Alexander A. Berlin

Molecular Dynamics Simulation of Thermomechanical Properties of Montmorillonite Crystal. 1. Isolated Clay Nanoplate

The structure and mechanical properties of clay nanoparticles is a subject of growing interest because of their numerous applications in engineering. We present the results of molecular dynamics simulation for a single nanoplate of pyrophyllite - a 2:1 clay mineral consisting of two tetrahedral sheets of SiO4 and an intervening octahedral AlO6 sheet. Simulations were performed in the temperature interval from 5 to 750 K using the ionic-type potentials of Cygan et al. On this basis the temperature dependences of structural parameters, characterizing both tetrahedral and octahedral sheets as well as single lamella, have been studied. Two slightly different structures were observed in this wide temperature interval. The mechanical properties of the nanoplate were calculated from stress-strain diagrams, which have been obtained at relatively slow rates of deformation (for molecular simulations). Using different types of loading, we calculated the full elasticity tensor and estimated the influence of temperature on its components. We estimated also the bending and torsion stiffnesses of the nanoplate as specific characteristics of this type of particle. Because the nanoplate is atomically thin, a reasonable determination of the thickness is a nontrivial problem, both in the modeling of mechanical properties and in physical interpretation of the obtained data. We propose a procedure for its calculation.

Molecular dynamics simulation of thermomechanical properties of montmorillonite crystal. 3. montmorillonite crystals with PEO oligomer intercalates.

We present the results of molecular dynamics (MD) simulation of the structure and thermomechanical behavior of Wyoming-type Na+-montmorillonite (MMT) with poly(ethylene oxide) (PEO) oligomer intercalates. Periodic boundary conditions in all three directions and simulation cells containing two MMT lamellae [Si248Al8][Al112Mg16]O640[OH]128 oriented parallel to the XY-plane were used. The interlamellar space, or gallery, between neighboring MMT lamellae was populated by 24 Na+ counterions and PEO macromolecules of different lengths, ranging from 2 up to 240 repeat units. We considered three different loadings of PEO within the gallery: 80, 160, and 240 repeat units, corresponding to 13, 23, and 31 wt % PEO based on total mass of the nanocomposite, respectively. In the cases of 13 and 23 wt %, the polymer chains formed one or two well-defined amorphous layers with interlayer distances of 1.35 and 1.8 nm, respectively. We have observed also formation of a wider monolayer gallery with interlayer distances of 1.6 nm. Three-layer PEO films formed in the case of 31 wt % loading. The thermal properties were analyzed over the range 300-400 K, and the isothermal linear compressibility, transversal moduli, and shear moduli were calculated at 300 K. These properties are compared with the results of our simulation of thermal and mechanical properties of MMT crystal with galleries filled by one or two water layers as well as with those of an isolated clay nanoplate.

Synthesis of an inorganic-organic polymer blend from orthoboric acid and caprolactam

The possibility of modifying boron polyoxide with an oligomeric amide upon thermal dehydration of orthoboric acid and oligomerization of caprolactam in a common melt is shown. The products obtained after thermal pretreatment of the initial blend containing 30 wt % caprolactam are investigated. It is shown that the main processes at T < 200°C are dehydration of orthoboric acid and hydrolysis of caprolactam with the formation of e-aminocaproic acid. At temperatures of 225–260°C, the predominant process is the formation of boron polyoxide and a caprolactam-based oligomeric product. The data of 11B NMR spectroscopy show that the chemical transformations of caprolactam occur against the background of the N:B donor-acceptor interaction. The two-dimensional [11B-1H] heteronuclear correlation spectrum indicates that the systems obtained upon thermal treatment are solid solutions.

Molecular Simulation of Plastic Deformation of Oligomer Systems

Molecular dynamic simulation of low-temperature uniaxial compression and tension of a glass from 1000 molecules of C13H28 oligomer is carried out. Stress-strain diagrams, an influence of deformation on density of the glass, and connection between local density and atom rearrangements are discussed. The influence of original level of stress on initial rate of stress relaxation are also investigated. The modeling results of mechanical behavior are in good agreement with experimental data for glassy polymers, which allows one to use MD modeling for further in-depth study of glass behavior mechanisms under mechanical actions.

Orientation Effects in Hybrid-Polymer Mixtures

Composites based on melts of boron-oxide oligomer (BOO) and low-density polyethylene (LDPE) in the polyoxide-concentration range of 0–64 vol % were synthesized. The measurements of the thermomechanical and mechanical properties of the composites showed the incompatibility of the mixture components. The abnormal increase in the strength and the Young’s modulus of the LDPE/boron-oxide oligomer mixtures under the tension of molded composite specimens was registered in the range of 25–50 vol % polyoxide. The anomalies were explained as being due to polyoxide-fiber formation and confirmed by the electron-microscopy images. The abnormal changes in the differential pressure in a melt flow and the torque of an extrusion auger were observed in the same polyoxide-concentration range, which was explained by the polyoxide orientation in a melt flow and its planar structure. The chemical structure of boron-oxide oligomer exposed to extrusion mixing and its distribution within a molded specimen of the mixture were analyzed by IR spectroscopy. The opportunity to synthesize hydrolytically stable composites in a wide range of ratios owing to the polyoxide encapsulation in a polyethylene matrix was shown.

The Contribution of the Semenov Institute of Chemical Physics to the Science of Combustion: A Historical Review

The Semenov Institute of Chemical Physics was established in 1931 under the direction of Prof. N. N. Semenov, Nobel Prize Winner in Chemistry (1956). One of the main areas of scientific activity of the institute is the physics and chemistry of combustion, shock waves and detonation. This article is a historical review of the main theoretical and experimental approaches of scientists in the Semenov Institute to the study of combustion phenomena. This school was founded by Academicians N.N. Semenov and Ya. B. Zel’dovich. The self-ignition theory of N.N. Semenov, founded on the laws of heat transfer and heat release, formed the basis of “chemical kinetics” and produced solutions for the safe use of combustible materials. Along with D. Frank-Kamenetskii, he developed the classical theory of thermal explosion, thus integrating chemical kinetics with the theory of mass and energy transfer. The theory of combustion and gas flame propagation that was developed by Academician Ya. B. Zel’dovich, based on the kinetics of high-temperature reactions and heat balance equations, drove the main direction of combustion theory development in gas-phase and condensed systems. We discuss the evolution of these basic ideas in the work of successors, i.e. D. Frank-Kamenetskii, A. F. Belyaev, P. F. Pokhil, K. K. Andreev, K. I. Shchelkin, V. N. Kondrat’ev and others. The theoretical and experimental approaches are still under continuous development and improvement.

Composite material based on fluoroplast and low melting oxyfluoride glass

The present work summarizes the results of studies of the samples fabricated through extrusion blending of mixtures composed of the perfluorocarbon polymer (polyvinylidene fluoride, PVDF), which presently undergoes intensive studies, and the inorganic glass (BF-glass) of the composition 3B2O3-97(40SnF2-30SnO-30P2O5). It is revealed as a result of application of the suggested technique the composite material whose structure depends on the component ratio in the mixture (from individual areas formed by each component to homogeneously distributed composite particles) has been fabricated. The peculiarities of formation of composites were studied on the basis of the results of studying their morphology, molecular structure and phase composition. It was revealed the preservation of the polymer molecular structure and the absence of interaction with the glass in the fabricated samples. We found that in the process of sample fabrication there occur melting of the mixture, mixing of particles and changing of the p...