Kinetics of oxygen exchange in strontium titanate

The kinetics of oxygen exchange are of primary importance for the application of titanates as fast resistive oxygen sensors. The sensor’s conductivity is correlated with the oxygen partial pressure pO₂ of the surrounding atmosphere: Due to oxygen surface transfer and subsequent diffusion of oxygen vacancies V _O ^·· , a pO₂ change gives rise to a conductivity change of the sample. While bulk diffusion usually occurs very fast, the surface transfer reaction becomes the rate determining step for thin samples and for low temperatures. We have shown that in the case of acceptor doped SrTiO₃ the kinetics of the surface transfer reaction can be strongly influenced through stoichiometric changes brought about by thin coatings of alkaline earth metal oxides (e.g. SrO). In contrast to the commonly used jump method (conductivity response to a sudden pO₂ change in the time domain), a model is presented which is based on the frequency-domain analysis of amplitude and phase shift of the response signal obtained from a pO₂ modulation in a fast kinetic measurement set-up. This method allows not only for measuring response times in the sub-millisecond range but also for distinguishing between behaviour either controlled by volume diffusion or by surface transfer reaction. Paper presented at the 9th EuroConference on Ionics, Ixia, Rhodes, Greece, Sept. 15 – 21, 2002.     

Oxygen quenching of toluene fluorescence at elevated temperatures

Gas-phase oxygen quenching of toluene laser-induced fluorescence (LIF) is studied between 300 and 650 K in a nitrogen/oxygen bath gas of 1-bar total pressure with oxygen partial pressures up to 400 mbar. With increasing vibrational excitation of the laser-excited toluene, intramolecular decay becomes faster, resulting in a decreasing relative strength of collisional quenching by oxygen. Additionally, Stern–Volmer plots are found to be non-linear for temperatures above 500 K in the case of 266-nm excitation and at all temperatures for 248-nm excitation. This is attributed to the onset of internal conversion from specific vibrational levels. A photophysical model is developed that describes the experimental data and predicts toluene LIF signal strengths for higher oxygen partial pressures. One important result for practical application is that oxygen quenching is not the dominant de-excitation process for engine-related temperature and pressure conditions, and thus application of the popular fuel–air ratio LIF (FARLIF) concept leads to erroneous signal interpretation.This revised version was published online in August 2005 with a corrected cover date.     

Toluene LIF at elevated temperatures: implications for fuel–air ratio measurements

Toluene laser-induced fluorescence (LIF) was investigated for 266- and 248-nm excitation in the temperature range of 300–650 K in a nitrogen/oxygen bath gas of 1 bar total pressure with oxygen partial pressure in the range 0–400 mbar. Contrary to a popular assumption, the toluene LIF signal is not directly proportional to the fuel–air ratio (termed the FAR-LIF assumption) for many conditions relevant to reciprocating IC engines. With increasing temperature, a higher oxygen partial pressure is required to justify the FAR-LIF assumption. The required oxygen pressure becomes unrealistic (>5 bar) for T>670 K at 266-nm excitation and for T>625 K at 248-nm excitation. PACS 33.50.-j; 42.62.-b     

On the phase formation of titanium oxide thin films deposited by reactive DC magnetron sputtering: influence of oxygen partial pressure and nitrogen doping

This work describes about the control on phase formation in titanium oxide thin films deposited by reactive dc magnetron sputtering. Various phases of titanium oxide thin films were deposited by controlling the oxygen partial pressure during the sputtering process. By adding nitrogen gas to sputter gas mixture of oxygen and argon, the oxygen partial pressure was decreased further below the usual critical value, below and above which the sputtering yields metallic and oxide films, respectively. Furthermore, nitrogen addition eliminated the typical hysteretic behaviour between the flow rate and oxygen partial pressure, and significantly influenced the sputter rate. On increasing the oxygen partial pressure, the ratio between anatase and rutile fraction and grain size increases. The fracture cross-sectional scanning electron microscopy together with the complementary information from X-ray diffraction and micro-Raman investigations revealed the evolution and spatial distribution of the anatase and rutile phases. Both the energy delivered to the growing film and oxygen vacancy concentrations are correlated with the formation of various phases upon varying the oxygen partial pressure.     

Imaging of the oxygen distribution in an isothermal turbulent free jet using two-color toluene LIF imaging

The results of a novel technique for the quantification of oxygen in an isothermal turbulent free jet using toluene laser induced fluorescence (LIF) are presented. This method relies on the red-shift of the toluene LIF emission spectrum with increasing oxygen concentration. Evaluating the LIF signal ratio from two different wavelength regions simultaneously produces results that depend only on the local oxygen concentration. From calibration data, obtained from repeated tests, the oxygen sensitivity of the two-color LIF technique is best for oxygen partial pressures p_O2 ￡ 120 mbarp_{\mathrm{O}_{2}} \leq 120\mbox{ mbar} in the current setup. Quantified images of oxygen distribution are presented for 40.4, 60.5, 80.5, and 103 mbar p_O2p_{\mathrm{O}_{2}} in the toluene-seeded jet flow that is shielded by a toluene-seeded nitrogen co-flow at atmospheric pressure and temperature. Based on the average oxygen concentration images (obtained from 100 instantaneous oxygen images), the error in accuracy of measuring the oxygen concentration was 0.8, 3.0, 7.7, and 7.3% with a precision of ± 8.6, 5.5, 13.3, and 11.6% for the jet p_O2 = 40.4, 60.5, 80.5, and 103 mbarp_{\mathrm{O}_{2}} = 40.4,\, 60.5,\, 80.5,\mbox{ and }103\mbox{ mbar} cases, respectively. The main jet flow characteristics have been captured by the technique as determined from the measured oxygen distribution images. Centerline profiles of average oxygen concentration, normalized to the value at the nozzle exit, demonstrate self-similar behavior from 5 mm above the nozzle exit. Radial oxygen concentration profiles exhibit a Gaussian-type distribution that broadens with distance above the nozzle exit, in agreement with literature.     

非标定波长调制吸收光谱气体测量研究

为消除可调谐激光调制吸收光谱气体测量技术对于标定过程的依赖,研究了二次谐波信号的非标定波长调制气体测量方法.通过对测量的二次谐波线型进行分析,给出相同工况下二次谐波模拟信号,并利用测量与模拟二次谐波信号进行线性拟合直接计算气体浓度.实验室内采用非标定波长调制气体测量方法,利用 6336.24 cm^-1处特征吸收谱线对10 cm长气体吸收池内的CO₂进行了测量.结果表明,非标定波长调制气体测量方法可适应各种不同条件,适合于现场气体在线测量.当调制系数在1.8—3. 关键词： 波长调制 二次谐波 吸收光谱 半导体激光器     

Transient absorption spectroscopy of a monofullerene C<Subscript>60</Subscript>-bis-(pyropheophorbide <Emphasis Type="Italic">a</Emphasis>) molecular system in polar and nonpolar environments

The population dynamics of the excited and ground states of the monofullerene-bis (pyropheophorbide a) complex (FP1) were studied in polar (DMF) and nonpolar (toluene) solvents using picosecond transient absorption techniques. A strong quenching of the fluorescence signal of FP1 was observed in both solvents, in comparison to the fluorescence of bis (pyropheophorbide a) (P2). This quenching is due to an intramolecular photoinduced electron transfer from the pyropheophorbide a (pyroPheo) moiety to the fullerene C₆₀ monoadduct. In DMF the charge-separated (CS) state of FP1 has a lifetime of 0.32 ns and undergoes a direct transition to the ground state, resulting in a very low value of photosensitised singlet oxygen generation. In toluene, energy transfer from the first excited triplet state of pyroPheo, which has been populated via relaxation of the CS state, generates a considerable amount of singlet oxygen. The lifetime of the CS state in the nonpolar solvent was estimated to be 0.29 ns. It was also shown that in both DMF and toluene the first excited singlet state as well as the triplet state of the fullerene moiety in FP1 are not occupied. PACS 31.70.Dk; 31.70.Hq; 33.50.-j; 34.70.+e     

可调谐二极管激光吸收光谱技术参数选择及优化

可调谐二极管激光吸收光谱技术(TDLAS)系统性能受调制参数,如调制度、调制频率、扫描幅度及扫描频率影响,实际测量中各参数不存在明确的选择依据。针对此问题,文章在一定的理论基础上通过实验分别观察各调制参数对二次谐波信号的影响,通过分析检测信号的特征,如幅值、信噪比、对称性及峰宽得出其变化规律,总结出在不同系统功能和需求下系统各调制参数的优化依据及方法。系统在计算浓度和温度时应优先考虑幅值和信噪比,从而使调制度达到最佳值,调制频率和扫描频率取较小值;在线形推导压强时优先考虑信号的对称性和峰宽,根据计算的具体要求确定调制参数;扫描幅度的确定以得到完整谐波信号为准;再根据系统的速度和精度需求调整扫描频率。该研究为此类系统工作状态的确定提供了实验依据。     

Modeling the influence of inherent envelope fluctuations in simultaneous masking experiments

Masked thresholds are measured and simulated for bandpass-noise signals ranging in bandwidth from 4 to 256 Hz in the presence of a masking bandpass noise also ranging in bandwidth from 4 to 256 Hz. Signal and masker are centered at 2 kHz. To investigate the role of temporal processing in simultaneous masking, simulations were performed with the modulation-filterbank model by Dau et al. [J. Acoust. Soc Am. 102, 2906-2919 (1997)]. For a fixed masker bandwidth, thresholds are independent of the signal bandwidth as long as the signal bandwidth does not exceed the masker bandwidth and thresholds decrease with increasing masker bandwidth in those conditions. A simple modulation-low-pass filter (energy integrator) would be sufficient to describe the experimental results in those conditions. In contrast, the processing by a modulation filterbank is necessary to account for the conditions of "asymmetry of masking," where thresholds for signals with bandwidths larger than the masker bandwidth are much lower than those for the reversed condition. In those conditions, the modulation-filterbank model is able to use the inherent higher modulation frequencies of the signal as an additional cue.     

La0.7Sr0.3MnO3外延膜缺陷性质的慢正电子束研究

用单能慢正电子束,测量了不同氧分压下生长的La0.7Sr0.3MnO3外延膜的S参数与入射正电子能量E的关系.结果发现La0.7Sr0.3MnO3外延膜中S参数与氧分压是非单调变化的;这与沉积氧分压的两种作用相关联的.在氧分压较高的LSMO薄膜中, 空位浓度的增加主要是由沉积原子(离子)与氧原子碰撞几率增大,使其缺乏足够的动能去填补空位引起的;在低氧分压的LSMO薄膜中, 空位浓度的增大则主要是提供成膜所需要的氧原子缺乏,从而导致氧空位及其相关缺陷增加.     

Effect of O2 gas partial pressure on structures and dielectric characteristics of rf sputtered ZrO2 thin films

Amorphous and polycrystalline zirconium oxide thin films have been deposited by reactive rf magnetron sputtering in a mixed argon/oxygen or pure oxygen atmosphere with no intentional heating of the substrate. The films were characterized by high-resolution transmission electron microscopy (HR-TEM), atomic force microscopy (AFM), spectroscopic ellipsometry (SE), and capacitance versus voltage (C-V) measurements to investigate the variation of structure, surface morphology, thickness of SiO₂-like interfacial layer as well as dielectric characteristics with different oxygen partial pressures. The films deposited at low oxygen partial pressures (less than 15%) are amorphous and dense with a smooth surface. In contrast, the films prepared at an oxygen partial pressure higher than 73% are crystallized with the microstructure changing from the mixture of monoclinic and tetragonal phases to a single monoclinic structure. The film structural transition is believed to be consequences of decrease in the oxygen vacancy concentration in the film and of increase of the energetically neutral particles in the plasma due to an increased oxygen partial pressure. SE measurements showed that significant interfacial SiO₂ growth has taken place above approximately 51%. The best C-V results in terms of relative dielectric constant values are obtained for thin films prepared at an oxygen partial pressure of 15%.     

Study of adsorption phenomena on aluminium by interatomic Auger transition spectroscopy: I. Initial oxidation of Al

The initial oxidation process of aluminium is studied by using the combined molecular beam evaporation and Auger electron spectroscopy under ultra-high vacuum. At the initial stage of oxygen exposure to the clean aluminium at room temperature, the chemisorption of the oxygen atoms on the surface of aluminium is turned out to be dominant from the behaviour of the energy shifted Auger signal of aluminium. Then, the formation of the alumina (Al₂O₃) type bonding is followed, which is concluded from the interatomic Auger signals.     

Nano-ionic thin films of gadolinia-doped ceria prepared by pulsed laser ablation

Microstructural properties of nano-ionic thin films of gadolinia-doped ceria (GDC) prepared by pulsed laser ablation from sintered targets of gadolinia (5–20 mol%) doped ceria are investigated. The ionic conductivity measurements of the sintered pellets showed a decrease in the activation energy from 1.1 to 0.65 eV for 5 and 30 mol% gadolinia-doped ceria, respectively. The microstructural properties of the GDC films as a function of substrate temperature, oxygen partial pressure, and laser energy show that the films are polycrystalline in the entire range of substrate temperature. The grain size is found to increase with increasing temperature up to 873 K. Further improved crystallinity is noticed for the films grown with oxygen partial pressure of 0.1–0.2 mbar. X-ray diffraction and transmission electron microscopy (TEM) reveal nanocrystalline grains with textured growth along <111> orientation in these films at low substrate temperature and at lower oxygen partial pressure. TEM study shows a uniform distribution of nanocrystal of 8–10 nm for energies ≤200 mJ/pulse, and nanocrystals embedded in a large crystalline matrix of doped ceria for energies in the range 400–600 mJ/pulse. Raman spectroscopy also confirms the defects in these films. The study also reveals that the substrate temperature and oxygen partial pressure could influence preferred orientation, while the laser energy could significantly influence defect concentration in these films. Invited paper presented at the Third International Conference on Ionic Devices (ICID 2006), Chennai, Tamilnadu, India, Dec. 7–9, 2006.     

基于7.6μm量子级联激光的光声光谱探测N_2O气体

近年来,气候变化对地球的生态环境产生严重影响,而大气温室气体在气候变化中具有重要的作用.一氧化二氮(N_2O)作为一种重要的温室气体,其浓度变化对大气环境产生重要影响,因此对其浓度的探测在大气环境研究中具有重要意义.本文开展了基于中国自主研发的7.6μm中红外量子级联激光的共振型光声光谱探测N_2O的研究,建立了N_2O光声光谱传感实验系统.此系统在传统的光声光谱探测的基础上优化改进,采用双光束增强的方式,增加了有效光功率,进一步提高了系统的探测灵敏度.探测系统以1307.66 cm~(-1)处的N_2O吸收谱线作为探测对象,结合波长调制技术对N_2O气体进行探测研究.通过对一定浓度的N_2O气体在不同调制频率和调制振幅的光声信号的探测,确定了系统的最佳调制频率和调制振幅分别为800 Hz和90 mV.在最优实验条件下对不同浓度的N_2O气体进行了测量,获得了系统的信号浓度定标曲线.实验表明,在锁相积分时间为30 ms时,系统的浓度探测极限为150×10~(-9).通过100次平均后,系统噪声进一步降低,实现了大气N_2O的探测,浓度探测极限达到了37×10~(-9).     

Cadmium oxidation in different environments: an XPS study

The behaviour of polycrystalline cadmium in different oxidative atmospheres was investigated. The interactions between cadmium and O₂, CO₂, water, and mixtures of these were studied. The cadmium sample was only reactive towards oxygen. A progressive growth of the O1s signal as a function of O₂ exposure was observed, together with a shift in the Cd3d and Cd MNN peaks towards the positions reported for CdO. The O1s spectra show the presence of several components in the range of exposures analysed and the best fit of the experimental signals is obtained for the components at 529.3 eV and 531.3 eV. The signal at lower binding energy is characteristic of O²⁻ in the oxide state, while the component at higher binding energy could be due to either chemisorbed oxygen or oxygen in a non-equivalent site in the oxide structure.     

Experimental and theoretical comparison of spatially resolved laser-induced incandescence (LII) signals of soot in backward and right-angle configuration

In-situ measurements of soot volume fraction in the exhausts of jet engines can be carried out using the laser-induced incandescence (LII) technique in backward configuration, in which the signal is detected in the opposite direction of the laser beam propagation. In order to improve backward LII for quantitative measurements, we have in this work made a detailed experimental and theoretical investigation in which backward LII has been compared with the more commonly used right-angle LII technique. Both configurations were used in simultaneous visualization experiments at various pulse energies and gate timings in a stabilized methane diffusion flame. The spatial near-Gaussian laser energy distribution was monitored on-line as well as the time-resolved LII signal. A heat and mass transfer model for soot particles exposed to laser radiation was used to theoretically predict both the temporal and spatial LII signals. Comparison between experimental and theoretical LII signals indicates similar general behaviour, for example the broadening of the spatial LII distribution and the hole-burning effect at centre of the beam due to sublimation for increasing laser pulse energies. However, our comparison also indicates that the current heat and mass transfer model overpredicts signal intensities at higher fluence, and possible reasons for this behaviour are discussed. PACS 42.62.Fi; 44.40.+a     

Electrode reactions at oxygen,noble metal / stabilized zirconia interfaces

The polarization behaviour of electrodes of the type “oxygen, noble metal / stabilized zirconia”, comprising different zirconia-based materials as electrolyte, platinum or gold as metal component and an oxygen containing gas atmosphere, was investigated at elevated temperatures under equilibrium and non-equilibrium conditions by means of impedance spectroscopy. Massive metal contacts were used as part of the working electrodes. Under non-polarized conditions, the experimental results for platinum indicate a basically uniform reaction mechanism in a vast range of temperature and oxygen partial pressure, involving the surface diffusion of dissociatively adsorbed oxygen on platinum towards the electrochemical reaction sites on the electrolyte surface as rate-determining step. The experimental findings for gold are consistent with the occurrence of two competing reaction mechanisms, namely a charge transfer controlled process and a surface diffusion controlled process, each of them prevailing in different regimes of temperature and oxygen partial pressure. Under polarized conditions, a significant decrease of the polarization resistance takes place, followed by the onset of low frequency loops in the impedance spectra. In the case of cathodic polarization, the onset voltage can be correlated with the partial electron conductivity of the electrolyte, thus confirming the hypothesis of direct participation of electronic species of the electrolyte in the electrode reaction under biased conditions. At moderate temperatures, the polarization induced changes in the electrode properties exhibit a slow relaxation behaviour. This can be attributed to the successive annihilation of additional metastable electrochemical reaction sites having been created during the preceding polarization treatment. Paper presented at the 3rd Euroconference on Solid State Ionics, Teulada, Sardinia, Italy     

Enhanced signal intensities obtained by out-of-phase rapid-passage EPR for samples with long electron spin relaxation times

To understand the signals that are observed under rapid-passage conditions for samples with long electron spin relaxation times, the E' defect in irradiated vitreous SiO(2) was studied. For these samples at room temperature, T(1) is 200 mciro s and T(2) ranged from 35 to 200 micro s, depending on spin concentration. At X band with 100-kHz modulation frequency and 1-G modulation amplitude there was minimal lineshape difference between the low-power, in-phase spectra and high-power spectra detected 90 degrees out-of-phase with respect to the magnetic field modulation. Signal enhancement, defined as the ratio of the intensities of the out-of-phase to the in-phase signals when B(1) for both observation modes is adjusted to give maximum signal, was 3.4 to 9.5 at room temperature. The origin of the out-of-phase signal was modeled by numerical integration of the Bloch equations including magnetic field modulation. The waveforms for the E' signal, prior to phase sensitive detection, were simulated by summing the contributions of many individual spin packets. Good agreement was obtained between experimental and calculated waveforms. At low B(1) the experimental values of T(1) and T(2) were used in the simulations. However, at higher B(1), T(2) was adjusted to match the experimental signal intensity and increased with increasing B(1). At high B(1), T(2)=T(1), consistent with Redfield's and Hyde's models. For the spin concentrations examined, the out-of-phase signals at very high power (B(1) approximately 0.33 G) displayed a linear relationship between peak-to-peak signal amplitude and spin concentration. Under the conditions used for spin quantitation the signal-to-noise for these spectra was up to 5 times higher than for the in-phase signal, which greatly facilitates quantitation for these types of samples. For samples in which T(2) is dominated by electron spin-spin interaction, lower spin concentration results in longer T(2) and the enhancement is increased.     

光声光谱与TDLAS技术在不同气压下的特性研究

基于PAS与TDLAS的基本原理,讨论了两者之间的联系,推导了光声信号和TDLAS信号与气压的关系式,设计并构造了一个可以同时进行PAS与TDLAS气体测量的对比装置,并对两者在不同气压条件下的测量结果进行了分析和研究,为不同气压条件下的气体测量技术选择提供了参考。试验研究表明：随着气压上升,光声光谱与TDLAS信号均变大,极限检测灵敏度均提高;随着气压上升,气体吸收能量转化为光声信号的效率变低;在低压时,使用光声光谱进行气体检测具有更好的效果。