CN104177091B - 一种高致密度六方氮化硼陶瓷材料的制备方法 - Google Patents

一种高致密度六方氮化硼陶瓷材料的制备方法 Download PDF

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CN104177091B
CN104177091B CN201410393724.7A CN201410393724A CN104177091B CN 104177091 B CN104177091 B CN 104177091B CN 201410393724 A CN201410393724 A CN 201410393724A CN 104177091 B CN104177091 B CN 104177091B
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powder
hbn
preparation
ethanol
tetraethoxy
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CN104177091A (zh
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张建峰
吴玉萍
李改叶
洪晟
郭文敏
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Hohai University HHU
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Priority to AU2014403693A priority patent/AU2014403693B2/en
Priority to KR1020167015455A priority patent/KR101821218B1/ko
Priority to PCT/CN2014/084358 priority patent/WO2016023200A1/zh
Priority to GB1609488.0A priority patent/GB2534530B/en
Priority to RU2016121911A priority patent/RU2662488C1/ru
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Abstract

本发明公开了一种高致密度六方氮化硼(hBN)陶瓷材料的制备方法，该方法采用正硅酸乙酯为原料在hBN粉体表面包覆均匀分散的SiO2纳米粒子层，然后采用无压烧结法获得高致密度的hBN陶瓷材料，制备的hBN陶瓷材料相对致密度达到80％以上。本发明的制备方法操作简单、工艺条件容易控制，成本低廉，通过在hBN粉体表面包覆SiO2实现SiO2烧结助剂的均匀分散，结合高温无压烧结获得高致密度的hBN陶瓷，在降低SiO2的使用量的同时提高hBN的高温使用温度及高温性能。

Description

一种高致密度六方氮化硼陶瓷材料的制备方法
技术领域
本发明属于材料加工领域，具体地涉及一种高致密度六方氮化硼陶瓷材料的制备方法。
背景技术
六方氮化硼(hBN)又称白色石墨，具有与石墨类似的层状结构。因其具有良好的电绝缘性、低介电常数及介电损耗、高温稳定、良好的润滑性及化学惰性、对金属不润湿等诸多优点，被广泛用作高温环境下的固体润滑剂、铸造成型和注射成型中的蜕膜剂、真空镀铝用蒸发舟、透波材料等等。
六方氮化硼陶瓷通常是由三氯化硼经过氮化或者氨分解后形成的粉末，与氧化硼烧结剂球磨混合，经过无压烧结、热压、热分解或者燃烧技术而制成。但由于hBN在C轴方向的结合力远远小于垂直于C轴方向的结合力，晶体主要沿板面方向生长，沿厚度方向的生长比较缓慢，从而形成片状晶体结构。这种片状晶体结构烧结时形成卡片搭桥结构，起到相互支撑的作用，阻碍材料的收缩，从而使得获得的hBN陶瓷致密度较低。例如，Hagio等人采用球磨方法将hBN粉体进行机械化学活化后，在2000℃的烧结温度下得到hBN陶瓷的致密度为1.64g·cm-3，只有理论密度的70％(JournaloftheAmericanCeramicSociety，72(8)1482-1484(1989))。Kurita等人采用AlN和无定形B为添加剂，在1500℃、N2气氛下无压烧结，获得相对密度为75.8％的hBN材料(Shigen-to-Sozai；105(2)201-204(1989))。
添加B2O3、Al2O3、Y2O3和SiO2等氧化物作为烧结助剂，通过在烧结时产生液相来提高烧结时的扩散系数和烧结动力，是解决hBN陶瓷致密度的一个有效措施。特别是SiO2，不仅能够促进hBN的烧结与致密化，还能提高hBN的抗氧化性和高温下的使用温度，因此受到人们的广泛关注。Chen等人在高压氮气气氛下燃烧制备了hBN陶瓷，并研究了SiO2对于hBN致密度的影响。研究结果发现，未添加SiO2的hBN致密度为71～75％，而添加重量百分比为10wt.％的SiO2后，hBN的致密度提高到了75.4～78％，表明SiO2的添加有效提高了hBN的致密度。但另外一个方面，由于球磨混料中SiO2难以均匀分散，相对密度仍然较低(低于80％)。(JournalofMaterialsScienceLetters，19(2000)81-83)。韩杰才等人在其公开专利中，(中国发明专利，公开号CN1310149A)，采用燃烧合成工艺方法制备了hBN陶瓷。将反应原料预先压制胚后，在不小于70MPa的N2压力下，进行自蔓延燃烧反应，添加了重量比不大于60％的SiO2粉末，合成了hBN-SiO2复合材料。但同样由于原料混合不均匀，复合材料的致密度仍然较低。
发明内容
发明目的：为解决现有技术中存在的技术问题，本发明提供一种操作简单、工艺条件容易控制的高致密度六方氮化硼陶瓷材料的制备方法，提高了六方氮化硼陶瓷材料的致密度和抗氧化性。
技术方案：解决上述技术问题，本发明提出了一种高致密度六方氮化硼陶瓷材料的制备方法，包括如下步骤：
(1)将hBN粉体加入去离子水中，搅拌配制成hBN粉体-去离子水的混合物；
(2)向步骤(1)所得的混合物中滴加乙醇，滴加乙醇的质量与上述混合物的质量比为0.08～0.1；然后，继续向混合物中滴加浓氨水至溶液pH值为9～10，其中，浓氨水的质量分数为28％，待混合物混合均匀后，再继续缓慢滴加正硅酸乙酯和乙醇的混合溶液，直至混合溶液中正硅酸乙酯和步骤(1)中去离子水的摩尔比为1∶4～1∶8，滴加完成后，密封瓶口，继续反应5～20小时；
(3)步骤(2)反应结束后，过滤得到的粉体，将所述粉体烘干并研磨过筛；
(4)将步骤(3)得到的过筛的粉体在高真空炉中预烧，预烧后再次均匀研磨过筛；
(5)将步骤(4)得到的粉体进行冷等静压成型，然后在N2气氛下进行高温无压烧结，然后保温1～3h，得到样品；
(6)烧结实验结束后，降温取出样品。
其中，所述hBN粉体的纯度大于98％，粒径≤10μm，hBN粉体的质量与去离子水的质量比为0.008～0.015。
具体地，步骤(1)中的搅拌条件为：采用磁力搅拌，搅拌速率为10～1000rpm，搅拌时间为1～10小时，优选地，搅拌条件为：在搅拌速率为600～800rpm下磁力搅拌6～8小时。
优选地，步骤(2)中，乙醇的滴加速度为1～10ml/min；浓氨水的滴加速度为1～10ml/min；正硅酸乙酯和乙醇的混合溶液的滴加速度为1～20ml/min。更为优选地，乙醇的滴加速度为4～6ml/min；浓氨水的滴加速度为4～6ml/min；正硅酸乙酯和乙醇的混合溶液的滴加速度为10～15ml/min。
作为优选，在步骤(2)正硅酸乙酯和乙醇的混合溶液中，正硅酸乙酯与乙醇的质量比为(1∶5)～(1∶10)。
在步骤(3)中，粉体的烘干条件为在90～110℃下烘干10～30小时；粉体的研磨条件为过200目筛2～4次。
步骤(4)中，粉体与少的条件为：预烧温度为700-900℃，预烧时间0.5～5h，研磨条件为过200目筛2～4次。
步骤(5)中，冷等静压成型的成型压力100～200MPa。
步骤(5)中，烧结温度为1600～1900℃。
有益效果：与现有技术相比，本发明具有如下优点：
(1)采用正硅酸乙酯水解方式在hBN粉体表面包覆SiO2纳米层，方法简单，成本低廉；
(2)通过在hBN粉体表面包覆SiO2实现SiO2烧结助剂的均匀分散，结合高温无压烧结获得高致密度的hBN陶瓷，在降低SiO2的使用量的同时提高hBN的高温使用温度及高温性能。
附图说明
图1为实施例2中2-1号实验的hBN粉体表面包覆SiO2纳米层的透射电镜图。
具体实施方式
实施例1
将市售hBN粉体10g(纯度大于98％，粒径为1μm)放入1000ml去离子水溶液中，用磁力搅拌器在600rpm的搅拌速率下磁力搅拌7小时，得到hBN粉体-去离子水的混合液，然后向该混合液中以5ml/min的速度滴加100ml的乙醇，然后继续5ml/min的速度滴加28wt％浓氨水直至溶液的pH值为9，待混合均匀后，再继续以8ml/min的速度缓慢滴加正硅酸乙酯和乙醇的混合液(正硅酸乙酯与乙醇的质量比为1∶5)，同时继续用磁力搅拌器搅拌，直至溶液中H2O和TEOS的摩尔比为8∶1，用聚氯乙烯薄膜密封瓶口，继续反应20小时；过滤粉体，90℃烘干30小时，在研钵中研磨后，过200目筛3次；然后在高真空炉中在900℃下预烧2h，然后再次均匀研磨，过200目筛3次；将预烧研磨后的粉体进行180MPa冷等静压成型，在N2气氛下进行无压烧结；烧结温度为1900℃，保温时间为3h，烧结实验结束后，降温取出样品。重复上述实验2次，分别记为1-1、1-2和1-3。
实施例2
将市售hBN粉体10g(纯度大于98％，粒径为3μm)放入1000ml去离子水溶液中，用磁力搅拌器在800rpm的搅拌速率下磁力搅拌8小时，得到hBN粉体-去离子水的混合液，然后向该混合液中以8ml/min的速度滴加100ml的乙醇，然后继续8ml/min的速度滴加28wt％浓氨水直至溶液的pH值为9，待混合均匀后，再继续在磁力搅拌的条件下以10ml/min的速度缓慢滴加正硅酸乙酯和乙醇的混合液(正硅酸乙酯与乙醇的质量比为1∶6)，直至溶液中H2O和TEOS的摩尔比为7∶1，用聚氯乙烯薄膜密封瓶口，反应10小时；过滤粉体，100℃烘干24小时，在研钵中研磨后，过200目筛3次；将干燥后的粉体在高真空炉中在800℃预烧4h，预烧后均匀研磨，然后过200目筛3次；将预烧研磨后的粉体进行200MPa冷等静压成型，在N2气氛下进行无压烧结；烧结温度为1800℃，保温时间为3h，烧结实验结束后，降温取出样品。对样品进行透射电镜表征，结果如图1所示。重复上述实验2次，分别记为2-1、2-2和2-3。
实施例3
将市售hBN粉体10g(纯度大于98％，粒径为5μm)放入1000ml去离子水溶液中，用磁力搅拌器在700rpm的搅拌速率下磁力搅拌9小时，得到hBN粉体-去离子水的混合液，然后向该混合液中以10ml/min的速度滴加100ml的乙醇，然后继续以10ml/min的速度滴加28wt％浓氨水直至溶液的pH值为9，待混合均匀后，再继续在磁力搅拌的条件下以12ml/min的速度缓慢滴加正硅酸乙酯和乙醇的混合液(正硅酸乙酯与乙醇的质量比为1∶7)直至溶液中H2O和TEOS的摩尔比为6∶1；用聚氯乙烯薄膜密封瓶口，反应15小时；过滤粉体，110℃烘干20小时，在研钵中研磨后，过200目筛3次；将干燥后的粉体在900℃高真空炉中预烧，预烧后均匀研磨并过200目筛3次；将预烧研磨后的粉体进行150MPa冷等静压成型，在N2气氛下进行无压烧结；烧结温度为1800℃，保温时间为2h，烧结实验结束后，降温取出样品。重复上述实验2次，分别记为3-1、3-2和3-3。
实施例4
将市售hBN粉体20g(纯度大于98％，粒径为8μm)放入1000ml去离子水溶液中，用磁力搅拌器在900rpm的搅拌速率下磁力搅拌7小时，得到hBN粉体-去离子水的混合液，然后向该混合液中以8ml/min的速度滴加100ml的乙醇，然后继续以8ml/min的速度滴加28wt％浓氨水直至溶液的pH值为9，待混合均匀后，再继续在磁力搅拌的条件下以15ml/min的速度缓慢滴加正硅酸乙酯和乙醇的混合液(正硅酸乙酯与乙醇的质量比为1∶8)直至溶液中H2O和TEOS的摩尔比为5∶1；用聚氯乙烯薄膜密封瓶口，反应10小时；过滤粉体，100℃烘干24小时，在研钵中研磨后，过200目筛3次；将干燥后的粉体在700℃高真空炉中预烧5h，预烧后均匀研磨并过200目筛3次；将预烧研磨后的粉体进行160MPa冷等静压成型，在N2气氛下进行无压烧结；烧结温度为1700℃，保温时间为2h，烧结实验结束后，降温取出样品。重复上述实验2次，分别记为4-1、4-2和4-3。
实施例5
将市售hBN粉体10g(纯度大于98％，粒径为10μm)放入1000ml去离子水溶液中，用磁力搅拌器在800rpm的搅拌速率下磁力搅拌6小时，得到hBN粉体-去离子水的混合液，然后向该混合液中以5ml/min的速度滴加100ml的乙醇，然后继续以5ml/min的速度滴加28wt％浓氨水直至溶液的pH值为9，待混合均匀后，再继续在磁力搅拌的条件下以20ml/min的速度缓慢滴加正硅酸乙酯和乙醇的混合液(正硅酸乙酯与乙醇的质量比为1∶10)直至溶液中H2O和TEOS的摩尔比为4∶1，用聚氯乙烯薄膜密封瓶口，反应5小时；过滤粉体，100℃烘干24小时，在研钵中研磨后，过200目筛3次；将干燥后的粉体在900℃高真空炉中预烧3h，预烧后均匀研磨并过200目筛3次；将预烧研磨后的粉体进行140MPa冷等静压成型，在N2气氛下进行无压烧结；烧结温度为1600℃，保温时间为1h，烧结实验结束后，降温取出样品。重复上述实验2次，分别记为5-1、5-2和5-3。
综上所述，本发明用一种简单易行的方法将SiO2均匀包覆在hBN表面，从而实现SiO2和hBN的均匀分散，并采用无压方法获得高致密度的hBN陶瓷(致密度大于80％)，对于提高hBN的致密度以及抗氧化性能都具有重要的意义。通过在六方氮化硼粉体表面均匀包覆SiO2烧结助剂纳米层，并结合高温无压烧结实现六方氮化硼陶瓷材料致密化的新方法制备出的高致密度六方氮化硼陶瓷在作为透波材料、绝缘材料、耐火材料等在航空航天等领域具有广阔的应用前景。
表1实施例1～5的hBN粉体包覆SiO2的粒径、含量及烧结后的性能指标

Claims (8)

1.一种高致密度六方氮化硼陶瓷材料的制备方法，其特征在于，包括如下步骤：
(1)将hBN粉体加入去离子水中，均匀搅拌混合配制成hBN粉体-去离子水的混合物；
(2)向步骤(1)所得的混合物中滴加乙醇，滴加乙醇的质量与上述混合物的质量比为0.08～0.1；然后，继续向混合物中滴加浓氨水至溶液pH值为9～10，待混合物混合均匀后，再继续缓慢滴加正硅酸乙酯和乙醇的混合溶液，直至混合溶液中正硅酸乙酯和步骤(1)中去离子水的摩尔比为(1∶4)～(1∶8)，滴加完成后，密封瓶口，继续反应5～20小时，其中，步骤(2)中，正硅酸乙酯和乙醇的混合溶液中，正硅酸乙酯与乙醇的质量比为(1∶5)～(1∶10)；
(3)步骤(2)反应结束后，过滤得到的粉体，将所述粉体烘干并研磨过筛；
(4)将步骤(3)得到的过筛的粉体在高真空炉中预烧，预烧后再次均匀研磨过筛；
(5)将步骤(4)得到的粉体进行冷等静压成型，然后在N2气氛下进行高温无压烧结，然后保温1～3h，得到样品；
(6)烧结实验结束后，降温取出样品。
2.根据权利要求1所述的制备方法，其特征在于，所述hBN粉体的纯度大于98％，粒径≤10μm；hBN粉体的质量与去离子水的质量比为0.008～0.015。
3.根据权利要求1所述的制备方法，其特征在于，步骤(1)中的搅拌条件为：采用磁力搅拌，搅拌速率为500～1000rpm，搅拌时间为1～10小时。
4.根据权利要求1所述的制备方法，其特征在于，步骤(2)中，乙醇的滴加速度为1～10ml/min；浓氨水的滴加速度为1～10ml/min；正硅酸乙酯和乙醇的混合溶液的滴加速度为1～20ml/min。
5.根据权利要求1所述的制备方法，其特征在于，步骤(3)中，粉体的烘干条件为在90～110℃下烘干10～30小时；粉体的研磨条件为过200目筛2～4次。
6.根据权利要求1所述的制备方法，其特征在于，步骤(4)中，粉体预烧的条件为：预烧温度为700～900℃，预烧时间0.5～5h，研磨条件为过200目筛2～4次。
7.根据权利要求1所述的制备方法，其特征在于，步骤(5)中，冷等静压成型的成型压力100～200MPa。
8.根据权利要求1所述的制备方法，其特征在于，步骤(5)中，烧结温度为1600～1900℃。
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