


Vol 79, No 1 (2017)
- Year: 2017
- Articles: 21
- URL: https://journal-vniispk.ru/1061-933X/issue/view/12547
Article
The effect of a lipophilic drug, felodipine, on the formation of nanoemulsions upon phase inversion induced by temperature variation
Abstract
The correlation between a dispersed phase/dispersion medium interfacial tension σ at a storage temperature of 22°C and the dispersity and stability of oil-in-water miniemulsions, which result from temperature-induced phase inversion, has been revealed for hydrocarbon/polyoxyethylene(4)lauryl ether/water systems (in the presence and absence of felodipine) with the help of conductometry, tensiometry, and dispersion analysis. At σ < 3.5 × 10–6 N/m, oil-in-water nanoemulsions, which have narrow monomodal particle size distributions and are stable for a month, are a fortiori formed. Felodipine has been shown to serve as a cosurfactant, which is incorporated into the adsorption layer of a basic stabilizing nonionic surfactant. Therewith, σ values increase and the temperature of phase inversion decreases, while the concentration of the basic surfactant in an optimal composition must be substantially reduced. A heptane/water nanoemulsion (droplet size of 75 nm) stabilized with a basic nonionic surfactant and Tween 80 exhibits a high solubilization capacity with respect to felodipine and ensures its efficient mass transfer through a model membrane.



The size dependence of thermal EMF for Au, Pd, and Pt nanoclusters deposited onto highly oriented pyrolitic graphite surface
Abstract
Data are presented on the tunnel current-voltage characteristics of gold, palladium, and platinum nanoclusters formed by pulsed laser deposition on the surface of highly oriented pyrolytic graphite. Differential tunnel current-voltage characteristics measured by scanning tunnel spectroscopy have been used to restore the size dependences of the thermal emf values of the studied nanoclusters. The behavior of the thermal emf of the nanoclusters as depending on their sizes has been found to depend on the nature of a metal. The data obtained have been analyzed.



Template synthesis of mesoporous silicas with the use of nanocrystalline cellulose
Abstract
The porous structure of silica samples prepared via sol–gel synthesis with the use of nanocrystalline cellulose particles as a template has been studied by low-temperature nitrogen adsorption. The influence of the concentration of a nanocrystalline cellulose dispersion, template content in the nanocrystalline cellulose/SiO2 composite, and the conditions of the sol–gel synthesis on the porous structure of silica has been investigated.



Surface tension of water droplets upon homogeneous droplet nucleation in water vapor
Abstract
A method has been proposed for determining interfacial free energy from the data of molecular dynamics simulation. The method is based on the thermodynamic integration procedure and is distinguished by applicability to both planar interfaces and those characterized by a high curvature. The workability of the method has been demonstrated by the example of determining the surface tension for critical nuclei of water droplets upon condensation of water vapor. The calculation has been performed at temperatures of 273–373 K and a pressure of 1 atm, thus making it possible to determine the temperature dependence of the surface tension for water droplets and compare the results obtained with experimental data and the simulation results for a “planar” vapor–liquid interface.



The use of the finite element method for calculating the thermophoresis velocity of large aerosol particles
Abstract
The finite element method has been employed to calculate the thermophoresis velocity of solid aerosol particles, the sizes of which are much larger than the mean free path of molecules in a gas. The thermophoretic velocities of axially symmetric particles moving along their rotation axes have been numerically calculated. Cylindrical particles, particles having a shape resulting from rhomb rotation around one of its diagonals, and spheroidal particles have been considered. The data obtained for spheroidal particles have been compared with the available results of analytical calculations.



Metal nanoparticles on polymer surfaces. 7. The growth kinetics of gold nanoparticles embedded into surface layers of glassy polymers
Abstract
It has been shown that citrate gold nanoparticles can be embedded (partly immersed) into the surface layers of different glassy polymers with subsequent seeded growth of the particles in an aqueous chloroauric acid–hydroxylamine mixed solution. Quantitative data have been obtained on the seeded growth kinetics, and it has been shown that its rate-limiting stage is the diffusion of metal ions from the bulk solution to the surface of gold nanoparticles.



On variations in size distributions of particles and aggregates upon dilution of magnetic fluids
Abstract
Variations in size distributions of particles and aggregates upon dilution of kerosene-based magnetic fluids have been studied by dynamic light scattering. The data obtained on samples of magnetic fluids produced by three different manufacturers have shown that the dilution of an initial concentrated magnetic fluid leads to the formation of a system of unstable aggregates with sizes ranging from 70−100 nm to 1 μm. The aggregates peptize for 2−4 days to result in the establishment of stationary particle and aggregate size distributions.



Nucleation of silica Stöber particles in the presence of methacryloxypropyltrimethoxysilane
Abstract
The effect of 3-methacryloxypropyltrimethoxysilane (MPTMOS) on the nucleation of silica particles synthesized in a water−ethanol−ammonia−tetraethoxysilane (TEOS) mixture by the Stöber−Fink−Bohn method has been studied. It has been shown, using atomic force microscopy, that, as the content of MPTMOS in a TEOS + MPTMOS precursor mixture is increased from 0 to 12.5 mol %, the final silica particle size decreases from 470 to 10 nm, because the number of nucleation centers increases by several orders of magnitude. In contrast to TEOS, hydrolysis of MPTMOS yields a smaller amount of deprotonated orthosilicic acid monomers, the condensation of which is hindered by electrostatic repulsion. The polycondensation of electrically neutral products of MPTMOS hydrolysis gives rise to a larger number of nucleation centers in the reaction mixture.



Electrohydrodynamic generation of monodisperse submicron aerosols
Abstract
Generation of aerosols by electrostatic spraying of liquids from the tip of a needle placed into a capillary has been studied at a voltage lower than that corresponding to the corona ignition in the regime of the formation of single monodisperse droplets. The peculiarities of the jet-type motion of low-volatile liquid droplets with submicron sizes have been considered.



Molecular dynamics study of micellization thermodynamics in AOT/hexane system
Abstract
The thermodynamics of reverse micelle formation from an ionic surfactant, sodium bis(2-ethylhexyl) sulfosuccinate (Aerosol OT, AOT), in hexane is studied by molecular dynamics simulation. A change in the Gibbs free energy upon the addition of one AOT molecule to a reverse micelle is calculated as depending on aggregation number N by the thermodynamic integration method. This dependence has a minimum at N ≈ 20 and maximum at N ≈ 35 and predetermines the monotonically decreasing character of the standard chemical potential of AOT in a micelle with the increase of the aggregation number. The simulation results predict the formation of reverse AOT micelles with an average aggregation number of ≈30, which is in good agreement with experimental data.



Why do we “feel” atoms in nano-scale friction?
Abstract
Atomic stick-slip patterns are readily observed in experiments. The traditional description of atomic-scale friction in terms of mechanical stick-slip instabilities (the Prandtl−Tomlinson model) appears so successful, that it obscures the actual mechanisms of energy dissipation. Here, we show that the conventional model fails completely, because it can only explain the atomic resolution of surface force maps at a level of dissipative forces that is many orders of magnitude higher than what we should expect for the slipping nano-contact. We demonstrate that we can “feel” atoms in nano-scale friction only because there is always a tiny mass that rapidly slips between atomic positions, well before the rest of the moving body follows.



The effect of the synthesis conditions of aluminum-modified nanosized titanium dioxide on the efficiency of its use in electrorheological dispersions
Abstract
A comparative study of the physicochemical properties of nanodispersed TiO2 samples synthesized from TiCl4 by the sol–gel and coprecipitation methods has shown the advantages of the former from the points of view of both the specific surface area and electrorheological response of the obtained filler in 5% electrorheological dispersions. A correlation has been revealed between the temperature of TiO2 treatment (600–800°C) and its structure, phase state and electrorheological response. The maximum shear stress increment has been observed for dispersions of TiO2 samples that contain 7–10 mol % Al and have been thermotreated at 700°C for 3.0–3.5 h.



A study of cryostructuring of polymer systems. 43. Characteristics of microstructure of chitosan-containing complex and composite poly(vinyl alcohol) cryogels
Abstract
The microstructure of complex and composite poly(vinyl alcohol) (PVA) cryogels containing water-soluble chitosan hydrochloride (ChHC) of dispersed particles of water-insoluble chitosan base (Ch), respectively, has been studied by optical microscopy and attenuated total reflection FTIR spectroscopy. The macroporous morphology of cryogels has been studied using preparations in the form of thin (~10 μm) sections and discs 1 mm thick. The introduction of non-gelling additives (NaCl and ChHC) into an initial PVA solution causes significant changes in the size and shapes of macropores in the complex cryogels formed by freezing–defrosting, as compared with the pores in the samples obtained under the same conditions without additives. The reasons for the changes are the process of phase segregation and the influence of low- and high-molecular-weight electrolytes on crystallization of ice, which plays the role of a porogen upon cryotropic gelation of aqueous PVA solutions. As a result of an alkaline treatment of the complex cryogels, which transforms ChHC into Ch, microcoagulation of chitosan yields discrete, almost spherical, particles with sizes of about 1–5 μm. IR spectral studies have shown that concentration gradients of the gelling and nongelling polymers arise along the thickness of the gel discs, with PVA concentration prevailing near the lower surface and ChHC or Ch concentration dominating near the upper surface of the disc.



Preparation and characterization of water-in-oil decane/AOT microemulsions containing silver and gold nanoparticles and large amounts of water
Abstract
Stable microemulsions with water contents as high as 10 vol % have been obtained, including those additionally containing silver and gold nanoparticles. Especial attention has been focused on the influence of water and stabilizer contents on the structure of adsorption layers on nanoparticles. The properties of nanoparticles obtained via the traditional microemulsion synthesis have been compared with the properties of nanoparticles that have preliminarily been concentrated with the help of electrophoresis and dried. The electrophoretic concentration and drying of nanoparticles have been shown to improve the stability of their microemulsions. Microemulsions with the highest content of water have been studied to determine the occurrence of percolation and the influence of nanoparticles on their percolation temperature and electrical conductivity.



Gas mixture flow in nanoporous media in the presence of surface forces. The dusty-gas model
Abstract
The dusty-gas model has been generalized to the case of gas mixture flow in nanoporous media under the conditions of the action of surface forces. A basic set of transport equations has been derived proceeding from kinetic equations for a gas mixture and dust particles. To take into account the surface forces, the interaction between a gas and dust particles has been represented as a sum of a long-range potential, which reflects the surface forces, and a short-range potential, which describes gas molecule scattering on the surface of pore walls. The contribution of the long-range component has been taken into account in the self-consistent approximation, while the short-range component has been considered in the standard manner. The surface forces have been shown to have a substantial effect on the transfer of mixed gases through porous bodies; in particular, it becomes possible to separate mixture components due to different potentials of the interaction of their molecules with pore surface.



Effect of alkylpyridinium chlorides on aggregation stability of aqueous dispersions of detonation nanodiamonds
Abstract
Adsorption of decyl-, dodecyl-, and hexadecylpyridinium chlorides (DePC, DoPC, and CPC, respectively) from aqueous solutions on the surface of detonation nanodiamonds (NDs) and its effect on the aggregation stability of ND hydrosols are studied. Hydrophobic interactions, which are enhanced with the length of hydrocarbon chains in surfactant molecules, are found to play the main role in surfactant adsorption on the ND surface. DePC is almost not adsorbed on NDs, and its addition has no effect on both the size and ζ potential of nanoparticles. Adsorption of DoPC decreases the ζ potential of ND particles, thus causing their coagulation. Superequivalent adsorption of CPC results in sign reversal of the ζ potential of ND particles, thereby leading to alternation of the zones of aggregation stability and coagulation of the hydrosols with a rise in the concentration of this surfactant.



Synthesis of Au nanoparticles with Bi adlayers using glucose as dispersant
Abstract
Well-dispersed Au/Bi nanoparticles with average size below 10 nm were prepared by using NaBH4 to reduce HAuCl4 with glucose as dispersant. The obtained Au/Bi NPs were well characterized by UV-Vis spectra, scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy and electrochemical measurements. The electrochemical study found that Bi adlayers on the surface of Au nanoparticles owns two kinds of surface structures, including a low coverage (2 × 2)-Bi adlayer and a close-packed (p × √3)-2 Bi adlayer due to the strong interaction between the two Bi layers and the below Au atoms, which is same with that bulk on Au surface.



Mathematical simulation of atomic hydrogen diffusion transfer through a multilayer metal membrane at finite pressures
Abstract
Diffusion transfer of atomic hydrogen through multilayer metal membranes has been studied within the lattice model of an ideal gas, with the transfer being described by a set of nonlinear algebraic equations. It has been shown that, for multilayer membranes composed of less than four layers, an analytical expression describing a diffusion flux can be derived. Atomic hydrogen transfer through a membrane consisting of a vanadium layer, the surfaces of which are coated with palladium films, has been analyzed in detail. It has been found that the value of the flux may depend on the transfer direction. The effect of diffusion asymmetry arises at finite pressures of hydrogen on the outer membrane surfaces, when its dissolution in metals is described by nonlinear sorption isotherms. The degree of the diffusion asymmetry increases with a rise in hydrogen pressure and depends on the arrangement of the layers composing a membrane.



Methane adsorption on microporous carbon adsorbent with wide pore size distribution
Abstract
Methane adsorption on a microporous carbon adsorbent with a bimodal pore size distribution is studied at temperatures of 303–333 K at pressures up to 30 MPa. The total micropore volume of the adsorbent, as determined by the Dubinin method, is as large as 1.02 cm3/g. Maximum values of methane adsorption of ≈18 mmol/g are attained at a temperature of 303 K and a pressure of 30 MPa. Methane adsorption isosteres are plotted based on experimental data, and adsorption equilibria at low temperatures are calculated using the linearity of the plots. Experimental isotherms of methane adsorption are compared with the isotherms calculated by the Dubinin–Nikolaev equation with variations in parameters E and n. Temperature dependences of these parameters are determined. Specific characteristics of methane adsorption accumulation are calculated.



Structural and dynamic features of water and amorphous ice
Abstract
Structural properties and microscopic dynamics of water and amorphous ice have been studied by the molecular dynamics method. It has been found that the distribution function of the tetrahedricity parameter exhibits two ranges, which correspond to local molecular formations with low and high degrees of tetrahedricity. The number of molecular clusters with a high degree of tetrahedricity grows as temperature decreases. It has been shown that the vibrational density of states comprises two vibrational modes. A low-frequency vibrational mode strongly depends on pressure and is almost independent of temperature, while a high-frequency mode is relevant to the pressure-independent heat motion of molecules. The geometric criterion of hydrogen bonds has been used to evaluate their continuous lifetime as depending on temperature for molecules with different coordination values. The average lifetime of a hydrogen bond substantially depends on the coordination of molecules, with the temperature dependence of the coordination obeying the activation dynamics.



Effect of magnetic field on the hydrodynamic permeability of a membrane built up by porous spherical particles
Abstract
In this paper, an analysis of steady, axi-symmetric Stokes flow of an electrically conducting viscous incompressible fluid through spherical particle covered by porous shell in presence of uniform magnetic field is presented. To model flow through the swarm of spherical particles, cell model technique has been used, i.e. porous spherical shell is assumed to be confined within a hypothetical cell of the same geometry. At the fluid-porous interface, the stress jump boundary condition for tangential stresses along with continuity of normal stress and velocity components are used. Four known boundary conditions on the hypothetical surface were considered and compared: Happel’s, Kuwabara’s, Kvashnin’s and Cunningham’s (Mehta−Morse’s) condition. The effect of stress jump coefficient, Hartmann number, and dimensionless permeability of the porous region as well as particle volume fraction on the hydrodynamic permeability and streamlines were discussed. The patterns of streamlines were also obtained.


