CARS diagnostics of fluid adsorption and condensation in small mesopores

Coherent anti‐Stokes Raman scattering (CARS) spectroscopy is applied to diagnostics of phase behavior of a fluid in pores of nanoporous glasses. Samples with mean pore radii of 2 and 3.5 nm were filled with compressed carbon dioxide at near‐room temperatures. CARS spectra of the 1388 cm⁻¹ Q‐branch were measured at isothermal compressing in a wide pressure range including the transition from gaseous to condensed state. The spectra show specific transformations caused by fluid adsorption and condensation in nanopores. We have carried out calculations of the spectral profiles based on the phase behavior of carbon dioxide in cylindrical glass nanopores. Phase behavior modeling was performed using thermodynamic concepts of surface adsorption and capillary condensation. A good agreement between experimental spectra and calculations was obtained. The potential of CARS technique for the diagnostics of fluid phase behavior in pores and for the characterization of nanoporous host structure is discussed. Copyright © 2011 John Wiley & Sons, Ltd.     

Conditions for growth of columnar and filamentary crystals

The computer model of the initial stage of condensation processes is developed. The stochastic processes of adsorption, surface diffusion, and desorption occur on the 70×70 lattice of adsorption vacancies. The model was tested by an example close to water vapor sorption on a conventional crystal surface. Computed results demonstrate the processes of nucleation, growth of crystals, and developed condensation. Computations were carried out for various adsorption energies. Results showed that with decreasing energy of adsorption the character and rate of nucleation and subsequent condensation vary. With decreasing energy of adsorption the probability of nucleation of islets on substrate reduces, the filling of the next atomic layers on islets occurs earlier than the filling of the substrate, the growth rate of islets in height increases as compared to condensation of a continuous film, and the growth rate of area of islets decreases. There is a typical energy of adsorption at which the growth rate of islets in height reaches its maximum. At a further drop of adsorption energy, there is a growth of islets only in height, the growth rate, however, reduces. The phenomena revealed in computations illustrate the mechanism of origin of columnar and filamentary crystals.     

The adsorption of ammonia on an Fe(110) single-crystal surface studied by high-resolution electron energy-loss spectroscopy (eels)

The EELS spectra of ammonia adsorbed on an Fe(110) surface at 110 K reveal four different adsorption states of molecular ammonia with increasing coverage : chemisorption at “on-top” sites, chemisorption at multi-coordinated sites, adsorption in a second layer, and multilayer condensation.Thermal processing of an ammonia-covered sample to 155 K causes desorption of both the condensed phase and the second layer without any fragmentation of ammonia.Further heating of the sample leads to a much weaker desorption of molecular ammonia up to a temperature of 260 K. EELS spectra recorded after heating to 290 K show only small amounts of atomic nitrogen and hydrogen present on the surface, indicating partial decomposition of ammonia.The formation of species such as NH₂ (ads) or NH (ads) during the thermal-processing experiments could not be observed.     

基于温度修正模型的柴油凝点快速检测方法

便携式近红外光谱仪现场快速检测是近红外光谱分析领域的一个重要的发展趋势。为了实现快速检测,便携式近红外光谱仪一般不配备温控装置,因此环境温度的变化会带来较大的测量误差。如何降低环境温度对检测结果带来的误差,是便携式近红外光谱仪在现场快速检测领域大规模推广所需要解决的一个重要问题。柴油的凝点值是评价柴油品质和适用范围的一个重要指标,对柴油凝点进行快速检测有重要的经济意义。通过便携式光谱仪采集了50种具有不同凝点的柴油样品在近红外波段（950～1 650 nm）的吸收光谱,研究了环境温度变化下的基于近红外光谱分析的柴油凝点快速检测方法。此光谱仪为基于数字微镜设计的便携式光谱仪,针对现场快检而研发,未配备温控样品池。在环境温度T₀=25 ℃时基于偏最小二乘法建立了柴油凝点的预测模型,并分别将不同环境温度（T_E=-10,0,10,20,30,40和50 ℃）条件下测量的近红外光谱带入上述凝点预测模型,分析预测偏差随环境温度相对参考值变化(T_E-T₀)的依赖关系。通过一次函数对预测误差随环境温度的变化关系进行拟合,发现凝点预测偏差的平均值随环境温度的变化关系为Δｃ＝-0.019 8(T_E-T₀)。将环境温度的修正因子带入25 ℃条件下预测模型,建立了针对环境温度变化的温度修正模型。在温度修正以后,10 ℃条件下预测凝点的均方根误差由原来的14.6降为8.8,相关系数由原来的0.4提升为0.7。研究表明,本温度修正模型可以有效降低环境温度对预测结果带来的误差。基于此温度修正模型,可以显著降低近红外光谱分析建模过程的工作量,在某一特定温度条件下建立预测模型后将此温度修正项带入模型即可用于在其他环境温度条件下进行柴油凝点值的预测,而不需要在其他多个温度条件下分别建立预测模型,可显著提高建模效率和便携式近红外光谱快速检测的温度适应性。     

Emission of Ag2 dimers from a substrate during vacuum deposition of the mixture of silver and water vapor

The work presents calculation of Ag₂ dimers emission from the substrate into the vapor medium in case of joint deposition of silver and water vapors on ideal substrate formally modeling the crystal of water ice in terms of energy properties. It is assumed that the dimers are formed on the condensation surface as a result of random collisions of atoms at their surface migration, and the dimers emission is conditioned by thermal fluctuations of crystal lattice of water ice. The calculations based on the modified Langmuir adsorption model allowed concluding that emission of silver and water dimers takes place in the entire range of the studied water vapor pressure, binding energy of silver-water, and crystal temperature. Dynamics of emission from the beginning of deposition and dependence of dimers emission on micro-roughness of the condensate surface have been investigated. Statistical processing of results has shown that the probability of dimers emission from the condensate surface is determined not only by the value of the binding energy between the dimer and condensate but by configuration of the nearest dimer environment on the condensation surface. It has been found that there is a certain value of micro-roughness of condensation surface providing the maximal intensity of dimer emission. Dimers emission from the surfaces bordering on the flows of vapor mixtures contaminates the flows with unsuspected admixtures. The latter one makes investigation of this phenomenon important for aeromechanics of vapor and gas mixtures.     

Hydrogen adsorption on Ni (100)

The adsorption of hydrogen on the (100) plane of nickel at room temperature has been investigated using the technique of flash desorption spectroscopy. It is shown that no variation in the adsorption enthalpy of 23.1 kcal/mole occurs during the chemical cleaning of the surface by repeated oxidation and reduction. The number of adsorption sites does however increase to 3.3×10¹⁴/cm² during this process. Determination of the partition functions of the adsorbed species and of the activated complex indicates that the hydrogen atoms are localised on specific adsorption sites but that greater liberty exists in the activated complex. Finally the experimental desorption spectra may be described using a model with a repulsive interaction of 400 cal/mole between nearest neighbours.     

Bosons as the origin for giant magnetic properties of organic monolayers

Recently, unusual giant magnetic properties were found experimentally in some organized organic monolayers adsorbed on solid substrates. A model is presented which explains the observed phenomenon. The model is based on the special properties of electrons transferred from the substrate to the layer as a result of the adsorption process. Triplet pairing of those electrons is forced by the special 2D properties of the organic layer. Such pairs are confined within domains in the organic layer and their quantum statistics provide a model that explains the unique magnetization as well as all other features of the experimental observations. The model suggests the possible existence of Bose-Einstein condensation at room temperature on the scale of the domains.     

Phase transitions of adsorbed fluids computed from multiple-histogram reweighting

This paper demonstrates the effectiveness of using multiple-histogram reweighting (MHR) to study phase transitions in confined fluids by examining capillary condensation, prewetting, and layering transitions for different systems. A comparison is made with previously published simulations, where available, to establish the accuracy of MHR as applied to inhomogeneous systems. Overlap between adjacent state points is assessed through single-histogram reweighting. Capillary condensation for methane adsorption in slit-like graphite pores exhibits 2D behaviour. Crossover of the effective exponent for the width of the coexistence curve from 2D Ising-like (1/8) further away from the critical point to mean-field (1/2) near the critical point is observed. The reduced critical temperature, the density and the effective value of the exponent for the model system are 0.77, 0.482, and 0.119, respectively, based on a fit to the simulation data. Prewetting transitions are observed for adsorption of Ar on solid CO₂ using model potentials. The wetting temperature is estimated based on the intersection of the pre-wetting and bulk vapour-liquid lines, and also by extrapolation to zero of the difference between the saturation and prewetting chemical potentials. The reduced wetting temperature is estimated to be around 0.69. The reduced prewetting critical temperature, calculated from the disappearance of the two peaks in the density probability distribution, is estimated to be 0.92. The monolayer to bilayer (1-2) transition for propane on graphite is computed over a range of temperatures. Results for the 1–2 layering transition computed from MHR from a small system are in good agreement with grand canonical Monte Carlo simulations for a much larger system.     

Water vapor adsorption onto activated carbons prepared from cattle manure compost (CMC)

Activated carbons were prepared from cattle manure compost (CMC) using zinc chloride activation. The structural and surface chemical characteristics of CMC-based activated carbons were determined by N₂ adsorption-desorption and Boehm titration, respectively. The water vapor adsorption properties of the prepared activated carbons with various pore structure and surface nature were examined, and the mechanism of water adsorbed onto activated carbon was also discussed. The results show that the adsorption of water vapor on carbons begins at specific active sites at low relative humidity (RH), followed by micropore filling at medium RH through the formation of pentamer cluster of water molecules in the narrow micropores. The water vapor adsorption capacity of activated carbon is predominantly dependent on its pore volume and surface area. Although capillary condensation is not the mechanism for water adsorption onto activated carbon, water can adsorb on narrow mesopore to some extent.     

Pore Structure Analysis of Porous Particles by Modelless and Micropore Method

The modelless (ML) and micropore (MP) methods for the pore structure analysis of porous particles have been studied. Concerning the ML method, it has been shown that the Kiselev equation can only be used to describe condensation and evaporation in capillaries, but cannot be used to describe the increase and decrease of the thickness of the adsorption layer. Strictly speaking, therefore, the ML method is not modelless even for the pore core size distribution. A comparison between the ML method and methods using an equivalent pore model is given. The results of using the ML method in conjunction with a certain pore model are little less accurate than those obtained by adopting the equivalent pore model straightaway. The parameters required for the calculation of both the pore core size and the pore size distribution as well as the conversion between these two calculations are given. Concerning the MP method, it has been shown that the three types of v-t curves, the theoretical foundation of the MP method, are not in one to one correspondance to the three kinds of adsorption mechanism. From the viewpoint of accuracy, the MP method has no advantage over the methods which are based on the condensation mechanism, both have their own merits.     

The dynamical holographic QCD method for hadron physics and QCD matter

In this paper we present a short overview on the dynamical holographic QCD (DhQCD) method for hadron physics and QCD matter. The five-dimensional DhQCD model is constructed in the graviton-dilaton-scalar framework with the dilaton background field Φ and the scalar field X dual to the gluon condensate and the chiral condensate operator thus can represent the gluodynamics (linear confinement) and chiral dynamics (chiral symmetry breaking), respectively. The dilaton background field and the scalar field are a function of the 5th dimension, which plays the role of the energy scale, in this way, the DhQCD model can resemble the renormalization group from ultraviolet (UV) to infrared (IR). By solving the Einstein equation, the metric structure at IR is automatically deformed by the nonperturbative gluon condensation and chiral condensation in the vacuum. We review the results on the hadron spectra including the glueball spectra, the light/heavy meson spectra, as well as on QCD phase transitions, and thermodynamical as well as transport properties in the framework of the DhQCD model.     

利用紫外透射光谱研究透射式GaN光电阴极的材料结构及光学特性

GaN紫外光电阴极是近年发展起来的一种高性能真空紫外探测器件,其中透射式结构作为光电阴极实际应用的工作模式,其多层结构参数及光学特性对阴极的最终光电发射性能有着重要的影响.测试了透射式GaN阴极材料的紫外透射光谱,通过建立透射式GaN阴极样品的透射模型,得到了GaN阴极样品的薄膜厚度、光学吸收系数与透射谱之间的函数关系.计算得到的GaN外延材料的厚度与实际值误差小,吸收系数与已发表数据一致,表明紫外透射光谱法能够准确地实现透射式GaN阴极材料结构及光学特性的评估.     

Predicting and researching adsorption configurations of pyridazine on Si(100) surface by means of X-ray spectroscopies in theory

The landscape of organic molecule on Si(100) surface has a great significance for organic functionalisation of Si semiconductor. Several possible adsorption configurations for pyridazine on Si(100) surface have been forecasted by systemic comparison and investigation. The C1s XPS and NEXAFS spectra of these adsorption systems based on density functional theory and full core-hole potential approximation have been calculated. Although the sensibility of XPS to these adsorption configurations is not very strong, these configurations can be absolutely distinguished by NEXAFS spectra, which will bring tremendous reference to the future experimental study. Mode II, III, V and VI have a significantly higher adsorption energy, which are most likely to be present in experiment. In addition, we have made the research on specific sources of the peaks in spectra by analysing their decomposed NEXAFS spectra, the results show that the Carbon atoms which do not bond to surface atoms, make the most contribute to the intensity of characteristic peaks in spectra.     

分形理论结合相变动力学的冷表面结霜过程模拟

运用分形理论并结合相变动力学模拟冷表面上结霜过程.在相变动力学基础上成功模拟了结霜初始阶段水蒸气在冷表面上凝结、液滴生长及冻结过程,随后运用分形理论的有限制的扩散凝聚(diffusion limited aggregation,DLA) 模型模拟了霜晶在冻结液滴表面上的形成生长过程.模拟结果与实验结果取得良好的一致,模拟过程中凝结液滴出现及冻结的时间与实验结果几乎完全符合;液滴冻结之前其表面接触半径随时间变化的模拟结果与实验结果基本一致,同时模拟霜层厚度与实验测得霜层厚度也非常接近.研究结果对于探讨分形理 关键词： 分形 相变动力学 结霜 模拟     

Collective bubble oscillations as a component of surf infrasound

Plunging surf is a known generator of infrasound, though the mechanisms have not been clearly identified. A model based on collective bubble oscillations created by demise of the initially entrained air pocket is examined. Computed spectra are compared to infrasound data from the island of Kauai during periods of medium, large, and extreme surf. Model results suggest that bubble oscillations generated by plunging waves are plausible generators of infrasound, and that dynamic bubble plume evolution on a temporal scale comparable to the breaking wave period may contribute to the broad spectral lobe of dominant infrasonic energy observed in measured data. Application of an inverse model has potential to characterize breaking wave size distributions, energy, and temporal changes in seafloor morphology based on remotely sensed infrasound.     

Condensation bidimensionnelle de l'oxygène sur les halogénures lamellaires

Sets of adsorption isotherms of oxygen on the cleavage face of a number of lamellar halides have been determined. The isotherms show three vertical steps, corresponding to the formation of three successive monomolecular layers during two-dimensional (2D) condensation. From the values taken by the entropy of the various layers and by their critical temperatures of 2D condensation, it is inferred that first layers have a cristalline structure influenced by the surface while the following ones are liquid-like.     

Effect of defects of plasmon resonance colloidal crystals on their extinction spectra

The effect of the temperature of a silver sol on its extinction spectra during formation of aggregates of plasmon resonance nanoparticles with varying degree of order and the effect exerted on these spectra by changes in the structure of a colloidal crystal during its heating, which lowers elastic properties of a polymer adsorption layer of particles are studied.     

Variation of extinction spectra of plasmon resonance colloidal crystals upon structural transitions

The effect of the temperature of a silver sol on its extinction spectra during formation of aggregates of plasmon resonance nanoparticles with varying degree of order and the effect exerted on these spectra by changes in the structure of a colloidal crystal during its heating, which lowers elastic properties of a polymer adsorption layer of particles are studied.     

Study of oxygen and carbon monoxide adsorption on molybdenum (110) by metastable helium de-excitation spectroscopy

The adsorption of oxygen and carbon monoxide on the (110) face of molybdenum is studied at room temperature by metastable helium atom de-excitation spectroscopy (MDS). On the basis of the interaction mechanism described by H.D. Hagstrum, and which was shown to be valid for the He¹?Mo couple in a previous article and again here, the secondary electron energy spectra are interpretated as relating to the self-convolution product of the electron state density of occupied valence band levels of the solid. The results obtained after deconvolution show the variations in this density of states during oxygen and carbon monoxide adsorption, and they are compared with photoemission spectra (UPS) obtained at the same time as the MDS spectra. They show that MDS is a technique well suited to the study of adsorption phenomena.