ON MORPHOLOGY AND MULTIPLE MELTING IN POLYPROPYLENE

A series of polypropylenes, including two modern high crystallinity materials (HCPP) were subjected to a stepwise crystallization procedure as a guide to their properties. The results were complicated by the development of double melting endotherms at the highest crystallization temperature. Both HCPP, when grown at the temperature of 145°C, give a double melting peak, but the proportions of the two peaks varied according to the density of nucleation. By partially melting a specimen between the two peaks, it was possible to assign the higher peak to radial dominant lamellae and the lower peak to mostly tangential subsidiary lamellae filling the space in between. Uniformly cross-hatched lamellae at the center of spherulites melt along with the lower melting population in the outer regions of the spherulites. Even if differences in crystallization temperature are eliminated, the properties of nucleated as opposed to nonnucleated PP may therefore be influenced by differences between the center and periphery of spherulites, with “central” properties much more in evidence in nucleated material. The development of these double endotherms is related to morphological constraint, rather than molecular fractionation. Their form is strongly influenced by cross-hatching, but the phenomenon is still found at 160°C where cross-hatching does not form.     

Pre-exponential factor for non-isothermal crystallization of glassy Se85− x Te15Sb x (0 ≤ x ≤ 10) alloys

We report observations of the Meyer–Neldel rule for the non-isothermal crystallization of glassy Se_{85? x} Te₁₅Sb _x (x =?0, 2, 4, 6, 8, 10) alloys. We found a strong co-relation between the pre-exponential factor K ₀ of the rate constant K(T) for crystallization and the activation energy of crystallization E _c. This indicates the presence of a compensation effect for the non-isothermal crystallization process in this glassy system. The composition dependence of the crystallization temperature T _c and the activation energy for crystallization E _c is discussed.     

Melting temperature and enthalpy variations of phase change materials (PCMs): a differential scanning calorimetry (DSC) analysis

Differential scanning calorimetry (DSC) analysis is a standard thermal analysis technique used to determine the phase transition temperature, enthalpy, heat of fusion, specific heat and activation energy of phase change materials (PCMs). To determine the appropriate heating rate and sample mass, various DSC measurements were carried out using two kinds of PCMs, namely N-octadecane paraffin and calcium chloride hexahydrate. The variations in phase transition temperature, enthalpy, heat of fusion, specific heat and activation energy were observed within applicable heating rates and sample masses. It was found that the phase transition temperature range increased with increasing heating rate and sample mass; while the heat of fusion varied without any established pattern. The specific heat decreased with the increase of heating rate and sample mass. For accuracy purpose, it is recommended that for PCMs with high thermal conductivity (e.g. hydrated salt) the focus will be on heating rate rather than sample mass.     

Study of thermal currents in powder β-spodumene ceramics doped with Cuo, FeO and TiO2

Ternary-phase ceramic system of Li₂O Al₂O₃ 4SiO₂ doped with CuO, FeO and TiO₂ has been prepared and subjected to dc electrical conductivity and thermally stimulated depolarization current (TSDC) measurements as a function of temperature (30-250 °C) and field strength. The electrical conductivity results are explained by assuming both ionic and electronic conduction mechanisms coexist with different contributions over the whole temperature range of experiments. TSDC spectra have been found to be characterized by a broad intense relaxation peak, which can be attributed to an ionic charge polarization. The broad relaxation transitions are apparently a result of the nonuniform nature of this process. Activation energies are calculated for both dc electrical conductivity and TSDC according to Arrhenius equation and initial rise method, respectively.     

Effect of Temperature and Comonomer Content on Thermal Behavior and Crystallization Property of the Propylene–Ethylene Random Copolymers

The effects of ethylene units content and crystallization temperature on the conformations, and the thermal and crystallization behavior were investigated by a combination of Fourier transform infrared (FTIR) spectroscopy, wide angle X-ray diffraction (WAXD), and differential scanning calorimetry (DSC). The characterization of FTIR spectroscopy proves that the longer helical conformation sequences of the propylene–ethylene random (PER) samples decrease, whereas the shorter helical conformation sequences increase with the increase in ethylene units content. The increase of the shorter helical conformation sequences is favorable for the formation of the γ-phase in the crystals. A group of broad endothermic peaks can be seen clearly in the DSC curves of PER copolymers, which may be associated with the melting of mixtures of the α- and γ-forms in the crystals. The melting point, crystallization temperature, and crystallinity degree of the PER copolymers decrease with the increase in ethylene units contents. Three typical melting peaks of the PER copolymers crystallized isothermally between 80°C and 130°C were observed. The two higher melting peaks result from melting of the α- and γ-phase in the crystals, whereas the materials crystallized on quenching give the lowest peak. The WAXD results confirm that the PER copolymers crystallize from the melt, as mixtures of α and γ forms, in a wide temperature range. The critical number ζ_lim of the crystallizable units for the α-form increases with the increase in crystallization temperature for PER copolymers, which is favorable for the formation of the γ phases. The amount of γ-form increases with the increase in crystallization temperature at the expense of its α component, then reaches a maximum value at the crystallization temperature of 115°C, and finally decreases with further increase in the crystallization temperature.     

Solution calorimetry of organic nonelectrolytes as a tool for investigation of intermolecular interactions

The paper is mainly the review and generalization of the previous publications of the authors. It demonstrates that solution calorimetry method gives the opportunities of more detailed understanding of various aspects of intermolecular interactions in solution. We are assured that prerequisite to such an understanding is the successive analysis of various solute–solvent systems from the simplest ones which include alkanes as a solute or as a solvent to the most complex systems with solvent self‐association via hydrogen bonding. Particular findings discussed in this paper are (i) an inconspicuous contribution of electrostatic solute–solvent interaction to the solvation enthalpy and, accordingly, the dominating contribution of dispersion interactions for nonspecifically solvated solutes; (ii) new, very general method for the extraction of specific interaction enthalpy from the enthalpy of solvation; (iii) new method of determination of self‐association enthalpies for the solvents associated via hydrogen bonding; (iv) new method for determination of cooperative hydrogen bonding enthalpies of proton acceptors with associated species of alcohols; (v) the unique method of experimental determination of the hydrophobic effect enthalpy. Copyright © 2007 John Wiley & Sons, Ltd.     

Crystal structure and thermal behavior of two new organic monosulfates NH3(CH2)5NH3SO4 1.5H2O and NH3(CH2)9NH3SO4 H2O

The chemical preparation, the calorimetric studies and the crystal structure are given for two new organic sulfates NH₃(CH₂)₅NH₃SO₄ 1.5H₂O (DAP-S) and NH₃(CH₂)₉NH₃SO₄·H₂O (DAN-S). DAP-S is monoclinic P2₁/n with unit cell dimensions: a=11.9330(2) Å; b=10.9290(2) Å; c=17.5260(2) Å; β=101.873(1)°; V=2236.77(6) Å³; and Z=8. Its atomic arrangement is described as inorganic layers of units and water molecules separated by organic chains. DAN-S is monoclinic P2₁/c with unit cell parameters: a=5.768(2) Å; b=25.890(10) Å; c=11.177(5) Å; β=115.70(4)°; V=1504.0(11) Å³ and Z=4. Its structure exhibits infinite chains, parallel to the [100] direction where the organic cations are interconnected. In both structures a network of strong and weak hydrogen bonds connects the different components in the building of the crystal.     

Thermal stability and reaction properties of passivated Al/CuO nano-thermite

Thermal stability and reaction properties of Al-CuO system, a mixture of 50-200 nm aluminum nanoparticles passivated by nitrocellulose and 12 nm copper (II) oxide, were investigated with microstructure characterization, differential thermal analysis (DTA), and thermogravimetric analysis (TGA). Transmission electron microscopy observation confirmed that the passivation coating successfully hinders the oxidization. TGA revealed that the passivation shell does not influence the ignition temperature of the thermite reaction. Reaction chemistry of the nano-thermite was elucidated by heating the composite both in inert ambient and vacuum. It was found that the thermite reaction composes of three continuing steps: At 570 °C, Al is oxidized into Al₂O₃ by reacting with CuO, which forms Cu₂O and produces a significant amount of heat. Subsequently two endothermic reactions occur. Starting at 800 °C, alumina reacts with Cu₂O and forms CuAlO₂. Above this temperature CuAlO₂ will decompose and eventually produce alumina, Cu, and O₂ at 1000 °C. Since the nano-thermite reaction pathway differs greatly from bulk thermite reactions, these results are important to develop a nano-thermite platform that can be used for a novel low cost, low temperature, and copper based microjoining and advance IC packaging.     

Phase diagram of aqueous solution at high pressure and low temperature

Abstract

This paper presents a constant mass high pressure isothermal calorimeter and describes the range of applications that this type of equipment can deal with. As an example, the thermophysical properties of an aqueous solution of MgSO₄ at low temperature and at high pressure have been investigated. The main results showed that the phase change heat of the solution decreased with increasing pressure and the phase change temperature of the eutectic concentration was depressed under high pressure. Those changes could be related to the MgSO₄ solubility and to water latent heat changes.     

Simple model for blistering mechanism

A simple model for blistering mechanism is proposed for energies higher than 20 keV. The model assumes that through the nucleation of smaller bubbles, a critical bubble radius is reached. The planar stress results of Jeffery for a semi-infinite plate with a circular hole subject to a uniform inner normal pressure are roughly taken as valid for the three-dimensional case. Under this assumption, the thickness of the blister's cover and critical ion dose for blister formation are calculated from the knowledge of the mean projected range of ions and blister diameter taken from experimental results. The resulting values are in agreement with the experimental values reported. The model can qualitatively explain breakage at the top of the dome-shaped blisters observed in molybdenum at 1100 K.