Dynamical properties of water-methanol solutions: Brillouin and depolarized Rayleigh scattering

Summary We have performed Brillouin and depolarized Rayleigh light scattering on water-methanol solutions as a function of methanol molar fraction and temperature. For this system, molecular-dynamics (MD) simulation predicts that a shell of water forms around a methanol molecule, prediction which has been recently confirmed by neutron diffraction experiments. The results obtained by light scattering and presented here confirm previous observations and show, in addition, an increase of the stability in time of the water structure in the shells when temperature decreases and methanol concentration approaches a particular value. Paper presented at the I International Conference on Scaling Concepts and Complex Fluids, Copanello, Italy, July 4–8, 1994.     

Small-angle light scattering in dense microemulsions,transition from droplet to bicontinuous phase

Summary We have performed extensive small-angle light scattering (SALS) measurements on a three-component microemulsion (AOT/decane/water) as a function of the dispersed phase concentration and the temperature. All samples have a water/AOT molar fractionw=40.8. Such a system presents a very complex phase diagram with many structural configurations. With the SALS technique, we have been able to observe all the phase separation lines. In particular we give details on the system structure on the percolation phenomenon and on the bicontinuous phase recently observed. In particular we show that the percolation is driven by a long-scale aggregation between microemulsion droplets. Paper presented at the I International Conference on Scaling Concepts and Complex Fluids, Copanello, Italy, July 4–8, 1994.     

Multiple-scattering suppression in dilute and concentrated colloidal dispersions

Summary We describe the design and operation of an improved two-colour dynamic light scattering (TCDLS) equipment which effectively suppresses multiple scattering and allows the study of the Brownian dynamics of optically turbid samples. The technique operates by cross correlating scattered light of two different colours. With the appropriate scattering geometry, only singly scattered light contributes to the time-dependent part of the measured intensity cross-correlation function thus allowing straightforward interpretation of the data. To test the performance of the instrument we have studied several dilute colloidal suspensions, which, although dilute enough that free diffusion of the particles can be assumed, ranged from quite transparent to distinctly turbid. We have confirmed that the measured cross-correlation functions accurately reflect only single scattering even in the presence of strong multiple scattering. As a first application of the technique, we have performed light scattering measurements on concentrated suspensions of PMMA particles in cis-decalin. Paper presented at the I International Conference on Scaling Concepts and Complex Fluids, Copanello, Italy, July 4–8, 1994.     

Polarized Multiply Scattered LIDAR Signals

In this paper we shall present our stochastic model for the transfer of polarized light. We introduce the polarized phase function which is necessary for the exact determination of the scattering distribution for polarized light. Finally, we compare results of variance reduction Monte Carlo simulations based on that model with measurements taken with the DLR-Microlidar. This LIDAR is designed especially for cloud and fog measurements and has two fields of view with two polarization channels each; see W. Krichbaumer et al. (Opt. Laser Technol. 25 (1993) p. 283).Presented at the 7th International Workshop on Multiple Scattering Lidar/Light Experiments (MUSCLE7), July 21–23 1994, Chiba, Japan.     

Analysis of dynamic light scattering of poly(N-isopropylacrylamide) across the collapse transition

Summary We analyse data from the dynamic light scattering of poly(N-isopropylacrilamide) in water solution as we cross the collapse transition. Experimental data are interpreted by the Gaussian self-consistent Zimm model that takes into account two- and three-body excluded-volume effects, and Oseen hydrodynamic interactions, as well as by the standard cumulant and Contin analyses. By fitting the dynamic structure factor we extract the temperature dependence of the diffusion coefficientD and the first relaxation time τ₁ across the collapse transition for a range of scattering angles. The relaxation time τ₁ possesses a characteristic peak at about 32.4 °C due to slowing of the internal motions of the polymer at the theta-point, and a minimum at 33.4 °C. We interpret this as a combination of collapse closely followed by the growth of critical correlations. At large scattering angles we reach the universalk ³ regime, and observe that this behaviour vanishes at the onset of collapse transition. Paper presented at the I International Conference on Scaling Concepts and Complex Fluids, Copanello, Italy, July 4–8, 1994.     

Density Fluctuations as Precursors of Crystallization in Polyamide 6,6 Using Time-Resolved X-Ray Scattering Techniques

In the present study, attempts are made to throw light on the mechanisms leading to primary nucleation in polymer crystallization. Previous studies in this field are not conclusive. Aiming to investigate the induction period prior to crystallization, time-resolved simultaneous small- and wide-angle X-ray scattering (SAXS and WAXS) measurements have been made in situ for polyamide 6,6, while it was crystallized from the melt. For this polymer, it is confirmed that at a low supercooling (ΔT≈28°C), during the induction period, a well-resolved SAXS pattern appears. The time evolution of this scattering pattern can be described by the kinetics of spinodal decomposition, as previously reported for the glass crystallization of PEKK and TPI. According to this analysis, a value for the most probable scattering vector q of density fluctuations at around 0.43 nm^?1 is found. It corresponds to a characteristic wavelength of 14.7 nm of long-range density fluctuations growing with time.     

In situ multi‐axial loading frame to probe elastomers using X‐ray scattering

An in situ tensile–shear loading device has been designed to study elastomer crystallization using synchrotron X‐ray scattering at the Synchrotron Soleil on the DiffAbs beamline. Elastomer tape specimens of thickness 2 mm can be elongated by up to 500% in the longitudinal direction and sheared by up to 200% in the transverse direction. The device is fully automated and plugged into the TANGO control system of the beamline allowing synchronization between acquisition and loading sequences. Experimental results revealing the evolution of crystallization peaks under load are presented for several tension/shear loading sequences.     

Light scattering by some nematic liquid crystals due to phase transitions

New computer modelling of light scattering and its propagation through liquid crystal has been presented using T-matrix method in the structural phase transition regions. Numerical aspects of light scattering process, which are based on numerically solving Maxwell's equations, were calculated for some nematic liquid crystals. Firstly, we described in detail T-matrix method for computing light scattering from nematic liquid crystals and presented results of benchmark computations for the considered model. We reported results of extensive calculations for polydisperse, randomly oriented rod-like multilayered systems (nematic liquid crystals). Our results are associated with light scattering by ferroelectric and ferroelastic materials.     

Large‐Scale Fluctuation Behavior Prior to the Crystallization of Poly(ethylene terephthalate) Glass: A Small‐Angle Light Scattering Study

The crystallization processes of amorphous, glassy‐state poly(ethylene terephthalate) (PET) at two temperatures, a low temperature near T _g where PET has a slow crystallization speed and a middle temperature (about 55°C above T _g ) where PET crystallization is rapid, were monitored in situ by a time‐resolved small‐angle light scattering (SALS) device. It was found that large‐scale fluctuations happened prior to the crystallization at both temperatures, but the kind of fluctuation had a temperature dependence: at the middle temperature, pure density fluctuation took place during the induction period, whereas at low temperature, both density fluctuation and orientation fluctuation occurred, but the latter was the dominant factor. Analyses of the kinetics of these two kinds of fluctuation processes demonstrated that the spinodal decomposition (SD) type of phase‐separation character was undistinguishable in the SALS scale, while the nucleation‐growth (NG) type of phase behavior could describe the scattering results as well.     

Transport and relaxation properties of isotopomeric hydrogen–helium binary mixtures. I. H2–He mixtures

An extensive comparison has been carried out between calculated and measured bulk properties of H₂–helium mixtures. Detailed comparisons are presented for the interaction second virial coefficient, binary diffusion, mixture shear viscosity and thermal conductivity, rotational relaxation, thermal diffusion field-effects, collision broadening of the depolarized Rayleigh light scattering spectrum, and flow birefringence. Scattering calculations have been carried out for the ab initio potential energy surfaces obtained by Tao (1994, J. chem. Phys., 100, 4947) and Schaefer and Köhler (1985, Physica A, 129, 469). The values for the various bulk gas properties calculated from these two potential surfaces are generally found to lie within or near the experimental uncertainties.     

Kerr effect from fractal aggregates of polystyrene microspheres

Summary We study the slow aggregation of aqueous suspensions of optically isotropic microspheres by means of transient electric birefringence. Aggregating clusters exhibit large Kerr constants, and consequently we provide direct experimental evidence that the clusters do posses form anisotropy. From the birefringence relaxation time we derive information on the average cluster size and on the size distribution, and determine their evolution during the aggregation process. Static and dynamic light scattering data confirm the validity of the transient electric birefringence results. Paper presented at the I International Conference on Scaling Concepts and Complex Fluids, Copanello, Italy, July 4–8, 1994.     

Mucin: Aggregation and colloidal interactions of relevance to some biomedical problems

Summary Mucus is the viscoelastic secretion that lines, most epithelial surfaces forming a protective, lubricating barrier. The viscoelastic properties of mucus arise from mucin, a glycoprotein of molecular weight ranging from 2–10 million. In this paper we address two problems where the aggregation and interactions of mucin with colloidal particles is of physiological relevance. The first deals with gastric mucin and the question of the mechanisms that prevent the stomach from digesting itself. Using dynamic light scattering techniques we show that solutions of gastric mucin aggregate belowpH 4. Very large aggregates with 100-fold slower diffusion constants than the mucin monomer are observed atpH 2. Viscosity measurements indicate that mucin will eventually gel at lowpH, thus acting as a diffusional, barrier and protecting the stomach. The second problem is concerned with the role of mucin in the nucleation of cholesterol crystals which lead to gallstone formation. Using dynamic light scattering we have shown that mucin at relatively low concentrations (4 mg/ml) promotes the fusion of phospholipid + cholesterol vesicles. The time evolution of the fusion process was measured. No changes in the aggregation state of the gallbladder mucin were observed during the fusion process, suggesting that this phenomenon is related to physico-chemical interactions between the polymer (mucin) and the colloidal particle (vesicle). Paper presented at the I International Conference on Scaling Concepts and Complex Fluids, Copanello, Italy, July 4–8, 1994.     

Large supramolecular structures in water-alcohol mixtures evidenced by elastic light scattering

Summary We report the results of different light scattering experiments, both elastic and quasi-elastic, performed as a function of temperature at different concentrations on a water-butoxyethanol (C₄E₁) mixture. The comparison of the obtained data with the results of SANS gives evidence of the amphiphilic character of the alcohol molecules. In particular, we observe such a property gives rise to a well-defined micellarlike structure. At low temperatures (T≤5°C) we find that the mixture exhibits a surprising behaviour, namely very large structures (of the order of 2000 ?) built by an intermicellar aggregation process. In addition when the light scattering data show the presence of such large aggregates, neutron data reveal the persisting presence of micelles of about 20 ?. Such a structural picture agrees with the behaviour of the viscosity data. Due to the relevance of its scientific content, this paper has been given priority by the Journal Direction.     

Scaling in the aggregation behaviour of zinc-free insulin studied by small-angle neutron scattering

Summary The aggregation behaviour of zinc-free insulin has been studied by small-angle neutron scattering as a function of protein concentration,pH, and ionic strength of the solution. The distance distribution functions for the 12 samples have been obtained by indirect Fourier transformation. The weight-averaged molecular mass and thez-averaged radius of gyration were determined. Both quantities vary systematically with the experimental conditions. They increase with decreasingpH and with increasing ionic strength. The radius of gyration scales as a power law of the weight-average mass with the exponent 0.44. A similar scaling is found for a set of oligomers structures based on the crystal structure of zinc-free insulin. The mass distribution between the oligomers was determined by a model based on these oligomers. The results from this model and the Fourier transformations have been compared to an equilibrium model recently introduced by Kadimaet al. The model takes into account the variation of the effective charge of the monomer withpH and ionic strength. The neutron scattering results agree well with the predictions of the model. Paper presented at the I International Conference on Scaling Concepts and Complex Fluids, Copanello, Italy, July 4–8, 1994.     

β-Relaxation in polymethylacrylate studied by light scattering

Summary The relaxation processes of glass-forming polymethylacrylate have been studied in a wide temperature range above the glass transition temperatureT _g by means of light scattering measurements. Experimental spectra give evidence of a self-similar behaviourI(ω) ∝ ω^−(1−a) over a spectral range of 2–3 decades, consistent with the predictions of the mode-coupling theory. Different from the prediction of the theory, the value ofa is strongly temperature dependent. This behaviour has been attributed to the presence of a slow secondary relaxation located in the GHz frequency region, whose strength progressively increases with temperature. Paper presented at the I International Conference on Scaling Concepts and Complex Fluids, Copanello, Italy, July 4–8, 1994.     

Experimental determination of scattering matrices of dust particles at visible wavelengths: The IAA light scattering apparatus

We present a new apparatus for measuring the complete scattering matrix as a function of the scattering angle of dust irregular particles. The design is based on the well-known apparatus located in Amsterdam, The Netherlands. In this improved version we have extended the scattering angle ranging from 3° to 177°. Moreover, the measurements are performed with a tunable argon–krypton laser that emit at a wavelength (λ) of 483, 488, 520, 568, or 647 nm. The apparatus has been developed at the Instituto de Astrofísica de Andalucía (IAA), Granada, Spain. To measure the scattering matrix elements we use a number of different optical components such as polarizers, a quarter-wave plate, and an electro-optic modulator. These components are used to manipulate the polarization state of light. By using eight different combinations for the orientation angles of the optical components, all scattering matrix elements are obtained as functions of the scattering angle. The accuracy of the instrument is tested by comparing the measured scattering matrices of water droplets at 488, 520, and 647 nm with Lorenz–Mie calculations for a distribution of homogeneous water droplets.     

Quasi-Rayleigh light scattering by internal elements of a metamaterial in a light-carrying core of a single-mode optical fiber based on the Veselago effect

At present, single-mode optical fibers composed of metamaterials—so-called “left-handed” optical media—for the far- and mid-IR ranges have already been created. In the near future, left-handed singlemode optical fibers for the visible and near-IR ranges will be created, light-carrying cores of which will be composed by an ordered structure of dielectric elements, the dimensions of which will be much smaller than the light wavelength, while the effective refractive index of the structure will be negative; i.e., the structure will possess the so-called “Veselago effect.” We show that, because the dimensions of these dielectric elements many times exceed the dimensions of molecules of optical media, the elements should strongly scatter light, with this scattering considerably exceeding the Rayleigh (molecular) light scattering that occurs in conventional quartz single-mode optical fibers. We propose to term this phenomenon the quasi-Rayleigh light scattering. Numerical estimates of the quasi-Rayleigh light scattering for left-handed single-mode optical fibers at a light wavelength of λ = 1.55 μm have been made.     

Depolarized light scattering study of equilibrium sedimentation profiles of colloidal dispersions

Summary Equilibrium sedimentation profiles of concentrated suspensions of charged optically anisotropic colloids are accurately determined by performing depolarized light scattering measurements. From the data we derive the osmotic pressure πvs. the particle volume fraction Φ. The π(Φ) values obtained with strongly screened colloids are in excellent agreement with the predicted hard-sphere equation of state. The data suggest that, besides gravitation, there is an additional force acting on the particles, probably due to the build-up of an electrostatic sedimentation potential. Paper presented at the I International Conference on Scaling Concepts and Complex Fluids Copanello, Italy, July 4–8, 1994.     

Modeling of light propagation in turbid medium using Monte Carlo simulation technique

The aim of the current study is to simulate the laser photon through biological tissue during PDT therapy using Monte Carlo simulation technique. The model is coded using MATLAB. Interaction of laser light with turbid medium e.g. human tissue depends on the optical properties of the medium i.e. refractive index n, absorption coefficient μ _a , scattering coefficient μ _s and anisotropy factor g. Laser light transport through tissue is governed by the radiative transport equations based on absorption and scattering. Direct sampling is used for step-size generation before interaction via absorption or scattering with the transmitting medium, for deflection and azimuthal angle (θ and ϕ) when the scattering even occurs. The tissue medium considered is divided into radial, axial and angular grid elements and an infinite narrow beam with normal incidence on the tissue is considered. The laser light absorbance inside the tissue, reflectance at the top boundary of the tissue and transmittance at the bottom are estimated and these quantities are shown varying radially and angularly. Results of reflectance, transmittance and fluence are compared with the already published results to confirm the authenticity of our coding and these results are found to lie at only 3–4% error.     

Coherent transmission and angular structure of light scattering by monolayer films of polymer dispersed liquid crystals with inhomogeneous boundary conditions

We consider monolayer polymer films with oriented droplets of a nematic liquid crystal (LC). Relations for the coherent transmission coefficients of a layer of oriented ellipsoidal droplets and for the intensity of light scattered by monolayers of spherical and spheroidal droplets have been obtained. The amplitude-phase screen model and the interference approximation of the theory of multiple wave scattering have been used. To describe light scattering by an individual ellipsoidal droplet with inhomogeneous surface binding, we have developed an anomalous diffraction approximation. For monolayers of spherical LC droplets, the coherent scattering coefficients and the angular scattering structure have been analyzed. The internal structure of nematic droplets have been calculated by the relaxation method based on the solution of the minimization problem of the free energy volume density. We have studied basic regular features of light scattering by a monolayer with homogeneous and inhomogeneous boundary conditions at the LC-polymer interface. We show that, for films that contain droplets with inhomogeneous boundary conditions of the tangentially normal type, the angular structure of the scattered light is asymmetric with respect to the polar scattering angle.