WO2020057094A1 - Silicon carbide closed-cell ceramic prepared by using industrial silicon-based waste residue and preparation method therefor - Google Patents
Silicon carbide closed-cell ceramic prepared by using industrial silicon-based waste residue and preparation method therefor Download PDFInfo
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- WO2020057094A1 WO2020057094A1 PCT/CN2019/080544 CN2019080544W WO2020057094A1 WO 2020057094 A1 WO2020057094 A1 WO 2020057094A1 CN 2019080544 W CN2019080544 W CN 2019080544W WO 2020057094 A1 WO2020057094 A1 WO 2020057094A1
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Definitions
- the invention belongs to the technical fields of industrial solid waste resource utilization and porous ceramic material preparation, and particularly relates to a silicon carbide closed-pore ceramic prepared by using industrial silicon-based waste residue and a preparation method thereof.
- Closed-hole ceramics can be used as heat insulation materials in metallurgy, construction, energy and other fields due to their excellent properties such as low thermal conductivity, low density, and impermeability. Therefore, it is one of the important research directions of porous materials to produce closed-cell ceramics that are resistant to high temperature and have no hidden dangers.
- SiC materials have high strength, low density, small specific gravity, excellent thermal shock resistance and oxidation resistance, etc., and are widely used in high temperature industries. Therefore, the use of industrial silicon-based waste slag as the raw material to prepare silicon carbide closed-cell ceramics can not only prepare high-temperature-resistant, safe and non-hazardous insulation materials, but also recycle industrial waste.
- the purpose of the present invention is to overcome the shortcomings of the prior art mentioned above, and provide a method for preparing silicon carbide closed-cell ceramics using industrial silicon-based waste slag and a method for preparing the same.
- the main steps of the method are as follows: first, the industrial silicon-based waste slag is pretreated To remove certain impurities, secondly, add an appropriate amount of reducing agent according to the components of the silicon-based waste residue; then, use the pre-treated silicon-based waste residue as a raw material, add a binder and a pore-forming agent, and mix the mixture; Finally, the silicon carbide closed-cell ceramics are prepared by dry pressing and sintering at high temperature under reducing conditions. .
- the present invention adopts the following technical solutions:
- the industrial silicon-based waste residue is one or more of coal gangue, iron ore tailings, polycrystalline silicon cutting waste, or rice hull ash, and its main component is SiO 2 .
- the reducing agent is one or more of carbon black, high-quality coal, or activated carbon.
- the amount of the reducing agent should be higher than the consumption of reacting the impurities such as impurities such as silicon-based solid waste SiO 2 , Si, and metal iron oxide with the reducing agent.
- the binder is one or more of a phenol resin, water glass, aluminum dihydrogen phosphate, or polyvinyl alcohol.
- the sintering aid is one or more of potassium feldspar, sodium feldspar, or anorthite.
- the pore-forming agent is one or more of starch, graphite, ammonium bicarbonate or ammonium chloride.
- the obtained silicon carbide closed-cell ceramic has a significant porosity of 30 to 55%, a closed porosity of 12 to 20%, a compressive strength at room temperature of 106 to 140 MPa, a thermal shock resistance of 103 to 111 times, and a thermal conductivity.
- the rate is 0.40 to 0.69 w / (m ⁇ K).
- the thermal shock resistance of the silicon carbide closed-cell ceramics is characterized by the number of air-cooling cycles. Specific operations: After heating in a high-temperature furnace at 1000 ° C for 15 minutes, the air-cooling is performed once for 10 minutes; and then returned to the furnace and held at 1000 ° C for 15 minutes. After air-cooling for 10 minutes, the operation was repeated in this manner until the sample broke.
- a method for preparing silicon carbide closed-cell ceramics by using industrial silicon-based waste slag includes the following steps:
- Step 3 Sintering at high temperature:
- the dried material is placed in a high-temperature furnace, sintered in a reducing atmosphere, and held for a certain period of time to prepare a silicon carbide closed-cell ceramic using industrial silicon-based waste residue.
- the industrial silicon-based waste slag is subjected to high-temperature calcination and sieving and sieving treatment before being mixed, which is used to remove impurities in the industrial silicon-based waste slag, and the silicon-based clinker is prepared and mixed according to the mixing ratio.
- the calcining operation is performed in a calcining furnace, the calcining temperature is 900 ° C, and the calcining time is 5 hours.
- the calcining furnace is a box-type resistance wire furnace and silicon carbon used in an unprotected atmosphere.
- the crushing and sieving process is as follows: a jaw crusher is used for crushing, and the powder is passed through a 200-mesh sieve to obtain a silicon-based clinker.
- the silicon-based clinker and the reducing agent are ball-milled before the materials are mixed.
- the equipment used for the silicon-based clinker and the reducing agent ball-milling is a planetary ball mill with 200-600 r ⁇ min -1 The speed runs unidirectionally for 5-10 hours.
- step 1 mentioned above the equipment used for ball milling after mixing all materials is a planetary ball mill, which runs unidirectionally at a speed of 300 r ⁇ min -1 for 5 hours.
- the forming pressure is 50 to 300 MPa, and the dwell time is 3 to 5 minutes.
- the drying temperature of the drying operation is 120 ° C.
- the drying time is 12-24 hours
- the drying equipment is a drying box or a tunnel drying kiln.
- the high-temperature furnace is one of a box-type resistance furnace, a tube-type resistance furnace, or a tunnel kiln that can pass through the atmosphere.
- the sintering temperature is 1400-1600 ° C, and the sintering holding time is 2-10 hours.
- the reducing atmosphere is a buried carbon or a CO-introduced atmosphere, wherein the conditions for the buried carbon are: dry-pressed material is placed in a graphite crucible, and the graphite crucible is placed in a large-sized corundum crucible. Put sufficient graphite powder in the corundum crucible, and cover the corundum plate with a corundum plate at the top end to isolate the graphite crucible from contact with the outside air.
- the CO entry conditions are: CO gas is introduced from the high temperature furnace bottom or one side of the kiln, and the gas flow rate It is 1 to 100 L / min.
- the invention uses industrial silicon-based waste slag to prepare silicon carbide closed-pore ceramics and a preparation method thereof, which realizes efficient recycling and reuse of industrial silicon-based waste slag, improves its utilization rate and added value, and greatly reduces its environmental impact. Pollution has good environmental benefits.
- the prepared high-performance silicon carbide closed-cell ceramic has good heat preservation effect, wide source of raw materials, low price, and certain economy. benefit.
- a silicon carbide closed-cell ceramic prepared by using industrial silicon-based waste slag according to the present invention and a preparation method thereof are simple and easy to operate and convenient for industrialized production.
- FIG. 1 is a process flowchart of Embodiments 1 to 6 of the present invention.
- Example 2 is an XRD pattern of a silicon carbide closed-cell ceramic prepared by using industrial silicon-based waste slag prepared in Example 2 of the present invention.
- the thermal shock resistance of the prepared silicon carbide closed-cell ceramics is characterized by the number of air cooling cycles.
- the specific operation is as follows: after heating in a high-temperature furnace at 1000 ° C for 15 minutes, air cooling is performed once for 10 minutes; Put it back into the furnace and keep it at 1000 ° C for 15 minutes, and then air-cool it for 10 minutes. This operation is repeated until the sample breaks.
- Step 1 Raw material handling and weighing
- the polycrystalline silicon cutting waste is calcined in a box-type resistance wire furnace, after being calcined at 900 ° C for 5 hours, crushed by a jaw crusher, and sieved at 200 mesh to obtain polycrystalline silicon clinker without polyethylene glycol and water;
- polycrystalline silicon clinker and carbon black are passed through a planetary ball mill at a speed of 200 to 600 r ⁇ min -1 and run unidirectionally for 5 to 10 hours for ball milling, then mixed with phenolic resin, potassium feldspar and ammonium bicarbonate, and Ball milling for 3h at a rate of 300r ⁇ min -1 to obtain a homogeneous material;
- Step 3 High temperature sintering
- the dried material was fully sintered in a box-type resistance furnace at 1500 ° C for 2 hours under the condition of buried carbon, and the high-temperature furnace was cooled to room temperature to prepare a silicon carbide closed-cell ceramic using industrial silicon-based waste residue.
- the main phase of the obtained silicon carbide closed-cell ceramic is 6H-SiC
- the apparent porosity is 30%
- the closed porosity is 12%
- the compressive strength at room temperature is 140MPa
- the thermal shock resistance is 106 times
- the thermal conductivity 0.69 w / (m ⁇ K).
- Step 1 Raw material handling and weighing
- the polycrystalline silicon cutting waste is calcined in a box-type resistance wire furnace, after being calcined at 900 ° C for 5 hours, crushed by a jaw crusher, and sieved at 200 mesh to obtain polycrystalline silicon clinker without polyethylene glycol and water;
- the polycrystalline silicon clinker and activated carbon are passed through a planetary ball mill and run unidirectionally at a speed of 200-600r ⁇ min -1 for 5-10 hours for ball milling, then mixed with water glass, potassium feldspar and ammonium chloride, and mixed with Mill at a rate of 300r ⁇ min -1 for 3h to obtain a homogeneous material;
- Step 3 High temperature sintering
- the dried material was fully sintered in a box-type resistance furnace at 1500 ° C for 2 hours under the condition of buried carbon, and the high-temperature furnace was cooled to room temperature to prepare a silicon carbide closed-cell ceramic using industrial silicon-based waste slag.
- the XRD diagram is shown in Figure 2. Show.
- the main phase of the obtained silicon carbide closed-cell ceramic is 6H-SiC
- the apparent porosity is 40%
- the closed porosity is 14%
- the compressive strength at room temperature is 120MPa
- the thermal shock resistance is 108 times
- Step 1 Raw material handling and weighing
- the rice husk ash is calcined in a box-type resistance wire furnace, calcined at 900 ° C for 5 hours, crushed by a jaw crusher, and sieved at 200 mesh to obtain a rice husk ash clinker with polyethylene glycol and water removed;
- the rice husk ash clinker and carbon black are subjected to ball milling through a planetary ball mill at a speed of 200 to 600 r ⁇ min-1 for one to five hours, and then mixed with phenolic resin, sodium feldspar and starch, and Ball milling for 3h at a rate of 300r ⁇ min -1 to obtain a homogeneous material;
- Step 3 High temperature sintering
- the dried material was fully sintered in a box-type resistance furnace at 1600 ° C for 2 hours under the condition of buried carbon, and the high-temperature furnace was cooled to room temperature to prepare a silicon carbide closed-cell ceramic using industrial silicon-based waste residue.
- the main phase of the obtained silicon carbide closed-cell ceramic is 6H-SiC
- the apparent porosity is 46%
- the closed porosity is 20%
- the compressive strength at room temperature is 106MPa
- the thermal shock resistance is 111 times
- Step 1 Raw material handling and weighing
- Coal gangue is calcined in a box-type resistance wire furnace, after being calcined at 900 ° C for 5 hours, crushed by a jaw crusher, and sieved with 200 mesh to obtain coal gangue clinker with polyethylene glycol and water removed;
- coal gangue clinker and carbon black are passed through a planetary ball mill at a speed of 200 to 600 r ⁇ min -1 for 5 to 10 hours in one direction, and then mixed with aluminum dihydrogen phosphate: calcium feldspar and graphite powder. And ball milling at a rate of 300 r ⁇ min -1 for 3 h to obtain a homogeneous material;
- Step 3 High temperature sintering
- the dried material was fully sintered in a box-type resistance furnace at 1500 ° C for 2 hours under the condition of buried carbon, and the high-temperature furnace was cooled to room temperature to prepare a silicon carbide closed-cell ceramic using industrial silicon-based waste residue.
- the main phase of the obtained silicon carbide closed-cell ceramic is 6H-SiC
- the apparent porosity is 45%
- the closed porosity is 18%
- the compressive strength at room temperature is 109MPa
- the thermal shock resistance is 110 times
- Step 1 Raw material handling and weighing
- Coal gangue is calcined in a box-type resistance wire furnace, after being calcined at 900 ° C for 5 hours, crushed by a jaw crusher, and sieved with 200 mesh to obtain coal gangue clinker with polyethylene glycol and water removed;
- coal gangue clinker and carbon black are passed through a planetary ball mill at a speed of 200 to 600 r ⁇ min -1 for 5 to 10 hours in one direction, and then mixed with aluminum dihydrogen phosphate, potassium feldspar and graphite powder. And ball milling at a rate of 300 r ⁇ min -1 for 3 h to obtain a homogeneous material;
- Step 3 High temperature sintering
- the dried material was fully sintered in a box-type resistance furnace at 1500 ° C for 2 hours under the condition of buried carbon, and the high-temperature furnace was cooled to room temperature to prepare a silicon carbide closed-cell ceramic using industrial silicon-based waste residue.
- the main phase of the obtained silicon carbide closed-cell ceramic is 6H-SiC
- the apparent porosity is 55%
- the closed porosity is 10%
- the compressive strength at room temperature is 101MPa
- the thermal shock resistance is 103 times
- Step 1 Raw material handling and weighing
- the rice husk ash is calcined in a box-type resistance wire furnace, calcined at 900 ° C for 5 hours, crushed by a jaw crusher, and sieved at 200 mesh to obtain a rice husk ash clinker with polyethylene glycol and water removed;
- the rice husk ash clinker and carbon black are subjected to ball milling through a planetary ball mill at a speed of 200 to 600 r ⁇ min -1 for 5 to 10 hours, and then mixed with phenolic resin, sodium feldspar and starch, and Ball milling for 3h at a rate of 300r ⁇ min -1 to obtain a homogeneous material;
- Step 3 High temperature sintering
- the dried material was fully sintered in a box-type resistance furnace at 1600 ° C for 2 hours under the condition of buried carbon, and the high-temperature furnace was cooled to room temperature to prepare a silicon carbide closed-cell ceramic using industrial silicon-based waste residue.
- the main phase of the silicon carbide closed-cell ceramics obtained was 6H-SiC, the apparent porosity was 40%, the closed porosity was 16%, the compressive strength at room temperature was 119 MPa, the thermal shock resistance was 109 times, and the thermal conductivity It was 0.58 w / (m ⁇ K).
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Abstract
Disclosed are a silicon carbide closed-cell ceramic prepared by using an industrial silicon-based waste residue and a preparation method therefor. The silicon carbide closed-cell ceramic comprises the following components and the mass ratio thereof: an industrial silicon-based waste residue : a reducing agent : an adhesive : a sintering aid : a pore former = 100 : (30-60) : (3-5) : (5-60) : (5-60). The preparation steps include: (1) uniformly mixing materials according to the ratio of the industrial silicon-based waste residue : the reducing agent : the adhesive : the sintering aid : the pore former = 100 : (30-60) : (3-5) : (5-60) : (5-60), and ball-milling same to obtain a blended material; (2) dry-pressing and shaping, and drying the blended material; and (3) placing the dried material into a high-temperature furnace, sintering same in a reducing atmosphere and performing thermal insulation for a certain time to prepare the silicon carbide closed-cell ceramic prepared by using the industrial silicon-based waste residue. The apparent porosity of the ceramic is 30%-55%, the closed porosity of the ceramic is 12%-20%, the normal-temperature compressive strength of the ceramic is 106-140 MPa, the thermal shock resistance of the ceramic is 103-111 times, and the thermal conductivity of the ceramic is 0.40-0.69 w/( m·K).
Description
本发明属于工业固体废弃物资源化利用及多孔陶瓷材料制备技术领域,具体涉及一种利用工业硅基废渣制备碳化硅闭孔陶瓷及其制备方法。The invention belongs to the technical fields of industrial solid waste resource utilization and porous ceramic material preparation, and particularly relates to a silicon carbide closed-pore ceramic prepared by using industrial silicon-based waste residue and a preparation method thereof.
随着社会日新月异的发展,资源枯竭的现象在世界各国普遍存在,其中,工业废渣因其大量堆积,已造成严重的环境问题与经济问题。因此,合理回收利用工业废渣,变废为宝显得尤为重要。With the rapid development of society, the phenomenon of resource exhaustion is common in all countries in the world. Among them, industrial waste residue has caused serious environmental and economic problems due to its large accumulation. Therefore, it is particularly important to reasonably recycle industrial waste residue and turn waste into treasure.
闭孔陶瓷因其具有热导率和密度低、不透水性等优异特性,可作为隔热材料应用于冶金、建筑、能源等领域。因此,制备耐高温、安全无隐患的闭孔陶瓷是多孔材料的重要研究方向之一。Closed-hole ceramics can be used as heat insulation materials in metallurgy, construction, energy and other fields due to their excellent properties such as low thermal conductivity, low density, and impermeability. Therefore, it is one of the important research directions of porous materials to produce closed-cell ceramics that are resistant to high temperature and have no hidden dangers.
SiC材料具有强度高、密度低、比重小、抗热震性与抗氧化性优异等性能,在高温工业上广泛应用。因此,以工业硅基废渣为原料制备碳化硅闭孔陶瓷,既可以制备出耐高温安全无隐患的保温材料,又可以对工业废渣进行回收再利用。SiC materials have high strength, low density, small specific gravity, excellent thermal shock resistance and oxidation resistance, etc., and are widely used in high temperature industries. Therefore, the use of industrial silicon-based waste slag as the raw material to prepare silicon carbide closed-cell ceramics can not only prepare high-temperature-resistant, safe and non-hazardous insulation materials, but also recycle industrial waste.
发明内容:Summary of the invention:
本发明的目的是克服上述现有技术存在的不足,提供一种利用工业硅基废渣制备碳化硅闭孔陶瓷及其制备方法,该方法的主要工序如下:首先,将工业硅基废渣进行预处理,除去一定的杂质,其次,根据硅基废渣的组分掺入适量的还原剂;然后,以预处理后的硅基废渣为原料,加入粘结剂与造孔剂,将混合料混匀;最后,经干压成型,于还原条件下高温烧结制得碳化硅闭孔陶瓷。。The purpose of the present invention is to overcome the shortcomings of the prior art mentioned above, and provide a method for preparing silicon carbide closed-cell ceramics using industrial silicon-based waste slag and a method for preparing the same. The main steps of the method are as follows: first, the industrial silicon-based waste slag is pretreated To remove certain impurities, secondly, add an appropriate amount of reducing agent according to the components of the silicon-based waste residue; then, use the pre-treated silicon-based waste residue as a raw material, add a binder and a pore-forming agent, and mix the mixture; Finally, the silicon carbide closed-cell ceramics are prepared by dry pressing and sintering at high temperature under reducing conditions. .
为实现上述目的,本发明采用以下技术方案:To achieve the above objective, the present invention adopts the following technical solutions:
一种利用工业硅基废渣制备碳化硅闭孔陶瓷,包括的组分及质量配比为:工业硅基废渣∶还原剂∶粘结剂∶烧结助剂∶造孔剂=100∶(30~60)∶(3~5)∶(5~60)∶(5~60)。A silicon carbide closed-pore ceramic prepared by using industrial silicon-based waste slag includes components and mass proportions as follows: industrial silicon-based waste slag: reducing agent: binder: sintering aid: pore former = 100: (30-60 ): (3 to 5): (5 to 60): (5 to 60).
所述的工业硅基废渣为煤矸石、铁矿石尾矿、多晶硅切割废料或稻壳灰中的一种或几种,其主要成分为SiO
2。
The industrial silicon-based waste residue is one or more of coal gangue, iron ore tailings, polycrystalline silicon cutting waste, or rice hull ash, and its main component is SiO 2 .
所述的还原剂为炭黑、优质煤或活性炭中的一种或多种。The reducing agent is one or more of carbon black, high-quality coal, or activated carbon.
所述的还原剂用量应高于硅基固体废弃物SiO
2、Si、金属铁的氧化物等杂质与还原剂反应的消耗量。
The amount of the reducing agent should be higher than the consumption of reacting the impurities such as impurities such as silicon-based solid waste SiO 2 , Si, and metal iron oxide with the reducing agent.
所述的粘结剂为酚醛树脂、水玻璃、磷酸二氢铝或聚乙烯醇中的一种或多种。The binder is one or more of a phenol resin, water glass, aluminum dihydrogen phosphate, or polyvinyl alcohol.
所述的烧结助剂为钾长石、钠长石或钙长石中的一种或多种。The sintering aid is one or more of potassium feldspar, sodium feldspar, or anorthite.
所述的造孔剂为淀粉、石墨、碳酸氢铵或氯化铵中的一种或多种。The pore-forming agent is one or more of starch, graphite, ammonium bicarbonate or ammonium chloride.
所述的制得的碳化硅闭孔陶瓷显气孔率为30~55%,闭口气孔率为12~20%,常温抗压强度为106~140MPa,抗热震性为103~111次,热导率为0.40~0.69w/(m·K)。The obtained silicon carbide closed-cell ceramic has a significant porosity of 30 to 55%, a closed porosity of 12 to 20%, a compressive strength at room temperature of 106 to 140 MPa, a thermal shock resistance of 103 to 111 times, and a thermal conductivity. The rate is 0.40 to 0.69 w / (m · K).
所述的碳化硅闭孔陶瓷的抗热震性能以空冷的循环次数来表征,具体操作:在1000℃的高温炉加热15min后,空冷10min为1次;然后再放回炉中于1000℃保温15min后空冷10min,如此循环操作直至试样碎裂。The thermal shock resistance of the silicon carbide closed-cell ceramics is characterized by the number of air-cooling cycles. Specific operations: After heating in a high-temperature furnace at 1000 ° C for 15 minutes, the air-cooling is performed once for 10 minutes; and then returned to the furnace and held at 1000 ° C for 15 minutes. After air-cooling for 10 minutes, the operation was repeated in this manner until the sample broke.
一种利用工业硅基废渣制备碳化硅闭孔陶瓷制备方法,包括以下步骤:A method for preparing silicon carbide closed-cell ceramics by using industrial silicon-based waste slag includes the following steps:
步骤1,原料混合:Step 1. Mix the ingredients:
按配比,工业硅基废渣∶还原剂∶粘结剂∶烧结助剂∶造孔剂=100∶(30~60)∶(3~5)(5~60)(5~60),将物料混合均匀,球磨得混匀物料;According to the ratio, industrial silicon-based waste residue: reducing agent: binder: sintering aid: pore-forming agent = 100: (30-60): (3-5) (5-60) (5-60), the materials are mixed Uniform, ball milled to obtain a homogeneous material;
步骤2,干压成型:Step 2. Dry pressing:
将混匀物料干压成型,并干燥;Dry mix the mixed material and dry it;
步骤3,高温烧结:Step 3. Sintering at high temperature:
将干燥后物料置于高温炉中,于还原气氛下烧结并保温一定时间,制得利用工业硅基废渣制备碳化硅闭孔陶瓷。The dried material is placed in a high-temperature furnace, sintered in a reducing atmosphere, and held for a certain period of time to prepare a silicon carbide closed-cell ceramic using industrial silicon-based waste residue.
所述的步骤1中,工业硅基废渣在混合前经高温煅烧与粉碎过筛处理,用于去除工业硅基废渣中的杂质,制得硅基熟料后按配比混合。In the step 1, the industrial silicon-based waste slag is subjected to high-temperature calcination and sieving and sieving treatment before being mixed, which is used to remove impurities in the industrial silicon-based waste slag, and the silicon-based clinker is prepared and mixed according to the mixing ratio.
所述的步骤1中,所述的煅烧操作在煅烧炉中进行,煅烧温度为900℃,煅烧时间为5h,所述的煅烧炉为在无保护气氛下使用的箱式电阻丝炉、硅碳棒炉、硅钼棒炉和隧道窑中的一种。In the step 1, the calcining operation is performed in a calcining furnace, the calcining temperature is 900 ° C, and the calcining time is 5 hours. The calcining furnace is a box-type resistance wire furnace and silicon carbon used in an unprotected atmosphere. One of rod furnace, silicon molybdenum rod furnace and tunnel kiln.
所述的步骤1中,所述的粉碎过筛处理过程为:采用颚式破碎机粉碎处理,粉末经200目筛后,制得硅基熟料。In the step 1, the crushing and sieving process is as follows: a jaw crusher is used for crushing, and the powder is passed through a 200-mesh sieve to obtain a silicon-based clinker.
所述的步骤1中,所述的硅基熟料和还原剂在物料混合之前,经过球磨处理,硅基熟料和还原剂球磨采用的设备为行星式球磨机,以200~600r·min
-1转速单向运行5~10h。
In the step 1, the silicon-based clinker and the reducing agent are ball-milled before the materials are mixed. The equipment used for the silicon-based clinker and the reducing agent ball-milling is a planetary ball mill with 200-600 r · min -1 The speed runs unidirectionally for 5-10 hours.
所述的步骤1中,所有物料混合后的球磨采用的设备为行星式球磨机,以300r·min
-1转速单向运行5h。
In step 1 mentioned above, the equipment used for ball milling after mixing all materials is a planetary ball mill, which runs unidirectionally at a speed of 300 r · min -1 for 5 hours.
所述的步骤2中,所述的成型压力为50~300MPa,保压时间为3~5min。In the step 2, the forming pressure is 50 to 300 MPa, and the dwell time is 3 to 5 minutes.
所述的步骤2中,所述的干燥操作的干燥温度为120℃,干燥时间为12~24h,干燥设备为干燥箱或隧道干燥窑。In the step 2, the drying temperature of the drying operation is 120 ° C., the drying time is 12-24 hours, and the drying equipment is a drying box or a tunnel drying kiln.
所述的步骤3中,所述的高温炉为可通气氛的箱式电阻炉、管式电阻炉或隧道窑中一种。In step 3, the high-temperature furnace is one of a box-type resistance furnace, a tube-type resistance furnace, or a tunnel kiln that can pass through the atmosphere.
所述的步骤3中,所述的烧结温度为1400~1600℃,烧结保温时间为2~10h。In the step 3, the sintering temperature is 1400-1600 ° C, and the sintering holding time is 2-10 hours.
所述的步骤3中,所述的还原气氛为埋碳或通入CO气氛下,其中:埋碳条件为:干压成型的物料置于石墨坩埚中,石墨坩埚置于大尺寸刚玉坩埚中,在刚玉坩埚中放入充足的石墨粉,刚玉坩埚上端盖一块刚玉板,隔绝石墨坩埚与外界空气的接触;通入CO条件为:由高温炉底或窑的一侧通入CO气体,气体流量为1~100L/min。In the step 3, the reducing atmosphere is a buried carbon or a CO-introduced atmosphere, wherein the conditions for the buried carbon are: dry-pressed material is placed in a graphite crucible, and the graphite crucible is placed in a large-sized corundum crucible. Put sufficient graphite powder in the corundum crucible, and cover the corundum plate with a corundum plate at the top end to isolate the graphite crucible from contact with the outside air. The CO entry conditions are: CO gas is introduced from the high temperature furnace bottom or one side of the kiln, and the gas flow rate It is 1 to 100 L / min.
本发明的有益效果:The beneficial effects of the present invention:
1.本发明的一种利用工业硅基废渣制备碳化硅闭孔陶瓷及其制备方法实现了工业硅基废渣的高效回收再利用,提高了其利用率和附加值,又大大减少其对环境产生的污染,具有很好的环境效益。1. The invention uses industrial silicon-based waste slag to prepare silicon carbide closed-pore ceramics and a preparation method thereof, which realizes efficient recycling and reuse of industrial silicon-based waste slag, improves its utilization rate and added value, and greatly reduces its environmental impact. Pollution has good environmental benefits.
2.本发明的一种利用工业硅基废渣制备碳化硅闭孔陶瓷及其制备方法,制备出的高性能碳化硅闭孔陶瓷,保温效果好,其原料来源广泛,价格低廉,具有一定的经济效益。2. A silicon carbide closed-cell ceramic prepared by using industrial silicon-based waste slag according to the present invention and a preparation method thereof. The prepared high-performance silicon carbide closed-cell ceramic has good heat preservation effect, wide source of raw materials, low price, and certain economy. benefit.
3.本发明的一种利用工业硅基废渣制备碳化硅闭孔陶瓷及其制备方法操作简单易行,便于工业化生产。3. A silicon carbide closed-cell ceramic prepared by using industrial silicon-based waste slag according to the present invention and a preparation method thereof are simple and easy to operate and convenient for industrialized production.
图1是本发明实施例1~6的工艺流程图;FIG. 1 is a process flowchart of Embodiments 1 to 6 of the present invention;
图2是本发明实施例2制备的利用工业硅基废渣制备碳化硅闭孔陶瓷的XRD图。2 is an XRD pattern of a silicon carbide closed-cell ceramic prepared by using industrial silicon-based waste slag prepared in Example 2 of the present invention.
下面结合实施例对本发明作进一步的详细说明。The present invention will be further described in detail with reference to the following embodiments.
以下实施例1~6中,制得的碳化硅闭孔陶瓷的抗热震性能以空冷的循环次数来表征,具体操作为:在1000℃的高温炉加热15min后,空冷10min为1次;然后再放回炉中于1000℃保温15min后空冷10min,如此循环操作直至试样碎裂。In the following Examples 1 to 6, the thermal shock resistance of the prepared silicon carbide closed-cell ceramics is characterized by the number of air cooling cycles. The specific operation is as follows: after heating in a high-temperature furnace at 1000 ° C for 15 minutes, air cooling is performed once for 10 minutes; Put it back into the furnace and keep it at 1000 ° C for 15 minutes, and then air-cool it for 10 minutes. This operation is repeated until the sample breaks.
实施例1Example 1
一种利用工业硅基废渣制备碳化硅闭孔陶瓷,包括的组分及质量配比为:多晶硅熟料∶炭黑∶酚醛树脂∶钾长石∶碳酸氢铵=100∶30∶5∶5∶10。A silicon carbide closed-pore ceramic prepared by using industrial silicon-based waste slag includes components and mass proportions of: polycrystalline silicon clinker: carbon black: phenolic resin: potassium feldspar: ammonium bicarbonate = 100: 30: 5: 5: 10.
一种利用工业硅基废渣制备碳化硅闭孔陶瓷制备方法,工艺流程图如图1所示,按以下步骤进行:A method for preparing silicon carbide closed-cell ceramics using industrial silicon-based waste slag. The process flow chart is shown in Figure 1, and the following steps are performed:
步骤1:原料处理和称量Step 1: Raw material handling and weighing
(1)将多晶硅切割废料于箱式电阻丝炉中,900℃下煅烧5h后,经颚式破碎机粉碎,200目过筛处理,得到去除聚乙二醇和水的多晶硅熟料;(1) The polycrystalline silicon cutting waste is calcined in a box-type resistance wire furnace, after being calcined at 900 ° C for 5 hours, crushed by a jaw crusher, and sieved at 200 mesh to obtain polycrystalline silicon clinker without polyethylene glycol and water;
(2)按配比,将多晶硅熟料与炭黑经行星式球磨机,以200~600r·min
-1转速单向运行5~10h进行球磨后,与酚醛树脂、钾长石和碳酸氢铵混合,并以300r·min
-1的速率球磨3h,得混 匀物料;
(2) According to the proportion, polycrystalline silicon clinker and carbon black are passed through a planetary ball mill at a speed of 200 to 600 r · min -1 and run unidirectionally for 5 to 10 hours for ball milling, then mixed with phenolic resin, potassium feldspar and ammonium bicarbonate, and Ball milling for 3h at a rate of 300r · min -1 to obtain a homogeneous material;
步骤2:干压成型Step 2: Dry pressing
将混匀物料置于压力机中干压成型,200MPa下保压5min,并置于干燥箱中120℃下保温24h。Put the mixed material in a press for dry pressing, hold it at 200 MPa for 5 minutes, and place it in a drying box at 120 ° C for 24 hours.
步骤3:高温烧结Step 3: High temperature sintering
将干燥后物料在1500℃的箱式电阻炉中,埋碳条件下充分烧结2h,待高温炉冷却至室温,制得利用工业硅基废渣制备碳化硅闭孔陶瓷。The dried material was fully sintered in a box-type resistance furnace at 1500 ° C for 2 hours under the condition of buried carbon, and the high-temperature furnace was cooled to room temperature to prepare a silicon carbide closed-cell ceramic using industrial silicon-based waste residue.
经检测,所得碳化硅闭孔陶瓷的主要物相为6H-SiC,显气孔率为30%,闭口气孔率为12%,常温抗压强度为140MPa,抗热震性为106次,热导率为0.69w/(m·K)。After testing, the main phase of the obtained silicon carbide closed-cell ceramic is 6H-SiC, the apparent porosity is 30%, the closed porosity is 12%, the compressive strength at room temperature is 140MPa, the thermal shock resistance is 106 times, and the thermal conductivity 0.69 w / (m · K).
实施例2Example 2
一种利用工业硅基废渣制备碳化硅闭孔陶瓷,包括的组分及质量配比为:多晶硅熟料∶活性炭∶水玻璃∶钾长石∶氯化铵=100∶30∶5∶5∶20。A silicon carbide closed-pore ceramic prepared by using industrial silicon-based waste slag includes components and mass ratios: polycrystalline silicon clinker: activated carbon: water glass: potassium feldspar: ammonium chloride = 100: 30: 5: 5: 20 .
一种利用工业硅基废渣制备碳化硅闭孔陶瓷制备方法,工艺流程图如图1所示,按以下步骤进行:A method for preparing silicon carbide closed-cell ceramics using industrial silicon-based waste slag. The process flow chart is shown in Figure 1, and the following steps are performed:
步骤1:原料处理和称量Step 1: Raw material handling and weighing
(1)将多晶硅切割废料于箱式电阻丝炉中,900℃下煅烧5h后,经颚式破碎机粉碎,200目过筛处理,得到去除聚乙二醇和水的多晶硅熟料;(1) The polycrystalline silicon cutting waste is calcined in a box-type resistance wire furnace, after being calcined at 900 ° C for 5 hours, crushed by a jaw crusher, and sieved at 200 mesh to obtain polycrystalline silicon clinker without polyethylene glycol and water;
(2)按配比,将多晶硅熟料与活性炭经行星式球磨机,以200~600r·min
-1转速单向运行5~10h进行球磨后,与水玻璃、钾长石和氯化铵混合,并以300r·min
-1的速率球磨3h,得混匀物料;
(2) According to the ratio, the polycrystalline silicon clinker and activated carbon are passed through a planetary ball mill and run unidirectionally at a speed of 200-600r · min -1 for 5-10 hours for ball milling, then mixed with water glass, potassium feldspar and ammonium chloride, and mixed with Mill at a rate of 300r · min -1 for 3h to obtain a homogeneous material;
步骤2:干压成型Step 2: Dry pressing
将混匀物料置于压力机中干压成型,200MPa下保压5min,并置于干燥箱中120℃下保温24h。Put the mixed material in a press for dry pressing, hold it at 200 MPa for 5 minutes, and place it in a drying box at 120 ° C for 24 hours.
步骤3:高温烧结Step 3: High temperature sintering
将干燥后物料在1500℃的箱式电阻炉中,埋碳条件下充分烧结2h,待高温炉冷却至室温,制得利用工业硅基废渣制备碳化硅闭孔陶瓷,其XRD图如图2所示。The dried material was fully sintered in a box-type resistance furnace at 1500 ° C for 2 hours under the condition of buried carbon, and the high-temperature furnace was cooled to room temperature to prepare a silicon carbide closed-cell ceramic using industrial silicon-based waste slag. The XRD diagram is shown in Figure 2. Show.
经检测,所得碳化硅闭孔陶瓷的主要物相为6H-SiC,显气孔率为40%,闭口气孔率为14%,常温抗压强度为120MPa,抗热震性为108次,热导率为0.67w/(m·K)。After testing, the main phase of the obtained silicon carbide closed-cell ceramic is 6H-SiC, the apparent porosity is 40%, the closed porosity is 14%, the compressive strength at room temperature is 120MPa, the thermal shock resistance is 108 times, and the thermal conductivity It was 0.67 w / (m · K).
实施例3Example 3
一种利用工业硅基废渣制备碳化硅闭孔陶瓷,包括的组分及质量配比为:稻壳灰熟料∶炭黑∶酚醛树脂∶钠长石∶淀粉=100∶60∶5∶5∶30。A silicon carbide closed-pore ceramic prepared by using industrial silicon-based waste slag includes components and mass ratios of: rice hull ash clinker: carbon black: phenolic resin: sodium feldspar: starch = 100: 60: 5: 5: 30.
一种利用工业硅基废渣制备碳化硅闭孔陶瓷制备方法,工艺流程图如图1所示,按以下步骤进行:A method for preparing silicon carbide closed-cell ceramics using industrial silicon-based waste slag. The process flow chart is shown in Figure 1, and the following steps are performed:
步骤1:原料处理和称量Step 1: Raw material handling and weighing
(1)将稻壳灰于箱式电阻丝炉中,900℃下煅烧5h后,经颚式破碎机粉碎,200目过筛处理,得到去除聚乙二醇和水的稻壳灰熟料;(1) The rice husk ash is calcined in a box-type resistance wire furnace, calcined at 900 ° C for 5 hours, crushed by a jaw crusher, and sieved at 200 mesh to obtain a rice husk ash clinker with polyethylene glycol and water removed;
(2)按配比,将稻壳灰熟料与炭黑经行星式球磨机,以200~600r·min-1转速单向运行5~10h进行球磨后,与酚醛树脂、钠长石和淀粉混合,并以300r·min
-1的速率球磨3h,得混匀物料;
(2) According to the mixing ratio, the rice husk ash clinker and carbon black are subjected to ball milling through a planetary ball mill at a speed of 200 to 600 r · min-1 for one to five hours, and then mixed with phenolic resin, sodium feldspar and starch, and Ball milling for 3h at a rate of 300r · min -1 to obtain a homogeneous material;
步骤2:干压成型Step 2: Dry pressing
将混匀物料置于压力机中干压成型,200MPa下保压5min,并置于干燥箱中120℃下保温24h。Put the mixed material in a press for dry pressing, hold it at 200 MPa for 5 minutes, and place it in a drying box at 120 ° C for 24 hours.
步骤3:高温烧结Step 3: High temperature sintering
将干燥后物料在1600℃的箱式电阻炉中,埋碳条件下充分烧结2h,待高温炉冷却至室温,制得利用工业硅基废渣制备碳化硅闭孔陶瓷。The dried material was fully sintered in a box-type resistance furnace at 1600 ° C for 2 hours under the condition of buried carbon, and the high-temperature furnace was cooled to room temperature to prepare a silicon carbide closed-cell ceramic using industrial silicon-based waste residue.
经检测,所得碳化硅闭孔陶瓷的主要物相为6H-SiC,显气孔率为46%,闭口气孔率为20%,常温抗压强度为106MPa,抗热震性为111次,热导率为0.46w/(m·K)。After testing, the main phase of the obtained silicon carbide closed-cell ceramic is 6H-SiC, the apparent porosity is 46%, the closed porosity is 20%, the compressive strength at room temperature is 106MPa, the thermal shock resistance is 111 times, and the thermal conductivity It was 0.46 w / (m · K).
实施例4Example 4
一种利用工业硅基废渣制备碳化硅闭孔陶瓷,包括的组分及质量配比为:煤矸石熟料∶炭黑∶磷酸二氢铝∶钙长石∶石墨粉=100∶40∶5∶10∶30。A silicon carbide closed-pore ceramic prepared by using industrial silicon-based waste slag includes the following components and mass ratio: coal gangue clinker: carbon black: aluminum dihydrogen phosphate: calcium feldspar: graphite powder = 100: 40: 5: 10:30.
一种利用工业硅基废渣制备碳化硅闭孔陶瓷制备方法,工艺流程图如图1所示,按以下步骤进行:A method for preparing silicon carbide closed-cell ceramics using industrial silicon-based waste slag. The process flow chart is shown in Figure 1, and the following steps are performed:
步骤1:原料处理和称量Step 1: Raw material handling and weighing
(1)将煤矸石于箱式电阻丝炉中,900℃下煅烧5h后,经颚式破碎机粉碎,200目过筛处理,得到去除聚乙二醇和水的煤矸石熟料;(1) Coal gangue is calcined in a box-type resistance wire furnace, after being calcined at 900 ° C for 5 hours, crushed by a jaw crusher, and sieved with 200 mesh to obtain coal gangue clinker with polyethylene glycol and water removed;
(2)按配比,将煤矸石熟料与炭黑经行星式球磨机,以200~600r·min
-1转速单向运行5~10h进行球磨后,与磷酸二氢铝:钙长石和石墨粉混合,并以300r·min
-1的速率球磨3h,得混匀物料;
(2) According to the proportion, coal gangue clinker and carbon black are passed through a planetary ball mill at a speed of 200 to 600 r · min -1 for 5 to 10 hours in one direction, and then mixed with aluminum dihydrogen phosphate: calcium feldspar and graphite powder. And ball milling at a rate of 300 r · min -1 for 3 h to obtain a homogeneous material;
步骤2:干压成型Step 2: Dry pressing
将混匀物料置于压力机中干压成型,200MPa下保压5min,并置于干燥箱中120℃下保温24h。Put the mixed material in a press for dry pressing, hold it at 200 MPa for 5 minutes, and place it in a drying box at 120 ° C for 24 hours.
步骤3:高温烧结Step 3: High temperature sintering
将干燥后物料在1500℃的箱式电阻炉中,埋碳条件下充分烧结2h,待高温炉冷却至室温,制得利用工业硅基废渣制备碳化硅闭孔陶瓷。The dried material was fully sintered in a box-type resistance furnace at 1500 ° C for 2 hours under the condition of buried carbon, and the high-temperature furnace was cooled to room temperature to prepare a silicon carbide closed-cell ceramic using industrial silicon-based waste residue.
经检测,所得碳化硅闭孔陶瓷的主要物相为6H-SiC,显气孔率为45%,闭口气孔率为18%,常温抗压强度为109MPa,抗热震性为110次,热导率为0.44w/(m·K)。After testing, the main phase of the obtained silicon carbide closed-cell ceramic is 6H-SiC, the apparent porosity is 45%, the closed porosity is 18%, the compressive strength at room temperature is 109MPa, the thermal shock resistance is 110 times, and the thermal conductivity It was 0.44 w / (m · K).
实施例5Example 5
一种利用工业硅基废渣制备碳化硅闭孔陶瓷制备方法,工艺流程图如图1所示,按以下步骤进行:A method for preparing silicon carbide closed-cell ceramics using industrial silicon-based waste slag. The process flow chart is shown in Figure 1, and the following steps are performed:
一种利用工业硅基废渣制备碳化硅闭孔陶瓷,包括的组分及质量配比为:煤矸石熟料∶炭黑∶磷酸二氢铝∶钾长石∶石墨粉=100∶30∶3∶5∶60。A silicon carbide closed-pore ceramic prepared by using industrial silicon-based waste slag includes the following components and mass ratio: coal gangue clinker: carbon black: aluminum dihydrogen phosphate: potassium feldspar: graphite powder = 100: 30: 3: 5:60.
一种利用工业硅基废渣制备碳化硅闭孔陶瓷制备方法,工艺流程图如图1所示,按以下步骤进行:A method for preparing silicon carbide closed-cell ceramics using industrial silicon-based waste slag. The process flow chart is shown in Figure 1, and the following steps are performed:
步骤1:原料处理和称量Step 1: Raw material handling and weighing
(1)将煤矸石于箱式电阻丝炉中,900℃下煅烧5h后,经颚式破碎机粉碎,200目过筛处理,得到去除聚乙二醇和水的煤矸石熟料;(1) Coal gangue is calcined in a box-type resistance wire furnace, after being calcined at 900 ° C for 5 hours, crushed by a jaw crusher, and sieved with 200 mesh to obtain coal gangue clinker with polyethylene glycol and water removed;
(2)按配比,将煤矸石熟料与炭黑经行星式球磨机,以200~600r·min
-1转速单向运行5~10h进行球磨后,与磷酸二氢铝、钾长石和石墨粉混合,并以300r·min
-1的速率球磨3h,得混匀物料;
(2) According to the mixing ratio, coal gangue clinker and carbon black are passed through a planetary ball mill at a speed of 200 to 600 r · min -1 for 5 to 10 hours in one direction, and then mixed with aluminum dihydrogen phosphate, potassium feldspar and graphite powder. And ball milling at a rate of 300 r · min -1 for 3 h to obtain a homogeneous material;
步骤2:干压成型Step 2: Dry pressing
将混匀物料置于压力机中干压成型,200MPa下保压5min,并置于干燥箱中120℃下保温24h。Put the mixed material in a press for dry pressing, hold it at 200 MPa for 5 minutes, and place it in a drying box at 120 ° C for 24 hours.
步骤3:高温烧结Step 3: High temperature sintering
将干燥后物料在1500℃的箱式电阻炉中,埋碳条件下充分烧结2h,待高温炉冷却至室温,制得利用工业硅基废渣制备碳化硅闭孔陶瓷。The dried material was fully sintered in a box-type resistance furnace at 1500 ° C for 2 hours under the condition of buried carbon, and the high-temperature furnace was cooled to room temperature to prepare a silicon carbide closed-cell ceramic using industrial silicon-based waste residue.
经检测,所得碳化硅闭孔陶瓷的主要物相为6H-SiC,显气孔率为55%,闭口气孔率为10%,常温抗压强度为101MPa,抗热震性为103次,热导率为0.40w/(m·K)。After testing, the main phase of the obtained silicon carbide closed-cell ceramic is 6H-SiC, the apparent porosity is 55%, the closed porosity is 10%, the compressive strength at room temperature is 101MPa, the thermal shock resistance is 103 times, and the thermal conductivity It was 0.40 w / (m · K).
实施例6Example 6
一种利用工业硅基废渣制备碳化硅闭孔陶瓷制备方法,工艺流程图如图1所示,按以下步骤进行:A method for preparing silicon carbide closed-cell ceramics using industrial silicon-based waste slag. The process flow chart is shown in Figure 1, and the following steps are performed:
一种利用工业硅基废渣制备碳化硅闭孔陶瓷,包括的组分及质量配比为:稻壳灰熟料∶炭黑∶酚醛树脂∶钠长石∶淀粉=100∶60∶5∶60∶30。A silicon carbide closed-pore ceramic prepared by using industrial silicon-based waste slag includes the following components and mass ratio: rice hull ash clinker: carbon black: phenolic resin: sodium feldspar: starch = 100: 60: 5: 60: 30.
一种利用工业硅基废渣制备碳化硅闭孔陶瓷制备方法,工艺流程图如图1所示,按以下 步骤进行:A method for preparing silicon carbide closed-cell ceramics using industrial silicon-based waste slag. The process flow chart is shown in Figure 1, and the following steps are performed:
步骤1:原料处理和称量Step 1: Raw material handling and weighing
(1)将稻壳灰于箱式电阻丝炉中,900℃下煅烧5h后,经颚式破碎机粉碎,200目过筛处理,得到去除聚乙二醇和水的稻壳灰熟料;(1) The rice husk ash is calcined in a box-type resistance wire furnace, calcined at 900 ° C for 5 hours, crushed by a jaw crusher, and sieved at 200 mesh to obtain a rice husk ash clinker with polyethylene glycol and water removed;
(2)按配比,将稻壳灰熟料与炭黑经行星式球磨机,以200~600r·min
-1转速单向运行5~10h进行球磨后,与酚醛树脂、钠长石和淀粉混合,并以300r·min
-1的速率球磨3h,得混匀物料;
(2) According to the mixing ratio, the rice husk ash clinker and carbon black are subjected to ball milling through a planetary ball mill at a speed of 200 to 600 r · min -1 for 5 to 10 hours, and then mixed with phenolic resin, sodium feldspar and starch, and Ball milling for 3h at a rate of 300r · min -1 to obtain a homogeneous material;
步骤2:干压成型Step 2: Dry pressing
将混匀物料置于压力机中干压成型,200MPa下保压5min,并置于干燥箱中120℃下保温24h。Put the mixed material in a press for dry pressing, hold it at 200 MPa for 5 minutes, and place it in a drying box at 120 ° C for 24 hours.
步骤3:高温烧结Step 3: High temperature sintering
将干燥后物料在1600℃的箱式电阻炉中,埋碳条件下充分烧结2h,待高温炉冷却至室温,制得利用工业硅基废渣制备碳化硅闭孔陶瓷。The dried material was fully sintered in a box-type resistance furnace at 1600 ° C for 2 hours under the condition of buried carbon, and the high-temperature furnace was cooled to room temperature to prepare a silicon carbide closed-cell ceramic using industrial silicon-based waste residue.
经检测,所得碳化硅闭孔陶瓷的主要物相为6H-SiC,显气孔率为40%,闭口气孔率为16%,常温抗压强度为119MPa,抗热震性为109次,热导率为0.58w/(m·K)。After testing, the main phase of the silicon carbide closed-cell ceramics obtained was 6H-SiC, the apparent porosity was 40%, the closed porosity was 16%, the compressive strength at room temperature was 119 MPa, the thermal shock resistance was 109 times, and the thermal conductivity It was 0.58 w / (m · K).
Claims (10)
- 一种利用工业硅基废渣制备碳化硅闭孔陶瓷,其特征在于,包括的组分及质量配比为:工业硅基废渣∶还原剂∶粘结剂∶烧结助剂∶造孔剂=100:(30~60):(3~5):(5~60):(5~60)。A silicon carbide closed-pore ceramic prepared by using industrial silicon-based waste slag is characterized in that it includes components and mass ratios: industrial silicon-based waste slag: reducing agent: binder: sintering aid: pore former = 100: (30 to 60): (3 to 5): (5 to 60): (5 to 60).
- 根据权利要求1所述的利用工业硅基废渣制备碳化硅闭孔陶瓷,其特征在于,所述的工业硅基废渣为煤矸石、铁矿石尾矿、多晶硅切割废料或稻壳灰中的一种或几种;所述的还原剂为炭黑、优质煤或活性炭中的一种或多种;所述的粘结剂为酚醛树脂、水玻璃、磷酸二氢铝或聚乙烯醇中的一种或多种;所述的烧结助剂为钾长石、钠长石或钙长石中的一种或多种;所述的造孔剂为淀粉、石墨、碳酸氢铵或氯化铵中的一种或多种。The method for preparing silicon carbide closed-pore ceramics using industrial silicon-based waste slag according to claim 1, wherein the industrial silicon-based waste slag is one of coal gangue, iron ore tailings, polycrystalline silicon cutting waste, or rice hull ash Or several; the reducing agent is one or more of carbon black, high-quality coal or activated carbon; the binder is one of phenolic resin, water glass, aluminum dihydrogen phosphate or polyvinyl alcohol Or more; the sintering aid is one or more of potassium feldspar, sodium feldspar or calcareous feldspar; the pore-forming agent is starch, graphite, ammonium bicarbonate or ammonium chloride One or more.
- 根据权利要求1所述的利用工业硅基废渣制备碳化硅闭孔陶瓷,其特征在于,所述的碳化硅闭孔陶瓷显气孔率为30~55%,闭口气孔率为12~20%,常温抗压强度为106~140MPa,抗热震性为103~111次,热导率为0.40~0.69w/(m·K)。The method for preparing silicon carbide closed-cell ceramics using industrial silicon-based waste slag according to claim 1, wherein the silicon carbide closed-cell ceramics exhibit a significant porosity of 30 to 55%, a closed porosity of 12 to 20%, and room temperature. The compressive strength is 106 to 140 MPa, the thermal shock resistance is 103 to 111 times, and the thermal conductivity is 0.40 to 0.69 w / (m · K).
- 根据权利要求3所述的利用工业硅基废渣制备碳化硅闭孔陶瓷,其特征在于,所述的碳化硅闭孔陶瓷的抗热震性能以空冷的循环次数来表征,具体操作:在1000℃的高温炉加热15min后,空冷10min为1次;然后再放回炉中于1000℃保温15min后空冷10min,如此循环操作直至试样碎裂。The method for preparing silicon carbide closed-cell ceramics using industrial silicon-based waste slag according to claim 3, characterized in that the thermal shock resistance of the silicon carbide closed-cell ceramics is characterized by the number of air cooling cycles, and the specific operation is at 1000 ° C. After heating in a high-temperature furnace for 15 minutes, air-cooling is performed once for 10 minutes; then put back in the furnace and kept at 1000 ° C for 15 minutes, and then air-cooled for 10 minutes. This cycle is performed until the sample is broken.
- 权利要求1所述的一种利用工业硅基废渣制备碳化硅闭孔陶瓷的制备方法,其特征在于,包括以下步骤:The method for preparing silicon carbide closed-cell ceramics using industrial silicon-based waste slag according to claim 1, comprising the following steps:步骤1,原料混合:Step 1. Mix the ingredients:按配比,工业硅基废渣∶还原剂∶粘结剂∶烧结助剂∶造孔剂=100:(30~60):(3~5)(5~60)(5~60),将物料混合均匀,球磨得混匀物料;According to the ratio, industrial silicon-based waste residue: reducing agent: binder: sintering aid: pore former = 100: (30-60): (3-5) (5-60) (5-60), the materials are mixed Uniform, ball milled to obtain a homogeneous material;步骤2,干压成型:Step 2. Dry pressing:将混匀物料干压成型,并干燥;Dry mix the mixed material and dry it;步骤3,高温烧结:Step 3. Sintering at high temperature:将干燥后物料置于高温炉中,于还原气氛下烧结并保温一定时间,制得利用工业硅基废渣制备碳化硅闭孔陶瓷。The dried material is placed in a high-temperature furnace, sintered in a reducing atmosphere, and held for a certain period of time to prepare a silicon carbide closed-cell ceramic using industrial silicon-based waste residue.
- 根据权利要求5所述的利用工业硅基废渣制备碳化硅闭孔陶瓷的制备方法,其特征在于,所述的步骤1中,工业硅基废渣在混合前经高温煅烧与粉碎过筛处理,用于去除工业硅基废渣中的杂质,制得硅基熟料后按配比混合。The method for preparing silicon carbide closed-cell ceramics using industrial silicon-based waste slag according to claim 5, characterized in that in said step 1, the industrial silicon-based waste slag is subjected to high-temperature calcination and crushing and sieving treatment before being mixed with After removing impurities in industrial silicon-based waste slag, silicon-based clinker is prepared and mixed according to the ratio.
- 根据权利要求5所述的利用工业硅基废渣制备碳化硅闭孔陶瓷的制备方法,其特征在于,所述的步骤1中,所述的煅烧操作在煅烧炉中进行,煅烧温度为900℃,煅烧时间为5h,所述的煅烧炉为在无保护气氛下使用的箱式电阻丝炉、硅碳棒炉、硅钼棒炉和隧道窑中的一种;所述的粉碎过筛处理过程为:采用颚式破碎机粉碎处理,粉末经200目筛后,制得硅基 熟料。The method for preparing silicon carbide closed-cell ceramics using industrial silicon-based waste slag according to claim 5, characterized in that in said step 1, said calcination operation is performed in a calciner, and the calcination temperature is 900 ° C, The calcining time is 5 hours. The calcining furnace is one of a box-type resistance wire furnace, a silicon carbon rod furnace, a silicon molybdenum rod furnace, and a tunnel kiln used in an unprotected atmosphere. The crushing and sieving process is as follows: : The jaw crusher is used for crushing treatment, and the powder is passed through a 200-mesh sieve to obtain a silicon-based clinker.
- 根据权利要求5所述的利用工业硅基废渣制备碳化硅闭孔陶瓷的制备方法,其特征在于,所述的步骤1中,所述的硅基熟料和还原剂在物料混合之前,经过球磨处理,硅基熟料和还原剂球磨采用的设备为行星式球磨机,以200~600r·min -1转速单向运行5~10h;所有物料混合后的球磨采用的设备为行星式球磨机,以300r·min -1转速单向运行5h。 The method for preparing silicon carbide closed-cell ceramics using industrial silicon-based waste slag according to claim 5, characterized in that, in the step 1, the silicon-based clinker and the reducing agent are subjected to ball milling before the materials are mixed. For processing, the equipment for ball milling of silicon-based clinker and reducing agent is a planetary ball mill, which runs unidirectionally at a speed of 200 ~ 600r · min -1 for 5 ~ 10h; the equipment for ball milling after all materials are mixed is a planetary ball mill with 300r · Min -1 speed running unidirectional for 5h.
- 根据权利要求5所述的利用工业硅基废渣制备碳化硅闭孔陶瓷的制备方法,其特征在于,所述的步骤2中,所用成型压力为50~300MPa,保压时间为3~5min;所所述的干燥操作的干燥温度为120℃,干燥时间为12~24h,干燥设备为干燥箱或隧道干燥窑。The method for preparing silicon carbide closed-cell ceramics using industrial silicon-based waste slag according to claim 5, characterized in that, in the step 2, the forming pressure used is 50-300 MPa, and the holding time is 3-5 minutes; The drying temperature of the drying operation is 120 ° C, the drying time is 12-24 hours, and the drying equipment is a drying box or a tunnel drying kiln.
- 根据权利要求5所述的利用工业硅基废渣制备碳化硅闭孔陶瓷的制备方法,其特征在于,所述的步骤3中,所述的烧结温度为1400~1600℃,烧结保温时间为2~10h;所述的还原气氛为埋碳或通入CO气氛下,其中:埋碳条件为:干压成型的物料置于石墨坩埚中,石墨坩埚置于大尺寸刚玉坩埚中,在刚玉坩埚中放入充足的石墨粉,刚玉坩埚上端盖一块刚玉板,隔绝石墨坩埚与外界空气的接触;通入CO条件为:由高温炉底或窑的一侧通入CO气体,气体流量为1~100L/min。The method for preparing silicon carbide closed-cell ceramics using industrial silicon-based waste slag according to claim 5, wherein in the step 3, the sintering temperature is 1400 to 1600 ° C, and the sintering holding time is 2 to 10h; the reducing atmosphere is buried carbon or CO-introduced, wherein: the conditions for buried carbon are: dry-pressed material is placed in a graphite crucible, the graphite crucible is placed in a large-sized corundum crucible, Fill sufficient graphite powder, cover a corundum plate on the upper end of the corundum crucible to isolate the graphite crucible from contact with the outside air; CO conditions are: CO gas is introduced from the bottom of the high temperature furnace or one side of the kiln, and the gas flow rate is 1 ~ 100L / min.
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DE102013114628A1 (en) * | 2013-12-20 | 2015-06-25 | Deutsches Zentrum Für Luft- Und Raumfahrt | Process for producing near net shape shaped silicon carbide ceramics |
CN107686369A (en) * | 2017-08-22 | 2018-02-13 | 东北大学 | A kind of method for preparing carborundum porous ceramics with the carborundum cutting waste material of crystalline silicon |
CN107892576A (en) * | 2017-10-25 | 2018-04-10 | 深圳市商德先进陶瓷股份有限公司 | Silicon carbide ceramics and preparation method thereof and fin and its application |
CN109133935A (en) * | 2018-09-20 | 2019-01-04 | 东北大学 | It is a kind of to prepare silicon carbide closed pore ceramics and preparation method thereof using industrial silicon substrate waste residue |
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2018
- 2018-09-20 CN CN201811099175.7A patent/CN109133935A/en active Pending
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- 2019-03-29 WO PCT/CN2019/080544 patent/WO2020057094A1/en active Application Filing
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
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DE102013114628A1 (en) * | 2013-12-20 | 2015-06-25 | Deutsches Zentrum Für Luft- Und Raumfahrt | Process for producing near net shape shaped silicon carbide ceramics |
CN107686369A (en) * | 2017-08-22 | 2018-02-13 | 东北大学 | A kind of method for preparing carborundum porous ceramics with the carborundum cutting waste material of crystalline silicon |
CN107892576A (en) * | 2017-10-25 | 2018-04-10 | 深圳市商德先进陶瓷股份有限公司 | Silicon carbide ceramics and preparation method thereof and fin and its application |
CN109133935A (en) * | 2018-09-20 | 2019-01-04 | 东北大学 | It is a kind of to prepare silicon carbide closed pore ceramics and preparation method thereof using industrial silicon substrate waste residue |
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