CN110563460A - 一种热释电传感器用敏感元材料大尺寸制备方法 - Google Patents

一种热释电传感器用敏感元材料大尺寸制备方法 Download PDF

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CN110563460A
CN110563460A CN201910785805.4A CN201910785805A CN110563460A CN 110563460 A CN110563460 A CN 110563460A CN 201910785805 A CN201910785805 A CN 201910785805A CN 110563460 A CN110563460 A CN 110563460A
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姚春华
郭少波
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Suzhou Yingrui Sensor Technology Co Ltd
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Abstract

本发明涉及一种热释电传感器用敏感元材料大尺寸制备方法，具体涉及一种大尺寸的高密度钛酸锶钡热释电陶瓷材料及其制备方法，所述高密度钛酸锶钡热释电陶瓷材料的化学式BaxSr1‑xTiO3，0≤x≤1；形状为圆片状，尺寸为直径A×厚度S，其中50 mm≤A≤105 mm，4 mm≤S≤20 mm；所述高密度钛酸锶钡热释电陶瓷材料的相对密度≥99%；优选地，A为至少为4英寸。

Description

一种热释电传感器用敏感元材料大尺寸制备方法
技术领域
本发明涉及一种热释电传感器用敏感元材料大尺寸制备方法，具体涉及一种大尺寸(例如4英寸)的高密度钛酸锶钡热释电陶瓷材料及其制备方法，属于热释电陶瓷材料技术领域。
背景技术
钛酸锶钡(BST,Ba1-xSrxTiO3，0≤x≤1)陶瓷材料由于具有可调居里温度、高介电常数、低介电损耗等特点，使其成为非常重要的热释电型非制冷红外焦平面用候选材料。
在实际应用中，随着对探测距离及精度要求的提高，目前的非制冷红外焦平面器件的像元数越来越大，已经达到320×240及640×480。如此多的像元数，要求BST陶瓷的尺寸较大；同时，为了与后续半导体工艺兼容，并满足产业化的需要，一般要求BST热释电陶瓷能够达到4英寸，即Φ100mm。第二，使用BST热释电陶瓷材料制作非制冷红外焦平面器件时，需要将其减薄到几十微米，这是由于越薄的基片可使吸收同样红外热量时温度变化更大，从而可以提高器件的灵敏度，这就需要BST陶瓷具有很高的致密度，才能够满足减薄加工的需要；另外，由于BST陶瓷工作时需要外加电场，如果BST陶瓷的致密度较低，存在较多气孔，则容易在加工过程中引入绝缘性能较差的杂质，引起导通，使探测器存在较多盲点直至无法使用，因此也要求BST陶瓷的致密度很高，一般来讲，需要其相对密度达到98％以上。
然而，由于功能陶瓷存在的固有脆性，尺寸越大的陶瓷材料，越难以成型和烧结，存在成型时易分层、易开裂，烧结时易开裂、难致密、不均匀等问题。所以，如何有效地解决大尺寸、高致密BST陶瓷的制备问题，使BST热释电陶瓷材料能满足制作非制冷红外焦平面器件的要求，是目前BST热释电陶瓷材料研究中亟需解决的。
发明内容
为解决现有技术制备大尺寸(例如，至少4英寸)高密度BST材料时存在成型时易分层、易开裂，烧结时易开裂、难致密、不均匀等问题，本发明提供一种4英寸高密度钛酸锶钡热释电陶瓷材料及其制备方法，以满足目前非制冷红外焦平面器件对BST材料的要求。
一方面，本发明提供了一种高密度钛酸锶钡热释电陶瓷材料，所述高密度钛酸锶钡热释电陶瓷材料的化学式BaxSr1-xTiO3，0≤x≤1；形状为圆片状，尺寸为直径A×厚度S，其中50mm≤A≤105mm，4mm≤S≤20mm；所述高密度钛酸锶钡热释电陶瓷材料的相对密度≥99％；优选地，A为至少为4英寸。
较佳的，所述高密度钛酸锶钡热释电陶瓷材料中还含有掺杂元素，所述掺杂元素选自Ca、Y、Mn、Sm中的至少一种。
另一方面，本发明还提供了一种上述的高密度钛酸锶钡热释电陶瓷材料的制备方法，包括如下步骤：
(1)按照所述高密度钛酸锶钡热释电陶瓷材料的化学式称取化学计量比的BaCO3粉体、SrCO3粉体和TiO2粉体作为原料粉体，混合均匀后，得到混合粉体；优选地，所述混合粉体中还加入掺杂元素对应的氧化物；
(2)将所得混合粉体烘干后压块，在通氧气氛下合成，合成温度为1000～1200℃，保温时间为1～3小时，得到BST粉体；
(3)将步骤(3)得到的BST粉体进行粉碎、过筛，再用搅拌磨工艺使粉体混合均匀；
(4)出料后烘干，加入粘结剂，再经造粒、陈化、过筛步骤之后，进一步经过预压、等静压过程，制得BST坯体；
(5)将步骤(4)得到的BST坯体在氧气气氛下进行烧结，烧结的工艺条件为：以1～4℃/min的速度升温；当升温到800～1000℃时开始通氧气，氧气流量为1～3L/min；当升温到1350～1450℃时，保温3～5小时；随炉冷却至室温，关闭氧气，即得4英寸高密度BST陶瓷。
较佳的，步骤(1)中，采用湿法球磨工艺使原料混合均匀，所述湿法球磨工艺的条件包括：料：球磨介质：去离子水的质量比＝1:(1.0～2.0):(1.0～1.5)，球磨时间为12～26小时，所述球磨介质为氧化锆球。
较佳的，步骤(2)中，在烘干之后、且压块之前加入总粉体4％～10％质量的去离子水。
较佳的，步骤(3)中，BST粉体在进行搅拌磨工艺之前，过40目筛。
较佳的，步骤(3)中，所述搅拌磨工艺的条件为：球磨料：球磨介质：去离子水的质量＝1:(1.5～2.0):(0.5～1.0)，球磨时间为24～48小时，所述球磨介质为氧化锆球。
较佳的，步骤(4)中，所述粘结剂选用无水酒精，加入量为BST粉体质量的10％～20％。
较佳的，步骤(4)中，所述陈化的时间为0～0.5小时；
较佳的，步骤(4)中，所述预压、等静压过程所用模具直径大小为60～140mm。
较佳的，步骤(4)中，所述等静压成型的压力为(2.0～3.0)×103千克力。
较佳的，步骤(4)中，所述排塑的温度为600～800℃。
有益效果：
(1)本发明的BST热释电陶瓷材料不仅具有4英寸大(～Φ100mm)、致密度高(相对密度≥99％)，且样品纯度高、性能高、均匀性好，可满足制作非制冷红外焦平面器件的要求，有效的解决了大尺寸(例如4英寸)功能陶瓷难成型、易开裂、难致密、不均匀的问题；
(2)本发明的制备方法具有工艺简单、无需特殊设备、成本低等优点，适合规模化生产，能满足工业化需求。
附图说明
图1为实施例1制得的4英寸高密度BST热释电陶瓷的照片；
图2为实施例1制得的4英寸高密度BST热释电陶瓷材料经表面抛光、热腐蚀后的扫描电镜照片；
图3为实施例1制得的4英寸高密度BST热释电陶瓷材料在外加直流电场下介电常数及介电损耗随温度的变化曲线图；
图4为实施例1制得的4英寸高密度BST热释电陶瓷材料在外加直流电场下采用准静态方法测试的热释电系数随温度的变化曲线图。
具体实施方式
以下通过下述实施方式进一步说明本发明，应理解，下述实施方式仅用于说明本发明，而非限制本发明。
在本公开中，本发明高密度钛酸锶钡热释电陶瓷材料是以普通固相法制粉、等静压成型和通氧烧结工艺而成。具体来说，主要过程如下：以BaCO3、SrCO3和TiO2粉体为主要原料，在一定媒质中进行球磨，并在一定温度下煅烧，之后粉碎、过筛、细化，然后烘干，加入粘结剂，经造粒、陈化、过筛，并经等静压成型、排塑等步骤，最后在氧气下烧结制备得到。
以下示例性地说明本发明提供的高密度钛酸锶钡热释电陶瓷材料的制备方法。
按照通式BaxSr1-xTiO3(0≤x≤1，BST)称取化学计量比的BaCO3、SrCO3和TiO2粉体等作为原料粉体，采用湿法球磨工艺使所有粉体混合均匀，得到混合粉体。优选化学通式中可以加入各种掺杂元素，如Ca、Y、Mn、Sm等，其所对应加入粉体为掺杂元素对应氧化物。所述湿法球磨工艺条件为：料：球磨介质：去离子水的质量比为1:(1.0～2.0):(1.0～1.5)，球磨时间为12～26小时，所述球磨介质为氧化锆球。
将混合粉体烘干后压块，在通氧气氛下合成，合成温度为1000～1200℃，保温时间为1～3小时，得到BST粉体。
将BST粉体进行粉碎、过筛，再用搅拌磨工艺使粉体混合均匀，然后出料后烘干，得到粒径合适的烧结用BST粉体。在烘干后、压块前加入总粉体4％～10％质量的去离子水。BST粉体在进行搅拌磨工艺处理之前过40目筛。例如，搅拌磨工艺条件为：球磨料：球磨介质：去离子水的质量比＝1:(1.5～2.0):(0.5～1.0)，球磨时间为24～48小时，所述球磨介质为氧化锆球。
将粒径合适的烧结用BST粉体加入一定量的粘结剂，经造粒、陈化、过筛步骤，之后经过预压、等静压等过程，制得大尺寸的BST坯体。粘结剂选用无水酒精，加入量可为BST粉体质量的10％～20％。陈化时间可为0～0.5小时。模具大小可为60～140mm。等静压压力可为(1.0～3.0)×103千克力。排塑的温度可为750～850℃。
将BST坯体在氧气气氛下进行烧结，烧结的工艺条件为：以1～4℃/min的速度升温；当升温到800～1000℃时开始通氧气，氧气流量为1～3L/min。当升温到1350～1450℃时，保温3～5小时。随炉冷却至室温，关闭氧气，即得大尺寸的(例如至少4英寸)高密度BST陶瓷。
在本发明中，高密度钛酸锶钡热释电陶瓷材料，具有如下尺寸及致密度：圆片ΦA(mm)×S(mm)，其中50≤A≤105(优选为4英寸)、4≤S≤20，相对密度≥99％。
本发明制备的钛酸锶钡热释电陶瓷具有尺寸大、致密度高等特点，且电性能高，可满足制作非制冷红外焦平面器件的要求。本发明有效地解决了大尺寸功能陶瓷难成型、易开裂、难致密、不均匀的问题，且制备方法简单、周期短成本低，适合规模化生产，能满足实际应用的需要。
下面进一步例举实施例以详细说明本发明。同样应理解，以下实施例只用于对本发明进行进一步说明，不能理解为对本发明保护范围的限制，本领域的技术人员根据本发明的上述内容作出的一些非本质的改进和调整均属于本发明的保护范围。下述示例具体的工艺参数等也仅是合适范围中的一个示例，即本领域技术人员可以通过本文的说明做合适的范围内选择，而并非要限定于下文示例的具体数值。
实施例1
首先称取BaCO3、SrCO3和TiO2粉体，并添加少量的Y2O3、MnCO3粉体，用搅拌磨工艺使所有粉体混合均匀；球磨料：球磨介质：去离子水的质量比＝1:1.5:1.2，球磨时间为24小时，所述球磨介质氧化锆球。
烘干，加入总粉体4％重量的去离子水，压块，在大气气氛下合成，合成温度为1150℃，保温时间为2小时，得到BST粉体；粉碎、过40目筛，再用搅拌磨工艺使粉体混合均匀；球磨料：球磨介质：去离子水的质量比＝1:2.0:0.8，球磨时间为48小时，所述球磨介质为氧化锆球。
烘干，加入无水酒精作为粘结剂，造粒，陈化0.2小时，过筛，预压后进行等静压成型，等静压压力为2.0×103千克力，在800℃排塑，即制得BST坯体(直径120mm×厚度7mm)；将BST坯体在氧气下烧结，烧结的条件为：以2.0℃/min的速度升温；当升温到800℃时开始通氧气，氧气流量为2L/min；当升温到1350℃时，保温5小时；冷却至室温，关闭氧气。
将烧结好的样品加工成需要的尺寸，超声清洗，丝网印刷银浆，烘干，在650～750℃下保温20～40分钟，在直流偏压下测试样品的介电和热释电性能。
图1为本实施例制得的4英寸BST热释电陶瓷的外观照片，由图1可见：陶瓷的尺寸大，直径～102mm，S为5mm且外观均匀，无开裂等现象。
图2为本实施例制得的4英寸BST热释电陶瓷经表面抛光、热腐蚀后的SEM照片，由图2可见：陶瓷的气孔少，致密度高，经阿基米德法测量得到的相对致密度为99.12％。
图3为本实施例制得的4英寸、高致密BST热释电陶瓷材料在外加直流电场下介电常数及介电损耗随温度的变化曲线图，由图3可见：陶瓷的居里温度在室温附近，介电常数在104数量级，随着电场的增加，居里温度向高温移动，介电常数下降，介电损耗降低，在1000V/mm电场下，居里温度处的介电损耗低至0.4％。
图4为本实施例制得的4英寸高密度BST热释电陶瓷材料采用准静态方法测试的热释电系数随温度和外加直流电场的变化曲线图，由图4可见：随温度增加，热释电系数先增加后减小，热释电系数峰值为18.0×10-8C·cm-2·K-1。
综上所述，采用本发明制备的BST热释电陶瓷材料的直径具有4英寸大(～Φ100mm)、致密度高(相对密度≥99％)的优点，而且电性能高，如样品介电常数大(104数量级)、介电损耗小(＜1％)，热释电性能高，在1000V/mm偏置电场时，其热释电系数可达到18.0×10-8C·cm-2·K-1，可满足制作非制冷红外焦平面器件的要求。
本发明有效地解决了大尺寸(例如，至少为4英寸)功能陶瓷难成型、易开裂、难致密、不均匀的问题，且制备方法简单、周期短成本低，适合规模化生产，能满足实际应用的需要。
有必要在此指出的是：以上实施例只用于对本发明进行进一步说明，不能理解为对本发明保护范围的限制，本领域的技术人员根据本发明的上述内容作出的一些非本质的改进和调整均属于本发明的保护范围。

Claims (10)

1.一种高密度钛酸锶钡热释电陶瓷材料，其特征在于，所述高密度钛酸锶钡热释电陶瓷材料的化学式BaxSr1-xTiO3，0≤x≤1；形状为圆片状，尺寸为直径A×厚度S，其中50 mm≤A≤105 mm，4 mm≤S≤20 mm；所述高密度钛酸锶钡热释电陶瓷材料的相对密度≥99%；优选地， A为至少为4英寸。
2.根据权利要求1所述的高密度钛酸锶钡热释电陶瓷材料，其特征在于，所述高密度钛酸锶钡热释电陶瓷材料中还含有掺杂元素，所述掺杂元素选自Ca、Y、Mn、Sm中的至少一种。
3.一种权利要求1或2所述的高密度钛酸锶钡热释电陶瓷材料的制备方法，其特征在于，包括如下步骤：
（1）按照所述高密度钛酸锶钡热释电陶瓷材料的化学式称取化学计量比的BaCO3粉体、SrCO3粉体和TiO2粉体作为原料粉体，混合均匀后，得到混合粉体；优选地，所述混合粉体中还加入掺杂元素对应的氧化物；
（2）将所得混合粉体烘干后压块，在通氧气氛下合成，合成温度为1000～1200℃，保温时间为1～3小时，得到BST粉体；
（3）将步骤（3）得到的BST粉体进行粉碎、过筛，再用搅拌磨工艺使粉体混合均匀；
（4）出料后烘干，加入粘结剂，再经造粒、陈化、过筛步骤之后，进一步经过预压、等静压过程，制得BST坯体；
（5）将步骤（4）得到的BST坯体在氧气气氛下进行烧结，烧结的工艺条件为：以1～4℃/min的速度升温；当升温到800～1000℃时开始通氧气，氧气流量为1～3L/min；当升温到1350～1450℃时，保温3～5小时；随炉冷却至室温，关闭氧气，即得4英寸高密度BST陶瓷。
4.根据权利要求3所述的制备方法，其特征在于，步骤（1）中，采用湿法球磨工艺使原料粉体混合均匀，所述湿法球磨工艺的条件包括：料：球磨介质：去离子水的质量比= 1:(1.0～2.0):(1.0～1.5)，球磨时间为12～26小时，所述球磨介质为氧化锆球。
5.根据权利要求3或4所述的制备方法，其特征在于，步骤（2）中，在烘干之后、且压块之前加入总粉体4%～10%质量的去离子水。
6.根据权利要求3-5中任一项所述的制备方法，其特征在于，步骤（3）中，BST粉体在进行搅拌磨工艺之前，过40目筛。
7.根据权利要求3-6中任一项所述的制备方法，其特征在于，步骤（3）中，所述搅拌磨工艺的条件为：球磨料：球磨介质：去离子水的质量=1:(1.5～2.0):(0.5～1.0)，球磨时间为24～48小时，所述球磨介质为氧化锆球。
8.根据权利要求3-7中任一项所述的制备方法，其特征在于，步骤（4）中，所述粘结剂选用无水酒精，加入量为BST粉体质量的10%～20%；所述陈化的时间为0～0.5小时。
9.根据权利要求3-8中任一项所述的制备方法，其特征在于，步骤（4）中，所述预压、等静压过程所用模具直径大小为60～140 mm；所述等静压成型的压力为（2.0～3.0）×103千克力。
10.根据权利要求3-9中任一项所述的制备方法，其特征在于，步骤（4）中，所述排塑的温度为600～800℃。
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