Comparison of Proutière and Carr-Zimm theories for static light-scattering molecular weight determination: application to surfactants in solution

Proutière's theory of molecular weight (M) determination by Rayleigh scattering has been tested on surfactants in solution, and it has been compared to the classical Carr-Zimm (CZ) method. Both methods make use of time-averaged scattering intensity, refractive index, and density measurements. Monoethers of poly(ethylene glycol) samples have been studied in the range 0.33-4.67 kg/mol of M. Under those conditions, it has been shown that Proutière's method leads to a far better agreement with formula weight (M) values than the CZ method because Proutière theory takes into account the specific mean polarizability of the solvent and derivative of the solution density with respect to the solute mass concentration, which is counter to CZ theory.     

High-pressure Brillouin scattering of amorphous BeH2

High-pressure micro-Brillouin scattering is employed to investigate the pressure dependence of the sound velocity, refractive index, equation of state, and mechanical properties of amorphous BeH2. The refractive index n has been determined by using two scattering geometries (70 degrees and 180 degrees). The equation of state is deduced from the pressure dependences of the sound velocity. The bulk modulus is 14.2 (+/-3.0) GPa and its pressure derivative is 5.3 (+/-0.5). The polarizability is calculated from the refractive index and the density of the material. It increases with pressure while Poisson's ratio decreases with pressure.     

Applications of index matching in reflectometry,SANS and Brewster angle microscopy

By index matching, we mean, the manipulation of the composition of a material such that heterogeneous regions of a sample present identical refractive indices. Such manipulation is commonly used to exaggerate deviations from bulk properties at the interface between two bulk phases. Whilst index matching is used routinely in small-angle scattering it is in the field of neutron reflection that the technique has only recently been exploited fully. Specific deuteration, either inter- or intramolecular combined with partial structure factor (PSF) analysis has allowed structural detail to be elucidated at resolutions of ∼4 Å. In light scattering Brewster angle microscopy exploits the extinction of ‘p’ polarised light to enhance surface inhomogeneites on the scale of microns.     

Small-Angle light scattering from an anisotropic sphere: Anisotropy and size effects

The recently developed theory of light scattering from an anisotropic sphere (taken as a model for a spherulite) summarizes all information obtainable from such scattering system when the Rayleigh-Gans-Debye approximation is appropriate. The commonly used procedure of size determination from the maximum of the H_v intensity is tested for a number of models differing in radius size, inherent anisotropy δn and mean refractive index ¯n. It has been confirmed, that the parameter (¯n - 1)/δn plays the decisive role in the angular dependence of the H_v intensity and the influence of that parameter on the size determination and resulting accuracy is specified. The results differ for positive and negative spherulites and the stabilizing role of increasing spherulite size in accuracy of procedure is demonstrated. It has been shown that the RGD approximation is appropriate especially for the case of homogeneous spherulite texture (thus implying, that the refractive index of the surrounding is close to the average refractive index of a single spherulite). The results extrapolated outside of the RGD approximation display invariable U_max position for isotropic contribution with increasing sphere size in contrast to the oscillatory character of U_max predicted by the LM solution. It is proposed to construct the anisotropic solution under an approximation recently suggested for thin anisotropic shell. © 1994 John Wiley & Sons, Inc.     

Effect of UV light scattering during photopolymerization on UV spectroscopy measurements

A photopolymerization reaction involving 2-hydroxyethylmethacrylate (HEMA), a hydroxytelechelic polybutadiene (HTPB) and 2,2-dimethyl-2-hydroxyacetophenone (Darocur 1173) as photoinitiator has been investigated by Real Time UV and Real Time IR spectroscopies. For this system, RTUV analyses are completely opposite to the expected curves, namely a decrease in the sample absorbance (photobleaching phenomenon). This apparent contradiction has been explained by a scattering phenomenon inside the sample, which can be linked to the formation of sub-structures that can create local fluctuations of refractive index during the polymerization. A four-flux theory, which takes into account the polymer absorption and scattering properties, has allowed us to describe the UV light intensity variation inside the sample.     

梯度折射率聚合物细棒的制备和数学模拟

在聚甲基丙烯酸甲酯 (Poly(methylmethacrylate) ,PMMA)管中 ,加入单体甲基丙烯酸甲酯 (Methylmethacrylate ,MMA)和另一种高折射率的掺杂剂溴苯 (Bromobenzene ,BB) ,用界面凝胶均聚合方法制备了梯度折射率聚合物光纤预制棒 .这种光纤预制棒的梯度折射率是通过具有不同折射率的分子扩散而形成的 .通过对界面凝胶聚合过程的描述 ,该工作讨论了预制棒中聚合物的浓度分布及边界条件的假设 .并根据自由体积理论对其折射率分布进行理论模拟 .将得到的折射率抛物线分布与实验结果进行对比 ,结果表明聚合浓度的分布为ω =a(r/R) 2 +b时 ,理论预计的光纤预制棒的折射率分布与实验结果有着较好的符合 .同时 ,对聚合体系中BB对聚合物浓度分布的影响进行了讨论     

Solution properties of polymers of pyridinium and ammonium methacrylates.

Solution properties of poly[1(2-hydroxyethyl)pyridiniumbenzene sulfonate methacrylate] and poly[1(2-hydroxyethyl)trimethylammoniumbenzene sulfonate methacrylate] were studied. Within a certain concentration range of some added low molecular weight electrolytes, phase separation occurs. The dependence of intrinsic viscosity on molecular weight was determined and the steric factor estimated for both polymers. For nonaqueous solvents, an extrapolation of the dependence of the refractive index increment of the polymer on the refractive index of the solvent leads to an apparent refractive index of the polymer, different from the refractive index determined directly by the immersion method. Some peculiarities of light scattering in solutions with no electrolyte added are mentioned.     

Size distribution analysis of polymer latex systems by use of extrema in the angular scattering intensity

The angular position of the extrema of the vertically polarized scattering intensity has previously been utilized for a method of particle size analysis for systems of monodisperse, spherical, isotropic particles which conform to the Rayleigh-Gans-Debye theory. The consequences of a finite polydispersity, which is always present in real systems, was not assessed and the application of the method has resulted in erroneous characterization of some latex systems. This work is concerned with (1) reporting the effects of finite polydispersity on the method of analysis, (2) pointing out previous misuse of the method, and (3) introducing a method of analysis which is based on the position of the extrema but which also considers polydispersity and the exact Mie calculation. This method enables one to characterize a scattering system in terms of a modal diameter and a distribution-width parameter by utilizing prepared diagrams for a particular relative refractive index.     

Laser-based refractive index detection for micro-channels

Laser-based refractive index detection, based upon refractive index changes in micro-channels, is a kind of laser-based optical determination for solutions. As it is capable of label-free determination, it has been regarded as a considerable growth prospect. The key aspect in related researches lay in the development of novel detection configurations, which would possibly result in better sensitivity. Over the past decade, micro-channel laser-based refractive index detection has been significantly improved, resulting in traversed, hologram-based, back-scattered, retro-reflected interference, optical ring resonant, etc., detection configurations. Moreover, laser-based refractive index detection has been combined with other laser-based detection strategies, in order to pursue a universal and sensitive detection. And last but not least, some utilizations of laser-based refractive index detection have been reported, while both advantages and drawbacks exist. In this paper, laser-based refractive index detection for micro-channels will be reviewed in proceeding sequence.     

Light scattering from coloured systems: an example of polyaniline dispersions

Static light scattering of highly diluted dispersions in 0.005 M H₂SO₄ was used to determine particle parameters of polyaniline dispersions stabilized with colloidal silica. The refractive index of polyaniline n = 1.8 and the refractive index increment (dn/dc) = 0.22 cm³g⁻¹ at λ = 532 nm were determined. The light scattering data are affected by the absorption of the green polyaniline and by a small amount of aggregates. The absorption has a negligible effect on the results. The influence of the aggregates was corrected by using the intensity‐weighed size distributions determined by dynamic light scattering at different angles and by the two‐component separation in static light scattering. Both procedures yield the same result.     

Organopolysiloxanes as Chemically Sensitive Coatings for Optical Fibers

Various types of UV-curable organically modified siloxanes have been synthesized by the sol-gel method with the aim of fabricating chemically sensitive coatings for silica optical fibers. The refractive index of the coating material can be tailored in the range from 1.46 to 1.56 and sensitivity towards CO2 is achieved by incorporation of amino groups. The interaction of the cured layers with CO2 or with hydrocarbons has been studied in immersion experiments. Both the reaction of CO2 with incorporated amino groups and the penetration of hydrocarbons into the layer induce changes of the light absorption coefficient and the refractive index of the coating which are detected by measuring the output light intensity from the fiber.     

Dye-activated hybrid organic/inorganic mesostructured titania waveguides

A room-temperature synthesis route for the fabrication of a new type of hybrid organic/inorganic mesostructured material based on titania instead of silica as the inorganic component has been developed. This approach enables facile processing of the titania/block copolymer surfactant precursor solution into optically activated, transparent, and crack-free fibers and planar waveguides with adjustable thickness. Stabilization of the structures occurs upon solvent evaporation by formation of a solid, glasslike material without heat treatment. These dye-activated, high refractive index, titania-based composites show efficient waveguiding and mirrorless lasing at low thresholds without the need of an ultralow refractive index support layer.     

Broadband and Highly Directional Visible Light Scattering by Laser-Splashed Lossless TiO2 Nanoparticles

All-dielectric nanoparticles, as the counterpart of metallic nanostructures have recently attracted significant interest in manipulating light-matter interaction at a nanoscale. Directional scattering, as an important property of nanoparticles, has been investigated in traditional high refractive index materials, such as silicon, germanium and gallium arsenide in a narrow band range. Here in this paper, we demonstrate that a broadband forward scattering across the entire visible range can be achieved by the low loss TiO₂ nanoparticles with moderate refractive index. This mainly stems from the optical interferences between the broadband electric dipole and the magnetic dipole modes. The forward/backward scattering ratio reaches maximum value at the wavelengths satisfying the first Kerker’s condition. Experimentally, the femtosecond pulsed laser was employed to splash different-sized nanoparticles from a thin TiO₂ film deposited on the glass substrate. Single particle scattering measurement in both the forward and backward direction was performed by a homemade confocal microscopic system, demonstrating the broadband forward scattering feature. Our research holds great promise for many applications such as light harvesting, photodetection and on-chip photonic devices and so on.     

Polymer cosolvent system—II. Preferential adsorption of binary solvent acetone/cyclohexane by poly(p-tert-butylphenyl methacrylate)

The cosolvent system poly(p-tert butylphenyl methacrylate) (3)/acetone(1)/cyclohexane (2) has been studied at 298 K by light scattering, refractive index increment of dialysis equilibrium and viscometry. The preferential adsorption coefficient, λ1, for the whole composition range of the binary mixture acetone (1)/cyclohexane(2) has been determined. The values have been compared with the theoretically calculated values. The results indicate that in this system it is necessary to take into account the tertiary interaction parameters χ₁₂₃, χ₁₂₂ and χ₂₃₃.     

THE SPATIAL DISTRIBUTION OF LIGHT EMISSION FROM LIQUID PHASE BIO- AND CHEMILUMINESCENCE: VARIATIONS WITH CONTAINER TYPES, TURBIDITY AND CONTAINER FROSTING

Abstract— The spatial distribution of emitted light from liquid phase bioluminescence and chemiluminescent sources in three common types of containers has been evaluated. These sources, while theoretically isotropic, exhibit considerable anisotropy due to reflection and refraction effects at the interfaces between the solution, the container and the surrounding air. This anisotropy represents a considerable systematic error (>25%) in some values of quantum yields reported in the literature. The degree of asymmetry in spatial distribution depends on the solution volume, the refractive index, and the degree of light scattering in the solution. Quantitative evaluation of the projected image of these sources using a video camera system indicates that a major contribution to this asymmetry is due to reflection at the meniscus. Since container frosting removes the variability due to scattering, volume changes, refractive index differences and even, to some extent, use of different types of containers, it is recommended that quantum yields and comparative measurements be determined using frosted containers and point source geometry. The container of choice is a frosted, 1 ± 7.5 cm test tube.     

Aggregation behavior of ionic liquids in aqueous solutions: effect of alkyl chain length, cations, and anions

Self aggregation of the ionic liquids, 1-butyl-3-methylimidazolium chloride [C4mim][Cl], 3-methyl-1-octylimidazolium chloride [C8mim][Cl], 1-butyl-3-methylimidazolium tetrafluoroborate [C4mim][BF4], N-butyl-3-methylpyridinium chloride [C4mpy][Cl], in aqueous solution has been investigated through 1H nuclear magnetic resonance (NMR) and steady-state fluorescence spectroscopy. Aggregation properties were determined by application of mass action theory to the concentration dependence of 1H NMR chemical shifts. Aggregation properties showed fairly good agreement with the previously reported results obtained from small angle neutron scattering, conductivity, and surface tension measurements. A detailed analysis of chemical shifts of water and various protons in ILs has been employed to probe the aggregate structure. Fluorescence spectroscopy provided important information about the critical aggregation concentration (cac) and the microenvironment of the aggregates. We could also observe a break point quite consistent with that of 1H NMR and fluorescence spectroscopy at cac from the concentration dependence of refractive index measurements. Standard free energies of aggregation DeltaGom of various ILs derived using the refractive index/concentration profiles were found comparable to those of classical ionic surfactants.     

Birefringence of native cellulosic fibers. Part II. Spiral structure of cotton

Interferometric studies have been made on cotton fibers as well as on twisted nylon filaments. The results so obtained provide strong evidence that the fibrils in the cotton fiber become less inclined to the fiber axis as one proceeds from the surface to the core. Also, studies on twisted nylon filaments by the fiber refractometer and Becke line techniques indicate that the latter, as practiced in this laboratory, does give values of refractive index which are heavily weighted towards the fiber periphery.     

Broadband Unidirectional Forward Scattering with High Refractive Index Nanostructures: Application in Solar Cells

High refractive index dielectric (HRID) nanoparticles are a clear alternative to metals in nanophotonic applications due to their low losses and directional scattering properties. It has been demonstrated that HRID dimers are more efficient scattering units than single nanoparticles in redirecting the incident radiation towards the forward direction. This effect was recently reported and is known as the “near zero-backward” scattering condition, attained when nanoparticles forming dimers strongly interact with each other. Here, we analyzed the electromagnetic response of HRID isolated nanoparticles and aggregates when deposited on monolayer and graded-index multilayer dielectric substrates. In particular, we studied the fraction of radiation that is scattered towards a substrate with known optical properties when the nanoparticles are located on its surface. We demonstrated that HRID dimers can increase the radiation emitted towards the substrate compared to that of isolated nanoparticles. However, this effect was only present for low values of the substrate refractive index. With the aim of observing the same effect for silicon substrates, we show that it is necessary to use a multilayer antireflection coating. We conclude that dimers of HRID nanoparticles on a graded-index multilayer substrate can increase the radiation scattered into a silicon photovoltaic wafer. The results in this work can be applied to the design of novel solar cells.