Microstructural and compositional aspects of ZnO-based varistor ceramics prepared by direct mixing of the constituent phases and high-energy milling

ZnO-based varistor samples were prepared by the direct mixing of the constituent phases (DMCP) and sintering at 1100 °C for 2 h. The influence of the starting powder mixture's composition – the amounts of the pre-reacted varistor compounds and their composition – and its preparation, either with or without mechano-chemical activation (MCA), on the microstructure, phase composition and electrical characteristics of the varistor samples was studied. It showed that MCA improved the density and microstructural homogeneity of the varistor samples. MCA strongly affected the grain growth: it enhanced the nucleation of inversion boundaries (IBs) in the ZnO grains and the IBs-induced grain-growth mechanism resulted in uniform grain growth and hence a microstructure with smaller ZnO grains and a narrower grain size distribution. The final phase composition of the samples prepared by the DMCP method mainly depended on the presence of varistor dopants that can prevent the formation of the pyrochlore phase, especially Cr₂O₃, while MCA can affect it mostly by providing a homogeneous distribution of those dopants. The DMCP varistor samples prepared with MCA had much better current–voltage characteristics than the samples of the same composition prepared from unactivated powders.     

Preparation, Physical Characterization, Mechanisms of Drug/Polymer Interactions, and Stability Studies of Controlled-Release Solid Dispersion Granules Containing Weak Base as Active Substance

Verapamil hydrochloride solid dispersion granules were prepared using solvent evaporation technique. Ethyl cellulose, hydroxypropyl cellulose, Eudragit L or Eudragit S were used as polymers for controlling the dissolution rate of the drug substance, and to avoid the continuous decrease of drug dissolution rate at higher pH values. By incorporating Eudragit L in ethyl cellulose network it is possible to prepare controlled-release formulation with increased release rate of active substance (weak base) at higher pH values without causing abrupt drug release at lower pH values. The release rate at low pH values was not highly influenced by Eudragit L content. The behavior of Eudragit L and Eudragit S in coprecipitates was different relating to the solubilization effect and the release of active substance. In order to understand the drug release mechanism better, the release data were tested assuming Higuchi model and first-order kinetic model. Since the calculated correlation coeflcients were very close for both kinetics, to distinguish between the mechanisms the differential forms of first-order and square root of time equation were used. The differential test showed that diffusion-controlled release was operative in solid dispersions, except for series with higher content of Eudragit S. X-ray powder difSraction method, IR spectroscopy studies, and differential thermal analysis were used for physical characterization of coprecipitates and drugpolymer interaction evaluation. After 24 months of real time stability studies, the prepared coprecipitates were still x-ray amorphous, with no changes in their IR spectra and DTA studies. Ehe dissolution rates of the tested formulations showed no significant changes during the stability studies, reflecting the stability of x-ray amorphous drug phase.     

Scientometric analysis of the research activities of chemists from the “Rugjer Bošković” Institute (Yugoslavia), 1976–1985

The research activity of chemists from the Rugjer Bokovi Institute (RBI, Zagreb, Yugoslavia) was analyzed for the period 1976–1985, covering 2018 research years of scientific work, and 1149 SCI registered papers (0.57 publications per research year). At the average, one paper was published by 3.05 scientists. The papers were published in 235 different journals, most frequently is the nationalCroatica Chemica Acta (171 papers). The publications were divided into two groups: for the periods 1976–1980 and 1981–1985, and for each paper citations were collected in the respective time period. An average publication had 2.58 citations. Chemical papers from the second period had 2.73 citations per paper, which is 85% of the expected value, and this was considerably more than for Yugoslav papers (66%) in general. The papers were classified according to the subfields used in theJournal Citation Reports, and the results compared with the data published bySchubert, Glänzel andBraun. The distribution of citations was also analyzed.     

Polyesterification and isomerization of maleic anhydride and 1,6-hexane diol as studied by 1H and 13C n.m.r.

The polyesterification and isomerization reaction of 1,6-hexane diol and maleic anydride in a melt without catalyst was studied by ¹³C and ¹H n.m.r. spectroscopy. The structure and concentration of oligoester species during the polyesterification and isomerization were determined depending on the reaction temperature and time. According to the number and configuration of repeating units determined from ¹H n.m.r. spectra kinetics of both reactions were also considered. The degree of isomerization is continuously increasing in the investigated reaction range.     

Vapour liquid equilibrium with association in both phases: A model with the concentration-dependent liquid phase association constant applied to acetic acid—benzene, -toluene, -p- and -o-xylene

A model employing the correction factors of Marek and Standart, but using a concentration-dependent liquid phase association factor of Jenkins—Robinson, has been used to model vapour—liquid equilibrium data for mixtures of acetic acid with benzene, toluene, o-xylene and p-xylene. With the aim to use systems of acetic acid—benzene and acetic acid—toluene as the test mixtures for distillation columns, the examination of the systems of acetic acid—aromatic hydrocarbons was undertaken. The model promises to be useful in modelling isobaric and isothermal data of acetic acid—benzine, acetic acid—toluene, acetic acid-p-xylene and acetic acid-o-xylene systems. Deviation plots show that the isothermal and isobaric data are represented well.     

Morphometric and some immunohistochemical characteristics of human choroids plexus stroma and psammoma bodies

Psammoma bodies (PBs) are one of many choroids plexus aging changes. The aim of our research was to perform the quantification of PBs' presence in human choroids plexus stroma, as well as to evaluate the characteristics of choroids plexus stroma in cases in which PBs were present. Afterwards, the observations of the histochemical analysis would be confirmed by immunohistochemical analysis. Choroid plexuses of 30 cadavers were used for the histochemical and, choroids plexuses of 15 cadavers in which PBs' presence was confirmed during the histochemical analysis, were used as material for the immunohistochemical analysis. Light microscopy, histochemical, immunohistochemical, and morphometric method were applied during the study. Classification of the cases was performed by cluster analysis. We observed increase of choroids plexus PBs' presence during the aging process. But this increase is not linear. Their presence is the largest in the second cluster that is younger than the third and older than the first. Nuclear morphometric parameters of the stroma in these cases showed that the cellular composition in this cluster is different than in other two and, that contain larger number of lymphoid cells. Immunohistochemical analysis showed PBs' positive reaction on vimentin, CD45R0, and LCA markers, while in their vicinity, as well as inside them, numerous T-cells were observed. So, the presence of CD45R0 and LCA-positive T cells, PBs' positive reaction on the same markers, indirectly connect these cells with PBs' formation process.     

Transition layer thickness in microlaminar deposits

A theoretical analysis was carried out on the change of composition of a deposit obtained by the dual pulse method of forming laminar metal foils, with transition from a low current to a high current pulse, both in the galvanostatic and the potentiostatic mode of deposition. It was shown that the existence of a transition layer of varying composition between a layer of pure metal 1 and a layer consisting predominantly of the metal 2 is an inherent consequence of the electrochemical process, primarily because of an induction period in the concentration polarization with respect to ions of metal 1. The importance of this transition layer increases as the thickness of the layers of the two metals decreases. Eventually this limits the possibility of obtaining a sharp boundary between the layers, when the nanometre region of layer thickness is reached. Equations are given for calculating the deposition current density and rate of stirring of the electrolyte which provide a deposit of a required level of metal 1 in the layer of metal 2, as well as a required sharpness of the boundary between two layers. Experimental proof of the correctness of the analysis was sought. It was found that significant changes in the properties of the deposit occur in the same range of layer thickness in which the transition of the composition takes places.Nomenclature _c,1, a_c,2 transfer coefficient of the cathodic processes - C interfacial capacitance - C₁, C₂ concentration of the ions of metals 1 and 2 at the interface r - C ₀ ¹ , C ₀ ² concentration of ions of the metals 1 and 2 in solution - D ₁ diffusion coefficient for the diffusion of ions of the metal 1 - E _r,1,E _r,2 reversible potentials of metals 1 and 2, respectively - F the Faraday constant - J ₀ ¹ ,J ₀ ² exchange current density of the metals 1 and 2, respectively - M ₁,M ₂ atomic weights of the metals 1 and 2, respectively - kinematic viscosity of solution - ₁, ₂ densities of the metals 1 and 2 respectively - rotation speed (r.p.s.) - z number of electrons exchanged in the deposition process This paper is dedicated to Professor Brian E. Conway on the occasion of his 65th birthday, and in recognition of his outstanding contribution to electrochemistry.