Quantitative absorption spectroscopy of residual water vapor in high-purity gases: pressure broadening of the 1.39253-microm H2O transition by N2, HCl, HBr, Cl2, and O2

We determined the respective pressure-broadening coefficients of HCl, HBr, Cl2, and O2 (expressed relative to that of the reference gas N2) for the (v1,v2,v3)J(Ka,Kc) = (0,0,0)3(0,3) --> (1,0,1)2(0,2) rovibrational transition of H2 16O that occurs at 1.39253 microm. The experiment used a continuous-wave cavity ring-down spectroscopy analyzer to measure the peak absorption losses as a function of added moisture concentration. The measured pressure-broadening coefficients for HCl, HBr, Cl2, and O2 are, respectively, 2.76, 2.48, 1.39, and 0.49 times that of the N2 pressure-broadening coefficient, and detection limits for water vapor range from 0.22 nmol mol(-1) for O2 matrix gas to 2.3 nmol mol(-1) for HBr matrix gas. The degradation of the detection limit (relative to the N2 matrix gas) is ascribed to a pressure-broadening-induced reduction in peak absorption cross section and to elevated background loss from the matrix gas.     

Absorption line shift with temperature and pressure: impact on laser-diode-based H2O sensing at 1.393 microm

High-resolution absorption measurements of the H2O line in the v1 + v3 band at 1.3928 microm were made in the temperature range of 296-1100 K by use of an InGaAsP distributed-feedback laser diode operating at 1.39 microm. Spectral line shift, line strength, and N2 broadening on the water-vapor line and their impact on the accuracy of optical-absorption-based gas sensing have been investigated. The results obtained were compared with values obtained from the HITRAN database and values reported in the literature, facilitating H2O sensing in a nonstandard temperature and pressure environment.     

PT／SiO2精细复合材料的制备及其特性

利用溶胶－凝胶工艺成功地制备出了ＰＴ／ＳｉＯ２精细复合材料，通过ＸＲＯ，介电频谱和Ｒａｍａｎ光谱对复合样品的结构和性能进行了分析，最后用四波混频方法对的非线性光学性能进行了测量。     

H2O absorption spectroscopy for determination of temperature and H2O mole fraction in high-temperature particle synthesis systems

Water absorption spectroscopy has been successfully demonstrated as a sensitive and accurate means for in situ determination of temperature and H2O mole fraction in silica (SiO2) particle-forming flames. Frequency modulation of near-infrared emission from a semiconductor diode laser was used to obtain multiple line-shape profiles of H2O rovibrational (v1 + v3) transitions in the 7170-7185-cm(-1) region. Temperature was determined by the relative peak height ratios, and XH2O was determined by use of the line-shape profiles. Measurements were made in the multiphase regions of silane/hydrogen/oxygen/ argon flames to verify the applicability of the diagnostic approach to combustion synthesis systems with high particle loadings. A range of equivalence ratios was studied (phi = 0.47 - 2.15). The results were compared with flames where no silane was present and with adiabatic equilibrium calculations. The spectroscopic results for temperature were in good agreement with thermocouple measurements, and the qualitative trends as a function of the equivalence ratio were in good agreement with the equilibrium predictions. The determinations for water mole fraction were in good agreement with theoretical predictions but were sensitive to the spectroscopic model parameters used to describe collisional broadening. Water absorption spectroscopy has substantial potential as a valuable and practical technology for both research and production combustion synthesis facilities.     

Role of nonresonant sum-frequency generation in the investigation of model liquid chromatography systems

In vibrationally resonant sum-frequency generation (VR-SFG) spectra, the resonant signal contains information about the molecular structure of the interface, whereas the nonresonant signal is commonly treated as a background and has been assumed to be negligible on transparent substrates. The work presented here on model chromatographic stationary phases contradicts this assumption. Model stationary phases, consisting of functionalized fused-silica windows, were investigated with VR-SFG spectroscopy, both with and without experimental suppression of the nonresonant response. When samples are moved from CD(3)OD to D(2)O, the VR-SFG spectrum was found to change over time when the nonresonant signal was present but not when the nonresonant signal was suppressed. No effect was seen when the solvent was changed and pressurized to 900 psi. These results suggest that the response to the new solvent manifests primarily in the nonresonant response, not the resonant response. Any structural changes caused by the new solvent environment appear to be minor. The nonresonant signal is significant and must be properly isolated from the resonant signal to ensure a correct interpretation of the spectral data. Curve-fitting procedures alone are not sufficient to guarantee a proper interpretation of the experimental results.     

N2O removal in N2 or air by ArF excimer laser photolysis at atmospheric pressure

A photochemical process is proposed as a new efficient N(2)O removal technique in N(2) or air at atmospheric pressure and room temperature without using any catalysts. N(2)O diluted in N(2) or air was decomposed into N(2), O(2), and NO by using a 193 nm ArF excimer laser. The maximum conversion of N(2)O in N(2)O/N(2) or N(2)O/N(2)/O(2) mixtures was 93% at a laser power of 136 mJ, a repetition frequency of 5 Hz, and an irradiation time of 30 min. The formation ratios of N(2):O(2):NO in N(2)O/N(2) and N(2)O/N(2)/O(2) mixtures were 64:31:5.1% and 60:27:13%, respectively. The decomposition mechanism of N(2)O under 193 nm photolysis was discussed by comparing experimental data with calculated model using known photochemical and gas kinetic data.     

A compact diode laser cavity ring-down spectrometer for atmospheric measurements of NO3 and N2O5 with automated zeroing and calibration

A compact rack-mounted cavity ring-down spectrometer (CRDS) for simultaneous measurements of the nocturnal nitrogen oxides NO(3) and N(2)O(5) in ambient air is described. The instrument uses a red diode laser to quantify mixing ratios of NO(3) (at its absorption maximum at 662 nm) and of N(2)O(5) following its thermal dissociation to NO(3) in a second detection channel. The spectrometer is equipped with an automated zeroing and calibration setup to determine effective NO(3) absorption cross-sections and NO(3) and N(2)O(5) inlet transmission efficiencies. The instrument response was calibrated using simultaneous measurements of NO(2), generated by thermal dissociation of N(2)O(5) and/or by titration of NO(3) with excess NO, using blue diode laser CRDS at 405 nm. When measuring ambient air, the (2σ, 10 s) precision of the red diode CRDS varied between 5 and 8 parts-per-trillion by volume (pptv), which sufficed to quantify N(2)O(5) concentrations under moderately polluted conditions. Sample N(2)O(5) measurements made on a rooftop on the University of Calgary campus in August 2010 are presented. A maximum N(2)O(5) mixing ratio of 130 pptv was observed, corresponding to a steady-state lifetime of less than 50 min. The NO(3) mixing ratios were below the detection limit, consistent with their predicted values based on equilibrium calculations. During the measurement period, the instrument response for N(2)O(5) was 70% of the theoretical maximum, rationalized by a slight mismatch of the laser diode output with the NO(3) absorption line and a N(2)O(5) inlet transmission efficiency less than unity. Advantages and limitations of the instrument's compact design are discussed.     

Photochemical removal of NO(2) by using 172-nm Xe(2) excimer lamp in N(2) or air at atmospheric pressure

Photochemical removal of NO(2) in N(2) or air (5-20% O(2)) mixtures was studied by using 172-nm Xe(2) excimer lamps to develop a new simple photochemical aftertreatment technique of NO(2) in air at atmospheric pressure without using any catalysts. When a high power lamp (300 mW/cm(2)) was used, the conversion of NO(2) (200-1000 ppm) to N(2) and O(2) in N(2) was >93% after 1 min irradiation, whereas that to N(2)O(5), HNO(3), N(2), and O(2) in air (10% O(2)) was 100% after 5s irradiation in a batch system. In a flow system, about 92% of NO(2) (200 ppm) in N(2) was converted to N(2) and O(2), whereas NO(2) (200-400 ppm) in air (20% O(2)) could be completely converted to N(2)O(5), HNO(3), N(2), and O(2) at a flow rate of 1l/min. It was found that NO could also be decomposed to N(2) and O(2) under 172-nm irradiation, though the removal rate is slower than that of NO(2) by a factor of 3.8. A simple model analysis assuming a consecutive reaction NO(2)-->NO-->N+O indicated that 86% of NO(2) is decomposed directly into N+O(2) and the rest is dissociated into NO+O under 172-nm irradiation. These results led us to conclude that the present technique is a new promising catalyst-free photochemical aftertreatment method of NO(2) in N(2) and air in a flow system.     

Comparison of Gas Temperatures Measured by Coherent Anti-Stokes Raman Spectroscopy (CARS) of O(2) and N(2)

We investigate the accuracy of temperature measurements by coherent anti-Stokes Raman spectroscopy (CARS) of O(2) and use measurements taken with N(2) CARS and a thermocouple for comparison. Scanning vibrational CARS spectra of O(2) and N(2) were recorded over a broad range of temperatures: between 294 K and 1900 K in air that was heated in a tube furnace and at approximately 2450 K in a fuel-lean CH(4)-O(2)-N(2) flame. Temperatures were derived from least-squares fits of simulated and experimental spectra. Both the fundamental vibrational band and the first hot vibrational band were included in fitting. In the case of the tube furnace, the N(2) and the O(2) CARS temperature measurements agreed to within 3%, and results were similar with the thermocouple; in the flame the agreement was to within 1%. We conclude that, for cases in which O(2) is present in sufficient concentrations ( approximately 10% or greater), the accuracy of O(2) thermometry is comparable with that of N(2).     

Multiphoton excitation ionization of N(2) following collisional energy transfer with H(2)O: a potential measure of molecular mixing

A multiphoton ionization excitation of N(2) following collisional energy exchange with optically excited H(2) O was demonstrated, and its potential for measuring H(2) O-N(2) mixing at the molecular level was evaluated. In this process, N(2) is sensitized by a collisional energy exchange with H(2)O molecules excited by a tunable KrF laser. The sensitized N(2) molecules are further excited and ionized by two additional photons of the same laser pulse. Independent images of sensitized N2(+) emission at 391.4 nm and by OH at 308 nm formed by the dissociation of excited H(2)O were obtained along a laser beam traversing slow dry-air and N(2) jets entering room air. Although effects of O(2) and N(2) collisional quenching were noted, such images can potentially be used to measure H(2)O-N(2) molecular mixing and the concentration of H(2)O independently. The detection of H(2)O nucleation by this technique suggests that imaging of H(2)O droplet evaporation or visualizing and monitoring H(2)O condensation may also be possible.     

Hollow waveguides with low intrinsic photoluminescence fabricated with Ta(2)O(5) and SiO(2) films

A type of integrated hollow core waveguide with low intrinsic photoluminescence fabricated with Ta(2)O(5) and SiO(2) films is demonstrated. Hollow core waveguides made with a combination of plasma-enhanced chemical vapor deposition SiO(2) and sputtered Ta(2)O(5) provide a nearly optimal structure for optofluidic biofluorescence measurements with low optical loss, high fabrication yield, and low background photoluminescence. Compared to earlier structures made using Si(3)N(4), the photoluminescence background of Ta(2)O(5) based hollow core waveguides is decreased by a factor of 10 and the signal-to-noise ratio for fluorescent nanobead detection is improved by a factor of 12.     

Near-resonance enhanced O2 detection for dual-broadband pure rotational coherent anti-Stokes Raman scattering with an ultraviolet-visible setup at 266 nm

Broadband and dual-broadband coherent anti-Stokes Raman scattering (CARS) are widely established tools for nonintrusive gas diagnostics. Up to now the investigations have been mainly performed for electronic nonresonant conditions of the gas species of interest. We report on the enhancement of the O2-N2 detection limit of dual-broadband pure rotational CARS by shifting the wavelength of the narrowband pump laser from the commonly used 532-266 nm. This enhancement is caused when the Schumann-Runge absorption band is approached near 176 nm. The principal concept of this experiment, i.e., covering the Raman resonance with a single- or dual-broadband combination of lasers in the visible range and moving only the narrowband probe laser near or directly into electronic resonant conditions in the UV range, should also be applicable to broadband CARS experiments to directly exploit electronic resonance effects for the purpose of single-shot concentration measurements of minority species. To quantify the enhancement in O2 sensitivity, comparative measurements at both a 266 and a 532 nm narrowband pump laser wavelength are presented, employing a 4-dicyanomethylene-2-methyl-6-(p-dimethylaminostyryl)-4H-pyram (DCM) dye laser as a broadband laser source at 635 nm. An increase of approximately equal to 13% in the ratio of the rotational CARS cross sections of O2 and N2 was obtained. The broad spectral width of the CARS excitation profile was approximately equal for both setups. Further enhancement should be achievable by shifting the narrowband pump laser closer toward 176 nm, for example, with a frequency-doubled optical parametric oscillator or an excimer laser. The principal concept of this experiment should also be applicable to broadband CARS experiments to directly exploit electronic resonance effects of the narrowband pump laser with electronic transitions of minority species for the purpose of single-shot concentration measurements of those species.     

EPR and Magnetic Susceptibility Investigations of Fe Containing TeO2-B2O3-SrF2 Glasses

1. IntroductionTellurite-borate vitreous systems[1] and binajry tellurite oxide systems containing transition metal ions[2]were investigated in detail due to their interestingproperties having a number of applications in microelectronics. They are optical glajsses with high refraction index (n>2) and a good iR transmission,being suitable as laser and opto-acoustical materials. Tellurite systems containing FeZO3 were studied to reveal their electrical properties as well asthe structural onesl…     

Eu2+、Dy3+、Li+共掺杂CaSi2O2N2荧光粉的发光性能

采用高温固相反应法制备了一系列白光LED用CaSi2O2N2:0.05Eu2+,xDy3+,xLi+(0≤x≤0.03)荧光粉.利用X射线衍射仪对样品的物相结构进行了分析,结果表明:Dy3+和Li+离子的掺入没有改变CaSi2O2N2:Eu2+荧光粉的主晶相.利用荧光光谱仪对样品的发光性能进行了测试,发现所有样品的激发光谱均覆盖了从近紫外到蓝光的较宽范围,400 nm激发下得到的发射光谱为宽波段的单峰,峰值位于545 nm左右,是Eu2+离子5d-4f电子跃迁引起的.Dy3+离子掺杂可以提高CaSi2O2N2:Eu2+荧光粉的发光强度,Dy3+与Li+共掺杂可进一步提高荧光粉的发光强度,当Dy3+和Li+的掺杂量为1mol%时,荧光粉的发光强度达到最大值,是单掺杂Eu2+的荧光粉发光强度的157%.     

A study on N2O catalytic decomposition over Co/MgO catalysts

Different oxide supported cobalt catalysts were prepared by co-precipitation method and tested for the decomposition of nitrous oxide. Co/MgO with cobalt loading of 15% showed the best activity and a 100% N(2)O conversion was obtained at temperatures higher than 700 K. The active phase of cobalt species in Co/MgO catalysts was Co(3)O(4) highly dispersed in the matrices of MgO, based on XRD and XPS results as well as the kinetic analysis. The existence of NO, O(2) and H(2)O in reaction system showed different negative effects on N(2)O decomposition. Nevertheless, a 100% N(2)O conversion could be achieved at 800 K under simulated conditions of tail gas from nitric acid plant. Moreover, Co/MgO catalyst exhibited quite good durability and no obvious activity loss was observed in the 100 h stability test.     

Emission characteristics of coal combustion in different O2/N2, O2/CO2 and O2/RFG atmosphere

This study investigates the emission characteristics of CO(2), SO(2) and NOx in the flue gas of coal combustion by varying the compositions and concentrations of feed gas (O(2)/CO(2)/N(2)) and the ratios of recycled flue gas. The differences between O(2)/recycled flue gas (O(2)/RFG) combustion and general air combustion are also discussed. Experimental results indicate that the maximum concentration of CO(2) in O(2)/CO(2) combustion system is 95% as the feed gas is 30% O(2)/70% CO(2). The average concentration of CO(2) in the flue gas of O(2)/CO(2) coal combustion system is higher than 90% and much higher than that of O(2)/N(2) coal combustion system. This high concentration of CO(2) is beneficial for the separation of CO(2) from the flue gas by adsorption or absorption technologies. The maximum concentration of CO(2) in O(2)/N(2) combustion system is only 34% at the feed gas 50% O(2)/50% N(2), the concentration of CO(2) is increased with the concentration of O(2) in feed gas. By O(2)/CO(2) combustion technology, higher concentration of SO(2) is produced as the feed gas is 30% O(2)/70% CO(2) or 40% O(2)/60% CO(2), while higher concentration of NOx is produced as the feed gas is 20% O(2)/80% CO(2) or 50% O(2)/50% CO(2). The mass flow rates of CO(2), SO(2) and NOx in the flue gas are all increased with the ratio of recycled flue gas except for the feed gas 20% O(2)/80% CO(2). The enhanced mass flow rates of air pollutants in such O(2)/RFG combustion system are also beneficial for improving the control efficiencies of air pollution control devices. By O(2)/N(2) combustion technology, higher concentrations of SO(2) and NOx are produced as the feed gas is 21% O(2)/79% N(2). The results also indicate that the formation of NOx in general air combustion system is higher than that in O(2)/RFG or O(2)/CO(2) combustion system.     

H(2)O--N(2) collision-induced absorption band intensity in the region of the N(2) fundamental: ab initio investigation of its temperature dependence and comparison with laboratory data

The present paper aims at ab initio and laboratory evaluation of the N(2) collision-induced absorption band intensity arising from interactions between N(2) and H(2)O molecules at wavelengths of around 4?μm. Quantum chemical calculations were performed in the space of five intermolecular coordinates and varying N--N bond length using M?ller-Plesset perturbation and CCSD(T) methods with extrapolation of the electronic energy to the complete basis set. This made it possible to construct the intermolecular potential energy surface and to define the surface of the N--N dipole derivative with respect to internal coordinate. The intensity of the nitrogen fundamental was then calculated as a function of temperature using classical integration. Experimental spectra were recorded with a BOMEM DA3-002 FTIR spectrometer and 2?m base-length multipass White cell. Measurements were conducted at temperatures of 326, 339, 352 and 363?K. The retrieved water-nitrogen continuum significantly deviates from the MT_CKD model because the relatively strong nitrogen absorption induced by H(2)O was not included in this model. Substantial uncertainties in the measurements of the H(2)O-N(2) continuum meant that quantification of any temperature dependence was not possible. The comparison of the integrated N(2) fundamental band intensity with our theoretical estimates shows reasonably good agreement. Theory indicates that the intensity as a function of temperature has a minimum at approximately 500?K.     

Nonresonant referenced laser-induced thermal acoustics thermometry in air

We report a detailed investigation of nonresonant laser-induced thermal acoustics (LITA) for the single-shot measurement of the speed of sound (v(S)) in an oven containing room air. A model for the speed of sound that includes important acoustic relaxation effects is used to convert the speed of sound into temperature. A reference LITA channel is used to reduce uncertainties in v(S). Comparing thermocouple temperatures with temperatures deduced from our v(S) measurements and model, we find the mean temperature difference from 300 to 650 K to be 1% (+/-2sigma). The advantages of using a reference LITA channel are discussed.     

Rapid, online quantification of H2S in JP-8 fuel reformate using near-infrared cavity-enhanced laser absorption spectroscopy

One of the key challenges in reforming military fuels for use with fuel cells is their high sulfur content, which can poison the fuel cell anodes. Sulfur-tolerant fuel reformers can convert this sulfur into H(2)S and then use a desulfurizing bed to remove it prior to the fuel cell. In order to optimize and verify this desulfurization process, a gas-phase sulfur analyzer is required to measure H(2)S at low concentrations (<1 ppm(v)) in the presence of other reforming gases (e.g., 25-30% H(2), 10-15% H(2)O, 15% CO, 5% CO(2), 35-40% N(2), and trace amounts of light hydrocarbons). In this work, we utilize near-infrared cavity-enhanced optical absorption spectroscopy (off-axis ICOS) to quantify H(2)S in a JP-8 fuel reformer product stream. The sensor provides rapid (2 s), highly precise (±0.1 ppm(v)) measurements of H(2)S in reformate gases over a wide dynamic range (0-1000 ppm(v)) with a low detection limit (3σ = ±0.09 ppm(v) in 1 s) and minimal cross-interferences from other present species. It simultaneously quantifies CO(2) (±0.2%), CH(4) (±150 ppm(v)), C(2)H(4) (±30 ppm(v)), and H(2)O (±300 ppm(v)) in the reformed gas for a better characterization of the fuel reforming process. Other potential applications of this technology include measurement of coal syngas and H(2)S in natural gas. By including additional near-infrared, distributive feedback diode lasers, the instrument can also be extended to other reformate species, including CO and H(2).     

Effects of Phase Composition on Microstructure and Mechanical Properties of Lu_2O_3-doped Porous Silicon Nitride Ceramics

Porous silicon nitride ceramics(Si3N4) were fabricated by pressureless sintering using different particle size of silicon nitride powder.Lu2O3 was used as sintering additive.According to phase relationships in the ternary system Si3N4-SiO2-Lu2O3,porous Si3N4 ceramics with different phase composition were designed through the change of the content of SiO2 which was formed by the oxidation at 800℃ in air.Porous Si3N4 with different phase compositions was obtained after sintering at 1800℃ in N2atmosphere.A small content of SiO2 favored the formation of secondary phase Lu4Si2O7N2,while large content of SiO2 favored the formation of secondary phase Lu2Si2O7 and Si2N2O.Porous Si3N4 ceramics with secondary phase Lu4Si2O7N2 had a flexural strength of 207 MPa,while that with secondary phase Si2N2O and Lu2Si2O7 had lower flexural strength.