CN111470867B - 一种碳化锆陶瓷空心微球及其制备方法 - Google Patents
一种碳化锆陶瓷空心微球及其制备方法 Download PDFInfo
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Abstract
本发明涉及一种碳化锆陶瓷空心微球及其制备方法。一种碳化锆陶瓷空心微球的制备方法，包括下列步骤：将含有聚锆氧烷、酚醛树脂和溶剂的前驱体溶液喷雾干燥，得到前驱体空心微球；将所述空心微球依次排胶碳化、烧结，得到碳化锆陶瓷空心微球。本发明以聚锆氧烷、酚醛树脂为原料，采用喷雾干燥法，不涉及高压条件，且工艺简单，既解决了现有技术不容易工业化大规模生产的问题，也解决了现有陶瓷空心微球耐温性低的问题。
Description
技术领域
本发明涉及空心微球领域，特别涉及一种碳化锆陶瓷空心微球及其制备方法。
背景技术
空心微球是一种具有球形中空结构的轻质颗粒粉体材料，具有绝热、隔音、高强度、耐腐蚀、化学稳定、分散性优良等特点。近年来它广泛应用于填充材料领域，例如：涂层材料中的填充物；海洋开发研究的深水技术浮力材料；航天航空和船舶技术设计中的轻质化结构材料填充剂等。
目前空心玻璃微球在这些领域中得到了广泛的应用，它在化学成分上主要由硅酸盐玻璃体系组成，通常优先采用的是含若干氧化物添加物的碱金属或碱土金属硼硅酸盐组成体系。在众多的空心玻璃微球制造专利技术中，已应用于工业化生产空心玻璃微球的制造技术目前主要是美国3M公司采用的固相玻璃粉末法和美国PQ公司采用的液相雾化法以及中科院理化所采用的软化学法。
3M公司固相玻璃粉末法的主要路线是：先将硅源、硼源及碱金属盐加发泡剂高温熔融，然后水淬，研磨粉碎，过筛分级得粗产品，再经高温发泡形成空心玻璃微球，所需高温为1200-1600℃。3M公司在美国申请了很多专利(如US3129086、US3230064、US 3365315、US4391646)，这些专利文件对其进行了详细描述，同时在中国申请了发明专利CN101068753A，此工艺的缺陷是工序复杂，能源消耗高。PQ公司液相雾化法的主要路线是：先将硅源和硼源混合形成均匀水溶液，然后喷雾干燥形成前驱体空心微球，最后将此微球在较低温度下烧结形成硼硅酸钠空心玻璃微球。美国专利US 5534348对此工艺进行了详细描述，此工艺的缺陷是：制备的空心微球碱性大，强度低，易吸水，团聚。中科院理化所软化学法的主要路线是：先将硅源、硼源、稳定剂、发泡剂、溶剂等混合研磨制备得到稳定浆料，再将此浆料进行喷雾干燥，筛分得到多孔的类球形前驱体微球，最后将此微球在600～1100℃烧结得到空心玻璃微球。中国专利CN105271784A对此工艺进行了详细描述，此工艺的缺陷同样是工艺复杂，且很难保证原料在浆料中的均匀分布。
以上广泛应用的空心玻璃微球耐温等级较低，软化点较低，应用范围有限。
为解决以上问题，研究人员将目光转向了陶瓷，将陶瓷做成空心结构得到的微球具有更高的耐温等级。中国专利申请CN102923771A利用锆酸正丁酯作为锆源，冰醋酸做络合剂，乙醇为溶剂，采用溶剂热法制备了粒径在4～6μm的氧化锆空心微球，但此方法需要高温高压的反应条件；反应过程复杂，微球形貌难以调控。专利申请CN101585708A以硝酸铝为铝源，葡萄糖炭化后微球作为模板，水热法制备得到氧化铝溶胶包裹碳模板的复合微球，将微球高温烧结后得到刚玉空心微球，其缺点在于工艺比较复杂，无法大规模制备。
可见，目前陶瓷空心微球的制备工艺存在因工艺条件苛刻或工艺过于复杂导致不容易工业化大规模生产的问题。
发明内容
本发明的目的在于提供一种碳化锆陶瓷空心微球的制备方法，该方法以聚锆氧烷、酚醛树脂为原料，采用喷雾干燥法，不涉及高压条件，且工艺简单，既解决了现有技术不容易工业化大规模生产的问题，也解决了现有陶瓷空心微球耐温性低的问题。
为了实现以上目的，本发明提供了以下技术方案：
一种碳化锆陶瓷空心微球的制备方法，包括下列步骤：
将含有聚锆氧烷、酚醛树脂和溶剂的前驱体溶液喷雾干燥，得到前驱体空心微球；
将所述空心微球依次排胶碳化、烧结，得到碳化锆陶瓷空心微球；
其中，所述前驱体溶液中酚醛树脂和聚锆氧烷的质量比优选为10-40：100，更优选为25-35:100。
本发明采用的碳源和锆源都可以均匀溶解于溶剂中，形成具有分子分散级别的透明溶液，为产品的均匀性和稳定性提供了先决条件，之后经过排胶碳化原位生成碳化锆晶粒，烧结后晶粒增长生成球壳结构。在以上过程中，碳化前和碳化后锆源和碳源均均匀分布于微球球壁，并且采用喷雾干燥方式，容易实现规模化和连续化生产，生产效率高，易于工业化生产。
本发明中所述的酚醛树脂主要提供碳源，因此可采用任意类型的酚醛树脂，可根据取材难度、碳化烧结难度等调整酚醛树脂的类型。
本发明中所述的聚锆氧烷主要用于提供锆源，聚锆氧烷的合成可以参照文献：TaoXY,Qiu WF,Li H,Zhao T,Wei XY.New route to synthesize preceramic polymers forzirconium carbide.Chinese Chemical Letters.2012；23:1075-1078。
本发明所述的溶剂选用利于聚锆氧烷、酚醛树脂溶解的类型。
本发明的排胶碳化过程主要在石墨炉中进行。
另外，在排胶碳化后和烧结前可对空心微球进行筛选，筛除形状不规则或者破壳的残渣等，筛选手段包括但不限于浮选等。在浮选之后可以烘干进行下一步。
在以上基础上，各步骤的工艺条件还可以进一步改进，具体如下。
优选地，所述前驱体溶液中还含有稳定剂，所述稳定剂为有机酸，优选对甲苯磺酸、甲酸、乙酸的一种或多种混合物，更优选对甲苯磺酸。
这些稳定剂有助于提高前驱体溶液的稳定性，延长其稳定时间。
优选地，所述稳定剂与聚锆氧烷的质量比为0.01～40:100，例如0.01:100、0.1:100、1:100、10:100、20:100、30:100、40:100等，优选5～30:100。
优选地，所述聚锆氧烷中锆的质量分数为25～40％，例如25％、26％、27％、28％、29％、30％、35％或40％等。
优选地，所述溶剂为乙醇、正丙醇、异丙醇、乙二醇甲醚、乙二醇乙醚、甲苯、二甲苯中的一种或多种混合物，优选乙醇或正丙醇。
优选地，所述前驱体溶液中聚锆氧烷的浓度为10％-60％，优选50％-60％。
优选地，所述喷雾干燥过程中，采用二流体雾化或离心雾化手段实现前驱体溶液的雾化，干燥温度为100～280℃。
优选地，所述排胶碳化的方法为：在排胶炉中于惰性气氛下，以0.5～10℃/min的速度升温至600～800℃，保温0.5～3h；
优选地，所述排胶碳化的方法为：在排胶炉中于惰性气氛下，以1～3℃/min的速度升温至700℃，保温2h。
优选地，所述烧结的方法为：于真空或惰性气氛下，以0.5～10℃/min的速度升温至1300～1600℃，保温0.5～3h；
优选地，所述烧结的方法为：于真空或惰性气氛下，以3～8℃/min的速度升温至1500℃，保温2h。
综上，与现有技术相比，本发明达到了以下技术效果：
(1)本发明制备的空心微球为碳化锆ZrC，是超高温陶瓷的一种，熔点达到3240℃，相比现有的氧化物陶瓷空心微球具有更高的耐温性；
(2)本发明选用的原料适宜喷雾干燥法制得前驱体空心微球，因喷雾干燥法具有生产效率高、能连续化生产，这解决了现有技术不容易规模化生产的难题；
(3)酚醛树脂与聚锆氧烷在常用溶剂中的溶解性好，降低了生产难度；
(4)本发明的制备方法不涉及高压环境，工艺比现有技术更温和；
(5)本发明制备的空心微球为碳化锆ZrC，相比现有的硅酸盐空心微球具有更高的耐温等级，应用范围更广。
附图说明
通过阅读下文优选实施方式的详细描述，各种其他的优点和益处对于本领域普通技术人员将变得清楚明了。附图仅用于示出优选实施方式的目的，而并不认为是对本发明的限制。而且在整个附图中，用相同的参考符号表示相同的部件。
图1为实施例1制得碳化锆空心陶瓷微球的SEM图；
图2为实施例1碳化后乙醇中上浮的空心微球SEM图；
图3为实施例1制得碳化锆空心陶瓷微球的XRD图。
具体实施方式
下面将结合实施例对本发明的实施方案进行详细描述，但是本领域技术人员将会理解，下列实施例仅用于说明本发明，而不应视为限制本发明的范围。实施例中未注明具体条件者，按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者，均为可以通过市售购买获得的常规产品。
以下所有实施例所用的酚醛树脂为蔚林化工WL-1806。
实施例1
将510g聚锆氧烷(锆含量为32.38wt.％)溶于1000g正丙醇中，搅拌至完全溶解，加入34g 75％的对甲苯磺酸水溶液，搅拌均匀后加入酚醛树脂WL-1806(蔚林化工)170g，搅拌均匀形成红棕色透明溶液。
将得到的溶液利用二流体雾化设备进行喷雾干燥得到前驱体空心微球粉体；干燥温度240℃。
将得到的前驱体空心微球粉体置于排胶炉中排胶，氩气气氛下自室温以3℃/min的升温速度至700℃，保温时间2h后自然降至室温；将排胶后的粉体用乙醇浮选，取乙醇中上浮的粉体于70℃烘箱烘干。
将烘干后的粉体置于石墨炉中，氩气气氛下以5℃/min的升温速度升温至1500℃，保温2h，5℃/min降至室温。得到碳化锆陶瓷空心微球，得到的空心微球形貌如图1和2所示，XRD如图3所示。
实施例2：
将525g聚锆氧烷(锆含量为31.36wt.％)溶于875g正丙醇中，搅拌至完全溶解，加入34g75％的对甲苯磺酸水溶液，搅拌均匀后加入酚醛树脂170g，搅拌均匀形成红棕色透明溶液；
将得到的溶液利用二流体雾化设备进行喷雾干燥得到前驱体空心微球粉体；干燥温度200℃。
将得到的前驱体空心微球粉体置于排胶炉中排胶，氩气气氛下自室温以3℃/min的升温速度至700℃，保温时间2h后自然降至室温；将排胶后的粉体用乙醇浮选，取乙醇中上浮的粉体于70℃烘箱烘干。
将烘干后的粉体置于石墨炉中，氩气气氛下以5℃/min的升温速度升温至1500℃，保温2h，5℃/min降至室温。得到碳化锆陶瓷空心微球。
实施例3：
将525g聚锆氧烷(锆含量为36.88wt.％)溶于1225g正丙醇中，搅拌至完全溶解，加入40g75％的对甲苯磺酸水溶液，搅拌均匀后加入酚醛树脂200g，搅拌均匀形成红棕色透明溶液。
将得到的溶液利用二流体雾化设备进行喷雾干燥得到前驱体空心微球粉体；干燥温度200℃。
将得到的前驱体空心微球粉体置于排胶炉中排胶，氩气气氛下自室温以5℃/min的升温速度至700℃，保温时间2h后自然降至室温；将排胶后的粉体用乙醇浮选，取乙醇中上浮的粉体于70℃烘箱烘干。
将烘干后的粉体置于石墨炉中，氩气气氛下以5℃/min的升温速度升温至1600℃，保温2h，5℃/min降至室温。得到碳化锆陶瓷空心微球。
实施例4：
将525g聚锆氧烷(锆含量为36.88wt.％)溶于1225g正丙醇中，搅拌至完全溶解，加入40g75％的对甲苯磺酸水溶液，搅拌均匀后加入酚醛树脂200g，搅拌均匀形成红棕色透明溶液。
将得到的溶液利用离心雾化设备进行喷雾干燥得到前驱体空心微球粉体；干燥温度120℃。
将得到的前驱体空心微球粉体置于排胶炉中排胶，氩气气氛下自室温以5℃/min的升温速度至700℃，保温时间2h后自然降至室温；将排胶后的粉体用乙醇浮选，取乙醇中上浮的粉体于70℃烘箱烘干。
将烘干后的粉体置于石墨炉中，氩气气氛下以5℃/min的升温速度升温至1600℃，保温2h，5℃/min降至室温。得到碳化锆陶瓷空心微球。
以上所述，仅为本发明较佳的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，可轻易想到的变化或替换，都应涵盖在本发明的保护范围之内。因此，本发明的保护范围应以所述权利要求的保护范围为准。
Claims (15)
1.一种碳化锆陶瓷空心微球的制备方法，其特征在于，包括下列步骤：
将含有聚锆氧烷、酚醛树脂和溶剂的前驱体溶液喷雾干燥，得到前驱体空心微球；将所述空心微球依次排胶碳化、烧结，得到碳化锆陶瓷空心微球；所述溶剂为乙醇或正丙醇；
所述排胶碳化的方法为：在排胶炉中于惰性气氛下，以0.5～10℃/min的速度升温至600～800℃，保温0.5～3h；
所述烧结的方法为：于真空或惰性气氛下，以0.5～10℃/min的速度升温至1300～1600℃，保温0.5～3h。
2.根据权利要求1所述的制备方法，其特征在于，所述前驱体溶液中酚醛树脂和聚锆氧烷的质量比为10-40：100。
3.根据权利要求1所述的制备方法，其特征在于，所述前驱体溶液中酚醛树脂和聚锆氧烷的质量比为25-35:100。
4.根据权利要求1所述的制备方法，其特征在于，所述前驱体溶液中还含有稳定剂，所述稳定剂为有机酸。
5.根据权利要求4所述的制备方法，其特征在于，所述稳定剂为对甲苯磺酸、甲酸、乙酸的一种或多种混合物。
6.根据权利要求4所述的制备方法，其特征在于，所述稳定剂为对甲苯磺酸。
7.根据权利要求4所述的制备方法，其特征在于，所述稳定剂与聚锆氧烷的质量比为0.01～40:100。
8.根据权利要求4所述的制备方法，其特征在于，所述稳定剂与聚锆氧烷的质量比为5～30:100。
9.根据权利要求1所述的制备方法，其特征在于，所述聚锆氧烷中锆的质量分数为25～40％。
10.根据权利要求1所述的制备方法，其特征在于，所述前驱体溶液中聚锆氧烷的浓度为10％-60％。
11.根据权利要求1所述的制备方法，其特征在于，所述前驱体溶液中聚锆氧烷的浓度为20％-50％。
12.根据权利要求1-11任一项所述的制备方法，其特征在于，所述喷雾干燥过程中，采用二流体雾化或离心雾化手段实现前驱体溶液的雾化，干燥温度为100～280℃。
13.根据权利要求1-11任一项所述的制备方法，其特征在于，
所述排胶碳化的方法为：在排胶炉中于惰性气氛下，以1～3℃/min的速度升温至700℃，保温2h。
14.根据权利要求1-11任一项所述的制备方法，其特征在于，
所述烧结的方法为：于真空或惰性气氛下，以3～8℃/min的速度升温至1500℃，保温2h。
15.采用权利要求1-14任一项所述的制备方法制得的碳化锆陶瓷空心微球。
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