CN104831107A - 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 the preparing technical field of resistance to ablative composite material.
Background technology
Along with the development of spationautics, more and more higher to the performance requriements of ablation resistant material.The most typical parts of resistance to ablation are larynx linings of punching engine, larynx lining is positioned at punching engine throat, it is the core of rocket, guided missile jet pipe material, if it is serious that larynx serves as a contrast operationally ablation, to directly affect thrust and the efficiency of engine, be difficult to keep stable aerodynamic configuration even to cause larynx to serve as a contrast cracked, cause engine to lose the job ability, therefore larynx lining becomes the key issue of development rocketry.
The requirement of the oxidation of the high temperature-resistant high-speed oxidizing atmosphere of throat liner material demand fulfillment rocket and guided missile, resistance to ablation, erosion and anti-thermal shock.Conventional throat liner material has refractory metal, graphite, copper-infiltrated graphite and carbon/carbon composite etc.For making the refractory metal mainly tungsten of tungsten, molybdenum and metallic cementation and the flame plating tungsten of larynx lining, what current development and application was more is that tungsten oozes copper larynx lining.Tungsten oozes the copper in copper product (copper content is 10% ~ 50%) or plays the effect of " Sweat coolling ", or plays the effect of " heat sink ", effectively improves the ablation resistance of material.But tungsten oozes copper product, and density is large; And thermal conductivity is also large, cause that in the finite space of its shell, to arrange effective heat-protection layer very difficult, the overheated scaling loss of heat-protection layer may be caused.Graphite resource enriches inexpensive, but graphite intensity is low, thermal shock resistance is poor.Graphite oozes copper and also comes into one's own as the novel throat liner material of one.Copper-infiltrated graphite is that its intensity is higher than graphite, and density is less than tungsten and oozes copper, low price, and the jet pipe throat lining being suitable for tactical missile is selected by a kind of matrix material infiltrating copper in graphite matrix micropore (copper content is 10% ~ 30%).Copper adds the heat conductivility of larynx lining, and simultaneously the fusing of copper and vaporization absorption heat in ablation process, improve the ablation resistance of graphite material.But the thermal shock resistance of graphite material itself is not enough, and causes copper-infiltrated graphite intensity low because graphite frame strength is low, makes the application of copper-infiltrated graphite be very restricted.
The unrivaled performances of other material such as carbon/carbon composite has specific tenacity and specific modulus is high, thermal conductivity is good, good thermal shock, unanimously thought to be used as at present the best materials of larynx lining, be thus widely used in the high-temperature components such as punching engine larynx lining, aircraft nose cone.But carbon/carbon composite is easily oxidized having in oxygen atmosphere, accelerate higher than oxidation when 500 DEG C.Meanwhile, in High Temperature And Velocity air-flow, the easy oxidized ablation of carbon/carbon composite and erosion, ablation velocity fast and with combustion chamber atmosphere pressures exponentially relation.Therefore, the oxidizable ablation of high temperature is the bottleneck that carbon/carbon composite uses as thermal structure material, and the carbon/carbon composite of anti-oxidant, the resistance to ablation of new generation is of crucial importance.
At present, anti-oxidant, the resistance to ablation mentality of designing of carbon/carbon composite has two kinds: first, by material itself to the inner base modification premised on oxidizing reaction anticatalysis, namely modification is carried out to Carbon fibe and carbon matrix, make them have stronger resistance of oxidation; The second, utilize top coat stop oxygen and substrate contact and spread in matrix.At present, the common practice of Chinese scholars in carbon/carbon composite, introduces refractory carbide and amount of copper to improve the ablation resistance of carbon/carbon composite.The country such as the United States, Russia, method adopts the mode of adding the refractory carbides such as tantalum carbide, hafnium carbide, zirconium carbide in carbon/carbon composite to improve antiscour and the ablation resistance of carbon/carbon composite, to bear higher fuel gas temperature or to obtain longer active time.
When adding the refractory carbides such as tantalum carbide, hafnium carbide, zirconium carbide in carbon/carbon composite, its conventional process has pressure sintering, slip/micro mist pickling process, polymer impregnation pyrolysis method, chemical vapor infiltration (CVI) and reaction infiltration method (RMI).In these methods, pressure sintering is large to fibre-tendering, easily destroys toughening effect; In slip/micro mist pickling process, the homogeneity of slip is difficult to ensure, additive is easily reunited in the base; CVI method preparation cycle is long, and cost is high, easily at precast body surface crust; Comparatively speaking, RMI has that preparation cycle is short, cost is low and the advantage such as near-net-shape, is one of effective ways preparing matrix material, has been widely used in preparing silicon carbide, zirconium carbide and the hafnium carbide based composites parts with complex construction.But by molten metal liquid, especially zirconium liquid is infiltrated in porous charcoal base substrate, due to the infiltrating temperature of zirconium higher (more than 1850 DEG C), cause preparation difficulty comparatively large, be unfavorable for suitability for industrialized production and application.
As for charcoal/carbon-copper composite material, because the wettability between copper and Carbon Materials is poor, cause the performance of its resulting materials not good.
In a word, up to the present yet there are no the pertinent literature report adopting element powders to prepare charcoal/charcoal-zirconium carbide-carbon/carbon-copper composite material and use thereof.
Summary of the invention
The present invention is directed to the weak point that prior art exists, a kind of charcoal of resistance to ablation/charcoal-zirconium carbide-carbon/carbon-copper composite material and preparation method thereof is provided; Obtain that porosity is low, thing phase composite evenly, 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/charcoal-zirconium carbide-carbon/carbon-copper composite material of the present invention by charcoal/charcoal composite body, zirconium carbide and copper and/or copper zirconium alloy in mass ratio, charcoal/charcoal composite body: zirconium carbide: copper and/or copper zirconium alloy=25 ~ 45:20 ~ 50:55 ~ 5, is preferably 30 ~ 45:25 ~ 45:45 ~ 10, more preferably 30 ~ 40:30 ~ 50:40 ~ 10 and forms.
A kind of charcoal of resistance to ablation/charcoal-zirconium carbide-carbon/carbon-copper composite material of the present invention, described charcoal/charcoal composite body is by Carbon fibe and pyrolytic carbon Carbon fibe in mass ratio: pyrolytic carbon=30 ~ 60:70 ~ 40, be preferably 35 ~ 55:65 ~ 45, more preferably 40 ~ 50:60 ~ 50 and form; Described pyrolytic carbon is evenly coated on carbon fiber surface.
A kind of charcoal of resistance to ablation/charcoal-zirconium carbide-carbon/carbon-copper composite material of the present invention, described zirconium carbide part is evenly coated on 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 on around the zirconium carbide on pyrolytic carbon surface.
A kind of charcoal of resistance to ablation/charcoal-zirconium carbide-carbon/carbon-copper composite material of the present invention, in the described charcoal of resistance to ablation/charcoal-zirconium carbide-carbon/carbon-copper composite material, the mass ratio of zr element and copper is 30 ~ 90:70 ~ 10, is preferably 35 ~ 85:65 ~ 15, more preferably 40 ~ 80:60 ~ 20.
The preparation method of a kind 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 for raw material, by vapor deposition pyrolytic charcoal, obtain the compound porous base substrate of charcoal/charcoal with open pore;
Step 2
The compound porous base substrate of step one gained charcoal/charcoal is placed in the mixed powder be made up of zirconium and copper, is less than or equal to 10 in vacuum tightness
-2under the condition of atm, in 1200 ~ 1600 DEG C of infiltration process, obtain the described charcoal of resistance to ablation/charcoal-zirconium carbide-carbon/carbon-copper composite material; In the described mixed powder be made up of zirconium and copper, the mass ratio of zirconium and copper is 35 ~ 85:65 ~ 15, is preferably 40 ~ 80:60 ~ 20, more preferably 50 ~ 75:50 ~ 25.
The preparation method of a kind of charcoal of resistance to ablation of the present invention/charcoal-zirconium carbide-carbon/carbon-copper composite material, the precast body of Carbon fibe described in step one is the overall felt of PAN-based carbon fiber acupuncture.
The preparation method of a kind of charcoal of resistance to ablation of the present invention/charcoal-zirconium carbide-carbon/carbon-copper composite material, described Carbon fibe precast body density is 0.4 ~ 0.6g/cm
3's
The preparation method of a kind of charcoal of resistance to ablation of the present invention/charcoal-zirconium carbide-carbon/carbon-copper composite material, in step one, the condition of vapor deposition pyrolytic charcoal is:
Carrier gas N
2;
Carbon-source gas C
3h
6;
Depositing temperature 850 ~ 1100 DEG C.
The preparation method of a kind of charcoal of resistance to ablation of the present invention/charcoal-zirconium carbide-carbon/carbon-copper composite material, Carbon fibe precast body carries out high-temperature heat treatment again after vapour deposition; The condition of described high-temperature heat treatment is:
Shielding gas Ar;
Thermal treatment temp 2000 ~ 2500 DEG C;
Time 1-5 hour.
The degree of graphitization that high-temperature heat treatment can be removed partial impurities, part closed pore be become perforate, improves pyrolytic carbon.High-temperature heat treatment can improve the over-all properties of the compound porous base substrate of charcoal/charcoal, for follow-up infiltration process provides base substrate basis.
The preparation method of a kind of charcoal of resistance to ablation of the present invention/charcoal-zirconium carbide-carbon/carbon-copper composite material, the porosity of the compound porous base substrate of step one gained charcoal/charcoal is 20 ~ 50%.
The preparation method of a kind of charcoal of resistance to ablation of the present invention/charcoal-zirconium carbide-carbon/carbon-copper composite material, the density described in step one with the compound porous base substrate of charcoal/charcoal of open pore is 1.0 ~ 1.6g/cm
3.
The preparation method of a kind of charcoal of resistance to ablation of the present invention/charcoal-zirconium carbide-carbon/carbon-copper composite material, in step 2, the described mixed powder be made up of zirconium and copper 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 is more than or equal to 99%.
The preparation method of a kind of charcoal of resistance to ablation of the present invention/charcoal-zirconium carbide-carbon/carbon-copper composite material, in step 2, after the compound porous base substrate of step one gained charcoal/charcoal is placed in the mixed powder be made up of zirconium and copper, be warming up to 1200 ~ 1600 DEG C with the temperature rise rate of 3 ~ 6 DEG C/min.
Principle and advantage
The present invention with zirconium and copper composition mixed powder for zirconium source and Tong Yuan, especially when using pure copper powder as copper source, utilize copper greatly can reduce the temperature of pure zirconium infiltration and then achieve at a lower temperature that infiltration zirconium, copper are in carbon/carbon composite, this reduces the damage of Carbon fibe in infiltration process to a certain extent.The present invention simultaneously also make use of zirconium dexterously in infiltration process, overcomes copper and this characteristic of charcoal wettability difference; When zirconium, copper enter the compound porous base substrate of charcoal/charcoal simultaneously, zirconium has precedence over copper and pyrolytic carbon and reacts and generate zirconium carbide, and along with the carrying out of infiltration, zirconium can diffuse into the inside of pyrolytic carbon, thus reaction is formed and the compact zirconium carbide of pyrolytic carbon; Simultaneously due in molten infiltrate journey, zirconium spreads along near the direction of pyrolytic carbon, this also just defines good transitional zone (this transitional zone is likely containing zirconium carbide, copper or zirconium carbide, copper, zirconium), this is conducive to the overall performance improving material, in addition, the copper in matrix material, working under high-temperature fuel gas condition can vaporization, and then take away matrix heat, this is conducive to the ablation resistance improving matrix material further.
The present invention adopts zirconium-copper mixed powder to be infiltration agent, and the preparation technology of matrix material is simple, and can regulate the ratio of penetration enhancer easily, and this is also convenient to control better the content of thing phase composite in finished-product material and each component.
The present invention is by controlling to organize constituent and phase composite thing and ratio thereof in the regulation and control such as distribution, penetration enhancer composition, the infiltration process matrix material of the porosity of charcoal/charcoal base substrate, carbon matrix.This substantially reduces the production cycle of preparing high-density carbon/carbon composite material, the zirconium carbide simultaneously obtained and amount of copper can improve the ablation resistance of matrix material.
In matrix material designed by the present invention, zirconium carbide has than tantalum carbide and the higher ratio Young's modulus of hafnium carbide and lower preparation cost, and antioxidant property is better than tantalum carbide, can match in excellence or beauty with hafnium carbide, and its density (6.73g/cm
3) be about hafnium carbide density (12.2g/cm
3) half, be suitable for the lightweight demand in aerospace application.In addition zirconium carbide has high strength, high rigidity and good high temperature thermal shock resistance energy; the zirconium white protective membrane fusing point formed after its oxidation, up to 2700 DEG C, guarantees obtained finished-product material and has longer work-ing life and more superior ablation resistance in process under arms.Simultaneously in the matrix material designed by the present invention, zirconium carbide is due to its rational thermal expansivity, in material military service process, well can regulate the thermal stresses of charcoal/between charcoal composite body and metal level, even if when this just makes temperature rise to copper vaporization, matrix material also can not there will be large-scale Local Cracking, and then causes the situation of material complete failure.
The present invention is by the appropriate design to composite structure, by the synergy of component each in matrix material, obtain that density is high, thing phase composite is even, weave construction 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 technology is simple, is convenient to realize commercial application.
Accompanying drawing explanation
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 XRD figure spectrums of charcoal/charcoal-zirconium carbide-carbon/carbon-copper composite material prepared by different infiltration agent;
As can be seen from Fig. 1 a, the hole of zirconium carbide, copper and/or copper zirconium alloy uniform filling charcoal/charcoal base substrate, defines matrix material fine and close continuously; As can be seen from Fig. 1 b, zirconium carbide part is evenly coated on " charcoal phase " surface be made up of Carbon fibe and pyrolytic carbon, and part Dispersed precipitate is in copper and/or copper zirconium alloy, and copper and/or copper zirconium alloy are evenly coated on around the zirconium carbide on " charcoal phase " surface; Can find out from Fig. 1 c, zirconium carbide particle is embedded in copper and/or copper zirconium alloy.
In Fig. 2, the XRD figure spectrum of a curve charcoal/charcoal-zirconium carbide-carbon/carbon-copper composite material prepared by embodiment 1, can find out in matrix material containing carbon, zirconium carbide, copper and zirconium copper alloy from a curve; The XRD figure spectrum of b curve charcoal/charcoal-zirconium carbide-carbon/carbon-copper composite material prepared by embodiment 2, can find out in matrix material containing carbon, zirconium carbide and copper from b curve; The XRD figure spectrum of c curve charcoal/charcoal-zirconium carbide-carbon/carbon-copper composite material prepared by embodiment 3, can find out in matrix material containing carbon, zirconium carbide, zirconium and zirconium copper alloy from c curve.
Embodiment
Below in conjunction with the drawings and specific embodiments, the invention will be further described.
Embodiment raw material used is the overall felt of accurate D refraction statics of PAN-based carbon fiber plain+net tire, through the C of purifying treatment
3h
6, high-purity N
2, high-purity Ar, zirconium powder (> 99%), copper powder (> 99%) and other chemical reagent (analytical pure) etc.
Embodiment 1:
(1) using the overall felt of PAN-based carbon fiber acupuncture, as precast body, (density is for 0.4g/cm
3), in high-purity N
2carrier gas, C
3h
6(density is 1.0g/cm to adopt CVI density and high-temperature heat treatment (Ar protective atmosphere, 2000 DEG C, 5h) technique to prepare the charcoal/charcoal composite body of porosity about 50% under carbon-source gas, the depositing temperature of 850 DEG C
3);
(2) prepare zirconium-copper powder mix, wherein the mass percent of zirconium powder is 50%;
(3) be embedded in the powder mix of step (2) by the charcoal of step (1)/charcoal composite body, at the vacuum conditions of 1200 DEG C, (vacuum tightness is less than or equal to 10
-2atm) infiltration process 4h under, obtains charcoal/charcoal-zirconium carbide-carbon/carbon-copper composite material after reaction; Its composition mass 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, under the condition of 3000 DEG C, carries out oxy-acetylene ablation experiments, ablation time 60s;
(5) performance index of charcoal/charcoal-zirconium carbide-carbon/carbon-copper composite material are measured, as shown in the table:
Embodiment 2:
(1) using the overall felt of PAN-based carbon fiber acupuncture, as precast body, (density is for 0.4g/cm
3), in high-purity N
2carrier gas, C
3h
6(density is 1.2g/cm to adopt CVI density and high-temperature heat treatment (Ar protective atmosphere, 2150 DEG C, 4h) technique to prepare the charcoal/charcoal composite body of porosity about 40% under carbon-source gas, the depositing temperature of 950 DEG C
3);
(2) prepare zirconium-copper powder mix, wherein the mass percent of zirconium powder is 60%;
(3) be embedded in the powder mix of step (2) by the charcoal of step (1)/charcoal composite body, at the vacuum conditions of 1350 DEG C, (vacuum tightness is less than or equal to 10
-2atm) infiltration process 3h under, obtains charcoal/charcoal-zirconium carbide-carbon/carbon-copper composite material after reaction; Its composition mass 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, under the condition of 3000 DEG C, carries out oxy-acetylene ablation experiments, ablation time 60s;
(5) performance index of charcoal/charcoal-zirconium carbide-carbon/carbon-copper composite material are measured, as shown in the table:
Embodiment 3:
(1) using the overall felt of PAN-based carbon fiber acupuncture, as precast body, (density is for 0.5g/cm
3), in high-purity N
2diluent gas, C
3h
6(density is 1.4g/cm to adopt CVI density and high-temperature heat treatment (Ar protective atmosphere, 2300 DEG C, 2h) technique to prepare the charcoal/charcoal composite body of porosity about 30% under carbon-source gas, the depositing temperature of 1050 DEG C
3);
(2) prepare zirconium-copper powder mix, wherein the mass percent of zirconium powder is 70%;
(3) be embedded in the powder mix of step (2) by the charcoal of step (1)/charcoal composite body, at the vacuum conditions of 1500 DEG C, (vacuum tightness is less than or equal to 10
-2atm) infiltration process 2h under, obtains charcoal/charcoal-zirconium carbide-carbon/carbon-copper composite material after reaction; Its composition mass 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, under the condition of 3000 DEG C, carries out oxy-acetylene ablation experiments, ablation time 60s;
(5), the performance index of charcoal/charcoal-zirconium carbide-carbon/carbon-copper composite material are measured, as shown in the table:
Embodiment 4:
(1) using the overall felt of PAN-based carbon fiber acupuncture, as precast body, (density is for 0.6g/cm
3), in high-purity N
2diluent gas, C
3h
6(density is 1.6g/cm to adopt CVI density and high-temperature heat treatment (Ar protective atmosphere, 2500 DEG C, 1h) technique to prepare the charcoal/charcoal compound composite body of porosity about 20% under carbon-source gas, the depositing temperature of 1100 DEG C
3);
(2) prepare zirconium-copper powder mix, wherein the mass percent of zirconium powder is 80%;
(3) be embedded in the powder mix of step (2) by the charcoal of step (1)/charcoal composite body, at the vacuum conditions of 1600 DEG C, (vacuum tightness is less than or equal to 10
-2atm) infiltration process 1h under, obtains charcoal/charcoal-zirconium carbide-carbon/carbon-copper composite material after reaction; Its composition mass 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, under the condition of 3000 DEG C, carries out oxy-acetylene ablation experiments, ablation time 60s;
(5) performance index of charcoal/charcoal-zirconium carbide-carbon/carbon-copper composite material are measured, as shown in the table:
Comparative example 1:
(1) using the overall felt of Carbon fibe acupuncture, as precast body, (density is for 0.5g/cm
3), by multiple chemical gas-phase permeation (CVI) density obtain porosity be 25% charcoal/charcoal composite body (density is 1.5g/cm
3);
(2) prepare copper-titanium powder mix, wherein the mass percent of copper powder is 90%;
(3) be embedded in the powder mix of step (2) by the charcoal of step (1)/charcoal composite body, at vacuum condition, (vacuum tightness is less than or equal to 10
-2atm) under, infiltration process prepares charcoal/carbon-copper composite material; Its composition mass ratio is, charcoal/charcoal composite body: copper=52.26:47.74.
(4) charcoal/carbon-copper composite material is processed into the cylinder of Φ 30*10mm, under the condition of 3000 DEG C, carries out oxy-acetylene ablation experiments, ablation time 40s;
(5) performance index of charcoal/charcoal-zirconium carbide-carbon/carbon-copper composite material are measured, as shown in the table:
Comparative example 2:
(1) using 2.5D Nomex as precast body, (density is for 0.5g/cm
3), with C
3h
6for raw material, high-purity N
2for carrier gas, under the depositing temperature of 1000 DEG C, adopting CVI density and high-temperature heat treatment (Ar protective atmosphere, 2500 DEG C, 1h) technique to prepare the charcoal/charcoal composite body of porosity about 20%, (density is 1.6g/cm
3);
(2) charcoal of step (1)/charcoal composite body is embedded in pure zirconium powder end, infiltration process under the vacuum conditions of 1900 DEG C (10Pa), after reaction, obtains charcoal/charcoal-zirconium carbide matrix material; Its composition mass ratio is, 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, under the condition of 3000 DEG C, carry out oxy-acetylene ablation experiments, ablation time 30s;
(4) performance index of charcoal/charcoal-zirconium carbide-carbon/carbon-copper composite material are measured, as shown in the table:
Can be found out by embodiment and comparative example, material designed by the present invention can be applied to the larynx lining of punching engine completely, designed by the present invention, the ablation rate of material is starkly lower than the material designed by comparative example and prior art, this is conducive to the thrust and the efficiency that improve punching engine, the aerodynamic configuration of stable ejection air-flow, extends larynx and serves as a contrast work-ing life in process under arms.This is also for the new rocket that exploitation performance is more superior provides prerequisite.
Claims (10)
1. the charcoal of resistance to ablation/charcoal-zirconium carbide-carbon/carbon-copper composite material; It is characterized in that,
Described matrix material by charcoal/charcoal composite body, zirconium carbide and copper and/or copper zirconium alloy in mass ratio, charcoal/charcoal composite body: zirconium carbide: copper and/or copper zirconium alloy=30 ~ 45:20 ~ 45:50 ~ 10 form.
2. the one 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 form; Described pyrolytic carbon is evenly coated on carbon fiber surface.
3. the one 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 on 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 on around the zirconium carbide on pyrolytic 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 is 30 ~ 90:70 ~ 10.
4. prepare the method for the charcoal of the resistance to ablation/charcoal-zirconium carbide-carbon/carbon-copper composite material as described in claim 1-3 any one for one kind; It is characterized in that, comprise the steps:
Step one
With Carbon fibe precast body for raw material, by vapor deposition pyrolytic charcoal, obtain the compound porous base substrate of charcoal/charcoal with open pore;
Step 2
The compound porous base substrate of step one gained charcoal/charcoal is placed in the mixed powder be made up of zirconium and copper, is less than or equal to 10 in vacuum tightness
-2under the condition of atm, in 1200 ~ 1600 DEG C of infiltration process, obtain the described charcoal of resistance to ablation/charcoal-zirconium carbide-carbon/carbon-copper composite material; In the described mixed powder be made up of zirconium and copper, the mass ratio of zirconium and copper is 35 ~ 85:65 ~ 15.
5. a kind of method preparing the charcoal of resistance to ablation/charcoal-zirconium carbide-carbon/carbon-copper composite material according to claim 4, is characterized in that: the precast body of Carbon fibe described in step one is the overall felt of PAN-based carbon fiber acupuncture; The density of the overall felt of described PAN-based carbon fiber acupuncture is 0.4 ~ 0.6g/cm
3.
6. a kind of method preparing the charcoal of resistance to ablation/charcoal-zirconium carbide-carbon/carbon-copper composite material according to claim 4, it is characterized in that, in step one, the condition of vapor deposition pyrolytic charcoal is:
Carrier gas N
2;
Carbon-source gas C
3h
6;
Depositing temperature 850 ~ 1100 DEG C.
7. a kind of method preparing the charcoal of resistance to ablation/charcoal-zirconium carbide-carbon/carbon-copper composite material according to claim 6, is characterized in that: Carbon fibe precast body carries out high-temperature heat treatment again after vapour deposition; The condition of described high-temperature heat treatment is:
Shielding gas Ar;
Thermal treatment temp 2000 ~ 2500 DEG C;
Time 1-5 hour.
8. a kind of method preparing the charcoal of resistance to ablation/charcoal-zirconium carbide-carbon/carbon-copper composite material according to claim 4, it is characterized in that, the porosity of the compound porous base substrate of step one gained charcoal/charcoal is 20 ~ 50%; Density is 1.0 ~ 1.6g/cm
3.
9. a kind of method preparing the charcoal of resistance to ablation/charcoal-zirconium carbide-carbon/carbon-copper composite material according to claim 4, it is characterized in that, in step 2, the described mixed powder be made up of zirconium and copper 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 is more than or equal to 99%.
10. a kind of method preparing the charcoal of resistance to ablation/charcoal-zirconium carbide-carbon/carbon-copper composite material according to claim 4, it is characterized in that, in step 2, after the compound porous base substrate of step one gained charcoal/charcoal is placed in the mixed powder be made up of zirconium and copper, be warming up to 1200 ~ 1600 DEG C with the temperature rise rate of 3 ~ 6 DEG C/min.
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| CN107058915A (en) * | 2017-04-20 | 2017-08-18 | 湖南锴博新材料科技有限公司 | 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 |
| CN108531767A (en) * | 2018-05-09 | 2018-09-14 | 台州学院 | A kind of preparation method of the ultra-fine zirconium carbide particle dispersed and strengthened copper-based composite material of spot-wedling electrode |
| CN110937910A (en) * | 2019-12-13 | 2020-03-31 | 中南大学 | Preparation method of composite nano refractory ceramic modified carbon/carbon composite material |
| CN110983208A (en) * | 2019-10-24 | 2020-04-10 | 中南大学 | C/C-SiC-Cu composite material and preparation method and application thereof |
| 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 |
| CN113213472A (en) * | 2021-05-20 | 2021-08-06 | 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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| CN110983208A (en) * | 2019-10-24 | 2020-04-10 | 中南大学 | C/C-SiC-Cu composite material and preparation method and application thereof |
| CN110983208B (en) * | 2019-10-24 | 2021-08-31 | 中南大学 | C/C-SiC-Cu composite material and preparation method and application thereof |
| CN110937910A (en) * | 2019-12-13 | 2020-03-31 | 中南大学 | Preparation method of composite nano refractory ceramic modified carbon/carbon composite material |
| 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 |
| CN113213472A (en) * | 2021-05-20 | 2021-08-06 | 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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