Preparation and mechanical properties of thermal energy storage microcapsules

A series of heat energy storage microcapsules was prepared using melamine-formaldehyde resin as the shell material and the mechanical properties of the shell were investigated. A phase change material whose melting point was 24 °C was used as core and the quantity of heat involved in phase transition was 225.5 J/g. Average diameter of the microcapsules varied from 5 to 10 μm, and the globular surface was smooth and compact. The mechanical properties of the shell were evaluated by observing the surface morphological structure change after application of pressure by means of scanning electron microscopy. When the mass ratio of the core and shell material is 3:1, a yield point of about 1.1×10⁵ Pa was found and when the compression was increased beyond this point the microcapsules showed plastic behavior. This has been attributed to the cross-link density and to the high degree of reaction of the shell material. Different yield points subsequently reflected differences in the mechanical behavior. It was also found that the mechanical intensity of double-shell microcapsules was better than that of single shelled ones.     

Inclusion complexes of trivalent lutetium cations with an acidic derivative of per(3,6-anhydro)-alpha-cyclodextrin

The cyclodextrin derivative (hexakis (2-O-carboxymethyl-3,6-anhydro)-alpha-cyclodextrin) forms mono- and bimetallic complexes with lutetium(III) in aqueous solution; the X-ray structure of the binuclear complex [Lu2(ACX)(H2O)2] is the first example of a lanthanide-cyclodextrin inclusion complex.     

Spectrum analysis of U-doped LaBr3 single crystals. Part 1: crystal-field analysis

Single crystals of U³⁺:LaBr₃ were grown by the Bridgman-Stockbarger technique. High-resolution polarized absorption spectra of the crystals were recorded at 4.2 K in the 4000-50,000 cm⁻¹ range. Sixty-four experimental crystal-field energy levels of the U³⁺ ion were fitted to a semiempirical Hamiltonian employing free-ion, one-electron crystal-field as well as two-particle correlation crystal-field (CCF) operators with an r.m.s. deviation of 28 cm⁻¹. The performed analysis of the spectra enabled the determination of crystal-field parameters and assignment of the observed 5f³→5f³ transitions. The effects of selected CCF operators on the splitting of some specific U³⁺ multiplets have been investigated and the obtained values of Hamiltonian parameters are discussed and compared with those reported in previous analyses.     

Role of OH-stretch/torsion coupling and quantum yield effects in the first OH overtone spectrum of cis-cis HOONO

A joint theoretical and experimental investigation is undertaken to study the effects of OH-stretch/HOON torsion coupling and of quantum yield on the previously reported first overtone action spectrum of cis-cis HOONO (peroxynitrous acid). The minimum energy path along the HOON dihedral angle is computed at the coupled cluster singles and doubles with perturbative triples level with correlation consistent polarized quadruple zeta basis set, at the structure optimized using the triple zeta basis set (CCSD(T)/cc-pVQZ//CCSD(T)/cc-pVTZ). The two-dimensional ab initio potential energy and dipole moment surfaces for cis-cis HOONO are calculated as functions of the HOON torsion and OH bond length about the minimum energy path at the CCSD(T)/cc-pVTZ and QCISD/AUG-cc-pVTZ (QCISD-quadratic configuration interaction with single and double excitation and AUG-augmented with diffuse functions) level of theory/basis, respectively. The OH-stretch vibration depends strongly on the torsional angle, and the torsional potential possesses a broad shelf at approximately 90 degrees , the cis-perp conformation. The calculated electronic energies and dipoles are fit to simple functional forms and absorption spectra in the region of the OH fundamental and first overtone are calculated from these surfaces. While the experimental and calculated spectra of the OH fundamental band are in good agreement, significant differences in the intensity patterns are observed between the calculated absorption spectrum and the measured action spectrum in the 2nu(OH) region. These differences are attributed to the fact that several of the experimentally accessible states do not have sufficient energy to dissociate to OH+NO(2) and therefore are not detectable in an action spectrum. Scaling of the intensities of transitions to these states, assuming D(0)=82.0 kJ/mol, is shown to produce a spectrum that is in good agreement with the measured action spectrum. Based on this agreement, we assign two of the features in the spectrum to Deltan=0 transitions (where n is the HOON torsion quantum number) that are blue shifted relative to the origin band, while the large peak near 7000 cm(-1) is assigned to a series of Deltan=+1 transitions, with predominant contributions from torsionally excited states with substantial cis-perp character. The direct absorption spectrum of cis-cis HOONO (6300-6850 cm(-1)) is recorded by cavity ringdown spectroscopy in a discharge flow cell. A single band of HOONO is observed at 6370 cm(-1) and is assigned as the origin of the first OH overtone of cis-cis HOONO. These results imply that the origin band is suppressed by over an order of magnitude in the action spectrum, due to a reduced quantum yield. The striking differences between absorption and action spectra are correctly predicted by the calculations.     

Novel electroanalytical techniques for pollution analysis

Summary Two new analytical techniques are described. The so-called injection technique operates on evaluating a dynamic concentration signal as a result of following the concentration change in a certain part of a flow-through channel after injecting a sample or reagent at a small volume into the current of an appropriate solution flowing at a constant rate.The second technique, the programmed coulometric titration technique, also uses the flow-through channel principle; that means this novel technique allows the more precise titrimetric way of analysis in flowing solutions. In the case of both techniques potentiometric and voltammetric detectors were involved. Several examples proved the multifold advantages of these techniques for environmental analysis.

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Neue elektroanalytische Verfahren für die Umweltanalyse

Zusammenfassung Zwei neue Methoden werden beschrieben. Die sog. Injektionstechnik wertet ein dynamisches Konzentrationssignal aus, das sich aus der Änderung in einem Durchflußkanal ergibt, wenn Probe oder Reagens in kleinen Volumina in einen konstant fließenden Flüssigstrom injiziert werden. Das zweite Verfahren, die programmierte coulometrische Titration, erlaubt die Anwendung der genaueren titrimetrischen Technik auf fließende Lösungen. Bei beiden Methoden werden potentiometrische und voltammetrische Detektoren verwendet. Mehrere Beispiele zeigen die vielfachen Vorteile dieser Verfahren bei der Anwendung auf die Analyse von Umweltmaterial.

Presented at the 6th Annual Symposium on Recent Advances in the Analytical Chemistry of Pollutants, April 21–23, 1976; Vienna, Austria     

Specific features of liquid-crystalline comb-like polymers with mesogenic groups

The results of structural investigation of the new type of the liquid-crystalline thermotropic methacrylic polymers are discussed. These polymers contain mesogenic groups as models for cholesteric, nematic and smectic types of low-molecular liquid crystals. The groups are attached to the backbone through methylene bridges of various lengths. The polymers of the first group have amorphous structure; the polymers of the second group are characterized by liquid crystalline structure and those of the third group can exist in both crystalline and liquid-crystalline states, manifesting properties of enantiotropic liquid crystals. The temperatures and heats of phase transitions have been determined. It is shown that the ability to realize the liquid-crystalline state of comb-like polymers with mesogenic groups depends on and is determined by the proceess of ordering of these groups.     

Spectrophotometric determination of the protolytic dissociation constants of the new chromogenic reagent "palladiazo"-I Investigations with sodium hydroxide, perchloric acid and different aqueous buffer solutions

The "palladiazo" reagent has been subjected to a detailed spectrophotometric investigation in concentrated perchloric acid, different aqueous buffers and concentrated sodium hydroxide solutions. K(1)-K(10) and (1)-(10) values corresponding to the instability constants of the protolytic equilibria involved and to the molar absorptivities at 540 and 630 run of the different proton complex species of the system have been calculated by a number of analytical and graphical spectrophotometric methods. Special attention has been paid to the study of the complicated phenomena implied by the interaction of the reagent with perchloric acid, which has been shown to give rise to alteration of the initial isomeric composition of the reagent and to the formation of addition and/or oxidation products derived from side-reactions undergone by the reagent with the medium. All the instability constants and molar absorptivities, which have been determined by several methods, are tabulated for comparison.     

Influence de la temperature de polymerisation sur le taux de branchement de divers polybenzofurannes obtenus par amorçage cationique

Several polybenzofuranes, obtained by cationic initiation at various temperatures, have been fractionated by preparative G.P.C. The fractions have been studied by various physical methods, mainly osmometry, light scattering, viscometry and G.P.C. These determinations have been made in benzene and the Mark-Houwink relations have been obtained. From the differences observed between these various relations, the gyration radii and the determination of branching indexes, we have found very numerous branches in the samples obtained at the highest temperatures. These branches very probably result from a Friedel-Crafts attack on benzene rings by the carbocations of growing chains. Quantum chemistry determinations are in agreement with this view.     

Reaction of methyl 4-nitrobenzenesulfonate with Br- in water-formamide tetradecyltrimethylammonium bromide micellar solutions

Summary The reaction methyl 4-nitrobenzenesulfonate + Br^- was studied in water-formamide tetradecyltrimethylammonium bromide micellar solutions. A pseudophase kinetic model was used to quantitatively rationalize the kinetic micellar effects observed     

Density and Sound Velocity Studies of Aqueous Solutions of Tetradecyltrimethylammonium Nitrate at Different Temperatures

The density and ultrasound velocity of aqueous solutions of tetradecyltrimethylammonium nitrate were measured in the temperature range of 15 to 35°C in 5°C intervals. The concentration range covered the premicellar and micellar regimes. By assuming a pseudophase separation model for the micellar system, we applied the densitometric data to estimate the apparent molar volumes and the apparent thermal expansibility coefficients of the surfactant in monomeric and micellar forms. Ultrasound velocity and density data enabled us to estimate the isentropic compressibility of the surfactant in both forms. The results are compared with relevant literature data for alkyltrimethylammonium bromides.