Optical waveguide sensor of volatile organic compounds based on PTA thin film

In this study, a sensitive optical waveguide (OWG) sensor for the detection and identification of volatile organic compounds (VOCs) was reported. The sensing membrane is constructed by immobilization of peroxopolytungsten acid (PTA) thin film over a single-mode potassium ion (K⁺) exchanged glass OWG by spin-coating method. A laser beam was coupled into and out of the glass optical waveguide using prism couplers, and dry air functioned as a carrier gas. The sensor was tested for various volatile organic compounds (VOCs), and it showed higher response to the chlorobenzene gas compared to other VOCs. Therefore, we used the OWG sensor to detect chlorobenzene gas as a typical example of VOCs. The sensor exhibits a linear response to chlorobenzene gas in the range of 0.4-1000 ppm with rapid response and good reversibility. The constructed sensor is easy to fabricate and it has some unique qualities which can be characterized as inexpensive, sensitive, and reusable.     

四苯基卟啉锌薄膜/K+交换玻璃光波导传感器检测挥发性有机化合物气体

利用Alder法合成了四苯基卟啉锌配合物并对它进行表征;用匀胶机将一定浓度的四苯基卟啉锌溶液做成薄膜固定在钾离子(K⁺)交换玻璃光波导表面研制了高灵敏的四苯基卟啉锌薄膜/K⁺交换玻璃光波导传感器,并对挥发性有机气体进行检测。 实验结果表明,在室温下该传感器对低浓度的苯乙烯、二甲苯、甲苯等蒸气具有一定的响应,其中对苯乙烯的响应最大;能够检测到1×10^-9(V(苯乙烯)/V(空气))的苯乙烯蒸气,其响应和恢复时间分别为2和7 s。 该传感器具有灵敏度高,回复-响应时间快,可逆性等特点。     

偶氮苯-PVP复合薄膜光波导传感器检测苯乙烯

将掺杂偶氮苯（Azo）的聚乙烯吡咯烷酮（PVP）作为敏感试剂,利用旋转甩涂法将其固定在钾离子（K⁺）交换玻璃光波导表面,研制了Azo-PVP复合薄膜/K⁺交换玻璃光波导气敏元件,并对其气敏特性进行研究。实验结果表明,该敏感元件对苯乙烯蒸汽有较好的选择性响应,其最低检测浓度为1.0×10^-8体积比（V/V₀）,响应-恢复时间分别为9 s和24 s。在浓度1.0×10^-81.0×10^-3（V/V₀）范围内,气体浓度与输出光强度之间有较好的线性关系。     

PVA薄膜光波导气敏元件及其应用研究

将纯聚乙烯醇(PVA)和掺有维生素C的PVA作为敏感试剂,通过旋转甩涂法分别研制出了PVA薄膜/锡掺杂玻璃光波导元件和VC-PVA薄膜/锡掺杂玻璃光波导元件并检测其气敏特性.实验结果表明,PVA薄膜/锡掺杂玻璃光波导元件对二甲苯气体有良好的选择性响应,其响应浓度范围为10-4～10-7(体积比);加入VC后,使此敏感元...     

MB-硬脂酸复合薄膜光波导传感器检测氯化氢气体

利用旋转甩涂法将亚甲基蓝(MB)掺杂的硬脂酸溶液涂成薄膜固定在钾离子(K⁺)交换玻璃光波导表面上, 研制了MB-硬脂酸复合薄膜/K⁺交换玻璃光波导传感器, 并对酸性气体进行了检测. 该复合薄膜与氯化氢(HCl)气体作用时, 薄膜颜色从深蓝色变为浅蓝色, 导致薄膜对倏逝波的吸收降低, 使传感器的输出光强度增强. 结果表明, 在室温下该传感器对低浓度的氯化氢气体仍具有较好的重复性和选择性响应, 可检测到体积分数为1×10^-6%的HCl气体, 响应和恢复时间分别为7和20 s, 相对标准偏差为±6.06%. 该传感器具有灵敏度高、 响应-恢复速度快、 可逆性好、 成本低和容易制备等特点.     

刚果红交联聚乙烯醇薄膜／K^＋交换玻璃光波导检测氯化氢气体

用环氧氯丙烷为交联剂合成了刚果红(CR)交联聚乙烯醇(PVA)CR-PVA敏感试剂.用匀胶机将其做成薄膜固定在钾离子交换玻璃光波导表面,研制出一种光波导氯化氢气体传感器.CR-PVA薄膜碱式结构的最大吸收波长在600 nm以下,对波长为632.8 nm的激光吸收很弱;薄膜与酸性气体发生反应后强烈吸收波长在632.8 nm附近的导波或消失波;检测输出光强度的变化,即能够测出酸性气体浓度.测试结果表明,本传感器对低浓度HCl气体有快速响应,且对1.6～192 mg/m3范围内有良好的线性响应;SO2、NO2气体的浓度大于18000 mg/m3时才有响应,而对于高、低浓度H2S气体均无响应.     

光波导乙醇气体传感器的研究

以聚偏氟乙烯(PVDF)作为敏感试剂固定在钾(K⁺)离子交换玻璃光波导表面,研制了光波导乙醇气体传感器.该传感器具有可逆性好、灵敏度高、响应速度快、选择性和重现性好、能在室温操作等特点.     

Thin film composite optical waveguides for sensor applications: a review

We review the design and fabrication of thin-film composite optical waveguides (OWG) with high refractive index for sensor applications. A highly sensitive optical sensor device has been developed on the basis of thin-film, composite OWG. The thin-film OWG was deposited onto the surface of a potassium-ion-exchanged (K⁺) glass OWG by sputtering or spin coating (5–9 mm wide, and with tapers at both ends). By allowing an adiabatic transition of the guided light from the secondary OWG to the thin-film OWG, the electric field of the evanescent wave at the thin film was enhanced. The attenuation of the guided light in the thin film layer was small, and the guided light intensity changed sensitively with the refractive index of the cladding layer. Our experimental results demonstrate that thin-film, composite OWG gas sensors or immunosensors are much more sensitive than sensors based on other technologies.     

Colorimetric Artificial Nose for Identification of Breath Volatile Organic Compounds of Patients with Lung Cancer

A novel and highly sensitive colorimetric sensor array was developed for the detection and identification of breath volatile organic compounds（VOCs） of patients with lung cancer.Employing dimeric metalloporphyrins,metallosalphen complexes,and chemically responsive dyes as the sensing elements,the developed sensor array of artificial nose shows a unique pattern of colorific changes upon its exposure to eight less-reactive VOCs and their mixture gas at a concentration of 735 nmol/L within 3 min.Potential of quantitative analysis of VOCs samples was proved.A good linear relationship of 490-3675 nmol/L was obtained for benzene vapor with a detection limit of 49 nmol/L（S/N=3）.Data analysis was carried out by Hierarchical cluster analysis（HCA） and principal component analysis（PCA）.Each category of breath VOCs clusters together in the PCA score plot.No errors in classification by HCA were observed in 45 trials.Additionaly,the colorimetric sensor array showed good reproducibility under the cyclic sensing experiments.These results demonstrate that the developed colorimetric artificial nose system is an excellent sensing platform for the identification and quantitative analysis of breath VOCs of patients with lung cancer.     

高灵敏复合光波导在检测臭氧的应用研究

介绍利用高灵敏复合光波导元件检测臭氧的一种新方法以及实验装置和臭氧的响应特征。通过在K^＋交换玻璃光波导表面形成高折射率TiO2（两端带斜坡带状）膜并在其表面上固定色素铜化酞箐（Coppertetra-（t-buthyl）phthalocyanine,TBPcCu）而制成高灵敏度的复合光波导元件。臭氧存在时TBPcCu薄膜被氧化而退色,由此减弱TBPcCu膜对633nm的导波光的吸收。本元件具有响应速度快,灵敏度高和检测极限在0．02mg/m^3等特点。     

Discrimination of Lung Cancer Related Volatile Organic Compounds with a Colorimetric Sensor Array

A simple and rapid discrimination of four lung cancer related volatile organic compounds (VOCs) was achieved with a novel colorimetric sensor array. Based on the cross-responsive mechanism, the sensor system exhibited high sensitivity to selected lung cancer biomarkers, including p-xylene, styrene, isoprene, and hexanal with concentrations varying from 50 ppb to 500 ppb. By extracting color information, it provided good selectivity and fine discrimination of selected gases via pattern recognition with Fisher linear discriminant (FLD). Additionally, with the employment of the Takagi-Sogeno Fuzzy Neural Network (TSFNN), different concentrations of selected VOCs were discriminated. It also suggested that the colorimetric sensor array proposed could not only distinguish different lung cancer related VOCs but also discriminate specific VOCs of different concentrations with an average rate of classification up to 95%. Our preliminary study demonstrated that the cross-responsive sensor array had infinite potential for further clinical and commercial use for early diagnosis of lung cancer.     

Combination of a Mid-infrared Hollow Waveguide Gas Sensor with a Supported Capillary Membrane Sampler for the Detection of Organic Compounds in Water

A Fourier transform infrared (FT-IR) spectroscopy based gas sensor for continuous analysis of liquid phase samples has been developed, coupling a short hollow waveguide (HWG) gas cell with a supported capillary membrane sampler (SCMS) probe. Passing an inert carrier gas through the thin-walled tubular silicon membrane enables the permeation of volatile organic compounds (VOCs) present in aqueous solution and facilitates their continuous and quantitative detection in the infrared hollow fiber by multiple internal reflection spectroscopy. The sensitivity of the sensor system has been determined at the ppb (μg/L) concentration level and the response time ranges from few minutes to 30 min, depending on the analyte and the permeation properties of the sampling membrane.

The experimental set-up consists of Bruker Vector 22 FT-IR spectrometer with an externally aligned 50 cm long silica HWG coupled to the SCMS, which is immersed into a glass flask filled with analyte solution and kept under constant stirring.

Aqueous solutions of benzene, toluene, xylene isomers and chloroform were qualitatively and quantitatively analyzed confirming the feasibility of this sensor approach for environmental analysis.     

光波导传感元件在检测酸性气体中的应用

采用旋转甩涂法将甲基紫传感薄膜固定在特制的锡(Sn2+,Sn4+)掺杂玻璃光波导(Sn doped glass slide)表面,研究了该传感薄膜与HCl、H2S、以及SO2作用前后的可见吸收光谱的变化,并在此基础上研制了玻璃光波导酸性气体(HCl、H2S、SO2)传感元件。传感薄膜与酸性气体作用时,薄膜的颜色发生变化,从而降低薄膜对倏逝波的吸收,使传感器的输出光强度(信号)增强。本文采用流动注射法对酸性气体进行了检测。实验结果表明,在室温下,该传感元件对硫化氢气体具有明显的响应,而对相同浓度的其他酸性气体的响应相对较小,对浓度在6×10-4～2.5×10-5(V/V)的硫化氢气体具有良好的线性响应(R=0.9979,n=4),相对标准偏差(RSD)为±3.5%,具有响应快、可逆性和重复性好、容易制备、可以在室温下工作等特点。     

Emission Profiles of Volatiles during 3D Printing with ABS,ASA, Nylon,and PETG Polymer Filaments

In this short communication we characterize the emission of volatile organic compounds (VOCs) from fused filament fabrication (FFF) 3D printing using four polymer materials, namely polyethylene terephthalate glycol-modified (PETG), acrylonitrile styrene acrylate (ASA), Nylon, and acrylonitrile butadiene styrene (ABS). Detailed emission profiles are obtained during thermal degradation of the polymers as a function of temperature and also in real-time during 3D printing. Direct quantitative measurement was performed using proton transfer reaction time-of-flight mass spectrometry (PTR-ToF-MS). Qualitative determination of the volatiles emitted from the printed elements at various temperatures was accomplished using gas chromatography-mass spectrometry (GC-MS). The emission rates of VOCs differ significantly between the different polymer filaments, with the emission from Nylon and PETG more than an order of magnitude lower than that of ABS.     

Investigation of relative humidity effects on the response behavior of a pH indicator-based OWG vapor sensor

The response of a pH indicator-based optical waveguide sensor was characterized with respect to the effects of relative humidity (RH) on the magnitude of the sensor response, and on the rate of response to both hydrochloric acid and ammonia/ammonium hydroxide vapors. Water vapor constitutes both a chemical and a systematic (optical) interference for the OWG sensor response to hydrochloric acid. Swelling of the polymer films upon exposure to water vapor results in a decrease in the loss of light at the polymer/air interface, resulting in an increase in the sensor signal. In addition, high RH conditions decrease the bromothymol blue indicator response to hydrochloric acid vapor. In contrast, the bromothymol blue indicator response to ammonia increases as the RH increases. High RH levels also increases the rate of diffusion (transport) of hydrochloric acid into (and out of) Nafion films, but does not affect the diffusion rate for poly(vinyl alcohol) polymer films. The RH does not appear to have any significant effect on the rate of transport of ammonia in any of the polymer films studied.     

氧化锌薄膜/锡掺杂玻璃光波导元件及其对氯苯的气敏性研究

建立了玻璃光波导气敏元件检测氯苯气体的方法.采用浸渍-提拉法将ZnO敏感膜固定在锡掺杂玻璃光波导表面,研制出了检测氯苯气体的ZnO薄膜/锡掺杂玻璃光波导气敏元件,并用该玻璃光波导气敏元件对挥发性有机气体进行了检测.实验结果表明,在室温下,气敏元件对氯苯气体有明显的响应,而对相同浓度的其它挥发性有机气体的响应相对较小,对...     

α-Fe2O3负载Ag复合纳米材料的制备、表征和气敏性能

采用简单的FeCl3溶液水热方法, 结合焙烧处理合成了α-Fe2O3 纳米粉体; 以所制备的α-Fe2O3为载体负载Ag纳米粒子, 得到Ag/α-Fe2O3 复合纳米材料. 使用X射线衍射、 透射电子显微镜、 氮气吸附-脱附和X射线光电子能谱等对样品进行表征, 并考察了Ag/α-Fe2O3复合材料在260℃下对甲醇、 乙醇、 乙醚、 丙酮、 正丁醇和正己醇等挥发性有机物的气敏行为. 结果表明, Ag/α-Fe2O3传感器对这几种挥发性有机物展示了较高的灵敏度和快速、 可逆的响应-恢复特性; 与纯α-Fe2O3相比, Ag/α-Fe2O3复合材料的气敏性能显著提高, 这可能与该复合材料表面独特的多孔结构和活性Ag纳米粒子对敏感反应的催化作用有关.     

Oximation reaction induced reduced graphene oxide gas sensor for formaldehyde detection

High-performance gas sensors can offer great potentials for monitoring and detection of volatile organic compounds (VOCs) in both domestic and industrial environment. In the present work, a new HCHO gas sensor was constructed with reduced graphene oxide (RGO) induced by the oximation reaction. The gas-sensing performance test results suggested that the RGO hydroxylamine hydrochloride (RGO/HA-HCl) sensor presented a high response of 75% at 16 ppm HCHO at room temperature, and a high selectivity for HCHO suffering little interference with high concentrations of volatile organic compounds, including methanol, ethanol, and methylbenzene, dichloromethane and water. Additionally, the RGO/HA-HCl sensor also showed a good long-term stability with RSD of 5.83% for a 15-day continuous sensing test, and the detection limit (DL) could reach 0.023 ppm under ambient conditions. Moreover, the mechanism for the high sensitivity and selectivity of formaldehyde was further established by in-situ gas chromatography mass spectrometry (GC–MS). This work would provide a reliable new HCHO gas sensor which could be used for monitoring and forewarning the emission of HCHO for a better protection and improvement of our environment.     

水热法制备MoO3-GQDs的三甲胺气敏性能

采用水热法制备了一系列具有不同碳量子点(GQDs)含量的MoO3?GQDs纳米复合材料,利用X射线衍射、扫描电子显微镜、透射电子显微镜、FTIR等对MoO3?GQDs复合材料进行了表征,研究了其气敏性能。结果表明,复合材料中GQDs的含量对MoO3?GQDs复合材料的气敏响应和选择性有显著影响。MoO3?GQDs纳米复合材料(S?6,GQDs悬浮液的含量为6 mL)传感器在230℃时对三甲胺(TMA)表现出高的气敏响应和好的气敏选择性;该传感器对1000μL·L^-1 TMA的响应为74.08;对1000μL·L^-1 TMA的响应时间和恢复时间分别为73和34 s;S?6复合材料气敏传感器在230℃时可以检测到1μL·L^-1的TMA。     

Humidity effect on the monolayer-protected gold nanoparticles coated chemiresistor sensor for VOCs analysis

Two gold-thiolate monolayer-protected nanoparticles were synthesized and used as interfacial layers on chemiresistor sensors for the analysis of violate organic compounds (VOCs). Toluene, ethanol, acetone and ethyl acetate were chosen as the target vapors. Both the resistance and capacitance were measured as the function of analyte concentrations. The effect of humidity on the sensor sensitivity to VOCs was investigated. The sensitivity decreases with humidity increasing, depending on the hydrophobicity of the target compounds. Less effect was observed on the higher hydrophobic compounds. While the relative humidity (RH) increased from 0 to 60%, the sensitivity to acetone decreased by 39 and 37%, respectively on the Au-octanethiol (C₈Au) and Au-2-phenylethanethiol (BC₂Au) coated sensors, while the sensitivity to toluene decreased by 12 and 14%, respectively. These results show that the sensors coated with hydrophobic compounds protected-metal nanoparticles can be employed in high humidity for hydrophobic compounds analysis. The resistance responses to VOCs are rapid, reversible, and linear, while the capacitance response is not sensitive and consequently not applicable for VOCs analysis. The response mechanism was also discussed based on the sensor response to water vapor. The capacitance response is not sensitive to the film swelling in dry environment.