Brillouin scattering from polymers and gels

We report results from Brillouin scattering on highly swollen and crosslinked polymeric gels, i.e. methyl methacrylate (MMA) gels crosslinked with ethylene dimethacrylate (EDMA). The study is performed varying the crosslink amount of the gels from 0 to 6%. The Brillouin spectra are measured at different scattering wavevectors in the angular ranges 90°–150°. Ve also measured the spectra at constant wavevector (90°) changing the scattering volume, in particular we select the size and the positions of the sample scattering volume. The wavevector dependence of the measured quantities confirms that in our system a micro—phase separation phenomenon takes place. In particular, for samples with crosslink contents higher than 3%, Brillouin data (studied in terms of the group velocity) give information about the existence of well defined solid- and liquid-like islands (heterogeneities in the gel structure) with an extent of several hundred Angstroms (as confirmed by elastic scattering data). Furthermore, selecting different spatial positions of the scattering volume (of micrometric sizes) and the overall sizes of the same, and performing the measurements at different times, we are able to observe (for the first time with Brillouin scattering) the non–ergodic behavior typical of this system. We report here preliminary results of such a study.     

Low-angle light scattering of ionotropic gels

Low-angle light-scattering patterns were obtained on ionotropic gels formed by the diffusion of Ca⁺⁺ into a polygalacturonate sol. Near the sol–gel boundary, diffraction patterns were obtained which indicated organized structures with repeating units of 1100, 250, and 12.5 μ. Microscopic investigations confirmed that at this gel boundary capillaries run parallel to each other and perpendicular to the direction of diffusion. The diameter of capillaries was 12 μ while their length was in the 1000 μ range. Short interconnecting capillaries were about 200–300 μ in length. Inside the gel, in the more highly crosslinked parts, a disorientation occurs during the aging process with the partial disappearance of capillaries. However, at the gel–sol and gel–semipermeable membrane boundaries, the highly organized structures remain even during prolonged aging. The kinetics of the gel formation was also investigated.     

Comparison between neutron and quasielastic light scattering by polyacrylamide gels

The authors describe small-angle neutron scattering measurements of the screening length ζ in polyacrylamide-water gels. Although these are inhomogeneous systems, the screening length is clearly observable and is in good numerical agreement with the relation E = 3kT/4πζ³, where E is the longitudinal elastic modulus of the gel obtained from measurements of the intensity of qu-asielastically scattered light. Static light scattering observations reveal a larger-scale (ca. 30 nm) superstructure in the gel.     

Laser light scattering study of polyacrylamide gels

Laser light scattering experiments with polyacrylamide gels containing diffusing bovine plasma albumin are described. Complete heterodyne beating has not been assumed, and an account is given of a novel method for finding the degree of spectral broadening by scanning angles of scatter while measuring the temporal autocorrelation function. Results obtained by this method for polyacrylamide gels and un-cross-linked solutions in the absence of diffusing protein, are compared with those of other authors. In the presence of the protein there is a complex interaction between the diffusion coefficient of the protein and the coefficient associated with the diffusing fluctuations in segment density of polyacrylamide. The diffusing protein dominates at low gel concentrations, and the gel density fluctuations dominates at high gel concentrations. It is proposed that the protein preferentially occupies the less dense regions of the gel, so that at low gel concentrations, where it diffuses faster than the gel fluctuations, it tends to cancel them out, whereas at high gel concentrations where the protein is highly impeded by the gel structure, it tends to be carried along by the gel density fluctuations.     

Dynamic and static light scattering by weakly ionized gels and solutions

Dynamic light scattering (DLS) and static light scattering (SLS) experiments have been performed on partially neutralized poly(acrylic acid) and poly(methacrylic acid) solutions and gels. The gels exhibit a non-ergodic behavior, much less marked however than that observed in neutral systems. By combining DLS and SLS, the fluctuating part of the light scattered from PAA gel was separated from the total scattered intensity and found to be almost equal to the intensity scattered by the solution. Also the diffusion coefficient associated with the dynamic fluctuation was found to be the same in the PAA gel and the PAA solution.     

Scattering structure factor of colloidal gels characterized by static light scattering, small-angle light scattering, and small-angle neutron scattering measurements

The scattering structure factor of a colloidal gel in a q range of 5 orders of magnitude has been determined by combining static light scattering, small-angle light scattering, and neutron scattering measurements. It exhibits simultaneously two types of structure information: a mass fractal scaling within the clusters that constitute the gel and a surface fractal scaling for length scales larger than that of the clusters. Such scattering behavior can be well interpreted by the pair-correlation function proposed in the literature to model an ideal structure constituted of mass fractal objects inside surface fractal objects.     

Flocculation mechanism induced by cationic polymers investigated by light scattering

Three cationic polymers with molecular weights and charge densities of 3.0 x 10(5) g/mol and 10%, 1.1 x 10(5) g/mol and 40%, and 1.2 x 10(5) g/mol and 100% were chosen as flocculants to aggregate silica particles (90 nm), under various conditions, including change in polymer dosage, particle concentration, background electrolyte concentration, and shear rate. The size and structure of flocs produced were determined using the static light scattering technique. On the basis of measurements of polymer adsorption and its effect on the zeta potential and floc properties, it has been found that the polymer charge density plays an important role in determining the flocculation mechanism. Polymers with a 10% charge density facilitate bridging, 40% charged polymers bring about either a combination of charge neutralization and bridging or bridging, depending on the polymer dosage, and polymers with the charge density of 100% induce electrostatic patch flocculation mechanism at the optimum polymer dosage and below but bring about bridging mechanism at the polymer dosage approaching the adsorption plateau value. Bridging aggregation can readily be affected by the particle concentration, and an increase in particle concentration results in the formation of larger but looser aggregates, whereas electrostatic patch aggregation is independent of particle concentration. The addition of a background electrolyte aids in bridging aggregation while it is detrimental to electrostatic patch aggregation. It has also been found that the effect of shear rate on the mass fractal dimension depends on polymer charge density.     

Dynamic light scattering by optically anisotropic colloidal particles in polyacrylamide gels

The translational and rotational motions of optically anisotropic spherical particles embedded in cross-linked polyacrylamide gels is studied by dynamic light scattering. The particles are liquid crystal droplets solidified in the nematic phase. The amount of cross linkers is varied to cross the sol-gel transition where the system becomes nonergodic for both translational and rotational diffusion modes of the probes. The translational and rotational dynamic correlation functions are obtained by measuring the intensity correlation function between crossed polarizers in the parallel and perpendicular geometries. Data from nonergodic systems is analyzed using an extension, to include rotations, of the method of Pusey and van Megen [Physica A 157, 705 (1989)]. Both diffusion modes are observed to be arrested as the rigidity of the gel increases.     

The problem of bimodal distributions in dynamic light scattering: Theory and experiment

A new method is proposed for analyzing the results of dynamic light scattering measurements of polymer solutions containing macromolecules with substantially different molecular masses. The processing algorithm makes it possible to correctly allow for effects of the quality of solvent and the conformation and polarizability of macromolecules on the contributions of components of a system to the intensity of scattering. The developed method is tested for a model mixture of two polystyrene samples dissolved in a good solvent (tetrahydrofurane) and a θ solvent (cyclohexane) and is applied to study a system containing a linear polymer and an interpolymer complex.     

Dynamic light scattering by weakly ionized gels: Effects of inhomogeneities and non-ergodicity

Small angle neutron scattering and light scattering experiments have been performed on partially neutralized poly(acrylic acid) solutions and gels. The structure factor obtained from small angle scattering and static light scattering reveals the absence of significant contribution from large scale inhomogeneities in the gels as soon as the ionization degree exceeds 9·10⁻³. The comparison of the time and ensemble averages of the autocorrelation function of scattered light intensity shows that the gels behave with respect to that experiment as ergodic media.     

Dumbbell-shaped polyelectrolyte brushes studied by depolarized dynamic light scattering

We present the synthesis and comprehensive characterization of dumbbell-shaped polyelectrolyte brushes (DPB). The core of these particles consists of poly(methyl methacrylate) (PMMA) and poly(styrene) onto which a dense brush shell of poly(styrene sulfonate) is grafted. The morphology of DPB particles is studied in solution by cryogenic-transmission electron microscopy. We demonstrate that well-defined DPB are generated that react to external stimuli such as surfactant and salt concentration. The rotational diffusion and collective relaxations of the DPB particles were monitored by depolarized dynamic light scattering (DDLS). Here we found a new relaxation mode in the DDLS-signal that can be ascribed to collective fluctuations of the polyelectrolyte layer affixed to the surface of the dumbbells.     

Quasielastic light scattering study of chemically crosslinked gelatin solutions and gels

Quasielastic light scattering measurements are reported for experiments performed on mixtures of gelatin and glutaraldehyde (GA) in the aqueous phase, where the gelatin concentration was fixed at 5 (w/v) and the GA concentration was varied from 1×10⁻⁵ to 1×10⁻³ (w/v). The dynamic structure factor, S(q,t), was deduced from the measured intensity autocorrelation function, g ₂(τ), with appropriate allowance for heterodyning detection in the gel phase. The S(q,t) data could be fitted to S(q,t)=Aexp(−D _f q ² t)+Bexp(−t/τ_c)^β, both in the sol (50 and 60 ^∘C) and gel states (25 and 40 ^∘C). The fast-mode diffusion coefficient, D _f showed almost negligible dependence on the concentration of the crosslinker GA; however, the resultant mesh size, ξ, of the crosslinked network exhibited strong temperature dependence, ξ∼(0.5−χ)^1/5exp(−A/RT) implying shrinkage of the network as the gel phase was approached. The slow-mode relaxation was characterized by the stretched exponential factor exp(−t/τ_c)^β. β was found to be independent of GA concentration but strongly dependent on the temperature as β=β₀+β₁ T+β₂ T ². The slow-mode relaxation time, τ_c, exhibited a maximum GA concentration dependence in the gel phase and at a given temperature we found τ_c(c)=τ₀+τ₁ c+τ₂ c ². Our results agree with the predictions of the Zimm model in the gel case but differ significantly for the sol state. Received: 25 May 1999 /Accepted in revised form: 27 July 1999     

Particle growth of hybrid materials followed by dynamic light scattering

The hydrolysis of distannylated compounds in which the tin atoms are linked by an organic spacer has been studied under microemulsion conditions using dynamic light scattering and infrared spectroscopy. The experiments provided evidence that the growth of hybrid material particles occurs in the aqueous phase, outside the organic phase of the microemulsion. The growth rates of the particles were found to be strongly dependent on the nature of the spacers, a polymethylene chain inducing the fastest process. This different behavior was explained by a slower condensation process rather than a slower hydrolysis. The high surface areas measured for the hybrid materials could be explained by a possible coating of the hybrid particles by surfactant molecules, thus preventing either their growth or their aggregation.     

Theory of light scattering from vesicles

The scattering and depolarization of light from spherical membrane systems, vesicles, is calculated in a new succinct formalism appropriate to spherical systems and the rotations of anisotropic elements composing them. The results of Tinker (1972) and Mishima (1980, 1981) are readily derived within this formalism and there is a considerable saving in numerical computation. The problem of fluctuations in the molecular packing of the component phospholipid molecules is also addressed.     

Three dimensional cross-correlation dynamic light scattering by non-ergodic turbid media

We investigate dynamic light scattering by non-ergodic turbid media with an adapted version of the method proposed by Pusey and van Megen [Physica A 157, 705 (1989)]. Our formulation follows the derivation of the original method by extending it to the three dimensional cross-correlation scheme (3DDLS). The main finding is an expression to obtain the dynamic structure factor from light scattering that takes into account the system turbidity and the peculiarities of the 3D geometry. From 3DDLS measurements in well-controlled solid-like systems of different turbidity, we confirm that our results can be interpreted reasonably well by the theoretical approach described here. Good agreement is found with earlier reported results on similar systems.     

Specifics of light scattering in solutions of fullerene-containing polymers

The molecular mass and hydrodynamic dimensions of molecules of two fullerene-containing polymers which differ in the preparation procedure and the mode of fullerene C₆₀ binding were determined by means of static and dynamic light scattering and transport techniques (diffusion, sedimentation, gel permeation chromatography). It was established that the molecular masses of polymeric C₆₀ derivatives determined by means of static light scattering are substantially above those measured by means of the transport techniques. Using as an example a polystyrene specimen containing 6.2 wt % C₆₀ prepared according to the widespread technique of solvent evaporation from a mutual fullerene and polymer solution, it was shown that the multicomponent nature, the compositional inhomogeneity, and a lack of coincidence in the signs of refractive index increments for structurally different components of fullerene-containing polymers may cause anomalies in the intensity of light scattering by solutions of these compounds.     

Self-diffusion and collective diffusion of charged colloids studied by dynamic light scattering

A microemulsion of decane droplets stabilized by a nonionic surfactant film is progressively charged by substitution of a nonionic surfactant molecule by a cationic surfactant. We check that the microemulsion droplets remain identical within the explored range of volume fraction (0.02-0.18) and of the number of charges per droplet (0-40). We probe the dynamics of these microemulsions by dynamic light scattering. Despite the similar structures of the uncharged and charged microemulsions, the dynamics are very different. In the neutral microemulsion, the fluctuations of polarization relax, as is well-known, via the collective diffusion of the droplets. In the charged microemulsions, two modes of relaxation are observed. The fast one is ascribed classically to the collective diffusion of the charged droplets coupled to the diffusion of the counterions. The slow one has, to our knowledge, not been observed previously neither in similar microemulsions nor in charged spherical colloids. We show that the slow mode is also diffusive and suggest that its possible origin is the relaxation of local charge fluctuations via the local exchange of droplets bearing different numbers of charges. The diffusion coefficient associated with this mode is then the self-diffusion coefficient of the droplets.     

Brillouin light scattering from poly(vinyl chloride) gels

The hypersonic velocity and attenuation in PVC gels have been measured as a function of gel network volume fraction, using the technique of Brillouin light scattering. The experimental data have been analysed using the full theory for the elastodynamics of gels proposed recently by Johnson. It has been found that for two asymptotic approximations of the dynamic damping factor the tortuosity parameter is nearly always less than unity, contrary to the theoretical expectation.