CN116477950B - 一种SiC-MC复相陶瓷先驱体及其复相陶瓷的制备方法 - Google Patents
一种SiC-MC复相陶瓷先驱体及其复相陶瓷的制备方法 Download PDFInfo
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Abstract
本发明公开了一种SiC‑MC复相陶瓷先驱体及其复相陶瓷的制备方法,包括如下步骤:以M(Zr,Ti,Hf)Clx金属氯化物作为超高温陶瓷金属源,以苯丙烯醇为碳源,以富Si‑H键聚硅烷高分子为硅源,二甲苯作为反应介质,加热回流,反应制得SiC‑M(Zr,Ti,Hf)C陶瓷先驱体,将此先驱体固化,高温裂解无机化最终制得SiC‑M(Zr,Ti,Hf)C复相陶瓷。本发明将金属氯化物醇解反应与硅氢加成反应相结合,制备条件温和,过程可控性高,组分易调节,制得M(Zr,Ti,Hf)C、SiC晶相分布均匀、相互嵌入。
Description
技术领域
本发明涉及一种超高温陶瓷的制备方法,特别涉及一种SiC-MC复相陶瓷先驱体及其复相陶瓷的制备方法。
背景技术
随着科技的进步与发展,对新型高温材料在极端条件下的服役性能提出更高要求,以难熔金属碳化物、氮化物和硼化物为代表的超高温陶瓷(Ultra High TemperatureCeramics,UHTCs)因其具有低密度、高硬度、耐高温、耐腐蚀、抗氧化等优异性能而受到广泛的关注与研究。过渡金属(尤其是第IVB族)碳化物M(Zr,Ti,Hf)C作为超高温陶瓷的重要成员,其熔点大于3000℃,硬度大,优良的抗烧蚀性能和化学惰性使其在飞行器热防护、结构材料、涡轮和火箭发动机耐热部件、武器装备、轻质耐磨制动材料、核反应装置等方面具有极大的应用潜力。在高温含氧气氛下,形成的高熔点氧化物,熔融形成氧化膜能够有效抑制含氧气氛向基体内部扩散,从而提高材料的抗氧化耐烧蚀性能。单相超高温陶瓷如ZrC则存在脆性大,抗热震动性差和低温抗氧化性能较差的问题,SiC单相陶瓷虽然能够形成难熔氧化物SiO2玻璃相,但其在超高温含氧条件下发生主动氧化,SiO2玻璃相大量蒸发,黏度逐渐减小,孔洞未能愈合导致基体被氧化。为了进一步提高M(Zr,Ti,Hf)C、SiC陶瓷抗氧化、耐烧蚀性能,将M(Zr,Ti,Hf)C与SiC形成SiC-M(Zr,Ti,Hf)C超高温复相陶瓷材料,在超高温含氧条件下形成硅酸盐氧化层,阻挡含氧气氛向基体内扩散,提高复合材料超高温抗氧化、耐烧蚀能力。
陶瓷材料的制备方法主要有溶胶/凝胶法、碳热还原法和有机先驱体转化法。溶胶/凝胶法在制备过程中除了选用金属醇盐,其中以含锆为代表的如正丙醇锆、乙醇锆作为锆源,还需添加碳源(如蔗糖、糠醛、酚醛树脂、二乙烯基苯等)和螯合剂(如乙酸、水杨酸、乙酰乙酸乙酯、乙酰丙酮等)或是添加其他化学改性剂(如氨水、氢氧化钠、聚乙二醇等)促进溶胶/凝胶反应,将所有原料在溶剂(如乙醇、乙酸等)中混合、反应,接着陈化,干燥,热解得到粉体陶瓷。
碳热还原法是在高温热处理过程中,如氧化锆、硅溶胶与碳源物质(如炭黑、酚醛类化合物)发生还原反应生成无机陶瓷的方法。
有机先驱体转化法是将化学合成得到的有机聚合物经成型、高温热解制得无机陶瓷材料的方法,这种有机聚合物即称为无机陶瓷的先驱体。相较于上文所述的两种方法,有机先驱体转化法在制备陶瓷材料过程中,实现原料在分子层面接触、混合及充分反应,能够根据目标陶瓷材料需求,对陶瓷先驱体进行改性和分子组成设计,制备构型复杂的目标陶瓷材料,使陶瓷材料制备工艺专业化、赋予陶瓷材料功能化、推进陶瓷材料应用领域多元化。有机先驱体转化法制备陶瓷材料生产效率高、适合工业生产、灵活的工艺性和加工性优势使其成为制备陶瓷材料的主要方法,也是未来制备超高温陶瓷材料工艺的发展方向。
发明内容
本发明的目的是提供一种SiC-MC(碳化硅-金属碳化物)复相陶瓷先驱体及其复相陶瓷的制备方法,该制备方法简洁、快速。本发明提出含超高温陶瓷元素、硅、碳的单一来源先驱体制备思路,进而制得SiC-MC复相陶瓷。
为实现上述目的,本发明提供以下技术方案:
本发明提供的这种SiC-MC复相陶瓷先驱体及其复相陶瓷的制备方法,包括如下步骤:
步骤一、以苯丙烯醇为碳源,将苯丙烯醇溶于二甲苯中,搅拌均匀,得到苯丙烯醇二甲苯溶液;
步骤二、以金属氯化物MClx为所述复相陶瓷金属源,将步骤一制得的苯丙烯醇二甲苯溶液加入金属氯化物MClx中,在惰性气氛保护下,加热醇解,制得含乙烯基MC陶瓷先驱体溶液;
步骤三、向步骤二制得的含乙烯基MC陶瓷先驱体溶液中加入富Si-H键聚硅烷高分子,加热回流,发生硅氢加成反应,制得SiC-MC复相陶瓷先驱体;
步骤四、将步骤三制得的SiC-MC复相陶瓷先驱体在惰性气氛保护下固化,然后在高温下裂解,制得SiC-MC复相陶瓷。
优选的,所述步骤一中,苯丙烯醇二甲苯溶液中苯丙烯醇的质量浓度为15%~60%。
优选的,所述步骤二中,金属氯化物MClx和苯丙烯醇的摩尔比为1∶(3~5)。
优选的,所述步骤二中,金属氯化物MClx为ZrCl4、TiCl4、HfCl4中的至少一种。
优选的,所述步骤二中,将苯丙烯醇二甲苯溶液加入金属氯化物MClx中,在惰性气氛保护下,加热醇解,升温速率为2~5℃/min,醇解反应温度为120~180℃,醇解反应时间为2~10h。
优选的,所述步骤三中,所述富Si-H键聚硅烷高分子在常温下为液态;所述富Si-H键聚硅烷高分子的数均相对分子量为700~1100;所述富Si-H键聚硅烷高分子为聚碳硅烷(PCS)、聚甲基硅烷(PMS)中的至少一种。
优选的,所述步骤三中,所述富Si-H键聚硅烷高分子与含乙烯基MC陶瓷先驱体溶液的质量比为1:(5~20)。
优选的,所述步骤三中,硅氢加成反应的反应温度为100~140℃,反应时间为2~10h。
优选的,所述步骤四中,SiC-MC复相陶瓷先驱体在惰性气氛保护下加热固化,升温速率为0.5~2℃/min,固化温度为320~460℃,固化时间为1~2h。
优选的,所述步骤四中,固化后的SiC-MC复相陶瓷先驱体在惰性气氛保护下高温裂解,升温速率为2~5℃/min,裂解温度为1500~1600℃,裂解时间为1~3h。
本发明的原理及有益效果:
本发明以金属氯化物M(Zr,Ti,Hf)Clx、带不饱和官能团的苯丙烯醇分别作为超高温陶瓷的金属来源和碳源,加热搅拌,在惰性气氛保护下,醇解反应制得含乙烯基M(Zr,Ti,Hf)C陶瓷先驱体溶液,以液态富Si-H键聚硅烷高分子作为硅源,将其加入所得含乙烯基M(Zr,Ti,Hf)C陶瓷先驱体溶液中,硅氢加成反应制备SiC-M(Zr,Ti,Hf)C陶瓷先驱体,接着依次进行固化、裂解制得SiC-M(Zr,Ti,Hf)C复相超高温陶瓷。采用醇解反应与硅氢加成反应相结合的方式,制得含超高温元素、硅、碳的单一来源先驱体,进而制备SiC-M(Zr,Ti,Hf)C复相超高温陶瓷。本发明操作过程具有原料易得、反应条件温和、过程可设计性高、组分可设计性强、对实验操作和设备要求低的特点。
附图说明
图1是本发明操作流程图;
图2是实施例1制备的SiC-ZrC复相陶瓷X射线衍射图;
图3是实施例1制备的SiC-ZrC复相陶瓷的SEM二次电子及背散射照片;
图4是实施例6制备的SiC-ZrC-HfC复相陶瓷X射线衍射图;
图5是实施例6制备的SiC-ZrC-HfC复相陶瓷SEM二次电子及背散射照片。
具体实施方式
下面结合实施例进一步阐述本发明技术方案,以下实施例是为了对本发明进行更好的阐述,但不用来限制本发明的范围。
实施例1
步骤1:苯丙烯醇二甲苯溶液的制备。在手套箱中,称取100g苯丙烯醇加至装有磁力搅拌子的三口烧瓶中,封闭三口烧瓶螺口橡胶塞,从手套箱中取出,加入95g二甲苯溶液,室温下搅拌至完全溶解,得到质量浓度为51.28%的苯丙烯醇二甲苯溶液。
步骤2:含乙烯基ZrC陶瓷先驱体的制备。按照四氯化锆与苯丙烯醇摩尔比为1:4配置反应溶液。在手套箱中准确称量10g四氯化锆粉末装于放有磁力搅拌子的三口烧瓶中,封闭三口烧瓶螺口橡胶塞后取出。取步骤1中制得的苯丙烯醇二甲苯溶液44.91g逐渐加至装有四氯化锆粉末的三口烧瓶中,在配有蛇形冷凝管、氩气保护条件下,以2℃/min升温速率升至170℃,回流反应6h,反应结束后自然降温冷却,得到含乙烯基ZrC陶瓷先驱体溶液。
步骤3:SiC-ZrC陶瓷先驱体的制备。搅拌条件下,将液态聚甲基硅烷(Mn=850)加至步骤2制得的含乙烯基ZrC陶瓷先驱体溶液中,其中,含乙烯基ZrC陶瓷先驱体溶液与液态聚甲基硅烷的质量比为20:1,在氩气气氛下,加热至140℃,回流反应10h,聚甲基硅烷与含乙烯基ZrC陶瓷先驱体中的不饱和乙烯基发生硅氢加成反应,最终制得SiC-ZrC陶瓷先驱体。
步骤4:将步骤3制备的SiC-ZrC陶瓷先驱体置于坩埚中,在氩气气氛下,于管式炉中,以1℃/min升至460℃固化1h后,冷却至室温。接着氩气气氛下,从室温以2℃/min升至1600℃,高温裂解1h制得SiC-ZrC复相陶瓷。
本实施例制得的SiC-ZrC复相陶瓷的X射线衍射图如图2所示。从图2可以看出,由本实施例制得的SiC-ZrC复相陶瓷的物相组成为SiC、ZrC,结晶程度高,不存在其他杂质相。
本实施例制得的SiC-ZrC复相陶瓷的SEM二次电子及背散射照片如图3所示。从图3可以观察到,SiC-ZrC复相陶瓷中SiC与ZrC两相分布均匀、相互嵌入。
实施例2
步骤1:同实施例1步骤1。
步骤2:含乙烯基ZrC陶瓷先驱体的制备。按照四氯化锆与苯丙烯醇摩尔比为1:3配置反应溶液。在手套箱中准确称量10g四氯化锆粉末装于放有磁力搅拌子的三口烧瓶中,封闭三口烧瓶螺口橡胶塞后取出。取步骤1苯丙烯醇二甲苯混合溶液33.69g逐渐加至装有四氯化锆粉末的三口烧瓶中,在配有蛇形冷凝管、氩气保护条件下,以3℃/min升温速率升温至140℃,回流反应8h,反应结束后自然降温冷却,得到含乙烯基ZrC陶瓷先驱体溶液。
步骤3:SiC-ZrC陶瓷先驱体的制备。搅拌条件下,将聚碳硅烷(Mn=790)加至步骤2制得的含乙烯基ZrC陶瓷先驱体溶液中,其中,含乙烯基ZrC陶瓷先驱体溶液与聚碳硅烷的质量比为10:1,在氩气气氛下,加热至140℃,回流反应6h,聚碳硅烷与含乙烯基ZrC陶瓷先驱体中的不饱和乙烯基团发生硅氢加成反应,最终制得SiC-ZrC陶瓷先驱体。
步骤4:将步骤3制备的SiC-ZrC陶瓷先驱体置于坩埚中,在氩气气氛下,于管式炉中,以2℃/min升至460℃固化1h后,冷却至室温。接着氩气气氛下,从室温以3℃/min升至1600℃,高温裂解2h制得SiC-ZrC复相陶瓷。
实施例3
步骤1:苯丙烯醇二甲苯溶液的制备。在手套箱中,称取100g苯丙烯醇加至装有磁力搅拌子的三口烧瓶中,封闭三口烧瓶螺口橡胶塞,从手套箱中取出,加入70g二甲苯溶液,室温下搅拌至完全溶解,得到质量浓度为58.82%的苯丙烯醇二甲苯混合溶液。
步骤2:含乙烯基TiC陶瓷先驱体的制备。按照四氯化钛与苯丙烯醇摩尔比为1:4配置反应溶液。在手套箱中准确称量10g四氯化钛装于放有磁力搅拌子的三口烧瓶中,封闭三口烧瓶螺口橡胶塞后取出。取步骤1制得的苯丙烯醇二甲苯混合溶液48.11g逐渐加至装有四氯化钛的三口烧瓶中,在配有蛇形冷凝管、氩气保护条件下,以3℃/min升温速率升至120℃,回流反应2h,反应结束后自然降温冷却,得到含乙烯基TiC陶瓷先驱体溶液。
步骤3:SiC-TiC陶瓷先驱体的制备。搅拌条件下,将液态聚甲基硅烷加至步骤2制得的含乙烯基TiC陶瓷先驱体溶液中,其中,含乙烯基TiC陶瓷先驱体溶液与液态聚甲基硅烷的质量比为5:1,在氩气气氛下,加热至140℃,回流反应2h,聚甲基硅烷与含乙烯基TiC陶瓷先驱体中的不饱和乙烯基团发生硅氢加成反应,最终制得SiC-TiC陶瓷先驱体。
步骤4:将步骤3制备的SiC-TiC陶瓷先驱体置于坩埚中,在氩气气氛下,于管式炉中,以0.5℃/min升至400℃固化1h后,冷却至室温。接着氩气气氛下,从室温以5℃/min升至1500℃,高温裂解1h制得SiC-TiC复相陶瓷。
实施例4
步骤1:苯丙烯醇二甲苯溶液的制备。在手套箱中,称取100g苯丙烯醇加至装有磁力搅拌子的三口烧瓶中,封闭三口烧瓶螺口橡胶塞,从手套箱中取出,加入560g二甲苯溶液,室温下搅拌至完全溶解,得到质量浓度为15.15%苯丙烯醇二甲苯混合溶液。
步骤2:含乙烯基TiC陶瓷先驱体的制备。按照四氯化钛与苯丙烯醇摩尔比为1:3配置反应溶液。在手套箱中准确称量10g四氯化钛装于放有磁力搅拌子的三口烧瓶中,封闭三口烧瓶螺口橡胶塞后取出。取步骤1制得的苯丙烯醇二甲苯混合溶液140.08g逐渐加至装有四氯化钛的三口烧瓶中,在配有蛇形冷凝管、氩气保护条件下,以3℃/min升温速率升至140℃,回流反应10h,反应结束后自然降温冷却,得到含乙烯基TiC陶瓷先驱体溶液。
步骤3:SiC-TiC陶瓷先驱体的制备。搅拌条件下,将聚碳硅烷加至步骤2制得的含乙烯基TiC陶瓷先驱体溶液中,其中,含乙烯基TiC陶瓷先驱体溶液与聚碳硅烷的质量比为20:1,在氩气气氛下,加热至100℃,回流反应10h,聚碳硅烷与含乙烯基TiC陶瓷先驱体中的不饱和乙烯基团发生硅氢加成反应,最终制得SiC-TiC陶瓷先驱体。
步骤4:将步骤3制备的SiC-TiC陶瓷先驱体置于坩埚中,在氩气气氛下,于管式炉中,以0.5℃/min升至460℃固化2h后,冷却至室温。接着在氩气气氛下,从室温以2℃/min升至1600℃,高温裂解3h,制得SiC-TiC复相陶瓷。
实施例5
步骤1:同实施例3步骤1。
步骤2:含乙烯基HfC陶瓷先驱体的制备。按照四氯化铪与苯丙烯醇摩尔比为1:5配置反应溶液。在手套箱中准确称量10g四氯化铪粉末装于放有磁力搅拌子的三口烧瓶中,封闭三口烧瓶螺口橡胶塞后取出。取步骤1制得的苯丙烯醇二甲苯混合溶液35.61g逐渐加至装有四氯化铪粉末的三口烧瓶中,在配有蛇形冷凝管、氩气保护条件下,以5℃/min升温速率升至180℃,回流反应8h,反应结束后自然降温冷却,得到含乙烯基HfC陶瓷先驱体溶液。
步骤3:SiC-HfC陶瓷先驱体的制备。搅拌条件下,将液态聚甲基硅烷加至步骤2制得的含乙烯基HfC陶瓷先驱体溶液中,其中,含乙烯基HfC陶瓷先驱体溶液与液态聚甲基硅烷的质量比为20:1,在氩气气氛下,升温至140℃,回流反应8h,聚甲基硅烷与含乙烯基HfC陶瓷先驱体中的不饱和乙烯基发生硅氢加成反应,最终制得SiC-HfC陶瓷先驱体。
步骤4:将步骤3制备的SiC-HfC陶瓷先驱体置于坩埚中,在氩气气氛下,于管式炉中,以1℃/min升至420℃固化2h后,冷却至室温。接着氩气气氛下,从室温以2℃/min升至1550℃,高温裂解3h制得SiC-HfC复相陶瓷。
实施例6
步骤1:同实施例3步骤1。
步骤2:含乙烯基ZrC-HfC陶瓷先驱体的制备。在手套箱中分别准确称量10g四氯化锆及13.74g四氯化铪粉末装于放有磁力搅拌子的三口烧瓶中,封闭三口烧瓶螺口橡胶塞后取出。取步骤1中制得的苯丙烯醇二甲苯混合溶液78.31g逐渐加至装有四氯化锆及四氯化铪粉末的三口烧瓶中,在配有蛇形冷凝管、氩气保护条件下,以3℃/min升温速率升至180℃,回流反应8h,反应结束后自然降温,得到含乙烯基ZrC-HfC陶瓷先驱体溶液。
步骤3:SiC-ZrC-HfC陶瓷先驱体的制备。搅拌条件下,将液态聚甲基硅烷加至步骤2所制的含乙烯基ZrC-HfC陶瓷先驱体溶液中,含乙烯基ZrC-HfC陶瓷先驱体溶液与液态聚甲基硅烷的质量比为20:1,在氩气气氛下,升温至140℃,回流反应10h,聚甲基硅烷与含乙烯基ZrC-HfC陶瓷先驱体中的不饱和乙烯基发生硅氢加成反应,最终制得SiC-ZrC-HfC复相陶瓷先驱体。
步骤4:将步骤3制备的SiC-ZrC-HfC陶瓷先驱体置于坩埚中,在氩气气氛下,于管式炉中,以1℃/min升至460℃固化2h,冷却至室温。接着在氩气气氛下,从室温以2℃/min升至1600℃,高温裂解2h,制得SiC-ZrC-HfC复相陶瓷。
本实施例制得的SiC-ZrC-HfC复相陶瓷X射线衍射图如图4所示。从图4可以看出,由本实施例制得的SiC-ZrC-HfC复相陶瓷的物相组成为SiC、ZrC、HfC,结晶性能好、结晶程度高。
本实施例制得的SiC-ZrC-HfC复相陶瓷的SEM二次电子及背散射照片如图5所示。从图中可以看出,生成致密SiC-ZrC-HfC复相陶瓷,所形成的陶瓷相之间相互嵌入,未出现相分离。
实施例7
步骤1:同实施例1步骤1。
步骤2:含乙烯基ZrC-TiC陶瓷先驱体的制备。在手套箱中分别准确称量10g四氯化锆及8.14g四氯化钛装于放有磁力搅拌子的三口烧瓶中,封闭三口烧瓶螺口橡胶塞后取出。取步骤1制得的苯丙烯醇二甲苯混合溶液112.28g逐渐加至装有四氯化锆及四氯化钛的三口烧瓶中,在配有蛇形冷凝管、氩气保护条件下,以3℃/min升温速率升至160℃,回流反应8h,反应结束后自然降温,得到含乙烯基ZrC-TiC陶瓷先驱体溶液。
步骤3:SiC-ZrC-TiC陶瓷先驱体的制备。搅拌条件下,将液态聚甲基硅烷加至步骤2制得的含乙烯基ZrC-TiC陶瓷先驱体溶液中,其中,含乙烯基ZrC-TiC陶瓷先驱体溶液与液态聚甲基硅烷的质量比为20:1,在氩气气氛下,以2℃/min升温速率加热至140℃,回流反应10h,聚甲基硅烷与含乙烯基ZrC-TiC陶瓷先驱体中的不饱和乙烯基发生硅氢加成反应,最终制得SiC-ZrC-TiC复相陶瓷先驱体。
步骤4:将步骤3制备的SiC-ZrC-TiC陶瓷先驱体置于坩埚中,在氩气气氛下,于管式炉中,以1℃/min升至460℃固化2h后,冷却至室温。接着在氩气气氛下,从室温以2℃/min升至1600℃,高温裂解2h,制得SiC-ZrC-TiC复相陶瓷。
Claims (6)
1.一种SiC-MC复相陶瓷先驱体及其复相陶瓷的制备方法,包括如下步骤:
步骤一、以苯丙烯醇为碳源,将苯丙烯醇溶于二甲苯中,搅拌均匀,制得苯丙烯醇二甲苯溶液;
步骤二、以金属氯化物MCl x 为复相陶瓷金属源,将步骤一制得的苯丙烯醇二甲苯溶液加入金属氯化物MCl x 中,在惰性气氛保护下,加热醇解,制得含乙烯基MC陶瓷先驱体溶液;
步骤三、向步骤二制得的含乙烯基MC陶瓷先驱体溶液中加入富Si-H键聚硅烷高分子,加热回流,发生硅氢加成反应,制得SiC-MC复相陶瓷先驱体;
步骤四、将步骤三制得的SiC-MC复相陶瓷先驱体在惰性气氛保护下固化,然后在高温下裂解,制得SiC-MC复相陶瓷;
所述步骤一中,苯丙烯醇二甲苯溶液中苯丙烯醇的质量浓度为15%~60%;
所述步骤二中,金属氯化物MCl x 与苯丙烯醇的摩尔比为1: (3~5);金属氯化物MCl x 为ZrCl4、TiCl4、HfCl4中的至少一种;
所述步骤三中,所述富Si-H键聚硅烷高分子与含乙烯基MC陶瓷先驱体溶液的质量比为1 : (5~20)。
2.根据权利要求1所述SiC-MC复相陶瓷先驱体及其复相陶瓷的制备方法,其特征在于,所述步骤二中,将苯丙烯醇二甲苯溶液加入金属氯化物MCl x 中,在惰性气氛保护下,加热醇解,升温速率为2~5℃/min,醇解反应温度为120~180℃,醇解反应时间为2~10 h。
3.根据权利要求1所述SiC-MC复相陶瓷先驱体及其复相陶瓷的制备方法,其特征在于,所述步骤三中,所述富Si-H键聚硅烷高分子在常温下为液态;所述富Si-H键聚硅烷高分子的数均相对分子量为700~1100;所述富Si-H键聚硅烷高分子为聚碳硅烷、聚甲基硅烷中的至少一种。
4.根据权利要求1所述SiC-MC复相陶瓷先驱体及其复相陶瓷的制备方法,其特征在于,所述步骤三中,硅氢加成反应的反应温度为100~140℃,反应时间为2~10 h。
5.根据权利要求1所述SiC-MC复相陶瓷先驱体及其复相陶瓷的制备方法,其特征在于,所述步骤四中,SiC-MC复相陶瓷先驱体在惰性气氛保护下加热固化,升温速率为0.5~2℃/min,固化温度为320~460℃,固化时间为1~2 h。
6.根据权利要求1所述SiC-MC复相陶瓷先驱体及其复相陶瓷的制备方法,其特征在于,所述步骤四中,固化后的SiC-MC复相陶瓷先驱体在惰性气氛保护下高温裂解,升温速率为2~5℃/min,裂解温度为1500~1600℃,裂解时间为1~3 h。
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