Molecular structure and granule morphology of native and heat‐moisture‐treated pinhão starch

Pinhão seed is an unconventional source of starch and the pines grow up in native forests of southern Latin America. In this study, pinhão starch was adjusted at 15, 20 and 25% moisture content and heated to 100, 110 and 120 °C for 1 h. A decrease in λ max (starch/iodine complex) was observed as a result of increase in temperature and moisture content of HMT. The ratio of crystalline to amorphous phase in pinhão starch was determined via Fourier transform infra red by taking 1045/1022 band ratio. A decrease in crystallinity occurred as a result of HMT. Polarised light microscopy indicated a loss of birefringence of starch granules under 120 °C at 25% moisture content. Granule size distribution was further confirmed via scanning electron microscopy which showed the HMT effects. These results increased the understanding on molecular and structural properties of HMT pinhão starch and broadened its food and nonfood industrial applications.     

Analysis of a two-dimensional symmetric problem on extension of an Al-polyimide-Cu layered structure with a model crack

To increase the efficiency of designing systems intended for monitoring surface cracks in aluminum structures during their working life, we have analyzed a two-dimensional symmetric problem on uniaxial extension of an Al-polyimide-Cu layered structure with ideal adhesion between layers and a model crack in the aluminum base. The problem has been first solved for a sample with the crack modeled by a zero-thickness notch using the ANSYS engineering simulation program package. It is shown that this setting of the problem can lead to inadequate results as manifested, in particular, by significantly overstated mechanical stresses in aluminum in the region of crack emergence on the surface. In order to eliminate this difficulty, we propose to use the structure with a model defect in the form of a notch of nonzero thickness in the initial unstressed state of the structure. Recommendations for selecting the thickness of a notch used in the model structure are given.

     

Modeling of diffusional limitations in styrene acrylonitrile random bulk copolymerization

Diffusional limitations (the gel, glass, and cage effects) are manifested in several bulk free radical homopolymerizations as well as in random copolymerizations. These are associated with decreases of several orders of magnitude of the rate constants of termination, propagation, and initiation (the initiator efficiency), respectively. These phenomena have been modeled earlier using the free volume theory for the diffusivities of primary radicals, macro‐radicals, and monomer molecules, and have been applied to homopolymerizations. In this study, a similar model is developed for random bulk copolymerizations. The parameters of the model are fitted using isothermal data on styrene acrylonitrile random copolymerization carried out in small ampoules. Thereafter, best‐fit global correlations have been developed for this system. This enables the model to be used for studying non‐isothermal copolymerizations, as well as for carrying out optimization of industrial reactors, where non‐isothermal conditions are a norm. POLYM. ENG. SCI., 55:2098–2110, 2015. © 2014 Society of Plastics Engineers     

Synthesis and physicochemical characteristics of polymolybdenum(VI) phenylsiloxanes by means of different methods

Interaction of molybdenyl(VI) bis(acetylacetonate) with polyphenylsiloxane in xylene and under mechanochemical activation conditions has been investigated. The interaction in solution proceeds with splitting of the siloxane bond and formation of polymolybdenum(VI) phenylsiloxane with different silicon/metal ratios. The fractions with the silicon/metal ratio < 2 are characterized with high degree of crystallinity and low solubility, whereas those with the ratio > 2 are amorphous. The interaction of the above reagents under mechanical activation conditions proceeds with the formation of soluble polymers similar to those obtained in a solution with the silicon/molybdenum ratio equal to 2.6. The crystal chemistry parameters of the fraction obtained in solution with the ratio Si/Mo equals to 1:2 have been calculated on the basis of the X-ray diffraction analysis data using the Debye–Shearer equation. It has been demonstrated that the chain cross section found using the Miller–Boyer method coincides with that calculated geometrically on the basis of literature data on bond lengths and angles. It is shown that the interaction of molybdenyl(VI) bis(acetylacetonate) with polyphenylsiloxane takes place in solution more deeply than under the conditions of mechanochemical activation and is accompanied by the process of separation siloxanes connection. This leads to the formation of a fraction with smaller ratio of substances than the initial ratio.