Rugged, portable tungsten coil atomic emission spectrometer

Tungsten coil atomic emission spectrometry is an ideal technique for field applications because of its simplicity, low cost, low power requirement, and independence from cooling systems. A new, portable, compact design is reported here. The tungsten coil is extracted from an inexpensive 24 V, 250 W commercial light bulb. The coil is housed in a small, aluminum cell. The emission signal exits from a small aperture in the cell, while the bulk of the blackbody emission from the tungsten coil is blocked. The resulting spectra exhibit extremely low background signals. The atomization cell, a single lens, and a hand-held charge coupled device (CCD) spectrometer are fixed on a 1 × 6 × 30 cm ceramic base. The resulting system is robust and easily transported. A programmable, miniature 400 W solid-state constant current power supply controls the temperature of the coil. Fifteen elements are determined with the system (Ba, Cs, Li, Rb, Cr, Sr, Eu, Yb, Mn, Fe, Cu, Mg, V, Al, and Ga). The precision ranges from 4.3% to 8.4% relative standard deviation for repetitive measurements of the same solution. Detection limits are in the 0.04 to 1500 μg/L range. Accuracy is tested using standard reference materials for polluted water, peach leaves, and tomato leaves. For those elements present above the detection limit, recoveries range from 72% to 147%.     

Fraunhofer effect atomic absorption spectrometry

The dark lines in the solar spectrum were discovered by Wollaston and cataloged by Fraunhofer in the early days of the 19th century. Some years later, Kirchhoff explained the appearance of the dark lines: the sun was acting as a continuum light source and metals in the ground state in its atmosphere were absorbing characteristic narrow regions of the spectrum. This discovery eventually spawned atomic absorption spectrometry, which became a routine technique for chemical analysis in the mid-20th century. Laboratory-based atomic absorption spectrometers differ from the original observation of the Fraunhofer lines because they have always employed a separate light source and atomizer. This article describes a novel atomic absorption device that employs a single source, the tungsten coil, as both the generator of continuum radiation and the atomizer of the analytes. A 25-microL aliquot of sample is placed on the tungsten filament removed from a commercially available 150-W light bulb. The solution is dried and ashed by applying low currents to the coil in a three-step procedure. Full power is then applied to the coil for a brief period. During this time, the coil produces white light, which may be absorbed by any metals present in the atomization cloud produced by the sample. A high-resolution spectrometer with a charge-coupled device detector monitors the emission spectrum of the coil, which includes the dark lines from the metals. Detection limits are reported for seven elements: 5 pg of Ca (422.7 nm); 2 ng of Co (352.7 nm); 200 pg of Cr (425.4 nm); 7 pg of Sr (460.7 nm); 100 pg of Yb (398.8 nm); 500 pg of Mn (403.1 nm); and 500 pg of K (404.4 nm). Simultaneous multielement analyses are possible within a 4-nm spectral window. The relative standard deviations for the seven metals are below 8% for all metals except for Ca (10.7%), which was present in the blank at measurable levels. Analysis of a standard reference material (drinking water) resulted in a mean percent recovery of 91%. This report attempts to give an historical perspective on the development of a novel atomic spectrometer based on the Fraunhofer effect.     

Detection of Sodium in Highly Pure Graphite via High-Resolution Electrothermal Atomic Absorption Spectrometry with a Continuous Spectrum Source

This study is dedicated to elucidating the analytical abilities of electrothermal atomic absorption spectrometry with a continuous spectrum source (ETAAS-CSS) to detect the presence of sodium in highly pure graphite powder. In order to plot the calibration dependence for sodium detection, a special technique based on argon dilution of the atomic vapor obtained by introducing the aqueous reference solution in the atomizer is applied. The conditions for thermal pretreatment of highly pure graphite powder and atomization of sodium are established, and the sodium detection threshold is evaluated via ETAAS-CSS (2.6 × 10^–4 ng) as well. The validity of the results is confirmed via the sample variation method.     

Nucleation and Oriented Textured Growth of Diamond Films on Si(100) via Electron Emission in Ho.t Filament Chemical Vapor Deposition

1. IntroductionIn recent years, there has been increasing illterest in the heteroepitaxial growth of diamond films'by chemicisl vapor deposition(CVD) owing to theirpromising applications for the electronic devices. Epitaxial diamond films have been successfully grown onc-BN and monocrystal diamond substrated~4]. However, it is a more imperative task to deposit heteroepitarial diamond films on St which was anticipated tobe as a low cost substrate to achieve synthesis of singlecrystalline diam…     

Vapor-solid-solid Si nano-whiskers growth using pure hydrogen as the source gas

This paper describes the growth mechanism and structure of Si whiskers grown on a Si substrate in a tungsten hot filament chemical vapor deposition reactor with pure hydrogen as source gas using a two step process. In the first step, atomic hydrogen etched the silicon surface, forming silicon hydrides that react with tungsten from the filament. The resulting silicide particles deposited on the silicon surface forming a mesh-like pattern. The particles work as an etching mask against hydrogen radical etching of the silicon surface and inverted-pyramids or V-groove-shaped surface texture were obtained. In the second step the filament current was reduced and whiskers grew onto the substrate due to the interaction of the silicon hydrides with the particles and subsequent precipitation of saturated Si. The whiskers were found to have tungsten silicide particles on their tip, suggesting the whisker growth was through the Vapor-Solid-Solid (VSS) mechanism. A balance between the hydrogen radical etching effect and the supply of silicon hydride from the etching reaction on the silicon surface is crucial for the growth of dense silicon whiskers.     

JY Ultima2ICP-OES光谱仪测定Ta-2.5W和Ta-10W中钨元素的分析方法研究

采用发射光谱仪建立发射光谱法测定Ta-2.5W和Ta-10W中钨含量的方法。使用高纯氢氧化钽基体的纯钨标准溶液制作工作曲线,钨的分析线为209.475 nm,方法的线性范围为1.25%~15.00%,加标回收率在93.0%~99.0%之间,测定结果的RSD值(n=11)小于0.8%。     

UV vapor generation for determination of selenium by heated quartz tube atomic absorption spectrometry

A new vapor generation technique utilizing UV irradiation coupled with atomic absorption for the determination of selenium in aqueous solutions is described. In the presence of low molecular weight organic acid solutions, inorganic selenium(IV) is converted by UV irradiation to volatile selenium species, which are then rapidly transported to a heated quartz tube atomizer for detection by atomic absorption spectrometry. Optimum conditions for photochemical vapor generation and interferences from concomitant elements were investigated. Identification of the volatile products using cryotrapping GC/MS analysis revealed that inorganic selenium(IV) is converted to volatile selenium hydride, selenium carbonyl, dimethyl selenide, and diethyl selenide in the presence of formic, acetic, propionic, and malonic acids, respectively. In acetic acid solution, the efficiency of generation was estimated to be 50 +/- 10%. No interference from Ni(2+) and Co(2+) at concentrations of 500 and 100 mg L(-)(1), respectively, was evident. A detection limit of 2.5 microg L(-)(1) and a relative sensitivity of 1.2 microg L(-)(1) (1% absorption) with a precision of 1.2% (RSD, n = 11) at 50 microg L(-)(1) were obtained.     

Continuous monitoring of alkali metals in gas flows using direct-current plasma excited atomic spectroscopy

A measuring instrument employing direct current (dc) plasma excited atomic line spectroscopy was developed for continuous measurement of alkali in combustion flue gases. Alkali compounds are dissociated by mixing sampled flue gas with a nitrogen plasma jet generated with a non-transferred dc plasma torch. The instrument can be used in two operating modes. The molar fraction is determined either by measuring the transmittance of the gas jet or by monitoring the emission. A tungsten halogen lamp and scanning monochromator are used for the measurement of the optical signals. Measurement of sodium and potassium has been demonstrated. The detection limits of the instrument are 50-70 ppb in the absorption mode. The detection limits are 2-3 ppb at 0.1 MPa pressure and 0.1-0.2 ppb at 1.0 MPa in the emission mode. The instrument is designed to withstand corrosive, particle laden, and pressurized flue gases at temperatures up to 1373 K.     

Atomization of hydride with a low-temperature, atmospheric pressure dielectric barrier discharge and its application to arsenic speciation with atomic absorption spectrometry

This paper describes a novel hydride atomizer based on atmospheric pressure dielectric barrier discharge (DBD) plasma. The plasma was generated with a 3700-V, 20.3-kHz, and 5-W electrical power supply and easily sustained with inert gases (He or Ar) at a flow rate of 250 mL.min(-1) after optimization. However, it cannot be sustained with N2. This atomizer offers the advantages of low operation temperature and low power consumption in comparison with the currently used electrothermal quartz atomization operated at 900 degrees C with a power supply of several hundred watts. To confirm the utility of the proposed atomizer, four arsenic species (As(III), As(V), monomethylarsonic acid (MMA), dimethylarsinic acid (DMA)) were determined by the present atomization technique. A hyphenation of HPLC coupled to hydride generation AAS with the optimized DBD atomizer has been successfully used for the speciation of arsenic in order to demonstrate the potential of this atomizer in the present study. The characteristics of the DBD atomizer and the effects of different parameters (discharge gas, gas flow rate, voltage, HCl concentration, KBH4 concentration) are discussed in the paper. Compared with other hydride atomization techniques, the proposed method shows the following features: (1) small size (70 mm x 15 mm x 5 mm), which is preferable for the miniaturization of the total analytical system; (2) low power consumption (< or =5 W), which indicates the possibility of the development of portable, fieldable analytical instrumentation for in situ detection using battery as power supply; (3) low atomizer temperature (approximately 70 degrees C), which is in favor of the compactness of the total instruments; (4) avoidance of residue moisture removal in comparison with the existed GD system, which leads to the facility of the system. The analytical figures of the present technique were evaluated. The detection limits of As(III), As(V), MMA, and DMA obtained with HG-DBD-AAS were 1.0, 11.8, 2.0, and 18.0 microg.L(-1), respectively. The accuracy of the system was verified by the determination of arsenic in reference material of orchard leaves SRM 1571. The concentration of As determined by the present method agreed well with the reference values. The speciation of arsenic in the freeze-dried urine SRM 2670 were carried out, and the results obtained were in agreement with the results of HPLC-ICPMS and the reported values by other laboratories.     

Study on W/SiC interface of SiC fiber fabricated by chemical vapor deposition on tungsten filament

SiC fiber was fabricated by chemical vapor deposition on tungsten filament heated by direct current in a CH₃SiCl₃-H₂ gas system. Microstructure of W/SiC interfacial reaction zone in the fiber was identified by means of scanning electron microscope and transmission electron microscope. Results showed that the thickness of the interfacial reaction zone is between 350 and 390 nm, and two reaction products of W₅Si₃ and WC were formed during fabricating SiC fiber. Electron diffraction analysis and composition detection indicated that W₅Si₃ is adjacent to tungsten core and WC is adjacent to SiC sheath, and the W/SiC interface can be described as W/W₅Si₃/WC/SiC. Furthermore, the formation mechanism of the interfacial reaction zone is discussed.     

Laser-excited atomic fluorescence in a pulsed hollow-cathode glow discharge

A pulsed glow discharge with low background noise is evaluated as an atom reservoir for laser-induced atomic fluorescence spectroscopy. Aqueous solutions are dried in graphite electrodes that are used as disposable hollow cathodes. Atomic vapor is produced in a flowing-gas glow discharge with a water-cooled cathode holder. A dye laser triggers a switching circuit that pulses that glow discharge, and fluorescence measurements are made 100 microseconds after the discharge is extinguished. The atomic population is large during this dark period, while the background emission is negligible. Linear calibration curves are obtained by nonresonance fluorescence for two elements, Pb and Ir. The detection limits for Pb are 100 pg/mL and 500 fg, and for Ir are 6 ng/mL and 20 pg. The experimental detection limit for Pb is compared to the intrinsic detection limit.     

Imaging time-resolved electrothermal atomization laser-excited atomic fluorescence spectrometry for determination of mercury in seawater

In this study, direct determination of mercury at the nanogram per liter level in the complex seawater matrix by imaging time-resolved electrothermal atomization laser-excited atomic fluorescence spectrometry (ITR-ETA-LEAFS) is described. In the case of mercury, the use of a nonresonant line for fluorescence detection with only one laser excitation is not possible. For measurements at the 253.652 nm resonant line, scattering phenomena have been minimized by eliminating the simultaneous vaporization of salts and by using temporal resolution and the imaging mode of the camera. Electrothermal conditions (0.1 M oxalic acid as matrix modifier, low atomization temperature) have been optimized in order to suppress chemical interferences and to obtain a good separation of specific signal and seawater background signal. For ETA-LEAFS, a specific response has been obtained for Hg with the use of time resolution. Moreover, an important improvement of the detection limit has been obtained by selecting, from the furnace image, pixels collecting the lowest number of scattered photons. Using optimal experimental conditions, a detection limit of 10 ng L(-1) for 10 μL of sample, close to the lowest concentration level of total Hg in the open ocean, has been obtained.     

Electrothermal atomic absorption spectrometric determination of gold by vapor formation and in situ trapping in graphite tubes

Gold was determined in ore samples following generation, separation, collection on a graphite cuvette inner wall, and atomization of its volatile species formed by combining an acidified sample solution with an aqueous sodium tetrahydroborate solution at room temperature. A detection limit of 2.6 microg L(-1) (3sigma) was obtained with a 5.0 mL sample volume. Precision of replicate measurements was typically 10% RSD. The overall efficiency of the volatile species generation, transport, and trapping process was 0.4%. Atomization of gold from Pd, Ir, Cu, Ag, and W coated graphite cuvettes, following by trapping of the gaseous volatile gold species on these surfaces, has been investigated. Pd coating was found to decrease the sensitivity. Five microg of Ir, 20 microg of Cu, 20 microg of Ag, and 5 microg of W were chosen as optimum masses. W treatment was the best one for sensitivity enhancement, having an improvement factor of 2.4. Silanization of glass surfaces significantly decreased memory effects; improved peak shapes were thus obtained for flow injection vapor generation atomic absorption spectrometry (FI-VGAAS). The method described in this study was used for the determination of gold in an ore reference material, Gold Ore (MA-1b), Canadian Reference Materials Program.     

提高HFCVD法合成金刚石中钨热解丝寿命的措施

ＨＦＣＶＤ法合成的金刚石中钨热解丝在沉积过程中因碳化而产生裂纹,在停机操作时钨热解丝因骤冷产生了热应力而断裂,停机操作前采用碳化钨还的技术及减缓钨丝冷却速度,可将钨丝的寿命提高３－５倍。     

微波消解-冷原子荧光光谱法测定V2O5-WO3/TiO2系脱硝催化剂中汞的含量

该文采用酒石酸+氢氟酸+硝酸体系微波消解处理V₂O₅-WO₃/TiO₂脱硝催化剂试样,以氢化物发生-冷原子荧光光谱法(HG-AFS)测定其中汞的含量。文中探讨原子化器炉温、原子化器高度、载气及屏蔽气流量及硼氢化钾-氢氧化钠浓度等关键参数对汞测定的影响,并通过系列试验确定上述关键参数的最优解:还原剂浓度为0.2 g/L(硼氢化钾)–2.0 g/L(氢氧化钠),载气和屏蔽气流量分别为600 mL/min和800 mL/min,原子化器炉温200℃,原子化器高为10 mm。共存元素干扰试验表明,在该实验条件下,少量As(Ⅲ)的干扰可加入高锰酸钾(1.0 g/L)将其氧化成As(Ⅴ)得以消除,Pb(Ⅱ)的干扰可加入1.0 mL硫酸(1+5)生成硫酸铅沉淀消除。汞的浓度在0~2.0μg/L范围内线性相关系数为0.9997,方法检出限为0.02μg/L。方法用于实际样品分析,相对标准偏差(RSD,n=7)小于4.0%,加标回收率为95%~104%。     

Continuum-source atomic absorption spectroscopy with an echelle spectrometer adapted to a charge injection device

An instrumental system for continuum-source atomic absorption spectroscopy has been developed for simultaneous multielement determinations. The system consists of an electrothermal atomizer and a charge injection device adapted to an echelle spectrometer to achieve multiplex detection. A continuous 40-nm spectral range in the two-dimensional echelle spectrum was acquired simultaneously through the capability of the charge injection device to integrate signals in its MOS capacitors. Novel methods were developed to compute absorbances by "scanning" through all orders in the entire echelle spectrum or selecting absorption lines randomly. In the range 300-430 nm, characteristic concentrations (1% absorption) were 1.6, 2.6, 2.9, and 3.8 ng mL-1 respectively for Cu, Mn, and two Cr lines; these values are similar to those (1.3, 2.2, 1.2, and 3.6 ng mL-1) obtained for single-element detection with an image-dissector system.     

Microwave-assisted photochemical reactor for the online oxidative decomposition and determination of p-hydroxymercurybenzoate and its thiolic complexes by cold vapor generation atomic fluorescence detection

We developed a photochemical method for the online oxidation of p-hydroxymercurybenzoate (PHMB), an organic mercury species widely used for mercaptan and thiolic compound labeling. The method is based on a fully integrated online UV/microwave (MW) photochemical reactor for the digestion of PHMB, followed by cold vapor generation atomic fluorescence spectrometry (CVG-AFS) detection. The MW/UV process led to the quantitative conversion of PHMB and thiol-PHMB complexes to Hg(II), with a yield between 91% and 98%, without using chemical oxidizing reagents and avoiding the use of toxic carcinogenic compounds. This reaction was followed by the reduction of Hg(II) to Hg(0), performed in a knitted reaction coil with NaBH(4) solution, and AFS detection in an Ar/H(2) miniaturized flame. The low MW power applied (18 W) allowed us to keep constant the temperature of the photochemical reactor (21 ± 1 °C), using a flowing water bath. This avoided peak widening due to diffusion processes generally occurring at high temperatures and in the additional cooling coil. This method has been applied to the determination of thiols in human plasma, blood, and wine.     

Handheld rectilinear ion trap mass spectrometer

A shoebox-sized, 10-kg, handheld mass spectrometer, Mini 10, based on a rectilinear ion trap mass analyzer has been designed, built, and characterized. This instrument has evolved from a decade-long experimental and simulation program in mass spectrometer miniaturization. The rectilinear ion trap has a simplified geometry and high trapping capacity, and when used with a miniature and ruggedized pumping system, it allows chemical analysis while the instrument is being carried. Compact electronics, including an air core RF drive coil, were developed to control the instrument and to record mass spectra. The instrument runs on battery power, consuming less than 70 W, similar to a laptop computer. Wired and wireless networking capabilities are implemented. The instrument gives unit resolution and a mass range of over m/z 500. Tandem mass spectrometry capabilities are implemented using collision-induced dissociation, and they are used to provide confirmation of chemical structure during in situ analysis. Continuous monitoring of air and solution samples is demonstrated, and a limit of detection of 50 ppb was obtained for toluene vapor in air and for an aqueous naphthalene solution using membrane sample introduction.     

Deposition of thermal and hot-wire chemical vapor deposition copper thin films on patterned substrates

In this work we study the hot-wire chemical vapor deposition (HWCVD) of copper films on blanket and patterned substrates at high filament temperatures. A vertical chemical vapor deposition reactor was used in which the chemical reactions were assisted by a tungsten filament heated at 650 degrees C. Hexafluoroacetylacetonate Cu(I) trimethylvinylsilane (CupraSelect) vapors were used, directly injected into the reactor with the aid of a liquid injection system using N2 as carrier gas. Copper thin films grown also by thermal and hot-wire CVD. The substrates used were oxidized silicon wafers on which trenches with dimensions of the order of 500 nm were formed and subsequently covered with LPCVD W. HWCVD copper thin films grown at filament temperature of 650 degrees C showed higher growth rates compared to the thermally ones. They also exhibited higher resistivities than thermal and HWCVD films grown at lower filament temperatures. Thermally grown Cu films have very uniform deposition leading to full coverage of the patterned substrates while the HWCVD films exhibited a tendency to vertical growth, thereby creating gaps and incomplete step coverage.     

Design and characterization of a theta-pinch imploding thin film plasma source for atomic emission spectrochemical analysis

A new atomization device for direct atomic spectrochemical analysis has been developed that uses the theta-pinch configuration to generate a pulsed, high-energy-density plasma at atmospheric pressure. Energy from a 20-kV, 6.05-μF capacitive electrical discharge was inductively coupled to a sacrificial aluminum thin film to produce a cylindrical plasma. Current waveform analysis indicates an average power dissipation of 0.5 MW in the plasma. Electromagnetic modeling studies were used to identify theta-pinch designs possessing characteristics favorable to both plasma initiation and plasma heating. The discharge was most robust when the induced current and rate of magnetic field change were maximized. Minimizing the ratio of the coil's width to its radius was also critical. Counter to intuition, a larger diameter was found to be more successful. Spectroscopic studies indicate that the discharge forms a heterogeneous plasma with a dense, cylindrical plasma sheet confined by the walls of the discharge tube surrounding a less energetic plasma in the center. Al(II) emission in the outer plasma cylinder was temporally aligned with the induced current whereas in the center it aligns with the magnetic field. Ionization of support gas species (Ar, He, and air) was not observed, although the identity of the gas had a significant influence on the plasma reproducibility. The optimized design utilized a 5.5-turn, 19-mm-diameter theta coil with argon as the support gas. Sb(I) emission from an antimony oxide solid powder sample deposited on the thin film was observed primarily in the outer part of the plasma. Analyte emission shows contributions from magnetic compression early in the discharge and from the induced current late in the discharge. The discharge produced analytically useful signals from solid antimony oxide samples. Using spatially and temporally resolved detection, the line-to-background ratio for Sb(I) was found to be greater than 4 for emission integrated from 55 to 120 μs.