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101.
E. Kramer J. Koppelmann J. Dobrowsky 《Journal of Thermal Analysis and Calorimetry》1989,35(2):443-457
Isothermal differential thermal analysis has been used to study the thermooxidative stability of two grades of crosslinked polyethylene in the temperature range from 120°C to 230°C. Induction times of thermooxidative degradation were measured from 2 minutes up to 3590 hours. Oxidation Induction time and mechanical failure in oven ageing experiments coincided over the measured temperature range. The degree of crosslinking was not strongly affected by the oxidative reaction. The Arrhenius-plots of DTA results showed curvature at 150°C, so straight line extrapolations from short-term experiments at elevated temperatures to low temperatures and long times are not possible. Thermoanalytically measured residual thermooxidative stability decreased linearly with ageing time and showed great scattering of the results.
Zusammenfassung Die isotherme Differentialthermoanalyse ist als Methode zur Abschätzung der thermooxidativen Beständigkeit von Polyolefinen seit längerem bekannt. In der vorliegenden Arbeit wird über isotherme DTA-Messungen an Proben aus vernetztem Polyäthylen im Temperaturbereich von 230°C bis 120°C berichtet, wobei Oxidationsinduktionszeiten bis zu 3590 Stunden gemessen wurden. Die Auftragung der Oxidationsinduktionszeiten in Arrhenius-Diagrammen zeigte für vernetztes Polyäthylen keine für Extrapolationszwecke geeignete Linearität des Logarithmus der Oxidationsinduktionszeiten über der reziproken absoluten Temperatur über weitere Bereiche der Meßzeiten bzw. Prüftemperaturen. Die thermoanalytisch bestimmten Oxidationsinduktionszeiten stimmten mit dem Steilabfall der Reißdehnung in Ofenalterungsversuchen überein während der über den Gelgehalt ermittelte Vernetzungsgrad vom thermooxidativen Abbau nicht signifikant beeinflußt wurde. Somit können aufwendige Ofenalterungsversuche durch experimentell einfache isotherme DTA-Versuche ersetzt werden. Die Messung der thermooxidativen Restbeständigkeit im isothermen DTA-Versuch bei erhöhter Prüftemperatur ermöglicht einen wesentlich deutlicheren Einblick in den thermooxidativen Schädigungszustand eines Polyolefins während der Induktionsperiode des thermooxidativen Abbaus als die Messungen des Vernetzungsgrades oder der Reißdehnung. Die Abnahme der thermooxidativen Restbeständigkeit erfolgt im Fall des vernetzten Polyäthylen in allen Fällen linear über der Alterungszeit.
120–230°. 2 3590 . . . 150°, . .相似文献
102.
Sharapov SE Alper B Fessey J Hawkes NC Young NP Nazikian R Kramer GJ Borba DN Hacquin S De La Luna E Pinches SD Rapp J Testa D;JET-EFDA contributors 《Physical review letters》2004,93(16):165001
A microwave interferometry technique is applied for the first time for detecting a discrete spectrum of Alfvén cascade (AC) eigenmodes excited with fast ions in reversed magnetic shear plasmas of the Joint European Torus. The interferometry measurements of plasma density perturbations associated with ACs show an unprecedented frequency and time resolution superior to that obtained with external magnetic coils. The measurements of ACs are used for monitoring the evolution of the safety factor and density of rational magnetic surfaces in the region of maximum plasma current. 相似文献
103.
I.A. Schneider D. Kramer A. Wokaun G.G. Scherer 《Electrochemistry communications》2005,7(12):1393-1397
A method for performing neutron radiography and locally resolved impedance spectroscopy simultaneously in situ in an operating polymer electrolyte fuel cell (PEFC) is presented. The new method provides concurrently spatially resolved information about the local cell performance, the locally limiting processes, and the liquid water distribution. Information about the impact of water on cell performance and limiting processes can be gained in situ on a local scale in an operating PEFC. The method was applied to a PEFC operated on pure H2/O2 in co-flow mode under low humidity operating conditions. The results show that in co-flow mode strong flooding and severe drying can occur at the very same time in different sections of a PEFC. 相似文献
104.
Possible mechanisms for degrading chloromethylmercury (CH(3)HgCl) and dimethylmercury [(CH3)2Hg] involving thiol and ammonium residues were investigated by DFT and atoms-in-molecules (QTAIM) calculations. Using H2S and HS- as models for thiol and thiolate groups RSH and RS-, respectively, we obtained transition states and energy barriers for possible decomposition routes to Hg(SH)2 based on a model proposed by Moore and Pitts (Moore, M. J.; Distefano, M. D.; Zydowsky, L. D.; Cummings, R. T.; Walsh, C. T. Acc. Chem. Res. 1990, 23, 301. Pitts, K. E.; Summers, A. O. Biochemistry 2002, 41, 10287). Demethylation was found to be a multistep process that involved initial substitution of Cl- by RS-. We found that successive coordination of Hg with thiolates leads to increased negative charge on the methyl group and facilitates the protonolysis of the Hg-C bond by H-SH. This was also found to be the case for (CH3)2Hg. We found that NH4(+) readily protonolyzes the Hg-C bond of these thiolate complexes, suggesting that ammonium residues of protonated amino acids might also act as effective proton donors. 相似文献
105.
Boryl‐Functionalized σ‐Alkynyl and Vinylidene Rhodium Complexes: Synthesis and Electronic Properties 下载免费PDF全文
Prof. Dr. Holger Braunschweig Christopher K. L. Brown Dr. Rian D. Dewhurst Dr. J. Oscar C. Jimenez‐Halla Thomas Kramer Dr. Ivo Krummenacher Dr. Bernd Pfaffinger 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(5):1427-1433
The synthesis, reactivity, and properties of boryl‐functionalized σ‐alkynyl and vinylidene rhodium complexes such as trans‐[RhCl(?C?CHBMes2)(PiPr3)2] and trans‐[Rh(C?CBMes2)(IMe)(PiPr3)2] are reported. An equilibrium was found to exist between rhodium vinylidene complexes and the corresponding hydrido σ‐alkynyl complexes in solution. The complex trans‐[Rh(C?CBMes2)(IMe)(PiPr3)2] (IMe=1,3‐dimethylimidazol‐2‐ylidene) was found to exhibit solvatochromism and can be quasireversibly oxidized and reduced electrochemically. Density functional calculations were performed to determine the reaction mechanism and to help rationalize the photophysical properties of trans‐[Rh(C?CBMes2)(IMe)(PiPr3)2]. 相似文献
106.
The Synthesis of B2(SIDip)2 and its Reactivity Between the Diboracumulenic and Diborynic Extremes 下载免费PDF全文
Julian Bhnke Holger Braunschweig Theresa Dellermann William C. Ewing Kai Hammond J. Oscar C. Jimenez‐Halla Thomas Kramer Jan Mies 《Angewandte Chemie (International ed. in English)》2015,54(46):13801-13805
A new compound with the formula L‐B2‐L wherein the stabilizing ligand (L) is 1,3‐bis[diisopropylphenyl]‐4,5‐dihydroimidazol‐2‐ylidene (SIDip) has been synthesized, isolated, and characterized. The π‐acidity of the SIDip ligand, intermediate between the relatively non‐acidic IDip (1,3‐bis[diisopropylphenyl]imidazol‐2‐ylidene) ligand and the much more highly acidic CAAC (1‐[2,6‐diisopropylphenyl]‐3,3,5,5‐tetramethylpyrrolidin‐2‐ylidene) ligand, gives rise to a compound with spectroscopic, electrochemical, and structural properties between those of L‐B2‐L compounds stabilized by CAAC and IDip. Reactions of all three L‐B2‐L compounds with CO demonstrate the differences caused by their respective ligands, as the π‐acidities of the CAAC and SIDip carbenes enabled the isolation of bis(boraketene) compounds (L(OC)B‐B(CO)L), which could not be isolated from reactions with B2(IDip)2. However, only B2(IDip)2 and B2(SIDip)2 could be converted into bicyclic bis(boralactone) compounds. 相似文献
107.
The offset dependence of homonuclear Hartmann-Hahn transfer is markedly different if a given multiple-pulse sequence is applied to dipolar coupled spins or to isotropically coupled spins. The different offset dependence of the transfer efficiency is studied by numerical simulations of a multiple-pulse sequence and by the analytical treatment of a simple model experiment. 相似文献
108.
S. Caroli M. Spagnoli G. Forte M. Alessandrelli R. Cresti S. D'Ilio J. Pauwels G. N. Kramer Gy. Zray 《Microchemical Journal》2000,67(1-3)
In the framework of the activities of the Community Reference Laboratory (CRL) for residues at the Istituto Superiore di Sanità (ISS) of Rome, a number of proficiency tests were performed in order to assess and improve, wherever necessary, the quality of regulatory residue analysis within the EU. In this context, a pilot study was undertaken with the purpose of ascertaining the feasibility of a project for the certification of a new reference material for trace elements in bovine muscle. On behalf of the ISS, approximately 70 kg of bovine muscle, collected at a slaughterhouse in Geel (Belgium), were freeze-dried, homogenized, stabilized and bottled under argon atmosphere by the Institute for Reference Materials and Measurements, Joint Research Centre, European Commission (IRMM-JRC-EC). Preliminary analyses were carried out with Quadrupole (Q) and High Resolution (HR) Inductively Coupled Plasma Mass Spectrometry (ICP-MS) to evaluate the content of As, Cd, Cu and Pb, whereas the Flow Injection Mercury System (FIMS) was used to quantify Hg. Digestion of the matrix was achieved by acid-assisted microwave irradiation. The mean values of experimentally obtained data were the following (in nanograms per gram): As, 24.2±1.2; Cd, 5.48±0.29; Cu, 4765±95; Hg, 3.37±0.73; and Pb, 184±7. Subsequently, 16 National Reference Laboratories (NRLs) for residues in the Member States plus the Norwegian one and eight Italian public laboratories were accepted to participate in the project and received one bottle of the freeze-dried bovine muscle. The laboratories were requested to perform three different analytical runs (in three different days), each consisting of three individual measurements. Preliminary results showed good agreement and fair evidence for homogeneity of the entire mass, thus setting the stage for the future certification of this candidate CRM. 相似文献
109.
A synthetic route towards surface modified, monodisperse, spherical particles is presented. The precursor particles exhibit epoxy‐functionalities which can be opened afterwards with an appropriate nucleophile. Via this route, dye labeled particles are obtained. Copyright © 2004 John Wiley & Sons, Ltd. 相似文献