WO2017016079A1 - 高纯超细ZrC-SiC复合粉体的合成方法 - Google Patents

高纯超细ZrC-SiC复合粉体的合成方法 Download PDF

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WO2017016079A1
WO2017016079A1 PCT/CN2015/092656 CN2015092656W WO2017016079A1 WO 2017016079 A1 WO2017016079 A1 WO 2017016079A1 CN 2015092656 W CN2015092656 W CN 2015092656W WO 2017016079 A1 WO2017016079 A1 WO 2017016079A1
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composite powder
zrc
sic composite
water
based slurry
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陈大明
蒋丹宇
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山东合创明业精细陶瓷有限公司
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Priority to JP2018517467A priority patent/JP6464319B2/ja
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Definitions

  • the invention belongs to the field of inorganic non-metal materials and relates to a method for synthesizing high-purity ultrafine ZrC-SiC composite powder.
  • ZrC is a refractory metal carbide with a high melting point (3530 ° C), high hardness (25.5 GPa) and high thermal conductivity and electrical conductivity similar to metals, high chemical stability and good radiation resistance.
  • High-purity ultra-fine ZrC powder is widely used in aerospace vehicles for ultra-high temperature structural ceramics and anti-oxidation coatings, nuclear industrial thermal photoelectric emitter coatings, nuclear fuel particle coatings, ultra-high temperature refractories and other fields.
  • SiC powder and ZrC powder it is sometimes necessary to add a certain amount of SiC powder and ZrC powder to obtain ZrC-SiC composite powder. To use. However, it is difficult to uniformly mix the two powders.
  • the preparation of high-purity ultrafine ZrC powder and SiC powder has a high technical content.
  • the industrial production method is mainly an electric arc furnace carbon-thermal reduction method.
  • the method uses zircon sand (ZrSiO 4 ) or oblique zircon (ZrO 2 ) as raw materials, and is added with an appropriate amount of petroleum coke powder or graphite powder to heat the electric arc furnace.
  • ZrSiO 4 zircon sand
  • ZrO 2 oblique zircon
  • oxygen and silicon in the raw material react with carbon to form CO and SiO gas, respectively, which are volatilized and eliminated, and ZrC powder is formed by this direct reduction carbonization.
  • the process has low raw material cost and mature production process, which is suitable for industrial production.
  • the ZrC powder produced by the method has low purity and coarse particle size, and cannot meet the requirements of ultra-high temperature resistant structural ceramics and various functional coatings.
  • the key to the process is the need to properly control the speed and temperature of the combustion synthesis reaction, with the advantages of simple process, energy saving, high production efficiency. However, the control of the combustion process is difficult, the synthetic powder particles are coarser, the particle size distribution is not uniform, and the consistency between batches is poor.
  • Sol-gel method has become a process technology for preparing various ultrafine powders. It uses a metal alkoxide containing Zr, a carbon source material, water, an alcohol and a necessary catalyst to form a sol liquid, which is hydrolyzed and polycondensed. The wet gel is formed, and dried, heat treated, and ground to obtain an ultrafine ZrC powder.
  • the process has the advantages that the synthesis reaction can be realized at a lower temperature, and the high-purity ultrafine nano-sized ZrC powder can be easily prepared, and is also suitable for the preparation of the ZrC film.
  • the raw material cost is high, the process is complicated, the production efficiency is low, and the waste gas and waste water are easily polluted. Generally, it is suitable for laboratory research and application, and it is difficult to carry out industrial production.
  • the raw material ZrO 2 powder and graphite powder or carbon black are both solid particles, it is very difficult to achieve complete uniform mixing, which makes the carbothermal reduction reaction difficult to proceed sufficiently, and the unreacted complete oxygen and free carbon are easily present in the powder. Therefore, it is usually carried out under high temperature conditions (1600 ° C ⁇ 1800 ° C), resulting in coarse powder particle size, increased energy consumption and easy equipment damage.
  • a liquid high residual carbon ratio organic substance such as a phenolic resin
  • a carbon source material such as a phenolic resin
  • a high-purity ZrO 2 powder or a zirconium oxychloride raw material which has the advantage of making the carbon source and the zirconium source material uniform. Mixing, the reaction is easy to carry out.
  • resins are expensive, usually do not dissolve in water, require the use of organic solvents, and their thermal decomposition products are very hard and difficult to pulverize.
  • sucrose as a carbon source to synthesize carbide powders
  • experiments have shown that sucrose The C component is easily foamed and lost during the thermal decomposition process, and its theoretical C content is 42 wt%, but the C yield is less than 20 wt% after thermal decomposition at 400 ° C, and the C yield will be different under different conditions. Changes, this makes it very difficult to accurately formulate the Zr:C ratio.
  • the above process technology is used to replace the zirconium source material with a silicon source material such as quartz sand, metal silicon powder, silica micropowder, silicon tetrachloride or silica sol, and is also suitable for the synthesis of SiC powder.
  • a silicon source material such as quartz sand, metal silicon powder, silica micropowder, silicon tetrachloride or silica sol.
  • the high-purity ultrafine ZrC-SiC composite powder which is highly homogeneously mixed in one step has not been reported so far.
  • the object of the present invention is to provide a method for synthesizing a high-purity ultrafine ZrC-SiC composite powder, and the synthesized ZrC-SiC composite powder is very uniformly mixed.
  • the method for synthesizing the high-purity ultrafine ZrC-SiC composite powder according to the present invention comprises zirconium silicate alone or in addition to zirconium silicate or one or two of zirconia or silica sol as a zirconium source and a silicon source material.
  • Sucrose or glucose is used as a carbon source material, and a high-purity ultrafine ZrC-SiC composite powder is prepared by using an acrylamide monomer and a methylenebisacrylamide cross-linking agent as a gel material.
  • the high-purity ultrafine ZrC-SiC composite powder according to the present invention is a ZrC-SiC composite powder having a purity of ⁇ 99% and a particle diameter d 50 ⁇ 1 ⁇ m.
  • zirconium silicate alone or in zirconium silicate is added with one or two of zirconia or silica sol as zirconium source and silicon source material, and the synthesized 50% ZrC-50% SiC composite powder can reach the molecular level. Uniform mixing because ZrSiO 4 decomposes in situ.
  • zirconium silicate alone or in the zirconium silicate is added with one or two of zirconia or silica sol as the zirconium source and the silicon source material, and the molar ratio of the total amount of Zr and Si to C is controlled to be 1:3.5 to 1: 4.
  • Zirconium silicate is used as the zirconium source and the silicon source material, and zirconium silicate can be matched with an appropriate amount of zirconium oxide (ZrO 2 ) or silica sol (SiO 2 ) as the zirconium source and the silicon source material.
  • the method for synthesizing the high-purity ultrafine ZrC-SiC composite powder comprises the following steps:
  • Deionized water is 50% to 100% by weight of the carbon source, including water added in the silica sol; the dispersing agent is ammonium polyacrylate dispersing agent, and the dispersing agent is added in an amount of 1% to 3% by weight of the zirconium source and the silicon source material. .
  • the acrylamide and methylene bisacrylamide are mixed in a weight ratio of 15:1 to 25:1.
  • the amount of the crosslinking agent methylene bis acrylamide in the step (2) is from 10% to 20% by weight based on the weight of the deionized water in the step (1).
  • the mixing time in the step (2) is 0.5-2 h.
  • step (3) the water-based slurry is solidified in situ by one of the following three methods:
  • step (2) adding the initiator to the gellable water-based slurry obtained in the step (2), adding a catalyst of tetramethylethylenediamine or triethanolamine aqueous solution, stirring uniformly, and then standing at room temperature to make the water-based slurry Bit gel curing;
  • step (2) adding an initiator to the gellable water-based slurry obtained in the step (2), and then heating to 60 ° C to 80 ° C to keep the water-based slurry in situ gel-cured;
  • redox agent is a mixture of ammonium persulfate and ammonium sulfite in a mass ratio of 1 to 2:1, and stirred. After homogenization, it was allowed to stand at room temperature to cure the water-based slurry in situ.
  • the in-situ gel curing of the water-based slurry in the step (3) adopts one of the following three methods:
  • the volume ratio of the added amount to the gellable water-based slurry is 0.5 -3:100; further adding a concentration of 40-60% of tetramethylethylenediamine or triethanolamine aqueous solution catalyst, the volume ratio of the amount of the gelatinizable water-based slurry is 0.5-2:100, after stirring evenly After standing at room temperature for 2 min to 10 min, the water-based slurry is gelled in situ;
  • the volume ratio of the gelatinizable water-based slurry is 1-3:100, and then heated to 60 ° C to 80 ° C for 2 min to 10 min, so that the water-based slurry is gelled in situ;
  • a redox agent is ammonium persulfate and ammonium sulfite in a mass ratio of 1 to
  • the mixture of 2:1 is added in a volume ratio of 2-4:100 to the gellable water-based slurry. After stirring, the mixture is allowed to stand at room temperature for 2 min to 10 min to cure the water-based slurry in situ.
  • the azo initiator is diazonium diisobutyl hydrazine hydrochloride or azobisisobutyrazoline hydrochloride.
  • the drying and dehydrating temperature in the step (4) is from 100 ° C to 120 ° C, and the pre-carbonization treatment temperature is from 180 ° C to 220 ° C.
  • the carbothermal reduction synthesis reaction is carried out under the condition of vacuum or argon gas protection, the temperature is raised to 1450 ° C to 1600 ° C, and the temperature is maintained for 1 h to 4 h to carry out the carbothermal reduction synthesis reaction.
  • the step (5) is: the ZrC-SiC composite powder synthesized in the step (4) is ground with anhydrous ethanol as a solvent, and is ground by a mill with a polyurethane or nylon inner liner and a WC-Co hard alloy grinding medium ball. Dispersion treatment, to avoid oxidation of the surface of the powder and the incorporation of impurities, after drying, high-purity ultra-fine ZrC-SiC composite powder is obtained.
  • a polymer material lining such as polyurethane or nylon and a grinding machine using WC-Co cemented carbide grinding media balls are used, and then the ethanol solvent is removed in an oven at a temperature of about 80 ° C to obtain a high-purity ultrafine ZrC-SiC composite powder.
  • the present invention has the following advantages:
  • the present invention is a low-cost and high-efficiency industrial production method of a high-purity ultrafine ZrC-SiC composite powder.
  • Both sucrose and glucose have high solubility in water, which does not affect the viscosity of water. It is easy to prepare high-concentration water-based slurry, and the price is low, the source is convenient, and the raw material cost can be greatly reduced.
  • the sucrose or glucose is heated and cracked.
  • the carbon has high purity and high reactivity, can effectively increase the rate of carbothermal reduction reaction and lower the reaction temperature, so that the powder block can be easily ground and pulverized, and the synthesized ZrC-SiC composite powder is very uniformly mixed.
  • the water-based slurry containing the acrylamide monomer and the methylene bisacrylamide crosslinking agent is in situ gel-cured, Avoid sucrose or glucose heating during dehydration drying and thermal decomposition, causing the loss of C component, ensuring that the (Zr+Si):C ratio in the formulation is accurate, the newly decomposed C activity is very high, and it can be very uniform
  • the ground is tightly coated on the surface of the solid phase powder particles, which avoids segregation of the raw materials in the process of drying and dehydration and reaction, and can effectively reduce the temperature of the carbothermal reduction reaction, which is beneficial to the carbothermal reduction synthesis reaction.
  • Example 1 is an XRD spectrum of a high-purity ultrafine 75 mol% ZrC-25 mol% SiC composite powder prepared in Example 2;
  • Example 2 is a SEM image of a high purity ultrafine 75 mol% ZrC-25 mol% SiC composite powder prepared in Example 2.
  • the reaction was synthesized to obtain a ZrC-SiC powder block.
  • Mix it with 100ml of ethanol, put it into a nylon tank, add 400g of 3cm diameter WC-Co cemented carbide grinding media ball, grind it in the planetary mill at 300 rpm for 8h, remove it and remove it in the 80°C temperature oven.
  • Ethanol solvent gave about 150 g of 50 mol% ZrC-50 mol% SiC high-purity ultrafine composite powder with a purity of 99.4% and a particle diameter d 50 ⁇ 1 ⁇ m.
  • Block mix it with 1000ml of ethanol, add 6000g of 3cm diameter and 1000g diameter of 8mm WC-Co hard alloy grinding media ball in a polyurethane-lined mixing mill, grind for 8h;
  • the ethanol solvent was removed from the oven at 80 ° C to obtain about 3500 g of high purity ultrafine 75 mol% ZrC-25 mol% SiC composite powder with a purity of 99.2% and a particle diameter d 50 ⁇ 1 ⁇ m.
  • Fig. 1 The XRD spectrum of the high-purity ultrafine 75 mol% ZrC-25 mol% SiC composite powder prepared in Example 2 is shown in Fig. 1, and the SEM image is shown in Fig. 2.
  • the synthesis reaction was carried out by carbothermal reduction to obtain a SiC-ZrC powder block. It was mixed with 300 ml of ethanol, placed in a 2 L nylon tank, and 800 g of a 3 mm diameter WC-Co cemented carbide grinding medium ball was added, and ground at a speed of 250 rpm in a planetary mill for 8 hours, and then taken out at a temperature of 80 ° C. The ethanol solvent was removed from the oven to obtain about 460 g of a 90 mol% SiC-10 mol% ZrC high-purity ultrafine composite powder having a purity of 99.1% and a particle diameter d 50 ⁇ 1 ⁇ m.

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Abstract

一种高纯超细ZrC-SiC复合粉体的合成方法。以硅酸锆单独或者在硅酸锆中添加氧化锆或硅溶胶中的一种或两种作为锆源和硅源材料，以蔗糖或葡萄糖作为碳源材料，以丙烯酰胺单体和亚甲基双丙烯酰胺交联剂作为凝胶材料，制备高纯超细ZrC-SiC复合粉体。

Description

高纯超细ZrC-SiC复合粉体的合成方法 技术领域
本发明属于无机非金属材料领域，涉及一种高纯超细ZrC-SiC复合粉体的合成方法。
背景技术
ZrC是一种难熔金属碳化物，具有高熔点(3530℃)、高硬度(25.5GPa)以及与金属相近的高热导率和电导率、高的化学稳定性和良好的耐辐射特性。高纯超细ZrC粉体广泛应用于航空航天器的耐超高温结构陶瓷及抗氧化涂层、核工业热光电辐射器涂层及核燃料颗粒涂层、超高温耐火材料等领域。为了降低ZrC陶瓷与涂层的烧结温度，改善其断裂韧性和抗氧化性，或者要获得一些其它特殊性能，有时需添加一定量的SiC粉体与ZrC粉体混合后得到ZrC-SiC复合粉体来使用。但两种粉体均匀混合比较困难，同时，高纯超细ZrC粉体和SiC粉体的制备也有很高的技术含量。
合成ZrC粉体和SiC粉体的方法很多，主要有电弧炉碳热还原法、自蔓延高温合成法、溶胶-凝胶法、气相反应法合成等。
以合成ZrC粉体为例描述：
目前工业化生产方法主要是电弧炉碳热还原法，该法以锆英砂(ZrSiO4)或斜锆石(ZrO2)为原料，配加适量的石油焦粉或石墨粉，在电弧炉内高温真空或氩气保护条件下，原料中的氧和硅与碳发生反应分别形成CO和SiO气体被挥发排除，通过这种直接还原碳化生成ZrC粉体。该工艺原材料成本低，生产工艺已比较成熟，适合于工业化生产。但该法生产的ZrC粉体纯度低，粒径粗大，不能满足耐超高温结构陶瓷及各类功能涂层的要求。
自蔓延高温合成法(SHS)是合成ZrC粉体的一种实用技术，在惰性气体保护下，将接近Zr：C＝1：1比例(略富碳)的机械活化的金属锆和石墨混合粉末点火后，利用化合物合成时的反应热，使反应持续进行下去，即可得到ZrC粉体。该工艺的要害是需要合理控制燃烧合成反应速度和温度，具有工艺过程简单、节能降耗、生产效率高等优点。但其燃烧工艺过程控制比较困难，合成粉体颗粒较粗大，粒径分布不均匀，各批次之间的一致性较差。
溶胶-凝胶法(sol-gel)现已成为制备各种超细粉体的工艺技术，使用含Zr的金属醇盐、碳源材料、水、醇及必要的催化剂组成溶胶液体，经水解缩聚形成湿凝胶，再经干燥、热处理、研磨，即可得到超细ZrC粉体。该工艺的优点是可以在较低温度实现合成反应，容易制得高纯超细纳米级ZrC粉体，也适于ZrC薄膜的制备。但其原材料成本高，工艺过程复杂，生产效率低，容易造成废气和废水污染，一般适合于实验室研究应用，难以进行工业化生产。
近年来发明了各种气相反应法合成难熔化合物超细粉体的工艺技术。例如，以高纯的ZrCl4和烷类气体为锆源和碳源材料，在合适气体保护条件下，将其注入到约10000K的超高温中形成离子状态，冷却过程中发生化学反应直接形成纳米ZrC粒子；将Zr(OC4H9)4在高能激光器激光束作用下分解，先形成Zr/O/C纳米粉末，然后在氩气环境中，经1500℃热处理合成得到纳米ZrC粒子。此类方法的优点是可以获得结晶状态良好、粒子形状可控和纯度高的纳米超细粉体，但由于设备要求高，原材料昂贵，耗能大及环保问题，致使其成本很高，工业化生产有较大困难。
为了获得高纯超细的ZrC粉体，人们改进了碳热还原法，使用高纯ZrO2微粉与石墨粉或碳黑为原料，按一定比例混合均匀后放入碳管炉中，在1600℃～1800℃惰性气体保护条件下进行碳热还原反应，可以获得质量较高的ZrC粉体。这种方法的优点是原材料来源方便，生产工艺过程可控，易实现工业化生产等优点。但由于原料ZrO2粉体与石墨粉或碳黑均为固体颗粒，达到完全均匀混合非常困难，这就使得碳热还原反应难以充分进行，粉体中容易存在未反应完全的氧和自由碳，因此通常需在较高的温度条件(1600℃～1800℃)下进行，造成粉体粒径粗大，并增加能耗和易造成设备损坏。
最近，有人使用液态高残碳率有机物(如酚醛树脂等)作为碳源材料与高纯ZrO2粉体或氯氧化锆原料反应合成ZrC粉体，其优点是可以使碳源和锆源材料均匀混合，反应易于进行。但此类树脂价格偏高，通常不能溶于水，需使用有机溶剂，且其热分解产物很坚硬，不易粉碎；也有关于使用蔗糖为碳源合成碳化物粉体的报道，但实验表明，蔗糖中C组分在热分解过程中极易发泡和流失，其理论含C量为42wt％，但在400℃热分解后C产率仅不足20wt％，且不同条件下C产率会有所变化，这就给Zr：C比例的准确配制带来很大困难。
采用上述工艺技术，以石英砂、金属硅粉、二氧化硅微粉、四氯化硅、硅溶胶等硅源材料代替锆源材料，也可适于SiC粉体的合成。但关于一步法合成高度均匀混合的高纯超细ZrC-SiC复合粉体至今未见报道。
发明内容
针对现有技术的不足，本发明的目的是提供一种高纯超细ZrC-SiC复合粉体的合成方法，合成的ZrC-SiC复合粉体混合非常均匀。
本发明所述的高纯超细ZrC-SiC复合粉体的合成方法，以硅酸锆单独或者在硅酸锆中添加氧化锆或硅溶胶中的一种或两种作为锆源和硅源材料，以蔗糖或葡萄糖作为碳源材料，以丙烯酰胺单体和亚甲基双丙烯酰胺交联剂作为凝胶材料，制备高纯超细ZrC-SiC复合粉体。
本发明所述的高纯超细ZrC-SiC复合粉体为纯度≥99％、粒径d50≤1μm的ZrC-SiC复合 粉体。
优选以硅酸锆单独或者在硅酸锆中添加氧化锆或硅溶胶中的一种或两种作为锆源和硅源材料，合成的50％ZrC-50％SiC复合粉体更可达到分子级别的均匀混合，因为ZrSiO4分解原位形成。
以硅酸锆单独或者在硅酸锆中添加氧化锆或硅溶胶中的一种或两种作为锆源和硅源材料，控制Zr和Si总量与C的摩尔比为1:3.5～1：4。以硅酸锆作为锆源和硅源材料，硅酸锆中可以配以适量的氧化锆(ZrO2)或硅溶胶(SiO2)作为锆源和硅源材料。
所述的高纯超细ZrC-SiC复合粉体的合成方法，包括以下步骤：
(1)将锆源和硅源材料、碳源材料混合，加入去离子水和分散剂混磨，配制成水基料浆；
(2)向步骤(1)得到的水基料浆中再加入丙烯酰胺单体和亚甲基双丙烯酰胺交联剂作为凝胶材料，混磨得到可凝胶化水基料浆；
(3)将水基料浆原位凝胶固化；
(4)在烘箱中干燥脱水并进行预碳化处理，再放入碳管加热炉中进行碳热还原合成反应，得到微晶结构ZrC-SiC复合粉体；
(5)再在乙醇溶剂中研磨分散细化处理，干燥后即得到高纯超细ZrC-SiC复合粉体。
其中：
去离子水为碳源重量的50％～100％，包括添加硅溶胶中所含的水；分散剂为聚丙烯酸铵分散剂，分散剂加入量为锆源和硅源材料重量1％～3％。
丙烯酰胺和亚甲基双丙烯酰胺按重量比为15：1～25：1混合。步骤(2)中交联剂亚甲基双丙烯酰胺的添加量为步骤(1)中去离子水重量的10％～20％。
步骤(2)中混磨时间为0.5-2h。
步骤(3)中将水基料浆原位凝胶固化采用以下三种方法中的一种：
a、向步骤(2)得到的可凝胶化水基料浆中加入引发剂，再加入四甲基乙二胺或三乙醇胺水溶液催化剂，搅拌均匀后在室温静置，使水基料浆原位凝胶固化；
b、向步骤(2)得到的可凝胶化水基料浆中加入引发剂，然后加热至60℃～80℃保温，使水基料浆原位凝胶固化；
c、向步骤(2)得到的可凝胶化水基料浆中加入氧化还原剂的水溶液，其中氧化还原剂为过硫酸铵和亚硫酸铵按质量比为1～2：1的混合物，搅拌均匀后在室温静置，使水基料浆原位凝胶固化。
作为一种优选方案，步骤(3)中将水基料浆原位凝胶固化采用以下三种方法中的一种：
a、向步骤(2)得到的可凝胶化水基料浆中加入浓度为5％～20％的过硫酸铵水溶液引发剂，加入量与可凝胶化水基料浆的体积比为0.5-3:100；再加入浓度为40-60％的四甲基乙二胺或三乙醇胺水溶液催化剂，加入量与可凝胶化水基料浆的体积比为0.5-2:100，搅拌均匀后在室温静置2min～10min，使水基料浆原位凝胶固化；
b、向步骤(2)得到的可凝胶化水基料浆中加入浓度为5％～20％的过硫酸铵水溶液引发剂或者浓度为5％～10％的偶氮引发剂水溶液，加入量与可凝胶化水基料浆的体积比为1-3:100，然后加热至60℃～80℃保温2min～10min，使水基料浆原位凝胶固化；
c、向步骤(2)得到的可凝胶化水基料浆中加入浓度为10％～20％的氧化还原剂水溶液，其中氧化还原剂为过硫酸铵和亚硫酸铵按质量比为1～2：1的混合物，加入量与可凝胶化水基料浆的体积比为2-4:100，搅拌均匀后在室温静置2min～10min，使水基料浆原位凝胶固化。
其中：
偶氮引发剂为氮二异丁脒盐酸盐或偶氮二异丁咪唑啉盐酸盐。
步骤(4)中干燥脱水温度为100℃～120℃，预碳化处理温度为180℃～220℃。
步骤(4)中进行碳热还原合成反应为：在真空或氩气保护条件下，升温至1450℃～1600℃，保温1h～4h，进行碳热还原合成反应。
步骤(5)为：步骤(4)合成的ZrC-SiC复合粉体以无水乙醇为溶剂，采用有聚胺脂或尼龙内衬和用WC-Co硬质合金研磨介质球的磨机进行研磨分散处理，避免粉体表面氧化和杂质混入，干燥后即得到高纯超细ZrC-SiC复合粉体。
步骤(5)以无水乙醇为溶剂，用磨机对合成的ZrC-SiC复合粉体进行研磨分散细化处理。为避免杂质混入，采用有聚胺脂或尼龙等高分子材料内衬和用WC–Co硬质合金研磨介质球的磨机处理，然后在80℃左右温度烘箱中排除乙醇溶剂，即得到高纯超细ZrC-SiC复合粉体。
综上所述，本发明具有以下优点：
(1)本发明是一种高纯超细ZrC-SiC复合粉体的低成本高效率工业化生产方法。采用高纯度硅酸锆微粉(ZrSiO4)单独或配以适量氧化锆(ZrO2)或硅溶胶(SiO2)作为锆源和硅源材料，以蔗糖(C12H22O11)或葡萄糖(C6H12O6)作为碳源材料，均不产生反应污染物。蔗糖和葡萄糖在水中均具有很高的溶解度，基本不影响水的粘度，便于配制高浓度水基料浆，且价格低廉，来源方便，可大大降低原材料成本；同时，蔗糖或葡萄糖加热裂解得到的碳纯度高且反应活性很高，可有效提高碳热还原反应速率和降低反应温度，使粉块容易研磨粉碎细化，合成的ZrC-SiC复合粉体混合非常均匀。
(2)含有丙烯酰胺单体和亚甲基双丙烯酰胺交联剂的水基料浆发生原位凝胶固化，可以 避免蔗糖或葡萄糖加热脱水干燥和热分解过程中发泡而引起C组分的流失，保证配方中(Zr+Si)：C比例准确不变，新分解出的C活性很高，且能非常均匀地紧密包覆于固相粉体颗粒表面，避免了原料在干燥脱水和反应过程中的偏析，可有效降低碳热还原反应温度，有利于碳热还原合成反应充分进行。
(3)以无水乙醇为溶剂，采用有WC–Co硬质合金内衬板和用WC–Co硬质合金研磨介质球的磨机中进行研磨分散细化处理ZrC-SiC复合粉体，可以防止粉体表面氧化和混入杂质，保证ZrC-SiC复合粉体的纯度≥99％、粒径d50≤1μm。
附图说明
图1为实施例2制备得到的高纯超细75mol％ZrC-25mol％SiC复合粉体XRD谱图；
图2为实施例2制备得到的高纯超细75mol％ZrC-25mol％SiC复合粉体SEM图。
具体实施方式
下面结合实施例对本发明做进一步说明。
实施例1：
合成50mol％ZrC-50mol％SiC复合粉体
准确称取200g硅酸锆微粉和249g蔗糖，即(Zr+Si)：C＝1：4，加入到150ml去离子水中，并加入3ml聚丙烯酸铵分散剂，在滚筒球磨机中混磨12h得到具有良好悬浮稳定性的水基料浆；加入30g丙烯酰胺单体，1.5g亚甲基双丙烯酰胺交联剂，继续混磨1h后倒入烧杯中，滴加10％浓度的过硫酸铵水溶液引发剂2ml，再滴加入50％浓度的四甲基乙二胺水溶液催化剂1.5ml，搅拌均匀后静置约3min后原位凝胶固化；将该湿凝胶体捣成碎块放入100℃烘箱中干燥16h，再升温至220℃预处理8h；将预处理后激胶块放入石墨坩埚，在碳管加热炉中，保持真空度为10Pa以下，升温至1500℃保温4h，通过碳热还原合成反应，得到ZrC-SiC粉块。将其与100ml乙醇混合，放入尼龙罐中，加入400g直径为3mm的WC–Co硬质合金研磨介质球，在行星磨机300转/分转速研磨8h，取出后在80℃温度烘箱中排除乙醇溶剂，得到约150g的50mol％ZrC-50mol％SiC高纯超细复合粉体，纯度99.4％、粒径d50≤1μm。
实施例2：
合成75mol％ZrC-25mol％SiC复合粉体
准确称取1833g硅酸锆微粉，2464g氧化锆微粉，3993g蔗糖，(Zr：Si：C＝0.75：0.25：3.5)，加入到2000ml去离子水中，并加入60ml聚丙烯酸铵分散剂，在滚筒球磨机中混磨12h得到具有良好悬浮稳定性的水基料浆。再加入200g丙烯酰胺单体，15gN’,N’-亚甲基双丙烯酰胺交联剂，继续混磨1h后倒入搪瓷罐中，加入15％浓度的氧化-还原剂水溶液15ml(过硫 酸铵：亚硫酸铵＝1.5：1)，搅拌均匀后静置约5min，水基料浆原位凝胶固化；将该湿凝胶体用氧化锆陶瓷刀切割成≤3mm厚的薄片，在120℃烘箱中干燥12h，再升温至180℃预处理24h；放入石墨坩埚，在碳管加热炉中氩气保护条件下，升温至1600℃保温1h，通过碳热还原合成反应，得到ZrC-SiC粉块；将其与1000ml乙醇混合，在有聚胺脂内衬的搅拌磨机中，加入6000g直径为3mm和1000g直径为8mm的WC-Co硬质合金研磨介质球，研磨处理8h；取出后在80℃温度烘箱中排除乙醇溶剂，即得到约3500g高纯超细75mol％ZrC-25mol％SiC复合粉体，纯度99.2％、粒径d50≤1μm。
实施例2制备得到的高纯超细75mol％ZrC-25mol％SiC复合粉体XRD谱见附图1，SEM图见附图2。
实施例3：
合成90mol％SiC-10mol％ZrC复合粉体
准确称取183.3g硅酸锆微粉，1200g葡萄糖，加入1600g硅溶胶(浓度为30wt％，即SiO2含量为480g，此时Si：Zr：C＝0.9：0.1：4)中，在滚筒球磨机中混磨8h得到具有良好悬浮稳定性的水基料浆。再加入150g丙烯酰胺单体，6g N’,N’-亚甲基双丙烯酰胺交联剂，继续混磨2h后出料至搪瓷盆中，加入浓度为5％的偶氮二异丁脒盐酸盐水溶液10ml，搅拌均匀后在70℃水浴中保温约5分钟，水基料浆原位凝胶固化。将该湿凝胶体捣成碎块在100℃烘箱中干燥16h，再升温至200℃预处理10h，放入石墨坩埚，在碳管加热炉中氩气保护条件下，升温至1450℃保温2h，通过碳热还原合成反应，得到SiC-ZrC粉块。将其与300ml乙醇混合，放入2L尼龙罐中，加入800g直径为3mm的WC–Co硬质合金研磨介质球，在行星磨机250转/分转速条件下研磨8h，取出后在80℃温度烘箱中排除乙醇溶剂，即得到约460g的90mol％SiC-10mol％ZrC高纯超细复合粉体，纯度99.1％、粒径d50≤1μm。

Claims (10)

  1. 一种高纯超细ZrC-SiC复合粉体的合成方法，其特征在于：以硅酸锆单独或者在硅酸锆中添加氧化锆或硅溶胶中的一种或两种作为锆源和硅源材料，以蔗糖或葡萄糖作为碳源材料，以丙烯酰胺单体和亚甲基双丙烯酰胺交联剂作为凝胶材料，制备高纯超细ZrC-SiC复合粉体。
  2. 根据权利要求1所述的高纯超细ZrC-SiC复合粉体的合成方法，其特征在于：以硅酸锆单独或者在硅酸锆中添加氧化锆或硅溶胶中的一种或两种作为锆源和硅源材料，控制Zr和Si总量与C的摩尔比为1:3.5～1：4。
  3. 根据权利要求1或2所述的高纯超细ZrC-SiC复合粉体的合成方法，其特征在于：按以下步骤进行：
    (1)将锆源和硅源材料、碳源材料混合，加入去离子水和分散剂混磨，配制成水基料浆；
    (2)向步骤(1)得到的水基料浆中再加入丙烯酰胺单体和亚甲基双丙烯酰胺交联剂作为凝胶材料，混磨得到可凝胶化水基料浆；
    (3)将水基料浆原位凝胶固化；
    (4)在烘箱中干燥脱水并进行预碳化处理，再放入碳管加热炉中进行碳热还原合成反应，得到微晶结构ZrC-SiC复合粉体；
    (5)再在乙醇溶剂中研磨分散细化处理，干燥后即得到高纯超细ZrC-SiC复合粉体。
  4. 根据权利要求3所述的高纯超细ZrC-SiC复合粉体的合成方法，其特征在于：去离子水为碳源重量的50％～100％；分散剂为聚丙烯酸铵分散剂，分散剂加入量为锆源和硅源材料重量1％～3％。
  5. 根据权利要求3所述的高纯超细ZrC-SiC复合粉体的合成方法，其特征在于：丙烯酰胺和亚甲基双丙烯酰胺按重量比为15：1～25：1混合。
  6. 根据权利要求3所述的高纯超细ZrC-SiC复合粉体的合成方法，其特征在于：步骤(2)中亚甲基双丙烯酰胺交联剂的添加量为步骤(1)中去离子水重量的10％～20％。
  7. 根据权利要求3所述的高纯超细ZrC-SiC复合粉体的合成方法，其特征在于：步骤(3)中将水基料浆原位凝胶固化采用以下三种方法中的一种：
    a、向步骤(2)得到的可凝胶化水基料浆中加入引发剂，再加入四甲基乙二胺或三乙醇胺水溶液催化剂，搅拌均匀后在室温静置，使水基料浆原位凝胶固化；
    b、向步骤(2)得到的可凝胶化水基料浆中加入引发剂，然后加热至60℃～80℃保温，使水基料浆原位凝胶固化；
    c、向步骤(2)得到的可凝胶化水基料浆中加入氧化还原剂的水溶液，其中氧化还原剂 为过硫酸铵和亚硫酸铵按质量比为1～2：1的混合物，搅拌均匀后在室温静置，使水基料浆原位凝胶固化。
  8. 根据权利要求3所述的高纯超细ZrC-SiC复合粉体的合成方法，其特征在于：步骤(4)中干燥脱水温度为100℃～120℃，预碳化处理温度为180℃～220℃。
  9. 根据权利要求3所述的高纯超细ZrC-SiC复合粉体的合成方法，其特征在于：步骤(4)中进行碳热还原合成反应为：在真空或氩气保护条件下，升温至1450℃～1600℃，保温1h～4h，进行碳热还原合成反应。
  10. 根据权利要求3所述的高纯超细ZrC-SiC复合粉体的合成方法，其特征在于：步骤(5)为：步骤(4)合成的ZrC-SiC复合粉体以无水乙醇为溶剂，采用有聚胺脂或尼龙内衬和用WC-Co硬质合金研磨介质球的磨机进行研磨分散处理，避免粉体表面氧化和杂质混入，干燥后即得到高纯超细ZrC-SiC复合粉体。
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