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Surface acoustic wave based sensors for selective detection of low concentration elemental mercury vapour

机译:基于声表面波的传感器,用于选择性检测低浓度元素汞蒸气

摘要

Due to their highly toxic nature, mercury (Hg) has lots of adverse effects on human health and the environment. It is of no surprise that Hg emissions are considered as a major global concern and governing bodies around the world are now introducing stringent rules in order to reduce emissions from major anthropogenic sources. Efficient detection of elemental mercury (Hg0) vapour is of particular interest as it represents 64-90% of total mercury emissions as well as being the main source of other, more toxic forms that end up in the environment and food chain. The detection of Hg0 is also the major step in evaluating the potency of any implemented mercury removal technology within an industrial process. In this context, the major aim of this PhD project was to develop and investigate surface acoustic wave (SAW) based Hg0 vapour sensors that can detect Hg0 vapour concentrations below 400 ppbv (~3.6 mg/m3) in the presence of co-existing interfering gases (i.e. volatile organic compounds, humidity etc.) that are commonly found in many industrial environments and processes. In the journey to develop such sensor, a critical literature review revealed that there were several major research questions and hence knowledge gap that needed to be fulfilled prior to successfully developing low concentration SAW based Hg0 vapour sensors. Upon attempting to address these challenges, SAW devices with different structural designs and sensitive materials were investigated for selective Hg0 vapour sensing where either interdigitated transducers (IDTs) or a dedicated sensitive layer were employed as the sensing element. These sensing elements were based on thin films of gold (Au), silver (Ag) or Ni-Au alloy nanostructures thereby allowed to determine the effect of SAW design and material type on Hg0 vapour sensing performance. The developed SAW sensors were all tested toward different concentrations of Hg0 vapour (24 to 365 ppbv) at various operating temperatures, ranging from 35 to 105°C depending on the sensor design and material. The data from each developed sensor was analysed in order to study the effect of operating temperature on each sensor’s performance in terms of response magnitudes, limit of detection, recovery efficiency, response time, sorption/desorption rates, calibration curve trends, sensitivity and selectivity, which are all important when employing such devices in real-world industrial conditions. The interfering gas species selected for different selectivity tests were chosen to be ammonia, acetaldehyde, ethyl mercaptan, dimethyl disulphide, methyl ethyl ketone and humidity, which are known to be commonly available at industrial processes such as Alumina refinery and mining industries. To obtain an in-depth fundamental insight into the Hg0 sorption characteristics on the sensor sensitive layers, finite element method (FEM) simulations were employed, which confirmed some of the assumptions that were made from the experimental data regarding the sorption and diffusion behaviour of Hg0 atoms on sensing surface. Analysis of Hg0 vapour sensing data showed that the performance of the sensor depended heavily on the combination of structural design of the SAW device and the sensing materials employed. For instance, a lower LoD and higher Hg0 sorption capacity was achieved by employing Ag as opposed to Au as the IDT electrodes. When comparing two different SAW designs have the same sensing element, it was found that the IDT sensing element based design showed relatively lower LoD at low operating temperatures (i.e. 35°C) while the opposite trend was observed at higher operating temperature (i.e. 75°C). It was also found that the sensitivity of a SAW based Hg0 vapour sensor could be tailored by controlling the growth of Ni-Au alloy nanostructures on the SAW sensing surface, which can be done simply by changing the deposition parameters. The developed Ni-Au alloy based sensors showed faster response time than the Au-electrode based sensor while showing a lower LoD at elevated operating temperatures. Overall, the potential of SAW devices as selective Hg0 vapour sensor was extensively tested and devices’ feasibility for industrial application was analysed in detail.
机译:汞(Hg)具有剧毒性质,因此对人体健康和环境具有许多不利影响。毫不奇怪,汞排放被视为全球关注的主要问题,世界各地的理事机构现在都在实行严格的规定,以减少主要的人为来源的排放。高效检测元素汞(Hg0)蒸气尤其令人关注,因为它占汞总排放量的64-90%,并且是最终出现在环境和食物链中的其他更具毒性形式的主要来源。 Hg0的检测也是评估工业过程中任何已实施的除汞技术效力的主要步骤。在此背景下,该博士项目的主要目的是开发和研究基于表面声波(SAW)的Hg0蒸汽传感器,该传感器可在存在共存干扰的情况下检测低于400 ppbv(〜3.6 mg / m3)的Hg0蒸汽浓度。在许多工业环境和过程中普遍存在的气体(即挥发性有机化合物,湿度等)。在开发这种传感器的过程中,一篇重要的文献综述显示,在成功开发基于低浓度SAW的Hg0蒸汽传感器之前,存在一些主要的研究问题,因此需要弥补知识差距。在试图解决这些挑战时,对具有不同结构设计和敏感材料的SAW器件进行了研究,以进行选择性Hg0蒸气感测,其中采用叉指式换能器(IDT)或专用的敏感层作为感测元件。这些感测元件基于金(Au),银(Ag)或Ni-Au合金纳米结构的薄膜,从而可以确定SAW设计和材料类型对Hg0蒸气感测性能的影响。所开发的SAW传感器均在不同的Hg0蒸气浓度(24至365 ppbv)下,根据传感器的设计和材料,在35至105℃的各种工作温度下针对不同浓度的Hg0蒸气进行了测试。为了研究工作温度对每个传感器性能的影响,包括响应幅度,检测极限,恢复效率,响应时间,吸附/解吸速率,校准曲线趋势,灵敏度和选择性,在现实工业条件下使用此类设备时,这都是非常重要的。选择用于不同选择性测试的干扰气体种类为氨,乙醛,乙硫醇,二硫化二甲基,甲乙酮和湿气,这些气体在工业流程(例如氧化铝精炼厂和采矿业)中普遍可用。为了获得对传感器敏感层上Hg0吸附特性的深入基础了解,采用了有限元方法(FEM)模拟,这证实了一些有关Hg0吸附和扩散行为的实验数据的假设。感应表面上的原子。对Hg0蒸气感测数据的分析表明,传感器的性能在很大程度上取决于声表面波装置的结构设计和所采用的感测材料的结合。例如,通过使用Ag而不是Au作为IDT电极,可以实现更低的LoD和更高的Hg0吸附能力。当比较具有相同感测元件的两个不同的SAW设计时,发现基于IDT感测元件的设计在低工作温度(即35℃)下显示出相对较低的LoD,而在较高工作温度(即75℃)下观察到相反的趋势。 C)。还发现可以通过控制SAW感应表面上Ni-Au合金纳米结构的生长来定制基于SAW的Hg0蒸汽传感器的灵敏度,这可以通过改变沉积参数来简单地实现。已开发的基于Ni-Au合金的传感器显示出比基于Au-电极的传感器更快的响应时间,同时在升高的工作温度下显示出较低的LoD。总体而言,广泛测试了声表面波器件作为选择性Hg0蒸汽传感器的潜力,并且该器件已被广泛使用。详细分析了工业应用的可行性。

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    Kabir K;

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