CN113502104A - 一种氢泄漏检测涂料及其应用 - Google Patents
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Abstract
本发明涉及一种功能涂料及其应用,具体涉及一种用于检测氢的功能涂料及其使用方法。功能涂料包含作为基体的涂料和能够与氢反应发生颜色变化的变色材料。功能涂料与氢接触时,其颜色会发生改变,因而可通过涂料的颜色变化判断材料是否接触氢。本发明本质安全,应用方式简便,应用场景广泛,弥补了现有检测技术泄漏定位能力有限、微小泄漏难以捕捉的问题,是常用氢泄漏检测方法的补充,具有极高的使用价值。
Description
技术领域
本发明涉及一种功能涂料及其应用,具体涉及一种用于检测氢的功能涂料及其使用方法。
背景技术
氢能是未来能源技术革命和产业发展的一个重要方向,是实现碳达峰和碳中和的重要手段。与此同时,氢具有易扩散、难液化、易燃易爆的特点,泄漏会带来很大的危险性,因此有效防范氢泄漏一直是亟待解决的问题。
氢浓度气体传感器虽然是目前使用最广泛、技术最成熟的氢泄漏监测方法,但仍存在一定局限性。固定式传感器由于成本较高,仅能在有限的位置上布设,因此只能提供泄漏点存在的大致范围,而无法提供泄漏点的准确位置,更不适于在开放环境下使用;便携式传感器常用于泄漏点的排查,但也需要进行耗时耗力的排查后才能够确认。压力/耗量监测也是目前常用的氢泄漏检测方法,其利用容器压力或气体流量的异常变化来提示泄漏的发生。但这种方法无法实现对泄漏点的定位;在一些大体积大流量的储氢用氢设备中,局部的氢泄漏难以引起系统内压力耗量的明显变化,使得这种方法无法实现对氢泄漏的有效监测。
现有氢泄漏检测手段在应用范围和使用效果上存在的各种问题,使其无法满足行业对氢资源利用安全性的需求。随着氢资源利用的不断推广和快速增长,发展和应用具有原位实时监测和泄漏点即时定位能力的氢泄漏检测手段,已成为氢资源安全利用中迫切需要解决的问题。
发明内容
本发明的技术解决问题是:克服现有技术的不足,提出一种用于检测氢的功能涂料及其应用。
本发明的目的是通过以下技术方案实现的。
一种用于检测氢的功能涂料,其特征在于包含作为基体的涂料和能够与氢反应发生颜色变化的变色材料;所述基底涂料中可添加改性助剂改善其透气性能,使变色材料与氢可充分接触而发生变色反应,从而判断材料是否接触或所处环境中是否含有氢。
所述的变色材料组成包括活性物质和金属纳米粒子;所述活性物质为钨/钼/钯的氧化物、含氧酸、含氧酸盐、杂多酸、杂多酸盐中的一种或几种;所述金属纳米粒子为钯、铂、铑、铱、钌、锇、银中的一种或几种。
所述的改性助剂包含铝矾土、石英粉、刚玉、滑石、云母、珍珠岩、石棉、蛭石中的一种或几种,使涂层内部及表面形成微孔结构。
所述的涂料包含聚甲基丙烯酸酯、聚氨酯丙烯酸酯、全氟磺酸树脂、水性环氧树脂、丙烯酸树脂等水性涂料的一种或几种。
一种用于检测氢的功能涂料的使用方法:将涂料涂覆在待检测设备表面或管路接口等位置,通过观察涂层的颜色变化判断是否接触氢,或所处环境中是否含有氢。
相比于现有技术,本发明具有如下有益效果:
(1)本发明本质安全,应用方式简便,可视化表示方式简单直观,可通过局部变色指示氢的存在,弥补了压力损耗氢泄漏检测检漏点定位能力有限、难以发现细小泄漏的缺点,弥补了电子式氢气检测设备布局成本高的缺点,是常用氢泄漏检测方法的补充,具有极高的推广使用价值。
(2)本发明含可逆变色、不可逆变色两种类型。其中可逆变色涂料可应用于管路接口、焊缝等固定位置,在泄漏点修复后,涂料逐渐恢复至原有颜色,实现了可重复使用的功能。不可逆变色涂料可应用于包装箱、储氢瓶等一次性应用场景,不需重复应用。
(3)本发明应用场景广泛,在任意氢潜在泄漏位置均可应用,在某些异型管路、狭窄接口位置固定式电子传感器难以布设、便携式电子传感器探头难以靠近,若在建设期间便涂覆氢泄漏检测涂料即可持续进行泄漏监测。
(4)本发明可实现对于细微泄漏的捕捉记录功能,对于现有检测手段不易识别的间歇性、偶然性泄漏事件,可由涂层的变色效果予以记录,在泄漏扩大前起到预警作用。
(5)本发明添加了铝矾土、石英粉、刚玉、滑石、云母、珍珠岩、石棉、蛭石中的一种或几种,使涂层内部及表面形成微孔结构,有利于氢分子的渗入,使变色反应可以充分进行。
(6)本发明使用聚甲基丙烯酸酯、聚氨酯丙烯酸酯、全氟磺酸树脂、水性环氧树脂、丙烯酸树脂等水性涂料作为基底,消除了施工时的火灾危险性,且具有更好的透气性能,适用于对含氢环境的泄漏检测
(7)本发明提供的针对还原性气体的变色检测涂料的研发思路,针对其他具有还原性的气体(如硫化氢,肼等)的变色泄漏检测涂料均在该专利的保护范围内。
具体实施方式
为使本发明实施例的目的、技术方案和优点更加清楚,下面对本发明实施例的技术方案进行清楚完整的描述。显然,所描述的实施例是本发明的一部分实施例,而不是全部的实施例。基于所描述的本发明的实施例,本领域普通技术人员在无创造性劳动的前提下所获得的所有其他实施例,都属于本发明保护的范围。
基于特定组成的氢泄漏检测涂料在氢气作用下发生颜色变化来指示氢气泄漏是一种具有广阔应用前景的氢泄漏检测手段。相比于其他技术,本发明的氢泄漏检测方法具有诸多的优势。首先:该方法可更为直观的指示氢的存在,通过肉眼可分辨的颜色变化即可实现对氢泄漏的辨识;其次,本发明应用场景广泛,可直接涂覆于产氢、储氢、输氢设备表面,不受位置限制,在异型管路、狭窄接口位置也可进行应用;最后,由于其直观的表现方式,本发明可省去电源和电路的设置,提高了监测方法在含氢环境下的应用安全性。
本发明实施例提供一种可应用于氢泄漏检测的功能涂料,该涂料可在接触氢气时发生颜色变化。
本发明实施例提供的活性物质可以是金属氧化物,可以是水合金属氧化物,可以是金属含氧酸,可以是金属羟基氧化物,亦可以是前述各种形式金属氧化物组成的混合体系。
本发明实施例中活性物质能够与氢气反应,并被氢气还原为颜色有别于原活性物质的金属单质和/或低价态金属氧化物,例如墨绿色氧化钯被氢气还原为黑色的钯单质;黄色钨酸被氢气还原为蓝色的低价态钨酸,同时这种低价态钨酸还可以在脱离氢气的环境下被空气中的氧气氧化为原有的黄色钨酸,实现涂料的可逆变色。
本发明实施例提供的金属纳米粒子够吸附氢气分子并使氢气分子中的化学键断裂形成活泼氢原子,从而催化氢与金属氧化物之间的反应。对于一些实施例中的活性物质,其本身与氢气的反应速度极为缓慢而难以直接应用于变色涂料,在其表面附着催化用金属纳米粒子可大幅提高反应速率,使其能够在较短的时间内发生颜色变化。对于另外一些实施例中的活性物质,其本身虽可以与氢气发生反应变色,但需要通过一段时间的氢气接触变色过程才开始进行,在其表面附着催化用金属纳米粒子可大幅缩短这些活性物质的变色响应时间。
本发明实施例提供的改性助剂可以改善涂料的透气性能,从而可以使氢分子轻易进入涂层内部,与涂层中的活性物质发生化学反应,形成变色效果。同时,不同改性助剂由于其不同的颗粒形状,对涂料的透气性有不同影响。例如,加入球形颗粒的石英和刚玉,会在涂层表面形成外露的微孔;加入片状颗粒的滑石和云母,会形成隐蔽的微孔;加入胞格状组织结构的珍珠岩及纤维结构的石棉和蛭石会使涂层内部形成无序结构,构成松散的多孔结构,透气性较高。将不同种类的改性助剂进行合理搭配可在一定范围内调节涂料的透气性。
本发明实施例提供的水性涂料基底以水作为溶剂,消除了施工时的火灾危险性,且具有更好的透气性能,适用于对含氢环境的泄漏检测。同时,水性涂料对材质表面适应性好,涂层附着力强,可应用于各类管道、罐体、包装箱等材质的涂覆。相比于油性涂料,水性涂料漆面不易变黄、不易开裂脱落,避免了由于涂料基底颜色变化而导致对活性物质变色的误判。
本发明实施例提供的氢泄漏检测涂料可以通过变色速度和/或变色时间半定量地指示氢浓度,变色速度越快/变色时间越短,表明涂料所处环境中的氢浓度越高。应用变色时间指示氢浓度时,可使用氢泄漏检测涂料从开始接触氢到出现可分辨颜色变化所需的响应时间,也可使用涂料从开始接触氢至颜色变化完成而不再发生进一步颜色改变所需的时间。
下面通过具体实施例进一步阐述本发明的技术方案,但是本发明的保护范围不受这些具体实施例的具体条件的限制。
实施例1:在聚甲基丙烯酸酯涂料基底中加入石英和刚玉,及掺入含铱纳米粒子的三氧化钨,搅拌均匀后涂覆于玻璃板上。待其干燥凝固后,将玻璃板置于气室中,向气室内通入体积分数为5%的氢气(氮气为平衡气),约10min后可观察到涂层的颜色由淡黄色逐渐变为淡绿色。继续通气10min后,可观察到涂层的颜色变为蓝色。
实施例2:在环氧树脂涂料基底中加入滑石和云母,及掺入含铑纳米粒子的三氧化钼,搅拌均匀后涂覆于玻璃板上。待其干燥凝固后,将玻璃板置于气室中,向气室内通入体积分数为1%的氢气(氮气为平衡气),10min后可观察到涂层由白色变为蓝色。
实施例3:在丙烯酸树脂涂料基底中加入石棉和蛭石,及掺入含铂纳米粒子的钼酸,搅拌均匀后涂覆于实际应用的管路外侧。待其干燥凝固后,向管路中以1L/min的速度通入体积分数为10%的氢气(氮气为平衡气)。使用一个月后,发现管路某接口涂料涂覆位置颜色变为蓝色,经检测发现变色处接口发生氢泄漏。
Claims (5)
1.一种用于检测氢的功能涂料,其特征在于包含作为基体的涂料和能够与氢反应发生颜色变化的变色材料;所述基底涂料中添加改性助剂改善其透气性能,使变色材料与氢可充分接触而发生变色反应,从而判断材料是否接触或所处环境中是否含有氢。
2.根据权利要求1所述的功能涂料,其特征在于所述的变色材料组成包括活性物质和金属纳米粒子;所述活性物质为钨/钼/钯的氧化物、含氧酸、含氧酸盐、杂多酸、杂多酸盐中的一种或几种;所述金属纳米粒子为钯、铂、铑、铱、钌、锇、银中的一种或几种。
3.根据权利要求1所述的功能涂料,其特征在于所述改性助剂包含铝矾土、石英粉、刚玉、滑石、云母、珍珠岩、石棉、蛭石中的一种或几种,使涂层内部及表面形成微孔结构。
4.根据权利要求1所述的功能涂料,其特征在于所述涂料包含聚甲基丙烯酸酯、聚氨酯丙烯酸酯、全氟磺酸树脂、水性环氧树脂、丙烯酸树脂等水性涂料的一种或几种。
5.一种用于检测氢的功能涂料的使用方法,其特征在于:将涂料涂覆在待检测设备表面或管路接口等位置,通过观察涂层的颜色变化判断是否接触氢,或所处环境中是否含有氢。
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