CN109133930A - 一种陶瓷复合材料 - Google Patents
一种陶瓷复合材料 Download PDFInfo
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Abstract
本发明公开了一种陶瓷复合材料及其制备方法,陶瓷复合材料包括以下重量份的成分:ZrB2‑SiC 75~90份、高岭土20~30份、纳米氧化锆6~10份、纳米氧化铝3~5份、纳米氧化镁2~6份、纳米二氧化钛1~6份、碳纤维3~10份、玻璃纤维4~8份、凹凸棒土6~8份、硅藻土10~12份、电气石10~15份、麦饭石10~15份、聚乙二醇5~10份、硅烷偶联剂3~6份。本发明的陶瓷材料以ZrB2‑SiC粉体为主要原料,制得的陶瓷材料具有良好的耐高温性能、导电和导热性能,较高的机械强度和化学稳定性,另外,添加的电气石、麦饭石、凹凸棒土和硅藻土等天然物质作为主要原料,原料来源广泛,并且具有释放负离子、辐射远红外线、抗菌、除氯、除贵金属等特性;本发明添加的碳纤维、玻璃纤维可以增加陶瓷的韧性。
Description
技术领域
本发明涉及陶瓷材料技术领域,具体是涉及一种陶瓷复合材料及其制备方法。
背景技术
陶瓷材料是用天然或合成化合物经过成形和高温烧结制成的一类无机非金属材料。它具有高熔点、高硬度、高耐磨性、耐氧化等优点。可用作结构材料、刀具材料,由于陶瓷还具有某些特殊的性能,又可作为功能材料。不同原料制备的陶瓷的各项性能不一样,提高陶瓷性能的力学性能、热特性、电特性等性能,是陶瓷材料需要进一步解决的问题。
复合材料通常具有不同材料相互取长补短的良好综合性能。复合材料兼有两种或两种以上材料的特点,能改善单一材料的性能,如提高强度、增加韧性和改善介电性能等。作为高温结构材料用的陶瓷复合材料,主要用于宇航,军工等部门。此外,在机械、化工、电子技术等领域也广泛采用各种陶瓷复合材料。陶瓷基复合材料是以陶瓷为基体与各种纤维复合的一类复合材料。陶瓷基体可为氮化硅、碳化硅等高温结构陶瓷。这些先进陶瓷具有耐高温、高强度和刚度、相对重量较轻、抗腐蚀等优异性能,而其致命的弱点是具有脆性,处于应力状态时,会产生裂纹,甚至断裂导致材料失效。而采用高强度、高弹性的纤维与基体复合,则是提高陶瓷韧性和可靠性的一个有效的方法。纤维能阻止裂纹的扩展,从而得到有优良韧性的纤维增强陶瓷基复合材料。陶瓷基复合材料具有优异的耐高温性能,主要用作高温及耐磨制品。其最高使用温度主要取决于基,
现有的陶瓷复合材料不能够满足使用需求,因此,需要陶瓷材料的性能进一步提高体特征。
发明内容
本发明的目的在于克服上述问题而提供了一种具有良好的耐高温性能、导电和导热性能,较高的机械强度和化学稳定性的陶瓷复合材料及其制备方法。
为实现上述目的,本发明采取的技术方案为:一种陶瓷复合材料,包括以下重量份的成分:ZrB2-SiC 75~90份、高岭土20~30份、纳米氧化锆6~10份、纳米氧化铝3~5份、纳米氧化镁2~6份、纳米二氧化钛1~6份、碳纤维3~10份、玻璃纤维4~8份、凹凸棒土6~8份、硅藻土10~12份、电气石10~15份、麦饭石10~15份、聚乙二醇5~10份、硅烷偶联剂3~6份。
ZrB2、SiC具有高熔点、高硬度、导电导热性好、良好的抗氧化性、耐腐蚀性等特点,在高温结构陶瓷材料、耐火材料、复合材料等领域中得到广泛开发和应用,本发明采用将ZrB2引用SiC后获得ZrB2-SiC,相对于采用单独的ZrB2、SiC,其可以明显改善抗氧化性能、抗侵蚀性能、抗热震性能,本发明的纳米氧化铝、纳米氧化镁、纳米二氧化钛等原料,提高了原料间的反应活性,同时还可以在较低的烧成温度(1000℃以下)下使产品获得较高的强度等特性,一方面降低了生产成本,同时保证即使长期与水接触,也不会出现溃散、开裂等现象,纳米氧化锆提高了陶瓷的耐磨性、抗热震性,采用了电气石、麦饭石、凹凸棒土和硅藻土等天然物质作为主要原料,原料来源广泛,并且具有释放负离子、辐射远红外线、抗菌、除氯、除贵金属等特性;本发明添加的碳纤维、玻璃纤维可以增加陶瓷的韧性。
优选地,包括以下重量份的成分:ZrB2-SiC 85份、高岭土27.5份、纳米氧化锆8份、纳米氧化铝5份、纳米氧化镁4.5份、纳米二氧化钛4份、碳纤维5份、玻璃纤维7份、凹凸棒土6.8份、硅藻土11.5份、电气石13份、麦饭石14份、聚乙二醇8份、硅烷偶联剂5份。本申请发明人经过大量研究发现,当各个成分在此含量配比下,具有最佳的硬度、破坏强度、断裂韧性。
优选地,包括以下重量份的成分:ZrB2-SiC 80份、高岭土25份、纳米氧化锆8份、纳米氧化铝4份、纳米氧化镁3份、纳米二氧化钛2份、碳纤维4.5份、玻璃纤维6.5份、凹凸棒土7.5份、硅藻土13.5份、电气石10.8份、麦饭石13份、聚乙二醇7.5份、硅烷偶联剂4.5份。
优选地,包括以下重量份的成分:ZrB2-SiC 85份、高岭土27.5份、纳米氧化锆8份、纳米氧化铝5份、纳米氧化镁4.5份、纳米二氧化钛4份、碳纤维5份、玻璃纤维7份、凹凸棒土6.8份、硅藻土11.5份、电气石13份、麦饭石14份、聚乙二醇8份、硅烷偶联剂5份。
优选地,所述ZrB2-SiC的含量为79~84重量份。本发明的ZrB2-SiC的含量对陶瓷复合材料的各项性能有直接的影响,当所述ZrB2-SiC的含量为79~84重量份时,所述的陶瓷复合材料具有优异的具有良好的耐高温性能、较高的机械强度,优选地,所述ZrB2-SiC的含量为82重量份。当ZrB2-SiC的含量为82重量份时,其机械强度最佳。
优选地,所述ZrB2-SiC的含量为79~82重量份。
优选地,包括以下重量份的成分:ZrB2-SiC 79~84份、高岭土25~27.5份、纳米氧化锆8份、纳米氧化铝4~5份、纳米氧化镁3~4.5份、纳米二氧化钛2~4份、碳纤维4.5~5份、玻璃纤维6.5~7份、凹凸棒土6.8~7.5份、硅藻土11.5~13.5份、电气石10.8~13份、麦饭石13~14份、聚乙二醇7.5~8份、硅烷偶联剂4.5~5份。
本发明还提供了一种陶瓷复合材料的制备方法,包括以下步骤:1)对碳纤维、玻璃纤维预制体进行预处理;预处理操作为:在温度为50℃温度条件下采用质量分数为40%的硝酸中浸泡6h,然后用去离子水冲洗至中性,干燥至恒重备用;
2)浆液配制:按成分含量比例称取ZrB2-SiC粉体、高岭土粉末、纳米氧化锆粉末、纳米氧化铝粉末、纳米氧化镁粉末、纳米二氧化钛粉末、碳纤维粉末、玻璃纤维粉末、凹凸棒土粉末、硅藻土粉末、电气石粉末、麦饭石粉末、聚乙二醇、硅烷偶联剂混合成浆料;各粉末的粒径均为270~325目;
3)浆液浸渍:将步骤1)处理后的碳纤维、玻璃纤维预制体置于步骤2)制备的混合浆料中进行浸渍,然后经热处理、冷却后获得坯体;
浸渍的具体步骤为:
步骤(31),首先在30~33℃温度条件下浸渍3h,然后取出后在60℃温度条件下干燥30h;
步骤(32),然后继续在50~55℃温度条件下浸渍1.5h,然后取出在90℃温度条件下干燥50h;
步骤(33),最后在60℃温度条件下浸渍0.5h,取出后在120℃温度条件下干燥至恒重;
热处理具体操作为:在惰性气氛中,以15℃/min升温速度升温至850℃,热处理1.5h;然后继续以5℃min的升温速度升温至1150℃,热处理1h;
4)对步骤3)之比的坯体进行机械加工;
5)对步骤4)加工后的坯料进行清洗、干燥处理获得成品。
优选地,所述ZrB2-SiC粉体由以下方法制成:称取锆英石、氧化硼和活性碳后,在行星式球磨机中干磨2h后混合均匀,以150Mpa的压力制成直径30mm的坯体,120℃/12h干燥后,将坯体埋在SiC粉体中,抽真空后,在流通氩气的气氛炉中进行碳热还原合成ZrB2-SiC粉体。
本发明的有益效果:本发明的陶瓷材料以ZrB2-SiC粉体为主要原料,制得的陶瓷材料具有良好的耐高温性能、导电和导热性能,较高的机械强度和化学稳定性,另外,添加的电气石、麦饭石、凹凸棒土和硅藻土等天然物质作为主要原料,原料来源广泛,并且具有释放负离子、辐射远红外线、抗菌、除氯、除贵金属等特性;本发明添加的碳纤维、玻璃纤维可以增加陶瓷的韧性。
具体实施方式
为更好的说明本发明的目的、技术方案和优点,下面将结合具体实施例对本发明作进一步说明。
本发明所述的ZrB2-SiC复合材料的制备方法包括以下步骤:
按比例称取锆英石、氧化硼和活性碳后,在行星式球磨机中干磨2h后混合均匀,以150Mpa的压力制成直径30mm的坯体,120℃/12h干燥后,将坯体埋在SiC粉体中,抽真空后,在流通氩气的气氛炉中进行碳热还原合成ZrB2-SiC粉体。
实施例1
作为本发明陶瓷复合材料的一种实施例,所述陶瓷复合材料包括以下重量份的成分:ZrB2-SiC 75份、高岭土25份、纳米氧化锆8份、纳米氧化铝3份、纳米氧化镁2份、纳米二氧化钛1.5份、碳纤维3.5份、玻璃纤维4份、凹凸棒土6份、硅藻土12份、电气石10份、麦饭石10份、聚乙二醇5份、硅烷偶联剂3份。
本实施例的陶瓷复合材料的制备方法包括以下步骤:
1)对碳纤维、玻璃纤维预制体进行预处理;预处理操作为:在温度为50℃温度条件下采用质量分数为40%的硝酸中浸泡6h,然后用去离子水冲洗至中性,干燥至恒重备用;
2)浆液配制:按成分含量比例称取ZrB2-SiC粉体、高岭土粉末、纳米氧化锆粉末、纳米氧化铝粉末、纳米氧化镁粉末、纳米二氧化钛粉末、碳纤维粉末、玻璃纤维粉末、凹凸棒土粉末、硅藻土粉末、电气石粉末、麦饭石粉末、聚乙二醇、硅烷偶联剂混合成浆料;各粉末的粒径均为270~325目;
3)浆液浸渍:将步骤1)处理后的碳纤维、玻璃纤维预制体置于步骤2)制备的混合浆料中进行浸渍,然后经热处理、冷却后获得坯体;
浸渍的具体步骤为:
步骤(31),首先在30~33℃温度条件下浸渍3h,然后取出后在60℃温度条件下干燥30h;
步骤(32),然后继续在50~55℃温度条件下浸渍1.5h,然后取出在90℃温度条件下干燥50h;
步骤(33),最后在60℃温度条件下浸渍0.5h,取出后在120℃温度条件下干燥至恒重;
热处理具体操作为:在惰性气氛中,以15℃/min升温速度升温至850℃,热处理1.5h;然后继续以5℃min的升温速度升温至1150℃,热处理1h;
4)对步骤3)之比的坯体进行机械加工;
5)对步骤4)加工后的坯料进行清洗、干燥处理获得成品。
实施例2
作为本发明陶瓷复合材料的一种实施例,所述陶瓷复合材料包括以下重量份的成分:ZrB2-SiC 78份、高岭土20份、纳米氧化锆6份、纳米氧化铝3.5份、纳米氧化镁2.5份、纳米二氧化钛1份、碳纤维3份、玻璃纤维4.5份、凹凸棒土6.5份、硅藻土10份、电气石12份、麦饭石12份、聚乙二醇6份、硅烷偶联剂4份。本实施例的陶瓷复合材料与实施例1相同。
实施例3
作为本发明陶瓷复合材料的一种实施例,所述陶瓷复合材料包括以下重量份的成分:ZrB2-SiC 80份、高岭土25份、纳米氧化锆8份、纳米氧化铝4份、纳米氧化镁3份、纳米二氧化钛2份、碳纤维4.5份、玻璃纤维6.5份、凹凸棒土7.5份、硅藻土13.5份、电气石10.8份、麦饭石13份、聚乙二醇7.5份、硅烷偶联剂4.5份。本实施例的陶瓷复合材料与实施例1相同。
实施例4
作为本发明陶瓷复合材料的一种实施例,所述陶瓷复合材料包括以下重量份的成分:ZrB2-SiC 82份、高岭土26份、纳米氧化锆8.5份、纳米氧化铝4.5份、纳米氧化镁3.5份、纳米二氧化钛3.2份、碳纤维6份、玻璃纤维4.8份、凹凸棒土8份、硅藻土10.5份、电气石12份、麦饭石13.8份、聚乙二醇10份、硅烷偶联剂6份。本实施例的陶瓷复合材料与实施例1相同。
实施例5
作为本发明陶瓷复合材料的一种实施例,所述陶瓷复合材料包括以下重量份的成分:ZrB2-SiC 85份、高岭土27.5份、纳米氧化锆8份、纳米氧化铝5份、纳米氧化镁4.5份、纳米二氧化钛4份、碳纤维5份、玻璃纤维7份、凹凸棒土6.8份、硅藻土11.5份、电气石13份、麦饭石14份、聚乙二醇8份、硅烷偶联剂5份。本实施例的陶瓷复合材料与实施例1相同。
实施例6
作为本发明陶瓷复合材料的一种实施例,所述陶瓷复合材料包括以下重量份的成分:ZrB2-SiC 90份、高岭土28份、纳米氧化锆10份、纳米氧化铝4份、纳米氧化镁5份、纳米二氧化钛5份、碳纤维8份、玻璃纤维6份、凹凸棒土8份、硅藻土12份、电气石14份、麦饭石13.5份、聚乙二醇8.5份、硅烷偶联剂5份。本实施例的陶瓷复合材料与实施例1相同。
实施例7
作为本发明陶瓷复合材料的一种实施例,所述陶瓷复合材料包括以下重量份的成分:ZrB2-SiC 85份、高岭土30份、纳米氧化锆8份、纳米氧化铝5份、纳米氧化镁6份、纳米二氧化钛6份、碳纤维10份、玻璃纤维8份、凹凸棒土6份、硅藻土10.5份、电气石15份、麦饭石15份、聚乙二醇10份、硅烷偶联剂6份。
对比例1
本对比例与实施例4不同之处仅在于,所述的ZrB2-SiC的含量不同,本对比例ZrB2-SiC含量为70份。
对比例2
本对比例与实施例7不同之处仅在于,所述的ZrB2-SiC的含量不同,本对比例ZrB2-SiC含量为95份。
对比例3
本对比例陶瓷复合材料包括以下重量份的成分:碳化锆82份、高岭土26份、纳米氧化锆8.5份、纳米氧化铝4.5份、纳米氧化镁3.5份、纳米二氧化钛3.2份、碳纤维6份、玻璃纤维4.8份、凹凸棒土8份、硅藻土10.5份、电气石12份、麦饭石13.8份、聚乙二醇10份、硅烷偶联剂6份。本对比例的陶瓷复合材料与实施例1相同。
对比例4
本对比例陶瓷复合材料包括以下重量份的成分:碳化硅82份、高岭土26份、纳米氧化锆8.5份、纳米氧化铝4.5份、纳米氧化镁3.5份、纳米二氧化钛3.2份、碳纤维6份、玻璃纤维4.8份、凹凸棒土8份、硅藻土10.5份、电气石12份、麦饭石13.8份、聚乙二醇10份、硅烷偶联剂6份。本对比例的陶瓷复合材料与实施例1相同。
对比例5
本对比例与实施例4不同之处仅在于不包含凹凸棒土、硅藻土、电气石、麦饭石成分。
实施例8
本发明的陶瓷复合材料的性能试验
分别对实施例1至7以及对比例1至5的陶瓷复合材料的性能进行测试,分别测试每组的硬度、破坏强度、断裂韧性、负离子释放量、5~14μm波长平均远红外线放射率,测试结果见表1:
表1陶瓷复合材料的性能测试结果
从表1可看出,本发明的陶瓷复合材料具有良好的耐高温性能、导电和导热性能,较高的机械强度和化学稳定性,且并且具有释放负离子、辐射远红外线、抗菌、除氯、除贵金属等特性,其中以实施例4效果最佳,对比例1的ZrB2-SiC的含量低于本发明最低值,从结果可看出,其各项性能均不如本发明,随着ZrB2-SiC复合材料含量的增加,本发明各项性能增加,当含量达到82份时,性能最佳,对比例2的ZrB2-SiC复合材料的含量略高于本发明的最大值,从测试结果可知,其性能没有多大改变,表明,当含量超过90份时,本发明的复合材料的性能没有显著增加,反而略有下降,对比例3、对比例4采用现有技术中的碳化硅、碳化锆代替本发明的ZrB2-SiC,而测试结果表明,性能不如本发明,对比例5中不包含电气石、麦饭石、凹凸棒土和硅藻土物质,其不具有释放负离子、辐射远红外线、抗菌、除氯、除贵金属等特性。
实施例9
本发明的陶瓷复合材料,ZrB2-SiC的含量对本发明的性能的影响试验
本实施例共设7组,实验组1至7的陶瓷复合材料包括以下重量份的成分ZrB2-SiC75~90份、高岭土20~30份、纳米氧化锆6~10份、纳米氧化铝3~5份、纳米氧化镁2~6份、纳米二氧化钛1~6份、碳纤维3~10份、玻璃纤维4~8份、凹凸棒土6~8份、硅藻土10~12份、电气石10~15份、麦饭石10~15份、聚乙二醇5~10份、硅烷偶联剂3~6份;本实施例除ZrB2-SiC的含量不同外,其余成分与含量均相同;其中ZrB2-SiC的含量如表2所示。
表2 ZrB2-SiC的含量
ZrB2-SiC含量(重量份) | |
试验组1 | 75 |
试验组2 | 77 |
试验组3 | 79 |
试验组4 | 80 |
试验组5 | 82 |
试验组6 | 84 |
试验组7 | 90 |
分别测试试验组1至7的硬度、破坏强度、断裂韧性,测试结果如表3所示。
表3 ZrB2-SiC的性能测试结果
硬度(HV) | 破坏强度(Mpa) | 断裂韧性(Mpa/m<sup>1/2</sup>) | |
试验组1 | 772 | 2221 | 2.30 |
试验组2 | 775 | 2223 | 2.38 |
试验组3 | 782 | 2234 | 2.48 |
试验组4 | 790 | 2236 | 2.49 |
试验组5 | 798 | 2245 | 2.56 |
试验组6 | 780 | 2234 | 2.33 |
试验组7 | 776 | 2226 | 2.30 |
本发明的ZrB2-SiC的含量对陶瓷复合材料的各项性能有直接的影响,当所述ZrB2-SiC的含量为79~84重量份时,所述的陶瓷复合材料具有优异的具有良好的耐高温性能、较高的机械强度,尤其是当ZrB2-SiC的含量为82重量份时,其机械强度最佳。
以上所述仅为本发明的较佳实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内,所做的任何修改、等同替换、改进等,均应包含在本发明保护的范围之内。
Claims (10)
1.一种陶瓷复合材料,其特征在于,包括以下重量份的成分:ZrB2-SiC75~90份、高岭土20~30份、纳米氧化锆6~10份、纳米氧化铝3~5份、纳米氧化镁2~6份、纳米二氧化钛1~6份、碳纤维3~10份、玻璃纤维4~8份、凹凸棒土6~8份、硅藻土10~12份、电气石10~15份、麦饭石10~15份、聚乙二醇5~10份、硅烷偶联剂3~6份。
2.根据权利要求1所述的陶瓷复合材料,其特征在于,包括以下重量份的成分:ZrB2-SiC85份、高岭土27.5份、纳米氧化锆8份、纳米氧化铝5份、纳米氧化镁4.5份、纳米二氧化钛4份、碳纤维5份、玻璃纤维7份、凹凸棒土6.8份、硅藻土11.5份、电气石13份、麦饭石14份、聚乙二醇8份、硅烷偶联剂5份。
3.根据权利要求1所述的陶瓷复合材料,其特征在于,包括以下重量份的成分:ZrB2-SiC80份、高岭土25份、纳米氧化锆8份、纳米氧化铝4份、纳米氧化镁3份、纳米二氧化钛2份、碳纤维4.5份、玻璃纤维6.5份、凹凸棒土7.5份、硅藻土13.5份、电气石10.8份、麦饭石13份、聚乙二醇7.5份、硅烷偶联剂4.5份。
4.根据权利要求1所述的陶瓷复合材料,其特征在于,包括以下重量份的成分:ZrB2-SiC85份、高岭土27.5份、纳米氧化锆8份、纳米氧化铝5份、纳米氧化镁4.5份、纳米二氧化钛4份、碳纤维5份、玻璃纤维7份、凹凸棒土6.8份、硅藻土11.5份、电气石13份、麦饭石14份、聚乙二醇8份、硅烷偶联剂5份。
5.根据权利要求1所述的陶瓷复合材料,其特征在于,所述ZrB2-SiC的含量为79~84重量份。
6.根据权利要求1所述的陶瓷复合材料,其特征在于,所述ZrB2-SiC的含量为82重量份。
7.根据权利要求1所述的陶瓷复合材料,其特征在于,所述ZrB2-SiC的含量为79~82重量份。
8.根据权利要求1所述的陶瓷复合材料,其特征在于,包括以下重量份的成分:ZrB2-SiC79~84份、高岭土25~27.5份、纳米氧化锆8份、纳米氧化铝4~5份、纳米氧化镁3~4.5份、纳米二氧化钛2~4份、碳纤维4.5~5份、玻璃纤维6.5~7份、凹凸棒土6.8~7.5份、硅藻土11.5~13.5份、电气石10.8~13份、麦饭石13~14份、聚乙二醇7.5~8份、硅烷偶联剂4.5~5份。
9.一种如权利要求1至8任一项所述的陶瓷复合材料的制备方法,其特征在于,包括以下步骤:
1)对碳纤维、玻璃纤维预制体进行预处理;预处理操作为:在温度为50℃温度条件下采用质量分数为40%的硝酸中浸泡6h,然后用去离子水冲洗至中性,干燥至恒重备用;
2)浆液配制:按成分含量比例称取ZrB2-SiC粉体、高岭土粉末、纳米氧化锆粉末、纳米氧化铝粉末、纳米氧化镁粉末、纳米二氧化钛粉末、碳纤维粉末、玻璃纤维粉末、凹凸棒土粉末、硅藻土粉末、电气石粉末、麦饭石粉末、聚乙二醇、硅烷偶联剂混合成浆料;各粉末的粒径均为270~325目;
3)浆液浸渍:将步骤1)处理后的碳纤维、玻璃纤维预制体置于步骤2)制备的混合浆料中进行浸渍,然后经热处理、冷却后获得坯体;
浸渍的具体步骤为:
步骤(31),首先在30~33℃温度条件下浸渍3h,然后取出后在60℃温度条件下干燥30h;
步骤(32),然后继续在50~55℃温度条件下浸渍1.5h,然后取出在90℃温度条件下干燥50h;
步骤(33),最后在60℃温度条件下浸渍0.5h,取出后在120℃温度条件下干燥至恒重;
热处理具体操作为:在惰性气氛中,以15℃/min升温速度升温至850℃,热处理1.5h;然后继续以5℃min的升温速度升温至1150℃,热处理1h;
4)对步骤3)之比的坯体进行机械加工;
5)对步骤4)加工后的坯料进行清洗、干燥处理获得成品。
10.根据权利要求9所述的陶瓷复合材料的制备方法,其特征在于,所述ZrB2-SiC粉体由以下方法制成:称取锆英石、氧化硼和活性碳后,在行星式球磨机中干磨2h后混合均匀,以150Mpa的压力制成直径30mm的坯体,120℃/12h干燥后,将坯体埋在SiC粉体中,抽真空后,在流通氩气的气氛炉中进行碳热还原合成ZrB2-SiC粉体。
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