CN113735569A - 一种氧化镁氮化硼复合微球的制备方法 - Google Patents

一种氧化镁氮化硼复合微球的制备方法 Download PDF

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CN113735569A
CN113735569A CN202111089188.8A CN202111089188A CN113735569A CN 113735569 A CN113735569 A CN 113735569A CN 202111089188 A CN202111089188 A CN 202111089188A CN 113735569 A CN113735569 A CN 113735569A
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boron nitride
magnesium oxide
composite microspheres
powder
heating
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CN113735569B (zh
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陈煌
尹志坚
李海静
肖展业
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Ningbo Siporai Machinery Remanufacturing Co ltd
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Abstract

本发明涉及一种氧化镁氮化硼复合微球的制备方法，以氧化镁粉体和氮化硼粉体为原料制备浆料，依次经过造粒、排胶处理和煅烧后，得到氧化镁氮化硼复合微球。本发明制备的氧化镁氮化硼复合微球结构致密，机械强度好，球形度高，可达96％以上，兼具很好的流动性，可实现在导热体系中高填充，同时大大降低氮化硼的用量，可节约导热粉体综合成本60％以上。本发明以碳酸钙‑氧化钇为烧结助剂，有效地促进了氮化硼晶体生长并呈现连续的架桥搭接方式，从而使整个氧化镁氮化硼复合微球导热粉表现出热传导各向同性。整个工艺简单，在制备过程中不使用危险化学品，不产生“三废”，对环境友好，适合大规模工业化推广，具有良好的经济效益和应用前景。

Description

一种氧化镁氮化硼复合微球的制备方法
技术领域
本发明属于多功能陶瓷粉体领域，涉及一种氧化镁氮化硼复合微球的制备方法，主要应用在电子行业导热填料和热喷涂涂层领域。
背景技术
随着5G时代的到来，5G新技术应用将推动导热材料及器件需求快速提升。高性能的通讯设备、计算机、智能手机、汽车等终端产品的广泛使用带动导热器件及相关产业应用迅速扩大的同时，电子元器件日趋小型化和集成化，从而对设备的散热性能提出了越来越高的要求。导热性高、比重低、介电常数低、耐高温、制品设计度高逐渐成为中高端导热绝缘材料的发展趋势。六方氮化硼因其独特的电绝缘性能、优异的导热及化学稳定性、超低的介电常数及热膨胀系数逐渐成为导热填料的最佳选择。
目前，电子散热行业主流绝缘导热填料应用的是球形氧化铝粉末，传统的球形氧化铝填料具有较好的绝缘性能，并且具有很好的流动性，可以致密地填充在空隙中，但氧化铝的导热系数较低(30wm-1K-1)、密度大(3.9g/cm3)、硬度高。氮化硼的导热系数(125wm-1K-1)相比于氧化铝更高，但是氮化硼为六方片状，密度较轻，大量填充后体系粘度会显著上升，作为填料会产生更多的空隙，不能充分发挥其优良的导热性能。其次，六方氮化硼的结构与石墨类似，具有六方层状结构，导热具有各向异性，其本身的结构特征使得其在体系应用时很容易产生趋向性且难以实现高填充。此外，相比于氧化铝，氮化硼的原料成本要高很多，如果制备成微米级球形氮化硼粉体后成本将继续大幅度上升，这极大地限制了其应用的普及。
发明内容
鉴于现有技术中存在的问题，本发明公开了一种新型氧化镁氮化硼复合微球的制备工艺，通过将六方氮化硼与更廉价的导热材料氧化镁(密度 3.58g/cm3，导热系数36wm- 1K-1)进行复合，既降低氮化硼的用量，节约成本，又可有效解决六方片状氮化硼导热各向异性和低填充量的问题，具体良好的经济效益和应用前景。
为达此目的，本发明采用以下技术方案：
本发明提供了一种氧化镁氮化硼复合微球的制备方法，所述方法包括以下步骤：
(1)以氧化镁粉体和氮化硼粉体为原料制备浆料，经过造粒后得到复合微球；
(2)对步骤(1)得到的复合微球进行排胶处理；
(3)将步骤(2)处理后的复合微球进行煅烧，得到氧化镁氮化硼复合微球。
本发明利用制备浆料、造粒、排胶、高温煅烧的方法，将氧化镁和氮化硼复合得到了致密的氧化镁氮化硼复合微球，其结构致密，中位粒径分布在30微米到200微米之间，具有良好的机械强度。
本发明采用的氮化硼材料优选六方氮化硼。
本发明中步骤1所述制备浆料的具体方法为：将氧化镁粉体、碳酸钙粉体和氧化钇粉体混合，加入聚乙烯醇溶液和水后混合搅拌，然后加入氮化硼粉体，搅拌后得到高固相低粘度浆料。
本发明在制备浆料过程中加入了一定量的碳酸钙粉体和氧化钇粉体作为烧结助剂，能够有效促进了六方氮化硼晶体生长并呈现连续的架桥搭接方式，从而使整个氧化镁氮化硼复合微球导热粉表现出热传导各向同性。并且，碳酸钙和氧化钇的加入能够在喷雾干燥制粒阶段有利于形成大小均匀的复合微球，增加微球的球化度。
本发明中所述氧化镁粉体、碳酸钙粉体、氧化钇粉体、聚乙烯醇溶液和水的质量比为1:(0.02-0.05):(0.01-0.02):(0.05-0.15):(1-1.2)。
本发明中所述氧化镁粉体和氮化硼粉体的质量比为1:(0.1-0.6)。其具体的比例可根据实际需求进行调整。
本发明中所述聚乙烯醇溶液的浓度为5-15wt％。
本发明中步骤(1)中采用喷雾干燥的方法进行造粒，所述喷雾干燥的温度为180-300℃。
本发明步骤(2)所述排胶处理的工艺为：对步骤(1)得到的复合微球分别进行第一阶段的升温、保温处理，第二阶段的升温、保温处理，第三阶段的升温、保温处理以及第四阶段的升温、保温处理。
本发明所述第一阶段的升温、保温处理为：将所述复合微球从室温以 8-10℃/min的速率升温至220-250℃保温2-3h；
所述第二阶段的升温、保温处理为：从220-250℃以10-15℃/min的速率升温至420-460℃保温1-3h；
所述第三阶段的升温、保温处理为：从420-460℃以4-8℃/min的速率升温至610-650℃保温4-6h；
所述第四阶段的升温、保温处理为：最后升温至750-850℃保温1-6h。
上述四个阶段连续进行，即第一阶段升温、保温后，在此基础上进入第二阶段升温、保温，以此类推。
排胶处理是将材料内部过多的有机物分解并氧化排除，若排胶不充分则会在材料内部留下一定量有机物残余，烧结时，有机物熔融、分解、挥发，导致变形、裂纹等缺陷。同时，由于有机物含碳量多，当氧气不足形成还原气氛时，会影响烧结质量。因此，需要在坯体烧成前将其中的有机物完全排除干净，以保证产品的形状和质量的要求。
目前常规的排胶处理一般为在某个温度(约100-400℃)保温一段时间，但往往不能完全排除有机物，通常会有约10-20％的残余，后续煅烧时影响材料的质量。
本发明在排胶处理过程中采用了连续进行的四个阶段的升温、保温处理，通过控制温度梯度、不同阶段的升温速率和保温时间，能够最大程度的排除复合微球中的有机物，有机物排除率可达99.5％左右。
作为本发明优选的方案，所述氧化镁氮化硼复合微球的制备方法包括以下步骤：
(1)按照1:(0.02-0.05):(0.01-0.02):(0.05-0.15):(1-1.2)的质量比将氧化镁粉体、碳酸钙粉体、氧化钇粉体、5-15wt％的聚乙烯醇溶液和水混合搅拌均匀，然后加入氧化镁粉体质量0.1-0.6倍的氮化硼粉体，搅拌均匀后得到浆料，利用喷雾干燥的方法在180-300℃下对所述浆料进行造粒，得到复合微球；
(2)对步骤(1)得到的复合微球进行排胶处理，具体工艺为：将所述复合微球从室温以8-10℃/min的速率升温至220-250℃保温2-3h，然后以 10-15℃/min的速率升温至420-460℃保温1-3h，然后以4-8℃/min的速率升温至 610-650℃保温4-6h，最后升温至750-850℃保温1-6h。
(3)将步骤(2)处理后的复合微球在1400-1900℃下进行煅烧处理，得到氧化镁氮化硼复合微球。
本发明通过将六方氮化硼与更廉价的导热材料氧化镁(密度3.58g/cm3，导热系数36wm-1K-1)进行复合，既降低氮化硼的用量，节约成本，又有效解决了六方片状氮化硼导热各向异性和低填充量的问题，非常适合作为导热填料使用。
本发明提供的制备方法同样适用于氧化铝、氧化硅、碳化硅，氮化硅和氮化硼复合微球的制备，为了制备能够最终销售的成品，可以采取控制喷雾干燥工艺条件将氧化镁氮化硼微球进行粒径控制处理的方法，也可以将制备好的氧化镁氮化硼微球根据导热粉体粒径要求进行气流分级。
与现有技术方案相比，本发明至少具有以下有益效果：
(1)本发明制备的氧化镁氮化硼复合微球导热粉，结构致密，球形度高，可达96％以上，兼具很好的流动性，可实现在导热体系中高填充。
(2)本发明制备的氧化镁氮化硼复合微球具有良好的机械强度。
(3)本发明以碳酸钙-氧化钇为烧结助剂，有效地促进了六方氮化硼晶体生长并呈现连续的架桥搭接方式，从而使整个氧化镁氮化硼复合微球导热粉表现出热传导各向同性。
(4)本发明通过将六方氮化硼与更廉价的导热材料氧化镁微球复合，大大降低氮化硼的用量，可节约导热粉体综合成本60％以上。
(5)本发明优化了排胶处理工艺，在排胶处理过程中采用了连续进行的四个阶段的升温、保温处理，通过控制温度梯度、不同阶段的升温速率和保温时间，最大程度排除了材料内部的有机物，排除率可达99.5％左右。
(6)本发明氧化镁氮化硼复合微球导热粉工艺简单，适于工业生产。在制备过程中不使用危险化学品，不产生“三废”，对环境友好，适合大规模工业化推广和应用。
具体实施方式
为更好地说明本发明，便于理解本发明的技术方案，本发明的典型但非限制性的实施例如下：
实施例1
本实施例提供了一种氧化镁氮化硼复合微球的制备方法，包括以下工艺步骤：
第一步：将氧化镁粉体800g、碳酸钙粉体30g、氧化钇粉体8g、10wt％的 PVA(聚乙烯醇)水溶液和超纯水1000g均匀混合制备成浆料，高速搅拌 30min；
第二步：将第一步混合好的浆料加入氮化硼粉体240g，添加过程中不断高速搅拌；
第三步：将上述步骤(1)中的浆料利用喷雾干燥工艺方法在220℃下造粒形成中位粒径范围30-200微米的复合微球；
第四步：将第三步中的喷雾干燥得到的复合微球进行排胶处理，具体排胶工艺为：从室温以9℃/min的速率升温至230℃保温2.5h；从230℃以12℃/min 的速率升温至450℃保温2h；从450℃以6℃/min的速率升温至650℃保温5h；最后升温至800℃保温4h，有机物去除率为99.7％；
第五步：将第四步得到的复合微球在1500℃高温煅烧处理2h，得到结构致密的氧化镁氮化硼复合微球导热粉，球化率高达97％，但六方氮化硼片体没有出现明显的晶体生长。
实施例2
本实施例与实施例1的制备过程基本相同，区别在于将高温煅烧的温度提高到1850℃，得到结构致密的氧化镁氮化硼复合微球导热粉，球化率高达97％，六方氮化硼片体出现晶体生长，晶体形状变得更加完整。
实施例3
氧化镁氮化硼复合微球的制备方法，包括以下工艺步骤：
第一步：将氧化镁粉体1000g、碳酸钙粉体35g、氧化钇粉体10g、10wt％的 PVA水溶液和超纯水1000g均匀混合制备成浆料；高速搅拌30min；
第二步：将第一步混合好的浆料加入氮化硼粉体300g，添加过程中不断高速搅拌；
第三步：将上述步骤(1)中的浆料利用喷雾干燥工艺方法在220℃下造粒形成中位粒径范围30-200微米的复合微球；
第四步：将第三步中的喷雾干燥得到的复合微球进行排胶处理，具体排胶工艺为：从室温以8℃/min的速率升温至220℃保温3h；从220℃以10℃/min的速率升温至420℃保温3h；从420℃以4℃/min的速率升温至610℃保温6h；最后升温至750℃保温6h，有机物去除率为99.5％；
第五步：将第四步得到的复合微球在1800℃高温煅烧处理2h，得到结构致密的氧化镁氮化硼复合微球导热粉，球化率高达97％。通过提高浆料的浓度和烧结助剂配比，六方片状氮化硼晶形完整，氧化镁氮化硼复合微球结构变得更加致密。
实施例4
氧化镁氮化硼复合微球的制备方法，包括以下工艺步骤：
第一步：将氧化镁粉体1000g、碳酸钙粉体35g、氧化钇粉体10g、10wt％的 PVA水溶液和超纯水1000g均匀混合制备成浆料；高速搅拌30min；
第二步：将第一步混合好的浆料加入氮化硼粉体300g，另添加第二种50g 小粒径氮化硼粉作为片状生长的原材料，添加过程中不断高速搅拌；
第三步：将上述步骤(1)中的浆料利用喷雾干燥工艺方法在250℃下造粒形成中位粒径范围30-200微米的复合微球；
第四步：将第三步中的喷雾干燥得到的复合微球进行排胶处理，具体排胶工艺为：从室温以10℃/min的速率升温至250℃保温2h；从250℃以15℃/min 的速率升温至460℃保温1h；从460℃以8℃/min的速率升温至650℃保温4h；最后升温至850℃保温1.5h，有机物去除率为99.7％；
第五步：将第四步得到的复合微球在1900℃高温煅烧处理2h，得到结构致密的氧化镁氮化硼复合微球导热粉，球化率高达98％。通过进一步提高煅烧温度六方片状氮化硼晶形更完整，小粒径氮化硼被大粒径颗粒熔合消失，同时微球中氮化硼片体厚度明显变厚。
对比例1
本对比例与实施例4的制备过程基本相同，区别在于在制备浆料阶段不加入碳酸钙粉体和氧化钇粉体，即无烧结助剂。得到的氧化镁氮化硼复合微球球化率为75％。
对比例2
本对比例与实施例4的制备过程基本相同，区别在于在排胶过程仅采用一次升温保温阶段，即将喷雾干燥后的复合微球从室温升温至250℃保温8.5h，排胶处理后有机物去除率为81.3％，得到的氧化镁氮化硼复合微球部分区域出现裂纹。
对比例3
本对比例与实施例4的制备过程基本相同，区别在于在排胶过程仅采用一次升温保温阶段，即将喷雾干燥后的复合微球从室温以升温至460℃保温8.5h，排胶处理后有机物去除率为85.7％，得到的氧化镁氮化硼复合微球球体不均匀，局部产生细小的裂纹。
对比例4
本对比例与实施例4的制备过程基本相同，区别在于在排胶过程仅采用一次升温保温阶段，即将喷雾干燥后的复合微球从室温以升温至650℃保温8.5h，排胶处理后有机物去除率为86.9％，得到的氧化镁氮化硼复合微球球体不均匀，部分区域产生较大的“凹坑”。
对比例5
本对比例与实施例4的制备过程基本相同，区别在于在排胶过程仅采用一次升温保温阶段，即将喷雾干燥后的复合微球从室温以升温至850℃保温8.5h，排胶处理后有机物去除率为92.0％，得到的氧化镁氮化硼复合微球球体不均匀，整体产生一定的形变。
以上详细描述了本发明的优选实施方式，但是，本发明并不限于上述实施方式中的具体细节，在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，这些简单变型均属于本发明的保护范围。
另外需要说明的是，在上述具体实施方式中所描述的各个具体技术特征，在不矛盾的情况下，可以通过任何合适的方式进行组合，为了避免不必要的重复，本发明对各种可能的组合方式不再另行说明。
此外，本发明的各种不同的实施方式之间也可以进行任意组合，只要其不违背本发明的思想，其同样应当视为本发明所公开的内容。

Claims (10)

1.一种氧化镁氮化硼复合微球的制备方法，其特征在于，所述方法包括以下步骤：
(1)以氧化镁粉体和氮化硼粉体为原料制备浆料，经过造粒后得到复合微球；
(2)对步骤(1)得到的复合微球进行排胶处理；
(3)将步骤(2)处理后的复合微球进行煅烧，得到氧化镁氮化硼复合微球。
2.根据权利要求1所述的氧化镁氮化硼复合微球的制备方法，其特征在于，步骤1所述制备浆料的具体方法为：将氧化镁粉体、碳酸钙粉体和氧化钇粉体混合，加入聚乙烯醇溶液和水后混合搅拌，然后加入氮化硼粉体，搅拌后得到浆料。
3.根据权利要求2所述的氧化镁氮化硼复合微球的制备方法，其特征在于，所述氧化镁粉体、碳酸钙粉体、氧化钇粉体、聚乙烯醇溶液和水的质量比为1:(0.02-0.05):(0.01-0.02):(0.05-0.15):(1-1.2)。
4.根据权利要求2所述的氧化镁氮化硼复合微球的制备方法，其特征在于，所述氧化镁粉体和氮化硼粉体的质量比为1:(0.1-0.6)。
5.根据权利要求2所述的氧化镁氮化硼复合微球的制备方法，其特征在于，所述聚乙烯醇溶液的浓度为5-15wt％。
6.根据权利要求1所述的氧化镁氮化硼复合微球的制备方法，其特征在于，步骤(1)中采用喷雾干燥的方法进行造粒，所述喷雾干燥的温度为180-300℃。
7.根据权利要求1所述的氧化镁氮化硼复合微球的制备方法，其特征在于，步骤(2)所述排胶处理的工艺为：对步骤(1)得到的复合微球分别进行第一阶段的升温、保温处理，第二阶段的升温、保温处理，第三阶段的升温、保温处理以及第四阶段的升温、保温处理。
8.根据权利要求7所述的氧化镁氮化硼复合微球的制备方法，其特征在于，所述第一阶段的升温、保温处理为：将所述复合微球从室温以8-10℃/min的速率升温至220-250℃保温2-3h；
所述第二阶段的升温、保温处理为：以10-15℃/min的速率升温至420-460℃保温1-3h；
所述第三阶段的升温、保温处理为：以4-8℃/min的速率升温至610-650℃保温4-6h；
所述第四阶段的升温、保温处理为：升温至750-850℃保温1-6h。
9.根据权利要求1所述的氧化镁氮化硼复合微球的制备方法，其特征在于，步骤(3)所述煅烧的温度为1400-1900℃。
10.根据权利要求1所述的氧化镁氮化硼复合微球的制备方法，其特征在于，所述方法包括以下步骤：
(1)按照1:(0.02-0.05):(0.01-0.02):(0.05-0.15):(1-1.2)的质量比将氧化镁粉体、碳酸钙粉体、氧化钇粉体、5-15wt％的聚乙烯醇溶液和水混合搅拌均匀，然后加入氧化镁粉体质量0.1-0.6倍的氮化硼粉体，搅拌均匀后得到浆料，利用喷雾干燥的方法在180-300℃下对所述浆料进行造粒，得到复合微球；
(2)对步骤(1)得到的复合微球进行排胶处理，具体工艺为：将所述复合微球从室温以8-10℃/min的速率升温至220-250℃保温2-3h，然后以10-15℃/min的速率升温至420-460℃保温1-3h，然后以4-8℃/min的速率升温至610-650℃保温4-6h，最后升温至750-850℃保温1-6h。
(3)将步骤(2)处理后的复合微球在1400-1900℃下进行煅烧处理，得到氧化镁氮化硼复合微球。
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