Nonreciprocal frequency doubling of electromagnetic waves through double resonance and Bragg reflection in photonic crystals

A computational study of the uni-directional second-harmonic generation in a one-dimensional dual photonic crystal structure made of GaAs, AlAs and SiO₂ with quadratic optical nonlinearity and material dispersion is presented. The computational approach uses a shooting method to solve nonlinear wave equations for coupled fundamental and second-harmonic fields and the invariant imbedding method to obtain the linear transmittance and group index spectra. The dual structure consists of two substructures, the conversion structure creating a strongly enhanced second-harmonic signal and the filter structure blocking the fundamental frequency field by Bragg reflection while permitting the passage of the second-harmonic field. The conversion structure is built with an elementary cell consisting of four sublayers whose thicknesses are systematically varied. Doubly resonant second-harmonic generation with very high conversion efficiency is achieved for light incident from the conversion structure side by choosing the geometrical parameters of the elementary cell optimally and controlling the band structure. A new mechanism to enhance second-harmonic generation by controlling the energy flow between the fundamental frequency and second-harmonic fields has also been found.     

Internal conversion of valence shell electrons: Measurement and analysis for the 10.84 keV transition in206Bi

Conversion electrons of the 10.84 keV transition in²⁰⁶Bi were measured with the iron-free magnetic spectrometer. The conversion line of the valence shell was observed to be narrower than those of the inner ones. The computer program which optimizes the line profiles given numerically is outlined and used for the spectrum analysis. The studied transition was proved to be pure M1 with the nuclear structure parameterλ=1.7±0.7. The internal conversion coefficients were calculated using the relativistic Hartree-Fock model for neutral atoms as well as various isolated ions. Altogether, 15 different valence-shell configurations were considered. The prediction for the 6s ₁ ^2/2 configuration (Bi³⁺) is in accord with the measured conversion intensities. This is consistent with probable chemical form Bi₂O₃ of bismuth atoms in the radioactive source.     

Phase change and pyroelectricity in natural hemimorphite

The phase change of a natural hemimorphite sample from Minas Gerais (Brazil) was investigated by two X-ray diffraction (XRD) methods and by near-infrared reflectance spectroscopy. Applying successive thermal treatments, the crystal structure undergoes two orientation conversions. The first one occurs at about 550 °C, and it was revealed by the Laue method. Below 500 °C, the water molecules were partially expelled without changing the crystal structure. A fact that supports this statement is the sequential disappearance of the water bands at 1400 and 1900 nm by thermal treatment. The second conversion takes place below 939 °C. Moreover, at 972 °C a phase change to the willemite mineral (α-Zn₂SiO₄) has been observed. This last conversion was confirmed by the power XRD. In addition, natural hemimorphite displayed a high pyroelectricity, which is related both to the absence of inverse centre and to the presence of molecular water and hydroxyl groups in the crystal structure.     

Second-Harmonic Generation in Domain-Inverted Grating Induced by Focused Ion Beam

The fabrication of a periodic domain inversion in LiTaO₃ and LiNbO₃ using direct ion-beam writing is presented. The polarization of these materials can be reversed at room temperature by irradiating Si²⁺ ions into +c faces. A first-order periodic domain inversion with a 50% duty cycle, a depth of 300μ, and an interaction length of 1 mm was realized in LiTaO₃. Using this structure, 300μW of blue light was generated for a conversion efficiency of 0.25%/W.     

Frequency doubling of phase-modulated femtosecond laser pulses in periodically poled and chirped nonlinear crystals

The second harmonic generation (SHG) at a wavelength of 0.8 μm by 50-and 10-fs pulses with and without phase modulation (PM) was systematically studied in LiNbO₃ crystals with regular domain structure and linearly varied domain thickness. The main results were obtained by numerical method, taking into account the difference between group velocities of interacting pulses and the group-velocity dispersion. In the approximation of the given field of the fundamental radiation, an analytical expression was derived for the spectral density of the second harmonic in the periodically poled nonlinear crystal (PPNC) under nonstationary excitation conditions. It was numerically found that the conversion efficiency of about 90% can be achieved by doubling the frequency of 50-fs laser pulses without PM in the LiNbO₃ PPNC. The maximum conversion efficiency for the SHG by PM pulses is achieved at a certain optimum chirp step in the crystal domain length, which depends on both the value and sign of frequency modulation.     

Nuclear structure and chemical effects in internal conversion of the 35 keVM1+E2 transition in125Te

The relative conversion line intensities of the 35 keV transition in¹²⁵Te were measured using the 50 cm π√2 iron-yoke magnetic spectrometer. The transition was proved to be ofM1+(8.7±1.5)×10^?4 E2 multipolarity, the magnetic component being affected by the nuclear structure with λ=2.4±1.4. The conversion intensity ratio,0/N ₁ , was determined to be 0.115+0.005 for both Ag¹²⁵ I and Cu¹²⁵ I sources. It is in accordance with previous measurements for the Zn^125m Te and Pb^125m Te sources and differs from those for the^125mTeO₂ and Na₂H ₄ ^125m TeO₆ ones. The conversion coefficients were calculated for 32 configurations of the valence shell of free tellurium atom and ions and were compared with the experimental results.     

The effect of chromic sulfate concentration and immersion time on the structures and anticorrosive performance of the Cr(III) conversion coatings on aluminum alloys

The main purpose of this study is to develop trivalent chromium, Cr(III), conversion coatings on aluminum alloys. The influence of Cr(III) concentration and immersion time on structures and anticorrosive performance of the coatings has been investigated. Corrosion behaviors of the coatings were evaluated in a 0.5 M H₂SO₄ aqueous solution at room temperature using potentiodynamic polarization. The structure and valence state of the coatings were examined by scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS). The addition of Cr(III) ions to the conversion bath considerably changes structures and compositions of the coatings. The coatings with Cr oxides possess a denser and thinner structure. Moreover, the corrosion resistance of Cr(III) coatings tends to decline with increasing immersion time due to the dissolution of coatings in the dipping period. According to XPS analysis, the Cr(III) conversion coatings are composed of Cr₂O₃, Cr(OH)₃, Al₂O₃, Al(OH)₃, ZrO₂, Zr(OH)₄, AlF₃, and ZrF₄, but no hexavalent chromium component in the coatings. The result indicates that the coatings prepared in the solution with 0.01 M Cr(III) for 5 min have the smoothest and densest structure and the best anticorrosive performance among all of conversion coatings in this work.     

Degenerate parametric frequency conversion of phase-modulated femtosecond laser pulses in crystals with a regular and chirped domain structure

A systematic theoretical analysis of the degenerate parametric frequency conversion in a LiNbO₃ crystal with a regular domain structure and a linearly varying domain thickness (chirped crystal) is presented for the pulses of a titanium-sapphire laser with a wavelength of 0.8 μm and durations of 100 and 50 fs in the presence and in the absence of phase modulation. The results are obtained with regard to the difference in the group velocities of interacting pulses and the group velocity dispersion. For an effective frequency conversion of the phase-modulated (PM) pump pulse, it is expedient to employ chirped crystals in which the domain thickness decreases from the entrance to the exit of the crystal. The pump energy is effectively converted into subharmonic energy when the pump carrier frequency decreases with time. It is demonstrated that the efficiency of the energy conversion to a subharmonic of 80% can be realized for PM pumping with a pulse duration of 100 fs in the chirped LiNbO₃ crystal. The efficiency of the parametric frequency conversion depends on the pump intensity as well as on the phase modulation of the pulse and the chirp of the crystal. Note that a variation in one of these parameters causes variations in the remaining parameters needed for the maximum efficiency of the parametric frequency conversion.     

Thermoelectric energy conversion in layered structures with strained Ge quantum dots grown on Si surfaces

The efficiency of the energy conversion devices depends in many ways on the materials used and various emerging cost-effective nanomaterials have promised huge potentials in highly efficient energy conversion. Here we show that thermoelectric voltage can be enhanced by a factor of 3 using layer-cake growth of Ge quantum dots through thermal oxidation of SiGe layers stacked in SiO₂/Si₃N₄ multilayer structure. The key to achieving this behavior has been to strain the Ge/Si interface by Ge dots migrating to Si substrate. Calculations taking into account the carrier trapping in the dot with a quantum transmission into the neighboring dot show satisfactory agreement with experiments above ≈200 K. The results may be of interest for improving the functionality of thermoelectric devices based on Ge/Si.     

Ordered porous TiO2 films obtained by freezing and the application in dye sensitized solar cells

TiO₂ films with ordered porous structure were prepared by freezing. By simply freezing wet TiO₂ film on a cold copper plate, ice crystals could grow from bottom of film. Removing such ice crystals then led to ordered, micro-sized pores in the films. With assistance of scanning electron microscopy and N₂ adsorption–desorption isotherms, micro-structural properties of the films were studied. Coarsening behavior of ice crystals was analyzed based on evolvement of the micro-structure. It was found that, both larger film thickness and longer freezing time were beneficial for the formation of ordered porous structure, which was caused by enhanced ice crystals growth. The films were then used to fabricate photoanode of dye sensitized solar cells, of which the photo-to-electric power conversion efficiency was evaluated. It was observed that, solar cell made of ordered porous TiO₂ film came out with 13% larger photo-current density comparing to that made of conventional doctor blading method, which is due to the enhanced light scattering by the ordered porous structure.     

Coincidence of rotational energy of H<Subscript>2</Subscript>O ortho-para molecules and translation energy near specific temperatures in water and ice

A hypothesis of the quantum nature of the specific temperatures T _s of water and ice, whose values is not random, was formulated. It was found that the quantum energy hΩ _mn of closely located rotational transitions in the ortho and para spin isomers of H₂O molecules coincides with the translation energy kT near the well-known specific temperatures T _s in ice and water. On the basis of this fact it was suggested that ortho-para conversion occurs at temperatures close to T _s upon inelastic collisions and resonance energy exchange kT _s ↔ hΩ _mn in the rotation-translation-rotation (RTR) processes. Such conversion can induce rearrangement of the H-bond set structure and repacking of H₂O molecules. The coincidence kT _s ≈ hΩ _mn was checked for ice and water at 12 known T _s, as well as for heavy water D₂O near T _s = 11.2°C (maximum density) and −140°C (glassy transition). The previously observe strong deformation of the OH Raman band near T _s = 4, 19, 36, and 76°C (maximum density, maximum surface tension, minimum heat capacity, and maximum speed of sound, respectively) was interpreted as a manifestation of the water structure rearrangement induced by H₂O ortho-para conversion.     

Second harmonic generation by intersubband transitions in step quantum wells

We report experimental evidence of Second-harmonic generation (SHG) due to intersubband transitions in GaAs/Al_zGa_1-xA8 step quantum wells using a multipass or "waveguide" structure. A SHG conversion efficiency of 3.46 × 10^-4 has been achieved which is one order of magnitude above the value obtained for the Brewster's angle arrangement.     

生物质气经由二甲醚两步法制备低碳烯烃

制备出NiSAPO-34及NiSAPO-34/HZSM-5催化剂,考察了其对二甲醚催化转化制备低碳烯烃的性能．利用Cu/Zn/Al/HZSM-5和筛选出的2%NiSAPO-34/HZSM-5催化剂进行生物质气经由二甲醚两步法制备低碳烯烃的实验, 结果表明在SAPO-34上添加2%的Ni不改变其结构, 但降低了酸中心数量, 并生成了较强的酸中心． 添加少量具有稳定酸中心的HZSM-5, 该催化剂的活性提高到3 h以上, 反应进行2 h获得了最高的低碳烯烃选择性为90.8%． 当把该催化剂应用到两步催化转化过程的第二个反应器中, 其高催化活性可达5 h以上． 当以低氢碳比生物质气(H₂/CO/CO₂/N₂/CH₄=41.5/26.9/14.2/14.6/2.89)作为原料时,经两步转化,低碳烯烃的收率达到84.6 g/m³_syngas．     

Experimental study of influence of temperature on fuel-N conversion and recycle NO reduction in oxyfuel combustion

Coal combustion in O₂/CO₂ environment was examined with a bituminous coal in which the gas-phase and char combustion stages were considered separately. The effects of temperature (1000–1300 °C) and the excess oxygen ratio λ (0.6–1.4) on the conversion of volatile-N and char-N to NOx were studied. Also, the reduction of recycle NOx by fuel-N was investigated under various conditions. The results show that fuel-N conversion to NO in O₂/CO₂ is lower than that in O₂/N₂. In O₂/CO₂ atmosphere, the volatile-N conversion ratios vary from 1–7% to 15–24% under fuel-rich and fuel-lean conditions, respectively. The char-N conversion ratios are 11–28% and 30–50% under fuel-rich and fuel-lean conditions, respectively. The influences of temperature on the conversion of volatile-N to NO under fuel-rich and fuel-lean conditions are contrary. A significant difference for char-N conversion in fuel-rich and fuel-lean conditions is observed. The experimental data of recycle NO reduction indicate that the reduction of recycle NO by gas-phase reaction can be enhanced by volatile-N addition in fuel-lean condition at high temperature, while in fuel-rich condition, the volatile-N influence cancelled out and the overall impact is small. NO/char reaction competes with the conversion of fuel-N to NO at higher temperatures.     

第三族金属氧化物离子对二氧化碳转化的红外光谱研究

本文利用红外光解离光谱研究了第三族金属氧化物离子对二氧化碳分子的转化机制. 研究表明,对于[ScO(CO₂)_n]⁺体系,在n≤4时,形成了溶剂化结构;在n=5时,形成了碳酸盐结构,实现了二氧化碳的转化. 对于[YO(CO₂)_n]⁺体系,需要4个二氧化碳分子就可以实现二氧化碳的转化. 而在[YO(CO₂)_n]⁺体系中,只发现了溶剂化结构,没有观察到碳酸盐结构. 理论计算表明,[YO(CO₂)_n]⁺体系拥有最小的溶剂化结构向碳酸盐结构转化能垒,[LaO(CO₂)_n]⁺体系拥有最大的溶剂化结构向碳酸盐结构转化能垒. 本文从分子水平揭示了不同金属氧化物离子对二氧化碳分子转化的影响规律.     

Nature of the electron-excited states and the mechanism of nonradiative energy transfer in aromatic bifluorophores

Quantum-chemical calculations have been carried out for molecules of the bifluorophores naphthalene-(CH₂)_n-anthracene. The electronic structure and molecular-orbital nature of the excited electronic states of the molecules was analyzed and the rate constants of the photophysical processes were estimated. It is shown that for molecules with n=1, 2, 3 the transfer of excitation energy from the donor fragment (naphthalene) to the acceptor (anthracene) is completely equivalent to internal conversion.The work was done under a grant from the Competition Center of St. Petersburg University.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 10, pp. 69–75, October, 1993.     

Brown coal gasification in combustion in supercritical water

The yield and composition of conversion products are investigated in a layout that provides countersupply of reagents (brown coal, supercritical water (SCW), and O₂) into a vertical tubular reactor and drain of reactants into replaceable collectors under isobaric conditions (30 MPa). The coal (gross formula CH_0.96N_0.01S_0.002O_0.31) incorporated into coal-water slurry (CWS) stabilized by starch addition (1 wt.%), was supplied through the top end of the reactor, while SCW and SCW/O₂ fluids were supplied through the bottom end. Based on the results of elemental analysis of liquid products and solid residue of conversion, and mass spectrometric analysis of volatile products, we obtained gross reactions of brown coal conversion in SCW and SCW/O₂ fluids. It was found that addition of O₂ to SCW leads to autothermal conversion conditions and an increase in the contribution from heterogeneous reactions between carbon and water, which provides additional yield of H₂ and CH₄.     

Laser Sintering of a Porous TiO2 Film in Dye-Sensitized Solar Cells

We investigate the possibility of modifying the porous structure of TiO₂ films in dye-sensitized solar cells (DSSC) in its sintering by a pulsed Nd:YAG laser (wavelength 1064 nm) to improve their parameters and characteristics. Sintering at various pulse energies enabled a porosity within the range of 0.45 to 0.20. The efficiency of the energy conversion in experimental DSSC specimens with TiO₂ films sintered by an optimum laser-radiation pulse energy of 150 mJ was 20–25% higher than that of commercial solar cells.     

Attrition of lignite char under fluidized bed gasification conditions: The effect of carbon conversion

The effect of carbon conversion on the attrition of lignite char particles during fluidized bed gasification by CO₂ was studied in a lab-scale apparatus. The influence of bed temperature and inlet CO₂ concentration on carbon conversion and, consequently, on attrition was studied. The mechanical resistance of the char particles was also characterized at different stages of char conversion by specific attrition experiments. A predictive kinetic model for CO₂ gasification of the lignite char was developed from the experimental results, that was able to correctly predict the evolution of carbon conversion versus time. On this basis a semi-empirical model was developed in order to simulate the evolution of carbon elutriation rate with carbon conversion degree, i.e. the gasification-assisted attrition enhancement effect.     

用不同类型的分子筛催化剂催化转化生物油制烯烃

研究了用一系列不同类型的分子筛催化剂催化转化制取低碳烯烃的过程,测试的催化剂包括HZSM-5、MCM-41、SAPO- 34和Y型分子筛．按照低碳烯烃的绝对收率和选择性,催化剂的活性排序为：HZSM-5>SAPO-34>MCM-41>Y型分子筛．研究表明,使用HZSM-5分子筛催化剂,获得的生物油最大低碳烯烃收率约为0.22 kg/(kg生物油),低碳烯烃的选择性约为50%,且生物油几乎实现完全转化．同时还研究了反应条件对生物油制低碳烯烃的影响．为了弄清催化剂结构与和低碳烯烃形成之间的关系,对相关催化剂进行了详细表征,对生物油热裂解和催化裂解过程进行了详细比较．