Studies of surface properties of Na- and La-montmorillonites

This paper presents possible applications of thermal analysis, sorptometry and porosimetry to study physico-chemical properties of Na- and La-montmorillonite samples, especially for determination of total surface heterogeneity. The quasi-isothermal thermogravimetric (Q-TG) mass loss and its first derivative (Q-DTG) curves with respect to temperature and time obtained during programmed liquid thermodesorption under quasi-isothermal conditions have been used to study adsorbed layers and heterogeneous properties of the Na- and La-montmorillonites. Calculations of the desorption energy distribution functions by analytical procedure using mass loss Q-TG and differential mass loss Q-DTG curves of thermodesorption under quasi-isothermal conditions of polar and non-polar liquid vapours preadsorbed on a material surface are presented. Parameters relating to porosity of samples were determined by sorptometry, mercury porosimetry and atomic force microscopy (AFM). From nitrogen sorption isotherms from sorptometry and porosimetry methods, the fractal dimensions of montmorillonites have been calculated. Moreover, a new approach is proposed to calculate fractal dimensions of materials obtained from Q-TG curve; this is compared with values obtained by the above methods. The total heterogeneous properties (energy distribution function and pore-size distribution functions) of samples studied were estimated. The radius and pore volume of the tested samples calculated on the basis of thermogravimetry, sorptometry and porosimetry techniques were compared and good correlations obtained.     

Exchange interactions in copper(II) complexes with tridentate Schiff bases: EPR and magnetic studies

The influence of the nature of ligands upon the magnetic and EPR properties was investigated for the series of polynuclear Cu(II) complexes with tridentate Schiff bases. A similar tendency of changes in the |J| and D parameters was found for binuclear Cu(II) complexes with ligands derived from condensation of 3-amino-1-propanol with 2-hydroxyaldehydes and acetylacetone as well as for Cu(II) complexes with condensation products of o-aminophenol and β-diketones. The Cu(II) complex with Schiff base of 1-amino-2-propanol and acetylacetone exhibits ferromagnetic behaviour suggesting tetrameric structure.     

Study of the drying zirconia gel-precipitates using thermal analysis

Thermoanalytical techniques (TG, DTG, DTA and EGA) can be helpful in studying gel compositions and relating the chemical history and the role of the precipitant to the chemical properties of gels. The objective of our work was to determine the influence of the initial conditions in the reaction mixture on the product characteristics. Zirconia gels were prepared by the gelprecipitation method by the hydrolysis of zirconium tetrachloride dissolved in methanol. The substitution of water by methanol was chosen in order to obtain a reaction medium in which better control of the hydrolysis and condensation reactions of the zirconium precursor were achieved and thus also better control of the final properties of the dried zirconia gel-precipitates could be obtained. The nature of the hydrated zirconia gels obtained during the gelation process is strongly influenced by the conditions of the reaction mixture, e.g. concentration of the zirconium precursor, the mixing rate and particularly by the amount of water added. To distinguish between various types of water in the gel-precipitates, the furnace atmosphere and the partial water pressure were altered appropriately. It was shown that initial zirconium to water molar ratio has a significant effect on the properties of the final products. It was assumed that, according to the preparation conditions, three different types of water are present in the formed zirconia gel-precipitates. Modification of the dehydration processes of zirconia gel-precipitates enables control of the final microstructural and surface properties of the dried gels which are suitable for further catalysts support as well as mixed oxide preparation.     

PA.FPNS: its synthesis and use in spectrophotometric determination of magnesium

A new polymeric chromogenic reagent PA.FPNS has been synthesized by condensing polyallylamine (PA) with 3-(4-formylphenylazo)-4,5-dihydroxynaphthalene-2,7-disulfonic acid (FPNS) and its properties studied. In alkaline media, PA.FPNS reacts with magnesium to form a water-soluble blue complex, whose absorption maximum is at 604 nm. The molar absorptivity (varepsilon) of the complex is 5.2 x 10(4)l mol(-1) cm(-1), which is four times that of the FPNS-Mg complex, and Beer's law is obeyed over the range 0-0.35 mug ml(-1) magnesium. Compared to the corresponding low-molecular-weight FPNS and other chromogenic reagents, PA.FPNS offers considerably improved sensitivity and selectivity for magnesium, which may be attributed to incorporating FPNS into a water-soluble polymer and the effect of the polymeric chain on the reaction microenvironment. Also, a simple and sensitive spectrophotometric method for the determination of magnesium has been developed and applied to water and human fluid samples with satisfactory results.     

Uniqueness and the global Markov property for Euclidean fields: The case of general exponential interaction

The uniqueness and the global Markov property for the regular Gibbs measure corresponding to the interaction $$U_\Lambda (\varphi ): = \lambda \int\limits_\Lambda {d_2 x\int {d\varrho (\alpha ):e^{\alpha \varphi } :_0 (x)} } $$ [forλ>0,d?(α) a probability measure with support in \(( - 2\sqrt {\pi ,} 2\sqrt \pi )\) ] is proved.     

Interaction of tetrandrine with human serum albumin: a fluorescence quenching study.

The interaction of tetrandrine with human serum albumin (HSA) was studied by measuring fluorescence quenching spectra, synchronous fluorescence spectra and ultra-violet spectra. The fluorescence quenching spectra of HSA in the presence of tetrandrine showed that tetrandrine quenched the fluorescence of HSA. The quenching constants of tetrandrine on HSA were determined using the Stern-Volmer equation. Static quenching and non-radiation energy transfer were the two main reasons leading to the fluorescence quenching of HSA by tetrandrine. According to the F?rster theory of non-radiation energy transfer, the binding distances (r) and the binding constants (K(A)) were obtained. The thermodynamic parameters obtained in this study revealed that the interaction between tetrandrine and HSA was mainly driven by a hydrophobic force. The conformational changes of HSA were investigated by synchronous spectrum studies.     

Crystallization kinetics of polyamide 6 containing pigments

In terms of the Avrami equation, the effects of selected organic pigments on the kinetic parameters of the isothermal crystallization of coloured polyamide 6 were examined in the temperature range 468–478 K. It was found that B Blue and BB Red are active nucleating agents, which is acribed to their crystalline structure. G Orange slightly accelerates the crystallization of PA 6 at lower temperatures and concentrations, whereas in other conditions its effect is the opposite.The isothermal data were confirmed by the results of non-isothermal crystallization. The degree of supercooling corresponding to the peak of the DSC curve was the measured feature in this case.It was found that B Blue and BB Red reduce the free energy of formation of criticalsize nuclei by 20 and 12%, respectively, which is reflected in the rates of crystallization.

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Zusammenfassung Mit Hilfe der Avrami Gleichung wurde der Einfluß einiger ausgewählter organischer Pigmente auf die kinetischen Parameter der isothermen Kristallisation gefärbter Polyamide 6 im Temperaturbereich 468–478 K untersucht. B Blue und BB Red erwiesen sich als aktive Keimbilder, was mit Hilfe ihrer kristallinen Struktur erklärt werden kann. Bei niedrigeren Temperaturen und geringeren Konzentrationen wird die Kristallisation von PA 6 durch G Orange leicht beschleunigt, unter anderen Bedingungen kann das Gegenteil beobachtet werden. Die isothermen Daten wurden durch die Ergebnisse bei nichtisothermer Kristallisation bekräftigt. In diesem Falle wurde das dem DSC Peak entsprechende Maß an Unterkühlung untersucht. Es wurde gefunden, daß B Blue und BB Red die freie Energie zur Bildung von Keimen kritischer Größe um 20 bzw. 12% herabsetzen, was sich in den Kristallisationsgeschwindigkeiten widerspiegelt.

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, -6 468–478 . , , . , . . . , , , 20 12%, .

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This work was supported by the Polish Academy of Science, goal 01.14.     

Long-range interaction in the D and D′ states of H2

The interaction energy between two hydrogen atoms in the D and D′ ¹Π_u states of the hydrogen molecule has been calculated for large internuclear distances (12 ? R ? 25 bohr). The variational method and a very flexible trial wave-function were used. The results indicate that for the states under consideration the Rayleigh-Schrödinger perturbation theory with the multipole expansion of the interaction hamiltonian gives reliable results only for R > 25 bohr i.e. in the region where the interaction energies are practically negligible.