CN112830790B - 一种铪铌基三元固溶体硼化物的导电陶瓷及其制备方法和应用 - Google Patents

一种铪铌基三元固溶体硼化物的导电陶瓷及其制备方法和应用 Download PDF

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CN112830790B
CN112830790B CN202110087760.0A CN202110087760A CN112830790B CN 112830790 B CN112830790 B CN 112830790B CN 202110087760 A CN202110087760 A CN 202110087760A CN 112830790 B CN112830790 B CN 112830790B
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张泽熙
郭伟明
张岩
许亮
林华泰
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Guangdong University of Technology
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Abstract

本发明属于陶瓷材料技术领域，公开了一种铪铌基三元固溶体硼化物导电陶瓷及其制备方法和应用，该导电陶瓷的分子式为(HfaNbbMec)B2，其中0.1≤a≤0.9，0<b<0.9，0<c<0.9且a+b+c＝1；Me为Zr、Ta或Ti，该导电陶瓷是将HfO2、Nb、Me氧化物、B4C、碳粉加入溶剂经球磨混合得到混合粉体，经压模后所得坯体放入石墨坩埚中，升温至1400～1600℃保温，进行真空热处理，得到(HfaNbbMec)B2铪铌基三元固溶体硼化物粉体；采用放电等离子烧结将上述硼化物粉体升温至1000～1400℃时充入保护气氛，然后升温至1900～2100℃，压力为10～100MPa煅烧制得。

Description

一种铪铌基三元固溶体硼化物的导电陶瓷及其制备方法和 应用
技术领域
本发明属于陶瓷材料技术领域，更具体地，涉及一种铪铌基三元固溶体硼化物的导电陶瓷及其制备方法和应用。
背景技术
过渡金属硼化物作为一种超高温陶瓷，具有高熔点、高硬度、优异的高温稳定性、耐腐蚀性和高温抗蠕变性等优点。其在航天发动机、超音速飞行器、炉体部件等恶劣环境中的应用具有极大的潜力。但由于其具有强的共价键和低的扩散系数，过渡金属硼化物很难烧结致密。制备致密的纯相过渡金属硼化物往往需要较高的温度和压力条件，但高温往往会导致晶粒粗化，降低陶瓷的机械性能。因此，为了促进过渡金属硼化物的致密化，许多学者常常通过添加烧结助剂来提高烧结驱动力，如Sciti等通过添加9vol%MoSi2，采用SPS在1700℃/100 MPa的条件下成功制备致密度为100%ZrB2陶瓷，但玻璃相MoSi2的存在可能会降低其固有机械强度和高温性能。除此之外，降低粉体粒径，提高粉体表面能，是增加粉体烧结活性，制备致密硼化物陶瓷的一种方法。除此之外，陶瓷的均匀性也在一定程度上影响其性能，外磁场为零时超导材料由正常态转变为超导态(或相反)的温度，以Tc表示，使超导材料的超导态破坏而转变到正常态所需的磁场强度，以Hc表示，在常压下有28种元素具超导电性，其中铌（Nb）的Tc最高为9.26K，超导元素加入某些其他元素作合金成分，可以使超导材料的全部性能提高。如最先应用的铌锆合金(Nb-75Zr)，其Tc为10.8K，Hc为8.7特。继后发展了铌钛合金，虽然Tc稍低了些，但Hc高得多，在给定磁场能承载更大电流。三元合金，性能进一步提高，Nb-60Ti-4Ta的Tc=9.9K，Hc=12.4特（4.2K）；Nb-70Ti-5Ta的Tc=9.8K，Hc=12.8特。之前报道高熵陶瓷中固溶NbB2会有偏析，由于其烧结温度或者保温时间不足，NbB2扩散较慢，均质的含NbB2的三元硼化物陶瓷预期会有更好的性能。
发明内容
为了解决上述现有技术存在的不足和缺点，提供一种铪铌基三元固溶体硼化物的导电陶瓷。该陶瓷的组织均匀，具有均一固溶体相、组元稳定、硬度高和导电率高的优点。
本发明另一目的在于提供上述铪铌基三元固溶体硼化物的导电陶瓷的制备方法。
本发明再一目的在于提供上述铪铌基三元固溶体硼化物的导电陶瓷的应用。
本发明的目的通过下述技术方案来实现：
一种铪铌基三元固溶体硼化物的导电陶瓷，所述导电陶瓷的分子式为(HfaNbbMec)B2，其中，0.1≤a≤0.9，0<b<0.9，0<c<0.9且a+b+c=1；Me为Zr、Ta或Ti，所述导电陶瓷是将HfO2、Nb、Me氧化物ZrO2、Ta2O5或TiO2中任意一种、B4C、碳粉加入溶剂经球磨混合得到混合粉体，经压模后所得坯体放入石墨坩埚中，升温至1400~1600℃保温，进行真空热处理，得到(HfaNbbMec)B2铪铌基三元固溶体硼化物粉体；采用放电等离子烧结将上述硼化物粉体升温至1000~1400℃时充入保护气氛，然后升温至1900~2100℃，压力为10~100MPa煅烧制得。
优选地，所述(HfaNbbMec)B2铪铌基三元固溶体硼化物粉末的纯度95~99.9wt%，粒径为2~7µm。
优选地，所述(HfaNbbMec)B2铪铌基三元固溶体硼化物粉体的氧含量为0.01~5wt%，碳含量为0.01~5wt%。
优选地，所述HfO2、ZrO2、Ta2O5和TiO2的纯度均为99.0~99.9wt%，粒径均为0.1~10µm；所述Nb的纯度为95~99wt%，粒径为10~20µm；所述B4C粉和碳粉的纯度均为97~99.99wt.%，粒径均为1~1.5 µm。
优选地，所述铪基三元固溶体硼化物陶瓷的相对密度为95~98%，硬度为20~30GPa，电阻率为1~5Ω。
优选地，所述溶剂为乙醇、丙醇、甲醇或丙酮。
优选地，所述保护气氛为N2或Ar。
优选地，所述升温至1400~1600℃的升温速率为5~15℃/min；所述保温时间为0.5~2h；所述升温至1000~1400℃的升温速率为100~400℃/min，所述升温至1900~2100℃时的升温速率为100~400℃/min。
所述的铪铌基三元固溶体硼化物的导电陶瓷的制备方法，包括如下具体步骤：
S1. 将HfO2、Nb、Me氧化物ZrO2、Ta2O5或TiO2中任意一种、B4C、碳粉加入溶剂和球磨介质，在球磨机上混合20~40h，干燥后得混合粉体；
S2. 将混合粉体模压后的坯体放入石墨坩埚中，以5~15℃/min的速率升温至1400~1600℃保温0.5~2h，真空热处理获得(HfaNbbMec)B2铪铌基三元固溶体硼化物粉体；
S3. (HfaNbbMec)B2铪铌基三元固溶体硼化物粉体放入石墨模具中，采用放电等离子烧结以100~400℃/min的速率升温至1000~1400℃并充入保护气氛，再以100~400℃/min的速率升温至1900~2100℃，保温10~30min，加压10~100MPa煅烧，制得(HfaNbbMec)B2铪铌基三元固溶体硼化物的导电陶瓷。
所述的铪铌基三元固溶体硼化物的导电陶瓷在电子零部件领域中的应用。
本发明的铪铌基三元固溶体硼化物导电陶瓷具有组织均匀，该陶瓷是以三种金属氧化物、Nb粉、B4C和C为原料，经过硼热碳热还原反应，制备出(HfaNbbMec)B2铪铌基三元固溶体硼化物粉末，该方法通过原位固溶制备铪基三元固溶体硼化物粉末，更容易形成单相，且粉末粒径小，纯度高，烧结驱动力大，更容易制备组织均匀(HfaNbbMec)B2铪铌基三元固溶体硼化物陶瓷，通过引入超导元素Nb，有效改善了(HfaNbbMec)B2铪铌基三元固溶体硼化物陶瓷的导电性能。
与现有技术相比，本发明具有以下有益效果：
1. 本发明制得的(HfaNbbMec)B2铪铌基三元固溶体硼化物陶瓷粉末，可以通过硼热碳热还原法将金属元素与金属氧化物固溶在一起，原位合成单相三元固溶体粉末，粉末粒径小(2~7µm)，纯度高(氧含量为0.01~5wt%，碳含量为0.01~5wt%)，烧结驱动力大，易于烧出单相固溶体陶瓷。
2. 本发明制备的(HfaNbbMec)B2铪铌基三元固溶体硼化物陶瓷，由于其粉末粒径烧结驱动力大，制备的(HfaNbbMec)B2铪铌基三元固溶体硼化物陶瓷的组织均匀。
3. 本发明制备的(HfaNbbMec)B2铪铌基三元固溶体硼化物陶瓷，由放电等离子烧结制备，由于烧结时间短，且快速冷却，(HfaNbbMec)B2铪铌基三元固溶体硼化物陶瓷的晶粒尺寸细小，分布均匀，内部缺陷小，组织较均匀，具有高导电率(电阻率为1~5Ω)，在导电领域有很高的应用前景。
说明附图
图1为实施例1制得的(Hf1/3Zr1/3Nb1/3)B2铪铌基三元固溶体硼化物导电陶瓷的元素面扫描分布图；
图2为实施例5制得的(Hf1/3Ta1/3Nb1/3)B2铪铌基三元固溶体硼化物导电陶瓷的元素面扫描分布图。
具体实施方式
下面结合具体实施例进一步说明本发明的内容，但不应理解为对本发明的限制。若未特别指明，实施例中所用的技术手段为本领域技术人员所熟知的常规手段。除非特别说明，本发明采用的试剂、方法和设备为本技术领域常规试剂、方法和设备。
实施例1
1. 以HfO2（粉末的纯度99%，粒径1μm）、ZrO2（粉末的纯度99.8%，粒径1μm）、Nb（粉末的纯度99%，粒径10μm）、和B4C（粉末的纯度99.9%，粒径0.5μm）、碳粉（粉末的纯度99%，粒径0.8μm）为原料，以乙醇为溶剂，以Si4N3为球磨介质，在球磨机上混合24h，干燥后得到混合粉体；
2. 将混合粉体模压后的坯体放入石墨坩埚中，以10℃/min的速率升温至1600℃保温1h，真空热处理获得(Hf1/3Zr1/3Nb1/3)B2铪铌基三元固溶体硼化物导电陶瓷粉末。
3. 将(Hf1/3Zr1/3Nb1/3)B2铪铌基三元固溶体硼化物导电陶瓷粉末放入石墨模具中，采用放电等离子烧结以150℃/min的速率升温至1000℃并充入Ar保护气氛，再以150℃/min的速率升温至2000℃，保温10min，加压30MPa煅烧，制得(Hf1/3Zr1/3Nb1/3)B2铪铌基三元固溶体硼化物导电陶瓷。
通过激光粒度分析测得本实施例的(Hf1/3Zr1/3Nb1/3)B2铪铌基三元固溶体硼化物导电陶瓷粉末的粒径为5μm，用碳氧分析仪测得固溶体粉末的含氧量为0.01wt%，固溶体粉末的碳含量为0.03wt%，制备得到的(Hf1/3Zr1/3Nb1/3)B2铪铌基三元固溶体硼化物导电陶瓷，其相对密度为98%，硬度为30GPa，四探针电阻仪测试的电阻为2Ω。
图1为实施例1制得的(Hf1/3Zr1/3Nb1/3)B2铪铌基三元固溶体硼化物导电陶瓷的元素面扫描分布图；从图1中可知，各元素分布均匀，大粒径的Nb未造成组织的偏析，而且其还发挥了导电的优异性能，四探针电阻仪测试的(Hf1/3Zr1/3Nb1/3)B2铪铌基三元固溶体硼化物导电陶瓷的电阻为1Ω。
实施例2
1. 以HfO2（粉末的纯度99%，粒径2μm）、TiO2（粉末的纯度99.8%，粒径2μm）、Nb（粉末的纯度99%，粒径10μm）、和B4C（粉末的纯度99.9%，粒径0.5μm）、碳粉（粉末的纯度99%，粒径0.8μm）为原料，以乙醇为溶剂，以Si4N3为球磨介质，在球磨机上混合24h，干燥后得到混合粉体；
2. 将混合粉体模压后的坯体放入石墨坩埚中，以10℃/min的速率升温至1600℃保温1h，真空热处理获得(Hf1/3Ti1/3Nb1/3)B2铪铌基三元固溶体硼化物导电陶瓷粉末。
3. 将(Hf1/3Ti1/3Nb1/3)B2铪铌基三元固溶体硼化物导电陶瓷粉末放入石墨模具中，采用放电等离子烧结以150℃/min的速率升温至1000℃并充入Ar保护气氛，再以150℃/min的速率升温至2000℃，保温30min，加压50MPa煅烧，制得(Hf1/3Ti1/3Nb1/3)B2铪铌基三元固溶体硼化物导电陶瓷。
通过激光粒度分析测得本实施例的(Hf1/3Ti1/3Nb1/3)B2铪铌基三元固溶体硼化物导电陶瓷粉末的粒径为6μm，用碳氧分析仪测得固溶体粉末的含氧量为0.01wt%，固溶体粉末的碳含量为0.03wt%，制备得到的(Hf1/3Ti1/3Nb1/3)B2铪铌基三元固溶体硼化物导电陶瓷，其相对密度为97%，硬度为28GPa，四探针电阻仪测试的电阻为3Ω。
实施例3
1. 以HfO2（粉末的纯度99%，粒径1μm）、TiO2（粉末的纯度99.8%，粒径1μm）、Nb（粉末的纯度99%，粒径10μm）、和B4C（粉末的纯度99.9%，粒径0.5μm）、碳粉（粉末的纯度99%，粒径0.8μm）为原料，以乙醇为溶剂，以Si4N3为球磨介质，在球磨机上混合24h，干燥后得到混合粉体；
2. 将混合粉体模压后的坯体放入石墨坩埚中，以10℃/min的速率升温至1600℃保温1h，真空热处理获得(Hf1/4Ti1/4Nb1/2)B2铪铌基三元固溶体硼化物导电陶瓷粉末。
3. 将(Hf1/4Ti1/4Nb1/2)B2铪铌基三元固溶体硼化物导电陶瓷粉末放入石墨模具中，采用放电等离子烧结以150℃/min的速率升温至1000℃并充入Ar保护气氛，再以150℃/min的速率升温至2000℃，保温30min，加压50MPa煅烧，制得(Hf1/4Ti1/4Nb1/2)B2铪铌基三元固溶体硼化物的导电陶瓷。
通过激光粒度分析测得本实施例的(Hf1/4Ti1/4Nb1/2)B2铪铌基三元固溶体硼化物导电陶瓷粉末的粒径为7μm，用碳氧分析仪测得固溶体粉末的含氧量为0.01wt%，固溶体粉末的碳含量为0.03wt%，制得的(Hf1/4Ti1/4Nb1/2)B2铪铌基三元固溶体硼化物导电陶瓷，其相对密度为96%，硬度为28GPa，四探针电阻仪测试的电阻为1Ω。
实施例4
1. 以HfO2（粉末的纯度99%，粒径1μm）、TiO2（粉末的纯度99.8%，粒径1μm）、Nb（粉末的纯度95%，粒径20μm）、和B4C（粉末的纯度99.9%，粒径0.5μm）、碳粉（粉末的纯度99%，粒径0.8μm）为原料，以乙醇为溶剂，以Si4N3为球磨介质，在球磨机上混合24h，干燥后得到混合粉体；
2. 将混合粉体模压后的坯体放入石墨坩埚中，以10℃/min的速率升温至1600℃保温1h，真空热处理获得(Hf1/2Ti1/4Nb1/4)B2铪铌基三元固溶体硼化物导电陶瓷粉末。
3. 将(Hf1/2Ti1/4Nb1/4)B2铪铌基三元固溶体硼化物导电陶瓷粉末放入石墨模具中，采用放电等离子烧结以150℃/min的速率升温至1000℃并充入Ar保护气氛，再以150℃/min的速率升温至2000℃，保温10min，加压40MPa煅烧，制得(Hf1/2Ti1/4Nb1/4)B2铪铌基三元固溶体硼化物导电陶瓷。
通过激光粒度分析测得本实施例的(Hf1/2Ti1/4Nb1/4)B2铪铌基三元固溶体硼化物导电陶瓷粉末的粒径为4.3μm，用碳氧分析仪测得固溶体粉末的含氧量为0.01wt%，固溶体粉末的碳含量为0.03wt%。
实施例5
1. 以HfO2（粉末的纯度99%，粒径1μm）、Ta2O5（粉末的纯度99.8%，粒径1μm）、Nb（粉末的纯度99%，粒径10μm）、和B4C（粉末的纯度99.9%，粒径0.5μm）、碳粉（粉末的纯度99%，粒径0.8μm）为原料，以乙醇为溶剂，以Si4N3为球磨介质，在球磨机上混合24h，干燥后得到混合粉体；
2. 将混合粉体模压后的坯体放入石墨坩埚中，以10℃/min的速率升温至1600℃保温1h，真空热处理获得(Hf1/3Ta1/3Nb1/3)B2铪铌基三元固溶体硼化物导电陶瓷粉末。
3. 将(Hf1/3Ta1/3Nb1/3)B2铪铌基三元固溶体硼化物导电陶瓷粉末放入石墨模具中，采用放电等离子烧结以150℃/min的速率升温至1000℃并充入Ar保护气氛，再以150℃/min的速率升温至2000℃，保温10min，加压30MPa煅烧，制得(Hf1/3Ta1/3Nb1/3)B2铪铌基三元固溶体硼化物导电陶瓷；
通过激光粒度分析测得本实施例的(Hf1/3Ta1/3Nb1/3)B2铪铌基三元固溶体硼化物导电陶瓷粉末的粒径为2μm，用碳氧分析仪测得固溶体粉末的含氧量为0.01wt%，固溶体粉末的碳含量为0.03wt%，制得的(Hf1/3Ta1/3Nb1/3)B2铪铌基三元固溶体硼化物导电陶瓷，其相对密度为95%，硬度为20GPa，四探针电阻仪测试的电阻为5Ω。
图2为实施例5制得的(Hf1/3Ta1/3Nb1/3)B2铪铌基三元固溶体硼化物导电陶瓷的元素面扫描分布图。从图2中可知，Nb元素出现偏析现象，组织分布不均匀，陶瓷的导电性较低，四探针电阻仪测试的(Hf1/3Ta1/3Nb1/3)B2铪铌基三元固溶体硼化物导电陶瓷的电阻为5Ω。
本发明制得的(HfaNbbMec)B2铪铌基三元固溶体硼化物陶瓷粉末，可以通过硼热碳热还原法将金属元素与金属氧化物固溶在一起，原位合成单相三元固溶体粉末，其粒径小(2~7µm)，纯度高(氧含量为0.01~5wt%，碳含量为0.01~5wt%)，烧结驱动力大，易于烧出单相固溶体陶瓷。(HfaNbbMec)B2铪铌基三元固溶体硼化物陶瓷的晶粒尺寸细小，分布均匀，内部缺陷小，组织较均匀，具有高导电率(电阻率为1~5Ω)，在导电领域有很高的应用前景。
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合和简化，均应为等效的置换方式，都包含在本发明的保护范围之内。

Claims (5)

1.一种铪铌基三元固溶体硼化物的导电陶瓷的制备方法，其特征在于，包括如下具体步骤：
S1. 将HfO2，Nb，Me氧化物ZrO2或TiO2，B4C，碳粉加入溶剂和球磨介质，在球磨机上混合20~40h，干燥后得混合粉体；所述HfO2、ZrO2和TiO2的纯度均为99.0~99.9wt%，粒径均为0.1~10µm；所述Nb的纯度为95~99wt%，粒径为10~20µm；B4C和碳粉的纯度均为97~99.99 wt.%，粒径均为1~1.5 µm；
S2. 将混合粉体模压后的坯体放入石墨坩埚中，以5~15℃/min的速率升温至1400~1600℃保温0.5~2h，真空热处理获得(HfaNbbMec)B2铪铌基三元固溶体硼化物粉体；所述(HfaNbbMec)B2铪铌基三元固溶体硼化物粉末的纯度95~99.9wt%，粒径为2~7µm；所述(HfaNbbMec)B2铪铌基三元固溶体硼化物粉体的氧含量为0.01~5wt%，碳含量为0.01~5wt%；
S3. (HfaNbbMec)B2铪铌基三元固溶体硼化物粉体放入石墨模具中，采用放电等离子烧结以100~400℃/min的速率升温至1000~1400℃时充入保护气氛，再以100~400℃/min的速率升温至1900~2100℃，保温10~30min，加压10~100MPa煅烧，制得(HfaNbbMec)B2铪铌基三元固溶体硼化物的导电陶瓷；所述导电陶瓷的分子式为(HfaNbbMec)B2，其中，0.1≤a≤0.9，0<b<0.9，0<c<0.9且a+b+c=1；Me为Zr或Ti；所述铪铌基三元固溶体硼化物陶瓷的相对密度为96~98%，硬度为28~30GPa，电阻率为1~3Ω。
2.根据权利要求1所述的铪铌基三元固溶体硼化物的导电陶瓷的制备方法，其特征在于，步骤S1中所述溶剂为乙醇、丙醇、甲醇或丙酮。
3.根据权利要求1所述的铪铌基三元固溶体硼化物的导电陶瓷的制备方法，其特征在于，步骤S3中所述保护气氛为N2或Ar。
4.一种铪铌基三元固溶体硼化物的导电陶瓷，其特征在于，所述导电陶瓷是由权利要求1-3任一项所述的方法制备得到。
5.权利要求4所述的铪铌基三元固溶体硼化物的导电陶瓷在电子零部件领域中的应用。
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