CN116835986A - 一种先驱体转化法制备碳化铪陶瓷的方法及陶瓷块体材料的碳化铪 - Google Patents
一种先驱体转化法制备碳化铪陶瓷的方法及陶瓷块体材料的碳化铪 Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 67
- 239000000919 ceramic Substances 0.000 title claims abstract description 53
- 239000002243 precursor Substances 0.000 title claims abstract description 52
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 35
- 239000000463 material Substances 0.000 title claims description 13
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- DFIPXJGORSQQQD-UHFFFAOYSA-N hafnium;tetrahydrate Chemical compound O.O.O.O.[Hf] DFIPXJGORSQQQD-UHFFFAOYSA-N 0.000 claims abstract description 21
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- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 14
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- 238000002360 preparation method Methods 0.000 claims description 11
- 229910052735 hafnium Inorganic materials 0.000 claims description 10
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- PDPJQWYGJJBYLF-UHFFFAOYSA-J hafnium tetrachloride Chemical compound Cl[Hf](Cl)(Cl)Cl PDPJQWYGJJBYLF-UHFFFAOYSA-J 0.000 claims description 6
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- 150000002362 hafnium Chemical class 0.000 claims description 4
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- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
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- 229910010293 ceramic material Inorganic materials 0.000 description 1
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- 229910002804 graphite Inorganic materials 0.000 description 1
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- 229910000449 hafnium oxide Inorganic materials 0.000 description 1
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
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Abstract
本发明涉及一种先驱体转化法制备碳化铪陶瓷的方法及陶瓷块体材料的碳化铪，通过凝胶‑溶胶法制备碳化铪前驱体与使其反应烧结产生碳化铪的工艺方法。采用氢氧化铪凝胶、聚乙烯醇树脂与乙二醇混合后固化干燥的方式制备碳化铪前驱体。经过热处理反应烧结制备碳化铪陶瓷。采取氢氧化铪凝胶、聚乙烯醇树脂与乙二醇混合后固化干燥的方式制备的碳化铪前驱体，经过热处理反应烧结制备碳化铪陶瓷中聚乙烯醇树脂、乙二醇与氢氧化铪凝胶之间产生氢键作用，得到碳化铪陶瓷块体成品。本发明中原材料简单易得、安全环保，工艺简易方便、节约成本。最终烧结产物碳化铪陶瓷均匀性好、致密度高、纯净度高。
Description
技术领域
本发明属于陶瓷材料领域，涉及一种先驱体转化法制备碳化铪陶瓷的方法及陶瓷块体材料的碳化铪，具体涉及一种通过凝胶-溶胶法制备碳化铪前驱体与使其反应烧结产生碳化铪的工艺方法。
背景技术
碳化铪熔点高达3900℃左右，是最耐高温的二元化合物之一，同时莫氏硬度高达9，在飞行器高温热结构部件中具有优异的应用前景，然而，由于它具有的高熔点和高硬度属性，碳化铪陶瓷难以直接加工成所需零件结构。传统的碳化铪合成方法包括化学气相沉积法、碳热还原二氧化铪、液相先驱体转化法等，这些方法存在合成过程污染大、成本高、无法精确成型等缺点。
文献1“Low thermal conductivity and high porosity ZrC and HfC ceramicsprepared by in-situ reduction reaction/partial sintering method for ultrahightemperature applications,Heng Chen,Huimin Xiang,Fu-Zhi Dai,Jiachen Liu,Yanchun Zhou.Journal of Materials Science&Technology,2019,35(12):2778-2784.”报道了通过使用炭黑高温还原二氧化铪制备碳化铪粉体的方法，该过程属固相反应，但固相反应存在反应物接触不充分，产品均匀性差，容易含有未反应物残余的缺点。
文献2“Synthesis of a novel single-source precursor for HfC ceramicsand its feasibility for the preparation of Hf-based ceramic fibres,Jun Cheng,Xiazhou Wang,Jun Wang,Hao Wang.Ceramics International,2018,44(6):7305-7309.”报道了通过四氯化铪、乙二胺和烯丙胺液相混合后固化制备的聚合物在高温下热解产生碳化铪纤维的方法。该方法原料中聚合物需要单独合成，工序复杂、成本较高；其中选用的有机原料具有毒性，可能造成污染，与当前清洁环保理念不符。
由此可见，提出一种新的低成本低毒环保的碳化铪前驱体，同时能满足碳化铪陶瓷最终产品均匀性、致密度和纯净度等要求的新方法，有着非常重要的意义。
先前已有的制备碳化铪的方法存在难以充分反应或前驱体合成复杂、成本高、毒性高等缺点，同时受限于合成粉体或纤维等微小尺度结构，制备构件需要以碳化铪粉体在2500℃再次高温烧结，成本较高。
本发明中提出一种新型碳化铪前驱体，使用聚乙烯醇和乙二醇等安全低毒有机物在水溶液中与氢氧化铪凝胶均匀混合，固化干燥得到碳化铪前驱体，之后通过高温热处理获得碳化铪陶瓷。本发明工艺简单环保，原料易于获取，可以一次性直接获得碳化铪陶瓷块体产品，同时所需烧结温度更低，节约成本，所制备碳化铪产品均匀性好、致密度高、纯净度高。
发明内容
要解决的技术问题
为了避免现有技术的不足之处，本发明提出一种先驱体转化法制备碳化铪陶瓷的方法及陶瓷块体材料的碳化铪，所要解决的是传统碳化铪陶瓷工艺存在的不足。
技术方案
一种先驱体转化法制备碳化铪陶瓷的方法，其特征在于通过凝胶-溶胶法制备碳化铪前驱体与使其反应烧结产生碳化铪，制备步骤如下：
步骤1：取铪源物质充分溶于水，加入过量碱性溶液产生氢氧化铪凝胶沉淀并过滤；
步骤2：在氢氧化铪凝胶中加入聚乙烯醇溶液和乙二醇，充分混合搅拌均匀后固化干燥，得到碳化铪前驱体；
步骤3：将所得碳化铪前驱体进行高温热处理，反应烧结得到碳化铪陶瓷。
所述聚乙烯醇溶液添加量与所加铪源物质中铪原子摩尔比为0:1-3:1。
所述乙二醇添加量与所加铪源物质中铪原子摩尔比为0:1-3:1。
所述步骤2的固化干燥过程，温度范围在0-100℃。
所述步骤3的高温热处理过程，温度范围在1500-2500℃。
所述铪源物质采用铪盐。
所述铪盐包括但不限于四氯化铪或氯氧化铪。
所述碱性溶液包括但不限于氨水、氢氧化钠溶液、氢氧化钾溶液、碳酸钠溶液、碳酸钾溶液、乌洛托品溶液中任意一种。
一种所述先驱体转化法制备的方法制备的陶瓷块体材料的碳化铪陶瓷，其特征在于：采取氢氧化铪凝胶、聚乙烯醇树脂与乙二醇混合后固化干燥的方式制备的碳化铪前驱体，经过热处理反应烧结制备碳化铪陶瓷中聚乙烯醇树脂、乙二醇与氢氧化铪凝胶之间产生氢键作用，得到碳化铪陶瓷块体成品。
有益效果
本发明提出的一种先驱体转化法制备碳化铪陶瓷的方法及陶瓷块体材料的碳化铪，通过凝胶-溶胶法制备碳化铪前驱体与使其反应烧结产生碳化铪的工艺方法。采用氢氧化铪凝胶、聚乙烯醇树脂与乙二醇混合后固化干燥的方式制备碳化铪前驱体。经过热处理反应烧结制备碳化铪陶瓷。本发明中原材料简单易得、安全环保，工艺简易方便、节约成本。最终烧结产物碳化铪陶瓷均匀性好、致密度高、纯净度高。
碳化铪陶瓷由于熔点过高难以熔化，很难像其它陶瓷一样烧结。在这里提出一种可以通过反应烧结获得碳化铪陶瓷的新型碳化铪前驱体。采用氢氧化铪凝胶与聚乙烯醇树脂、乙二醇等低成本绿色环保有机材料，分别做铪源与碳源，将这些原料混合后固化干燥制备碳化铪前驱体。采取的溶剂是水，与已有工艺中所采用的有机溶剂相比，具有低毒、低污染等优点，满足了绿色化学的要求。
氢氧化铪凝胶、聚乙烯醇树脂、乙二醇与作为溶剂的水，由于都含有羟基结构，可以相互产生稳定的氢键结合，因此聚乙烯醇树脂与乙二醇溶解在水中形成溶液，同时与氢氧化铪凝胶形成均匀混合的溶胶。在固化干燥过程中，溶胶中的水分不断蒸发，逐渐陈化产生凝胶，其中氢氧化铪逐渐转化为二氧化铪，最终与保留下来的聚乙烯醇树脂与乙二醇形成了传统工艺难以实现的均匀的固态混合物，即为所制碳化铪前驱体。
将获取的碳化铪前驱体高温热处理完成反应烧结。在高温热处理过程中，聚乙烯醇树脂与乙二醇作为还原剂与碳源，发生热解并还原二氧化铪产生碳化铪，得到碳化铪陶瓷块体成品。由于碳源与铪源接触充分，反应充分彻底，在反应烧结过程中形成了紧密结合，残余碳源物质分解为气态物质挥发无残留，从而充分保证了碳化铪陶瓷产品的均匀性、致密度和纯净度。
本发明相比于已有碳化铪制备方法，原材料简单易得、安全环保，工艺简易方便、节约成本。传统工艺产生碳化铪陶瓷粉体后，仍需再次烧结处理才能获得块体结构，本发明所制碳化铪前驱体仅需一次反应烧结制得碳化铪陶瓷块体成品。
附图说明
图1为本发明制备的一种碳化铪前驱体高温烧结产品SEM照片。前驱体反应烧结后凝结成均匀致密的陶瓷块体材料，而非传统碳化铪制备工艺产生的仍需再次高温烧结的碳化铪粉体材料。
图2为图1所述产品的XRD测试结果。其中所有显示的峰均为碳化铪的特征峰，而并没有出现二氧化铪和石墨等常见杂质的特征峰，证明产品是高度纯净的碳化铪陶瓷。
具体实施方式
现结合实施例、附图对本发明作进一步描述：
实施例1：
1)原料配制：取3.203g四氯化铪充分溶于40ml水，加入5ml浓氨水产生氢氧化铪含水沉淀
2)将上述沉淀过滤洗涤，去除沉淀中氯离子和铵离子；
3)分别称取聚乙烯醇含量为0.4405g的聚乙烯醇溶液和0.3104g乙二醇加入上述沉淀，充分混合搅拌均匀；
4)将上述的混合物在70℃下固化干燥得到碳化铪前驱体；
5)反应烧结：将上述碳化铪前驱体以5℃/min的速度加热至1800℃保温2h，自然冷却至室温得到碳化铪产品。产品SEM照片如图1所示，产品XRD测试结果如图2所示。
实施例2：
1)原料配制：取3.203g四氯化铪充分溶于40ml水，加入5ml浓氨水产生氢氧化铪含水沉淀
2)将上述沉淀过滤洗涤，去除沉淀中氯离子和铵离子；
3)分别称取聚乙烯醇含量为0.5507g的聚乙烯醇溶液和0.1552g乙二醇加入上述沉淀，充分混合搅拌均匀；
4)将上述的混合物在70℃下固化干燥得到碳化铪前驱体；
5)反应烧结：将上述碳化铪前驱体以5℃/min的速度加热至1800℃保温2h，自然冷却至室温得到碳化铪产品。
实施例3：
1)原料配制：取3.203g四氯化铪充分溶于40ml水，加入5ml浓氨水产生氢氧化铪含水沉淀
2)将上述沉淀过滤洗涤，去除沉淀中氯离子和铵离子；
3)称取聚乙烯醇含量为0.6608g的聚乙烯醇溶液加入上述沉淀，充分混合搅拌均匀；
4)将上述的混合物在70℃下固化干燥得到碳化铪前驱体；
5)反应烧结：将上述碳化铪前驱体以5℃/min的速度加热至1800℃保温2h，自然冷却至室温得到碳化铪产品。
本发明相比于已有碳化铪制备方法，原材料简单易得、安全环保，工艺简易方便、节约成本。传统工艺产生碳化铪陶瓷粉体后，仍需再次烧结处理才能获得块体结构，本发明所制碳化铪前驱体仅需一次反应烧结制得碳化铪陶瓷块体成品。
Claims (9)
1.一种先驱体转化法制备碳化铪陶瓷的方法，其特征在于通过凝胶-溶胶法制备碳化铪前驱体与使其反应烧结产生碳化铪，制备步骤如下：
步骤1：取铪源物质充分溶于水，加入过量碱性溶液产生氢氧化铪凝胶沉淀并过滤；
步骤2：在氢氧化铪凝胶中加入聚乙烯醇溶液和乙二醇，充分混合搅拌均匀后固化干燥，得到碳化铪前驱体；
步骤3：将所得碳化铪前驱体进行高温热处理，反应烧结得到碳化铪陶瓷。
2.根据权利要求1所述先驱体转化法制备碳化铪陶瓷的方法，其特征在于：所述聚乙烯醇溶液添加量与所加铪源物质中铪原子摩尔比为0:1-3:1。
3.根据权利要求1所述先驱体转化法制备碳化铪陶瓷的方法，其特征在于：所述乙二醇添加量与所加铪源物质中铪原子摩尔比为0:1-3:1。
4.根据权利要求1所述先驱体转化法制备碳化铪陶瓷的方法，其特征在于：所述步骤2的固化干燥过程，温度范围在0-100℃。
5.根据权利要求1所述先驱体转化法制备碳化铪陶瓷的方法，其特征在于：所述步骤3的高温热处理过程，温度范围在1500-2500℃。
6.根据权利要求1所述先驱体转化法制备碳化铪陶瓷的方法，其特征在于：所述铪源物质采用铪盐。
7.根据权利要求1所述先驱体转化法制备碳化铪陶瓷的方法，其特征在于：所述铪盐包括但不限于四氯化铪或氯氧化铪。
8.根据权利要求1所述先驱体转化法制备碳化铪陶瓷的方法，其特征在于：所述碱性溶液包括但不限于氨水、氢氧化钠溶液、氢氧化钾溶液、碳酸钠溶液、碳酸钾溶液、乌洛托品溶液中任意一种。
9.一种权利要求1～8任一项所述先驱体转化法制备的方法制备的陶瓷块体材料的碳化铪陶瓷，其特征在于：采取氢氧化铪凝胶、聚乙烯醇树脂与乙二醇混合后固化干燥的方式制备的碳化铪前驱体，经过热处理反应烧结制备碳化铪陶瓷中聚乙烯醇树脂、乙二醇与氢氧化铪凝胶之间产生氢键作用，得到碳化铪陶瓷块体成品。
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| KR20200078395A (ko) * | 2018-12-21 | 2020-07-01 | 한국세라믹기술원 | 하프늄 카바이드 세라믹 전구체 및 이를 이용한 하프늄 카바이드 세라믹의 제조방법 |
| CN112142471A (zh) * | 2020-09-21 | 2020-12-29 | 西北工业大学 | 一种碳化锆陶瓷前驱体及制备方法 |
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| CN108083808A (zh) * | 2016-11-21 | 2018-05-29 | 武汉科技大学 | 一种纳米碳化铪陶瓷有机前驱体及其制备方法 |
| KR20200078395A (ko) * | 2018-12-21 | 2020-07-01 | 한국세라믹기술원 | 하프늄 카바이드 세라믹 전구체 및 이를 이용한 하프늄 카바이드 세라믹의 제조방법 |
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