CN104291822B - 一种负热膨胀材料ZrScMo2VO12及其固相烧结合成方法 - Google Patents

一种负热膨胀材料ZrScMo2VO12及其固相烧结合成方法 Download PDF

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CN104291822B
CN104291822B CN201410511065.2A CN201410511065A CN104291822B CN 104291822 B CN104291822 B CN 104291822B CN 201410511065 A CN201410511065 A CN 201410511065A CN 104291822 B CN104291822 B CN 104291822B
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梁二军
葛向红
程永光
袁保合
晁明举
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Zhengzhou University
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Abstract

本发明属于无机非金属材料技术领域，特别公开了一种新型负热膨胀材料ZrScMo2VO12及其固相烧结合成方法。以摩尔比计，按二氧化锆ZrO2：三氧化二钪Sc2O3：三氧化钼MoO3：五氧化二钒V2O5=2：1：4：1称取原料，研磨混合均匀，将混合均匀的原料直接或压片后烧结合成，自然冷却得到目标产物ZrScMo2VO12；其中，烧结条件：温度为600-800℃，时间为30min-5h，压强为常压，气氛为空气。本发明新型负热膨胀材料ZrScMo2VO12，在室温(RT)-600℃范围内具有稳定的负热膨胀性质，且无相变，具有工程应用价值；本发明可一次烧结完成，反应过程简单，在常压空气中烧结600-800℃，烧结时间为30min-5h，在高温下反应充分，制成的产品纯度高，适合批量生产。

Description

一种负热膨胀材料ZrScMo2VO12及其固相烧结合成方法
技术领域
本发明属于无机非金属材料技术领域，特别涉及了一种新型负热膨胀材料ZrScMo2VO12及其固相烧结合成方法。
背景技术
自然界中大多数材料都具有热胀冷缩的性质，在温度剧烈变化或变化较大的场合，由于不同材料热膨胀系数差异产生的热应力常常会引起材料或器件的性能指标变差，负热膨胀材料的出现，为解决这一问题提供了机遇和可能性，与传统材料的“热胀冷缩”不同，负热膨胀材料在一定温度范围内的平均线膨胀系数或体膨胀系数为负值，这类材料具有巨大的潜在应用前景，例如可以利用此类负热膨胀材料复合制备各种各样超低膨胀系数、甚至零膨胀系数、且具有特定功能的复合材料，在微电子器件材料、精密光学镜面、医用器材、传感器、航空航天、发动机部件和精密机械等领域都具有十分重要的应用价值。
目前，普遍研究的氧化物负热膨胀材料主要包括以ZrW2O8为代表的O8系列、以ZrV2O7为代表的O7系列、通式为A2M3O12的O12系列（A为三价阳离子，可以为过渡族金属或稀土元素，A也可以由一个四价阳离子和一个二价阳离子替代；M为W或Mo）等，这些材料都因其特殊性能而得到广泛关注。但目前为止，所发现的负热膨胀材料种类十分有限，而且这类材料的研究尚不完善，至今还没有得到大规模应用，还有很多问题尚待解决，如原材料的选取、相变、吸水性问题，机械性能的提高，生产工艺复杂、A2M3O12系列须由单斜相转变为正交相后才表现出负热膨胀性能等。
因此，研发负热膨胀性能稳定、无相变、制备工艺简单、适合规模化生产的新型负膨胀材料是非常必要并且具有显著意义的。
发明内容
为克服现有技术中存在的不足之处及材料的局限性，本发明的目的在于提供一种新型负热膨胀材料ZrScMo2VO12及其固相烧结合成方法。
为实现上述目的，本发明采取的技术方案如下：
一种新型负热膨胀材料，分子式为：ZrScMo2VO12。
新型负热膨胀材料的固相烧结合成方法：以摩尔比计，按二氧化锆ZrO2：三氧化二钪Sc2O3：三氧化钼MoO3：五氧化二钒V2O5=2：1：4：1称取原料，研磨混合均匀，将混合均匀的原料直接或压片后烧结合成，自然冷却得到目标产物ZrScMo2VO12；其中，烧结条件：温度为600-800℃，时间为30min-5h，压强为常压，气氛为空气。
本发明的有益效果在于：
1.本发明采用四价Zr4+和三价Sc3+取代A2M3O12中的A离子，同时用V5+取代一个Mo6+以保持价态平衡，制备出一种新型的负热膨胀材料，分子式为ZrScMo2VO12，其在室温(RT)-600℃范围内具有稳定的负热膨胀性质，且无相变，具有工程应用价值。
2.本发明可一次烧结完成，反应过程简单，在常压空气中烧结600-800℃，烧结时间为30min-5h，在高温下反应充分，制成的产品纯度高，适合批量生产。
附图说明
图1为实施例1合成的ZrScMo2VO12的XRD图谱(800℃烧结30min)；
图2为实施例2合成的ZrScMo2VO12的XRD图谱(800℃烧结1h)；
图3为实施例3合成的ZrScMo2VO12的XRD图谱(800℃烧结3h)；
图4为实施例4合成的ZrScMo2VO12的XRD图谱(800℃烧结5h)；
图5为实施例5合成的ZrScMo2VO12的XRD图谱(600℃烧结5h)；
图6为实施例4合成的ZrScMo2VO12的XRD图谱(变温XRD)；
图7为实施例4和实施例5合成的ZrScMo2VO12的相对长度与测试温度的变化关系。
具体实施方式
以下结合具体实施例对本发明的技术方案做进一步的详细介绍，但本发明的保护范围并不局限于此。
实施例1：
将分析纯试剂ZrO2、Sc2O3、MoO3、V2O5按摩尔比2：1：4：1称重取料，在玛瑙研钵内混合均匀，加入无水乙醇后研磨2h。在300MPa的单轴方向压强下压制成直径10mm、高约6mm的圆柱体。设置低温管式炉800℃，将装有样品的刚玉坩埚在烧结温度下放入管式炉，常压空气中烧结30min，在空气中自然冷却。产品对应的XRD图谱物相分析见图1。图1的XRD结果显示形成了纯相的ZrScMo2VO12，经过结构精修，确定所制备材料是空间群为Pbcn（60）的正交相结构。
实施例2：
与实施例1不同之处在于：烧结时间为1h。产品对应的XRD图谱物相分析见图2，图2的XRD结果显示形成了纯相的ZrScMo2VO12，经过结构精修，确定所制备材料是空间群为Pbcn（60）的正交相结构。
实施例3：
与实施例1不同之处在于：烧结时间为3h。产品对应的XRD图谱物相分析见图3，图3的XRD结果显示形成了纯相的ZrScMo2VO12，经过结构精修，确定所制备材料是空间群为Pbcn（60）的正交相结构。
实施例4：
与实施例1不同之处在于：烧结时间为5h。产品对应的XRD图谱物相分析见图4，图4的XRD结果显示形成了纯相的ZrScMo2VO12，经过结构精修，确定所制备材料是空间群为Pbcn（60）的正交相结构。
实施例5：
与实施例4不同之处在于：设置管式炉600℃。产品对应的XRD图谱物相分析见图5，图5的XRD结果显示形成了纯相的ZrScMo2VO12，经过结构精修，确定所制备材料是空间群为Pbcn（60）的正交相结构。
性能表征：
1、采用实施例4制得的样品，从30℃开始测XRD，随后加热升温，并且自100℃起每间隔100℃采样一次，得到的变温XRD图谱见图6，从图中可以看出，随着温度的升高，衍射峰逐渐向大角度偏移，根据布拉格衍射规律可知所制备材料具有负热膨胀特性。变温XRD图谱表明所制备的材料没有相变，负热膨胀性能稳定。根据不同温度下XRD图谱计算出不同温度下的晶格常数，进而计算得到线膨胀系数为-2.19×10-6℃-1。
2、对实施例4和实施例5制备的ZrScMo2VO12的陶瓷块体，用热膨胀仪测试其相对长度随测试温度的变化曲线见图7（800℃-5h对应实施例4，600℃-5h对应实施例5）。用热膨胀仪测试得到实施例4和实施例5样品的线膨胀系数分别为-2.41×10-6℃-1和-2.57×10-6℃-1。

Claims (2)

1.一种负热膨胀材料，其特征在于分子式为：ZrScMo2VO12；按下述方法制备获得：以摩尔比计，按ZrO2：Sc2O3：MoO3：V2O5=2：1：4：1称取原料，研磨混合均匀，将混合均匀的原料直接或压片后烧结合成，自然冷却得到目标产物ZrScMo2VO12；其中，烧结条件：温度为600-800℃，时间为30min-5h，压强为常压，气氛为空气。
2.如权利要求1所述的负热膨胀材料的固相烧结合成方法，其特征在于：以摩尔比计，按ZrO2：Sc2O3：MoO3：V2O5=2：1：4：1称取原料，研磨混合均匀，将混合均匀的原料直接或压片后烧结合成，自然冷却得到目标产物ZrScMo2VO12；其中，烧结条件：温度为600-800℃，时间为30min-5h，压强为常压，气氛为空气。
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