CN103044075B - Method for preparing carbon/carbon composite MoSi2-ZrSiO4-SiC gradient complex outer coating - Google Patents
Method for preparing carbon/carbon composite MoSi2-ZrSiO4-SiC gradient complex outer coating Download PDFInfo
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Abstract
The invention discloses a method for preparing a carbon/carbon composite MoSi2-ZrSiO4-SiC gradient complex outer coating. The MoSi2-ZrSiO4-SiC gradient complex outer coating is prepared with a cathode rotating microwave hydrothermal pulsed arc discharge deposition method; microwave presents self-heating and high efficiency in a reaction system, and generated partial high temperature and high pressure can effectively reduce the reaction activation energy of MoSi2, ZrSiO4 and SiC suspended particles, so that reaction of the suspended particles is more complete and sufficient in a pulsed arc discharge depotition process, and the coating with a dense structure is obtained. In addition, as a cathode rotates at a high speed, the defect that a coating with a dense and uniform structure can only be obtained through coating repeatedly with the traditional hydrothermal method is avoided, and the dense MoSi2-ZrSiO4-SiC gradient complex outer coating with microscopic cracks and different thicknesses can be obtained under controllable conditions. According to the MoSi2-ZrSiO4-SiC gradient complex outer coating prepared with the method, nano silicon carbide is diffused in the coating in a gradient manner, so that the defect is filled, the coating is densified, and the interfacial binding force is good.
Description
Technical field
The present invention relates to a kind of method of preparing the compound external coating (EC) of carbon/carbon compound material, be specifically related to a kind of carbon/carbon compound material MoSi for preparing
2-ZrSiO
4the method of the compound external coating (EC) of-SiC gradient.
Background technology
The advantages such as the C/C matrix material carbon fiber carbon based composites that is otherwise known as, forms because it only has single carbon, not only has the ablation resistance of charcoal and graphite material excellence, and low density, thermal expansivity are low, and under high temperature, also have excellent mechanical property.Especially the performance that the increase of its intensity temperature goes up not down, becomes one of hi tech and new material of development prospect, is widely used as ablator and the thermal structure material of aerospace technical field.But C/C matrix material surpasses oxidation rapidly under the oxidizing atmosphere of 500 ℃ in temperature, this has limited its application greatly, so the oxidation protection problem of C/C matrix material becomes one of study hotspot in recent years.It is carried out to high-temperature oxidation resistant protection has great importance to its high temperature application simultaneously.
Oxidation resistant coating is considered to solve the effective ways of carbon/carbon compound material oxidant protection under high temperature problem.SiC coating due to the physics with C/C matrix material, chemical compatibility is good and generally as transition layer, use, but single SiC coating can not provide effective protection to C/C matrix, thereby compound coating becomes current study hotspot.Simultaneously nano particle disperse strengthens gradient composite coating and becomes and improve that coating is combined with basal body interface and the novel method of strength of coating.
Up to the present, the compound coating of preparation has a variety of, yttrium silicate [Huang J F for example, Li H J, Zeng X R, et al.A new SiC/yttrium silicate/glass multi-layer oxidation protective coating for carbon/carbon composites.Carbon, 2004,42 (11): 2367-2370.], C-AlPO
4coating [Jianfeng Huang, Wendong Yang and Liyun Cao.Preparation of a SiC/Cristobalite-AlPO
4multi-layer Protective Coating on Carbon/Carbon Composites and Resultant Oxidation Kinetics and Mechanism.2010,26 (11): 1021-1026.], [Yang Wendong, Huang Jianfeng, Cao Liyun, Xia Changkui. water heat electrophoresis deposition legal system is for C-AlPO
4high-temperature oxidation resistant coating and sign thereof. aeronautical material journal, 2010,30 (2): 68-72.], MoSi
2coating [Wang Bo, Huang Jianfeng, Liu Miao, Cao Liyun, Wu Jianpeng. deposition voltage is to SiC-C/C composite material surface SiC
n-MoSi
2the impact of compound anti-oxidation coating. Journal of Inorganic Materials, 2010,25 (12): 1-7.], the crystal whisker toughened MoSi of SiC
2-SiC-Si coating [Fu Qian-Gang, Li He-Jun, Li Ke-Zhi, Shi Xiao-Hong, Hu Zhi-Biao, Huang Min.SiC whisker-toughened MoSi
2– SiC – Si coating to protect carbon/carbon composites against oxidation, Carbon.2006,44,1866.], ZrSiO
4coating [Jia Liu, Li-Yun Cao, Jian-Feng Huang, Yu Xin, Wen-Dong Yang, Jie Fei, Chun-Yan Yao.A ZrSiO
4/ SiC oxidation protective coating for carbon/carbon composites.
Surf.Coat.Technol, 2012,206 (1): 3270-3274.], SiC-MoSi
2-(Ti
0.8mo
0.2) Si
2compound coating [Jiao G S, Li H J, Li K Z, et al.SiC-MoSi
2-(Ti
0.8mo
0.2) Si
2multi-composition coating for carbon/carbon composites.Surf.Coat.Technol, 2006,201 (6): 3452-3456.], Y
2si
2o
7whisker strengthens MoSi
2compound coating [Wang Yaqin, Huang Jianfeng, Cao Liyun, Wu builds roc .Y
2si
2o
7whisker strengthens MoSi
2the preparation and property of compound coating. matrix material journal, 2010,2 (27): 58-61.], prepare single SiC coating [old warbling of the oriole, Wang Chengguo, Zhao Wei. two-step approach preparation has the pure SiC coating of self-healing capability. Acta PhySico-Chimica Sinica, 2012,28 (1): 239-244] etc.The compound coating of preparation can play self-healing to crackle, at high temperature has good protective capacities.But the larger difference of the thermal expansivity between inside and outside coating further causes again the generation of tiny crack in coating, reduced again to a certain extent the oxidation protection ability of coating.
Up to the present the preparation method of external coating (EC) is varied, mainly contains following several: supercritical fluid technology, and chemical vapour deposition, entrapping method, formed in situ, sol-gel method, molten slurry applies reaction, detonation flame spraying and ultrasonic spray method etc.Adopt supercritical fluid technology to prepare C/C composite coating because the process implementing of preparing need to carry out under High Temperature High Pressure, to having relatively high expectations of equipment, and the external coating (EC) forming will be heat-treated under inert atmosphere, long [the Bemeburg P L of preparation cycle, Krukonis V J.Processing of carbon/carbon composites using supercritical fluid technology[P] .United States Patent US5035921, 1991], adopt the standby coating of formed in situ legal system need to be at 1500 ℃ pyroprocessing, and can not once prepare [Huang Jian-Feng, Li He-Jun, Zeng Xie-Rong, Li Ke-Zhi.Surf.coat.Technol.2006, 200, 5379.], the surperficial easily cracking of external coating (EC) that adopts sol-gel method to prepare and shortcoming [the Huang Jian-Feng of coat-thickness deficiency, Zeng Xie-Rong, Li He-Jun, Xiong Xin-Bo, Sun Guo-ling.Surf.coat.Technol.2005, 190, 255.], and adopt molten slurry to apply reaction method, prepare coating and still deposit and will repeatedly brush and can not once prepare, need later stage heat treated drawback [Fu Qian-Gang, Li He-Jun, Wang Yong-Jie, Li Ke-Zhi, Tao Jun.Surface & Coating Technology.2010, 204, 1832.], although same, adopt detonation flame spraying and ultrasonic spray method to prepare alloy part coating, but, this technique also has a lot of incomplete places, prepared high-temp antioxidizing performance is still needed and will further be improved [Terentieva V S, Bogachkova O P, Goriatcheva E V.Method for protecting products made of a refractory material against oxidation, and resulting products[p] .US5677060, 1997.], adopt in addition water heat electrophoresis deposition legal system for coating [Huang Jianfeng, Wang Bo, Li Hejun, Liu Miao, Cao Liyun, Yao Chunyan.A MoSi
2/ SiC oxidation protective coating for carbon/carbon composites[J] .Corrosion Science, 2011,2 (53): 834-839.].
First its feature of pulse arc discharge sedimentation is the arc-over due to negative and positive two interpolars, makes the electrically charged particle that is deposited on matrix surface produce sintering phenomenon, thereby obtains the coating of compact and uniform structure.The phase transformation and the embrittlement that adopt this method can avoid adopting conventional high-temperature to apply and cause, solve the thermal damage to matrix in coating preparation process to a certain extent; Secondly, deposition process is non-streamlined process, can form at the matrix surface of complex-shaped or porous surface uniform settled layer, and can accurately control coated component, thickness and porosity, make the heterogeneous compound coating of simple efficient preparation and gradient ceramic coating become possibility; In addition in pulse arc discharge process, within the pulse conducting phase, electrochemical polarization increases, and near positively charged ion cathodic area is fully deposited, and the crystallization of coating is careful, porosity is low.In pulse-off in the phase, in cathode zone solution, the mass concentration of conductive ion can obtain rise in various degree, solution resistance rate reduces, be conducive to improve cathode efficiency and cathode current density the dispersiveness of the further quickening of sedimentation rate and suspension is improved, the good uniformity of the coating of gained.
Summary of the invention
The object of the present invention is to provide a kind of not only preparation cost low, and simple to operate, preparation cycle is short prepares carbon/carbon compound material MoSi
2-ZrSiO
4the method of the compound external coating (EC) of-SiC gradient, the non-microcracked generation of compound external coating (EC) surface uniform prepared by the present invention, and thickness homogeneous is good without penetrability hole and crackle generation, good bonding strength, antioxidant property.
For achieving the above object, the technical solution used in the present invention is:
1) get molybdenum disilicide powder, the analytically pure ZrSiO of micron order
4powder and nano silicon carbide powder, press respectively ZrSiO
4: SiC: MoSi
2=(1 ~ 10): (10 ~ 20): the mass ratio of (1 ~ 10) is scattered in after mixing and is mixed with the suspending liquid A that concentration is 40g/L in ethanol; ;
Press ZrSiO
4: SiC: MoSi
2=(5 ~ 15): (5 ~ 20): the mass ratio of (5 ~ 15) is scattered in after mixing and is mixed with the suspension B that concentration is 50g/L in ethanol;
Press ZrSiO
4: SiC: MoSi
2=(10 ~ 20): (1 ~ 20): the mass ratio of (10 ~ 20) is scattered in after mixing and is mixed with the suspension C that concentration is 60g/L in ethanol;
2) respectively by suspending liquid A, B, C puts into ultrasonic generator and shakes, and is placed on respectively again and on magnetic stirring apparatus, stirs 12 ~ 36h after taking-up;
3), respectively to suspending liquid A, B, adds simple substance tellurium in C, the concentration of controlling simple substance tellurium is 0.5 ~ 2.0g/L, then will be added with the suspending liquid A of simple substance tellurium, B respectively, the ultrasonic generator that C puts into shakes, and after taking-up, is placed on respectively on magnetic stirring apparatus and stirs 12 ~ 36h again, obtains suspension D, E and F;
4) suspension D is poured in water heating kettle, then will at the negative electrode of water heating kettle, press from both sides with the internally coated carbon/carbon compound material sample holder of SiC, immerse in suspension D, sealing water heating kettle is also put into microwave ultraviolet excess phonosynthesis instrument by water heating kettle; Again negative and positive the two poles of the earth of water heating kettle are received respectively on the corresponding the two poles of the earth of constant voltage power supply, control hydrothermal temperature at 80 ~ 420 ℃, voltage of supply is at 500 ~ 5000V, pulse-repetition is controlled at 500-5000Hz, pulse duty factor is controlled at 10%-90%, cathode rotary rotating speed is at 800 ~ 4000r/min, and pulse arc discharge depositing time is 5 ~ 50min, after cathode rotary microwave hydrothermal pulse arc discharge deposition finishes, naturally cools to room temperature;
5) take out the carbon/carbon compound material sample after step 4) is processed, then with suspension E, F, according to the processing condition in step 4), carry out pulse arc discharge deposition successively;
6) take out the carbon/carbon compound material sample after step 5) is processed, then at 40 ~ 80 ℃, be dried, finally obtain carbon/carbon compound material MoSi
2-ZrSiO
4the compound external coating (EC) of-SiC gradient.
Described molybdenum disilicide powder is that by commercially available molybdenum disilicide powder, through dry ball milling, to make particle diameter be 3 ~ 6 μ m.
The particle diameter of described nano silicon carbide powder is 40nm.
Purity >=99.8% of described ethanol.
Purity >=99.7% of described simple substance tellurium
The power of described ultrasonic generator is 500 ~ 1500W, and the concussion time is 40 ~ 100min.
Described dry employing be electric drying oven with forced convection.
Described water heating kettle be take Graphite Electrodes as anode, and negative electrode is fixed on rotator.
The model of described microwave ultraviolet excess phonosynthesis instrument is UVave-1000.
The present invention adopts cathode rotary microwave hydrothermal pulse arc discharge deposition method to prepare MoSi
2-ZrSiO
4-SiC
nthe compound external coating (EC) of gradient, microwave presents heating certainly in reaction system, efficiency is high, and then the localized hyperthermia and the high pressure that produce effectively reduce MoSi
2, ZrSiO
4, SiC suspended particles Activation energy, it is reacted more completely in pulse arc discharge deposition process and fully, thereby obtains the coating of compact structure.By negative electrode high speed rotating, avoided traditional hydrothermal method need repeatedly apply the shortcoming that just can obtain the coating of compact and uniform structure simultaneously, realized and under controlled condition, obtained fine and close, MoSi that there is micro-flaw, different thickness
2-ZrSiO
4the compound external coating (EC) of-SiC gradient.In addition, pulse arc discharge sedimentation also has the features such as simple to operation, cost is low, depositing operation is easy to control.Simultaneously due to zirconium silicate (ZrSiO
4) there is the very low oxygen rate of oozing, can be under 1500 ℃ of hot environments stable existence, and do not undergo phase transition, therefore select zirconium silicate as top layer material, there is cost low, effective feature.MoSi
2(thermal expansivity is 8.0 * 10
-6/ ℃) stupalith is because the character such as refractoriness is high, thermal shock resistance is good, volume stability is good cause people's attention, it is desirable high grade refractory, have very high fusing point (2030 ℃) and good high temperature oxidation resistance (being greater than 1800 ℃ in air), these hot propertiess are obviously better than SiC; As most metals material, there is high temperature toughness and self-healing capability.Yet in order to improve the interface binding power of inside and outside coating and compactness and the intensity of coating itself, introduce nanometer silicon carbide (SiC), and make it in coating, become gradient to be uniformly distributed, thereby interface binding power and the compactness of raising coating.So ZrSiO
4and MoSi
2excellent performance makes both as high temperature thermal barrier/thermal protection coating material, have a good application prospect, and the present invention prepares MoSi
2-ZrSiO
4the compound external coating (EC) of-SiC gradient, filling defect is played in the disperse of nanometer silicon carbide gradient in coating, impels coating fine and close, and interface binding power is good.
Accompanying drawing explanation
Fig. 1 is that the present invention prepares MoSi
2-ZrSiO
4the SEM figure of the compound external coating (EC) section of-SiC gradient.
Embodiment
Below in conjunction with accompanying drawing, the present invention is described in further detail.
Embodiment 1:
1) get that commercially available through dry ball milling, to obtain particle diameter be 3 ~ 6 μ m molybdenum disilicide powders, the analytically pure ZrSiO of micron order
4powder and particle diameter are 40nm nano silicon carbide powder, press respectively ZrSiO
4: SiC: MoSi
2=1: the mass ratio of 10: 1 is scattered in after mixing in the ethanol of purity>=99.8% and is mixed with the suspending liquid A that concentration is 40g/L;
Press ZrSiO
4: SiC: MoSi
2=5: the mass ratio of 5: 5 is scattered in after mixing and in purity>=99.8% ethanol, is mixed with the suspension B that concentration is 50g/L;
Press ZrSiO
4: SiC: MoSi
2=12: the mass ratio of 5: 10 is scattered in after mixing and in purity>=99.8% ethanol, is mixed with the suspension C that concentration is 60g/L;
2) respectively by suspending liquid A, B, the ultrasonic generator that C puts into 500W shakes 100min, is placed on respectively again and on magnetic stirring apparatus, stirs 12h after taking-up;
3) respectively to suspending liquid A, B, in C, add purity >=99.7% simple substance tellurium, the concentration of controlling simple substance tellurium is 0.5g/L, then will be added with the suspending liquid A of simple substance tellurium respectively, B, the ultrasonic generator that the power that C puts into is 500W shakes 100min, after taking-up, be placed on respectively on magnetic stirring apparatus and stir 12h again, obtain suspension D, E and F;
4) suspension D is poured in water heating kettle, then will at the negative electrode of water heating kettle, press from both sides with the internally coated carbon/carbon compound material sample holder of SiC, take Graphite Electrodes as anode, immerse in suspension D, sealing water heating kettle is also put into UVave-1000 type microwave ultraviolet excess phonosynthesis instrument by water heating kettle; Again negative and positive the two poles of the earth of water heating kettle are received respectively on the corresponding the two poles of the earth of constant voltage power supply, control hydrothermal temperature at 130 ℃, voltage of supply is at 2000V, pulse-repetition is controlled at 1600Hz, pulse duty factor is controlled at 30%, cathode rotary rotating speed is at 3000r/min, and pulse arc discharge depositing time is 30min, after cathode rotary microwave hydrothermal pulse arc discharge deposition finishes, naturally cools to room temperature;
5) take out the carbon/carbon compound material sample after step 4) is processed, then with suspension E, F, according to the processing condition in step 4), carry out pulse arc discharge deposition successively;
6) take out the carbon/carbon compound material sample after step 5) is processed, then in electric drying oven with forced convection in 80 ℃ dry, finally obtain carbon/carbon compound material MoSi
2-ZrSiO
4the compound external coating (EC) of-SiC gradient.
Embodiment 2:
1) get that commercially available through dry ball milling, to obtain particle diameter be 3 ~ 6 μ m molybdenum disilicide powders, the analytically pure ZrSiO of micron order
4powder and particle diameter are 40nm nano silicon carbide powder, press respectively ZrSiO
4: SiC: MoSi
2=5: the mass ratio of 13: 8 is scattered in after mixing in the ethanol of purity>=99.8% and is mixed with the suspending liquid A that concentration is 40g/L;
Press ZrSiO
4: SiC: MoSi
2=10: the mass ratio of 10: 12 is scattered in after mixing and in purity>=99.8% ethanol, is mixed with the suspension B that concentration is 50g/L;
Press ZrSiO
4: SiC: MoSi
2=15: the mass ratio of 10: 12 is scattered in after mixing and in purity>=99.8% ethanol, is mixed with the suspension C that concentration is 60g/L;
2) respectively by suspending liquid A, B, the ultrasonic generator that C puts into 800W shakes 80min, is placed on respectively again and on magnetic stirring apparatus, stirs 18h after taking-up;
3) respectively to suspending liquid A, B, in C, add purity >=99.7% simple substance tellurium, the concentration of controlling simple substance tellurium is 0.8g/L, then will be added with the suspending liquid A of simple substance tellurium respectively, B, the ultrasonic generator that the power that C puts into is 800W shakes 80min, after taking-up, be placed on respectively on magnetic stirring apparatus and stir 18h again, obtain suspension D, E and F;
4) suspension D is poured in water heating kettle, then will at the negative electrode of water heating kettle, press from both sides with the internally coated carbon/carbon compound material sample holder of SiC, take Graphite Electrodes as anode, immerse in suspension D, sealing water heating kettle is also put into UVave-1000 type microwave ultraviolet excess phonosynthesis instrument by water heating kettle; Again negative and positive the two poles of the earth of water heating kettle are received respectively on the corresponding the two poles of the earth of constant voltage power supply, control hydrothermal temperature at 80 ℃, voltage of supply is at 4000V, pulse-repetition is controlled at 58000Hz, pulse duty factor is controlled at 70%, cathode rotary rotating speed is at 2000r/min, and pulse arc discharge depositing time is 20min, after cathode rotary microwave hydrothermal pulse arc discharge deposition finishes, naturally cools to room temperature;
5) take out the carbon/carbon compound material sample after step 4) is processed, then with suspension E, F, according to the processing condition in step 4), carry out pulse arc discharge deposition successively;
6) take out the carbon/carbon compound material sample after step 5) is processed, then in electric drying oven with forced convection in 70 ℃ dry, finally obtain carbon/carbon compound material MoSi
2-ZrSiO
4the compound external coating (EC) of-SiC gradient.
Embodiment 3:
1) get that commercially available through dry ball milling, to obtain particle diameter be 3 ~ 6 μ m molybdenum disilicide powders, the analytically pure ZrSiO of micron order
4powder and particle diameter are 40nm nano silicon carbide powder, press respectively ZrSiO
4: SiC: MoSi
2=10: the mass ratio of 20: 10 is scattered in after mixing in the ethanol of purity>=99.8% and is mixed with the suspending liquid A that concentration is 40g/L;
Press ZrSiO
4: SiC: MoSi
2=8: the mass ratio of 12: 10 is scattered in after mixing and in purity>=99.8% ethanol, is mixed with the suspension B that concentration is 50g/L;
Press ZrSiO
4: SiC: MoSi
2=10: the mass ratio of 1: 15 is scattered in after mixing and in purity>=99.8% ethanol, is mixed with the suspension C that concentration is 60g/L;
2) respectively by suspending liquid A, B, the ultrasonic generator that C puts into 1000W shakes 60min, is placed on respectively again and on magnetic stirring apparatus, stirs 24h after taking-up;
3) respectively to suspending liquid A, B, in C, add purity >=99.7% simple substance tellurium, the concentration of controlling simple substance tellurium is 1.3g/L, then will be added with the suspending liquid A of simple substance tellurium respectively, B, the ultrasonic generator that the power that C puts into is 1000W shakes 60min, after taking-up, be placed on respectively on magnetic stirring apparatus and stir 24h again, obtain suspension D, E and F;
4) suspension D is poured in water heating kettle, then will at the negative electrode of water heating kettle, press from both sides with the internally coated carbon/carbon compound material sample holder of SiC, take Graphite Electrodes as anode, immerse in suspension D, sealing water heating kettle is also put into UVave-1000 type microwave ultraviolet excess phonosynthesis instrument by water heating kettle; Again negative and positive the two poles of the earth of water heating kettle are received respectively on the corresponding the two poles of the earth of constant voltage power supply, control hydrothermal temperature at 200 ℃, voltage of supply is at 500V, pulse-repetition is controlled at 4000Hz, pulse duty factor is controlled at 50%, cathode rotary rotating speed is at 1500r/min, and pulse arc discharge depositing time is 50min, after cathode rotary microwave hydrothermal pulse arc discharge deposition finishes, naturally cools to room temperature;
5) take out the carbon/carbon compound material sample after step 4) is processed, then with suspension E, F, according to the processing condition in step 4), carry out pulse arc discharge deposition successively;
6) take out the carbon/carbon compound material sample after step 5) is processed, then in electric drying oven with forced convection in 50 ℃ dry, finally obtain carbon/carbon compound material MoSi
2-ZrSiO
4the compound external coating (EC) of-SiC gradient.
Embodiment 4:
1) get that commercially available through dry ball milling, to obtain particle diameter be 3 ~ 6 μ m molybdenum disilicide powders, the analytically pure ZrSiO of micron order
4powder and particle diameter are 40nm nano silicon carbide powder, press respectively ZrSiO
4: SiC: MoSi
2=3: the mass ratio of 15: 3 is scattered in after mixing in the ethanol of purity>=99.8% and is mixed with the suspending liquid A that concentration is 40g/L;
Press ZrSiO
4: SiC: MoSi
2=15: the mass ratio of 20: 15 is scattered in after mixing and in purity>=99.8% ethanol, is mixed with the suspension B that concentration is 50g/L;
Press ZrSiO
4: SiC: MoSi
2=18: the mass ratio of 15: 18 is scattered in after mixing and in purity>=99.8% ethanol, is mixed with the suspension C that concentration is 60g/L;
2) respectively by suspending liquid A, B, the ultrasonic generator that C puts into 1200W shakes 50min, is placed on respectively again and on magnetic stirring apparatus, stirs 30h after taking-up;
3) respectively to suspending liquid A, B, in C, add purity >=99.7% simple substance tellurium, the concentration of controlling simple substance tellurium is 1.6g/L, then will be added with the suspending liquid A of simple substance tellurium respectively, B, the ultrasonic generator that the power that C puts into is 1200W shakes 50min, after taking-up, be placed on respectively on magnetic stirring apparatus and stir 30h again, obtain suspension D, E and F;
4) suspension D is poured in water heating kettle, then will at the negative electrode of water heating kettle, press from both sides with the internally coated carbon/carbon compound material sample holder of SiC, take Graphite Electrodes as anode, immerse in suspension D, sealing water heating kettle is also put into UVave-1000 type microwave ultraviolet excess phonosynthesis instrument by water heating kettle; Again negative and positive the two poles of the earth of water heating kettle are received respectively on the corresponding the two poles of the earth of constant voltage power supply, control hydrothermal temperature at 300 ℃, voltage of supply is at 1000V, pulse-repetition is controlled at 500Hz, pulse duty factor is controlled at 10%, cathode rotary rotating speed is at 4000r/min, and pulse arc discharge depositing time is 10min, after cathode rotary microwave hydrothermal pulse arc discharge deposition finishes, naturally cools to room temperature;
5) take out the carbon/carbon compound material sample after step 4) is processed, then with suspension E, F, according to the processing condition in step 4), carry out pulse arc discharge deposition successively;
6) take out the carbon/carbon compound material sample after step 5) is processed, then in electric drying oven with forced convection in 40 ℃ dry, finally obtain carbon/carbon compound material MoSi
2-ZrSiO
4the compound external coating (EC) of-SiC gradient.
Embodiment 5:
1) get that commercially available through dry ball milling, to obtain particle diameter be 3 ~ 6 μ m molybdenum disilicide powders, the analytically pure ZrSiO of micron order
4powder and particle diameter are 40nm nano silicon carbide powder, press respectively ZrSiO
4: SiC: MoSi
2=8: the mass ratio of 18: 5 is scattered in after mixing in the ethanol of purity>=99.8% and is mixed with the suspending liquid A that concentration is 40g/L;
Press ZrSiO
4: SiC: MoSi
2=12: the mass ratio of 15: 8 is scattered in after mixing and in purity>=99.8% ethanol, is mixed with the suspension B that concentration is 50g/L;
Press ZrSiO
4: SiC: MoSi
2=20: the mass ratio of 20: 20 is scattered in after mixing and in purity>=99.8% ethanol, is mixed with the suspension C that concentration is 60g/L;
2) respectively by suspending liquid A, B, the ultrasonic generator that C puts into 1500W shakes 40min, is placed on respectively again and on magnetic stirring apparatus, stirs 36h after taking-up;
3) respectively to suspending liquid A, B, in C, add purity >=99.7% simple substance tellurium, the concentration of controlling simple substance tellurium is 2.0g/L, then will be added with the suspending liquid A of simple substance tellurium respectively, B, the ultrasonic generator that the power that C puts into is 1500W shakes 40min, after taking-up, be placed on respectively on magnetic stirring apparatus and stir 36h again, obtain suspension D, E and F;
4) suspension D is poured in water heating kettle, then will at the negative electrode of water heating kettle, press from both sides with the internally coated carbon/carbon compound material sample holder of SiC, take Graphite Electrodes as anode, immerse in suspension D, sealing water heating kettle is also put into UVave-1000 type microwave ultraviolet excess phonosynthesis instrument by water heating kettle; Again negative and positive the two poles of the earth of water heating kettle are received respectively on the corresponding the two poles of the earth of constant voltage power supply, control hydrothermal temperature at 420 ℃, voltage of supply is at 5000V, pulse-repetition is controlled at 3000Hz, pulse duty factor is controlled at 90%, cathode rotary rotating speed is at 800r/min, and pulse arc discharge depositing time is 5min, after cathode rotary microwave hydrothermal pulse arc discharge deposition finishes, naturally cools to room temperature;
5) take out the carbon/carbon compound material sample after step 4) is processed, then with suspension E, F, according to the processing condition in step 4), carry out pulse arc discharge deposition successively;
6) take out the carbon/carbon compound material sample after step 5) is processed, then in electric drying oven with forced convection in 60 ℃ dry, finally obtain carbon/carbon compound material MoSi
2-ZrSiO
4the compound external coating (EC) of-SiC gradient.
The present invention prepares MoSi as seen from Figure 1
2-ZrSiO
4the compound external coating (EC) of-SiC gradient is fine and close and evenly, thickness homogeneous, is approximately 300 ~ 400 μ m.
Useful effect is embodied in:
1) adopt cathode rotary microwave hydrothermal pulse arc discharge deposition method to prepare MoSi
2-ZrSiO
4the compound external coating (EC) thickness of-SiC gradient homogeneous, surperficial flawless.
2) MoSi that prepared by the present invention
2-ZrSiO
4the compound external coating (EC) crystallinity of-SiC gradient is good, strength of coating is high, good toughness and interface be in conjunction with better, effectively reduces the roughness of coating, has greatly improved the high temperature ablation resistance of coating.
3) the present invention prepares MoSi
2-ZrSiO
4the compound external coating (EC) technique of-SiC gradient is simple, easy to operate, and raw material is easy to get, and efficiency is high, and cost is low.
4) gradient composite coating that prepared by the present invention has good antioxidant property, can under the oxidizing atmosphere of 1650 ℃, to C/C matrix material, effectively protect 300h, and oxidation weight loss is less than 2%.
Claims (9)
1. prepare carbon/carbon compound material MoSi for one kind
2-ZrSiO
4the method of the compound external coating (EC) of-SiC gradient, is characterized in that comprising the following steps:
1) get molybdenum disilicide powder, the analytically pure ZrSiO of micron order
4powder and nano silicon carbide powder, press respectively ZrSiO
4: SiC: MoSi
2=(1 ~ 10): (10 ~ 20): the mass ratio of (1 ~ 10) is scattered in after mixing and is mixed with the suspending liquid A that concentration is 40g/L in ethanol;
Press ZrSiO
4: SiC: MoSi
2=(5 ~ 15): (5 ~ 20): the mass ratio of (5 ~ 15) is scattered in after mixing and is mixed with the suspension B that concentration is 50g/L in ethanol;
Press ZrSiO
4: SiC: MoSi
2=(10 ~ 20): (1 ~ 20): the mass ratio of (10 ~ 20) is scattered in after mixing and is mixed with the suspension C that concentration is 60g/L in ethanol;
2) respectively by suspending liquid A, B, C puts into ultrasonic generator and shakes, and is placed on respectively again and on magnetic stirring apparatus, stirs 12 ~ 36h after taking-up;
3), respectively to suspending liquid A, B, adds simple substance tellurium in C, the concentration of controlling simple substance tellurium is 0.5 ~ 2.0g/L, then will be added with the suspending liquid A of simple substance tellurium, B respectively, the ultrasonic generator that C puts into shakes, and after taking-up, is placed on respectively on magnetic stirring apparatus and stirs 12 ~ 36h again, obtains suspension D, E and F;
4) suspension D is poured in water heating kettle, then will at the negative electrode of water heating kettle, press from both sides with the internally coated carbon/carbon compound material sample holder of SiC, immerse in suspension D, sealing water heating kettle is also put into microwave ultraviolet excess phonosynthesis instrument by water heating kettle; Again negative and positive the two poles of the earth of water heating kettle are received respectively on the corresponding the two poles of the earth of constant voltage power supply, control hydrothermal temperature at 80 ~ 420 ℃, voltage of supply is at 500 ~ 5000V, pulse-repetition is controlled at 500-5000Hz, pulse duty factor is controlled at 10%-90%, cathode rotary rotating speed is at 800 ~ 4000r/min, and pulse arc discharge depositing time is 5 ~ 50min, after cathode rotary microwave hydrothermal pulse arc discharge deposition finishes, naturally cools to room temperature;
5) take out the carbon/carbon compound material sample after step 4) is processed, then with suspension E, F, according to the processing condition in step 4), carry out pulse arc discharge deposition successively;
6) take out the carbon/carbon compound material sample after step 5) is processed, then at 40 ~ 80 ℃, be dried, finally obtain carbon/carbon compound material MoSi
2-ZrSiO
4the compound external coating (EC) of-SiC gradient.
2. the carbon/carbon compound material MoSi for preparing according to claim 1
2-ZrSiO
4the method of the compound external coating (EC) of-SiC gradient, is characterized in that: described molybdenum disilicide powder is that by commercially available molybdenum disilicide powder, through dry ball milling, to make particle diameter be 3 ~ 6 μ m.
3. the carbon/carbon compound material MoSi for preparing according to claim 1
2-ZrSiO
4the method of the compound external coating (EC) of-SiC gradient, is characterized in that: the particle diameter of described nano silicon carbide powder is 40nm.
4. the carbon/carbon compound material MoSi for preparing according to claim 1
2-ZrSiO
4the method of the compound external coating (EC) of-SiC gradient, is characterized in that: purity>=99.8% of described ethanol.
5. the carbon/carbon compound material MoSi for preparing according to claim 1
2-ZrSiO
4the method of the compound external coating (EC) of-SiC gradient, is characterized in that: purity>=99.7% of described simple substance tellurium.
6. the carbon/carbon compound material MoSi for preparing according to claim 1
2-ZrSiO
4the method of the compound external coating (EC) of-SiC gradient, is characterized in that: the power of described ultrasonic generator is 500 ~ 1500W, and the concussion time is 40 ~ 100min.
7. the carbon/carbon compound material MoSi for preparing according to claim 1
2-ZrSiO
4the method of the compound external coating (EC) of-SiC gradient, is characterized in that: described dry employing be electric drying oven with forced convection.
8. the carbon/carbon compound material MoSi for preparing according to claim 1
2-ZrSiO
4the method of the compound external coating (EC) of-SiC gradient, is characterized in that: described water heating kettle be take Graphite Electrodes as anode, and conducting base is negative electrode, and negative electrode is fixed on rotator.
9. the carbon/carbon compound material MoSi for preparing according to claim 1
2-ZrSiO
4the method of the compound external coating (EC) of-SiC gradient, is characterized in that: the model of described microwave ultraviolet excess phonosynthesis instrument is UVave-1000.
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| CN103332963B (en) * | 2013-06-19 | 2014-08-27 | 陕西科技大学 | Method for modifying C/C composite material at low temperature by microwave-ultraviolet process |
| CN103342581B (en) * | 2013-06-19 | 2014-08-27 | 陕西科技大学 | Method for modifying C/C composite material by microwave-ultrasonic method |
| CN103601529B (en) * | 2013-11-05 | 2014-12-24 | 陕西科技大学 | Preparation method of external SiB6 oxidation-resistant coating of carbon/carbon composite material |
| CN103601530B (en) * | 2013-11-05 | 2015-01-28 | 陕西科技大学 | Preparation method of external TaB oxidation-resistant coating of carbon/carbon composite material |
| CN103601531B (en) * | 2013-11-05 | 2014-12-24 | 陕西科技大学 | Preparation method of external TiB2 oxidation-resistant coating of carbon/carbon composite material |
| CN109806824A (en) * | 2019-03-25 | 2019-05-28 | 南京工业大学 | A kind of extensive, the quickly hydrophilic microwave method of improvement carbon substrate and its application |
| CN111548164B (en) * | 2020-05-19 | 2021-06-29 | 中钢集团洛阳耐火材料研究院有限公司 | Continuous self-toughening nitride-bonded silicon carbide refractory material |
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