Differential scanning calorimetry and thermogravimetric analysis investigation of the thermal properties and degradation of some radiation‐grafted films and membranes

The influence of irradiation and grafting on the crystallinity of three base polymers has been investigated with differential scanning calorimetry. Grafting has the largest effect on the base polymer crystallinity and results in a reduction of the crystallinity. The thermal degradation of the base polymers and grafted films has been investigated with thermogravimetric analysis. The extent of the fluorination of the base polymer, the irradiation method, and the graft level all influence the thermal degradation and its activation energy. It is proposed that the variation of the chain lengths of the grafted polystyrene chains is actually a primary underlying factor responsible for the influence of these various parameters on the degradation process. The first results of a comparative thermal analysis of some fuel‐cell membranes are also presented, and the promise and shortcomings of this method are discussed. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2612–2624, 2004     

Electronic molecule-like spectrum of quantum wells in crossed fields

We show that an electron confined to a single finite parabolic quantum well in crossed electric and magnetic fields can behave as a double quantum well system. The magnetic field is parallel to the heterostructure layers and the electric field is perpendicular to those. For a suitable choice of both fields and quantum well width, the electron can be confined to a double quantum well effective potential that is very similar to the electronic potential model for diatomic molecules. The double quantum well spectrum is calculated using a numerical algorithm based on semiclassical methods. A physical interpretation of this quantum system is given based on the analogy to the electrons bound to diatomic molecules.     

On nonspecular “total internal reflection” of powerful electromagnetic waves

It is shown that the nonstable character of nonlinear interaction of a system of waves similar to that resulting from double stimulated Brillouin scattering is retained upon the oblique incidence of a powerful electromagnetic wave on a layer of supercritical plasma. In this case we have nonlinear back reflection from a layer of supercritical plasma. The threshold intensity of the pump wave is greater than that in the case of subcritical plasma for TE polarization waves but can markedly decrease for waves polarized in the incidence plane. Instability is possible only for a layer of finite thickness.Radiophysical Research Institute, Nizhny Novgorod. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Radiofizika, Vol. 38, Nos. 3–4, pp. 298–303, March–April, 1995.     

Optical detection of NO3 and NO2 in “pure” HNO3 vapor,the liquid-phase decomposition of HNO3

Flowing and static gas-phase samples of HNO₃ in O₂ and N₂ were analyzed by long-path ultraviolet/visible (UV/VIS) spectroscopy to reveal the presence of both NO₂ and NO₃, the concentrations of which were calculated using differential absorption cross sections. NO₂ is produced predominantly by the heterogeneous decomposition of HNO₃, whereas NO₃ is generated in the gas phase by the thermal decomposition of N₂O₅, a product of the self-disproportionation of liquid HNO₃. © 1993 John Wiley & Sons, Inc.     

Selective quenching of tryptophanyl fluorescence in bovine serum albumin by the iodide ion

Modified Stern-Volmer equation is obeyed by bovine serum albumin (BSA)-iodide system showing selective quenching of tryptophanyl fluorescence of BSA. The fraction of accessible protein fluorescence is 0.56 and the effective Stern-Volmer constant is 290 M^-1 at pH 7.4 in 0.005 M phosphate buffer at 25°C. Collisional quenching is operative both in the BSA -I⁻¹ system and the model system, tryptophan-I⁻¹. It is supported by the observed relationship between the ratio of quenching rate constants (k _q ) and diffusion coefficients and alsok _q with bulk viscosity.     

EPMA of interfaces applied to the solid oxide fuel cell

Chemical interactions at the phase boundaries of materials applied for the solid oxide fuel cell (SOFC) have been studied by EPMA. The chemical reactivity at the interface of La_y-xSr_xMnO₃/ZrO₂-Y₂O₃ is dependent on the stoichiometry (y) and the Sr content (x) of the perovskite. Typical reaction products (zirconates) and a diffusion zone in the ZrO₂–Y₂O₃ have been observed. The extension of cation release (Mn) is related to the increasing chemical activity of Mn oxide in the perovskite by the Sr substitution for La. The wettability of the metal/oxide interface in the anode cermet (Ni/ZrO₂–Y₂O₃) has been found to be influenced by chemical reactions resulting from the applied reducing atmosphere with high carbon activity. The disintegration of ZrO₂–Y₂O₃ in contact with molten Ni or Ni-Ti and Ni-Cr alloys leads to the redeposition of Y₂O₃-enriched oxides and also to Zr-rich intermetallic compounds and eutectics.     

Silver nitrate-acetonitrile and iodine-benzene complexes as studied by NMR in thermotropic liquid crystals

Silver nitrate-acetonitrile and π iodine-benzene complexes in thermotropic liquid crystals have been studied by ¹H, ²H, and ¹³C NMR spectroscopy and by optical microscopy. Evidence for at least two silver complexes in each liquid crystal is presented.     

On practical metrology and chemical analysis: etalons and traceability systems

 National measurement systems are infrastructures to ensure, for each nation, a consistent and internationally recognised basis for measurement. Such complex systems have historical, technical, legal, organisational and institutional aspects to connect scientific metrology with practical measurements. Underlying any valid measurement is a chain of comparisons linking the measurement to an accepted standard. The ways the links are forged and the etalons (measurement standards) to which they connect are defining characteristics of all measurement systems. This is often referred to as traceability which aims at basing measurements in common measurement units – a key issue for the integration of quantitative chemical analysis with the evolving physical and engineering measurement systems. Adequate traceability and metrological control make possible new technical capabilities and new levels of quality assurance and confidence by users in the accuracy and integrity of quantitative analytical results. Traceability for chemical measurements is difficult to achieve and harder to demonstrate. The supply of appropriate etalons is critical to the development of metrology systems for chemical analysis. An approach is suggested that involves the development of networks of specialised reference laboratories able to make matrix-independent reference measurements on submitted samples, which may then be used as reference materials by an originating laboratory using its practical measurement procedures. Received: 31 July 1995 Accepted: 19 August 1995