Haze and extinction for a composite medium with quasitransparent optically stratified particles

Haze and extinction are studied for coreshell particles in a matrix near transparency. It is shown that, close to transparency, a core-shell particle behaves optically differently from a nonstructured particle due to the presence of a minimum in the scattering pattern for any particle size. For small particles or domains (<λ/2), this difference is more pronounced. In particular, compositional effects on haze and extinction are studied. It is found that under certain conditions, for the same global composition, strongly optically stratified par-ticles give lower haze than the homogeneously distributed one by one to two orders of magnitude. The same occurs with the extinction coefficient, however the global composition at which this becomes important differs from that corresponding to a minimum haze. The origin of this difference is discussed in the light of the structure of the scattering pattern in each case. This implies that, for a transparent polymer blend with stratified domains, the minimum haze, maximum transmission and the theoretically perfect matching com-positions, are all different. Finally, it is shown that, for small highly optically inhomogeneous core-shell particles, haze goes through an inflection point with increasing particle size, in contrast with the usual monotonically increasing, singly concave, behavior. © 1993 John Wiley & Sons, Inc.     

Pattern recognition on the structure-activity relationship of nano Pt-Ru catalysts: methodology and preliminary demonstration

The activity of nano Pt-Ru catalysts is a multivariate function of particle size, alloyed degree, oxide composition, and so forth. The monodependencies of catalytic activity on individual structure parameters (structure-activity relationship, SAR) are of great importance but, unfortunately, unobtainable in practical measurements. A pattern-recognition methodology is proposed for the first time to extract SAR information from all of the relative experimental data, which we hope will cast new light on the in-depth understanding of this important catalyst. As a preliminary demonstration, a multivariate linear regression and a generalized regression neural network were applied to analyze a small data set for methanol oxidation. It was found that both increasing the content of hydrous ruthenium oxides and decreasing the particle size would benefit the catalytic activity, whereas the effect of the Pt-Ru alloy degree turned out to be unremarkable.     

Wetting behavior of spherical nanoparticles at a vapor-liquid interface: a density functional theory study

The wetting behavior of spherical nanoparticles at a vapor-liquid interface is investigated by using density functional theory, and the line tension calculation method is modified by analyzing the total energy of the vapor-liquid-particle equilibrium. Compared with the direct measurement data from simulation, the results reveal that the thermodynamically consistent Young's equation for planar interfaces is still applicable for high curvature surfaces in predicting a wide range of contact angles. The effect of the line tension on the contact angle is further explored, showing that the contact angles given by the original and modified Young's equations are nearly the same within the region of 60° < θ < 120°. Whereas the effect is considerable when the contact angle deviates from the region. The wetting property of nanoparticles in terms of the fluid-particle interaction strength, particle size, and temperature is also discussed. It is found that, for a certain particle, a moderate fluid-particle interaction strength would keep the particle stable at the interface in a wide temperature range.     

Wettability determined by capillary rise with pressure increase and hydrostatic effects

Capillary rise is the basis of some methods that are widely applied for the determination of contact angles as well as wettabilities of small particles. The equivalent hydraulic radius r(d) in the Classical Washburn equation is assumed to be particle-specific. But it seems that r(d) is not always constant when the type of liquids is different. The new equation with the pressure increment and the hydrostatic effects are theoretically derived based on the Washburn equation, so contact angles of small particles can be measured experimentally independently of r(d). The result shows the validity of the proposed method, and therefore, it becomes possible to accurately measure the wettability of small particles.     

An inexpensive, portable and microcontrolled near infrared LED-photometer for screening analysis of gasoline

A microcontrolled, portable and inexpensive photometer is proposed. It uses a near infrared light emitting diode (NIR LED) as radiation source, a PbSe photoresistor as infrared detector and a programmable interrupt controller (PIC) microcontroller as control unit. The detector system presents a thermoresistor and a thermoelectric cooling to control the detector temperature and keep the noise at low levels. The microcontroller incorporated total autonomy on the proposed photometer. As its components are inexpensive and of easy acquisition, the proposed NIR LED-photometer is an economical alternative for chemical analyses in small routine, research and/or teaching laboratories. By being portable and microcontrolled, it also allows carrying out field chemical analyses. The instrument was successfully applied on the screening analysis to verify adulteration in gasoline samples.     

Use of spatial emission profiles and a nomenclature system as aids in interpreting matrix effects in the low-power argon inductively coupled plasma

An automated profiling system was used to determine vertical intensity distributions for atomic and ionic lines of several elements in the ICP and to measure the effect of matrix components on those distributions. Most atomic lines show maximum signal (not necessarily maximum signal/noise) rather low in the plasma. Ion lines predominate in the plasma region used most frequently for analysis. In the region of high atomic emission, enhancements are observed for both atom and ion lines with many analytes when matrix elements are added. The enhancements either disappear or become much less severe in the region of high ionic emission normally viewed. The zone where the interferences occur can be shifted higher or lower in the plasma depending primarily on the central gas flow and the power level. Plasma structure can be used to predict regions of high interference. A Nomenclature System for the plasma zone is used as an aid in comparing plasma conditions.     

Feasibility study of three-dimensional XRF spectrometry using μ-X-ray beams under grazing-exit conditions

Grazing-exit XRF (GE-XRF), where the X-ray fluorescence is measured at small take-off angles, is a method related to TXRF. It has been demonstrated that GE-XRF is useful for surface, thin-film and particle analyses. In GE-XRF, it is possible to use a μ-X-ray beam at a normal incidence. Thus, a laboratory GE-XRF instrument was developed in combination with a μ-XRF setup. A μ-X-ray beam was produced by the combination of a single capillary and a pinhole aperture. It was demonstrated that depth information could be obtained by using this setup and changing the exit angle. Therefore, this instrument enables measurement of surface-sensitive line scanning and elemental mapping under grazing-exit conditions. In principle, measuring the elemental X-ray mappings at different exit angles enables the reconstruction of three-dimensional elemental distributions. To confirm the feasibility of three-dimensional XRF, a type of Japanese lacquerware, ‘Tamamushi-nuri’, which has a layered structure near the surface, was measured.     

Grazing-emission electron probe microanalysis of particles near the substrate edge

The distribution of X-ray radiation from a small particle, situated near the sharp edge of a flat substrate and excited by an electron beam, is analyzed theoretically taking into account the effects of the radiation reflection and its partial penetration through the substrate lateral surface. It has been shown that in some cases this dependence is strongly related to the distribution of primary X-ray sources above the substrate, which allows to use the signal — grazing-angle dependence for structure investigations of particles. The proposed technique was tested in experiments with CaCO₃ particles, situated on a pure Si substrate and exposed to a highly concentrated HNO₃ environment. Comparison of the observed angle dependencies for Ca and O characteristic X-ray radiation with calculated results revealed the intrinsic structure of the particles caused by their preliminary chemical treatment.     

The Angular Distribution of Solar Ultraviolet, Visible and Near-Infrared Radiation from Cloudless Skies

Abstract— The amount of solar radiation intercepted by an object depends on the orientation of the object with respect to the sun and the angular distribution of the diffuse component of solar radiation, which is commonly considered to be approximately isotropic. The angular distribution of the diffuse UV, visible and near-infrared insolation was measured at several solar zenith angles between 32° and 68° under cloudless skies at Lauder, New Zealand (45S), and shown to be anisotropic. The diffuse solar UV radiation increases markedly with solar elevation and is a large proportion of the total UV irradiance. The diffuse visible light and infrared radiation are small components of the total irradiance and almost independent of solar elevation. The angular distribution of erythemal UV radiation was tabulated and is available on request.     

Radiation and Chemical Grafting of Styrene to Polybutadiene Latex

Earlier studies of the gamma radiation and potassium persulfate grafting of styrene to uncrosslinked small particle size polybutadiene latices have been extended to a commercial cross-linked large particle size latex. The larger size particles and high gel content of the substrate latex was found to lead to a more complicated pattern of behavior. The conversion curves and the molecular weights were found to be complex functions of the initial monomer concentration, number of particles and temperature with both methods of initiation. The simple Smith-Ewart theory did not, in general, apply to these systems, and the k_p and E_p varied with conditions and were not in agreement with the generally accepted literature values. The molecular weights of the extracted polystyrene homopolymer were lower in the case of radiation initiation, in agreement with the previous work. This suggests that shorter but numerous grafted side chains are possible with radiation presumably due to the higher radical fluxes. (Some parallel experiments indicated that the molecular weights of the extracted homopolystyrene are similar to those of the grafted side chains.) This phenomenon also leads to somewhat lower graft efficiency with radiation initiation. Nevertheless, radiation was found to give grafting efficiencies of more than 80% under the best conditions. The conversions were also quite efficient with economical yields per radiation dose. These results, coupled with the ease of control and other features of radiation, make it a viable alternative method of initiation for industrial use.     

Toxicological classification of urine samples using pattern recognition techniques and capillary electrophoresis

In toxicology, hazardous substances detected in organisms may often lead to different pathological conditions depending on the type of exposure and level of dosage; hence, further analysis on this can suggest the best cure. Urine profiling may serve the purpose because samples typically contain hundreds of compounds representing an effective metabolic fingerprint. This paper proposes a pattern recognition procedure for determining the type of cadmium dosage, acute or chronic, administrated to laboratory rats, where urinary profiles are detected using capillary electrophoresis. The procedure is based on the composition of a sample data matrix consisting of areas of common peaks, with appropriate pre-processing aimed at reducing the lack of reproducibility and enhancing the potential contribution of low-level metabolites in discrimination. The matrix is then used for pattern recognition including principal components analysis, cluster analysis, discriminant analysis and support vector machines. Attention is particularly focussed on the last of these techniques, because of its novelty and some attractive features such as its suitability to work with datasets that are small and/or have low samples/variable ratios. The type of cadmium administration is detected as a relevant feature that contributes to the structure of the sample matrix, and samples are classified according to the class membership, with discriminant analysis and support vector machines performing complementarily on a training and on a test set.     

Elimination of interference information by a new hybrid algorithm for quantitative calibration of near infrared spectra

A new hybrid algorithm is proposed to eliminate the interference information for multivariate calibration of near-infrared (NIR) spectra that includes noise, background and systemic spectral variation irrelevant to concentration. The method consists of two parts: approximate derivative based on continuous wavelet transform (CWT) and orthogonal signal correction (OSC). After the approximate derivative calculated by CWT, OSC was performed. It was successfully applied to real complex NIR spectral data to eliminate the interference information. Correction for the interference of NIR spectra resulted in a substantial improvement in the predicted precision, and a more concise calibration model was obtained. The proposed procedure also compared favourably with several pretreatment methods, and the new method appears to provide a high-performance pretreatment tool for multivariate calibration of NIR spectra. In addition, the strategy proposed here can be applied to various other spectral data for quantitative purposes as well.     

Delta-electron emission in fast heavy ion — atom collisions: observations of new phenomena and breakdown of common scaling laws

Double differential cross sections for the emission of Delta-electrons have been measured in fast uranium-rare gas collisions. The well-known Binary Encounter peak reveals unexpected structures for certain observation angles and its intensity increases towards smaller angles, which is in contradiction to results and scaling laws obtained by experiments with light ion impact. The observed dependencies are fairly well described by recent calculations in the framework of IA and CTMC. From systematic experimental as well as theoretical studies we can derive that the potential of the partially stripped projectile ion gives rise to rainbow and glory scattering of the target electron in the field of the projectile. The rainbow scattering is observed in the laboratory frame as pronounced interference structures, whereas the glory scattering is responsible for the steep increase of the cross sections for binary-encounter electrons towards small laboratory ejection angles. The observed effects have a dramatic influence on the commonq ² scaling laws derived from experiments with light ions. Furthermore, since the binary-encounter electrons ejected at forward angles have approximately twice the projectile velocity, these new phenomena have an important influence on the electronic stopping power of heavy ions and therefore have to be taken into account for the investigation of radiation damage by these ions e.g. in biological matter.     

Optical effects in stratified colloidal particles near transparency

Non-isotropic scattering patterns showing a minimum for small and almost transparent core-shell particles are discussed. It is shown that for any particle size, close to transparency, a core-shell particle behaves optically differently from a non-structured particle due to the presence of a minimum in the scattering pattern. Transparency criteria are discussed in the light of the non-isotropic character of the scattered light. Direct experimental evidence of the existence of this minimum is presented and compared with the theoretical predictions of the scattering by colloids having a distribution of particle composition.     

Characteristics and origins of common chemical noise ions in negative ESI LC-MS

Ionic chemical background noise in LC-MS has been one of the major problems encountered in trace analysis. In this study, the typical negative background ions in ESI LC-MS are investigated exemplarily. It was carried out using tandem mass spectrometry to study the products and precursors of the major background ions to examine their structures and structure relationship. Various typical LC eluents with different compositions and additives such as ammonium formate/formic acid and ammonium acetate/acetic acid have been studied. Several types of negative noise ions are concluded, which include the cluster chemical background ions only from mobile phase components and additives. Furthermore, there are also abundant clusters resulting from the solvation of some typical individual contaminants (e.g. additives and degradation products from tubing, impurities in the mobile phase, etc.), accompanied by some minor contribution from contaminants. The elemental composition of some selected ions was confirmed using the FT-ICR accurate mass measurement. This work provides us insight into information about the structures and types of common negative background ions and will help to understand their formation and origins. More importantly, it will guide us to prevent chemical noise interference in practice and also contribute to develop methods for noise reduction based on selective ion-molecule reactions.     

转动传能中的量子干涉: 干涉角和相对速度的关系

考虑一级含时波恩近似和长程相互作用势, Sun提出了转动传能中的量子干涉模型.在静态池中CO A1Π～ e 3Σ-和He碰撞的实验已经成功模拟.为了从实验中直接获得碰撞速度和干涉角的关系, Sha提出了利用分子束和离子速度成像技术的实验.作为理论研究干涉角和碰撞速度的关系,计算了不同速度下的干涉角,同时获得了变化的趋势.对在分子束条件下(通过控制碰撞速度来控制干涉角)实验具有指导意义.     

Particle Analysis by SEM/EDXS and Specimen Damage

 Quantitative analysis of particles, especially environmental particles in the submicron region, is hampered mainly by radiation damage. It can already be observed for probe currents smaller than 1 nA and analysis times of 10 seconds. The main reason for radiation damage is the storage of thermal energy in the particle, until the melting temperature is reached, and the subsequent loss of one or more of the elements of the respective material, e.g. SO_x in K₂SO₄. The lower the melting point, the more severe the specimen damage. The amount of specimen damage can vary substantially even for particles of the same size and composition. Specimen damage on inorganic materials can be observed for energies as low as 1 keV. Thus radiation damage is the greatest obstacle to accurate quantitative analysis for particles in the submicron region, even for analysis times as low as those used in automated particle analysis by CCSEM/EDXS.     

Fluid phase stability and equilibrium calculations in binary mixtures: Part I: Theoretical development for non-azeotropic mixtures

A framework is proposed for the solution of fluid phase equilibrium (P–T flash) for binary mixtures described by equations of state of general form. The framework is based on decomposing the phase equilibrium problem into sub-problems with more convenient and tractable mathematical and numerical properties. Systematic procedures are used to identify the mapping of the problem in the density and composition space, referred to as the density–composition pattern, at specified temperature and pressure. A series of stability tests is then carried out to explore the existence or non-existence of phases. Once the existence of a phase has been determined, the limits of stability and physical bounds on the problem are used to define the search area for that phase in the density–composition pattern. Finally, all available information from this detailed analysis is used for the solution of phase equilibrium between the phases identified in order to find the stable state at the specified conditions. The features of the proposed approach are exposed in detail through an algorithm for the fluid phase equilibria of the augmented van der Waals equation of state applied to non-azeotropic mixtures.     

Contact angles of aluminosilicate clays as affected by relative humidity and exchangeable cations

Contact angles of aluminosilicate clays are difficult to determine. Not only does their small particle size present measurement difficulties, but contact angles may vary with relative humidity and cation composition. In this paper, we determined the effects of relative humidity and exchangeable cations on contact angles of three aluminosilicate clays (smectite, kaolinite, illite). Contact angles were measured on clay films with the sessile drop method under different relative humidity (19, 33, 75, 100%), and with clays saturated either with Na, K, Mg, or Ca. The results showed that the water contact angles on smectite increased with relative humidity between 19 and 75%, but for kaolinite and illite, little differences in water contact angles between 19 and 75% relative humidity were observed. For all three clays, however, the water contact angles decreased at 100% relative humidity as compared to the lower relative humidities. Cations affected not only the adsorption of water but also the surface charge, and both factors influenced the contact angles of the clays. Negligible effect of the different cations Na⁺, K⁺, Mg²⁺, or Ca²⁺ on contact angles was observed.