Potentiometric studies of oxidation–reduction reactions with redox copolymers

Polymeric oxidants in the bead form that were macroporous styrene/divinylbenzene copolymers containing N‐chlorosulfonamide functional groups (in sodium or hydrogen form) or N‐bromosulfonamide groups (in sodium form) were synthesized and investigated to determine their oxidizing powers. The redox potentials of the N‐chlorosulfonamide/sulfonamide and N‐bromosulfonamide/sulfonamide systems were determined by potentiometric studies at different pH values with aqueous solutions of Na₂SO₃, KCN, and KSCN as reducers. The formal redox potentials of the N‐chlorosulfonamide copolymers were 0.79, 0.44, and ?0.12 V at pH's of 1.8, 8.45, and 13.6, respectively. The formal redox potential of the N‐bromosulfonamide copolymer was about 100 mV higher in comparable conditions and in solutions over pH = 5 (e.g., 0.56 V at pH = 8.56). The comparatively higher oxidizing power of the N‐bromosulfonamide copolymer was particularly evident in a strong alkaline medium (in which the N‐chlorosulfonamide copolymer was not reactive). In contrast, the N‐chlorosulfonamide copolymer showed strong oxidative properties in acidic media (in which the N‐bromosulfonamide copolymer decomposed itself). © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Separation of weak and strong acids by electro-electrodialysis—Experiment and theory

The experimental results of the separation of acetic acid (HA) from the sulfuric acid by the electro-electrodialysis (EED) method and the modeling of process have been presented. The Neosepta membranes CMX and ACM have been used. It has been found that the efficiency of retention of HA is high (>0.9) when the process is conducted below the limiting current density with respect to HSO₄⁻ or SO₄²⁻ anions. The observed current efficiency of the H₂SO₄ removal was rather low (CE_S = ca. 0.7, when the initial concentration of H₂SO₄ in the mixture was 1 or 2 M) which was caused by the nonideal selectivity of the anion-exchange membrane. The experimental results have been described by the model based on the extended Nernst-Planck equation and the Donnan equilibrium. Since the efficiency of the process depended mainly on the selectivity of anion-exchange membrane (ACM), the concentration of fixed charges of that membrane, , and the ratio of volume fraction of pores to their squared tortuosity, V_p/θ², have been chosen as the main fitting parameters. It has been found that the fitting of the EED data depends mainly on , whereas in the modeling of diffusion experiment (or an EED experiment conducted at low current density) both parameters are important. The best fit has been obtained for , i.e. ca. one order smaller than that determined experimentally. The obtained optimal value of V_p/θ², equal to 0.013, is consistent with those previously obtained for other Neosepta anion-exchange membrane.     

Effect of annealing on the structure and electrical properties of sulfur-doped amorphous c-BN layers

Undoped and sulfur doped amorphous cubic boron nitride (a-cBN) layers were deposited on to silicon substrates by reactive pulse plasma (RPP) method. Subsequently they were annealed at 475, 500 and 700 K for 1 h in pure nitrogen atmosphere. In this study structural and electronic properties of unannealed and annealed layers were investigated. The results show that a consequence of annealing is formation of microstructural stable nanocrystalline cubic boron nitride film as well as substitutional location of introducedin situ donor impurities. This resulted in creation of a-cBN(n-type)-Si(p-type) heterojunction.     

Determination of porous glass surface free energy components from contact angles

The contact angles of water drops and diiodomethane drops on pellets made of controlled porosity glasses have been measured. The surface of the glasses was modified by thermal treatment at 873 K which led to an increase in the surface concentration of boron atoms. Glass modified with Carbowax 20M (polyethylene glycol) and fully hydroxylated glass have also been studied. Using the measured contact angles and modified Young equation, the dispersion and nondispersion components of the glass surface free energy have been calculated. The values show that with increasing heating time (increasing surface density of boron atoms) an increase in the surface polarity takes place. However, the polarity of the same samples decreases after treatment with Carbowax, increasingly so with higher boron atom concentrations.     

Allotropic phase transformations induced by ultraviolet power laser irradiation of graphite

Optically induced allotropic phase transformations of carbon were studied. Under irradiation with a laser beam of 337.1 nm wavelength, at an energy density of 1.9 mJ per 0.1 mm², graphite transformed into -carbin, and amorphous carbon-film transformed into rhombohedral graphite with no evidence of high-temperature effects. The transformations differ from the changes occurring due to heating alone. We suggest that the results could be explained by the one-photon excitation and recombination of electrons.     

Allotropie phase transformation induced by UV power laser irradiation of boron nitride

The optically induced allotropic phase transformations of boron nitride were studied. Under irradiation with laser beam of 337.1 nm wavelength, at energy density of 1.9mJ per 0.1 mm² a hexagonal boron nitride transformed into the cubic form. The suggestion is made that the results obtained could be explained by the multiphoton excitation and recombination of electrons.     

Sensing properties of the CB-PCV composites for chlorinated hydrocarbon vapours

The conductivity measurements of carbon black (CB)-polyvinyl chloride (PCV) composite in a tetrachloride (CCl₄), trichloromethane (chloroform, CHCl₃) or methylene chloride (CH₂Cl₂) vapour ambient have been performed. The composite contains 20% Chezacarb K2 carbon black and was prepared as a plastic strip. Based on the =f(t) dependence, three methods to determine the vapour concentration,c, are presented. The investigations could allow one to construct a CCl₄ and CHCl₃ vapour detector.     

A universal dependence for thermal conductivity of metals and dilute alloys

A universal curve relating the maximum of thermal conductivity and its respective temperature with the residual electrical resistivity has been proposed for metals and dilute alloys. Based on the equation of that curve, a comparative analysis of selected literature data of thermal conductivity of metals, which have residual electrical resistivity in the range 10^–11<₀<10^–5. cm, have been performed. Using the data for 33 metals, confirmation of the Wiedemann-Franz law for the impurity component/T of thermal conductivity was obtained, which means that _th/_el1, where _th and _el are the parameters of the electron-lattice defect interaction obtained from measurements of thermal and electrical conductivity, respectively. Examples of the failure of the Wiedemann-Franz law are also presented, exhibiting the values of _th/_el in the range 0.16 to 25. Measurements of thermal conductivity in the range 2 to 20 K and determination of the residual electrical resistivity for the samples of Cd doped with Zn and quenched were performed, resulting in values _th/_el1.     

Mediator-Related Symptoms and Anaphylaxis in Children with Mastocytosis

Mastocytosis is characterized by the pathological accumulation of mast cells (MC) in various organs. In these patients, MC may degranulate and thereby contribute to clinical symptoms, especially when a concomitant allergy is present. However, MC activation can not only be induced by high-affinity receptors for IgE, but also by anaphylatoxins, neuropeptides, IgG immune complexes, complement-components, drugs, products of bacteria or parasites, as well as physical factors such as heat, cold, vibration, stress, sun, or physical effort. Symptoms due to mediators released by activated MC may develop in adults suffering from systemic mastocytosis, but also evolve in children who usually have cutaneous mastocytosis (CM). Clinically, CM is otherwise characterized by typical brown, maculopapular skin lesions or mastocytoma associated with a positive Darier’s sign. Pruritus and flushing are common and blistering may also be recorded, especially in diffuse CM (DCM). Pediatric patients with mastocytosis may also have gastrointestinal, respiratory, and neurologic complaints. Although anaphylaxis is not a typical finding, pediatric patients with massive skin involvement and high tryptase levels have a relatively high risk to develop anaphylaxis. This paper reviews MC mediator-related symptoms and anaphylaxis in children with mastocytosis, with special emphasis on risk factors, triggers, and management.     

Effect of Ca2+ and Mg2+ ions on the sintering and spectroscopic properties of cr-doped yttrium aluminum garnet ceramics

In this work, we investigated the effects of Ca²⁺ and Mg²⁺ ions and annealing temperature on the spectroscopic parameters of chromium-doped yttrium aluminum garnet ceramics (Cr:YAG). Samples were obtained with either a separate or a simultaneous addition of calcium and magnesium oxides. To achieve this, aqueous suspensions were prepared using Y₂O₃, Al₂O₃, Cr₂O₃, MgO, and CaO high-purity powders as raw materials. The obtained suspensions were freeze-granulated, pressed into pellets, debinded, and subjected to reactive sintering in vacuum at 1715°C for 6 h. Each material was annealed in air with temperatures between 1300 and 1700°C. Samples were also compared to Cr:YAG ceramics with the addition of silica as a sintering aid. All the materials obtained were then exposed to 445 nm excitation, and emission spectra in the visible and infrared wavelengths were recorded. The results showed that the emission spectra of Cr:YAG ceramics varied according to the annealing conditions: as-sintered samples exhibited strong emissions of around 680 nm and, after air annealing, of around 1400 nm. This phenomenon is attributed to the Cr³⁺→Cr⁴⁺ transition. Samples doped solely with MgO exhibited the highest emission intensity in the infrared region. Thus, Mg²⁺ ions provided the best conversion efficiency of chromium ions.