CN115073182A - 一种超高温材料及其制备方法 - Google Patents

一种超高温材料及其制备方法 Download PDF

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CN115073182A
CN115073182A CN202210729368.6A CN202210729368A CN115073182A CN 115073182 A CN115073182 A CN 115073182A CN 202210729368 A CN202210729368 A CN 202210729368A CN 115073182 A CN115073182 A CN 115073182A
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CN115073182B (zh
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蒋进明
袁琦
封�波
王雯洁
王甲富
屈绍波
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Air Force Engineering University of PLA
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Abstract

本发明公开了一种超高温材料及其制备方法，制备方法包括：将难熔元素的硼化物和/或碳化物纳米粉体和烧结助剂混合后的原料在无氧、500℃‑800℃下烧结，得到所述超高温材料；所述烧结助剂包括活性矿化剂、导向助烧剂和溶盐介质，所述活性矿化剂为含硼矿物，所述导向助烧剂为难熔元素的卤化物。本发明能够在超低温度下实现了超高温材料的致密化，大幅降低了现有超高温材料制备的温度，且无需考虑传统高温制备条件下的晶粒粗化和纤维损伤等问题，从而制备工艺大大简化，成本显著降低。

Description

一种超高温材料及其制备方法
技术领域
本发明涉及无机材料技术领域，特别涉及一种超高温材料及其制备方法。
背景技术
耐超高温陶瓷(UHTCs)，尤其是难熔金属Ta、Hf、Zr的碳化物和硼化物(如TaC、HfC、ZrC、TaB2、HfB2、ZrB2)，具有3000℃以上高熔点、高热导率、高弹性模量，高硬度、在高温下保持高强度，是未来超高温领域最有前途的材料。此外，难熔金属的氧化物还具有天然的抗氧化性，也具有2000℃以上高熔点，耐冲刷、抗腐蚀，同样具备作为耐超高温、抗氧化烧蚀材料的潜力，目前已在军事空天和民用耐火领域取得良好效用。
由于这类超高温材料都具有极强的共价键、极高的熔点，且自扩散系数低，通常采用热压工艺烧结制备。专利号为CN102190495B的专利公布了一种反应助剂促进烧结硼化锆或碳化锆陶瓷的制备方法，烧结温度为1800～2000℃。可见，传统的烧结温度高(>1600℃)，易导致晶粒粗化、异质材料界面高温退化等问题，因而在原料选材、工艺优化以及复材制备等方面需要严格控制，且难以实现大型复杂工件的制备。
发明内容
本发明要解决的技术问题是克服现有技术的不足，提供一种大幅降低制备温度、工艺设备要求简单、成本低的超高温材料的其制备方法，还相应提供一种该方法制得的超高温材料。
为解决上述技术问题，本发明采用以下技术方案：
一种超高温材料的制备方法，包括：将难熔元素的硼化物和/或碳化物纳米粉体和烧结助剂混合后的原料在无氧、500℃-800℃下烧结，得到所述超高温材料；所述烧结助剂包括活性矿化剂、导向助烧剂和溶盐介质，所述活性矿化剂为含硼矿物，所述导向助烧剂为难熔元素的卤化物。
上述的超高温材料的制备方法，优选的，所述难熔元素为Zr、Hf、Ta、Ti、Si中的至少一种。
进一步的，难熔元素的卤化物为MClx(M＝Zr、Hf、Ta、Ti、Si)。
上述的超高温材料的制备方法，优选的，所述含硼矿物为LiBH4、NaBH4和KBH4中的至少一种。
上述的超高温材料的制备方法，优选的，所述溶盐介质为LiCl、KCl和NaCl中的至少一种。
上述的超高温材料的制备方法，优选的，所述活性矿化剂、导向助烧剂和溶盐介质的质量比为1-2∶3-4∶1-2。
上述的超高温材料的制备方法，优选的，所述原料中，所述难熔元素的硼化物和/或碳化物纳米粉体的质量分数为85％-95％，所述烧结助剂的质量分数为5％-15％。
上述的超高温材料的制备方法，优选的，所述烧结的工艺为：在惰性气氛保护下升温至500-800℃，保温1-3h，随炉冷却至室温。
该制备方法中烧结温度极低(<800℃)、烧结时间周期短(≤3h)，满足了超高温材料低温低成本制造要求，发展了低能耗低碳排放先进制造技术。
上述的超高温材料的制备方法，优选的，所述烧结采用热压烧结或等静压烧结，所述烧结的压力为300-600Mpa。
上述的超高温材料的制备方法，优选的，采用球磨对难熔元素的硼化物和/或碳化物纳米粉体和烧结助剂进行混合；所述球磨的工艺为：球磨在惰性气氛下进行，球磨转速为200-400rpm，球料比为4-15∶1，球磨过程中单次旋转以30min为上限，停止5min后，再以反方向旋转形式进行球磨，以此循环，球磨总时间为10h-30h。
本发明的具体操作工艺简单，参数可控性强，工程化优势明显。
作为一个总的发明构思，本发明还提供一种上述的制备方法制得的超高温材料。
与现有技术相比，本发明的优点在于：
1、本发明大幅降低了现有超高温材料的制备工艺温度。材料的烧结必须通过颗粒间的固相扩散来完成元素间的传质，受限于超高温材料本征极强的共价键和极低的自扩散系数，材料的烧结温度必然很高(>1600℃)。本发明提出利用活性矿化剂和导向助烧剂在超高温材料颗粒间，构建低温液态熔融环境、高活性反应区域，为超高温材料颗粒间的扩散传质“架桥修路”，可实现超低温度下超高温材料的致密化；
2、本发明发展了基于自然仿生的精细矿化致密化烧结技术思想。生物体牙的无机质结构，可在常温常压的口腔环境就可以实现致密化。基于自然仿生的技术原理，在陶瓷粉体烧结环境中构建出利于元素扩散、晶界溶解、颗粒重排的等效精细矿化环境，可实现陶瓷材料的烧结；
3、本发明适用范围广、可移植性强，能够制备包括单相陶瓷、复相陶瓷以及纤维增强陶瓷基复合材料在内的超高温材料，且由于工艺温度低，避免了传统高温晶粒粗化、异质材料界面高温退化等问题。
附图说明
图1为实施例1制备的ZrB2超高温材料的实物图。
图2为实施例2制备的ZrB2-SiC超高温材料的微观结构图。
图3为实施例2中对比样件ZrB2-SiC超高温材料的微观形貌图。
具体实施方式
以下结合具体优选的实施例对本发明作进一步描述，但并不因此而限制本发明的保护范围。
实施例1：
一种本实施例的ZrB2超高温材料的制备方法，包括以下步骤：
(1)球磨混合复合粉体：按照质量分数比例85wt.％：15wt.％称取原料粉体和烧结助剂，原料粉体为市售纯度≥99％、粒径为0.4μm的ZrB2粉体，烧结助剂中各成分质量分数分别为：20wt.％NaBH4，50wt.％ZrCl4，30wt.％LiCl。将原料粉体和烧结助剂进行球磨混合，球磨混合时转速为400rpm，球料比为15∶1，球磨时间为24h，全程实施氩气保护。
(2)烧结ZrB2超高温材料：将步骤(1)所得球磨混合物进行热压烧结，施加压力500MPa，氩气氛保护下升温至800℃，保温处理3h，最后随炉冷却，得到ZrB2超高温材料。
如图1所示，本实施例所得的ZrB2超高温材料，相对密度达到95％。经力学性能测试，三点弯曲强度为520MPa，韧度4.3MPa·m1/2。材料综合性能优异、制备工艺简单、成本能耗低，具有较好的应用前景。
实施例2：
一种本实施例的ZrB2-SiC超高温材料的制备方法，包括以下步骤：
(1)球磨混合复合粉体：按照质量分数比例95wt.％：5wt.％称取原料粉体和烧结助剂，原料粉体中各成分质量分数分别为：80wt.％ZrB2，20wt.％SiC，其中ZrB2粉体特征为市售纯度≥99％、粒径为0.8μm，SiC粉体特征为市售纯度≥99.9％、粒径为0.2μm，烧结助剂中各成分质量分数分别为：15wt.％LiBH4，60wt.％ZrCl4，25wt.％KCl。将原料粉体和烧结助剂进行球磨混合，球磨混合时转速为300rpm，球料比为4∶1，球磨时间为12h，全程实施氩气保护。
(2)烧结ZrB2-SiC超高温材料：将步骤(1)所得球磨混合物进行热等静压烧结，施加压力600MPa，氩气氛保护下升温至800℃，保温处理2h，最后随炉冷却，得到ZrB2-SiC超高温材料。
本实施例所得的ZrB2-SiC超高温材料，如图2所示，材料的微观结构致密，排煤油法测定的相对密度达到96％。图3是直接混合80wt.％ZrB2，20wt.％SiC在800℃热压烧结2h后的形貌特点，呈现松散无烧结状态。对本实施例所得的ZrB2-SiC超高温材料进行力学性能测试，三点弯曲强度为650MPa，韧度7.6MPa·m1/2。对该材料进行了2000℃高温氧化烧蚀实验，线烧蚀率仅为3.1μm/s，质量烧蚀率低至0.13mg/s。材料综合性能优异、制备工艺简单、成本能耗低，具有较好的应用前景。
以上所述，仅是本申请的较佳实施例，并非对本申请做任何形式的限制，虽然本申请以较佳实施例揭示如上，然而并非用以限制本申请，任何熟悉本专业的技术人员，在不脱离本申请技术方案的范围内，利用上述揭示的技术内容做出些许的变动或修饰均等同于等效实施案例，均属于技术方案范围内。

Claims (10)

1.一种超高温材料的制备方法，其特征在于，包括：将难熔元素的硼化物和/或碳化物纳米粉体和烧结助剂混合后的原料在无氧、500℃-800℃下烧结，得到所述超高温材料；所述烧结助剂包括活性矿化剂、导向助烧剂和溶盐介质，所述活性矿化剂为含硼矿物，所述导向助烧剂为难熔元素的卤化物。
2.根据权利要求1所述的超高温材料的制备方法，其特征在于，所述难熔元素为Zr、Hf、Ta、Ti、Si中的至少一种。
3.根据权利要求1所述的超高温材料的制备方法，其特征在于，所述含硼矿物为LiBH4、NaBH4和KBH4中的至少一种。
4.根据权利要求1所述的超高温材料的制备方法，其特征在于，所述溶盐介质为LiCl、KCl和NaCl中的至少一种。
5.根据权利要求1所述的超高温材料的制备方法，其特征在于，所述活性矿化剂、导向助烧剂和溶盐介质的质量比为1-2∶3-4∶1-2。
6.根据权利要求1所述的超高温材料的制备方法，其特征在于，所述原料中，所述难熔元素的硼化物和/或碳化物纳米粉体的质量分数为85％-95％，所述烧结助剂的质量分数为5％-15％。
7.根据权利要求1-6任一项所述的超高温材料的制备方法，其特征在于，所述烧结的工艺为：在惰性气氛保护下升温至500-800℃，保温1-3h，随炉冷却至室温。
8.根据权利要求7所述的超高温材料的制备方法，其特征在于，所述烧结采用热压烧结或等静压烧结，所述烧结的压力为300-600Mpa。
9.根据权利要求1-5任一项所述的超高温材料的制备方法，其特征在于，采用球磨对难熔元素的硼化物和/或碳化物纳米粉体和烧结助剂进行混合；所述球磨的工艺为：球磨在惰性气氛下进行，球磨转速为200-400rpm，球料比为4-15∶1，球磨过程中单次旋转以30min为上限，停止5min后，再以反方向旋转形式进行球磨，以此循环，球磨总时间为10h-30h。
10.一种如权利要求1-9任一项所述的制备方法制得的超高温材料。
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