CN106045550B - The preparation method of SiC-ZrC gradient modifying carbon/carbon composite materials - Google Patents

The preparation method of SiC-ZrC gradient modifying carbon/carbon composite materials Download PDF

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CN106045550B
CN106045550B CN201610374618.3A CN201610374618A CN106045550B CN 106045550 B CN106045550 B CN 106045550B CN 201610374618 A CN201610374618 A CN 201610374618A CN 106045550 B CN106045550 B CN 106045550B
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sic
sio
zro
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CN106045550A (en
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李克智
石郭戈
赵志刚
王昌聪
李贺军
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Wuxi Bozhi Composite Materials Co ltd
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Northwestern Polytechnical University
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Abstract

The invention discloses a kind of preparation method of SiC ZrC gradient modifying carbon/carbon composite materials, the technical issues of SiC ZrC modifying carbon/carbon composite material poor mechanical properties for solving existing method preparation.Technical solution is successively to prepare one layer of SiO in the carbon fiber surface of carbon fiber precast body using Ludox dipping and microwave-hydrothermal method2And ZrO2Ceramics deposit one layer of pyrolytic carbon using CVI techniques respectively between oxide and carbon fiber and between two oxides, pyrolytic carbon/SiO is formd in carbon fiber surface2/ pyrolytic carbon/ZrO2Structure, make oxide ceramics in-situ reducing be carbide ceramics by high-temperature heat treatment, then be densified to obtain the C/C SiC ZrC composite materials of SiC and the ZrC distribution gradient around carbon fiber.Since the SiC and ZrC of distribution gradient around carbon fiber improve the interface cohesion of carbon fiber and matrix, the mechanical property of composite material is improved.

Description

The preparation method of SiC-ZrC gradient modifying carbon/carbon composite materials
Technical field
The invention belongs to field of compound material, more particularly to a kind of preparation of SiC-ZrC gradients modifying carbon/carbon composite material Method.
Background technology
Carbon/carbon compound material has the excellent performances such as high specific strength, high ratio modulus, low-density, high temperature resistant and anti-yaw damper, The high temperature structural members such as guided missile warhead, high-speed aircraft nose cone, solid rocket motor nozzle and larynx lining are widely used in, are current One of hyperthermal material most with prospects.But because carbon material needs the shortcomings that being easy oxidation to carbon/carbon compound material It is modified.Numerous studies show that by SiC-ZrC biphase ceramics modifying carbon/carbon composite material carbon/carbon composite wood can be improved The anti-oxidant ablation property of material.But traditional modified technique such as reacts melting osmosis, polymer impregnation pyrolysis method use Low-density carbon/carbon compound material is skeleton, the ceramic phase introduced by way of recycling infiltration pyrolysis and high-temperature fusion dipping, It is unevenly distributed in material, and is easy to reunite, to which the mechanical property of SiC-ZrC modifying carbon/carbon composite materials can be influenced.Institute Realize that the design of ceramics distribution is of great significance so as to improve the mechanical property of composite material to develop new modified technique.
Document 1 " Li Xiuqian, Qiu Haipeng, Jiao Jian, wait .ZrC/SiC multicomponents be modified C/C composite materials microstructure and Mechanical property research [J] charcoal element technology .2014,33 (01):28-31. " discloses a kind of ZrC/SiC modifying carbon/carbons composite wood The method of material, this method is with density for 1.3~1.4g/cm3Carbon/carbon compound material idiosome be material skeleton, use poly- carbon silicon The mixture of alkane and organic zirconium presoma is split as modified ceramic constituent element, using polymer impregnation pyrolysis technique by 12 dippings Solution cycle prepares ZrC/SiC multicomponent modifying carbon/carbon composite materials.SiC and ZrC is with mixed in composite material prepared by the technique The presence of the form of molten complex phase ceramic, and ceramic phase is mainly distributed on the outer layer of composite material, material internal ceramic phase content It is less.
Document 2 " make a whistling sound, Su Zhean, Huang Qizhong, and .2 kind C/C material at high temperature infiltrations is waited to prepare C/C-SiC-ZrC composite materials by room Mechanical property [J] Materials Science and Engineering of Powder Metallurgies .2013,18 (06):899-905. " discloses a kind of SiC and ZrC Density is 1.4g/cm by the method for the ceramic modified carbon/carbon compound material of double base, this method32.5D carbon/carbon compound materials be placed in In the embedding powder of the powder containing Si and Zr, high temperature infiltration obtained density is carried out under the conditions of 1800~2100 DEG C and is up to 2.16g/ cm3SiC-ZrC modifying carbon/carbon composite materials.But SiC the and ZrC ceramics that this method introduces are in segregation state in the composite Distribution, material mechanical performance are bad.
The preparation method of SiC-ZrC modifying carbon/carbon composite materials disclosed in above-mentioned document, the SiC-ZrC introduced is in material It is unevenly distributed in material, and is easy to reunite, composite materials property is caused to reduce.
Invention content
In order to overcome the shortcomings of the SiC-ZrC modifying carbon/carbon composite material poor mechanical properties of existing method preparation, the present invention A kind of preparation method of SiC-ZrC gradients modifying carbon/carbon composite material is provided.This method is impregnated using Ludox and microwave hydrothermal Method successively prepares one layer of SiO in the carbon fiber surface of carbon fiber precast body2And ZrO2Ceramics, and using CVI techniques oxide with The carbon that one layer of pyrolytic carbon is converted as oxide to carbide ceramics is deposited between carbon fiber and between two oxides respectively Source, to form pyrolytic carbon/SiO in carbon fiber surface2/ pyrolytic carbon/ZrO2Structure, oxygen is then made by high-temperature heat treatment Compound Situ of Ceramics is reduced to carbide ceramics, then is densified to have obtained SiC and the ZrC distribution gradient around carbon fiber C/C-SiC-ZrC composite materials.Prefabricated carbon fiber volume density used is 0.40~0.45g/cm3, gap is big, can promote oxygen The diffusion of compound ceramics, improves the uniformity of ceramics, and is first heat-treated and carries out the reunion that densification also avoids ceramics again.In addition The SiC and ZrC of distribution gradient can improve the interface cohesion of carbon fiber and matrix around carbon fiber, improve composite material Mechanical property.
The technical solution adopted by the present invention to solve the technical problems：A kind of SiC-ZrC gradients modifying carbon/carbon composite material Preparation method, its main feature is that including the following steps：
Step 1: being 0.40~0.45g/cm by density3Carbon fiber precast body be placed in isothermal chemical vapor deposition stove Pyrolytic carbon layer is deposited, using natural gas as carbon source, depositing temperature is 1050~1150 DEG C, and sedimentation time is 3~8h, after deposition It is cooled to room temperature taking-up, 30~60min is cleaned with EtOH Sonicate, is placed in drying box and is dried for standby for 70~90 DEG C；
Step 2: by ethyl orthosilicate:Ethyl alcohol:Deionized water is with molar ratio 1:4:2 mixing adjust mixed liquor with concentrated hydrochloric acid PH=3 be placed in 60~70 DEG C of thermostat water baths stir 10~20h obtain SiO2Colloidal sol；
Carbon fiber precast body containing pyrolytic carbon prepared by step 1 is immersed in Ludox after 2~6h of ultrasonic immersing and is taken Go out, is stored at room temperature after 2~6h in 70~90 DEG C of drying boxes dry 10~20h, obtains C/C-SiO2Dry glue precast body；
By C/C-SiO2Dry glue precast body is placed in isothermal chemical vapor deposition stove, and pyrolysis is deposited according to the parameter of step 1 Carbon-coating obtains C/C-SiO2- PyC precast bodies；
Step 3: (1) is by ZrClO2·8H2O and PEG-400 are dissolved in deionized water, are used under agitation a concentration of 1mol/LNaOH solution adjusts the pH=5 of solution, and preparation obtains the ZrO of a concentration of 0.5mol/L of zirconium2Precursor solution；It is added The amount of PEG-400 is ZrO2The 10~20% of precursor solution total volume.
(2) by C/C-SiO2- PyC precast bodies are immersed in above-mentioned ZrO2It is anti-that polytetrafluoroethylene (PTFE) is moved into precursor solution together Kettle is answered, reaction kettle sealing postposition is entered in microwave hydrothermograph, 30~90min is reacted under the conditions of 180~220 DEG C, is cooled to room By precast body taking-up and dry 10~20h in 70~90 DEG C of drying boxes after temperature, C/C-SiO is obtained2-PyC-ZrO2Precast body；
(3) it repeats the above steps (1) and step (2), until C/C-SiO2ZrO in-PyC precast bodies2Reach C/C- SiO2Until the 15~30% of the prefabricated body weights of-PyC；
Step 4: the C/C-SiO that will be obtained2-PyC-ZrO2Precast body is placed in high temperature sintering furnace and is heat-treated, with 3~ The heating rate of 5 DEG C/min is raised to 1~3h of heat preservation at 1500~1600 DEG C, and protective atmosphere is argon gas, is cooled to room temperature and obtains C/ C-SiC-ZrC precast bodies；
It is densified Step 5: obtained C/C-SiC-ZrC precast bodies are placed in isothermal chemical vapor deposition stove, with Natural gas is carbon source, and depositing temperature is 1050~1150 DEG C, and sedimentation time is 120~140h, and room temperature is cooled to after deposition Obtain the carbon/carbon compound material of SiC-ZrC gradients modification.
The beneficial effects of the invention are as follows：This method is using Ludox dipping and microwave-hydrothermal method successively in carbon fiber precast body Carbon fiber surface prepare one layer of SiO2And ZrO2Ceramics, and utilize CVI techniques between oxide and carbon fiber and two kinds of oxygen The carbon source that one layer of pyrolytic carbon is converted as oxide to carbide ceramics is deposited between compound respectively, in carbon fiber surface shape At pyrolytic carbon/SiO2/ pyrolytic carbon/ZrO2Structure, then by high-temperature heat treatment make oxide ceramics in-situ reducing be carbonization Object ceramics, then be densified to have obtained the C/C-SiC-ZrC composite materials of SiC and the ZrC distribution gradient around carbon fiber. Prefabricated carbon fiber volume density used is 0.40~0.45g/cm3, gap is big, promotes the diffusion of oxide ceramics, improves pottery The uniformity of porcelain, and be first heat-treated and carry out the reunion that densification also avoids ceramics again.In addition divide in gradient around carbon fiber The SiC and ZrC of cloth improve the interface cohesion of carbon fiber and matrix, improve the mechanical property of composite material.
It elaborates with reference to the accompanying drawings and detailed description to the present invention.
Description of the drawings
Fig. 1 is the flow chart of the preparation method of SiC-ZrC gradients modifying carbon/carbon composite material of the present invention.
Fig. 2 is SiC-ZrC gradient modifying carbon/carbon composite material material phase analysis XRD diagram prepared by the method for the present invention embodiment 1 Spectrum.
Fig. 3 is the back scattering photo of SiC-ZrC gradient modifying carbon/carbon composite materials prepared by the method for the present invention embodiment 1.
Fig. 4 is the high power scanning electricity of SiC-ZrC gradient modifying carbon/carbon composite materials prepared by the method for the present invention embodiment 1 Mirror photo.
Specific implementation mode
Following embodiment referring to Fig.1-4.
Embodiment 1.
Step 1：It is 0.40g/cm by density3Carbon fiber precast body be placed in deposition pyrolysis in isothermal chemical vapor deposition stove Carbon-coating, using natural gas as carbon source, depositing temperature is 1050 DEG C, sedimentation time 3h, and room temperature taking-up is cooled to after deposition, is used EtOH Sonicate cleans 20min, is placed in 70 DEG C and dries, and one layer of pyrolysis carbon protective layer is made in carbon fiber surface；
Step 2：SiO2Introducing, detailed process is：
A. by ethyl orthosilicate, ethyl alcohol, deionized water with molar ratio 1:4:2 mixing, the pH of mixed liquor is adjusted with concentrated hydrochloric acid =3, the solution for mixing up pH value is placed in stirring 20h in 60 DEG C of thermostat water baths and obtains SiO2Colloidal sol；
B. the carbon fiber precast body containing pyrolytic carbon prepared by step 1 is immersed in Ludox after ultrasonic immersing 2h and is taken Go out, is stored at room temperature after 2h in 70 DEG C of drying boxes dry 20h, obtains C/C-SiO2Dry glue precast body；
C. by C/C-SiO2Dry glue precast body, which is placed in isothermal chemical vapor deposition stove, deposits pyrolytic carbon layer, and depositing temperature is 1050 DEG C, sedimentation time 3h, room temperature is cooled to after deposition, obtains C/C-SiO2- PyC precast bodies；
Step 3：ZrO2Introducing, detailed process is：
A. the ZrClO of 8.06g is taken2·8H2The PEG-400 of O and 5ml is dissolved in 30ml deionized waters, is delayed under agitation Slowly the pH=5 that a concentration of 1mol/LNaOH adjusts solution is added dropwise, it is a concentration of then to obtain 50ml zirconiums with deionized water constant volume The ZrO of 0.5mol/L2Precursor solution；
B. by C/C-SiO2- PyC precast bodies are immersed in above-mentioned ZrO2Polytetrafluoroethyl-ne alkene reaction is moved into precursor solution together Reaction kettle sealing postposition is entered in microwave hydrothermograph, reacts 30min under the conditions of 180 DEG C, is cooled to precast body after room temperature by kettle Taking-up and the dry 20h in 70 DEG C of drying boxes, obtain C/C-SiO2-PyC-ZrO2Precast body；
C. repeat the above steps a and b, and ZrO is constantly introduced into sample2, until the ZrO of introducing2Reach sample weight 15%, it completes to introduce ZrO into material2；
Step 4：The C/C-SiO that will be obtained2-PyC-ZrO2Precast body is placed in high temperature sintering furnace and is heat-treated, with 3 DEG C/ The heating rate of min is raised to 1500 DEG C of heat preservation 1h, and protective atmosphere is argon gas, is cooled to room temperature and obtains C/C-SiC-ZrC precast bodies；
Step 5：Obtained C/C-SiC-ZrC precast bodies are placed in isothermal chemical vapor deposition stove and are densified, with Natural gas is carbon source, and depositing temperature is 1050 DEG C, sedimentation time 120h, and room temperature taking-up is cooled to after deposition, is obtained close Degree is 1.79g/cm3SiC-ZrC gradient modifying carbon/carbon composite materials.
It can be observed from fig. 2 that composite material illustrates that oxide is completely transformed into carbide by tri- phase composition of C, SiC and ZrC Ceramics.
As seen from Figure 3, white phase is carbide ceramics, illustrates that carbide ceramics is uniformly dispersed nothing in the composite Reunite, and is mainly distributed at carbon fiber and basal body interface.
From fig. 4 it can be seen that SiC and ZrC are distributed in around carbon fiber, and internal is SiC, and outside is ZrC, in carbon fiber Gradient-structure is presented around dimension, realizes SiC-ZrC gradient modifying carbon/carbon composite materials.
Embodiment 2.
Step 1：It is 0.43g/cm by density3Carbon fiber precast body be placed in deposition pyrolysis in isothermal chemical vapor deposition stove Carbon-coating, using natural gas as carbon source, depositing temperature is 1100 DEG C, sedimentation time 5h, and room temperature taking-up is cooled to after deposition, is used Absolute ethyl alcohol ultrasonic cleaning 40min, which is placed in 80 DEG C of drying boxes, dries, and one layer of pyrolysis carbon protective layer is made in carbon fiber surface；
Step 2：SiO2Introducing, detailed process is：
A. by ethyl orthosilicate, ethyl alcohol, deionized water with molar ratio 1:4:2 mixing, the pH of mixed liquor is adjusted with concentrated hydrochloric acid =3, the solution for mixing up pH value is placed in stirring 15h in 65 DEG C of thermostat water baths and obtains SiO2Colloidal sol；
B. the carbon fiber precast body containing pyrolytic carbon made from step 1 is immersed in Ludox after ultrasonic immersing 4h and is taken Go out, is stored at room temperature after 4h the dry 15h in 80 DEG C of drying boxes again, obtains C/C-SiO2Dry glue precast body；
C. by C/C-SiO2Dry glue precast body, which is placed in isothermal chemical vapor deposition stove, deposits pyrolytic carbon layer, and depositing temperature is 1100 DEG C, sedimentation time 5h, room temperature is cooled to after deposition, obtains C/C-SiO2- PyC precast bodies；
Step 3：ZrO2Introducing, detailed process is：
A. the ZrClO of 32.24g is taken2·8H2The PEG-400 of O and 30ml is dissolved in 100ml deionized waters, under stirring condition The pH=5 that a concentration of 1mol/LNaOH adjusts solution is slowly added dropwise, it is a concentration of then to obtain 200ml zirconiums with deionized water constant volume The ZrO of 0.5mol/L2Precursor solution；
B. by C/C-SiO2- PyC precast bodies are immersed in above-mentioned ZrO2Polytetrafluoroethyl-ne alkene reaction is moved into precursor solution together Reaction kettle sealing postposition is entered in microwave hydrothermograph, reacts 60min under the conditions of 200 DEG C, is cooled to precast body after room temperature by kettle Taking-up and the dry 15h in 80 DEG C of drying boxes, obtain C/C-SiO2-PyC-ZrO2Precast body；
C. repeat the above steps a and b, and ZrO is constantly introduced into sample2, until the ZrO of introducing2Reach sample weight 25%, it completes to introduce ZrO into material2；
Step 4：The C/C-SiO that will be obtained2-PyC-ZrO2Precast body is placed in high temperature sintering furnace and is heat-treated, with 4 DEG C/ The heating rate of min is raised to 1550 DEG C of heat preservation 2h, and protective atmosphere is argon gas, to obtain C/C-SiC-ZrC precast bodies；
Step 5：Obtained C/C-SiC-ZrC precast bodies are placed in isothermal chemical vapor deposition stove and are densified, with Natural gas is carbon source, and depositing temperature is 1100 DEG C, sedimentation time 130h, and room temperature taking-up is cooled to after deposition, is obtained close Degree is 1.73g/cm3SiC-ZrC gradient modifying carbon/carbon composite materials.
The SiC-ZrC gradients modifying carbon/carbon composite material that the present embodiment obtains and pure carbon/carbon made from same process are compound Material improves 16% compared to bending strength.
Embodiment 3.
Step 1：It is 0.45g/cm by density3Carbon fiber precast body be placed in deposition pyrolysis in isothermal chemical vapor deposition stove Carbon-coating, using natural gas as carbon source, depositing temperature is 1150 DEG C, sedimentation time 8h, and room temperature taking-up is cooled to after deposition, is used EtOH Sonicate cleaning 60min is placed on 90 DEG C of drying in drying box, and one layer of pyrolysis carbon protective layer is made in carbon fiber surface；
Step 2：SiO2Introducing, detailed process is：
A. by ethyl orthosilicate, ethyl alcohol, deionized water with molar ratio 1:4:2 mixing, the pH of mixed liquor is adjusted with concentrated hydrochloric acid =3, the solution for mixing up pH value is placed in stirring 10h in 70 DEG C of thermostat water baths and obtains SiO2Colloidal sol；
B. the carbon fiber precast body obtained containing pyrolytic carbon in step 1 is immersed in Ludox after ultrasonic immersing 6h and is taken Go out, is stored at room temperature after 6h the dry 10h in 90 DEG C of drying boxes again, obtains C/C-SiO2Dry glue precast body；
C. by C/C-SiO2Dry glue precast body, which is placed in isothermal chemical vapor deposition stove, deposits pyrolytic carbon layer, and depositing temperature is 1150 DEG C, sedimentation time 8h, room temperature is cooled to after deposition, obtains C/C-SiO2- PyC precast bodies；
Step 3：ZrO2Introducing, detailed process is：
A. the ZrClO of 48.36g is taken2·8H2The PEG-400 of O and 60ml is dissolved in 120ml deionized waters, in stirring condition Under the pH=5 that a concentration of 1mol/LNaOH adjusts solution is slowly added dropwise, it is a concentration of then to obtain 300ml zirconiums with deionized water constant volume The ZrO of 0.5mol/L2Precursor solution；
B. by C/C-SiO2- PyC precast bodies are immersed in above-mentioned ZrO2Polytetrafluoroethyl-ne alkene reaction is moved into precursor solution together Reaction kettle sealing postposition is entered in microwave hydrothermograph, reacts 90min under the conditions of 220 DEG C, is cooled to precast body after room temperature by kettle Taking-up and the dry 10h in 90 DEG C of drying boxes, obtain C/C-SiO2-PyC-ZrO2Precast body；
C. repeat the above steps a and b, and ZrO is constantly introduced into sample2, until the ZrO of introducing2Reach sample weight 30%, it completes to introduce ZrO into material2；
Step 4：The C/C-SiO that will be obtained2-PyC-ZrO2Precast body is placed in high temperature sintering furnace and is heat-treated, with 5 DEG C/ The heating rate of min is raised to 1600 DEG C of heat preservation 3h, and protective atmosphere is argon gas, to obtain C/C-SiC-ZrC precast bodies；
Step 5：Obtained C/C-SiC-ZrC precast bodies are placed in isothermal chemical vapor deposition stove and are densified, with Natural gas is carbon source, and depositing temperature is 1150 DEG C, sedimentation time 140h, and room temperature taking-up is cooled to after deposition, is obtained close Degree is 1.75g/cm3SiC-ZrC gradient modifying carbon/carbon composite materials.
The SiC-ZrC gradients modifying carbon/carbon composite material that the present embodiment obtains and pure carbon/carbon made from same process are compound Material improves 30% compared to interlaminar shear strength.
Compared with the background art, prepared SiC-ZrC gradient modifying carbon/carbon composite materials, SiC-ZrC ceramics mainly with The graded interface layer form of internal layer SiC, outer layer ZrC are coated on around carbon fiber, ensure that ceramics are dispersed and equal in the material Even property, and the interface cohesion of carbon fiber and matrix is improved, improve the bending strength and interlaminar shear strength of composite material.

Claims (1)

1. a kind of preparation method of SiC-ZrC gradients modifying carbon/carbon composite material, it is characterised in that include the following steps：
Step 1: being 0.40~0.45g/cm by density3Carbon fiber precast body be placed in deposition heat in isothermal chemical vapor deposition stove Carbon-coating is solved, using natural gas as carbon source, depositing temperature is 1050~1150 DEG C, and sedimentation time is 3~8h, is cooled to after deposition Room temperature is taken out, and cleans 30~60min with EtOH Sonicate, is placed in drying box and is dried for standby for 70~90 DEG C；
Step 2: by ethyl orthosilicate:Ethyl alcohol:Deionized water is with molar ratio 1:4:2 mixing, the pH of mixed liquor is adjusted with concentrated hydrochloric acid =3, which are placed on 10~20h of stirring in 60~70 DEG C of thermostat water baths, obtains SiO2Colloidal sol；
Carbon fiber precast body containing pyrolytic carbon prepared by step 1 is immersed in SiO2It is taken out after 2~6h of ultrasonic immersing in colloidal sol, It is stored at room temperature after 2~6h in 70~90 DEG C of drying boxes dry 10~20h, obtains C/C-SiO2Dry glue precast body；
By C/C-SiO2Dry glue precast body is placed in isothermal chemical vapor deposition stove, and pyrolytic carbon layer is deposited according to the parameter of step 1, Obtain C/C-SiO2- PyC precast bodies；
Step 3: (1) is by ZrClO2·8H2O and PEG-400 are dissolved in deionized water, are used under agitation a concentration of 1mol/LNaOH solution adjusts the pH=5 of solution, and preparation obtains the ZrO of a concentration of 0.5mol/L of zirconium2Precursor solution；It is added The amount of PEG-400 is ZrO2The 10~20% of precursor solution total volume；
(2) by C/C-SiO2- PyC precast bodies are immersed in above-mentioned ZrO2Ptfe autoclave is moved into precursor solution together, Reaction kettle sealing postposition is entered in microwave hydrothermograph, 30~90min is reacted under the conditions of 180~220 DEG C, is incited somebody to action after being cooled to room temperature Precast body takes out and dry 10~20h in 70~90 DEG C of drying boxes, obtains C/C-SiO2-PyC-ZrO2Precast body；
(3) it repeats the above steps (1) and step (2), until C/C-SiO2ZrO in-PyC precast bodies2Reach C/C-SiO2-PyC Until the 15~30% of prefabricated body weight；
Step 4: the C/C-SiO that will be obtained2-PyC-ZrO2Precast body is placed in high temperature sintering furnace and is heat-treated, with 3~5 DEG C/ The heating rate of min is raised to 1500~1600 DEG C, and 1~3h is kept the temperature at 1500~1600 DEG C, and protective atmosphere is argon gas, is cooled to Room temperature obtains C/C-SiC-ZrC precast bodies；
It is densified Step 5: obtained C/C-SiC-ZrC precast bodies are placed in isothermal chemical vapor deposition stove, with natural Gas is carbon source, and depositing temperature is 1050~1150 DEG C, and sedimentation time is 120~140h, and being cooled to room temperature after deposition obtains The carbon/carbon compound material that SiC-ZrC gradients are modified.
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