CN101449147A - 氢传感器 - Google Patents
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Abstract
一种氢传感器,在树脂等基板的表面形成薄膜层,进一步在该薄膜层的表面形成催化剂层。当该催化剂层与泄漏的氢气接触时则通过其催化剂作用而使薄膜层迅速地进行氢化作用,并使薄膜层的光反射率变化。该氢传感器具备:在基板与薄膜层之间或在催化剂层表面的任一侧或两侧形成的保护膜。
Description
技术领域
本发明涉及用于检测环境中氢气的氢传感器。
背景技术
氢作为能够抑制排出二氧化碳的能源而被关注。但氢气向环境中(例如用于使用氢燃料电池的汽车的地下停车场或氢气站等环境中)有泄漏时,则泄漏的氢气有可能爆炸。因此,必须迅速地检测氢气的泄漏并制止其泄漏。作为检测该泄漏氢气的氢传感器,使用氧化锡的半导体传感器被使用。
但该半导体传感器不被加热到摄氏400度左右就不能检测氢气。因此,需要有随着加热的对于泄漏氢气的防爆对策,作为检测泄漏的氢气的装置其结构复杂,招致成本上升。
于是,作为不需要加热且不需要防爆对策的氢传感器,有图4所示那样的氢传感器被日本国特开2005-83832号公报(以下叫做专利文献1)所提案。如图4所示,该氢传感器10在树脂(例如乙烯基树脂片)或玻璃等基板11的表面11a形成薄膜层12。进一步在该薄膜层12的表面12a形成催化剂层13,当该催化剂层13与泄漏的氢气的接触,则通过其催化剂作用而使薄膜层12迅速地进行氢化作用,由此而薄膜层12的光反射率变化。
但不可否认在具有吸湿性的树脂等基板11的表面11a形成了薄膜层12的氢传感器10中,基板11所含有的或基板11从环境中吸收的水分和氧等浸透薄膜层12并使薄膜层12氧化而恶化的情况。若薄膜层12产生这种恶化,则有会给迅速检测泄漏的氢气带来障碍的问题。即使使用吸湿性少的玻璃基板11,也不能说完全没有吸湿性,所以上述薄膜层12会出现恶化。另外,催化剂层13吸收环境中的水分和氧等则催化剂层13恶化,催化剂作用降低,当进而水分和氧等浸透到薄膜层12则薄膜层12恶化。由于这种催化剂层13或薄膜层12的恶化而有可能在迅速检测泄漏的氢气中产生障碍。
发明内容
本发明适用于:在玻璃或树脂等基板的表面形成薄膜层,进一步在该薄膜层的表面形成催化剂层,当该催化剂层与泄漏的氢气接触则通过其催化剂作用而使薄膜层迅速地进行氢化作用,并使薄膜层的光反射率变化的氢传感器。
为了解决上述问题,本发明的目的在于提供一种氢传感器,能够防止基板所含有的或基板从环境中吸收的水分或氧等浸透薄膜层,防止催化剂层或薄膜层的恶化。
为了解决上述问题,本发明的目的在于提供一种氢传感器,能够防止催化剂层吸收环境中的水分或氧等,防止催化剂层或薄膜层的恶化。
为了达到上述目的,本发明的氢传感器具有:基板、在该基板上形成的薄膜层、形成在该薄膜层的表面且利用环境中含有的氢气使所述薄膜层进行氢化作用而使所述薄膜层的光反射率变化的催化剂层,其中,具备:在所述基板与所述薄膜层之间或在所述催化剂层表面的任一侧或两侧形成的保护膜。
通过在氢传感器的基板与薄膜层之间形成保护膜,能够防止基板所吸收的水分或氧等浸透所述保护膜。通过在催化剂层的表面形成保护膜,能够防止催化剂层吸收环境中的水分或氧等。从而,能够防止保护膜和催化剂层的恶化。
本发明的氢传感器由于能够防止薄膜层和催化剂层的恶化,所以能够长期维持恰当检测泄漏的氢气这样的氢气检测性能。
具体说就是所述薄膜层也可以是镁镍合金薄膜层或镁薄膜层。
通过把氢传感器的薄膜层设定成镁镍合金薄膜层或镁薄膜层,能够形成若接触到泄漏的氢气则其光反射率变化的薄膜层。
具体说就是所述催化剂层也可以由钯或铂形成。
通过把催化剂层由钯或铂形成,则能够利用其催化剂作用而使薄膜层进行氢化作用。
更具体地所述催化剂层的厚度也可以是1nm到100nm。
当厚度是1nm到100nm的催化剂层与泄漏的氢气接触时,薄膜层急速地进行氢化作用。
具体地所述保护膜也可以由含硅化合物、含氟化合物或油脂构成。
通过把保护膜由含硅化合物、含氟化合物或油脂(例如矿物油、植物油等)等形成,能够一边防止环境中的水分或氧等浸透薄膜层或催化剂层一边发挥催化剂层的催化剂作用。
更具体地所述保护膜的厚度也可以是5nm到200nm。
只要把保护膜的厚度设定成5nm到200nm,就对催化剂层引起的薄膜层的迅速氢化作用几乎没有妨碍。
附图说明
图1是表示本发明一实施例氢传感器剖面结构例的图;
图2是表示有无保护膜的薄膜层恶化(时效恶化)的曲线;
图3是表示图1所示氢传感器变形例剖面结构例的图;
图4是表示现有氢传感器剖面结构例的图。
具体实施方式
以下按图1说明本发明一实施例的氢传感器。对于与现有氢传感器10具有同样功能的结构元件则付与同样的符号而省略其说明。
图1所示的氢传感器10a在丙烯酸类树脂、聚乙烯片(聚乙烯膜)等基板11的表面11a上形成由二氧化硅(SiO2)构成的第一保护膜14,在第一保护膜14的表面14a上形成由镁镍合金或镁构成的薄膜层12。且在薄膜层12的表面12a上形成由钯或铂构成的催化剂层13,在催化剂层13的表面13a上形成由二氧化硅构成的第二保护膜15。
这样,氢传感器10a经由第一保护膜14而在基板11的表面11a上形成薄膜层12,且在催化剂层13的表面13a上形成第二保护膜15。氢传感器10a由于具有这种结构则由第一保护膜14来防止基板11吸收水分和氧等对薄膜层12的浸透,且由第二保护膜15来防止环境中的水分和氧等被催化剂层13吸收。其结果是薄膜层12和催化剂层13的恶化被防止。
图2是表示有无保护膜的薄膜层12和催化剂层13恶化(时效恶化)的曲线。薄膜层12与氢接触则进行氢化作用而光反射率变化,而且电阻上升。该薄膜层12由于氧化(恶化)而电阻也上升。因此,薄膜层12的恶化能够从其电阻的上升而进行下面的评价。
连结在基板11上刚刚形成薄膜层12和催化剂层13后而没与氢气接触状态下测定的电阻值与接触了氢气并经过了一定时间(约10秒)后的电阻值而得到曲线,求其曲线斜率的值即电阻值/秒。然后每经过规定时间就反复测定该电阻值/秒,若随着时间的经过而电阻值/秒几乎不减少,则能够认为薄膜层12恶化少。另一方面,若随着时间的经过而电阻值/秒减少,则能够认为薄膜层12的恶化在进展。因此,图2表示出具有保护膜的氢传感器中薄膜层的恶化少,不具有保护膜的氢传感器中薄膜层的恶化在进展。
薄膜层12能够由喷溅法、真空蒸镀法、电子束蒸镀法、电镀法等形成。薄膜层12的组成例如是MgNix(0≤x<0.6)。催化剂层13能够通过向薄膜层12的表面12a涂布等形成。催化剂层13的厚度是1nm到100nm。第一保护膜14能够由喷溅法、真空蒸镀法、电镀法等形成。第二保护膜15除了第一保护膜14的形成方法之外,能够由喷射法、浸渍涂布法、旋转涂布法或刷涂形成。
第一保护膜14为了在其表面14a形成薄膜层12则需要把表面14a形成得平滑。而第二保护膜15的表面就不需要如保护膜14的表面14a那样平滑。
在此,第一保护膜14的厚度只要根据基板11的吸湿性(吸收水分或氧等的程度)等来适当设定便可。第二保护膜15优选设定为5nm到200nm的厚度。具有上述厚度的第二保护膜15能够一边防止催化剂层13吸收环境中的水分或氧等,一边迅速发挥催化剂层13的催化剂作用(催化剂层13与环境中的氢气接触而使薄膜层12进行氢化作用的催化剂作用)。
因此,氢传感器10a当与氢浓度100ppm到1%的下限值以上的环境接触时,则催化剂层13利用其催化剂作用而使薄膜层12进行氢化作用,能够在数秒到10秒左右使薄膜层12的光反射率迅速产生变化。其结果是氢传感器10a能够迅速检测氢气的泄漏。
第二保护膜15即使比上述的厚度薄,氢传感器10a也能够减少从环境中向催化剂层13和薄膜层12浸透的水分和氧等。因此,减少了催化剂层13和薄膜层12的恶化,能够比较长期地维持良好的氢气检测性能。另一方面,在第二保护膜15比上述的厚度厚的情况下,催化剂层13利用其催化剂作用用于使薄膜层12进行氢化作用的时间就变长。但这时由于能够把从环境中向催化剂层13和薄膜层12浸透的水分和氧等充分减少,所以能够更加可靠地防止催化剂层13和薄膜层12的恶化。这样,第二保护膜15的厚度能够考虑作为氢传感器所要求的氢气检测时间和寿命的综合平衡关系来适当设定。
下面在图3中说明本发明氢传感器的变形例。对于与氢传感器10a具有同样功能的结构元件则付与同样的符号而省略说明。
图3所示的氢传感器10b把几乎不吸收环境中水分和氧等的金属或玻璃等作为基板11使用。该氢传感器10b中水分和氧等几乎不从基板11向薄膜层12浸透。因此,即使不具有第一保护膜14,而由第二保护膜15防止水分和氧等从环境中向催化剂层13和薄膜层12浸透,也能够防止催化剂层13和薄膜层12的恶化。其结果是能够长期维持氢传感器10b良好的氢气检测性能。
本发明的氢传感器并不限定于上述的各实施例,在不脱离其旨趣的范围能够适当变形。
Claims (6)
1、一种氢传感器,具有:基板、在该基板上形成的薄膜层、形成在该薄膜层的表面且利用环境中含有的氢气使所述薄膜层进行氢化作用而使所述薄膜层的光反射率变化的催化剂层,所述氢传感器的特征在于,
具备:在所述基板与所述薄膜层之间或在所述催化剂层表面的任一侧或两侧形成的保护膜。
2、如权利要求1所述的氢传感器,其特征在于,所述薄膜层是镁镍合金薄膜层或镁薄膜层。
3、如权利要求2所述的氢传感器,其特征在于,所述催化剂层由钯或铂形成。
4、如权利要求3所述的氢传感器,其特征在于,所述催化剂层的厚度是1nm到100nm。
5、如权利要求1所述的氢传感器,其特征在于,所述保护膜由含硅化合物、含氟化合物或油脂构成。
6、如权利要求5所述的氢传感器,其特征在于,所述保护膜的厚度是5nm到200nm。
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JP076352/2006 | 2006-03-20 | ||
JP2006076352A JP2007248424A (ja) | 2006-03-20 | 2006-03-20 | 水素センサ |
PCT/JP2007/053421 WO2007108276A1 (ja) | 2006-03-20 | 2007-02-23 | 水素センサ |
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CN101449147A true CN101449147A (zh) | 2009-06-03 |
CN101449147B CN101449147B (zh) | 2011-04-06 |
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US (1) | US20100290050A1 (zh) |
EP (1) | EP1998169A4 (zh) |
JP (1) | JP2007248424A (zh) |
KR (1) | KR20080106239A (zh) |
CN (1) | CN101449147B (zh) |
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CN104730114A (zh) * | 2013-12-19 | 2015-06-24 | 中国科学院上海硅酸盐研究所 | 一种用于氢气传感器的镁合金薄膜及其制备方法 |
CN105289588A (zh) * | 2014-07-28 | 2016-02-03 | 中国科学院上海硅酸盐研究所 | 一种钯合金催化薄膜材料及其制备方法 |
CN108027333A (zh) * | 2015-09-16 | 2018-05-11 | Koa株式会社 | 氢传感器 |
CN108717053A (zh) * | 2018-06-13 | 2018-10-30 | 佛山市澄澜点寸科技有限公司 | 一种氢气传感器 |
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JP5164435B2 (ja) * | 2007-06-04 | 2013-03-21 | 株式会社アツミテック | 水素センサ |
CN101418080B (zh) * | 2008-11-13 | 2011-06-22 | 北京科技大学 | 一种氢传感器用壳聚糖质子交换膜的制备方法 |
JP5232045B2 (ja) * | 2009-03-06 | 2013-07-10 | 株式会社アツミテック | 水素センサ |
JP5150533B2 (ja) * | 2009-03-06 | 2013-02-20 | 株式会社アツミテック | 水素センサ |
KR101704122B1 (ko) | 2014-10-08 | 2017-02-07 | 현대자동차주식회사 | 수소 검출 채색 센서 |
KR101645661B1 (ko) * | 2014-12-18 | 2016-08-05 | 울산대학교 산학협력단 | 백금/팔라듐 코어―셀 그래핀 하이브리드 기반 수소센서 및 그 제조방법 |
JP6709429B2 (ja) * | 2015-12-21 | 2020-06-17 | スタンレー電気株式会社 | 水素濃度測定装置 |
KR101772328B1 (ko) * | 2016-05-03 | 2017-08-29 | 한양대학교 에리카산학협력단 | 수분 수소 흡착 게터 및 그 제조 방법 |
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CN104730114A (zh) * | 2013-12-19 | 2015-06-24 | 中国科学院上海硅酸盐研究所 | 一种用于氢气传感器的镁合金薄膜及其制备方法 |
CN105289588A (zh) * | 2014-07-28 | 2016-02-03 | 中国科学院上海硅酸盐研究所 | 一种钯合金催化薄膜材料及其制备方法 |
CN108027333A (zh) * | 2015-09-16 | 2018-05-11 | Koa株式会社 | 氢传感器 |
CN108027333B (zh) * | 2015-09-16 | 2021-06-25 | Koa株式会社 | 氢传感器 |
CN108717053A (zh) * | 2018-06-13 | 2018-10-30 | 佛山市澄澜点寸科技有限公司 | 一种氢气传感器 |
Also Published As
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JP2007248424A (ja) | 2007-09-27 |
CN101449147B (zh) | 2011-04-06 |
US20100290050A1 (en) | 2010-11-18 |
KR20080106239A (ko) | 2008-12-04 |
EP1998169A1 (en) | 2008-12-03 |
CA2645592A1 (en) | 2007-09-27 |
EP1998169A4 (en) | 2011-10-12 |
WO2007108276A1 (ja) | 2007-09-27 |
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