Improvement of the scintillation properties of Gd3Ga3Al2O12:Ce,B single crystals having tailored defect structure

A novel approach is reported to minimize various defect centers in Ce doped Gd₃Ga₃Al₂O₁₂ single crystals to improve the scintillation properties. The crystals of Gd₃Ga₃Al₂O₁₂ codoped with 0.2 at% Ce and B (GGAG:Ce,B) have been grown in air and argon ambient using the Czochralski technique. The scintillation light output of crystals grown in Ar ambient was significantly increased after annealing the crystals in air. The measured light output of 60000 ph/MeV for annealed crystals is the highest value reported among this class of materials. As a consequence, the energy resolution at 662 keV gamma‐rays from a ¹³⁷Cs source was improved from 8% for the crystals grown in air to 6% for crystals grown in Ar and subsequently annealed in air. Further, the thermal quenching energy of photoluminescence (PL) emission was increased to be 470 meV for the annealed crystals. The thermoluminescence (TL) measurements suggest that the crystals grown in Ar ambient and post‐growth annealed in air may have a lesser concentration of trap centers which subsequently lead to the improvement in optical and scintillation properties leading to a superior detector performance. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Realization of oxyfuel combustion for near zero emission power generation

Oxyfuel combustion is one of the promising carbon capture and storage (CCS) technologies for coal-fired boilers. In oxyfuel combustion, combustion gas is oxygen and recirculating flue gas (FGR) and main component of combustion gas is O₂, CO₂ and H₂O rather than O₂, N₂ in air combustion. Fundamental researches showed that flame temperature and flame propagation velocity of pulverized cloud in oxyfuel combustion are lower than that in air with the same O₂ concentration due to higher heat capacity of CO₂. IHI pilot combustion test showed that stable burner combustion was obtained over 30% O₂ in secondary combustion gas and the same furnace heat transfer as that of air firing at 27% O₂ in overall combustion gas. Compared to emissions in air combustion, NOx emission per unit combustion energy decreased to 1/3 due to reducing NOx in the FGR, and SO_x emission was 30% lower. However SO_x concentration in the furnace for the oxyfuel mode was three to four times greater than for the air mode due to lower flow rate of exhaust gas. The higher SO₃ concentration results that the sulphuric acid dew point increases 15–20 °C compared to the air combustion. These results confirmed the oxyfuel pulverized coal combustion is reliable and promising technology for coal firing power plant for CCS.In 2008, based on R&D and a feasibility study of commercial plants, the Callide Oxyfuel Project was started in order to demonstrate entire oxyfuel CCS power plant system for the first time in the world. The general scope and progress of the project are introduced here. Finally, challenges for present and next generation oxyfuel combustion power plant technologies are addressed.     

Oxidation mechanism of hydrogen-terminated Ge(1 0 0) surface

Control of the surface chemistry to prepare a robust termination on the Ge surface is crucial for the development of high-end Ge devices. In this study, oxidation of a H-terminated Ge surface was studied in air ambient and H₂O using a multiple internal reflection Fourier transform infrared spectroscopy (MIR FT-IR) technique. Ge surface treated in less diluted HF exhibited a stronger Ge-H peak intensity, and the surface was easily oxidized in the air ambient. Therefore, it is believed that the treatment of the Ge surface in highly diluted HF solution has an advantage in suppressing the oxidation of Ge in the air ambient. For the oxidation of Ge(1 0 0) surface in air ambient, the Ge surface is attacked by oxidizing agents to break Ge-H and Ge-Ge bonds, and the transition GeO_x layer is first formed, followed by a layer-by-layer GeO₂ formation with the increase in exposure time. When the H-terminated Ge surface was treated in H₂O, GeO_x was mainly formed, the thickness of the oxide layer was not changed with an increase in treatment time, and the Ge surface was maintained in a suboxide state, which exhibits a different oxidation mechanism from that in air ambient.     

Two-stage thermochemical conversion of solid fuel in a setup with steam ejection

The paper presents a set of tests with a setup using steam supply into ejector instead of compressed air. Experi-ments measured the gas analysis data — volumetric concentrations O₂, CO, CO₂, C _n H _m , NO _x , H₂ at different propor-tions of air and steam. The data are compared with calculations for thermodynamic equilibrium compositions for the reacting mixture С+Н₂О+air performed by “Terra” computer code including the case of air excess (α ≤ 1). The cal-culations were also compared with available data on gasification output at a high content of ballasting gas. It was demonstrated that in these operation modes, the steam was an inert dilution agent, which did not exclude the outcome of coal gas production with high Н₂/СО and СО/СО₂ ratios corresponding to different modes of gasification.     

Continuous measurements of stable isotopes of carbon dioxide and water vapour in an urban atmosphere: isotopic variations associated with meteorological conditions

Isotope ratios of carbon dioxide and water vapour in the near-surface air were continuously measured for one month in an urban area of the city of Nagoya in central Japan in September 2010 using laser spectroscopic techniques. During the passages of a typhoon and a stationary front in the observation period, remarkable changes in the isotope ratios of CO₂ and water vapour were observed. The isotope ratios of both CO₂ and water vapour decreased during the typhoon passage. The decreases can be attributed to the air coming from an industrial area and the rainout effects of the typhoon, respectively. During the passage of the stationary front, δ¹³C–CO₂ and δ¹⁸O–CO₂ increased, while δ²H–H₂Ov and δ¹⁸O–H₂Ov decreased. These changes can be attributed to the air coming from rural areas and the air surrounding the observational site changing from a subtropical air mass to a subpolar air mass during the passage of the stationary front. A clear relationship was observed between the isotopic CO₂ and water vapour and the meteorological phenomena. Therefore, isotopic information of CO₂ and H₂Ov could be used as a tracer of meteorological information.     

Flame propagation of mixtures of air with high molecular weight neat hydrocarbons and practical jet and diesel fuels

Laminar flame speeds of mixtures of air with n-C₁₄H₃₀, n-C₁₆H₃₄, a petroleum-derived JP-5 jet fuel, a camelina-derived hydrotreated renewable JP-5 jet fuel, a petroleum-derived F-76 diesel fuel, and an algae-derived hydrotreated renewable F-76 diesel fuel, were measured in the counterflow configuration at atmospheric pressure and elevated unburned mixture temperatures. Digital particle image velocimetry was used to measure the axial flow velocities along the stagnation streamline. The experiments for n-C₁₄H₃₀/air and n-C₁₆H₃₄/air mixtures were modeled using recently developed kinetic models, and the experimental data were predicted satisfactorily. Both experiments and simulations revealed that the laminar flame speeds of n-C₁₄H₃₀/air and n-C₁₆H₃₄/air mixtures are very close to each other, as expected. On the other hand, the laminar flame speeds for the four practical fuels were found to be lower than n-C₁₄H₃₀ and n-C₁₆H₃₄, due to the presence of aromatics and branched hydrocarbons. Similarly, the laminar flame speeds for the alternative fuels were found to be higher than the petroleum-derived ones, again due to the presence of aromatic compounds in the latter. Further insight into the effects of kinetics and molecular transport was obtained through sensitivity analysis.     

Effects of OH concentration and temperature on NO emission characteristics of turbulent non-premixed CH4/NH3/air flames in a two-stage gas turbine like combustor at high pressure

This study examined the effects of OH concentration and temperature on the NO emission characteristics of turbulent, non-premixed methane (CH₄)/ammonia (NH₃)/air swirl flames in two-stage combustors at high pressure. Emission data were obtained using large-eddy simulations with a finite-rate chemistry method from model flames based on the energy fraction of NH₃ (E_NH3) in CH₄/NH₃ mixtures. Although NO emissions at the combustor exit were found to be significantly higher than those generated by CH₄/air and NH₃/air flames under both lean and stoichiometric primary zone conditions, these emissions could be lowered to approximately 300 ppm by employing far-rich equivalence ratios (?) of 1.3 to 1.4 in the primary zone. This effect was possibly due to the lower OH concentrations under far-rich conditions. An analysis of local flame characteristics using a newly developed mixture fraction equation for CH₄/NH₃/air flames indicated that the local temperature and NO and OH concentration distributions with local ? were qualitatively similar to those in NH₃/air flames. That is, the maximum local NO and OH concentrations appeared at local ? of 0.9, although the maximum temperature was observed at local ? of 1.0. Both the temperature and OH concentration were found to gradually decrease with the partial replacement of CH₄ with NH₃. Consequently, NO emissions from CH₄/NH₃ flames were maximized at E_NH3 in the range of 20% to 30%, after which the emissions decreased. Above 2100 K, the NO emissions from CH₄/NH₃ flames increased exponentially with temperature, which was not observed in NH₃/air flames because of the lower flame temperatures in the latter. But, the maximum NO concentration in CH₄/NH₃ flames was occurred at a temperature slightly below the maximum temperature, just as in NH₃/air flames. The apparent exponential increase in NO emissions from CH₄/NH₃ flames is attributed to a similar trend in the OH concentration at high temperatures.     

Coherence gating in optical heterodyne detection measurements of scattering and absorption in highly scattering media

Laser-Induced Fluorescence (LIF) from the S₁ state of acetone and 3-pentanone was studied as a function of temperature and pressure using excitation at 248 nm. Additionally, LIF of 3-pentanone was investigated using 277 and 312 nm excitation. Added gases were synthetic air, O₂, and N₂ respectively, in the range 0–50 bar. At 383 K and for excitation at 248 nm, all the chosen collision partners gave an initial enhancement in fluorescence intensity with added gas pressure. Thereafter, the signal intensity remained constant for N₂ but decreased markedly for O₂. For synthetic air, only a small decrease occurred beyond 25 bar. At longer excitation wavelengths (277 and 312 nm), the corresponding initial rise in signal with synthetic air pressure was less than that for 248 nm. The temperature dependence of the fluorescence intensity was determined in the range 383–640 K at a constant pressure of 1 bar synthetic air. For 248 nm excitation, a marked fall in the fluorescence signal was observed, whereas for 277 nm excitation the corresponding decrease was only half as strong. By contrast, exciting 3-pentanone at 312 nm, the signal intensity increased markedly in the same temperature range. These results are consistent with the observation of a red shift of the absorption spectra (9 nm) over this temperature range. Essentially, the same temperature dependence was obtained at 10 and 20 bar pressure of synthetic air. It is demonstrated that temperatures can be determined from the relative fluorescence intensities following excitation of 3-pentanone at 248 and 312 nm, respectively. This new approach could be of interest as a non-intrusive thermometry method, e.g., for the compression phase in combustion engines.     

Introducing CdS into two- and three-dimensional photonic crystals

SiO₂/air three-dimensional (3D) periodic structures were fabricated by removing Si layers partially from Si/SiO₂ 3D photonic crystals (PhCs) formed by using autocloning. CdS/SiO₂ 3D periodic structures were formed by introducing CdS into the SiO₂/air structures by the TEA method and photoluminescence (PL) was observed from the introduced CdS. TiO₂/air/CdS two-dimensional (2D) PhCs were also fabricated by introducing CdS into the voids of TiO₂/air 2D periodic structures, in which SiO₂ layers were partially etched out from TiO₂/SiO₂ 2D PhCs fabricated by using autocloning. PL radiating normal to the surface was measured and large polarization dependence was observed.     

Phase composition and low-frequency internal friction of ZrO2 + 4 mol % Y2O3 ceramics

Low-frequency internal friction was studied at a torsional-vibration frequency of 24 Hz in polycrystalline samples of ZrO₂ + 4 mol % Y₂O₃ ceramics. The samples were prepared using cold isostatic pressing of a powder followed by sintering in air, hot isostatic pressing of the sample in an argon atmosphere, subsequent mechanical deformation of the surface, and further calcination in air. The x-ray phase analysis method is used to study the variation in the phase composition after mechanical deformation of the sample surface followed by calcination in air. The internal friction was measured in the temperature range 280–380 K on a sample subjected to calcination in air. At 315 K, an internal-friction peak was revealed, which is explained by stress relaxation at the boundaries of the T’-phase domains.     

Mechanism of magnetic field effect on OH density distribution in a methane–air premixed jet flame

The mechanism of magnetic field effect on OH density distribution in a methane-air premixed jet flame was investigated by means of PLIF measurement and numerical simulation. In the experiment, magnetically induced change in the OH density profile in the flame in a N₂ atmosphere was much smaller than that in air (mixture of 80% N₂ and 20% O₂), and such a phenomenon was qualitatively reproduced by solving the equations for reactive gas dynamics and magnetism in the numerical simulation. Here, N₂ is diamagnetic and little affected by the magnetic field, while O₂ is paramagnetic and influenced due to the magnetic field. This provided the experimental and numerical verification for the mechanism of the magnetic field effect suggested in our previous study. That is, the magnetic force does not directly and selectively induce the change in the diffusion velocity of OH itself. Alternatively, the magnetic force acting on O₂ in the surrounding air, whose mass density and magnetic susceptibility are much larger than that of other chemical species in the flame, causes the change in the convection velocity of the gas mixture and displaces the OH density distribution indirectly and passively. In other words, the most important cause of the OH density change is not the diffusion of OH, but the convection of air containing a large amount of O₂. Furthermore, by careful examination of the magnetic field effect on the flame in the N₂ atmosphere, it was found out that the magnetic force does not only act on O₂ in the surrounding air, but also on O₂ in the premixed gas injected from the burner.     

Trace detection of C<Subscript>2</Subscript>H<Subscript>2</Subscript> in ambient air using continuous wave cavity ring-down spectroscopy combined with sample pre-concentration

Continuous wave cavity ring-down spectroscopy (cw-CRDS) coupled with sample pre-concentration has been used to measure acetylene (C₂H₂) mixing ratios in ambient air. Measurements were made in the near-infrared region (λ∼1535.393 nm), using the P(17) rotational line of the (ν₁+ν₃) vibrational combination band, a region free from interference by overlapping spectral absorption features of other air constituents. The spectrometer is shown to be capable of fast, quantitative and precise C₂H₂ mixing ratio determinations without the need for gas chromatographic (GC) separation. The current detection limit of the spectrometer following sample pre-concentration is estimated to be 35 parts per trillion by volume (pptv), which is sufficient for direct atmospheric detection of C₂H₂ at concentrations typical of both urban and rural environments. The CRDS apparatus performance was compared with an instrument using GC separation and flame ionization detection (GC-FID); both techniques were used to analyze air samples collected within and outside the laboratory. These measurements were shown to be in quantitative agreement. The indoor air sample was found to contain C₂H₂ at a mixing ratio of 3.87±0.22 ppbv (3.90±0.23 ppbv by GC-FID), and the C₂H₂ fractions in the outside air samples collected on two separate days from urban locations were 1.83±0.20 and 0.69±0.14 ppbv (1.18±0.09 and 0.60±0.04 ppbv by GC-FID). The discrepancy in the first outdoor air sample is attributed to degradation over a 2-month interval between the cw-CRDS and GC-FID analyses. PACS 82.80.Gk; 39.30.+w; 42.62.Fi; 42.68.Ca     

Characterizing the fuel-specific combustion chemistry of acetic acid and propanoic acid: Laminar flame propagation and kinetic modeling studies

In order to study the combustion chemistry of carboxyl functionality, the laminar burning velocity of acetic acid/air and propanoic acid/air mixtures was investigated in a high-pressure constant-volume cylindrical combustion vessel at 423 K, 1 atm and equivalence ratios of 0.7–1.4. Experimental results reveal that the flame propagation of propanoic acid flame is much faster than that of acetic acid flame, especially under rich conditions, and the laminar burning velocity of propanoic acid/air mixtures peaks at richer conditions than that of acetic acid. The present theoretical calculations for the isomerization and decomposition of propanoic acid radicals indicate that the primary radical products are HOCO, H and C₂H₅, while those in acetic acid flame are CH₃ and OH based on previous studies. A kinetic model of the two acids was developed mainly based on previous and the present theoretical calculation results. It could reasonably capture the measured laminar burning velocities of acetic acid/air and propanoic acid/air mixtures in this work, as well as the previous experimental data in literature. Based on the present model, CH₃- and ketene-related pathways play an important role in acetic acid flames. Under rich conditions, ketene is mostly converted to CH₃ via CH₂CO+HCH₃+CO, and the chain-termination reaction of CH₃+H(+M)=CH₄(+M) is enhanced, which strongly inhibits the propagation of rich acetic acid flames. In contrast, C₂H₅ and ethylene chemistry play an important role in propanoic acid flames. Rich conditions promote the decomposition of C₂H₅, yielding ethylene and H, which can facilitate the flame propagation. This can explain the shift of the peak laminar burning velocity of propanoic acid/air mixtures towards a slightly richer condition compared with that of acetic acid/air mixtures.     

Photocatalytic oxidation of natural organic adsorbates on anatase TiO2 films observed by infrared adsorption spectroscopy with a multiple internal reflection geometry

Photocatalytic oxidation of organic adsorbates on anatase TiO₂ films has been examined in different atmospheres of humid air, dry air and vacuum. The photocatalytic oxidation was observed by IR absorption spectroscopy (IRAS) with a multiple-internal-reflection (MIR) geometry. The photocatalytic oxidation is the fastest in the air at a humidity of 70% where oxygen and water vapor are consuming to produce OH radicals and O₂⁻ anions on the TiO₂ surface with the UV exposure. In the dry air, a rate of the photocatalytic oxidation is almost 30% of that in the humid air, where only O₂⁻ anions oxidize the organic adsorbates. In vacuum, on the other hand, it is negligible, which suggests that adsorbed H₂O molecules do not play an important role in the photocatalytic reaction. It is suggested that an addition of the water vapor is necessary to achieve the higher catalytic activity.     

Ionic conductivity of gadolinium-doped barium praseodymium oxide

To clarify the ionic conduction of Ba(Pr_0.6Gd_0.4)O_3−α, the electrical conductivity was measured in moist air and hydrogen atmospheres. The ionic transport number was estimated by a steam concentration cell, a hydrogen permeation cell, and a fuel cell. Temperature dependence of the conductivity in a moist air atmosphere differed from that in a moist H₂ atmosphere. The conductivity under reducing conditions increases with time according to the crystal structure change of Ba(Pr_0.6Gd_0.4)O_3−α due to oxygen loss in the lattice site. Under moist air conditions, the dominant conduction species in the Ba(Pr_0.6Gd_0.4)O_3−α electrolyte were mainly holes. However, the species changed into proton, oxide ion and hole by means of structure change in a reducing atmosphere. It was considered that the ionic conduction occurred due to the crystal structure change. It was predicted that this peculiarity of the conductivity of barium praseodymium oxide influenced the nonstoichiometric behaviour of Pr in the crystal structure.     

DC corona discharge influence on chemical composition in mixtures of natural gas with air and its combustion exhaust with air

Experiments in dc supplied corona discharge in natural gas + air mixture and in combustion exhaust of natural gas + air mixture were realized. The influence of discharge on CO, CO₂, NO _x and other minority components was studied using IR absorption spectrometry. Production of NCO radicals in gas and consequent formation of NCO containing surface layers on a plate electrode was detected. In natural gas + air mixture after about 1 min oxygen poor combustion exhaust was produced due to slow combustion by corona discharge. Occurrence of various pulses in discharge current was typical.     

Continuous flame oxidation in supercritical water

Abstract

Continuous flames have been observed in Supercritical water oxidation (scWO) of isopropyl alcohol (IPA), using a vertical continuous reactor with sapphire windows and a mixing nozzle. Two types of continuous flame were confirmed: the one was long pale blue colored and the other was red short cone shaped, changing blue to red at around air ratio 2.0. The flame was strongly influenced by IPA concentration, air ratio and design of the mixing nozzle. Results for decomposition of PA are presented for IPA concentrations ranging from 600 up to 28260 ppm as TOC and initial reactor temperatures, were mostly around 490°C, at 25 MPa. Decomposition rate at steady state was over 99.9%. Experimentally measured CO₂ and O₂ concentrations at the flue gas were in good agreement with theoretically calculated values. Even for low air ratio as 1.1, high decomposition rate without CO, NO, NO₂ was achieved.     

A skeletal mechanism for flame inhibition by trimethylphosphate

On the basis of a multi-step kinetic mechanism for flame inhibition by organophosphorus compounds including more than 200 reactions, a skeletal mechanism for flame inhibition by trimethylphosphate was developed. The mechanism consists of 22 irreversible elementary reactions, involving nine phosphorus-containing species. Selection of the crucial steps was performed by analysing P-element fluxes from species to species and by calculating net reaction rates of phosphorus-involving reactions versus the flames zone. The developed mechanism was validated by comparing the modelling results with the measured and simulated (using the starting initial mechanism) speed and the chemical structure of H₂/O₂, CH₄/O₂ and syngas/air flames doped with trimethylphosphate. The mechanism was shown to satisfactorily predict the speed of H₂/O₂/N₂ flames with various dilution ratios, CH₄/air and syngas/air flames doped with trimethylphosphate. The skeletal mechanism was also shown to satisfactorily predict the spatial variation of H and OH radicals and the final phosphorus-containing products of the inhibitor combustion. Further reduction of the skeletal mechanism without modification of the rate constants recommended in the starting mechanism was shown to result in noticeable disagreement of the flame speed and structure.     

Kinetic analysis of n-decane–hydrogen blend combustion in premixed and non-premixed supersonic flows

Numerical analysis of ignition and combustion of an n-decane–hydrogen fuel blend in a premixed supersonic flow and in a model scramjet duct is performed using a reduced reaction mechanism built especially to describe the oxidation of blended n-C₁₀H₂₂–H₂ fuel in air at the temperature T₀ > 900–1000 K in the pressure range P₀ = 0.1–13 atm. The developed kinetic mechanism involves the principal reactions responsible for chain mechanism development both for n-decane and for hydrogen oxidation. It has been shown that using blended n-C₁₀H₂₂–H₂ fuel makes it possible to enhance the ignition and combustion both in premixed and in non-premixed supersonic fuel–air flows compared to burning pure hydrogen–air and n-decane–air mixtures. This allows high combustion completeness in the scramjet duct at the distance of ～1 m even at extremely low air temperature T₀ = 1000 K and pressure P₀ = 0.3 atm. This is due to the interaction of kinetics of the formation of highly reactive atoms and radicals, carriers of chain mechanism, in H₂–air and n-C₁₀H₂₂–air mixtures.