Liquid–gas critical phenomena under confinement: small-angle neutron scattering studies of CO2 in aerogel

Small angle neutron scattering (SANS) is a well-established technique for investigating the behavior of confined binary liquid solutions, as it can probe the correlation length and susceptibility in pores on length scales 1 – 100 nm. We applied SANS to explore the influence of confinement on critical behavior of an individual fluid carbon dioxide (CO₂) in a highly porous aerogel. The results demonstrate that quenched disorder induced by aerogel significantly depresses density fluctuations. Despite the negligible volume occupied by aerogel (< 4%), the macroscopic phase separation of confined CO₂ into coexisting liquid and gaseous phases is suppressed and below the critical temperature of the bulk fluid frozen methastable microdomains are formed. Experimental data show that critical adsorption is as important as the effect of confinement in defining the behavior of confined fluids.     

X-ray scattering studies of the structure of aqueous hydroxy-propylcellulose solutions

X-ray diffraction studies have been undertaken on aqueous solutions of hydroxy propylcellulose (HPC) over a wide range of the scattering vector Q. The experiments revealed only modest differences in local structure on a distance scale ca. 5–300 Å despite the fact that they covered concentrations generally interpreted as ranging from the isotropic (35.1 wt %) to the anisotropic liquid crystalline (LC) phase (53.5 wt %). Several models were used to interpret the small-angle scattering data, and each gave similar structural parameters and extrapolated intensities ( Q → 0) for both solutions. Peaks were observed with d-spacings ca. 12–17 Å in both materials. Wide-angle x-ray scattering (WAXS) showed slightly increased local order over a size range ca. 5–20 Å for the anisotropic solution, and this is consistent with a greater intensity of the 13 Å peak in this material. It is difficult to reconcile these findings with an interpretation of the LC state involving major differences with the isotropic phase and a high degree of orientational order extending over long length scales.     

An alternative approach to quantum phenomena

This paper outlines the qualitative foundations of a quasiclassical theory in which particles are pictured as spatially extended periodic excitations of a universal background field, interacting with each other via nonlinearity in the equations of motion for that field, and undergoing collapse to a much smaller volume if and when they are detected. The theory is based as far as possible directly on experiment, rather than on the existing quantum mechanical formalism, and it offers simple physical interpretations of such concepts as mass, 4-momentum, interaction, potentials, and quantization; it may lead directly to the standard equations of quantum theory, such as the multiparticle Schrödinger equation, without going through the conventional process of quantizing a classical theory. The theory also provides an alternative framework in which to discuss wave-particle duality and the quantum measurement problem; in particular, it is suggested that the unpredictability of quantum phenomena may arise from deterministic chaos in the behavior of the background field.     

The nonrelativistic Schrödinger equation in “quasi-classical” theory

The author has recently proposed a quasi-classical theory of particles and interactions in which particles are pictured as extended periodic disturbances in a universal field (x, t), interacting with each other via nonlinearity in the equation of motion for . The present paper explores the relationship of this theory to nonrelativistic quantum mechanics; as a first step, it is shown how it is possible to construct from a configuration-space wave function (x ₁,x ₂,t), and that the theory requires that satisfy the two-particle Schrödinger equation in the case where the two particles are well separated from each other. This suggests that the multiparticle Schrödinger equation can be obtained as a direct consequence of the quasi-classical theory without any use of the usual formalism (Hilbert space, quantization rules, etc.) of conventional quantum theory and in particular without using the classical canonical treatment of a system as a crutch theory which has subsequently to be quantized. The quasi-classical theory also suggests the existence of a preferred absolute gauge for the electromagnetic potentials.     

Self-assembly of phosphate fluorosurfactants in carbon dioxide

Anionic phosphodiester surfactants, possessing either two fluorinated chains (F/F) or one hydrocarbon chain and one fluorinated chain (H/F), were synthesized and evaluated for solubility and self-assembly in liquid and supercritical carbon dioxide. Several surfactants, of both F/F and H/F types and having varied counterions, were found to be capable of solubilizing water-in-CO2 (W/C), via the formation of microemulsions, expanding upon the family of phosphate fluorosurfactants already found to stabilize W/C microemulsions. Small-angle neutron scatteringwas used to directly characterize the microemulsion particles at varied temperatures, pressures, and water loadings, revealing behavior consistent with previous results on W/C microemulsions.     

New phosphate fluorosurfactants for carbon dioxide

Anionic phosphate fluorosurfactants were shown to self-assemble into water-in-carbon dioxide microemulsions. The surfactants, having either two fluorinated chains or one fluorinated chain and one hydrocarbon chain, facilitated significant water uptake in CO2. Small angle neutron scattering (SANS) measurements of surfactant/water/CO2 solutions confirmed the presence of nanometer-scale aggregates, indicative of microemulsion formation.     

Elastic antiproton-deutron scattering below 1.0 GeV/c

We present differential cross sections for elastic $\text{p}$d scattering at beam momenta 0.735 and 0.940 GeV/c and momentum transfers in the range 0.04<|t|<0.5(GeV/c)². The $\text{p}$d elastic differential cross section is expressed in terms of a deutron form factor and the I=0 t-channel exchange $\text{N}$N amplitudes, enabling us to isolate the corresponding I=0 t-channel exchange cross sections.     

On the structure and conformation of polymer chains in latex particles. I. Small-angle neutron scattering characterization of polystyrene latexes of small diameter

Polystyrene latexes with 40-60 nm diameter and molecular weights ranging from 6 × 10⁴ to 6 × 10⁶ g/mol were synthesized by a two-step equilibrium swelling method, with deuterated polymer forming either the first or second step. Below about 1 × 10⁶ g/mol, small-angle neutron scattering gave zero-angle scattering intensities much higher than expected on the basis of gel permeation chromatography molecular weights. Several models were examined, the leading model based on a core-shell latex structure. The development of such structure was found to depend on the ratio of the radius of gyration of the polymer chain to that of the diameter of the latex particle, reaching a maximum in the range where the polymer chain dimensions are about half that of the latex particle. For the highest molecular weights, normal scattering intensities were found. These results lead to the finding that the polymer chains were compressed in the latex particles with constraining in the range of one to four, for this molecular weight range.     

Synthesis and characterization of poly(vinylcyclohexane) derivatives

Six nearly monodisperse substituted poly(styrene) homopolymers, poly(styrene) (PS), poly(2-methylstyrene) (P2MS), poly(3-methylstyrene) (P3MS), poly(4-methylstyrene) (P4MS), poly(tertiary-butylstyrene) (PtBS), and poly(α-methylstyrene) (FαMS) were anionically polymerized and subsequently saturated using heterogeneous hydrogenation techniques to poly(vinylcyclohexane) (PVCH), poly(2-methylvinylcyclohexane) (P2MVCH), poly(3-methylvinylcyclohexane) (P3MVCH), poly(4-methylvinylcyclohexane) (P4MVCH), and poly(tertiary-butylvinylcyclohexane) (PtBVCH), respectively. In each case, except PαMS, the materials were saturated to > 99% conversion with no chain degradation. PS hydrogenations required the addition of small amounts of tetrahydrofuran to the reaction solvent cyclohexane to enhance miscibility and eliminate large-scale chain degradation. Density gradient and differential scanning calorimetry (DSC) measurements were used to characterize the density and glass transition temperature, T_g, of the unsaturated and saturated polymers. Saturation reduces the density by 3% to 11% and changes T_g substantially. The greatest variation in T_g is obtained with the 3-methyl substituted species where a 63°C increase is observed, while the highest measured T_g is 186°C for P2MVCH. Small-angle neutron scattering (SANS) experiments on binary mixtures of hydrogenous and deuterium labeled PVCH derivatives provided a determination of bulk chain statistics. The statistical segment length is relatively insensitive to vinylcyclohexane ring substitution, except with P3MVCH where a 20% greater value is obtained. ©1995 John Wiley & Sons, Inc.