CN103044075A - 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 for 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 C/C matrix material carbon fiber carbon based composites that is otherwise known as, because it only has single carbon to form, the ablation resistance that not only has charcoal and graphite material excellence, the advantage such as low density, thermal expansivity are low, and also have excellent mechanical property under the high temperature.Especially the performance that goes up not down of the increase of its intensity temperature makes it become 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 the C/C matrix material surpasses rapidly oxidation under 500 ℃ the oxidizing atmosphere in temperature, and this has greatly limited it and has used, so the oxidation protection problem of C/C matrix material becomes one of study hotspot in recent years.Simultaneously it being carried out the high-temperature oxidation resistant protection has great importance to its high temperature application.
Oxidation resistant coating is considered to solve the effective ways of carbon/carbon compound material oxidant protection under high temperature problem.The SiC coating is because good and generally use as transition layer with physics, the chemical compatibility of C/C matrix material, and still single SiC coating can not provide effective protection to the 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. the standby C-AlPO of water heat electrophoresis deposition legal system
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
2[Cao Liyun, Wu build roc .Y to compound coating for Wang Yaqin, Huang Jianfeng
2Si
2O
7Whisker strengthens MoSi
2The preparation and property of compound coating. matrix material journal, 2010,2 (27): 58-61.], the preparation single SiC coating [old warbling of the oriole, Wang Chengguo, Zhao Wei. the 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 preferably protective capacities.But the larger difference of the thermal expansivity between the inside and outside coating further causes again the generation of tiny crack in the coating, has 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: the 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.The process implementing of preparation adopt the supercritical fluid technology to prepare the C/C composite coating owing to need to carry out under High Temperature High Pressure, to having relatively high expectations of equipment, and the external coating (EC) that forms 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], the standby coating of employing formed in situ legal system need to be 1500 ℃ of lower pyroprocessing, and can not once prepare and finish [Huang Jian-Feng, Li He-Jun, Zeng Xie-Rong, Li Ke-Zhi.Surf.coat.Technol.2006,200,5379.], adopt the easy cracking in external coating (EC) surface of sol-gel method preparation 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.], prepare coating and still deposit repeatedly to brush once to prepare and finish and adopt molten slurry to apply reaction method, need later stage heat treated drawback [Fu Qian-Gang, Li He-Jun, Wang Yong-Jie, Li Ke-Zhi, Tao Jun.Surface﹠amp; Coating Technology.2010,204,1832.], although same detonation flame spraying and the ultrasonic spray method of adopting prepared the 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 standby coating [the Huang Jianfeng of water heat electrophoresis deposition legal system, 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.].
Its characteristics of pulse arc discharge sedimentation at first are because the arc-over of 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.Phase transformation and the embrittlement adopting this method can avoid adopting conventional high-temperature to apply and cause solve in the coating preparation process thermal damage to matrix 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, so that the simple efficient heterogeneous compound coating of preparation and gradient ceramic coating become possibility; In the pulse arc discharge process, within the pulse conducting phase, electrochemical polarization increases in addition, and near the positively charged ion the cathodic area is fully deposited, and the crystallization of coating is careful, porosity is low.In pulse-off in the phase, the mass concentration of conductive ion can obtain rise in various degree in the cathode zone solution, the solution resistance rate reduces, be conducive to improve cathode efficiency and cathode current density so that sedimentation rate is further accelerated and the dispersiveness of suspension improves 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 preparation carbon/carbon compound material MoSi simple to operate, that preparation cycle is short
2-ZrSiO
4The method of the compound external coating (EC) of-SiC gradient, the non-microcracked generation of compound external coating (EC) surface uniform of the present invention preparation, and the 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) gets the molybdenum disilicide powder, the analytically pure ZrSiO of micron order
4Powder and nano silicon carbide powder are pressed respectively ZrSiO
4: SiC: MoSi
2=(1 ~ 10): (10 ~ 20): be scattered in after the mass ratio of (1 ~ 10) mixes and be mixed with the suspending liquid A that concentration is 40g/L in the ethanol;
Press ZrSiO
4: SiC: MoSi
2=(5 ~ 15): (5 ~ 20): be scattered in after the mass ratio of (5 ~ 15) mixes and be mixed with the suspension B that concentration is 50g/L in the ethanol;
Press ZrSiO
4: SiC: MoSi
2=(10 ~ 20): (1 ~ 20): be scattered in after the mass ratio of (10 ~ 20) mixes and be mixed with the suspension C that concentration is 60g/L in the ethanol;
2) respectively with suspending liquid A, B, C put into ultrasonic generator and shake, and are placed on respectively after the taking-up again and stir 12 ~ 36h on the magnetic stirring apparatus;
3) respectively to suspending liquid A, B adds simple substance tellurium among the C, the concentration of control simple substance tellurium is 0.5 ~ 2.0g/L, then will be added with respectively the suspending liquid A of simple substance tellurium, B, the ultrasonic generator that C puts into shakes, and is placed on respectively after the taking-up again and stirs 12 ~ 36h on the magnetic stirring apparatus, obtains suspension D, E and F;
4) suspension D is poured in the water heating kettle, then will with the internally coated carbon/carbon compound material sample holder of SiC on the negative electrode folder of water heating kettle, immerse among the suspension D, seal water heating kettle and water heating kettle is put into microwave ultraviolet excess phonosynthesis instrument; 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, the control hydrothermal temperature is 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%, the cathode rotary rotating speed is at 800 ~ 4000r/min, and the pulse arc discharge depositing time is 5 ~ 50min, naturally cools to room temperature after cathode rotary microwave hydrothermal pulse arc discharge deposition finishes;
5) then the carbon/carbon compound material sample after the taking-up step 4) is processed carries out the pulse arc discharge deposition with suspension E, F according to the processing condition in the step 4) successively;
6) then the carbon/carbon compound material sample after the taking-up step 5) is processed 40 ~ 80 ℃ of dryings, finally obtains carbon/carbon compound material MoSi
2-ZrSiO
4The compound external coating (EC) of-SiC gradient.
Described molybdenum disilicide powder is that to make particle diameter by commercially available molybdenum disilicide powder through dry ball milling be 3 ~ 6 μ m.
The particle diameter of described nano silicon carbide powder is 40nm.
The purity of described ethanol 〉=99.8%.
The purity of described simple substance tellurium 〉=99.7%
The power of described ultrasonic generator is 500 ~ 1500W, and the concussion time is 40 ~ 100min.
What described drying adopted is electric drying oven with forced convection.
Described water heating kettle is take Graphite Electrodes as anode, and negative electrode is fixed on the 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 present in reaction system from heating, efficient height, and then the localized hyperthermia and the high pressure that produce effectively reduce MoSi
2, ZrSiO
4, the SiC suspended particles Activation energy, make it in the pulse arc discharge deposition process, react more complete and abundant, thereby obtain the coating of compact structure.By the negative electrode high speed rotating, avoid traditional hydrothermal method to need repeatedly to apply the shortcoming that just can obtain the coating of compact and uniform structure simultaneously, realized under controlled condition, obtaining fine and close, MoSi that have micro-flaw, different thickness
2-ZrSiO
4The compound external coating (EC) of-SiC gradient.In addition, the pulse arc discharge sedimentation also has the characteristics such as simple to operation, that cost is low, depositing operation is easy to control.Simultaneously because zirconium silicate (ZrSiO
4) have a 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, have low, the effective characteristics of cost.MoSi
2(thermal expansivity is 8.0 * 10
-6/ ℃) stupalith is high owing to refractoriness, thermal shock resistance is good, volume stability is good etc., and character causes people's attention, it is desirable high grade refractory, have very high fusing point (2030 ℃) and good high temperature oxidation resistance (in the air greater than 1800 ℃), these hot propertiess obviously are better than SiC; As the most metals material, have high temperature toughness and self-healing capability.Yet for the interface binding power that improves inside and outside coating and compactness and the intensity of coating itself, introduce nanometer silicon carbide (SiC), and so that it becomes gradient evenly to distribute in coating, thereby interface binding power and the compactness of raising coating.So ZrSiO
4And MoSi
2Excellent performance is so that both have a good application prospect as high temperature thermal barrier/thermal protection coating material, 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, impel coating fine and close, and interface binding power is good.
Description of drawings
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) gets that commercially available to obtain particle diameter through dry ball milling be 3 ~ 6 μ m molybdenum disilicide powders, the analytically pure ZrSiO of micron order
4Powder and particle diameter are the 40nm nano silicon carbide powder, press respectively ZrSiO
4: SiC: MoSi
2=1: be scattered in after 10: 1 mass ratio mixes in the ethanol of purity 〉=99.8% and be mixed with the suspending liquid A that concentration is 40g/L;
Press ZrSiO
4: SiC: MoSi
2=5: be scattered in after 5: 5 mass ratio mixes and be mixed with the suspension B that concentration is 50g/L in purity 〉=99.8% ethanol;
Press ZrSiO
4: SiC: MoSi
2=12: be scattered in after 5: 10 mass ratio mixes and be mixed with the suspension C that concentration is 60g/L in purity 〉=99.8% ethanol;
2) respectively with suspending liquid A, the ultrasonic generator that B, C put into 500W shakes 100min, is placed on respectively after the taking-up again and stirs 12h on the magnetic stirring apparatus;
3) respectively to suspending liquid A, B, add purity 〉=99.7% simple substance tellurium among the C, the concentration of control simple substance tellurium is 0.5g/L, then will be added with respectively the suspending liquid A of simple substance tellurium, the power that B, C put into is that the ultrasonic generator of 500W shakes 100min, be placed on respectively again after the taking-up and stir 12h on the magnetic stirring apparatus, obtain suspension D, E and F;
4) suspension D is poured in the water heating kettle, then will be with the internally coated carbon/carbon compound material sample holder of SiC on the negative electrode folder of water heating kettle, take Graphite Electrodes as anode, immerse among the suspension D, seal water heating kettle and water heating kettle is put into UVave-1000 type microwave ultraviolet excess phonosynthesis instrument; 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, the control hydrothermal temperature is at 130 ℃, voltage of supply is at 2000V, pulse-repetition is controlled at 1600Hz, pulse duty factor is controlled at 30%, the cathode rotary rotating speed is at 3000r/min, and the pulse arc discharge depositing time is 30min, naturally cools to room temperature after cathode rotary microwave hydrothermal pulse arc discharge deposition finishes;
5) then the carbon/carbon compound material sample after the taking-up step 4) is processed carries out the pulse arc discharge deposition with suspension E, F according to the processing condition in the step 4) successively;
6) take out carbon/carbon compound material sample after step 5) is processed, then in electric drying oven with forced convection in 80 ℃ of dryings, finally obtain carbon/carbon compound material MoSi
2-ZrSiO
4The compound external coating (EC) of-SiC gradient.
Embodiment 2:
1) gets that commercially available to obtain particle diameter through dry ball milling be 3 ~ 6 μ m molybdenum disilicide powders, the analytically pure ZrSiO of micron order
4Powder and particle diameter are the 40nm nano silicon carbide powder, press respectively ZrSiO
4: SiC: MoSi
2=5: be scattered in after 13: 8 mass ratio mixes in the ethanol of purity 〉=99.8% and be mixed with the suspending liquid A that concentration is 40g/L;
Press ZrSiO
4: SiC: MoSi
2=10: be scattered in after 10: 12 mass ratio mixes and be mixed with the suspension B that concentration is 50g/L in purity 〉=99.8% ethanol;
Press ZrSiO
4: SiC: MoSi
2=15: be scattered in after 10: 12 mass ratio mixes and be mixed with the suspension C that concentration is 60g/L in purity 〉=99.8% ethanol;
2) respectively with suspending liquid A, the ultrasonic generator that B, C put into 800W shakes 80min, is placed on respectively after the taking-up again and stirs 18h on the magnetic stirring apparatus;
3) respectively to suspending liquid A, B, add purity 〉=99.7% simple substance tellurium among the C, the concentration of control simple substance tellurium is 0.8g/L, then will be added with respectively the suspending liquid A of simple substance tellurium, the power that B, C put into is that the ultrasonic generator of 800W shakes 80min, be placed on respectively again after the taking-up and stir 18h on the magnetic stirring apparatus, obtain suspension D, E and F;
4) suspension D is poured in the water heating kettle, then will be with the internally coated carbon/carbon compound material sample holder of SiC on the negative electrode folder of water heating kettle, take Graphite Electrodes as anode, immerse among the suspension D, seal water heating kettle and water heating kettle is put into UVave-1000 type microwave ultraviolet excess phonosynthesis instrument; 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, the control hydrothermal temperature is at 80 ℃, voltage of supply is at 4000V, pulse-repetition is controlled at 58000Hz, pulse duty factor is controlled at 70%, the cathode rotary rotating speed is at 2000r/min, and the pulse arc discharge depositing time is 20min, naturally cools to room temperature after cathode rotary microwave hydrothermal pulse arc discharge deposition finishes;
5) then the carbon/carbon compound material sample after the taking-up step 4) is processed carries out the pulse arc discharge deposition with suspension E, F according to the processing condition in the step 4) successively;
6) take out carbon/carbon compound material sample after step 5) is processed, then in electric drying oven with forced convection in 70 ℃ of dryings, finally obtain carbon/carbon compound material MoSi
2-ZrSiO
4The compound external coating (EC) of-SiC gradient.
Embodiment 3:
1) gets that commercially available to obtain particle diameter through dry ball milling be 3 ~ 6 μ m molybdenum disilicide powders, the analytically pure ZrSiO of micron order
4Powder and particle diameter are the 40nm nano silicon carbide powder, press respectively ZrSiO
4: SiC: MoSi
2=10: be scattered in after 20: 10 mass ratio mixes in the ethanol of purity 〉=99.8% and be mixed with the suspending liquid A that concentration is 40g/L;
Press ZrSiO
4: SiC: MoSi
2=8: be scattered in after 12: 10 mass ratio mixes and be mixed with the suspension B that concentration is 50g/L in purity 〉=99.8% ethanol;
Press ZrSiO
4: SiC: MoSi
2=10: be scattered in after 1: 15 mass ratio mixes and be mixed with the suspension C that concentration is 60g/L in purity 〉=99.8% ethanol;
2) respectively with suspending liquid A, the ultrasonic generator that B, C put into 1000W shakes 60min, is placed on respectively after the taking-up again and stirs 24h on the magnetic stirring apparatus;
3) respectively to suspending liquid A, B, add purity 〉=99.7% simple substance tellurium among the C, the concentration of control simple substance tellurium is 1.3g/L, then will be added with respectively the suspending liquid A of simple substance tellurium, the power that B, C put into is that the ultrasonic generator of 1000W shakes 60min, be placed on respectively again after the taking-up and stir 24h on the magnetic stirring apparatus, obtain suspension D, E and F;
4) suspension D is poured in the water heating kettle, then will be with the internally coated carbon/carbon compound material sample holder of SiC on the negative electrode folder of water heating kettle, take Graphite Electrodes as anode, immerse among the suspension D, seal water heating kettle and water heating kettle is put into UVave-1000 type microwave ultraviolet excess phonosynthesis instrument; 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, the control hydrothermal temperature is at 200 ℃, voltage of supply is at 500V, pulse-repetition is controlled at 4000Hz, pulse duty factor is controlled at 50%, the cathode rotary rotating speed is at 1500r/min, and the pulse arc discharge depositing time is 50min, naturally cools to room temperature after cathode rotary microwave hydrothermal pulse arc discharge deposition finishes;
5) then the carbon/carbon compound material sample after the taking-up step 4) is processed carries out the pulse arc discharge deposition with suspension E, F according to the processing condition in the step 4) successively;
6) take out carbon/carbon compound material sample after step 5) is processed, then in electric drying oven with forced convection in 50 ℃ of dryings, finally obtain carbon/carbon compound material MoSi
2-ZrSiO
4The compound external coating (EC) of-SiC gradient.
Embodiment 4:
1) gets that commercially available to obtain particle diameter through dry ball milling be 3 ~ 6 μ m molybdenum disilicide powders, the analytically pure ZrSiO of micron order
4Powder and particle diameter are the 40nm nano silicon carbide powder, press respectively ZrSiO
4: SiC: MoSi
2=3: be scattered in after 15: 3 mass ratio mixes in the ethanol of purity 〉=99.8% and be mixed with the suspending liquid A that concentration is 40g/L;
Press ZrSiO
4: SiC: MoSi
2=15: be scattered in after 20: 15 mass ratio mixes and be mixed with the suspension B that concentration is 50g/L in purity 〉=99.8% ethanol;
Press ZrSiO
4: SiC: MoSi
2=18: be scattered in after 15: 18 mass ratio mixes and be mixed with the suspension C that concentration is 60g/L in purity 〉=99.8% ethanol;
2) respectively with suspending liquid A, the ultrasonic generator that B, C put into 1200W shakes 50min, is placed on respectively after the taking-up again and stirs 30h on the magnetic stirring apparatus;
3) respectively to suspending liquid A, B, add purity 〉=99.7% simple substance tellurium among the C, the concentration of control simple substance tellurium is 1.6g/L, then will be added with respectively the suspending liquid A of simple substance tellurium, the power that B, C put into is that the ultrasonic generator of 1200W shakes 50min, be placed on respectively again after the taking-up and stir 30h on the magnetic stirring apparatus, obtain suspension D, E and F;
4) suspension D is poured in the water heating kettle, then will be with the internally coated carbon/carbon compound material sample holder of SiC on the negative electrode folder of water heating kettle, take Graphite Electrodes as anode, immerse among the suspension D, seal water heating kettle and water heating kettle is put into UVave-1000 type microwave ultraviolet excess phonosynthesis instrument; 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, the control hydrothermal temperature is at 300 ℃, voltage of supply is at 1000V, pulse-repetition is controlled at 500Hz, pulse duty factor is controlled at 10%, the cathode rotary rotating speed is at 4000r/min, and the pulse arc discharge depositing time is 10min, naturally cools to room temperature after cathode rotary microwave hydrothermal pulse arc discharge deposition finishes;
5) then the carbon/carbon compound material sample after the taking-up step 4) is processed carries out the pulse arc discharge deposition with suspension E, F according to the processing condition in the step 4) successively;
6) take out carbon/carbon compound material sample after step 5) is processed, then in electric drying oven with forced convection in 40 ℃ of dryings, finally obtain carbon/carbon compound material MoSi
2-ZrSiO
4The compound external coating (EC) of-SiC gradient.
Embodiment 5:
1) gets that commercially available to obtain particle diameter through dry ball milling be 3 ~ 6 μ m molybdenum disilicide powders, the analytically pure ZrSiO of micron order
4Powder and particle diameter are the 40nm nano silicon carbide powder, press respectively ZrSiO
4: SiC: MoSi
2=8: be scattered in after 18: 5 mass ratio mixes in the ethanol of purity 〉=99.8% and be mixed with the suspending liquid A that concentration is 40g/L;
Press ZrSiO
4: SiC: MoSi
2=12: be scattered in after 15: 8 mass ratio mixes and be mixed with the suspension B that concentration is 50g/L in purity 〉=99.8% ethanol;
Press ZrSiO
4: SiC: MoSi
2=20: be scattered in after 20: 20 mass ratio mixes and be mixed with the suspension C that concentration is 60g/L in purity 〉=99.8% ethanol;
2) respectively with suspending liquid A, the ultrasonic generator that B, C put into 1500W shakes 40min, is placed on respectively after the taking-up again and stirs 36h on the magnetic stirring apparatus;
3) respectively to suspending liquid A, B, add purity 〉=99.7% simple substance tellurium among the C, the concentration of control simple substance tellurium is 2.0g/L, then will be added with respectively the suspending liquid A of simple substance tellurium, the power that B, C put into is that the ultrasonic generator of 1500W shakes 40min, be placed on respectively again after the taking-up and stir 36h on the magnetic stirring apparatus, obtain suspension D, E and F;
4) suspension D is poured in the water heating kettle, then will be with the internally coated carbon/carbon compound material sample holder of SiC on the negative electrode folder of water heating kettle, take Graphite Electrodes as anode, immerse among the suspension D, seal water heating kettle and water heating kettle is put into UVave-1000 type microwave ultraviolet excess phonosynthesis instrument; 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, the control hydrothermal temperature is at 420 ℃, voltage of supply is at 5000V, pulse-repetition is controlled at 3000Hz, pulse duty factor is controlled at 90%, the cathode rotary rotating speed is at 800r/min, and the pulse arc discharge depositing time is 5min, naturally cools to room temperature after cathode rotary microwave hydrothermal pulse arc discharge deposition finishes;
5) then the carbon/carbon compound material sample after the taking-up step 4) is processed carries out the pulse arc discharge deposition with suspension E, F according to the processing condition in the step 4) successively;
6) take out carbon/carbon compound material sample after step 5) is processed, then in electric drying oven with forced convection in 60 ℃ of dryings, 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, the 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 of the present invention's preparation
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 efficient is high, and cost is low.
4) gradient composite coating of the present invention's preparation has good antioxidant property, can effectively protect 300h to the C/C matrix material under 1650 ℃ oxidizing atmosphere, and oxidation weight loss is less than 2%.
Claims (9)
1. one kind prepares carbon/carbon compound material MoSi
2-ZrSiO
4The method of the compound external coating (EC) of-SiC gradient is characterized in that may further comprise the steps:
1) gets the molybdenum disilicide powder, the analytically pure ZrSiO of micron order
4Powder and nano silicon carbide powder are pressed respectively ZrSiO
4: SiC: MoSi
2=(1 ~ 10): (10 ~ 20): be scattered in after the mass ratio of (1 ~ 10) mixes and be mixed with the suspending liquid A that concentration is 40g/L in the ethanol;
Press ZrSiO
4: SiC: MoSi
2=(5 ~ 15): (5 ~ 20): be scattered in after the mass ratio of (5 ~ 15) mixes and be mixed with the suspension B that concentration is 50g/L in the ethanol;
Press ZrSiO
4: SiC: MoSi
2=(10 ~ 20): (1 ~ 20): be scattered in after the mass ratio of (10 ~ 20) mixes and be mixed with the suspension C that concentration is 60g/L in the ethanol;
2) respectively with suspending liquid A, B, C put into ultrasonic generator and shake, and are placed on respectively after the taking-up again and stir 12 ~ 36h on the magnetic stirring apparatus;
3) respectively to suspending liquid A, B adds simple substance tellurium among the C, the concentration of control simple substance tellurium is 0.5 ~ 2.0g/L, then will be added with respectively the suspending liquid A of simple substance tellurium, B, the ultrasonic generator that C puts into shakes, and is placed on respectively after the taking-up again and stirs 12 ~ 36h on the magnetic stirring apparatus, obtains suspension D, E and F;
4) suspension D is poured in the water heating kettle, then will with the internally coated carbon/carbon compound material sample holder of SiC on the negative electrode folder of water heating kettle, immerse among the suspension D, seal water heating kettle and water heating kettle is put into microwave ultraviolet excess phonosynthesis instrument; 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, the control hydrothermal temperature is 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%, the cathode rotary rotating speed is at 800 ~ 4000r/min, and the pulse arc discharge depositing time is 5 ~ 50min, naturally cools to room temperature after cathode rotary microwave hydrothermal pulse arc discharge deposition finishes;
5) then the carbon/carbon compound material sample after the taking-up step 4) is processed carries out the pulse arc discharge deposition with suspension E, F according to the processing condition in the step 4) successively;
6) then the carbon/carbon compound material sample after the taking-up step 5) is processed 40 ~ 80 ℃ of dryings, finally obtains carbon/carbon compound material MoSi
2-ZrSiO
4The compound external coating (EC) of-SiC gradient.
2. preparation carbon/carbon compound material MoSi 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 to make particle diameter by commercially available molybdenum disilicide powder through dry ball milling be 3 ~ 6 μ m.
3. preparation carbon/carbon compound material MoSi 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. preparation carbon/carbon compound material MoSi according to claim 1
2-ZrSiO
4The method of the compound external coating (EC) of-SiC gradient is characterized in that: the purity of described ethanol 〉=99.8%.
5. preparation carbon/carbon compound material MoSi according to claim 1
2-ZrSiO
4The method of the compound external coating (EC) of-SiC gradient is characterized in that: the purity of described simple substance tellurium 〉=99.7%.
6. preparation carbon/carbon compound material MoSi 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. preparation carbon/carbon compound material MoSi according to claim 1
2-ZrSiO
4The method of the compound external coating (EC) of-SiC gradient is characterized in that: what described drying adopted is electric drying oven with forced convection.
8. preparation carbon/carbon compound material MoSi 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 is take Graphite Electrodes as anode, and conducting base is negative electrode, and negative electrode is fixed on the rotator.
9. preparation carbon/carbon compound material MoSi 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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