Mimicking the sense of olfaction: A conducting-polymer-based electronic nose

Abstract— We describe herein the construction of a simple, low-power, broadly responsive vapor sensor. Carbon-black-organic-polymer composites have been shown to swell reversibly upon exposure to vapors. Thin films of carbon-black-organic-polymer composites have been deposited across two metallic leads, with swelling-induced resistance changes of the films signaling the presence of vapors. To identify and classify vapors, arrays of such vapor-sensing elements have been constructed, with each element containing a different organic polymer as the insulating phase. The differing gas-solid partition coefficients for the various polymers of the sensor array produce a pattern of resistance changes that can be used to classify vapors and vapor mixtures. This type of sensor array has been shown to resolve all organic vapors that have been analyzed, and can even resolve H²O from D²O.     

Polyaniline–TiO2 nano-composite-based trimethylamine QCM sensor and its thermal behavior studies

Inorganic/organic composites are very attractive due to synergetic behavior and a wide range of potential use. A polyaniline–TiO₂ nano-composite, obtained by combination of chemical polymerization and a sol–gel method, was deposited on the electrode of quartz crystal to implement a quartz crystal microbalance (QCM) chemical sensor. The morphology of the composite film was studied by scanning electron microscopy (SEM) measurements. The coated quartz crystal and a non-coated quartz crystal were mounted in a sealed chamber, and their frequency difference was monitored. When analyte vapor was injected into the chamber, gas absorption decreased the frequency of the coated quartz crystal and thereby caused an increase of the frequency difference between the two crystals. The frequency difference change response towards trimethylamine was evident and could be recovered by N₂ purgation easily. The calibration curve towards trimethylamine, its long-term stability and selectivity were investigated. The thermal behavior of the sensing characteristics was compared with that of a polyaniline QCM sensor. Fourier transform infrared (FTIR) spectra of polyaniline and polyaniline–TiO₂ nano-composite and QCM data under various conditions were used to study the effect of thermal treatment.     

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.     

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.     

Mesoporous nanoparticle TiO2 thin films for conductometric gas sensing on microhotplate platforms

Mesoporous TiO₂ nanoparticle thin films were prepared on MEMS microhotplate (μHP) platforms and evaluated as high-sensitivity conductometric gas sensor materials. The nanoparticle films were deposited onto selected microhotplates in a multi-element array via microcapillary pipette and were sintered using the microhotplate. The films were characterized by optical and scanning electron microscopies and by conductometric measurements. The thin films were evaluated as conductometric gas sensors based on the critical performance elements of sensitivity, stability, speed and selectivity. The nanoparticle films were compared with compact TiO₂ films deposited via chemical vapor deposition (CVD) and the nanoparticle films were found to demonstrate higher sensitivity to target analytes. The nanoparticle films were also stable with regard to both baseline conductance and signal response over 60 h of continuous operation at high temperatures (up to 475 °C). Sensor response times were evaluated and the TiO₂ nanoparticle films showed fast responses to the presence of analyte (≈5 s) and a response-time dependence on the analyte concentration. Control of the sensor operating temperature, an inherent benefit of the microhotplate platform, was employed to demonstrate the selectivity of the nanoparticle films.     

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.     

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.     

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.     

Synthesis and enhanced gas sensing properties of crystalline CeO2/TiO2 core/shell nanorods

Crystalline CeO₂/TiO₂ core/shell nanorods were fabricated by a hydrothermal method and a subsequent annealing process under the hydrogen and air atmosphere. The thickness of the outer shell composed of crystal TiO₂ nanoparticles can be tuned in the range of 5-11 nm. The crystal core/shell nanorods exhibited enhanced gas-sensing properties to ethanol vapor in terms of sensor response and selectivity. The calculated sensor response based on the change of the heterojunction barrier formed at the interface between CeO₂ and TiO₂ is agreed with the experimental results, and thus the change of the heterojunction barrier at different gas atmosphere can be used to explain the enhanced ethanol sensing properties.     

Development of molecularly imprinted electrochemical sensor with titanium oxide and gold nanomaterials enhanced technique for determination of 4-nonylphenol

4-Nonylphenol (4-NP) was reported to affect the health of wildlife and humans through altering endocrine function. A novel electrochemical sensor for sensitive and fast determination of 4-NP was developed. Titanium oxide (TiO₂) nanoparticles and gold nanoparticles (AuNPs) were introduced for the enhancement of electron conduction and sensitivity. 4-NP-imprinted functionalized AuNPs composites with specific binding sites for 4-NP was modified on electrode. The resulting electrodes were characterized by cyclic voltammetry (CV). Rebinding experiments were carried out to determine the specific binding capacity and selective recognition. The linear range was over the range from 4.80 × 10⁻⁴ to 9.50 × 10⁻⁷ mol L⁻¹, with the detection limit of 3.20 × 10⁻⁷ mol L⁻¹ (S/N = 3). The sensor was successfully employed to detect 4-NP in real samples.     

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.     

Microstructure control of TiO2 nanotubular films for improved VOC sensing

Porous gas sensing films composed of TiO₂ nanotubes were fabricated for the detection of volatile organic compounds (VOCs), such as alcohol and toluene. In order to control the microstructure of TiO₂ nanotubular films, ball-milling treatments were used to shorten the length of TiO₂ nanotubes and to improve the particle packing density of the films without destroying their tubular morphology and crystal structure. The ball-milling treatment successfully modified the porosity of the gas sensing films by inducing more intimate contacts between nanotubes, as confirmed by scanning electron microscopy (SEM) and mercury porosimetry. The sensor using nanotubes after the ball-milling treatment for 3 h exhibited an improved sensor response and selectivity to toluene (50 ppm) at the operating temperature of 500 °C. However, an extensive ball-milling treatment did not enhance the original sensor response, probably owing to a decrease in the porosity of the film. The results obtained indicated the importance of the microstructure control of sensing layers in terms of particle packing density and porosity for detecting large sized organic gas molecules.     

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.     

Selective gas sensing response from different loading of Ag in sol-gel mesoporous titania powders

Bare and Ag loaded TiO₂ (0.05, 0.5, and 5.0 mol% Ag) powders prepared by sol-gel process have been used for the detection of ethanol, LPG, acetone and toluene gases. These materials were well characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution TEM (HRTEM), X-ray photoelectron spectroscopy (XPS) and Brunauer-Emmett-Teller (BET) specific surface area analysis techniques. Specific surface area increased with increasing Ag loading in these mesoporous materials. A thorough TEM/HRTEM investigation with X-ray maps of the modified particles shows the extent of TiO₂ surface coverage by Ag nanoparticles. From the comparative study of the sensor response of Ag-TiO₂ powders for various gases, it is observed that each Ag loading resulted in the highest response towards a particular gas or in other words, every gas responded best towards a particular Ag loading of the sensor material, i.e. 0.05 mol% Ag-TiO₂ sensor showed highest response towards ethanol, 0.5 mol% Ag-TiO₂ sensor showed best response towards toluene, whereas, bare TiO₂ proved to be the best sensor for both acetone and LPG gases. This establishes that Ag loading is not required for detection of acetone and LPG gases. On the basis of detailed materials characterization, a mechanism for the gas sensing response of each analyte has been 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.     

Alpha-1-fetoprotein antibody functionalized Au nanoparticles: Catalytic labels for the electrochemical detection of α-1-fetoprotein based on TiO2 nanoparticles synthesized with ionic liquid

A novel strategy for the preparation of amperometric immunosensor for rapid determination of α-1-fetoprotein (AFP) in human serum has been developed. TiO₂ nanoparticles (NPs) were prepared by solvothermal reaction using TiCl₄ as raw materials and the mixture of ionic liquids and doubly distilled water as solvent. α-1-fetoprotein antibody (AFP Ab) was mixed with TiO₂ NPs/chitsotan (CHIT) solution and immobilized onto the surface of a glassy carbon electrode. AFP (Ab) functionalized Au NPs were used as catalytic labels for the amperometric detection of AFP by means of the electrocatalyzed reduction of Au NPs to H₂O₂. The electrochemical behavior of the immunosensor was studied. Other experimental conditions such as pH, immunoreactions temperature and time were also studied. The prepared immunosensor offers an excellent amperometric response for AFP ranging from 1.0 to 160.0 ng/mL with a detection limit of 0.1 ng/mL. The result shows that the immunosensor displays rapid response, high sensitivity, good reproducibility and favorable stability.     

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.     

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.     

Using a TiO2/ZnO double-layer film for improving the sensing performance of ZnO based NO gas sensor

NO gas sensors, based on ZnO thin film (ZnO_film), TiO₂ nanoparticulate film (TiO₂NP), and TiO₂NP/ZnO_film double-layer film, were fabricated, and their sensing characteristics towards NO gas were investigated in this study. The maximal response of a ZnO_film deposited onto a rougher Al₂O₃ substrate, towards NO gas, was higher than that of a ZnO_film deposited on a smoother glass substrate. Although the sensing response of the TiO₂NPs itself towards NO gas was minute, the TiO₂NP/ZnO_film double-layer film showed enhanced response as compared with TiO₂NP or ZnO_film single-layer film. In addition, the sensor response of the TiO₂NP/ZnO_film double-layer film was strongly influenced by the annealing time for the film preparation; the maximum response to NO was enhanced about 6.2 times as the annealing time was increased from 30 min to 2 h. Based on the XPS results, the increase in the transition zone between TiO₂NP and ZnO_film along with the appearance of Ti³⁺ state was noticed when the annealing time was increased. With the high sensitive TiO₂NP/ZnO_film/Al₂O₃ electrode, the limit of detection (S/N = 3) can be achieved at 8.8 ppb. The double-layer TiO₂NP/ZnO_film also showed improved selectivities with respect to NO₂ and CO.     

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.