Composites of carboxylate-capped TiO2 nanoparticles and carbon black as chemiresistive vapor sensors

Titanium (IV) dioxide (TiO₂) nanoparticles (NPs) with a 1-5 nm diameter were synthesized by a sol-gel method, functionalized with carboxylate ligands, and combined with carbon black (CB) to produce chemiresistive chemical vapor sensor films. The TiO₂ acted as an inorganic support phase for the swellable, organic capping groups of the NPs, and the CB imparted electrical conductivity to the film. Such sensor composite films exhibited a reproducible, reversible change in relative differential resistance upon exposure to a series of organic test vapors. The response of such chemiresistive composites was comparable to, but generally somewhat smaller than, that of thiol-capped Au NPs. For a given analyte, the resistance response and signal-to-noise ratio of the capped TiO₂-NP/CB composites varied with the identity of the capping ligand. Hence, an array of TiO₂-NP/CB composites, with each film having a compositionally different carboxylate capping ligand, provided good vapor discrimination and quantification when exposed to a series of organic vapors. Principal components analysis of the relative differential resistance response of the sensor array revealed a clear clustering of the response for each analyte tested. This approach expands the options for composite-based chemiresistive vapor sensing, from use of organic monomeric or polymeric sorbent phases, to use of electrically insulating capped inorganic NPs as the nonconductive phase of chemiresistive composite vapor sensors.     

Vapor recognition with an integrated array of polymer-coated flexural plate wave sensors

Preliminary testing of a prototype instrument employing an integrated array of six polymer-coated flexural plate wave (FPW) sensors and an adsorbent preconcentrator is described. Responses to thermally desorbed samples of individual organic solvent vapors and binary and ternary vapor mixtures are linear with concentration, and mixture responses are equivalent to the sums of the responses of the component vapors, which co-elute from the preconcentrator in most cases. Limits of detection as low as 0.3 ppm are achieved from a 60-s (34 cm³) air sample and peak widths at half-maximum range from 1 to 4 s. Tests at different flow rates suggest that the kinetics of vapor sorption in the sensor coating films may limit responses at higher flow rates, however, low data acquisition rates may also be contributory. Assessments of array performance using independent test data and Monte Carlo simulations with pattern recognition indicate that individual vapors and certain binary and ternary mixtures can be recognized/discriminated with very low error. More complex mixtures, and those containing homologous vapors, are problematic. This is the first report demonstrating multi-vapor analysis with an integrated FPW sensor array.     

可视嗅觉传感器阵列研究及图像分析

针对目前电子鼻系统普遍存在的检测范围窄、受环境湿度影响较大等缺点,本文依据金属卟啉配合物与有机气体反应会产生颜色变化的原理,研制了一种新型的气体敏感膜,设计了可视嗅觉传感器阵列的实验系统.系统通过分析敏感膜与不同的气体反应所呈现的颜色变化识别气体,具有完全不受外界水蒸气影响和检测精度高等特点.用该传感器敏感膜分别对环己胺、乙腈和四氢呋喃进行了试验,试验结果表明该传感器阵列能够正确地识别这三种有机物.     

Modeling Carbon-Black/Polymer Composite Sensors

Conductive polymer composite sensors have shown great potential in identifying gaseous analytes. To more thoroughly understand the physical and chemical mechanisms of this type of sensor, a mathematical model was developed by combining two sub-models: a conductivity model and a thermodynamic model, which gives a relationship between the vapor concentration of analyte(s) and the change of the sensor signals. In this work, 64 chemiresistors representing eight different carbon concentrations (8-60 vol% carbon) were constructed by depositing thin films of a carbon-black/polyisobutylene composite onto concentric spiral platinum electrodes on a silicon chip. The responses of the sensors were measured in dry air and at various vapor pressures of toluene and trichloroethylene. Three parameters in the conductivity model were determined by fitting the experimental data. It was shown that by applying this model, the sensor responses can be adequately predicted for given vapor pressures; furthermore the analyte vapor concentrations can be estimated based on the sensor responses. This model will guide the improvement of the design and fabrication of conductive polymer composite sensors for detecting and identifying mixtures of organic vapors.     

Chemo-sensitivity of latex-based films containing segregated networks of carbon nanotubes

In contrast to conventional hydrophobic Conductive Polymer nanoComposites (CPCs) used to design vapor sensors, which are mostly soluble in organic solvents, monodispersed acrylate copolymer latexes present the double advantage of being more sensitive and selective towards polar vapors such as water. A hierarchically structured latex based CPC film was obtained by co-dispersion of an aqueous acrylic emulsion with multiwalled carbon nanotubes (CNTs), followed by spray layer by layer (sLbL) assembly. The analysis of CPC films morphology by AFM and TEM show that a segregated network of CNT as been achieved by partial coalescence of latex nanoparticles and homogeneously assembled in 3D. Transducer sensitivity was investigated as a function of CNT content, latex glass transition temperature (T_g), organic vapor nature and vapor concentration. The source of the high sensitivity and selectivity observed for these latex-based composites towards water vapor is assumed to mainly result from ionic interaction of SDS with water molecules offering interesting perspectives of development. The different diffusion regimes through the CPC transducer are visualized, modeled and interpreted with the Langmuir-Henry-Clustering (LHC) model, showing that only water is reaching a clustering mode at high vapor concentration. Finally it is believed that the unique hierarchical architecture of BA latex-CNT sensors is responsible for their quick, stable and reproducible responses to vapors.     

A hybrid chemiresistive sensor system for the detection of organic vapors

A five node sensor array, consisting of three films of gold nanoparticles functionalized with p-terphenylthiol, dodecanethiol and mercapto-(triethylene glycol) methyl ether, and films of poly(3-hexylthiophene) and polypyrrole, was integrated into a portable, microprocessor-based system. The system was evaluated for the detection of chloroform, diisopropyl methylphosphonate (DIMP), ethanol, hexane, methanol, and toluene vapors. Direct comparison of the five sensor films with respect to sensitivity, response time and recovery time was made by measurement of the resistance changes upon simultaneous exposure to each analyte. In general, the sensor films responded, with greatest sensitivity, to organic analyte molecules with similar chemical functionality (e.g., polarity). For example, the dodecanethiol-functionalized gold nanoparticle film sensor excelled at detecting hexane, while the mercapto-(triethylene glycol) methyl ether-functionalized nanoparticle film exhibited superb detection of ethanol and chloroform. Although the poly(3-hexylthiophene) film was very sensitive to polar analytes, including DIMP, in many cases it suffered from relatively long recovery times. Following training of the sensor system, successful differentiation and detection of the analytes were realized using a relatively simple algorithm based on “minimization of the squares of differences” method. The ability of the system to optimally differentiate these analytes is considered within the context of principal component analysis, and the effects of long-term sensor drift are discussed.     

Thin film characterization and vapor sensing properties of a novel perylenediimide material

A novel N,N′-(glycine tert-butylester)-3,4,9,10-perylenediimide was chosen for the study of Langmuir–Blodgett (LB) thin film characterization and the sensing properties against selected volatile organic vapors. Different number of LB film layer was deposited onto a glass and quartz crystal substrate. The thin film fabrication process was monitored with UV–vis and quartz crystal microbalance (QCM) measurement techniques. The results indicated that absorbance increased linearly with the number of the layers on film. A similar linear relationship between frequency shift and number of the layers was observed by the QCM measurement. It can be concluded that high quality and uniform LB films were produced by using this novel perylenediimide material. Chloroform, toluene, benzene, ethyl alcohol and isopropyl alcohol vapors were selected to test this material's applicability in room temperature as a vapor sensor. This novel material showed a fast, large and reproducible response to chloroform and isopropyl alcohol vapor.     

A distributed Bragg reflector porous silicon layer for optical interferometric sensing of organic vapor

In this study, we successfully demonstrated the rapid, sensitive, and reversible sensing of organic vapor using a distributed Bragg reflector (DBR) porous silicon (PS) layer. We fabricated the DBR PS layer on a p⁺-type silicon substrate and investigated its reflectance spectra before, during, and after exposure to the different concentrations of various organic vapors. When the DBR PS layer sample was exposed to methanol, acetone, ethanol, and isopropanol vapors, the maximum reflectance peak promptly shifted toward longer wavelengths by about 4.5, 23.2, 26.0, and 38.2 nm, respectively. We determined that the red-shift in the reflectance spectrum could be attributed to the changes in the refractive index induced by the capillary condensation of the organic vapor within the pores of the DBR PS layer. The DBR PS layer showed excellent sensing ability under the different concentrations and types of organic vapors. In addition, a slight hysteresis of the red-shift was observed during repeated exposure to organic vapors at different concentrations. After removing the organic vapors, the reflectance spectrum promptly returned to its original state.     

Synthesis of ZnO thin films and their application as humidity sensors

Humidity sensors were fabricated using ZnO thin films synthesized on a Si wafer substrate. The ZnO thin films were grown via a vapor solid (VS) approach at temperatures ranging from 400 to 700 °C. Experiments were executed to observe the relationships between the relative humidity (RH) and resistance of these devices fabricated under various VS temperatures. Experimental results show that the ZnO thin films grown at a temperature of 700 °C using the VS approach exhibits an optimum sensitivity to humidity. The measured sensor resistance ranges from 495 × 10⁶ to 46 × 10³ Ω for RH ranging from 11 to 95 % at room temperature. The variance of sensor resistance exceeds 10⁴ times, indicating that the proposed method can produce a highly sensitive humidity sensor.     

Poly(3-hexylthiophene) and hexafluoro-2-propanol-substituted polysiloxane based OFETs as a sensor for explosive vapor detection

The organic field effect transistors (OFETs) with regioregular poly 3-hexylthiophene (rr-P3HT) and hexafluoro-2-propanol-substituted polysiloxane (SXFA) as an organic layer, have been used for detection of explosive vapors with excellent sensitivity of less than 70 ppt for 1,3,5-trinitro-1,3,5-triazacyclohexane (RDX) and less than 100 ppt for 2,4,6-trinitrotoluene (TNT). The sensor response (% change in saturation current) was found to be 125 ± 10% for TNT and 90 ± 10% for RDX. It was also observed that the incorporation of Cu^II tetraphenylporphyrin (CuTPP) into rr-P3HT/SXFA matrix resulted in an improved selectivity for the vapors of nitro based analytes (TNT, RDX and DNB) as compared to the vapors of non explosive oxidizing agents such as nitrobenzene (NB), benzoquinone (BQ) and benzophenone (BP). This is attributed to the increased binding of the vapors containing nitro compound to the thin films due to the presence of CuTTP. Spin coated thin films were further characterized by Atomic Force Microscopy (AFM) and Electrostatic Force Microscopy (EFM).     

Corrosion resistant and adsorbent plasma polymerized thin film

Adsorbent and corrosion resistant films are useful for sensor development. Therefore, the aim of this work is the production and characterization of plasma polymerized fluorinated organic ether thin films for sensor development. The polymerized reactant was methyl nonafluoro(iso)butyl ether. Infrared Spectroscopy showed fluorinated species and eventually CO but CH_n is a minor species. Contact angle measurements indicated that the film is hydrophobic and organophilic but oleophobic. Optical microscopy reveals not only a good adherence on metals and acrylic but also resistance for organic solvents, acid and basic aqueous solution exposure. Double layer and intermixing are possible and might lead to island formation. Quartz Crystal Microbalance showed that 2-propanol permeates the film but there is no sensitivity to n-hexane. The microreactor manufactured using a 73 cm long microchannel can retain approximately 9 × 10⁻⁴ g/cm² of 2-propanol in vapor phase. Therefore, the film is a good candidate for preconcentration of volatile organic compounds even in corrosive environment.     

Multi frequency interrogation of polypyrrole based gas sensors for organic vapors

Polypyrrole exhibits reversible changes in their direct current resistance on exposure to organic volatiles. However, one needs to employ an array of such sensors to discriminate organic volatiles present in a mixture. Hence, polypyrrole based gas sensor is designed for the detection and discrimination of different organic volatiles. Multi frequency impedance measurement technique is used to detect the organic vapors, such as acetone, ethanol and Isopropyl alcohol, in the gas phase, over a frequency range 10 Hz to 2 MHz. The sensor response is monitored by measuring the changes in its capacitance, resistance and the dissipation factor upon exposure to organic volatiles. It is observed that the capacitive property of the sensor is more sensitive to these volatiles than its resistive property. Each volatile responds to the sensor in terms of dissipation factor at specific frequency and found that the peak magnitude has a linear relationship with their concentrations.     

Vapor sensing properties of thermoplastic polyurethane multifilament covered with carbon nanotube networks

The volatile organic compound (VOC) vapor sensing properties of a novel kind of thermoplastic polyurethane multifilament - carbon nanotubes (TPU-CNTs) composites is studied. And the sensing is based on changes in the electrical resistance of the composites due to vapor contact. The composites were readily obtained by adhering CNTs on the surface layer of TPU by means of simply immersing pure TPU multifilament into CNT dispersion. The uniformly formed nanotube networks on the outer layer of composite multifilament are favorable for providing efficient conductive pathways. The resulting TPU-CNTs composites show good reproducibility and fast response (within seconds) of electrical resistance change in cyclic exposure to diluted VOC and pure dry air. The vapor sensing behaviors of the composites are related to CNT content, vapor concentration, and polar solubility parameters of the target vapors. A relatively low vapor concentration of 0.5% is detectable, and a maximum relative resistance change of 900% is obtained for the composite with 0.8 wt.% CNT loading when sensing 7.0% chloroform. It is proposed that both the disconnection of CNT networks caused by swelling effects of the TPU matrix and the adsorption of VOC molecules on the CNTs are responsible for the vapor sensing behavior of TPU-CNTs composite, while the former effect plays the major role.     

Assembly of Cu nanoparticles in a polyacrylamide grafted poly(vinyl alcohol) copolymer matrix and vapor-induced response

A vapor-sensitive electroconductive film was designed and assembled by inserting Cu²⁺ particles into a polyacrylamide grafted poly(vinyl alcohol) (PAM-g-PVA) in virtue of a complexation between Cu²⁺ and PVA even PAM, as well as the establishment of inter- and intramolecular attractions between polymer matrices, which were in turn reduced into Cu nanoparticles by sodium hypophosphite as a reducing agent. The PAM-g-PVA graft copolymer was prepared via a simple free radical polymerization reaction initiated by a redox reaction. The resistance responsiveness of the film samples to various organic vapor surroundings was investigated. The responsive magnitude, response time and recovery properties depend on the molecular weight of the graft polymer or the PAM chain length and initial resistances of the film samples or Cu particle contents upon exposed to ether and petroleum ether vapor, etc. The structure and morphologies of the PAM-g-PVA/Cu were characterized by a Fourier transform infrared spectroscope and a transmission electron microscope. The response mechanism of the PAM-g-PVA/Cu films to solvent vapors was accounted for by a swelling theory and an interaction between solvent vapor molecules and nanocomposites as well as the type and strength of interaction that each solvent vapor exhibits on the material.     

Improvement of gas sensing performance of carbon black/waterborne polyurethane composites: Effect of crosslinking treatment

When carbon black (CB) filled waterborne polyurethane (WPU) composites are exposed to organic solvent vapors, electrical resistance of the materials increases rapidly. They can thus serve as gas sensors. To improve the composites’ performance for practical applications, crosslinking agent was added to the composite latexes, forming intra-molecular crosslinked networks among the matrix polymer of the composites. The method greatly increased the filler/matrix interfacial interaction and reduced the mobility of CB particles. In the composites that had absorbed solvent vapors, reconstruction of conduction paths through re-aggregation of the disconnected filler particulates became difficult. As a result, the unwanted negative vapor coefficient (NVC) effect was significantly weakened, while the gas sensitivity and the performance reproducibility were enhanced as well.     

Optical parameters of calix[4]arene films and their response to volatile organic vapors

The Langmuir-Blodgett (LB) technique was employed to produce thin LB films using an amphiphilic calix-4-resorcinarene onto different substrates such as quartz, gold coated glass and quartz crystals. The characteristics of the calix LB films are assessed by UV-visible, quartz crystal microbalance (QCM) and surface plasmon resonance (SPR) measurements. UV-vis and QCM measurements indicated that this material deposited very well onto the solid substrates with a transfer ratio of >0.95. Using SPR data, the thickness and refractive index of this LB film are determined to be 1.14 nm/deposited layer and 1.6 respectively. The sensing application of calixarene LB films towards volatile organic vapors such as chloroform, benzene, toluene and ethanol vapors is studied by the SPR technique. The response of this LB film to saturated chloroform vapor is much larger than for the other vapors. The response is fast and fully recoverable. It can be proposed that this sensing material deposited onto gold coated glass substrates has a good sensitivity and selectivity for chloroform vapor. This material may also find potential applications in the development of room temperature organic vapor sensing devices.     

Effect of trace residual ionic impurities on the response of chemiresistor sensors with dithiol-linked monolayer-protected gold (nano)clusters as sensing interfaces

Column liquid–solid chromatography was used to remove residual impurities of isolated n-octanethiol (C₈H₁₇SH) monolayer-protected gold nano-clusters (MPCs) which were synthesized by a Brust two-phase method. Three-dimensional (3D) cross-linked MPC films were prepared directly on interdigitated electrodes to form chemiresistor sensors through the exchange reactions of the chromatographically purified MPCs with 1,6-hexanedithiol (HDT) or 1,4-benzenedimethanethiol (BDT). Ionic current induced by trace residual ionic impurities in MPCs was qualitatively detected by comparing the resistance responses of the sensors interfaced with the chromatographically purified and unpurified MPC films by employing volatile organic compounds (VOCs) and water vapor as probes, respectively. The existence of the ionic current significantly decreases the sensor sensitivities to VOCs. As for water vapor with high permittivity, the ionic current totally distorted the resistance responses from positive to negative with increasing humidity. Capacitance was also measured to characterize the permittivity change. The effect of ionic current on capacitance was not obvious. The humidity effects on the sensor responses to VOCs were also investigated. Fewer effects were observed on the higher hydrophobic compounds. A ternary sensor array was constructed with C₈Au MPCs, HDT and BDT cross-linked MPC films as sensing interfaces. The response pattern showed that the sensor array could discriminate VOCs with different functional groups. The as-prepared sensor showed the same sensitivities as the acoustic wave sensors.     

Gas sensing properties of a composite composed of electrospun poly(methyl methacrylate) nanofibers and in situ polymerized polyaniline

Poly(methyl methacrylate) (PMMA) nanofibers with different diameters were fabricated by electrospinning and their composites with polyaniline (PANI) were formed by virtue of in situ solution polymerization. The coaxial composite nanofibers so prepared were then transferred to the surface of a gold interdigitated electrode to construct a gas sensor. The structure and morphology of the PANI/PMMA composite fibers were characterized by UV–vis spectroscopy and scanning electron microscopy, which indicated that the coaxial nanofibres of PANI emeraldine salt and PMMA were successfully prepared. The electrical responses of the gas sensor based on the composite nanofibres towards triethylamine (TEA) vapors were investigated at room temperature. It was revealed that the sensor showed a sensing magnitude as high as 77 towards TEA vapor of 500 ppm. In addition, the responses were linear, reversible and reproducible towards TEA vapors ranging from 20 to 500 ppm. The diameters of the electrospun PMMA fibers had an effect on the sensing magnitude of the gas sensor, which is proposed to relate to the difference in the surface-to-volume ratio of the fibers. Furthermore, it was found that the concentration of doping acids only led to changes in resistance of the sensor, but could not affect its sensing characteristics. In contrast, the nature of the doping acids was determinative for the sensing magnitude of the sensor. The gas sensor with toluene sulfonic acid as the doping acid exhibited the highest sensing magnitude, which is explained by taking into account of the sensing mechanism and the interactions of doping acids with TEA vapor.     

炭黑填充聚乙烯导电复合材料气敏性能研究

采用溶液共混法成功制备出炭黑/聚乙烯导电气敏复合材料,研究了在苯、甲苯、二甲苯三种有机溶剂蒸汽中的电阻变化.实验结果表明,该复合材料在二甲苯蒸汽中电阻变化最大,在苯蒸汽中电阻变化最小.进一步研究了其在100 ppm至800 ppm(ppm=10-6)二甲苯蒸汽中的气敏响应性,实验结果表明:复合材料的灵敏度从0.04增大至0.11.     

Orthogonal gas sensor arrays with intelligent algorithms for early warning of electrical fires

The feasibility of utilizing chemical sensor arrays and multivariable analyses as the basis for an early-warning combustion alarm for electrical fires was evaluated. During the pre-combustion phase of electrical fires, electronic components will heat up, resulting in an out-gassing of chemical vapors, which generally will precede the formation of smoke, scorching and fire. A variety of materials (PVC, Teflon^®, Kapton^®, and silicone rubber) that are frequently used as wire insulation were subjected to electrically induced thermal excursions, thereby simulating an electrical failure and possible pre-combustion condition. The off-gassing vapors from the various coatings can serve as chemical signatures for a pending fire and were detected by an array of chemical sensors (e.g., an electronic nose). Principal component analyses and KNN identification algorithms applied to the sensor response patterns successfully identified the various vapor sources. A 20-sensor array including electrochemical sensors, quartz microbalance (QMB) sensors with different polymer coatings, and heated metal oxide sensors (MOXs) was evaluated and the optimal performance was obtained using the electrochemical and MOXs. The use of heterogeneous orthogonal sensors increased the information content of sensor array signals and a diminutive array can still identify fire materials and extent of damage. The small, lightweight, inexpensive and low power sensors used to detect vapors during pre-fire conditions were ideal for space or commercial aircraft applications.