SnO/sub 2/ gas sensing array for combustible and explosive gas leakage recognition

A gas-sensing array with ten different SnO/sub 2/ sensors was fabricated on a substrate for the purpose of recognizing various kinds and quantities of indoor combustible gas leakages, such as methane, propane, butane, LPG, and carbon monoxide, within their respective threshold limit value (TLV) and lower explosion limit (LEL) range. Nano-sized sensing materials with high surface areas were prepared by coprecipitating SnCl/sub 4/ with Ca and Pt, while the sensing patterns of the SnO/sub 2/-based sensors were differentiated by utilizing different additives. The sensors in the sensor array were designed to produce a uniform thermal distribution along with a high and differentiated sensitivity and reproducibility for low concentrations below 100 ppm. Using the sensing signals of the array, an electronic nose system was then applied to classify and identify simple/mixed explosive gas leakages. A gas pattern recognizer was implemented using a neuro-fuzzy network and multi-layer neural network, including an error-back-propagation learning algorithm. Simulation and experimental results confirmed that the proposed gas recognition system was effective in identifying explosive and hazardous gas leakages. The electronic nose in conjunction with a neuro-fuzzy network was also implemented using a digital signal processor (DSP).     

Determination of alpha- and beta-hydroxycarbonyls and dicarbonyls in snow and rain samples by GC/FID and GC/MS employing benzyl hydroxyl oxime derivatization

A flame ionization detector (FID) combined with capillary gas chromatography (GC/FID) and gas chromatography/ mass spectrometry (GC/MS) has been used to identify multifunctional carbonyls in wet precipitation samples. The carbonyl groups were first derivatized to O-benzylhydroxyloxime (BH oxime) by using O-benzylhydroxylamine. The BH oxime derivatives were then treated with N,O-bis(trimethylsilyl)acetamide for the hydroxyl group to derive their TMS ethers. The BH oxime/TMS derivatives were measured using GC/FID as well as GC/MS on positive EI and CI (isobutane was used as CI gas) modes. Three groups of carbonyl compounds (monoaldehydes, dicarbonyls, hydroxycarbonyls) were identified in the samples by using this method. We have identified, for the first time, a group of alpha- and beta-hydroxycarbonyls, glycolaldehyde, hydroxyacetone, and 4-hydroxy-2-butanone, in wet precipitation samples. Concentrations of hydroxycarbonyls ranged from 0.9 to 53.8 microg/L in the precipitation samples. Their concentration level is similar to that of low molecular weight dicarboxylic acids, which have been reported as major water-soluble organic compounds in rain.     

低浓度氟化氢标准气体的FTIR分析方法研究

提出一种基于FTIR的氟化氢标准气体分析方法,使用其特征吸收区域(波数4100～4300cm-1)进行定量分析。通过稀释方法形成120、 100、 80.0、 60.0、 40.0、 20.0μmol/mol共6个浓度点的氟化氢标准气体,并对其重复性、标准曲线线性、检出限进行考察。结果显示：在20.0～120μmol/mol范围内仪器响应值与标气浓度呈线性,R2为0.9979; 各浓度点的重复性介于0.34%～1.1%之间; 检出限约为2.04μmol/mol。     

Probing charge transfer at surfaces using graphene transistors

Graphene field effect transistors (FETs) are extremely sensitive to gas exposure. Charge transfer doping of graphene FETs by atmospheric gas is ubiquitous but not yet understood. We have used graphene FETs to probe minute changes in electrochemical potential during high-purity gas exposure experiments. Our study shows quantitatively that electrochemistry involving adsorbed water, graphene, and the substrate is responsible for doping. We not only identify the water/oxygen redox couple as the underlying mechanism but also capture the kinetics of this reaction. The graphene FET is highlighted here as an extremely sensitive potentiometer for probing electrochemical reactions at interfaces, arising from the unique density of states of graphene. This work establishes a fundamental basis on which new electrochemical nanoprobes and gas sensors can be developed with graphene.     

Measurement of drift velocities and Lorentz angles for xenon-hydrocarbon gas mixtures

We have measured drift velocities and Lorentz angles for xenon gas with various types of quench gas mixtures. The measurement was motivated to help designing a new type of detector for an e⁺e⁻ collider experiment, where synchrotron radiation X-rays generated by electrons passing through a high magnetic field are detected to identify the electrons.     

A Novel Gas Sensor Based on Tunneling-Field-Ionization on Whisker-Covered Gold Nanowires

Typical gas ionization sensors (GISs) work by fingerprinting the ionization breakdown voltages of the gases to be identified. In this work, we developed a GIS that operates by field-ionizing the unknown gas at exceptionally low voltages. The resultant field-ion current-voltage (I-V) characteristic was then used to identify the gas. Freestanding gold nanowires (AuNW), terminated with nanoscale whisker-like features, were employed as field-amplifiers to reduce the field ionization threshold voltages. Synthesis of the AuNWs was carried out by the template-assisted technique accompanied by two alterations: 1) polystyrene (PS) microspheres were incorporated to reduce the compactness of the pores, thus prevent the nanostructures from collapse, and 2) the template was impregnated by HAuCl₄ to form gold nanowhiskers during the electrochemical nucleation of AuNWs. The sensor was tested in three elemental gases: Ar, N₂ and He, in a pressure range of 0.01 < P < 100 torr. Each gas demonstrated a distinctive I-V curve, particularly in the field-limited regime. The threshold ionization voltages ranged from 1 to 10 V, almost three orders of magnitude lower than the voltages used in field-ion-microscopy. The low-voltage field ionization was attributed to the field-amplifying nanoscale whiskers on the AuNW tips, as well as the presence of residual amorphous alumina with semiconducting characteristics, due to incomplete removal of the porous anodized alumina (PAA) template.     

Environmental Analysis by ab Initio Quantum Mechanical Computation and Gas Chromatography/Fourier Transform Infrared Spectrometry

Computational chemistry, in conjunction with gas chromatography/mass spectrometry/Fourier transform infrared spectrometry (GC/MS/FT-IR), was used to tentatively identify seven tetrachlorobutadiene (TCBD) isomers detected in an environmental sample. Computation of the TCBD infrared spectra was performed with the Gaussian quantum chemistry software. The Hartree-Fock/6-31G* level of theory was employed, with IR frequencies scaled by a standard factor of 0.89. This approach shows great promise as a means of characterizing or confirming environmental analyte identifications when standard spectra, or pure standards required to measure standard spectra, are unavailable.     

Metabolomic approach to evaluate the toxicological effects of nonylphenol with rat urine

Metabolomics has focused on toxicological applications to (1) understand the mechanisms of toxicity, (2) identify novel biomarkers of toxicity, and (3) provide in vivo assessment in animal models through simple and fast methods to date. The toxicological effects of nonylphenol (NP) were evaluated after intraperitoneal injection of rats with 0, 50, and 250 mg kg(-1) day(-1) NP for four consecutive days. In the nontargeted approach, different extraction conditions were introduced to investigate the effects of NP on rats through gas chromatography/mass spectrometry (GC/MS). The GC/MS data obtained were further analyzed with partial least-squares discriminant analysis to compare toxicological effects between control and treated groups. The targeted approach was also used in combination with GC/MS to quantify endocrine hormones and to identify possible biomarkers in rat urine under optimal extraction conditions. In addition, we considered the metabolic trajectory to examine the metabolite profiles and patterns related to steroid metabolism in rats that were treated with NP, considering both treatment amount and time. The data suggest that tetrahydrocorticosterone and 5alpha-tetrahydrocorticosterone are possible urinary biomarkers of NP-induced toxicity. This metabolomic approach is a promising tool to assist with screening in toxicological studies.     

Characterization of tin dioxide film for chemical vapors sensor

Recently, oxide semiconductor material used as transducer has been the central topic of many studies for gas sensor. In this paper we investigated the characteristic of a thick film of tin dioxide (SnO₂) film for chemical vapor sensor. It has been prepared by screen-printing technology and deposited on alumina substrate provided with two gold electrodes. The morphology, the molecular composition and the electrical properties of this material have been characterized respectively by Atomic Force Spectroscopy (AFM), Fourier Transformed Infrared Spectroscopy (FTIR) and Impedance Spectroscopy (IS). The electrical properties showed a resistive behaviour of this material less than 300 °C which is the operating temperature of the sensor. The developed sensor can identify the nature of the detected gas, oxidizing or reducing.     

Effect of mixture ratios and nitrogen carrier gas flow rates on the morphology of carbon nanotube structures grown by CVD

We report on the growth of carbon nanotubes (CNTs) by thermal Chemical Vapor Deposition (CVD) and investigate the effects of nitrogen carrier gas flow rates and mixture ratios on the morphology of CNTs on a silicon substrate by vaporizing the camphor/ferrocene mixture at 750 °C in a nitrogen atmosphere. Carbon layers obtained after each CVD growth run of 15 min are characterized by scanning electron microscopy (SEM) and Raman spectroscopy. Growth of CNTs is found to occur on silicon substrates. The SEM micrographs helped better understand the nanotube growth morphology while Raman Spectroscopy was used to detect the presence of nanotubes and also identify their nature vizely semiconducting or metallic, single-walled or multi-walled. Raman Spectra was also useful to estimate the quality of the samples as a ratio of nanotube to non-nanotube content. The length and diameters of the aligned CNTs were found to depend on the pyrolysis temperatures, mixture ratio, and the nitrogen carrier gas flow rates.     

Droplet cooling in atomization sprays

Transport between droplets/particles and a gas phase plays an important role in numerous material processing operations. These include rapid solidification operations such as gas atomization and spray forming, as well as chemical systems such as flash furnaces. Chemical reaction rates and solidification are dependent on the rate of gas-particle or gas-droplet transport mechanisms. These gas-based processes are difficult to analyze due to their complexity which include particle and droplet distribution and the flow in a gas field having variations in temperature and velocity both in the jet cross-section and in the axial distance away from the jet source. Thus to study and properly identify the important variables in transport, these gas and droplet variations must be eliminated or controlled. This is done in this work using models based on a single fluid atomization system. Using a heat transport model (referred to as thermal model) validated using single fluid atomization of molten droplets and a microsegregation model, the effect of process variables on heat losses from droplets was examined. In this work, the effect of type of gas, droplet size, gas temperature, gas-droplet relative velocity on the heat transport from AA6061 droplets was examined. It is shown that for a given gas type, the most critical process variable is the gas temperature particularly as affected by two-way thermal coupling and the droplet size. The results are generalized and applied to explain the difference in droplet cooling rate from different atomization processes.     

应用差分气相色谱/质谱法提高色谱分辨率

当用气相色谱/质谱(GC/MS)分析样品时,如果样品中包含保留时间接近的成分,将导致总离子流图中信号峰的重叠,最终影响样品成分的鉴定。为了解决这个问题,首先讨论了GC/MS数据的性质,用矩阵表示GC/MS数据。接下来,提出一种提高色谱分辨率的方法。该方法对GC/MS相邻扫描谱图相减,得到差分GC/MS谱图,差分数据包括正值和负值差分数据。然后将正值和负值差分数据进行移位并重新组合,得到的新数据与原始的GC/MS数据相比,色谱分辨率有了明显的改善。     

A solid-phase microextraction device for the analysis of electrochemical reaction products by gas chromatography/mass spectrometry

Presented is a solid-phase microextraction syringe-electrode assembly that may be used to identify electrode reaction products. After an electrochemical experiment, the electrode within this syringe-electrode assembly can be introduced into the injection port of a gas chromatograph. Electrochemical reaction products can be analyzed, provided they adhere to the electrode surface and are amenable to gas chromatographic/mass spectrometric analysis. We highlight the potential usefulness of this device using well-known electrochemical reaction of quinones.     

Hochleistungsplasmen zur Synthese diamantähnlicher Kohlenstoffschichten

HPPMS high‐performance plasmas for the deposition of diamond‐like carbon coatings Diamond‐like carbon (DLC) coatings Diamond‐like carbon (DLC) coatings can be used in many different applications, due to their adjustable properties like hardness as wear reduction. Regarding to the synthesis of these coatings, research is upon the High Power Pulsed/Impulse Magnetron Sputtering (HPPMS/HiPIMS), which in contrast to conventional processes like the Pulsed Laser Deposition (PLD) provides smooth coatings and therefore less postprocessing. Previous to the coating deposition in‐situ plasma analysis can be utilized to identify the process parameters. The aim relevantof this work was to identify process parameters which enable to generate a high amount and energy of carbon ions, which are required to synthesize hard DLC coatings. Regarding to the carbon ionization the promising process parameters mixture and pressure of the process gas as well as the HPPMS pulse parameters were varied. Finally, process parameters for the DLC coating deposition could be derived from these investigations.     

Degradation of 2,4-dichlorophenol by using glow discharge electrolysis

Degradation of 2,4-dichlorophenol (2,4-DCP) in aqueous by glow discharge electrolysis (GDE) has been investigated. Ultraviolet (UV) absorption spectra, atomic force microscopy (AFM), high performance liquid chromatography (HPLC) and gas chromatogram-mass spectrum (GC/MS) are used to monitor the degradation process and to identify the major oxidation intermediate products. It has been found that 2,4-DCP undergoes a series of intermediate step, which leads to form a number of intermediate products, mainly isomeric chlorophenols and aliphatic acids. These products are further oxidized, eventually, mineralized into CO(2) and Cl(-). A degradation pathway for 2,4-DCP is proposed on the basis of detection of intermediate compounds.     

Cooling and clusters: when is heating needed?

There are (at least) two unsolved problems concerning the current state of the ther- mal gas in clusters of galaxies. The first is to identify the source of the heating which onsets cooling in the centres of clusters with short cooling times (the 'cooling-flow' problem). The second to understand the mechanism which boosts the entropy in cluster and group gas. Since both of these problems involve an unknown source of heating it is tempting to identify them with the same process, particularly since active galactic nuclei heating is observed to be operating at some level in a sample of well-observed 'cooling-flow' clusters. Here we show, using numerical simulations of cluster formation, that much of the gas ending up in clusters cools at high redshift and so the heating is also needed at high redshift, well before the cluster forms. This indicates that the same process operating to solve the cooling-flow problem may not also resolve the cluster-entropy problem.     

Identification of Different Vapors Using a Single Temperature Modulated Polymer Sensor With a Novel Signal Processing Technique

This paper reports on a novel temperature modulation technique to improve the ability of a single carbon black/polymer resistive sensor to discriminate, identify and characterize environmental pollutants. Such a sensor can be low cost, low-power consumption, highly reliable, and thus ideal for indoor gas monitoring. Here, a carbon black/polyvinylpyrrolidone film was deposited onto an SOI-CMOS microhotplate. A novel temperature modulation technique is proposed that allows the detection of vapors using a single chemoresistor. Identification and quantification of water, methanol and ethanol vapors with different concentrations (water: 0–6000 ppm, methanol: 1360–5430 ppm and ethanol: 2270–9080 ppm) are shown.      

Toward the accurate analysis of C1-C4 polycyclic aromatic sulfur heterocycles

Polycyclic aromatic sulfur heterocycles (PASH) are sulfur analogues of polycyclic aromatic hydrocarbons (PAH). Alkylated PAH attract much attention as carcinogens, mutagens, and as diagnostics for environmental forensics. PASH, in contrast, are mostly ignored in the same studies due to the conspicuous absence of gas chromatography/mass spectrometry (GC/MS) retention times and fragmentation patterns. To obtain these data, eight coal tar and crude oils were analyzed by automated sequential GC-GC. Sample components separated based on their interactions with two different stationary phases. Newly developed algorithms deconvolved combinatorially selected ions to identify and quantify PASH in these samples. Simultaneous detection by MS and pulsed flame photometric detectors (PFPD) provided additional selectivity to differentiate PASH from PAH when coelution occurred. A comprehensive library of spectra and retention indices is reported for the C(1)-C(4) two-, three-, and four-ring PASH. Results demonstrate the importance of using multiple fragmentation patterns per homologue (MFPPH) compared to selected ion monitoring (SIM) or extraction (SIE) to identify isomers. Since SIM/SIE analyses dramatically overestimate homologue concentrations, MFPPH should be used to correctly quantify PASH for bioavailability, weathering, and liability studies.     

Development of an inverse method to identify the kinetics of heavy metal release during waste incineration in fluidized bed

This paper deals with the emission of heavy metals (HM) during the incineration of municipal solid waste in a fluidized bed reactor. This study focused on the development of a general method to identify the kinetics of vaporization of heavy metals from the on-line analysis of exhaust gas. This method is an inverse method, which requires only the time evolution of the HM concentration in exhaust gases (experimental data) and a global bubbling bed model developed for transient conditions at the reactor scale. First, a lab-scale fluidized bed incinerator was set-up to simulate the HM release during the thermal treatment of metal-spiked model wastes. A specific on-line analysis system based on ICP-OES was developed to measure in real time the variation of the relative concentration of HM in exhaust gases. Then, a two-phase flow bubbling bed model was developed and validated to calculate the kinetics of vaporization of HM from its measured concentration time profile in the outlet gas. The technique was first validated with model waste (metal-spiked mineral matrices), thus enabling at each time both solid sampling for measuring the HM vaporization kinetic and on-line analysis for measuring the HM concentration in the outlet gas. The inverse method was then applied to realistic artificial wastes (derived from real wastes) to identify the HM vaporization kinetics from the on-line analysis results.     

Isotope dilution gas chromatography/mass spectrometry for the determination of nickel in biological materials

Precise and accurate methods are required to measure nickel in urine and serum samples to identify clinical states of either deficiency or toxicity. This paper presents an isotope dilution gas chromatography/mass spectrometry method for the measurement of nickel in biological samples. The method involves the preparation of a thermally stable and volatile nickel chelate using lithium bis(trifluoroethyl)dithiocarbamate as the chelating agent. Conditions were optimized for the digestion of the sample and quantitative preparation of chelate as well as the precise and accurate measurements of the isotope ratios using a capillary column gas chromatograph with a general purpose mass spectrometer. The memory effect between samples of different isotope ratios was evaluated and was found to be negligible. The quantitative accuracy of isotope dilution was validated by measuring nickel in the NIST freeze-dried urine reference material, SRM 2670, with comparison to the recommended value.