CN105237034A - Method for preparing porous silicon carbide ceramic based on template - Google Patents
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Abstract
本发明涉及一种基于模板制备多孔碳化硅陶瓷的方法，创造性地将模板法的思想与CVI工艺的特点结合起来，提出采用CVI法制备多孔SiC陶瓷，该法得到的多孔SiC陶瓷孔径较为均匀，且孔隙率可控，材料具有很大的比表面积。该方法可解决其他模板法出现的制备工艺较复杂，烧结温度较高等技术问题，且该工艺易于制备复杂构件，大大扩展了该法制备的多孔SiC陶瓷的使用范围。
The invention relates to a method for preparing porous silicon carbide ceramics based on a template. It creatively combines the idea of the template method with the characteristics of the CVI process, and proposes to use the CVI method to prepare porous SiC ceramics. The porous SiC ceramics obtained by this method have relatively uniform pore diameters. And the porosity is controllable, and the material has a large specific surface area. The method can solve technical problems such as complicated preparation process and high sintering temperature in other template methods, and the process is easy to prepare complex components, which greatly expands the application range of porous SiC ceramics prepared by the method.
Description
技术领域technical field
本发明属于多孔碳化硅陶瓷制备方法，具体涉及一种采用模板制备多孔碳化硅陶瓷的方法。The invention belongs to a method for preparing porous silicon carbide ceramics, in particular to a method for preparing porous silicon carbide ceramics by using a template.
背景技术Background technique
多孔碳化硅陶瓷是一种内部具有大量相通或闭合孔道结构的新型陶瓷材料，因其具有低密度，高强度，比表面积大，优异的热稳定性和化学稳定性等性能而广泛应用到工业中，如热气体微粒过滤器，熔融金属过滤器，催化剂载体，气体燃烧介质，轻质结构部件等。Porous silicon carbide ceramics is a new type of ceramic material with a large number of interconnected or closed pore structures inside. It is widely used in industry because of its low density, high strength, large specific surface area, excellent thermal stability and chemical stability. , such as hot gas particulate filters, molten metal filters, catalyst supports, gas combustion media, lightweight structural components, etc.
制备多孔SiC陶瓷的方法有很多，如烧结法，发泡法，粘结法，模板法等。为了更好地调控多孔SiC陶瓷的孔隙率，孔径分布和孔隙形貌，模板法逐渐成为人们的研究热点。模板法是指通过混合模板和SiC颗粒或者SiC有机前驱体，形成一种两相混合的复合材料，然后除去模板再烧结得到多孔SiC陶瓷。文献“S.H.LeeandY.W.Kim,ProcessingofCellularSiCCeramicsUsingPolymerMicrobeads[J].J.KoreanCeram.Soc.,43,458–462(2006).”中以SiC粉末为原料，以Al2O3-Y2O3为烧结助剂，以聚合物微球为模板构架，先将三种物质混合均匀压制成一定形状，再热处理该混合物燃烧除去聚合物微球，形成具有一定孔隙结构的素坯，最后烧结坯体得到所需的多孔SiC陶瓷材料。通过控制聚合物微球的含量和烧结的温度，可以把多孔SiC陶瓷的气孔率控制在16％～69％之间。该法制备的多孔SiC陶瓷孔隙均匀，且孔隙率为40％时，强度可达到40MPa，强度较高，但该法烧结温度较高，温度高于1700℃，不利于成本降低。文献“Y.J.JinandY.W.Kim,Lowtemperatureprocessingofhighlyporoussiliconcarbideceramicswithimprovedflexuralstrength[J].J.Mater.Sci.,45,282–285(2010).”中，以聚碳硅烷作为SiC先驱体，以聚合物微球为模板构架，以聚硅氧烷为粘结剂，混合均匀后在200℃下干燥，然后在1100～1400℃条件下进行热分解，最终得到多孔SiC陶瓷。该法得到的多孔陶瓷孔隙率的范围在60％～90％之间，当气孔率为70％是也能达到30MPa，但该法还是存在烧结温度较高的问题。文献“M.Fukushima,M.Nakata,Y.Zhou,T.OhjiandY.Yoshizawa,Fabricationandpropertiesofultrahighlyporoussiliconcarbidebythegelation–freezingmethod[J].J.Eur.Ceram.Soc.,30,2889–2896(2010).”中，以凝胶，水和SiC颗粒为原料，采用凝胶冷冻干燥法制备出具有定向排列的高气孔率的多孔SiC陶瓷。该法可以制备各种形状的部件，且通过改变冷冻温度可以把多孔陶瓷的孔隙直径控制在34～147μm范围内，但该法也存在工艺复杂，烧结温度较高的问题。There are many methods to prepare porous SiC ceramics, such as sintering method, foaming method, bonding method, template method and so on. In order to better control the porosity, pore size distribution and pore morphology of porous SiC ceramics, the template method has gradually become a research hotspot. The template method refers to forming a two-phase mixed composite material by mixing templates and SiC particles or SiC organic precursors, and then removing the templates and sintering to obtain porous SiC ceramics. In the document "S.H.Lee and Y.W.Kim, Processing of Cellular SiCCeramics Using Polymer Microbeads [J]. J. Korean Ceram. Soc., 43, 458–462 (2006)." SiC powder is used as raw material, Al2O3-Y2O3 is used as sintering aid, and polymer microsphere To form a template frame, the three materials are mixed uniformly and pressed into a certain shape, and then the mixture is heat treated to burn off the polymer microspheres to form a green body with a certain pore structure, and finally the green body is sintered to obtain the required porous SiC ceramic material. By controlling the content of polymer microspheres and the sintering temperature, the porosity of porous SiC ceramics can be controlled between 16% and 69%. The porous SiC ceramic prepared by this method has uniform pores, and when the porosity is 40%, the strength can reach 40MPa, which is relatively high. However, the sintering temperature of this method is high, and the temperature is higher than 1700 ° C, which is not conducive to cost reduction. In the document "Y.J.Jin and Y.W.Kim, Low temperature processing of highly porous silicon carbide ceramics with improved flexural strength [J]. J. Mater. Sci., 45, 282–285 (2010).", polycarbosilane was used as the SiC precursor, polymer microspheres were used as the template framework, and Polysiloxane is used as a binder, and after mixing evenly, it is dried at 200°C, and then thermally decomposed at 1100-1400°C to finally obtain porous SiC ceramics. The porosity of the porous ceramics obtained by this method ranges from 60% to 90%, and can reach 30 MPa when the porosity is 70%, but this method still has the problem of high sintering temperature. In the literature "M.Fukushima, M.Nakata, Y.Zhou, T.OhjiandY.Yoshizawa, Fabrication and properties of ultrahighly porous silicon carbide by the gelation–freezing method [J].J.Eur.Ceram.Soc.,30,2889–2896(2010)." Using glue, water and SiC particles as raw materials, porous SiC ceramics with directional alignment and high porosity were prepared by gel freeze-drying. This method can prepare parts of various shapes, and the pore diameter of porous ceramics can be controlled within the range of 34-147 μm by changing the freezing temperature, but this method also has the problems of complicated process and high sintering temperature.
化学气相沉积(ChemicalVaporDeposition，简称CVD)技术最初是由表面工程的需要发展起来的。后来，人们引导气体深入到多孔材料内部沉积以达到使材料致密化的目的，进而发展出化学气相渗透技术(ChemicalVaporInfiltration，简称CVI)。材料内部致密化是陶瓷相的生成造成的，该种陶瓷相可以起到填充和粘结作用，并且，借助催化剂可以使SiC陶瓷相呈现为纳米线的形态，可以极大地提升多孔陶瓷的比表面积，为制备具有较大比较面积和孔隙可控的多孔SiC陶瓷提供了可能性。CVI法具有制备温度低，易于制备复杂构件等优点，越来越受到人们的关注。Chemical vapor deposition (Chemical Vapor Deposition, referred to as CVD) technology was originally developed by the needs of surface engineering. Later, people guided the gas deep into the porous material for deposition to achieve the purpose of densifying the material, and then developed the chemical vapor infiltration technology (Chemical Vapor Infiltration, referred to as CVI). The densification inside the material is caused by the generation of ceramic phase, which can play a role of filling and bonding, and, with the help of a catalyst, the SiC ceramic phase can appear in the form of nanowires, which can greatly increase the specific surface area of porous ceramics , which provides the possibility to prepare porous SiC ceramics with large specific area and controllable pores. The CVI method has the advantages of low preparation temperature and easy preparation of complex components, and has attracted more and more attention.
发明内容Contents of the invention
要解决的技术问题technical problem to be solved
为了解决多孔碳化硅陶瓷现有技术中存在的制备工艺较复杂，烧结温度较高，等技术问题，本发明提出一种采用模板，再在模板上沉积SiC陶瓷相，形成多孔碳化硅陶瓷，最后再在多孔陶瓷内部生长SiC纳米线，进而得到具有较大比表面积的多孔SiC陶瓷的方法。In order to solve technical problems such as complex preparation process and high sintering temperature in the prior art of porous silicon carbide ceramics, the present invention proposes a method of using a template, and then depositing SiC ceramic phases on the template to form porous silicon carbide ceramics. A method for growing SiC nanowires inside the porous ceramics to obtain porous SiC ceramics with a larger specific surface area.
技术方案Technical solutions
一种基于模板制备多孔碳化硅陶瓷的方法，其特征在于步骤如下：A method for preparing porous silicon carbide ceramics based on a template, characterized in that the steps are as follows:
步骤1：将按照设计要求加工的模板放入化学气相渗透炉CVI炉，以MTSCH3SiCl3作为先驱体，氢气作为载气和稀释气体，氩气作为保护气体进行化学气相渗透；在CVI过程中，生成的SiC陶瓷相覆盖在模板上得到多孔SiC陶瓷；所述模板为泡沫镍、泡沫碳或金属泡沫模板；Step 1: Put the template processed according to the design requirements into the chemical vapor infiltration furnace CVI furnace, use MTSCH 3 SiCl 3 as the precursor, hydrogen as the carrier gas and dilution gas, and argon as the protective gas for chemical vapor infiltration; during the CVI process , the generated SiC ceramic phase is covered on the template to obtain porous SiC ceramics; the template is nickel foam, carbon foam or metal foam template;
步骤2、去除模板：当模板为泡沫镍或金属泡沫模板时采用酸化方法去除模板，当模板是泡沫碳时利用低温氧化燃烧的方法去除模板，得到多孔SiC陶瓷。Step 2. Removing the template: when the template is nickel foam or metal foam template, the template is removed by acidification; when the template is carbon foam, the template is removed by low-temperature oxidation and combustion to obtain porous SiC ceramics.
在步骤2完成后，将得到的多孔SiC陶瓷再放入化学气相渗透炉CVI炉，以MTSCH3SiCl3作为先驱体，氢气作为载气和稀释气体，氩气作为保护气体沉积制备SiC纳米线，以调节多孔陶瓷孔隙，提高多孔陶瓷的比表面积。After step 2 is completed, the obtained porous SiC ceramics are put into a chemical vapor infiltration furnace CVI furnace, MTSCH 3 SiCl 3 is used as a precursor, hydrogen is used as a carrier gas and a dilution gas, and argon is used as a protective gas to deposit and prepare SiC nanowires. To adjust the pores of porous ceramics and increase the specific surface area of porous ceramics.
所述模板的孔隙率范围为40％～90％。The porosity of the template ranges from 40% to 90%.
所述步骤1中CVI过程中MTS∶H2∶Ar的比例为1∶5～15∶10～20。The ratio of MTS:H 2 :Ar in the CVI process in step 1 is 1:5˜15:10˜20.
所述步骤1中CVI过程中工艺参数为：总气压为0.5～5kPa，沉积温度为900-1200℃，沉积时间为10～200h。The process parameters in the CVI process in step 1 are: the total air pressure is 0.5-5kPa, the deposition temperature is 900-1200°C, and the deposition time is 10-200h.
所述步骤2中低温氧化燃烧的燃烧温度范围为400～700℃。The combustion temperature range of the low-temperature oxidation combustion in the step 2 is 400-700°C.
所述制备SiC纳米线时添加Fe、Co、Ni的氯化物或硝酸盐的任意一种或多种组合为催化剂。When preparing the SiC nanowires, any one or combination of Fe, Co, Ni chloride or nitrate is added as a catalyst.
所述制备SiC纳米线的工艺参数为总气压为0.5～5kPa，沉积温度为800-1100℃，沉积时间为1～10h。The process parameters for preparing SiC nanowires are as follows: the total air pressure is 0.5-5kPa, the deposition temperature is 800-1100°C, and the deposition time is 1-10h.
所述制备SiC纳米线时MTS∶H2∶Ar的比例为1∶5～20∶3～15。The ratio of MTS:H 2 :Ar when preparing SiC nanowires is 1:5-20:3-15.
有益效果Beneficial effect
本发明提出的一种基于模板制备多孔碳化硅陶瓷的方法，创造性地将模板法的思想与CVI工艺的特点结合起来，提出采用CVI法制备多孔SiC陶瓷，该法得到的多孔SiC陶瓷孔径较为均匀，且孔隙率可控，材料具有很大的比表面积。该方法可解决其他模板法出现的制备工艺较复杂，烧结温度较高等技术问题，且该工艺易于制备复杂构件，大大扩展了该法制备的多孔SiC陶瓷的使用范围。The present invention proposes a template-based method for preparing porous silicon carbide ceramics, which creatively combines the idea of the template method with the characteristics of the CVI process, and proposes the use of the CVI method to prepare porous SiC ceramics. The porous SiC ceramics obtained by this method have relatively uniform pore diameters , and the porosity is controllable, and the material has a large specific surface area. The method can solve technical problems such as complex preparation process and high sintering temperature in other template methods, and the process is easy to prepare complex components, which greatly expands the application range of porous SiC ceramics prepared by the method.
附图说明Description of drawings
图1为该工艺的流程示意图Figure 1 is a schematic flow chart of the process
图2为以泡沫镍为模板制备的多孔陶瓷的形貌Figure 2 is the morphology of porous ceramics prepared with nickel foam as a template
图3为多孔陶瓷表面SiC纳米线的放大图Figure 3 is an enlarged view of SiC nanowires on the porous ceramic surface
具体实施方式detailed description
实施例一Embodiment one
步骤1：原料准备：模板采用泡沫镍，气孔率为40％。Step 1: Raw material preparation: The template is made of nickel foam with a porosity of 40%.
步骤2：将模板加工成指定形状。Step 2: Process the template into a specified shape.
步骤3：将步骤2中得到的不同形状的模板放入化学气相渗透炉(CVI炉)进行化学气相渗透，在CVI过程中，生成的SiC陶瓷相逐渐覆盖在模板上，当生成的SiC陶瓷相达到一定程度时就可以形成具有一定强度的，孔隙率可控的多孔SiC陶瓷。CVI法生成SiC陶瓷相的工艺条件为：利用MTS(CH3SiCl3)作为先驱体，氢气作为载气和稀释气体，氩气作为保护气体。MTS:H2:Ar的比例为1:12:10，总气压为5kPa，沉积温度为1000℃，沉积时间为20h。Step 3: Put the templates of different shapes obtained in step 2 into a chemical vapor infiltration furnace (CVI furnace) for chemical vapor infiltration. During the CVI process, the generated SiC ceramic phase gradually covers the template. When the generated SiC ceramic phase When reaching a certain level, porous SiC ceramics with certain strength and controllable porosity can be formed. The process conditions for generating SiC ceramic phase by CVI method are as follows: MTS (CH 3 SiCl 3 ) is used as the precursor, hydrogen is used as the carrier gas and dilution gas, and argon is used as the protective gas. The ratio of MTS:H 2 :Ar is 1:12:10, the total gas pressure is 5kPa, the deposition temperature is 1000°C, and the deposition time is 20h.
步骤4：去除模板。将得到的多孔SiC陶瓷酸化处理。Step 4: Remove the template. The obtained porous SiC ceramics are acidified.
步骤5：沉积SiC纳米线。在步骤4中得到的多孔陶瓷内部沉积制备SiC纳米线，进一步调节多孔陶瓷孔隙，提高多孔陶瓷的比表面积。SiC纳米线的沉积工艺是：利用MTS(CH3SiCl3)作为先驱体，氢气作为载气和稀释气体，氩气作为保护气体。MTS:H2:Ar的比例为1:5～20:3～15，总气压为0.5～5kPa，沉积温度为800-1100℃，沉积时间为1～10h。使用的催化剂为Fe、Co、Ni的氯化物或硝酸盐的任意一种或多种组合。最后，可得到具有较大比表面积，且孔隙可控的多孔SiC陶瓷。Step 5: Deposit SiC nanowires. SiC nanowires are prepared by depositing inside the porous ceramic obtained in step 4 to further adjust the pores of the porous ceramic and increase the specific surface area of the porous ceramic. The deposition process of SiC nanowires is as follows: MTS (CH 3 SiCl 3 ) is used as a precursor, hydrogen is used as a carrier gas and a dilution gas, and argon is used as a protective gas. The ratio of MTS:H 2 :Ar is 1:5-20:3-15, the total gas pressure is 0.5-5kPa, the deposition temperature is 800-1100°C, and the deposition time is 1-10h. The catalyst used is any one or combination of Fe, Co, Ni chloride or nitrate. Finally, porous SiC ceramics with large specific surface area and controllable pores can be obtained.
实施例二Embodiment two
步骤1：原料准备：模板采用泡沫镍，气孔率为60％。Step 1: Preparation of raw materials: The template is made of nickel foam with a porosity of 60%.
步骤2：将模板加工成指定形状。Step 2: Process the template into a specified shape.
步骤3：将步骤2中得到的不同形状的模板放入化学气相渗透炉(CVI炉)进行化学气相渗透，在CVI过程中，生成的SiC陶瓷相逐渐覆盖在模板上，当生成的SiC陶瓷相达到一定程度时就可以形成具有一定强度的，孔隙率可控的多孔SiC陶瓷。CVI法生成SiC陶瓷相的工艺条件为：利用MTS(CH3SiCl3)作为先驱体，氢气作为载气和稀释气体，氩气作为保护气体。MTS:H2:Ar的比例为1:12:10，总气压为5kPa，沉积温度为1000℃，沉积时间为50h。Step 3: Put the templates of different shapes obtained in step 2 into a chemical vapor infiltration furnace (CVI furnace) for chemical vapor infiltration. During the CVI process, the generated SiC ceramic phase gradually covers the template. When the generated SiC ceramic phase When reaching a certain level, porous SiC ceramics with certain strength and controllable porosity can be formed. The process conditions for generating SiC ceramic phase by CVI method are as follows: MTS (CH 3 SiCl 3 ) is used as the precursor, hydrogen is used as the carrier gas and dilution gas, and argon is used as the protective gas. The ratio of MTS:H 2 :Ar is 1:12:10, the total gas pressure is 5kPa, the deposition temperature is 1000°C, and the deposition time is 50h.
步骤4：去除模板。将得到的多孔SiC陶瓷酸化处理。Step 4: Remove the template. The obtained porous SiC ceramics are acidified.
步骤5：沉积SiC纳米线。在步骤4中得到的多孔陶瓷内部沉积制备SiC纳米线，进一步调节多孔陶瓷孔隙，提高多孔陶瓷的比表面积。SiC纳米线的沉积工艺是：利用MTS(CH3SiCl3)作为先驱体，氢气作为载气和稀释气体，氩气作为保护气体。MTS:H2:Ar的比例为1:5～20:3～15，总气压为0.5～5kPa，沉积温度为800-1100℃，沉积时间为1～10h。使用的催化剂为Fe、Co、Ni的氯化物或硝酸盐的任意一种或多种组合。最后，可得到具有较大比表面积，且孔隙可控的多孔SiC陶瓷。Step 5: Deposit SiC nanowires. SiC nanowires are prepared by depositing inside the porous ceramic obtained in step 4 to further adjust the pores of the porous ceramic and increase the specific surface area of the porous ceramic. The deposition process of SiC nanowires is as follows: MTS (CH 3 SiCl 3 ) is used as a precursor, hydrogen is used as a carrier gas and a dilution gas, and argon is used as a protective gas. The ratio of MTS:H 2 :Ar is 1:5-20:3-15, the total gas pressure is 0.5-5kPa, the deposition temperature is 800-1100°C, and the deposition time is 1-10h. The catalyst used is any one or combination of Fe, Co, Ni chloride or nitrate. Finally, porous SiC ceramics with large specific surface area and controllable pores can be obtained.
实施例三Embodiment three
步骤1：原料准备：模板采用泡沫镍，气孔率为70％。Step 1: Preparation of raw materials: The template is made of nickel foam with a porosity of 70%.
步骤2：将模板加工成指定形状。Step 2: Process the template into a specified shape.
步骤3：将步骤2中得到的不同形状的模板放入化学气相渗透炉(CVI炉)进行化学气相渗透，在CVI过程中，生成的SiC陶瓷相逐渐覆盖在模板上，当生成的SiC陶瓷相达到一定程度时就可以形成具有一定强度的，孔隙率可控的多孔SiC陶瓷。CVI法生成SiC陶瓷相的工艺条件为：利用MTS(CH3SiCl3)作为先驱体，氢气作为载气和稀释气体，氩气作为保护气体。MTS:H2:Ar的比例为1:12:10，总气压为5kPa，沉积温度为1100℃，沉积时间为20h。Step 3: Put the templates of different shapes obtained in step 2 into a chemical vapor infiltration furnace (CVI furnace) for chemical vapor infiltration. During the CVI process, the generated SiC ceramic phase gradually covers the template. When the generated SiC ceramic phase When reaching a certain level, porous SiC ceramics with certain strength and controllable porosity can be formed. The process conditions for generating SiC ceramic phase by CVI method are as follows: MTS (CH 3 SiCl 3 ) is used as the precursor, hydrogen is used as the carrier gas and dilution gas, and argon is used as the protective gas. The ratio of MTS:H 2 :Ar is 1:12:10, the total gas pressure is 5kPa, the deposition temperature is 1100°C, and the deposition time is 20h.
步骤4：去除模板。将得到的多孔SiC陶瓷酸化处理。Step 4: Remove the template. The obtained porous SiC ceramics are acidified.
步骤5：沉积SiC纳米线。在步骤4中得到的多孔陶瓷内部沉积制备SiC纳米线，进一步调节多孔陶瓷孔隙，提高多孔陶瓷的比表面积。SiC纳米线的沉积工艺是：利用MTS(CH3SiCl3)作为先驱体，氢气作为载气和稀释气体，氩气作为保护气体。MTS:H2:Ar的比例为1:5～20:3～15，总气压为0.5～5kPa，沉积温度为800-1100℃，沉积时间为1～10h。使用的催化剂为Fe、Co、Ni的氯化物或硝酸盐的任意一种或多种组合。最后，可得到具有较大比表面积，且孔隙可控的多孔SiC陶瓷。Step 5: Deposit SiC nanowires. SiC nanowires are prepared by depositing inside the porous ceramic obtained in step 4 to further adjust the pores of the porous ceramic and increase the specific surface area of the porous ceramic. The deposition process of SiC nanowires is as follows: MTS (CH 3 SiCl 3 ) is used as a precursor, hydrogen is used as a carrier gas and a dilution gas, and argon is used as a protective gas. The ratio of MTS:H 2 :Ar is 1:5-20:3-15, the total gas pressure is 0.5-5kPa, the deposition temperature is 800-1100°C, and the deposition time is 1-10h. The catalyst used is any one or combination of Fe, Co, Ni chloride or nitrate. Finally, porous SiC ceramics with large specific surface area and controllable pores can be obtained.
实施例四Embodiment Four
步骤1：原料准备：模板采用泡沫镍，气孔率为90％。Step 1: Preparation of raw materials: The template is made of nickel foam with a porosity of 90%.
步骤2：将模板加工成指定形状。Step 2: Process the template into a specified shape.
步骤3：将步骤2中得到的不同形状的模板放入化学气相渗透炉(CVI炉)进行化学气相渗透，在CVI过程中，生成的SiC陶瓷相逐渐覆盖在模板上，当生成的SiC陶瓷相达到一定程度时就可以形成具有一定强度的，孔隙率可控的多孔SiC陶瓷。CVI法生成SiC陶瓷相的工艺条件为：利用MTS(CH3SiCl3)作为先驱体，氢气作为载气和稀释气体，氩气作为保护气体。MTS:H2:Ar的比例为1:12:10，总气压为5kPa，沉积温度为1100℃，沉积时间为50h。Step 3: Put the templates of different shapes obtained in step 2 into a chemical vapor infiltration furnace (CVI furnace) for chemical vapor infiltration. During the CVI process, the generated SiC ceramic phase gradually covers the template. When the generated SiC ceramic phase When reaching a certain level, porous SiC ceramics with certain strength and controllable porosity can be formed. The process conditions for generating SiC ceramic phase by CVI method are as follows: MTS (CH 3 SiCl 3 ) is used as the precursor, hydrogen is used as the carrier gas and dilution gas, and argon is used as the shielding gas. The ratio of MTS:H 2 :Ar is 1:12:10, the total gas pressure is 5kPa, the deposition temperature is 1100°C, and the deposition time is 50h.
步骤4：去除模板。将得到的多孔SiC陶瓷酸化处理。Step 4: Remove the template. The obtained porous SiC ceramics are acidified.
步骤5：沉积SiC纳米线。在步骤4中得到的多孔陶瓷内部沉积制备SiC纳米线，进一步调节多孔陶瓷孔隙，提高多孔陶瓷的比表面积。SiC纳米线的沉积工艺是：利用MTS(CH3SiCl3)作为先驱体，氢气作为载气和稀释气体，氩气作为保护气体。MTS:H2:Ar的比例为1:5～20:3～15，总气压为0.5～5kPa，沉积温度为800-1100℃，沉积时间为1～10h。使用的催化剂为Fe、Co、Ni的氯化物或硝酸盐的任意一种或多种组合。最后，可得到具有较大比表面积，且孔隙可控的多孔SiC陶瓷。Step 5: Deposit SiC nanowires. SiC nanowires are prepared by depositing inside the porous ceramic obtained in step 4 to further adjust the pores of the porous ceramic and increase the specific surface area of the porous ceramic. The deposition process of SiC nanowires is as follows: MTS (CH 3 SiCl 3 ) is used as a precursor, hydrogen is used as a carrier gas and a dilution gas, and argon is used as a protective gas. The ratio of MTS:H 2 :Ar is 1:5-20:3-15, the total gas pressure is 0.5-5kPa, the deposition temperature is 800-1100°C, and the deposition time is 1-10h. The catalyst used is any one or combination of Fe, Co, Ni chloride or nitrate. Finally, porous SiC ceramics with large specific surface area and controllable pores can be obtained.
实施例五Embodiment five
步骤1：原料准备：模板采用泡沫碳，气孔率为70％。Step 1: Raw material preparation: the template is made of carbon foam with a porosity of 70%.
步骤2：将模板加工成指定形状。Step 2: Process the template into a specified shape.
步骤3：将步骤2中得到的不同形状的模板放入化学气相渗透炉(CVI炉)进行化学气相渗透，在CVI过程中，生成的SiC陶瓷相逐渐覆盖在模板上，当生成的SiC陶瓷相达到一定程度时就可以形成具有一定强度的，孔隙率可控的多孔SiC陶瓷。CVI法生成SiC陶瓷相的工艺条件为：利用MTS(CH3SiCl3)作为先驱体，氢气作为载气和稀释气体，氩气作为保护气体。MTS:H2:Ar的比例为1:12:10，总气压为5kPa，沉积温度为1000℃，沉积时间为20h。Step 3: Put the templates of different shapes obtained in step 2 into a chemical vapor infiltration furnace (CVI furnace) for chemical vapor infiltration. During the CVI process, the generated SiC ceramic phase gradually covers the template. When the generated SiC ceramic phase When reaching a certain level, porous SiC ceramics with certain strength and controllable porosity can be formed. The process conditions for generating SiC ceramic phase by CVI method are as follows: MTS (CH 3 SiCl 3 ) is used as the precursor, hydrogen is used as the carrier gas and dilution gas, and argon is used as the protective gas. The ratio of MTS:H 2 :Ar is 1:12:10, the total gas pressure is 5kPa, the deposition temperature is 1000°C, and the deposition time is 20h.
步骤4：去除模板。将得到的多孔SiC陶瓷500℃氧化去除泡沫碳模板。Step 4: Remove the template. The obtained porous SiC ceramics were oxidized at 500°C to remove the foamed carbon template.
步骤5：沉积SiC纳米线。在步骤4中得到的多孔陶瓷内部沉积制备SiC纳米线，进一步调节多孔陶瓷孔隙，提高多孔陶瓷的比表面积。SiC纳米线的沉积工艺是：利用MTS(CH3SiCl3)作为先驱体，氢气作为载气和稀释气体，氩气作为保护气体。MTS:H2:Ar的比例为1:5～20:3～15，总气压为0.5～5kPa，沉积温度为800-1100℃，沉积时间为1～10h。使用的催化剂为Fe、Co、Ni的氯化物或硝酸盐的任意一种或多种组合。最后，可得到具有较大比表面积，且孔隙可控的多孔SiC陶瓷。Step 5: Deposit SiC nanowires. SiC nanowires are prepared by depositing inside the porous ceramic obtained in step 4 to further adjust the pores of the porous ceramic and increase the specific surface area of the porous ceramic. The deposition process of SiC nanowires is as follows: MTS (CH 3 SiCl 3 ) is used as a precursor, hydrogen is used as a carrier gas and a dilution gas, and argon is used as a protective gas. The ratio of MTS:H 2 :Ar is 1:5-20:3-15, the total gas pressure is 0.5-5kPa, the deposition temperature is 800-1100°C, and the deposition time is 1-10h. The catalyst used is any one or combination of Fe, Co, Ni chloride or nitrate. Finally, porous SiC ceramics with large specific surface area and controllable pores can be obtained.
实施例六Embodiment six
步骤1：原料准备：模板采用泡沫碳，气孔率为90％。Step 1: Preparation of raw materials: The template is made of foamed carbon with a porosity of 90%.
步骤2：将模板加工成指定形状。Step 2: Process the template into a specified shape.
步骤3：将步骤2中得到的不同形状的模板放入化学气相渗透炉(CVI炉)进行化学气相渗透，在CVI过程中，生成的SiC陶瓷相逐渐覆盖在模板上，当生成的SiC陶瓷相达到一定程度时就可以形成具有一定强度的，孔隙率可控的多孔SiC陶瓷。CVI法生成SiC陶瓷相的工艺条件为：利用MTS(CH3SiCl3)作为先驱体，氢气作为载气和稀释气体，氩气作为保护气体。MTS:H2:Ar的比例为1:12:10，总气压为5kPa，沉积温度为1100℃，沉积时间为20h。Step 3: Put the templates of different shapes obtained in step 2 into a chemical vapor infiltration furnace (CVI furnace) for chemical vapor infiltration. During the CVI process, the generated SiC ceramic phase gradually covers the template. When the generated SiC ceramic phase When reaching a certain level, porous SiC ceramics with certain strength and controllable porosity can be formed. The process conditions for generating SiC ceramic phase by CVI method are as follows: MTS (CH 3 SiCl 3 ) is used as the precursor, hydrogen is used as the carrier gas and dilution gas, and argon is used as the protective gas. The ratio of MTS:H 2 :Ar is 1:12:10, the total gas pressure is 5kPa, the deposition temperature is 1100°C, and the deposition time is 20h.
步骤4：去除模板。将得到的多孔SiC陶瓷500℃氧化去除泡沫碳模板。Step 4: Remove the template. The obtained porous SiC ceramics were oxidized at 500°C to remove the foamed carbon template.
步骤5：沉积SiC纳米线。在步骤4中得到的多孔陶瓷内部沉积制备SiC纳米线，进一步调节多孔陶瓷孔隙，提高多孔陶瓷的比表面积。SiC纳米线的沉积工艺是：利用MTS(CH3SiCl3)作为先驱体，氢气作为载气和稀释气体，氩气作为保护气体。MTS:H2:Ar的比例为1:5～20:3～15，总气压为0.5～5kPa，沉积温度为800-1100℃，沉积时间为1～10h。使用的催化剂为Fe、Co、Ni的氯化物或硝酸盐的任意一种或多种组合。最后，可得到具有较大比表面积，且孔隙可控的多孔SiC陶瓷。Step 5: Deposit SiC nanowires. SiC nanowires are prepared by depositing inside the porous ceramic obtained in step 4 to further adjust the pores of the porous ceramic and increase the specific surface area of the porous ceramic. The deposition process of SiC nanowires is as follows: MTS (CH 3 SiCl 3 ) is used as a precursor, hydrogen is used as a carrier gas and a dilution gas, and argon is used as a protective gas. The ratio of MTS:H 2 :Ar is 1:5-20:3-15, the total gas pressure is 0.5-5kPa, the deposition temperature is 800-1100°C, and the deposition time is 1-10h. The catalyst used is any one or combination of Fe, Co, Ni chloride or nitrate. Finally, porous SiC ceramics with large specific surface area and controllable pores can be obtained.
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