DSC study of stabilizing effect of antioxidant mixtures in styrene-butadiene rubber

The type of cooperation between antioxidants in the binary mixtures of four substituted diphenylamines and phenotiazine in the stabilization of styrene-butadiene rubber has been tested. Thermooxidation of the samples has been studied by differential scanning calorimetry under non-isothermal conditions. The protection factors of the individual stabilizers and their mixtures were determined. The synergy factors were applied to asses the type of cooperation of antioxidants in the mixtures. From their values it can be concluded that the type of cooperation depends on temperature. The highest synergistic effect has been observed for the mixture of phenotiazine and [4-(1-methyl-1-phenyl-ethyl)-phenyl]-phenylamine.     

Analysis of NH3-TPD Profiles for CuSSZ-13 SCR Catalyst of Controlled Al Distribution – Complexity Resolved by First Principles Thermodynamics of NH3 Desorption,IR and EPR Insight into Cu Speciation**

NH₃ temperature-programmed desorption (NH₃-TPD) is frequently used for probing the nature of the active sites in CuSSZ-13 zeolite for selective catalytic reduction (SCR) of NO_x. Herein, we propose an interpretation of NH₃-TPD results, which takes into account the temperature-induced dynamics of NH₃ interaction with the active centers. It is based on a comprehensive DFT/GGA+D and first-principles thermodynamic (FPT) modeling of NH₃ adsorption on single Cu²⁺, Cu⁺, [CuOH]⁺ centers, dimeric [Cu-O-Cu]²⁺, [Cu-O₂²⁻-Cu]² species, segregated CuO nanocrystals and Brønsted acid sites (BAS). Theoretical TPD profiles are compared with the experimental data measured for samples of various Si/Al ratios and distribution of Al within the zeolite framework. Copper reduction, its relocation, followed by the intrazeolite olation/oxolation processes, which are concomitant with NH₃ desorption, were revealed by electron paramagnetic resonance (EPR) and IR. DFT/FPT results show that the peaks in the desorption profiles cannot be assigned univocally to the particular Cu and BAS centers, since the observed low-, medium- and high-temperature desorption bands have contributions coming from several species, which dynamically change their speciation and redox states during NH₃-TPD experiment. Thus, a rigorous interpretation of the NH₃-TPD profiles of CuSSZ-13 in terms of the strength and concentration of the active centers of a particular type is problematic. Nonetheless, useful connections for molecular interpretation of TPD profiles can be established between the individual component peaks and the corresponding ensembles of the adsorption centers.     

Tellurium delta‐doped InGaP layers grown by metalorganic vapour phase epitaxy

Heavily n‐type doped and several nanometres thick In_0.485Ga_0.515P layers are necessary for various devices. We studied the delta‐doping of this ternary with tellurium; the layers were grown by metalorganic vapour phase epitaxy (MOVPE), and diethyltelluride was used as the precursor. A maximum Hall sheet concentration of 2.75 × 10¹³ cm^–2 was achieved in our samples grown at 560 °C. The Te profiles were analyzed with secondary ion mass spectrometry (SIMS), and a very narrow spectrum with a full width at half maximum of 7.5 nm was measured. This value indicates that the memory effect, referred to in the literature, was practically eliminated with appropriate growth conditions. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Polymer surface patterning by laser scanning

Proposed work develops method of polymer surface patterning, suggested in our laboratory. Surface structures with different symmetry and shape are prepared on PMMA and photoresist (Su-8) surface. For surface modification, periodic laser scanning from confocal microscope was used. For optical response improvement meso tetraphenylporphyrine was added either in the polymer bulk or on the top of pristine polymer by vacuum evaporation method. Applications of vacuum deposition methods allow increasing applicability of the technique and preparation of more complex structure. Parameters of the created structures were studied with the aim to better understand the driving forces of the surface modification. Application of prepared structures in photonics as diffraction grating or light coupling elements is also given.     

An AB Initio Correlated Computation of Vibrations in the CIONO2 Molecule

Abstract

ClONO₂ is treated ab initio by the second order M?ller-Plesset perturbation approach with the 6-31G? basis set. The minimum-energy structure is planar (C_s symmetry) while in the activated complex for internal rotation around the NO bond the Cl atom exhibits torsion by 90° but the structure has the C_s symmetry, too. For both structures harmonic vibrational frequencies and IR intensities are calculated. The agreement with available observed data from matrix isolation is very good. The MP₂ frequencies are mostly somewhat lower comparing to related SCF values. The energetics is also evaluated in the MP4 fourth order perturbation treatment. The best value found for the barrier of internal rotation is 31 kJ/mol, i.e. significantly low.     

Interior C 1, γ-Regularity for Weak Solutions of Nonlinear Second Order Parabolic Systems

The interior C ^{γ, γ/2}-regularity for the first gradient with respect to the space variables of a weak solution to a class of nonlinear second order parabolic systems is proven under the assumption that oscillations of coefficients are controlled by the ellipticity constant.     

Utilization of W/Mg(NO3)2 modifiers for the direct determination of As and Sb in soils,sewage sludge and sediments by solid sampling electrothermal atomic absorption spectrometry

A simple method has been developed for the determination of arsenic and antimony in environmental samples by solid sampling electrothermal atomic absorption spectrometry, which was validated using certified reference materials of soils (S-VM — Soil Eutric Cambisol; S-MS — Soil Orthic Luvisols; S-SP — Soil Rendzina), sewage sludge (WT-L; WT-M) and sediments (NIES2; GBW07906). The analytical procedure combines solid sampling with utilization of a matrix modifier admixture containing 5 µg of W and 5 µg of Mg. The tungsten in the admixture serves to stabilize the solid matrix during atomisation, which results in dramatically reduced non-specific absorption compared with the conventional palladium modifier. Magnesium was efficient in reducing the accumulation of the matrix residue on the platform. An alternative resonance line of 197.2 nm for arsenic and 206.8 nm for Sb was used in order to eliminate the spectral interferences caused by aluminum compounds, and silicon and iron compounds, respectively. Under optimized experimental conditions, the effective in situ analyte/matrix separation was achieved so that the use of aqueous standards for calibration became possible. With the modifier, a 3 SD detection limit of 0.5 µg g⁻¹ As and 0.1 µg g⁻¹ Sb and 10 SD quantification limit of 1.7 µg g⁻¹As and 0.3 µg g⁻¹ Sb and a characteristic mass of 65 pg As and 53 pg Sb were obtained. For all the matrices under scrutiny, a good agreement with certified values was achieved with RSD values less than 10%.     

Strategies on the evaluation of binomial coefficients for all integers

Binomial coefficients are used in many fields such as computational and applied mathematics, statistics and probability, theoretical physics and chemistry. For accurate numerical results, the correct calculation of these coefficients is very important. We present some new recurrence relationships and numerical methods for the evaluation of binomial coefficients for negative integers. For this purpose, we give some comparisons of the outputs for different computer programming languages in case of negative integers, and also we wrote two new algorithms for computations.     

Long-term operation of a domestic wastewater treatment plant with membrane filtration

Possibilities of membrane technology and the use of membrane processes in wastewater treatment were investigated. The main focus was the monitoring of the starting phase of a domestic wastewater treatment plant. Experimental part of the study was realized at the municipal wastewater treatment plant (WWTP) Devínska Nová Ves — Bratislava during the period from February 2005 to September 2006. The system was stable without any external chemical treatment of the membrane modules and the permeate quality was very high. Observed decrease of COD and BOD₅ values ranged between 91 % and 98 %. The process of nitrification was very successful considering its high efficiency (> 95 %). Presented at the 34th International Conference of the Slovak Society of Chemical Engineering, Tatranské Matliare, 21–25 May 2007.