparing gradient superhigh temperature ceramic modified C/C composite material by selective reaction infiltration method |
| CN116120095B (en) * | 2022-12-13 | 2024-04-19 | 西北工业大学 | Method for preparing gradient superhigh temperature ceramic modified C/C composite material by selective reaction infiltration method |
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