CN104831107B - Ablation-resistant carbon/carbon-zirconium carbide-copper composite material and preparation method thereof - Google Patents
Ablation-resistant carbon/carbon-zirconium carbide-copper composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of an ablation-resistant carbon/carbon-zirconium carbide-copper composite material. The preparation method comprises preparing a porous carbon/carbon composite blank from polyacrylonitrile-based carbon fiber needled integral felt as a preform by a chemical vapor infiltration densification and high-temperature heat treatment technology, and carrying out reactive melt infiltration on zirconium-copper mixed powder into the carbon/carbon composite blank so that the ablation-resistant carbon/carbon-zirconium carbide-copper composite material is prepared. Performance indexes of the ablation-resistant carbon/carbon-zirconium carbide-copper composite material are determined. The preparation method utilizes the zirconium-copper mixed powder and prepares the ablation-resistant carbon/carbon-zirconium carbide-copper composite material with low porosity, uniform phase composition, good hardness and bending strength and excellent ablation performances at a low melt infiltration temperature.
Description
Technical field
The present invention relates to a kind of charcoal of resistance to ablation/charcoal-zirconium carbide-carbon/carbon-copper composite material and preparation method thereof；Belong to resistance to ablation multiple
Condensation material preparing technical field.
Background technology
With the development of space technology, the performance requirement more and more higher to ablation resistant material.The most typical part of resistance to ablation
It is the larynx lining of punching engine, larynx lining is located at punching engine throat, is rocket, the core of guided missile jet pipe material, if larynx lining
Operationally ablation is serious, will directly affect thrust and the efficiency of electromotor, and the aerodynamic configuration being difficult to keep stable even causes
Larynx serves as a contrast fragmentation, leads to electromotor to be lost the job ability, and therefore larynx lining becomes the key issue of development rocketry.
Throat liner material need to meet the oxidation of high temperature-resistant high-speed oxidizing atmosphere of rocket and guided missile, resistance to ablation, erosion and
The requirement of anti-thermal shock.Conventional throat liner material has refractory metal, graphite, copper-infiltrated graphite and carbon/carbon composite etc..For
The refractory metal making larynx lining is mainly tungsten and the flame-spraying tungsten of tungsten, molybdenum and metallic cementation, develops at present and using more is
Tungsten oozes copper larynx lining.Tungsten oozes copper or the effect playing " Sweat coolling " in copper product (copper content is 10%～50%),
Or play the effect of " heat sink ", effectively improve the ablation resistance of material.But tungsten oozes copper product, and density is big；And heat conduction system
Number is also big, causes that to arrange effective heat shield in the confined space of its shell very difficult, may cause the overheated burning of heat shield
Damage.Graphite resource enriches inexpensive, but graphite low intensity, thermal shock resistance are poor.Graphite oozes copper as a kind of new throat liner material
It is taken seriously.Copper-infiltrated graphite be by graphite matrix micropore penetrate into copper a kind of composite (copper content be 10%～
30%), its intensity is higher than graphite, and density oozes copper, low price less than tungsten, and the jet pipe throat lining being suitable for tactical missile is selected.Copper
Increased the heat conductivility of larynx lining, the fusing of copper and vaporization absorption heat in ablation process, improve the resistance to of graphite material simultaneously
Ablative.But the thermal shock resistance of graphite material itself is not enough, and leads to copper-infiltrated graphite because graphite frame strength is low
Low intensity is so that the application of copper-infiltrated graphite is very restricted.
It is no comparable that carbon/carbon composite has the other materials such as specific strength and specific modulus height, the good, good thermal shock of heat conductivity
The performance intended, is unanimously considered the optimal material currently used as larynx lining, thus is widely used in punching engine larynx lining, flight
The high-temperature components such as device nose cone.But carbon/carbon composite is susceptible to aoxidize in having oxygen atmosphere, oxidation during higher than 500 DEG C adds
Speed.Meanwhile, in High Temperature And Velocity air-flow, the easily oxidized ablation of carbon/carbon composite and erosion, ablation velocity fast and with burning
Room atmosphere pressures have exponent relation.Therefore, the oxidizable ablation of high temperature is the bottle that carbon/carbon composite uses as thermal structure material
Neck, new generation antioxidation, resistance to ablation carbon/carbon composite of crucial importance.
At present, the antioxidation of carbon/carbon composite, resistance to ablation mentality of designing have two kinds: first, with material itself to oxidation
Inner base premised on reaction anticaltalysis is modified, Carbon fibe and carbon matrix is modified processing, so that them is had stronger
Oxidation resistance；Second, stop that oxygen spreads with substrate contact with matrix using face coat.At present, learn both at home and abroad
The common practice of person is that introducing refractory carbide and amount of copper to improve carbon/carbon composite in carbon/carbon composite
Ablation resistance.The country such as the United States, Russia, method is using the difficulty such as interpolation ramet, hafnium carbide, zirconium carbide in carbon/carbon composite
The mode of molten carbide improving antiscour and the ablation resistance of carbon/carbon composite, with bear higher fuel gas temperature or
Obtain longer active time.
When adding the refractory carbides such as ramet, hafnium carbide, zirconium carbide in carbon/carbon composite, its conventional process has
Pressure sintering, slip/micropowder infusion process, polymer impregnation pyrolysis method, chemical vapor infiltration (cvi) and reaction infiltration method (rmi).
In these methods, pressure sintering is big to fibre damage, is easily destroyed toughening effect；The uniformity of slip in slip/micropowder infusion process
It is difficult to ensure that, additive is easily reunited in the base；Cvi method long preparation period, high cost, easily crusts in precast body surface；
Comparatively, rmi has the advantages that short preparation period, low cost and near-net-shape, be prepare composite effective ways it
One, have been widely used for preparing carborundum, zirconium carbide and the hafnium carbide based composites part with labyrinth.But will melt
Melt state molten metal, especially penetrate into zirconium liquid in porous charcoal base substrate, due to the infiltrating temperature of zirconium higher (more than 1850 DEG C), lead to
Preparation difficulty is larger, is unfavorable for industrialized production and application.
As for charcoal/carbon-copper composite material, because the wettability between copper and Carbon Materials is poor, lead to the property of its resulting materials
Can not be good.
In a word, up to the present yet there are no and prepare charcoal/charcoal-zirconium carbide-carbon/carbon-copper composite material and its use using element powders
Pertinent literature report.
Content of the invention
Present invention part in view of the shortcomings of the prior art, provides a kind of charcoal of resistance to ablation/charcoal-zirconium carbide-composite copper material
Material and preparation method thereof；Obtained that porosity is low, thing phase composition uniformly, hardness and bending strength is good, ablation property is excellent
Charcoal/charcoal-zirconium carbide-carbon/carbon-copper composite material.
A kind of charcoal of resistance to ablation of the present invention/charcoal-zirconium carbide-carbon/carbon-copper composite material is by charcoal/charcoal composite body, zirconium carbide and copper
And/or copper zirconium alloy is in mass ratio, charcoal/charcoal composite body: zirconium carbide: copper and/or copper zirconium alloy=25～45:20～50:55
～5, preferably 30～45:25～45:45～10, more preferably 30～40:30～50:40～10 composition.
A kind of charcoal of resistance to ablation of the present invention/charcoal-zirconium carbide-carbon/carbon-copper composite material, described charcoal/charcoal composite body is by Carbon fibe and warm
Solution charcoal Carbon fibe in mass ratio: pyrolytic carbon=30～60:70～40, be preferably 35～55:65～45, more preferably 40～
50:60～50 form；Described pyrolytic carbon is evenly coated at carbon fiber surface.
A kind of charcoal of resistance to ablation of the present invention/charcoal-zirconium carbide-carbon/carbon-copper composite material, described zirconium carbide part is evenly coated at pyrolysis
The surface of charcoal, part Dispersed precipitate is in copper and/or copper zirconium alloy；Described copper and/or copper zirconium alloy are evenly coated at pyrolytic carbon
Around the zirconium carbide on surface.
A kind of charcoal of resistance to ablation of the present invention/charcoal-zirconium carbide-carbon/carbon-copper composite material, the described charcoal of resistance to ablation/charcoal-zirconium carbide-copper is combined
In material, zr element and the mass ratio of copper are 30～90:70～10, are preferably 35～85:65～15, more preferably
40～80:60～20.
A kind of preparation method of charcoal of resistance to ablation of the present invention/charcoal-zirconium carbide-carbon/carbon-copper composite material, comprises the steps:
Step one
With Carbon fibe precast body as raw material, by vapor deposition pyrolytic charcoal, the charcoal/charcoal obtaining having interconnected pore is compound many
Hole base substrate；
Step 2
Step one gained charcoal/compound porous base substrate of charcoal is placed in the mixed-powder being made up of zirconium and copper, little in vacuum
In equal to 10-2Under conditions of atm, process in 1200～1600 DEG C of infiltrations, obtain the described charcoal of resistance to ablation/charcoal-zirconium carbide-copper and be combined
Material；In the described mixed-powder being made up of zirconium and copper, zirconium is 35～85:65～15, is preferably 40～80 with the mass ratio of copper:
60～20, it is more preferably 50～75:50～25.
A kind of preparation method of charcoal of resistance to ablation of the present invention/charcoal-zirconium carbide-carbon/carbon-copper composite material, Carbon fibe described in step one
Precast body is PAN based carbon fiber acupuncture entirety felt.
A kind of preparation method of charcoal of resistance to ablation of the present invention/charcoal-zirconium carbide-carbon/carbon-copper composite material, described Carbon fibe precast body is close
Spend for 0.4～0.6g/cm3's
A kind of preparation method of charcoal of resistance to ablation of the present invention/charcoal-zirconium carbide-carbon/carbon-copper composite material, vapour deposition heat in step one
The condition of solution charcoal is:
Carrier gas n2；
Carbon-source gas c3h6；
850～1100 DEG C of depositing temperature.
A kind of preparation method of charcoal of resistance to ablation of the present invention/charcoal-zirconium carbide-carbon/carbon-copper composite material, Carbon fibe precast body is through gas phase
Carry out high-temperature heat treatment again after deposition；The condition of described high-temperature heat treatment is:
Protective gas ar；
2000～2500 DEG C of heat treatment temperature；
Time 1-5 hour.
High-temperature heat treatment can remove partial impurities, degree of graphitization part closed pore becoming perforate, improving pyrolytic carbon.High
Warm processes the combination property that can improve the compound porous base substrate of charcoal/charcoal, provides base substrate basis for follow-up infiltration process.
A kind of preparation method of charcoal of resistance to ablation of the present invention/charcoal-zirconium carbide-carbon/carbon-copper composite material, step one gained charcoal/charcoal is combined
The porosity of porous body is 20～50%.
A kind of preparation method of charcoal of resistance to ablation of the present invention/charcoal-zirconium carbide-carbon/carbon-copper composite material, has described in step one even
The density of the compound porous base substrate of charcoal/charcoal of through hole gap is 1.0～1.6g/cm3.
A kind of preparation method of charcoal of resistance to ablation of the present invention/charcoal-zirconium carbide-carbon/carbon-copper composite material, in step 2, described by zirconium and
The mixed-powder of copper composition is made up of zirconium powder and copper powder；The purity of described zirconium powder is more than or equal to 99%；The purity of described copper powder
More than or equal to 99%.
A kind of preparation method of charcoal of resistance to ablation of the present invention/charcoal-zirconium carbide-carbon/carbon-copper composite material, in step 2, by step one institute
After the compound porous base substrate of charcoal/charcoal is placed in the mixed-powder being made up of zirconium and copper, heated up with the heating rate of 3～6 DEG C/min
To 1200～1600 DEG C.
Principle and advantage
The present invention with the mixed-powder of zirconium and copper composition for zirconium source and Tong Yuan, especially when pure copper powder being used as copper source
When, the temperature of pure zirconium infiltration can be substantially reduced using copper and then achieve infiltration zirconium, copper at a lower temperature and be combined in charcoal/charcoal
In material, this reduces the damage of Carbon fibe during infiltration to a certain extent.The present invention also dexterously make use of zirconium simultaneously
Copper and charcoal wettability this characteristic of difference is overcome during infiltration；When zirconium, copper simultaneously enter the compound porous base substrate of charcoal/charcoal
When, zirconium is had precedence over copper and is reacted with pyrolytic carbon and generates zirconium carbide, and with the carrying out of infiltration, zirconium can diffuse into the interior of pyrolytic carbon
Portion, thus react formation and the compact zirconium carbide of pyrolytic carbon；Simultaneously because during molten oozing, zirconium is along near pyrolysis
Charcoal direction diffusion, this be also the formation of good intermediate zone (this intermediate zone be possible to containing zirconium carbide, copper or zirconium carbide,
Copper, zirconium), this is conducive to improving the overall performance of material, in addition, and copper in composite, work under the conditions of high-temperature fuel gas
Work can vaporization, and then take away matrix heat, this is conducive to improving the ablation resistance of composite further.
It is infiltrant that the present invention adopts zirconium-copper mixed-powder, the preparation process is simple of composite, and can be conveniently adjusted
The ratio of penetration enhancer, this also allows for better controling over the content of thing phase composition and each component in finished-product material.
The present invention is by regulation and control such as the porosity of control charcoal/charcoal base substrate, the distribution of carbon matrix, penetration enhancer composition, infiltration process
Tissue constituent in composite and phase composition thing and its ratio.This substantially reduces and prepare high-density carbon/carbon/charcoal composite wood
The production cycle of material, the zirconium carbide simultaneously obtaining and amount of copper can improve the ablation resistance of composite.
In composite designed by the present invention, zirconium carbide have the ratio elastic modelling quantity higher than ramet and hafnium carbide with
And lower preparation cost, and antioxygenic property is better than ramet, can match in excellence or beauty with hafnium carbide, and its density (6.73g/cm3) about
For hafnium carbide density (12.2g/cm3) half, be suitable for the lightweight demand in AEROSPACE APPLICATION.In addition zirconium carbide has
High intensity, high rigidity and good high temperature thermal shock resistance energy, up to 2700 DEG C of the zirconium oxide protecting film fusing point being formed after its oxidation,
Guarantee obtained finished-product material under arms during there is longer service life and more superior ablation resistance
Energy.In composite designed by simultaneously in the present invention, zirconium carbide due to its rational thermal coefficient of expansion, in material military service process
In, the thermal stress of charcoal/between charcoal composite body and metal level can be adjusted well, even if this allows for temperature rises to copper vaporization
When, composite also will not occur large-scale Local Cracking, and then leads to the situation of material complete failure.
The present invention, by the appropriate design to composite structure, by the synergism of component each in composite, obtains
Arrived that consistency is high, thing phase composition is uniform, organizational structure is controlled, hardness and bending strength is good, ablation property is excellent charcoal/
Charcoal-zirconium carbide-carbon/carbon-copper composite material.
In a word, composite structure of the present invention is reasonable in design, and preparation process is simple facilitates implementation commercial application.
Brief description
Accompanying drawing 1 is the sem pattern of the charcoal/charcoal-zirconium carbide-carbon/carbon-copper composite material prepared by embodiment 2；
Accompanying drawing 2 is the xrd collection of illustrative plates of the charcoal/charcoal-zirconium carbide-carbon/carbon-copper composite material of different infiltrant preparations；
It can be seen that from FIG. 1 a that zirconium carbide, copper and/or copper zirconium alloy have uniformly filled the hole of charcoal/charcoal base substrate, formed
Continuous fine and close composite；As can be seen that zirconium carbide part is evenly coated at by Carbon fibe and pyrolytic carbon group from Fig. 1 b
" charcoal phase " surface becoming, in copper and/or copper zirconium alloy, copper and/or copper zirconium alloy are evenly coated at " charcoal to part Dispersed precipitate
Around the zirconium carbide on phase " surface；Can be seen that from Fig. 1 c, zirconium carbide particle is embedded in copper and/or copper zirconium alloy.
In Fig. 2, a curve is the xrd collection of illustrative plates of charcoal/charcoal-zirconium carbide-carbon/carbon-copper composite material prepared by embodiment 1, from a curve
It can be seen that containing carbon, zirconium carbide, copper and zirconium copper alloy in composite；B curve is charcoal/charcoal-carbon prepared by embodiment 2
Change the xrd collection of illustrative plates of zirconium-carbon/carbon-copper composite material, from b curve it can be seen that in composite, contain carbon, zirconium carbide and copper；C is bent
Line is the xrd collection of illustrative plates of charcoal/charcoal-zirconium carbide-carbon/carbon-copper composite material prepared by embodiment 3, from c curve it can be seen that in composite
Containing carbon, zirconium carbide, zirconium and zirconium copper alloy.
Specific embodiment
The invention will be further described with reference to the accompanying drawings and detailed description.
Raw material used by embodiment is the quasi- D refraction statics entirety felt of PAN based carbon fiber plain+net tire, through net
Change the c processing3h6, high-purity n2, high-purity ar, zirconium powder (＞ 99%), copper powder (＞ 99%) and other chemical reagent (analysis is pure)
Deng.
Embodiment 1:
(1) with PAN based carbon fiber acupuncture entirety felt, as precast body, (density is as 0.4g/cm3), in high-purity n2Carry
Gas, c3h6Cvi density and high-temperature heat treatment (ar protective atmosphere, 2000 DEG C, 5h) is adopted under carbon-source gas, 850 DEG C of depositing temperature
Technique prepare porosity about 50% charcoal/charcoal composite body (density be 1.0g/cm3)；
(2) prepare zirconium-copper mixed powder, the wherein mass percent of zirconium powder is 50%；
(3) charcoal of step (1)/charcoal composite body is embedded in the mixed powder of step (2), in 1200 DEG C of vacuum condition
(vacuum is less than or equal to 10-2Atm under), infiltration processes 4h, obtains charcoal/charcoal-zirconium carbide-carbon/carbon-copper composite material after reaction；It forms matter
Measuring ratio is, charcoal/charcoal composite body: zirconium carbide: copper and/or copper zirconium alloy=32.28:23.1:44.62.
(4) charcoal/charcoal-zirconium carbide-carbon/carbon-copper composite material is processed into the cylinder of φ 30*10mm, enters under conditions of 3000 DEG C
Row oxy-acetylene ablation experiments, ablation time 60s；
(5) performance indications of charcoal/charcoal-zirconium carbide-carbon/carbon-copper composite material are measured, as shown in the table:
Embodiment 2:
(1) with PAN based carbon fiber acupuncture entirety felt, as precast body, (density is as 0.4g/cm3), in high-purity n2Carry
Gas, c3h6Cvi density and high-temperature heat treatment (ar protective atmosphere, 2150 DEG C, 4h) is adopted under carbon-source gas, 950 DEG C of depositing temperature
Technique prepare porosity about 40% charcoal/charcoal composite body (density be 1.2g/cm3)；
(2) prepare zirconium-copper mixed powder, the wherein mass percent of zirconium powder is 60%；
(3) charcoal of step (1)/charcoal composite body is embedded in the mixed powder of step (2), in 1350 DEG C of vacuum condition
(vacuum is less than or equal to 10-2Atm under), infiltration processes 3h, obtains charcoal/charcoal-zirconium carbide-carbon/carbon-copper composite material after reaction；It forms matter
Measuring ratio is, charcoal/charcoal composite body: zirconium carbide: copper and/or copper zirconium alloy=28.38:43.2:28.42.
(4) charcoal/charcoal-zirconium carbide-carbon/carbon-copper composite material is processed into the cylinder of φ 30*10mm, enters under conditions of 3000 DEG C
Row oxy-acetylene ablation experiments, ablation time 60s；
(5) performance indications of charcoal/charcoal-zirconium carbide-carbon/carbon-copper composite material are measured, as shown in the table:
Embodiment 3:
(1) with PAN based carbon fiber acupuncture entirety felt, as precast body, (density is as 0.5g/cm3), in high-purity n2Dilution
Gas, c3h6Adopt under carbon-source gas, 1050 DEG C of depositing temperature cvi density and high-temperature heat treatment (ar protective atmosphere, 2300 DEG C,
2h) technique prepare porosity about 30% charcoal/charcoal composite body (density be 1.4g/cm3)；
(2) prepare zirconium-copper mixed powder, the wherein mass percent of zirconium powder is 70%；
(3) charcoal of step (1)/charcoal composite body is embedded in the mixed powder of step (2), in 1500 DEG C of vacuum condition
(vacuum is less than or equal to 10-2Atm under), infiltration processes 2h, obtains charcoal/charcoal-zirconium carbide-carbon/carbon-copper composite material after reaction；It forms matter
Measuring ratio is, charcoal/charcoal composite body: zirconium carbide: copper and/or copper zirconium alloy=44.74:40.5:14.76.
(4) charcoal/charcoal-zirconium carbide-carbon/carbon-copper composite material is processed into the cylinder of φ 30*10mm, enters under conditions of 3000 DEG C
Row oxy-acetylene ablation experiments, ablation time 60s；
(5) performance indications of charcoal/charcoal-zirconium carbide-carbon/carbon-copper composite material, are measured, as shown in the table:
Embodiment 4:
(1) with PAN based carbon fiber acupuncture entirety felt, as precast body, (density is as 0.6g/cm3), in high-purity n2Dilution
Gas, c3h6Adopt under carbon-source gas, 1100 DEG C of depositing temperature cvi density and high-temperature heat treatment (ar protective atmosphere, 2500 DEG C,
1h) technique prepare porosity about 20% charcoal/charcoal be combined composite body (density be 1.6g/cm3)；
(2) prepare zirconium-copper mixed powder, the wherein mass percent of zirconium powder is 80%；
(3) charcoal of step (1)/charcoal composite body is embedded in the mixed powder of step (2), in 1600 DEG C of vacuum condition
(vacuum is less than or equal to 10-2Atm under), infiltration processes 1h, obtains charcoal/charcoal-zirconium carbide-carbon/carbon-copper composite material after reaction；It forms matter
Measuring ratio is, charcoal/charcoal composite body: zirconium carbide: copper and/or copper zirconium alloy=43.54:44.1:12.36.
(4) charcoal/charcoal-zirconium carbide-carbon/carbon-copper composite material is processed into the cylinder of φ 30*10mm, enters under conditions of 3000 DEG C
Row oxy-acetylene ablation experiments, ablation time 60s；
(5) performance indications of charcoal/charcoal-zirconium carbide-carbon/carbon-copper composite material are measured, as shown in the table:
Comparative example 1:
(1) with Carbon fibe acupuncture entirety felt, as precast body, (density is as 0.5g/cm3), by multiple chemical gas-phase permeation
(cvi) density obtain porosity be 25% charcoal/charcoal composite body (density be 1.5g/cm3)；
(2) prepare copper-titanium mixed powder, the wherein mass percent of copper powder is 90%；
(3) charcoal of step (1)/charcoal composite body is embedded in the mixed powder of step (2), in vacuum condition (vacuum
Less than or equal to 10-2Atm under), infiltration processes and prepares charcoal/carbon-copper composite material；It forms mass ratio, charcoal/charcoal composite billet
Body: copper=52.26:47.74.
(4) charcoal/carbon-copper composite material is processed into the cylinder of φ 30*10mm, carries out oxygen-second under conditions of 3000 DEG C
Alkynes ablation experiments, ablation time 40s；
(5) performance indications of charcoal/charcoal-zirconium carbide-carbon/carbon-copper composite material are measured, as shown in the table:
Comparative example 2:
(1) with 2.5d Nomex, as precast body, (density is as 0.5g/cm3), with c3h6For raw material, high-purity n2For carrier gas,
Cvi density and high-temperature heat treatment (ar protective atmosphere, 2500 DEG C, 1h) technique is adopted to prepare porosity under 1000 DEG C of depositing temperature
(density is 1.6g/cm to about 20% charcoal/charcoal composite body3)；
(2) charcoal of step (1)/charcoal composite body is embedded in pure zirconium powder, at 1900 DEG C of vacuum conditions (10pa)
Lower infiltration is processed, and obtains charcoal/charcoal-carbonization zirconium composite material after reaction；It forms mass ratio, charcoal/charcoal composite body: zirconium carbide
=51,95:48.05.
(3) charcoal/charcoal-zirconium carbide composite processing is become the cylinder of φ 30*10mm, carry out under conditions of 3000 DEG C
Oxy-acetylene ablation experiments, ablation time 30s；
(4) performance indications of charcoal/charcoal-zirconium carbide-carbon/carbon-copper composite material are measured, as shown in the table:
Can be seen that the material designed by the present invention to be fully able to be applied to punching engine by embodiment and comparative example
Larynx lining, the ablating rate of material designed by the present invention is significantly lower than comparative example and the material designed by prior art, and this is favourable
In the thrust improving punching engine and efficiency, stably spray the aerodynamic configuration of air-flow, extend making during larynx serves as a contrast under arms
Use the life-span.This is also that the more superior new rocket of exploitation performance provides essential condition.
Claims (5)
1. a kind of charcoal of resistance to ablation/charcoal-zirconium carbide-carbon/carbon-copper composite material；It is characterized in that,
Described composite by charcoal/charcoal composite body, zirconium carbide and copper and/or copper zirconium alloy in mass ratio, charcoal/charcoal composite billet
Body: zirconium carbide: copper and/or copper zirconium alloy=30～45:20～45:40～10 composition；
The preparation method of described composite, comprises the steps:
Step one
With Carbon fibe precast body as raw material, by vapor deposition pyrolytic charcoal, obtain the compound porous base of charcoal/charcoal with interconnected pore
Body；Carbon fibe precast body described in step one is PAN based carbon fiber acupuncture entirety felt；Described PAN based carbon fiber
The density of acupuncture entirety felt is 0.4～0.6g/cm3；The porosity of step one gained charcoal/compound porous base substrate of charcoal be 20～
50%；Density is 1.0～1.6g/cm3；
Step 2
Step one gained charcoal/compound porous base substrate of charcoal is placed in the mixed-powder being made up of zirconium and copper, be less than in vacuum etc.
In 10-2Under conditions of atm, it is warming up to 1200～1600 DEG C with the heating rate of 3～6 DEG C/min, and molten in 1200～1600 DEG C
Ooze process, obtain the described charcoal of resistance to ablation/charcoal-zirconium carbide-carbon/carbon-copper composite material；In the described mixed-powder being made up of zirconium and copper, zirconium
Mass ratio with copper is 35～85:65～15；In step 2, described is by zirconium powder and copper powder by the mixed-powder that zirconium and copper form
Composition；The purity of described zirconium powder is more than or equal to 99%；The purity of described copper powder is more than or equal to 99%.
2. a kind of charcoal of resistance to ablation according to claim 1/charcoal-zirconium carbide-carbon/carbon-copper composite material；It is characterized in that:
Described charcoal/charcoal composite body by Carbon fibe and pyrolytic carbon in mass ratio, Carbon fibe: pyrolytic carbon=30～60:70～40 group
Become；Described pyrolytic carbon is evenly coated at carbon fiber surface.
3. a kind of charcoal of resistance to ablation according to claim 1/charcoal-zirconium carbide-carbon/carbon-copper composite material；It is characterized in that:
Described zirconium carbide part is evenly coated at the surface of pyrolytic carbon, and part Dispersed precipitate is in copper and/or copper zirconium alloy；Described
Copper and/or copper zirconium alloy are evenly coated at around the zirconium carbide of pyrolysis carbon surface；
In the described charcoal of resistance to ablation/charcoal-zirconium carbide-carbon/carbon-copper composite material, the mass ratio of zr element and copper be 30～90:70～
10.
4. a kind of charcoal of resistance to ablation according to claim 1/charcoal-zirconium carbide-carbon/carbon-copper composite material；It is characterized in that:
In step one, the condition of vapor deposition pyrolytic charcoal is:
Carrier gas n2；
Carbon-source gas c3h6；
850～1100 DEG C of depositing temperature.
5. a kind of charcoal of resistance to ablation according to claim 4/charcoal-zirconium carbide-carbon/carbon-copper composite material；It is characterized in that:
Carbon fibe precast body carries out high-temperature heat treatment after vapour deposition again；The condition of described high-temperature heat treatment is:
Protective gas ar；
2000～2500 DEG C of heat treatment temperature；
Time 1-5 hour.
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| CN201510162852.5A CN104831107B (en) | 2015-04-08 | 2015-04-08 | Ablation-resistant carbon/carbon-zirconium carbide-copper composite material and preparation method thereof |
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| CN107058915B (en) * | 2017-04-20 | 2019-04-09 | 湖南中南智造新材料协同创新有限公司 | A kind of infiltration powder containing chromium and its application in copper chrome-silicon modified carbon/ceramic friction material |
| CN107217168A (en) * | 2017-05-05 | 2017-09-29 | 南京云启金锐新材料有限公司 | A kind of infiltration method zirconium oxide copper composite metal ceramics and preparation method thereof |
| CN107311684A (en) * | 2017-07-24 | 2017-11-03 | 哈尔滨工业大学 | A kind of dissipation heat-resistant composite material and preparation method thereof |
| CN108531767B (en) * | 2018-05-09 | 2020-01-10 | 台州学院 | Preparation method of superfine zirconium carbide particle dispersion-strengthened copper-based composite material for spot welding electrode |
| CN110983208B (en) * | 2019-10-24 | 2021-08-31 | 中南大学 | C/C-SiC-Cu composite material and preparation method and application thereof |
| CN110937910B (en) * | 2019-12-13 | 2021-09-07 | 中南大学 | Preparation method of composite nano refractory ceramic modified carbon/carbon composite material |
| CN112573937A (en) * | 2020-12-29 | 2021-03-30 | 中京吉泰(北京)科技有限责任公司 | C/C-SiC-Cu composite material and preparation method thereof |
| CN113213472B (en) * | 2021-05-20 | 2022-09-20 | 哈尔滨工业大学 | Method for preparing complex-structure carbon material anti-oxidation coating with assistance of metal liquid phase |
| CN115231923A (en) * | 2022-07-15 | 2022-10-25 | 航天特种材料及工艺技术研究所 | Structure function integrated ceramic matrix composite and preparation method thereof |
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