Mechanism of gross melt fracture elimination in the extrusion of polyethylenes in the presence of boron nitride

The mechanism by which the addition of a small amount of boron nitride into a polyethylene eliminates gross melt fracture is elucidated. Simple elongational viscosity measurements at high rates revealed that the presence of boron nitride decreases the extensional viscosity of polyethylenes. The extensional rates at which these effects are present were found to be about the same with those at which gross melt fracture is obtained (calculated from Cogswells analysis). Thus, it can be argued that the well dispersed boron nitride particles decrease extensional stresses that are responsible for gross melt fracture and/or their presence dissipate the release of energy resulting from isolated rupture or slip planes within the melt originating at the entrance to the capillary.     

Mass transfer and free convective MHD flow past an accelerated vertical porous plate

The effects of variable suction/injection on the unsteady two-dimensional free convective flow with mass transfer of an electrically conducting fluid past a vertical accelerated plate in presence of a transverse magnetic field is considered. Solutions of the equations governing the flow are obtained with the help of the power series. The paper is concluded with a discussion of the results obtained.

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Stofftransport und MHD-Strömung bei freier Konvektion an einer beschleunigten senkrechten porösen Platte

Zusammenfassung In dieser Arbeit werden die Wirkungen verÄnderlicher Absaugung/Ausblasung auf die instationÄre zweidimensionale freie Strömung mit Stoffübertragung eines elektrisch leitenden Fluids an einer senkrecht beschleunigten Wand mit magnetischem Querfeld betrachtet. Lösungen erhÄlt man mit Hilfe von PotenzansÄtzen. Die Ergebnisse werden diskutiert.

     

Bagley correction: the effect of contraction angle and its prediction

The excess pressure losses due to end effects (mainly entrance) in the capillary flow of a branched polypropylene melt were studied both experimentally and theoretically. These losses were first determined experimentally as a function of the contraction angle ranging from 10° to 150°. It was found that the excess pressure loss function decreases for the same apparent shear rate with increasing contraction angle from 10° to about 45°, and consequently slightly increases from 45° up to contraction angles of 150°. Numerical simulations using a multimode K-BKZ viscoelastic and a purely viscous (Cross) model were used to predict the end pressures. It was found that the numerical predictions do agree well with the experimental results for small contraction angles up to 30°. However, the numerical simulations under-predict the end pressure for larger contraction angles. The effects of viscoelasticity, shear, and elongation on the numerical predictions are also assessed in detail. Shear is the dominant factor controlling the overall pressure drop in flows through small contraction angles. Elongation becomes important at higher contraction angles (greater than 45°). It is demonstrated in abrupt contractions (angle of 180°) that both the entrance pressure loss and the vortex size are strongly dependent on the extensional viscosity for this branched polymer. It is suggested that such an experiment (visualisation of entrance flow) can be useful in evaluating the validity of constitutive equations and it can also be used to fitting parameters of rheological models that control the elongational viscosity.     

Unsteady Flow Through a Highly Porous Medium in the Presence of Radiation

The unsteady natural convection flow of a viscous and incompressible fluid through a porous medium with high porosity bounded by a vertical infinite stationary plate in the presence of radiation has been investigated. The fluid is assumed to be a gray, emitting and absorbing radiation, but non-scattering medium. The effects of the radiation parameter, Grashof number and permeability parameter of the medium on the velocity field as well as the effects of the radiation parameter and Prandtl number on the temperature field have been included in the analysis.     

Measurement of non-separated U/Pu samples: optimization of TIMS procedures for safeguards purposes at Rokkasho on-site laboratory

The on-site laboratory (OSL) at Rokkasho Reprocessing Plant (RRP) is jointly operated by the Japanese authority Nuclear Material Control Centre and the International Atomic Energy Agency (IAEA) and provides, together with the Nuclear Material Laboratory (NML) at Seibersdorf, analytical services to the IAEA’s inspectorate. OSL deals with a variety of samples typical to a reprocessing plant including pure product solutions of uranium and plutonium but also mixed U/Pu solutions originating from various stages of the chemical process. For a significant proportion of the samples, the requirement on measurement accuracy and precision from the Inspectorate makes the use of thermal ionization mass spectrometry (TIMS) indispensible. Until recently, all samples intended for TIMS had to undergo time-consuming U/Pu separation before isotope dilution measurement. The need for rapid reporting of analytical results for certain safeguards samples evoked the idea of performing TIMS measurements without prior U/Pu separation for mixed U/Pu products as they are obtained from the PUREX process at RRP. For this purpose, a systematic study was initiated to probe the figure of merits and limitations of conducting TIMS analyses on mixed U/Pu samples and, in particular, whether the accuracy and precision of the main ratios of interest, n(²³⁵U)/n(²³⁸U) and n(²⁴⁰Pu)/n(²³⁹Pu), are influenced by the presence of larger amounts of the other element. A series of synthetic mixtures with U/Pu ratios ranging from 1:10 up to 100:1 were prepared and measured in both laboratories—OSL and NML—using ThermoFisher TRITON multi-collector TIMS instruments. For the n(²³⁵U)/n(²³⁸U) ratio, interference due to ²³⁸Pu was observed which can be significant depending on the U/Pu ratio and the ²³⁸Pu abundance. However, for the n(²⁴⁰Pu)/n(²³⁹Pu) ratio, which is of premier importance for safeguarding RRP, no significant interference arising from the concomitant U was detected independently of enrichment. Even in samples with an excess of U (U/Pu ratio of 100:1), compliance with International Target Values (ITV2010) was demonstrated for n(²⁴⁰Pu)/n(²³⁹Pu) results with a relative difference to certified not exceeding 0.01 %.     

Exclusion of canonical weakly interacting massive particles by joint analysis of Milky Way dwarf galaxies with data from the Fermi Gamma-Ray Space Telescope

Dwarf spheroidal galaxies are known to be excellent targets for the detection of annihilating dark matter. We present new limits on the annihilation cross section of weakly interacting massive particles based on the joint analysis of seven Milky Way dwarfs using a frequentist Neyman construction and Pass 7 data from the Fermi Gamma-Ray Space Telescope. We exclude generic weakly interacting massive particle candidates annihilating into bb with a mass less than 40 GeV that reproduce the observed relic abundance. To within 95% systematic errors on the dark matter distribution within the dwarfs, the mass lower limit can be as low as 19 GeV or as high as 240 GeV. For annihilation into τ+ τ-, these limits become 19, 13, and 80 GeV, respectively.     

Preparation and certification of new thorium isotopic reference materials

Preparation of two Isotopic Reference Materials of thorium has been performed, starting from highly enriched ²³²Th (99.99%) and ²³⁰Th (99.8%). After full characterization (chemical and isotopic) of these purified base materials the thorium nitrate was transformed to thorium dioxide. Accurately weighed amounts of the two isotopes in the dioxide form were subsequently dissolved in nitric acid and resulted in solutions with amount ratios n(²³⁰Th)/n(²³²Th) close to 10^–5 (IRMM-035) and 3 · 10^–6 (IRMM-036). These gravimetrically prepared ratios were finally verified by means of Thermal Ionization Mass Spectrometry (TIMS). The purpose of the Reference Materials is to calibrate thorium isotope amount ratio measurements. Received: 7 July 1997 / Revised: 1 December 1997 / Accepted: 7 December 1997     

Synthetic,structural, spectroscopic and solution speciation studies of the binary Al(III)–quinic acid system. Relevance of soluble Al(III)–hydroxycarboxylate species to molecular toxicity

Efforts to delineate the interactions of Al(III), a known metallotoxin, with low molecular mass physiological substrates involved in cellular processes led to the investigation of the structural speciation of the binary Al(III)–quinic acid system. Reaction of Al(NO₃)₃ · 9H₂O with d-(−)-quinic acid at a specific pH (4.0) afforded a colorless crystalline material K[Al(C₇H₁₁O₆)₃] · (OH) · 4H₂O (1). Complex 1 was characterized by elemental analysis, FT-IR, DSC–TGA, ¹³C-MAS NMR, solution ¹H and ¹³C NMR, and X-ray crystallography. The structure of 1 reveals a mononuclear octahedral complex of Al(III) with three singly ionized quinate ligands bound to it. The three ligand alcoholic side chains do not participate in metal binding and dangle away from the complex. The concurrent study of the aqueous speciation of the binary Al(III)–quinic acid system projects a number of species complementing the synthetic studies on the binary system Al(III)–quinic acid. The structural and spectroscopic data of 1 in the solid state and in solution emphasize its physicochemical properties emanating from the projections of the aqueous structural speciation scheme of the Al(III)–quinic acid system. The employed pH-specific synthetic work (a) exemplifies essential structural and chemical attributes of soluble aqueous species, arising from biologically relevant interactions of Al(III) with natural α-hydroxycarboxylate substrates, and (b) provides a potential linkage to the chemical reactivity of Al(III) toward O-containing molecular targets influencing physiological processes and/or toxicity events.     

Synthesis, characterization, and study of octanuclear iron-oxo clusters containing a redox-active Fe4O4-cubane core

A one-pot synthetic procedure yields the octanuclear Fe(III) complexes Fe(8)(micro(4-)O)(4)(micro-pz(*))(12)X(40, where X = Cl and pz(*) = pyrazolate anion (pz = C(3)H(3)N(2)-) (1), 4-Cl-pz (2), and 4-Me-pz (3) or X = Br and pz(*) = pz (4). The crystal structures of complexes 1-4, determined by X-ray diffraction, show an Fe(4)O(4)-cubane core encapsulated in a shell composed of four interwoven Fe(micro-pz(*))(3)X units. Complexes 1-4 have been characterized by 1H NMR, infrared, and Raman spectroscopies. M?ssbauer spectroscopic analysis distinguishes the cubane and outer Fe(III) centers by their different isomer shift and quadrupole splitting values. Electrochemical analyses by cyclic voltammetry show four consecutive, closely spaced, reversible reduction processes for each of the four complexes. Magnetic susceptibility studies, corroborated by density functional theory calculations, reveal weak antiferromagnetic coupling among the four cubane Fe centers and strong antiferromagnetic coupling between cubane and outer Fe atoms of 1. The structural similarity between the antiferromagnetic Fe(8)(micro(4-)O)(4) core of 1-4 and the antiferromagnetic units contained in the minerals ferrihydrite and maghemite is demonstrated by X-ray and M?ssbauer data.