CN113574369A - 气体检测器 - Google Patents
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Abstract
本发明的气体传感器具备由在主链的双键碳原子上键合有取代基的取代聚乙炔制成的气体分离膜、和检测透过气体分离膜后的气体的传感元件。
Description
技术领域
本发明涉及气体检测器。
背景技术
对于气体传感器，存在因环状硅氧烷、SOx等催化剂毒而气体灵敏度降低的问题。此外存在难以识别检测对象气体和除其以外的气体的问题。为了解决这些问题，使用了活性炭、硅胶、沸石等吸附剂作为气体传感器的过滤器。
专利文献1(WO2018/053656)提出了将特氟龙AF(注册商标)(“テフロンAF(注册商标)”为DuPont公司的商品名)等气体分离膜作为气体传感器的过滤器。该过滤器作为与气体分子的尺寸相应的筛起作用，阻挡环状硅氧烷等大分子，使CO、H2、乙醇等小分子透过。此外，为了不延迟气体传感器的响应，作为1μm厚左右的薄膜，将特氟龙AF(注册商标)在多孔质的支撑膜上进行成膜。
现有技术文献
专利文献
专利文献1：WO2018/053656
发明内容
发明所要解决的课题
本发明的课题是提供具备新颖的气体分离膜的气体检测器。
用于解决课题的手段
本发明的气体检测器具备由在主链的双键碳原子上键合有取代基的取代聚乙炔制成的气体分离膜、和检测透过气体分离膜后的气体的传感元件。气体检测器也可以为气体传感器单体，或者为具备气体传感器、和不同于气体传感器的另外的壳体及周边电路的气体检测装置等较佳。在气体传感器的情况下，气体分离膜例如固定于传感器的壳体上，在气体检测装置的情况下，固定于气体的流路中或气体的取入口等处。
取代聚乙炔例如有下述的物质。
·聚[1-(三甲基甲硅烷基)-1-丙炔](poly[1-(trimethylsilil)-1-propyne]，PTMSP)、聚[1-(三甲基甲锗烷基)-1-丙炔](poly[1-(trimethylgermyl)-1-propyne]，PTMGP)等包含Si、Ge等杂原子作为(CH3)3Si-、(CH3)3Ge-等取代基的物质。
·聚[4-(甲基)-2-戊炔](poly[4-(methyl)-2-pentyne]，PMP)、聚[1,2-二苯基乙炔](poly[1,2-diphenyl acetylene]，PDPA)等不含杂原子、并且包含异丙(iso-propyl)基、苯基等大的取代基的物质。
·聚[1,4,5-(CF3)3-苯基乙炔](poly[1,4,5-(CF3)3-phenylacetylene])、聚[1,5-(CF3)2-苯基乙炔](poly[1,5-(CF3)2-phenylacetylene])等具有包含CF3基的大的取代基的物质。
·聚[1-苯基-2-[(对三甲基甲硅烷基)苯基]乙炔](poly[1-phenyl-2-[(p-trimethylsilyl)phenyl]acetylene]，PTMSDPA)等包含(CH3)3Si-、(CH3)3Ge-等取代基和苯基的物质。特别是PTMSDPA由于包含对三甲基甲硅烷基-苯基和苯基，因此具有大的细孔，在对探测对象气体的透过性和阻挡大型的环状硅氧烷化合物的性能这两点上优选。
取代聚乙炔可以以-(CA＝CB)n-表示，A、B中的一者为取代基而另一者为氢，或A、B这两者为取代基。所谓气体分离膜由取代聚乙炔制成是指气体透过性由取代聚乙炔支配。优选气体分离膜以取代聚乙炔作为主要成分。
取代聚乙炔分子由于主链包含双键，因此刚直，与具有大取代基互相结合而自由容积大。而且耐热性和化学稳定性高。因此，若以取代聚乙炔作为气体分离膜的材料，则气体的透过性高，并且甲苯等大分子也会透过。由于气体透过性高，因此即使不将取代聚乙炔膜层叠于支撑膜上而制成比较厚(膜厚为10～50μm左右)的单层膜，也能够维持对气体的响应性。而且，单层膜比层叠膜容易成膜。需要说明的是，若将膜厚为1μm左右的取代聚乙炔膜层叠于多孔质的支撑膜上，则能够提高对气体的响应性。
取代聚乙炔使异丁烷、甲苯等大分子也透过。由于使异丁烷透过，因此能够用于LPG的检测，此外由于使甲苯透过，因此也可以用于VOC(挥发性有机物)的检测。环状硅氧烷是比甲苯充分大的物质，因此实质上不透过取代聚乙炔。因此，能够防止因硅氧烷而引起的气体传感器的中毒。
优选传感元件为支撑电阻值根据气体发生变化的金属氧化物半导体膜的MEMS芯片。MEMS金属氧化物半导体气体传感器对于中毒特别敏感，并且要求为小尺寸，因此优选不是吸附剂过滤器，而通过取代聚乙炔来防止中毒。作为MEMS金属氧化物半导体气体传感器的应用之一，有时安装于智能手机等上，监视环境中的VOC。在该用途中，由于使甲苯透过、使环状硅氧烷实质上不透过，因此聚乙炔膜最适于MEMS金属氧化物半导体气体传感器。
取代聚乙炔与特氟龙AF(注册商标)相比亲油性高，因此使丙酮、乙醛、甲基硫醇等比水蒸气优先透过。在呼气中包含大量水蒸气，但通过取代聚乙炔可以限制水蒸气的透过。若能够以低浓度来检测人的呼气中的这些化合物，则能够实现代谢的简易检查、糖尿病的简易检查、口腔的简易检查等。需要说明的是，就呼气中的丙酮检测等而言，由于检测目标浓度低，因此难以受到水蒸气的影响的电化学气体传感器不适合。
优选气体检测器进一步具备从透过气体分离膜后的气体中吸附检测对象以外的气体的吸附过滤器。这种情况下，取代聚乙炔成为吸附过滤器的例如预滤器，通过取代聚乙炔与吸附过滤器的组合，将无用的气体阻断。例如在与乙醇相区别来检测甲烷的情况下，优选在气体分离膜的后段(靠近传感元件)设置活性炭、硅胶、沸石等吸附乙醇的过滤器。不仅硅氧烷，在苯乙烯、蒎烯等作为催化剂毒起作用的情况下，也优选将取代聚乙炔与活性炭或硅胶等吸附过滤器组合，用吸附过滤器将苯乙烯、蒎烯等除去。
特别优选气体分离膜兼作吸附过滤器的外气侧壳。这样的话，可以将气体分离膜和吸附过滤器紧凑地安装。
附图说明
图1是实施例的气体传感器的剖面图。
图2是第2实施例的气体传感器的局部剖面图。
图3是在气体流路中设置有气体分离膜的气体检测器的示意性俯视图。
图4是表示在硅氧烷中暴露的前后的对CH4的响应的特性图。
图5是表示在硅氧烷中暴露的前后的对H2的响应的特性图。
具体实施方式
以下，示出用于实施本发明的最佳实施例。
实施例
图1表示关于MEMS气体传感器的实施例。2为气体传感器，支撑膜6将Si芯片4(传感元件)的空腔5覆盖。SnO2、WO3等通过与气体接触而电阻值发生变化的金属氧化物半导体膜8被设置于支撑膜6上，在支撑膜6上还设置有未图示的加热器、电极。气体传感器2进一步具备基体10和陶瓷、塑料、金属等壳12，Si芯片4经由引线和金属化部11与外部连接。
壳12为通气性，例如在顶部具备通气孔13，在通气孔13的Si芯片4侧的面上设置有由取代聚乙炔制成的气体分离膜14(取代聚乙炔膜)。取代聚乙炔膜14为PMP、PDPA等不含Si、Ge等杂原子的物质，从没有因杂原子而引起的污染的可能性的方面考虑优选。取代聚乙炔膜14由于气体透过性高，因此例如制成膜厚为10μm～50μm左右的厚膜，作为无支撑膜的单层膜，固定于壳12的顶部内表面上。
周围的气体成分中，环状硅氧烷等中毒物质由于分子尺寸过大，因此不会透过取代聚乙炔膜14。与此相对，氢～甲苯程度的尺寸的分子会透过取代聚乙炔膜14，被Si芯片4检测到。因此，气体传感器2还可以检测VOC。
金属氧化物半导体膜8若长时间放置于高湿气氛中则有时受到影响。但是，由于取代聚乙炔膜14为亲油性且水蒸气的透过慢，因此能够缓和高湿气氛的影响。进而，若检测呼气中的丙酮、乙醛、甲基硫醇等，则能够简易检查代谢或健康状态。取代聚乙炔膜14由于水蒸气的透过率低，因此容易地检测呼气中的这些物质。进而，取代聚乙炔膜14由于丙酮的透过率比乙醇高，因此丙酮的检测变得容易。
图2表示在原先的气体传感器中设置有与图1和实施例同样的取代聚乙炔膜14作为吸附过滤器30的预滤器的例子。在陶瓷或塑料等基体24上经由管脚25安装有基板26。基板26具备未图示的加热器和电极，支撑与图1的实施例同样的金属氧化物半导体膜8。
具备塑料、陶瓷或金属等壳28，从外气侧起依次在壳28的顶部内表面重叠有取代聚乙炔膜14、吸附过滤器30、多孔质膜32。34为通气孔，在壳28的原材料自身为通气性的情况下不需要。取代聚乙炔膜14将环状硅氧烷等阻断，兼作吸附过滤器30的外侧壳。吸附过滤器30为活性炭、硅胶、沸石等且例如为片材状，但也可以为粒状。吸附过滤器30将乙醇等气体吸附，假如产生未被取代聚乙炔膜14完全阻断的中毒物质的情况下，吸附并除去。多孔质膜32为吸附过滤器30的内侧的壳，支撑过滤器30，同时将过滤器30的细粉阻断。
在图1、图2中，在金属氧化物半导体气体传感器中安装取代聚乙炔膜14。但是，作为电化学气体传感器的过滤器、或接触燃烧式气体传感器的过滤器，也可以使用取代聚乙炔膜14。
图3表示在智能手机42中安装有气体传感器48的气体检测器。将智能手机42的外壳的气体导入孔45和排气孔46通过与图1的实施例同样的取代聚乙炔膜14覆盖，保护气体传感器48免于中毒物质。此外，在通过气体传感器48来进行呼气的分析的情况下，通过取代聚乙炔膜14来限制水蒸气的透过，容易检测丙酮、乙醛、甲基硫醇等。
硅氧烷耐久试验
观察在环状硅氧烷(D4)1ppm中暴露1小时前后的气体传感器2对于CH4及H2的响应的变化。气体传感器2的金属氧化物半导体膜8是膜厚为40μm的SnO2膜，动作条件为每30秒进行0.1秒钟、加热至最高加热温度约430℃为止的间歇加热。在气体传感器2上连接负载电阻，测定加热结束时的金属氧化物半导体8的电阻值。将在多孔质PTFE膜上层叠膜厚为10μm左右的PTMSDPA膜而得到的膜作为气体分离膜14，实施例中设置气体分离膜14，比较例中设置单纯的多孔质PTFE膜来代替气体分离膜14。气体传感器数在实施例中为3，在比较例中为2，探测对象气体为CH4(图4)及H2(图5)，浓度均为1000-9000ppm。图4、图5的上段表示实施例的结果，下段表示比较例的结果。由图4、图5获知，通过气体分离膜14能够缓和硅氧烷的影响。
补充
取代聚乙炔膜在气体选择透过膜中自由容积大，并且亲油性高。对于膜的气体选择性，考虑下述两种机理：
·由细孔尺寸和气体分子的尺寸的相对值带来的选择性；
·由气体分子在膜内溶解的溶解度、溶解后的气体分子的扩散速度带来的选择性。
在利用细孔尺寸的机理中，利用比细孔尺寸大的气体分子无法侵入细孔中这点。在利用溶解度等的机理中，利用大尺寸的气体分子溶解于膜内后被捕获到比较大的细孔中、难以在膜内透过这点。就取代聚乙炔膜而言，认为除了由细孔尺寸与硅氧烷分子的尺寸的不同带来的选择性以外，溶解于膜内的硅氧烷分子的扩散慢也有贡献。此外，就取代聚乙炔膜而言，小的气体分子不会被捕获到这样的细孔中而快速地透过膜，对气体传感器的检测速度的影响小。
符号的说明
2、22 气体传感器
4 Si芯片
5 空腔
6 支撑膜
8 金属氧化物半导体膜
10、24 基体
11 金属化部
12、28 壳
13、34 通气孔
14 气体分离膜
25 管脚
26 基板
30 吸附过滤器
32 多孔质膜
42 智能手机
45 气体导入孔
46 排气孔
48 气体传感器
Claims (7)
1.一种气体检测器，其具备：
由在主链的双键碳原子上键合有取代基的取代聚乙炔制成的气体分离膜，和
检测透过气体分离膜后的气体的传感元件。
2.根据权利要求1的气体检测器，其特征在于，气体分离膜为无支撑膜的单层膜。
3.根据权利要求1或2的气体检测器，其特征在于，传感元件为支撑电阻值根据气体发生变化的金属氧化物半导体膜的MEMS芯片。
4.根据权利要求1～3中任一项的气体检测器，其特征在于，按照通过气体分离膜阻断人的呼气中的水蒸气的方式构成。
5.根据权利要求1～3中任一项的气体检测器，其特征在于，按照将环境中的VOC(挥发性有机物)与环状硅氧烷通过气体分离膜而分离的方式构成。
6.根据权利要求1～3中任一项的气体检测器，其特征在于，其进一步具备从透过气体分离膜后的气体中吸附检测对象以外的气体的吸附过滤器。
7.根据权利要求6的气体检测器，其特征在于，气体分离膜兼作吸附过滤器的外气侧壳。
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