CN112028640B - TiC-ZrO2复合粉体及复合纤维的制备方法 - Google Patents

TiC-ZrO2复合粉体及复合纤维的制备方法 Download PDF

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CN112028640B
CN112028640B CN202010729293.2A CN202010729293A CN112028640B CN 112028640 B CN112028640 B CN 112028640B CN 202010729293 A CN202010729293 A CN 202010729293A CN 112028640 B CN112028640 B CN 112028640B
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余磊
纪网金
宋云
张世文
刘辉
王哲飞
刘泉
韦波
王旭红
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Changshu Institute of Technology
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Abstract

本发明公开了一种TiC‑ZrO2复合粉体的制备方法，包括以下步骤：1、称取钛酸四丁酯、正丁醇锆和乙酰丙酮，进行油浴加热混合均匀，然后缓慢滴加去离子水继续油浴加热搅拌，制得透明稳定的聚钛‑锆氧烷前驱体溶液；2、将前驱体溶液进行预处理后在保护气氛下进行高温热处理，制备得到TiC‑ZrO2复合粉体。本发明还公开了一种TiC‑ZrO2复合纤维的制备方法，在得到聚钛‑锆氧烷前驱体溶液后添加PVP为纺丝助剂进行静电纺丝，对前驱体纤维进行预处理后在保护气氛下进行高温热处理，制备得到TiC‑ZrO2复合纤维。本发明方法能够得到组织均匀的TiC‑ZrO2复合材料，制备工艺适于大规模生产。

Description

TiC-ZrO2复合粉体及复合纤维的制备方法
技术领域
本发明涉及一种TiC复合材料的制备方法，特别是涉及一种TiC-ZrO2复合粉体及复合纤维的制备方法。
背景技术
C/SiC复合材料由于其低密度和杰出的热机械性能受到广泛的关注和研究，但是过高的氧化环境条件制约着C/SiC复合材料的应用，因此制备超高温陶瓷涂层，可以用来提高C/SiC复合材料的在高温下抗氧化烧蚀能力。在碳化物陶瓷中SiC和HfC近些年被广泛研究，但是在超高温条件下，它们并不能满足要求，SiC会被迅速地氧化蒸发，而 HfC则会形成多孔的HfO2，所以它们都不是合适的涂层材料。TiC粉体作为一种典型的难熔金属碳化物(熔点3140℃)，硬度高、耐磨性强、热振性能良好，导电率良好的特点，其在超高温(>2000℃)工作环境下，很容易被氧化熔融成TiO2，熔融的TiO2可以填充裂缝和孔隙，保护C/SiC复合材料进一步烧蚀氧化，所以TiC可以作为良好的涂层材料，但是随时间增长熔融层厚度迅速增长并且剥落，成为制约TiC作为涂层用在抗高温烧蚀环境下。ZrO2作为高熔点氧化物被添加到TiC中，可以显著改善TiC涂层的抗烧蚀能力。
目前制备TiC-ZrO2复合材料的方法主要是粉末合成法，如公开号为CN105461300A、公开号为CN101857438A的技术方案。这种方法制备的TiC-ZrO2复合材料混合不均匀，且制备得到的产物颗粒与原料有关，想要制备得到纳米级的产物，所选的原料也必须为纳米级，并且该方法的制备温度要求较高，增加了成本，影响材料的使用性能和推广应用。
发明内容
针对上述现有技术缺陷，本发明的任务在于提供一种TiC-ZrO2复合粉体的制备方法，以及提供一种TiC-ZrO2复合纤维的制备方法，解决制备纳米级复合材料需要采用纳米级原料的问题，解决成品材料均匀性依赖原料粉末混合搅拌的充分程度的问题。
本发明技术方案是这样的：一种TiC-ZrO2复合粉体的制备方法，包括以下步骤：1、称取钛酸四丁酯、正丁醇锆和乙酰丙酮，进行油浴加热混合均匀，然后缓慢滴加去离子水继续油浴加热搅拌，制得透明稳定的聚钛-锆氧烷前驱体溶液；2、将前驱体溶液进行预处理后在保护气氛下进行高温热处理，制备得到TiC-ZrO2复合粉体。
进一步地，所述前驱体溶液进行预处理是在空气气氛下将前驱体溶液加热至 150℃-250℃，保温4-8小时。
进一步地，所述高温热处理时是在惰性气氛下以5℃/min速率升温至800-820℃，保温2-4小时，然后以3℃/min速率升温至1200-1400℃保温1-2小时。
本发明的另一技术方案是这样的：一种TiC-ZrO2复合纤维的制备方法，包括以下步骤：1、称取钛酸四丁酯、正丁醇锆和乙酰丙酮，进行油浴加热混合均匀，然后缓慢滴加去离子水继续油浴加热搅拌，制得透明稳定的聚钛-锆氧烷前驱体溶液；2、以前驱体溶液为溶剂，添加PVP为纺丝助剂，加热搅拌得到透明的纺丝溶液后进行静电纺丝制得前驱体纤维；3、将前驱体纤维进行预处理后在保护气氛下进行高温热处理制备得到 TiC-ZrO2复合纤维。
进一步地，所述前驱体纤维进行预处理是在空气气氛下将前驱体纤维加热至 150℃-250℃，保温10-12小时。
进一步地，所述高温热处理时是在惰性气氛下以5℃/min速率升温至800-820℃，保温2-4小时，然后以3℃/min速率升温至1200-1400℃保温1-2小时。
进一步地，所述钛酸四丁酯、正丁醇锆和乙酰丙酮的摩尔比为1︰1︰6.4-9.6。
进一步地，所述钛酸四丁酯和所述正丁醇锆的摩尔量之和与所述去离子水的摩尔比为1︰5.6-8。
进一步地，所述钛酸四丁酯、正丁醇锆和乙酰丙酮进行油浴加热混合时温度为85-105℃，混合时间为48-72小时，滴加去离子水后温度为100-120℃，继续搅拌5-8小时。
进一步地，所述静电纺丝时的电压为12.0-13.0kV，纺丝针头与接收铝箔板的距离为20-30cm，纺丝液推进速度为0.3-0.5ml/h。
本发明与现有技术相比的优点在于：
1、本发明采用的锆源为正丁醇锆，钛源为钛酸丁酯，采用的正丁醇锆会和乙酰丙酮先形成较稳定的螯合物，可以和钛的螯合物共存，在添加水缩聚反应后，这两种金属元素可以复合形成聚钛-锆氧烷溶液，使得前驱体中锆、钛等元素达到分子级别的接触且分布均匀，因此可以制备出粒径大小为500-700nm左右的TiC-ZrO2粉体和直径为1μm 左右的TiC-ZrO2纤维，且制备得到的TiC-ZrO2复合材料的组分更为均匀，且制备得到的TiC-ZrO2复合材料的组分更为均匀。
2、选用的原料简单，来源广泛易获得，且价格便宜易保存，制备得到的聚钛-锆烷前驱体溶液稳定易保存、流动性好，能够适应大规模工业化生产。
附图说明
图1为实施例1制得的TiC-ZrO2粉体的XRD图。
图2为实施例1制得的TiC-ZrO2粉体的SEM图。
图3为实施例2制得的TiC-ZrO2粉体的SEM图。
图4为实施例2制得的TiC-ZrO2粉体的Mapping图。
图5为实施例3制得的TiC-ZrO2粉体的SEM图。
图6为实施例3制得的TiC-ZrO2粉体的Mapping图。
图7为实施例4制得的TiC-ZrO2纤维的SEM图。
图8为实施例4制得的TiC-ZrO2纤维的Mapping图。
图9为实施例5制得的TiC-ZrO2纤维的SEM图。
图10为实施例5制得的TiC-ZrO2纤维的Mapping图。
图11为实施例6制得的TiC-ZrO2纤维的XRD图。
图12为实施例6制得的TiC-ZrO2纤维的SEM图。
具体实施方式
下面结合实施例对本发明作进一步说明，但不作为对本发明的限定。
实施例1：
称取0.015mol钛酸丁酯(TBOT)，0.015mol正丁醇锆(Zr(OBu)4)和0.096mol乙酰丙酮(Hacac)在85℃下油浴加热均匀混合48小时，并在该温度下缓慢滴加0.168mol 超纯水，升高温度至100℃下油浴加热5小时，水解缩聚制备得到均一稳定透明的液态前驱体。将前驱体在150℃下空气气氛中固化8小时，然后在Ar气氛下，800℃下保温 2小时，之升温至1200℃保温2小时，制备得到TiC-ZrO2复合粉体材料。制得的TiC-ZrO2复合粉体的XRD和SEM图如图1和图2所示。
实施例2：
称取0.015mol钛酸丁酯(TBOT)，0.015mol正丁醇锆(Zr(OBu)4)和0.12mol乙酰丙酮(Hacac)在95℃下油浴加热均匀混合60小时，并在该温度下缓慢滴加0.21mol超纯水，升高温度至110℃下油浴加热6小时，水解缩聚制备得到稳定的均一稳定透明的液态前驱体。将前驱体在200℃下空气气氛中固化6小时，然后在Ar气氛下，800℃下保温3小时，之后在1300℃保温1小时，制备得到TiC-ZrO2复合粉体材料。制得的TiC-ZrO2复合粉体的SEM和Mapping图如图3和图4所示。
实施例3：
称取0.015mol钛酸丁酯(TBOT)，0.015mol正丁醇锆(Zr(OBu)4)和0.144mol乙酰丙酮(Hacac)在105℃下油浴加热均匀混合72小时，并在该温度下缓慢滴加0.24mol 超纯水，升高温度至120℃下油浴加热8小时，水解缩聚制备得到稳定的均一稳定透明的液态前驱体。将前驱体在250℃下空气气氛中固化4小时，然后在Ar气氛下，800℃下保温4小时，之后在1400℃下保温1小时，制备得到TiC-ZrO2复合粉体材料。制得的TiC-ZrO2复合粉体的SEM和Mapping图如图5和图6所示。
实施例4：
称取0.015mol钛酸丁酯(TBOT)，0.015mol正丁醇锆(Zr(OBu)4)和0.096mol乙酰丙酮(Hacac)在85℃下油浴加热均匀混合48小时，并在该温度下缓慢滴加0.168mol 超纯水，升高温度至100℃下油浴加热5小时，水解缩聚制备得到稳定的均一稳定透明的液态前驱体。按质量比称取适量的聚钛-锆氧烷溶液和聚乙烯吡咯烷酮(PVP)(20wt.％)。在80℃下搅拌6小时后冷却至常温继续搅拌4小时形成均一稳定透明的纺丝液，将制备的纺丝液倒入针筒中，放置在推进器上，推进速度为0.3毫升/小时，接收器为铝箔板，电压为12.0千伏，接收板的距离为30厘米。将纺丝制备得到的纤维前驱体，在150℃下预处理12小时，然后在Ar气氛下，800℃下保温2小时，之后在1200℃下保温2小时，制备得到TiC-ZrO2复合纤维材料。制得的TiC-ZrO2复合纤维的SEM和Mapping 图如图7和图8所示。
实施例5：
称取0.015mol钛酸丁酯(TBOT)，0.015mol正丁醇锆(Zr(OBu)4)和0.12mol乙酰丙酮(Hacac)在95℃下油浴加热均匀混合60小时，并在该温度下缓慢滴加0.21mol超纯水，升高温度至110℃下油浴加热6小时，水解缩聚制备得到稳定的均一稳定透明的液态前驱体。按质量比称取适量的聚钛-锆氧烷溶液和聚乙烯吡咯烷酮(PVP)(15wt.％)。在70℃下搅拌5小时后冷却至常温继续搅拌5小时形成均一稳定透明的纺丝液，将制备的纺丝液倒入针筒中，放置在推进器上，推进速度为0.4毫升/小时，接收器为铝箔板，电压为12.5千伏，接收板的距离为25厘米。将纺丝制备得到的纤维前驱体，在200℃下预处理10小时，然后在Ar气氛下，800℃下保温3小时，之后在1300℃下保温1小时，制备得到TiC-ZrO2复合纤维材料。制得的TiC-ZrO2复合纤维的SEM和Mapping 图如图9和图10所示。
实施例6：
称取0.015mol钛酸丁酯(TBOT)，0.015mol正丁醇锆(Zr(OBu)4)和0.144mol乙酰丙酮(Hacac)在105℃下油浴加热均匀混合72小时，并在该温度下缓慢滴加0.24mol 超纯水，升高温度至120℃下油浴加热8小时，水解缩聚制备得到稳定的均一稳定透明的液态前驱体。按质量比称取适量的聚钛-锆氧烷溶液和聚乙烯吡咯烷酮(PVP)(10wt.％)。在60℃下搅拌4小时后冷却至常温继续搅拌6小时形成均一稳定透明的纺丝液，将制备的纺丝液倒入针筒中，放置在推进器上，推进速度为0.5毫升/小时，接收器为铝箔板，电压为13.0千伏，接收板的距离为20厘米。将纺丝制备得到的纤维前驱体，在250℃下预处理8小时，然后在Ar气氛下，800℃下保温4小时，之后在1400℃下保温1小时，制备得到TiC-ZrO2复合纤维材料。制得的TiC-ZrO2复合纤维的XRD和SEM图如图11和图12所示。

Claims (7)

1.一种 TiC-ZrO2 复合粉体的制备方法，其特征在于，包括以下步骤：1、按摩尔比为1︰1︰6.4-9.6称取钛酸四丁酯、正丁醇锆和乙酰丙酮，进行油浴加热至 85-105℃均匀混合48-72 小时，然后缓慢滴加去离子水继续油浴加热至 100-120℃，继续搅拌 5-8 小时，制得透明稳定的聚钛-锆氧烷前驱体溶液；2、将前驱体溶液进行预处理后在保护气氛下进行高温热处理，制备得到 TiC-ZrO2 复合粉体。
2.根据权利要求1所述的TiC-ZrO2复合粉体的制备方法，其特征在于，所述钛酸四丁酯和所述正丁醇锆的摩尔量之和与所述去离子水的摩尔比为1︰5.6-8。
3.根据权利要求1所述的TiC-ZrO2复合粉体的制备方法，其特征在于，所述前驱体溶液进行预处理是在空气气氛下将前驱体溶液加热至150℃-250℃，保温4-8小时，所述高温热处理时是在惰性气氛下以5℃/min速率升温至800-820℃，保温2-4小时，然后以3℃/min速率升温至1200-1400℃保温1-2小时。
4.一种TiC-ZrO2复合纤维的制备方法，其特征在于，包括以下步骤：1、按摩尔比为 1︰1︰6.4-9.6称取钛酸四丁酯、正丁醇锆和乙酰丙酮，进行油浴加热至85-105℃均匀混合48-72小时，然后缓慢滴加去离子水继续油浴加热至100-120℃，继续搅拌5-8小时，制得透明稳定的聚钛-锆氧烷前驱体溶液；2、以前驱体溶液为溶剂，添加PVP为纺丝助剂，加热搅拌得到透明的纺丝溶液后进行静电纺丝制得前驱体纤维；3、将前驱体纤维进行预处理后在保护气氛下进行高温热处理制备得到TiC-ZrO2复合纤维。
5.根据权利要求4所述的TiC-ZrO2复合纤维的制备方法，其特征在于，所述钛酸四丁酯和所述正丁醇锆的摩尔量之和与所述去离子水的摩尔比为1︰5.6-8。
6.根据权利要求4所述的TiC-ZrO2复合纤维的制备方法，其特征在于，所述前驱体纤维进行预处理是在空气气氛下将前驱体纤维加热至150℃-250℃，保温10-12小时，所述高温热处理时是在惰性气氛下以5℃/min速率升温至800-820℃，保温2-4小时，然后以3℃/min速率升温至1200-1400℃保温1-2小时。
7.根据权利要求4所述的TiC-ZrO2复合纤维的制备方法，其特征在于，所述静电纺丝时的电压为12.0-13.0 kV，纺丝针头与接收铝箔板的距离为20-30cm，纺丝液推进速度为0.3-0.5 ml/h。
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