Phthalocyanines as sensitive coatings for QCM sensors: Comparison of gas and liquid sensing properties

The quartz crystal microbalance (QCM) was used to investigate the liquid sensing properties of a set of phthalocyanines (Pcs) which were systematically varied by attaching the substituent 2,2,3,3-tetrafluoropropyloxy to different positions and by introducing a central metal ion (i.e. Ni²⁺, Zn²⁺, and Cu²⁺). The responses to low concentrations of organic compounds such as hydrocarbons and chlorocarbons dissolved in water were recorded. The materials were very sensitive to the tested compounds with detection limits in the lower parts-per-million range and they exhibited a good sensing performance as the sensors have been working fully reversibly and reliably over long periods of time. Besides, the influence of substitution pattern and choice of central metal ion on the liquid sensing properties of Pcs were studied for the first time. The results show that the responses differ notably from each other depending on the modifications made to the Pc. Finally, it is demonstrated that the gas and liquid sensing responses of the materials are highly correlated and can be linked to each other with the help of a basic physical model.     

Ionic liquids used as QCM coating materials for the detection of alcohols

Six imidazolium-based ionic liquids (ILs) were synthesized and employed as sensing materials coated on quartz crystal microbalance for the detection of organic vapors. Acetone, ethanol, dichloromethane, benzene, toluene and hexane were selected as representatives for common environmental pollutants, and good linear responses from 0 to 100% of concentrations were observed. The halogen-anion-containing imidazolium ILs-coated sensors showed fast response, excellent reversibility, and considerable sensitivity and selectivity towards alcohols, and the selective factors were up to 30 times for ethanol versus other VOCs. The existence of water vapor reduced the frequency response of the sensor, but a good linear relationship remained.     

Poly(acrylamide) derivatives for QCM-based HCl gas sensor applications

Quartz resonators coated with three kinds of poly(acrylamide) derivatives were studied for simply but accurately detecting HCl gas in air. The exposure of the resonator to HCl gas reversibly decreased the oscillation frequencies. The sensitivity, response time, and reversibility were found to depend on the structure of the amide group. Among the polymers used, poly(N,N-dimethylacrylamide) (PDMAA) showed the most relevant data for the HCl sensor. The HCl sensitivity obtained for PDMAA was ca. 250 ppb/Hz. On the other hand, the irreversible response toward NO₂ gas was considerably high, and great interference was also produced by changes in the test gas humidity.     

On a new class of fuzzy implications: h-Implications and generalizations

A new class of fuzzy implications called the h-implications is introduced. They are implications generated from an additive generator of a representable uninorm in a similar way of Yager’s f- and g-implications which are generated from additive generators of continuous Archimedean t-norms and t-conorms. Basic properties of these implications are studied in detail. Modifications and generalizations of the initial definition are presented and their properties studied and compared between them. One of the modifications, called (h, e)-implications, is another example of a fuzzy implication satisfying the exchange principle but not the law of importation for any t-norm, in fact for any function F : [0, 1]² → [0, 1].     

A new optochemical chlorine gas sensor based on the application of amphiphilic co-networks as matrices

A sensor for chlorine gas detection, consisting of an amphiphilic polymer co-network with an immobilised oxidation indicator, o-tolidine, is described. Data describing gas sensing properties and long-term stability will be presented. This study focuses on APCN thin films as a matrix for indicator immobilisation.Thin films of poly(2-hydroxyethyl acrylate)-l-polydimethylsiloxane PHEA-l-PDMS were prepared as immobilisation matrices for o-tolidine.We present a simple, non-expensive, but highly sensitive optical sensor for chlorine gas detection. The thin film response is reproducible and irreversible. With our kinetic-optical method rapid response times were achieved. The determination of chlorine is performed on the basis of the oxidation of o-tolidine as the chromogenic reagent to a coloured product which can be monitored at 650 nm. The results reveal a fast response to chlorine gas down to concentrations of 0.01 ppm.     

SnO2-based R134a gas sensor: Sensing materials preparation, gas response and sensing mechanism

Undoped SnO₂ and porous Al₂O₃ powders were obtained through a simple chemical precipitation process. SnO₂-based gas sensing materials and Al₂O₃ catalytic coating loaded with a noble metal were prepared by impregnation. The SnO₂ and Al₂O₃ powders were characterized by TEM, SEM, nitrogen adsorption-desorption experiment, FT-IR and in situ XRD. Gas responses of the SnO₂-based gas sensors were measured in a static state. The experimental results indicated that the response towards R134a of the SnO₂-based gas sensor can be significantly enhanced by loading noble metal and using catalytic coating. The sensor based on a double layer film SnO₂ (Au)/Al₂O₃ (Au) showed satisfactory results including large response, good selectivity, high long-term stability, fast response and recovery, revealing its potential application in the detection of refrigerants and the maintenance of air condition systems. Finally, a gas sensing mechanism for R134a is suggested and proved by bond energy data, FT-IR spectrum and in situ XRD.     

A nano-copper electrochemical sensor for sensitive detection of chemical oxygen demand

Copper nanoparticle (nano-Cu) was electrodeposited on the surface of Cu disk electrode under −1 V for 60 s, and then used to construct an electrochemical sensor for chemical oxygen demand (COD). The electrochemical oxidation behavior of glycine, a standard compound for evaluating the COD, was investigated. The potential shifts negatively, and the current increases greatly at the surface of nano-Cu, indicating remarkable enhancement effect on the detection of COD. The analytical conditions such as electrolyte, deposition potential, deposition time and detected potential were studied. As a result, a sensitive, simple and rapid electroanalytical method was developed for COD using amperometric detection. The linear range is from 4.8 to 600 mg L⁻¹, and the limit of detection is as low as 3.6 mg L⁻¹. Moreover, this method exhibits high tolerance level to chloride ion, and 0.02 M chloride ion has no influence. Finally, the sensor was used to detect the COD values of different water samples, and the results were testified by the standard dichromate method.     

Highly sensitive detection of HCl gas using a thin film of meso-tetra(4-pyridyl)porphyrin coated glass slide by optochemical method

The meso-tetra(4-pyridyl)porphyrin (MTPyP) deposited on glass slide by dip coating was used as a solid state sensor for HCl gas detection by optochemical method. Exposure of MTPyP coated glass slide to HCl gas results in the formation of protonated meso-tetra(4-pyridyl)porphyrin (PMTPyP). UV-vis and fluorescence spectral methods were used to study the protonation of MTPyP both in solution and on solid state. The absorption spectrum of MTPyP modified glass slide shows an intense Soret band at 427 nm, which is shifted to 470 nm upon exposure to HCl gas. The concentration of HCl gas was monitored from the absorbance changes of Soret band of PMTPyP at 470 nm. The detection limit of the solid state sensor was found to be 0.01 ppm. The recovery rate of the solid state was very fast and it was monitored by UV-vis and fluorescence techniques with successive exposure to HCl gas and ammonia vapor with nitrogen gas. The planarity and energy of the molecule have changed after exposed to HCl gas which was confirmed by ab-intio calculation using Gaussian software. The response of the solid state sensor towards HCl gas was highly stable for several months.     

Diesel engine dynamometer testing of impedancemetric NOx sensors

Prototype solid-state electrochemical sensors using a dense gold sensing electrode, porous yttria-stabilized zirconia (YSZ) electrolyte, and a platinum counter electrode (Au/YSZ/Pt) were evaluated for measuring NO_x (NO and NO₂) in diesel exhaust. Both electrodes were exposed to the test gas (i.e., there was no reference gas for the counter electrode). An impedancemetric method was used for NO_x measurements, where the phase angle was used as the response signal. A portion of the tailpipe exhaust from the dynamometer test stand was extracted and fed into a furnace containing the experimental sensor. The prototype sensor was tested along with a commercially available NO_x sensor. Simultaneous measurements for NO_x, O₂, CO₂, H₂O, CO, and CH₄ in a separate feed stream were made using Fourier transform infrared (FTIR) spectroscopy and an oxygen paramagnetic analyzer. The experimental sensor showed very good measurement capability for NO in the range of 25-250 ppm, with a response paralleling that of the FTIR and commercial sensor. The prototype sensor showed better sensitivity to NO_x at the lower concentration ranges. O₂ is an interferent for the experimental sensor, resulting in decreased sensitivity for measurement of NO_x. Methods to overcome this interference are discussed.     

The effect of La2CuO4 sensing electrode thickness on a potentiometric NOx sensor response

In order to further understand the different contributions to NO_x sensing mechanism as well as the importance of electrode geometry, solid state potentiometric sensors with varying La₂CuO₄ sensing electrode thicknesses were studied. These sensors (with a Pt counter electrode) showed a dependence of NO₂ sensitivity which decreased with increasing thickness in the temperature range of 550-650 °C. They also showed NO sensitivity that was independent of thickness at 400 °C and 600 °C, but varied at temperatures between. This behavior was attributed to multiple mechanistic contributions explained by Differential Electrode Equilibria.     

Improvement of the NOx selectivity for a planar YSZ sensor

In recent years planar yttria-stabilized zirconia (YSZ) based electrochemical gas sensors for automotive exhaust applications have become a major source of interest. The present work aims to develop a sensor for industrialisation. For this reason planar YSZ-based electrochemical sensors using two metallic electrodes (platinum and gold) were fabricated using screen-printing technology and tested in a laboratory test bench for different concentrations of pollutant gas such as CO, NO, NO₂ and hydrocarbons in oxygen rich atmosphere. It was furthermore shown that the selectivity towards NO_x could be highly reinforced by deposing a catalytic filter consisting of 1.7-4.5 wt.% Pt dispersed on alumina directly on the sensing elements. This filter was characterized by the use of SEM, TPD and XRD.     

Development and evaluation of piezoelectric-polymer thin film sensors for low concentration detection of volatile organic compounds related to food safety applications

In this study, the regioregular poly (3-hexyl thiophene) (rr-P3HT) based piezoelectric sensors were developed and evaluated to detect alcoholic volatile organic compounds (VOCs) associated with spoiled and Salmonella typhimurium contaminated packaged beef headspace. The drop coating technique was used to deposit thin films of rr-P3HT on both the sides of quartz crystal microbalance (QCM) electrode. The QCM polymer sensors were found to provide repeatable and reproducible sensor response to alcohol VOCs with a fast recovery (<2 min) at room temperature (25 °C). The principal component analysis on the sensors sensitivities was performed to discriminate the sensed alcohol VOCs, namely: 3-methyl-1-butanol from 1-hexanol. The QCM polymer sensors demonstrated selective response to low concentration of 3-methyl-1-butanol (average estimated lowest detection limit (LDL): 4.35 ppm) and to 1-hexanol (average estimated LDL: 3.20 ppm). The 30 days storage study performed on QCM sensors showed identical sensitivity responses for sensing 3-methyl-1-butanol and 1-hexanol at low concentrations.     

Effect of La2CuO4 electrode area on potentiometric NOx sensor response and its implications on sensing mechanism

The intent of this work is to look at the effects of varying the La₂CuO₄ electrode area and the asymmetry between the sensing and counter electrode in a solid state potentiometric sensor with respect to NO_x sensitivity. NO₂ sensitivity was observed at 500-600 °C with a maximum sensitivity of ∼22 mV/decade [NO₂] observed at 500 °C for the sensor with a La₂CuO₄ electrode area of ∼30 mm². The relationship between NO₂ sensitivity and area is nearly parabolic at 500 °C, decreases linearly with increasing electrode area at 600 °C, and was a mixture of parabolic and linear behavior 550 °C. NO sensitivity varied non-linearly with electrode area with a minima (maximum sensitivity) of ∼−22 mV/decade [NO] at 450 °C for the sensor with a La₂CuO₄ electrode area of 16 mm². The behavior at 400 °C was similar to that of 450 °C, but with smaller sensitivities due to a saturation effect. At 500 °C, NO sensitivity decreases linearly with area.We also used electrochemical impedance spectroscopy (EIS) to investigate the electrochemical processes that are affected when the sensing electrode area is changed. Changes in impedance with exposure to NO_x were attributed to either changes in La₂CuO₄ conductivity due to gas adsorption (high frequency impedance) or electrocatalysis occurring at the electrode/electrolyte interface (total electrode impedance). NO₂ caused a decrease in high frequency impedance while NO caused an increase. In contrast, NO₂ and NO both caused a decrease in the total electrode impedance. The effect of area on both the potentiometric and impedance responses show relationships that can be explained through the mechanistic contributions included in differential electrode equilibria.     

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.     

h-Blossoming: A new approach to algorithms and identities for h-Bernstein bases and h-Bézier curves

A new variant of the blossom, the h-blossom, is introduced by altering the diagonal property of the standard blossom. The significance of the h-blossom is that the h-blossom satisfies a dual functional property for h-Bézier curves over arbitrary intervals. Using the h-blossom, several new identities involving the h-Bernstein bases are developed including an h-variant of Marsden?s identity. In addition, for each h-Bézier curve of degree n, a collection of n! new, affine invariant, recursive evaluation algorithms are derived. Using two of these recursive evaluation algorithms, a recursive subdivision procedure for h-Bézier curves is constructed. Starting from the original control polygon of an h-Bézier curve, this subdivision procedure generates a sequence of control polygons that converges rapidly to the original h-Bézier curve.     

Synthesis of novel SnO2/ZnSnO3 core-shell microspheres and their gas sensing properities

Large-scale novel core-shell structural SnO₂/ZnSnO₃ microspheres were successfully synthesized by a simple hydrothermal method with the help of the surfactant poly(vinyl pyrrolidone) PVP. The as-synthesized samples were characterized using X-ray powder diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and high-resolution transmission electron microscopy (HRTEM). The results indicate that the shell was formed by single crystalline ZnSnO₃ nanorods and the core was formed by aggregated SnO₂ nanoparticles. The effects of PVP and hydrothermal time on the morphology of SnO₂/ZnSnO₃ were investigated. A possible formation mechanism of these hierarchical structures was discussed. Moreover, the sensor performance of the prepared core-shell SnO₂/ZnSnO₃ nanostructures to ethanol was studied. The results indicate that the as-synthesized samples exhibited high response and quick response-recovery to ethanol.     

A selective room temperature formaldehyde gas sensor using TiO2 nanotube arrays

A new gas sensor using TiO₂ nanotube arrays was fabricated and explored for formaldehyde detection at room temperature. Highly ordered vertically grown TiO₂ nanotube arrays were synthesized by using the conventional electrochemical anodization process. The sensor using the fabricated nanotube arrays as the sensing elements demonstrated a good response to different concentrations of formaldehyde from 10 to 50 ppm and a very good selectivity over other reducing gas species such as ethanol and ammonia at room temperature. While the exact sensing mechanism is unclear, some possibilities are briefly discussed.     

Glucose-mediated hydrothermal synthesis and gas sensing characteristics of WO3 hollow microspheres

Tungsten-coated carbon microspheres were prepared by one-pot hydrothermal reaction of an aqueous solution containing glucose and sodium tungstate. The spheres were converted into WO₃ hollow microspheres by the decomposition of their core carbon. The [glucose]/[sodium tungstate] ratio of the stock solution determined not only the morphology of the precursors but also the phase of the powders after calcination. The WO₃ hollow microspheres showed a higher gas response and more selective detection of 0.5–2.5 ppm NO₂ than WO₃ solid and nano-porous microspheres did. The enhanced NO₂ sensing characteristics are explained in relation to the surface area, pore volume, and hollow morphology.     

Studies on the gas sensing behaviour of nanosized CuNb2O6 towards ammonia, hydrogen and liquefied petroleum gas

Appreciable changes in resistance of polycrystalline nanosized CuNb₂O₆ upon exposure to reducing gases like hydrogen, liquefied petroleum gas (LPG) and ammonia in ambient atmosphere recognize the material as a gas sensor. Nanosized CuNb₂O₆ synthesized by thermal decomposition of an aqueous precursor solution containing copper nitrate, niobium tartrate and tri-ethanol amine (TEA), followed by calcination at 700 °C for 2 h, has been characterized using X-ray diffraction (XRD) study, transmission electron microscopy (TEM), field-emission scanning electron microscope (FESEM), energy dispersive X-ray (EDX) analysis and Brunauer–Emmett–Teller (BET) surface area measurement. The synthesized CuNb₂O₆ exhibits monoclinic structure with crystallite size of 25 nm, average particle size of 25–40 nm and specific surface area of 55 m² g⁻¹.