Rheological properties and the mechanism of a viscous flow of aqueous pectin solutions

The rheological properties and mechanisms of a viscous flow of diluted apple pectin solutions are investigated. It is found that the rise in solution viscosity upon an increase in concentration and a drop in temperature is, along with the corresponding degree to which the interaction between pectin molecules and solvent is reduced, associated with the processes of structuring. The entropy of a viscous flow of pectin solutions is found to be positive: it grows with a rise in concentration is virtually temperature independent. It is established that the entropy factor makes the main contribution to the free energy value of a viscous flow.     

On a mechanism of low-pressure insertion of chain molecules into crystalline matrices

A microscopic mechanism of low-pressure insertion and separation of chain-like molecules in host matrices is proposed. It is shown that the intramolecular correlations combined to appropriate host activities are responsible for a low-pressure condensation of chain molecules. This allows to recover a fine structure of the isotherms and to explain recent experiments on the insertion of C(2)H(2) and CO(2) guest species into metal-organic microporous materials. We argue that the mechanism should be dominant in low-dimensional host geometries, where the effects related to the chain conformations or reorientations are strongly suppressed and the major factors are the chain connectivity and the segment packing.     

On the theory of capillarity of three-phase disperse systems

The distribution of a liquid over the height of a vertical column (with the lower part immersed in a wetting liquid) of close-packed solid spherical particles is studied. For such a system, the equilibrium distribution of the liquid in the three-phase region with a high expansion ratio is shown to be described by the same formulas as for a two-phase disperse system (high-expansion monodisperse foam), but the radius of spherical particles is used in the three-phase case instead of the radius of polyhedral foam cells of equivalent volume. Linear, surface, and bulk capillary forces acting in model three-phase systems with liquid “collars” between close-packed spherical particles are considered. Specific forces of capillary adhesion are shown to be independent of the specific volume of the liquid if it is small enough, but they increase with decreasing size of the particles. In the two-dimensional case with hexagonal packing of particles, these forces are also independent of the particle size. Original Russian Text ? V.V. Krotov, 2006, published in Kolloidnyi Zhurnal, 2006, Vol. 68, No. 2, pp. 214–218.     

Nonequilibrium modeling of low-pressure argon plasma jets; Part I: Laminar flow

This paper presents a modeling attempt related to low-pressure plasma spraying processes which find increasing applications for materials processing. After a review of the various models for ionization and recombination processes, a two-temperature model for argon plasmas in chemical (ionization) nonequilibrium is established using finite rate chemistry. Results of sample calculations manifest departures from kinetic as well as chemical equilibrium, demonstrating that the conventional models based on the LTE (local thermodynamic equilibrium) assumption cannot provide proper prediction for low-pressure plasma jets.     

Nonequilibrium modeling of low-pressure argon plasma jets; Part II: Turbulent flow

The nonequilibrium behavior of low-pressure, turbulent plasma jets has been tested using the k- turbulence model and the model described in the previous paper. It also has been shown that nonequilibrium effects cannot be excluded in the case of turbulent jets.     

A mechanism for the electron beam lithography of solvent-soluble photosensitive polyimides

Solvent-soluble and intrinsically photosensitive polyimides were prepared, and their electron beam reaction was investigated. Negative tone patterns were formed by the electron beam irradiation of PI(BTDA/DEDPM) and PI(BEDA/DEDPM). The mechanism for the pattern formation of PI(BTDA/DEDPM) was determined from transient absorption measurements, changes in the molecular weights, and IR spectrum measurements to be crosslinking via hydrogen abstraction by the triplet excited state benzophenone moiety. For the case of PI(BEDA/DEDPM), the pattern was formed by insolubilization due to chemical change in the polymer. These reactions are found to be so inhomogeneous that insolubilization of the polymer occurs at an early stage of gelation.     

Wetting in hydrophobic nanochannels: a challenge of classical capillarity

We report an investigation of the water-hydrophobic interface in well-defined nanochannels (R approximately 2-4 nm). Wetting in these systems cannot be described by classical (macroscopic) capillary theory: (1) water occupies only a fraction ( approximately 60%) of the pore volume, and (2) the capillary pressures are approximately 60-90% greater than predicted by the Laplace equation. The results suggest the presence of approximately 0.6 nm layer of low-density fluid (vapor) separating water from the hydrophobic solid.     

Extended version of the van der Waals capillarity theory

An extended version of the van der Waals capillarity theory describing the liquid-vapor interface in the temperature range from the triple to the critical point is suggested. A model functional of thermodynamic potential for a two-phase Lennard-Jones system taking into account the effect of the highest degree terms of gradient expansion has been constructed. The identity of the thermodynamic and the mechanical definition of Tolman's length has been proved in the framework of the adopted form of functional. The properties of nuclei of the liquid and the vapor phase are described. The paper determines: the work of formation of a nucleus, density profiles, size dependences of the surface tension, and the parameter delta in the Gibbs-Tolman-Koenig-Buff equation.     

The influence of flow rate and pressure on the excitation conditions in low-pressure microwave induced plasmas

Using a double probe technique, electron temperatures and electron concentrations together with spectral line intensities have been measured in low-pressure microwave induced plasmas at various pressures and flow rates of monoatomic and polyatomic support gases. For two distinct pressures viz. 0.2 and 1.0 torr (0.267–1.333 mbar) the flow rate has been independently varied.

Measurements of spectral-line intensities in the absence and presence of the probes demonstrate that the probes exert little or no influence upon the plasma conditions. The results show that when low-pressure microwave induced plasmas in flow systems are applied for quantitative analytical purposes exact specification of both flow rate and pressure of the carrier gas is required.     

Thermodynamic activation parameters for viscous flow of aqueous solutions of butylamines

The thermodynamic activation parameters, enthalpies, ΔH?^≠, free energies, ΔG ^≠, and entropies, ΔS?^≠, for viscous flow of the systems, water (W)?+?n-butylamine (NBA), W?+?sec-butylamine (SBA) and W?+?tert-butylamine (TBA), have been determined by using the density and the viscosity data. These properties and their excess values have been represented graphically against their composition. With respect to the composition, ΔG ^≠ show a typical behaviour for all the systems – a fast rise in the water-rich region with a maximum followed by the values that decline up to the pure state of amines. The ΔH?^≠ and ΔS?^≠ versus composition curves follow the similar trend. For all systems the excess properties, ΔG ^≠E, ΔH ^?≠E and ΔS?^≠E are characterized by sharp maxima in the water-rich region, which are thought to be mainly due to the hydrophobic hydration and the hydrophilic effect.