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81.
The La0.6Sr0.4Co0.2Fe0.8O3 (LSCF48) cathode material was used as a protective-conducting coating on an interconnect made of Crofer 22 APU ferritic steel intended for application in intermediate-temperature solid oxide fuel cell (IT-SOFC) stacks. The LSCF48 coating was deposited on the surface of the steel via screen-printing followed by appropriate thermal treatment. The oxidation kinetics of the Crofer 22 APU steel—uncoated and coated with LSCF48—approximately obeys the parabolic rate law in air at 1,073 K under isothermal and cyclic oxidation conditions. The oxidation rate for uncoated steel is higher than that for coated steel. SEM–EDS and XRD investigations showed that the LSCF48 coating interacts with the steel during long-term oxidation in the afore-mentioned thermal conditions, and an intermediate multilayer interfacial zone is formed. This intermediate layer leads to lower area specific resistance in air at 1,073 K in comparison to the Crofer 22 APU steel without surface modification. 相似文献
82.
Eduard Hryha Henrik Borgström Karin Sterky Lars Nyborg 《Journal of Thermal Analysis and Calorimetry》2014,118(2):695-704
Binders present an important part of the powder metallurgy technology as they are vital to provide efficient powder agglomeration and/or lubrication during shaping. At the same time, they have to be easily removed from the compacts during initial stages of sintering without any harmful effect for the base material, as well as for the environment. Therefore, behavior of gelatin as a binder for stainless- and tool-steel gas-atomised powder compacts was studied by thermal analysis and electron microscopy. Thermal analysis showed that peak mass-loss occurred in the range between 340 and 370 °C, depending on the base powder and heating rate. Risk for base powder oxidation at temperatures below 425 °C was detected. Based on the obtained results, it is recommended to perform debinding at ~425 °C after applying a heating rate of around 7.5 °C min?1. Only in this way efficient enough binder removal can be obtained concurrently to avoiding base powder oxidation. 相似文献
83.
Regiospecific Formation and Unusual Optical Properties of 2,5‐Bis(arylethynyl)rhodacyclopentadienes: A New Class of Luminescent Organometallics 下载免费PDF全文
Dr. Andreas Steffen Dr. Richard M. Ward Dr. Meng Guan Tay Dr. Robert M. Edkins Dr. Fabian Seeler Magda van Leeuwen Dr. Lars‐Olof Pålsson Prof. Dr. Andrew Beeby Dr. Andrei S. Batsanov Prof. Dr. Judith A. K. Howard Prof. Dr. Todd B. Marder 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(13):3652-3666
A series of 2,5‐bis(arylethynyl)rhodacyclopentadienes has been prepared by a rare example of regiospecific reductive coupling of 1,4‐(p‐R‐phenyl)‐1,3‐butadiynes (R?H, Me, OMe, SMe, NMe2, CF3, CO2Me, CN, NO2, ?C?C‐(p‐C6H4?NHex2), ?C?C?(p‐C6H4?CO2Oct)) at [RhX(PMe3)4] ( 1 ) (X=?C?C?SiMe3 ( a ), ?C?C‐(p‐C6H4?NMe2) ( b ), ?C?C?C?C?(p‐C6H4?NPh2) ( c ) or ?C?C?{p‐C6H4‐C?C?(p‐C6H4‐N(C6H13)2)} ( d ) or Me ( e )), giving the 2,5‐bis(arylethynyl) isomer exclusively. The rhodacyclopentadienes bearing a methyl ligand in the equatorial plane (compound 1 e ) have been converted into their chloro analogues by reaction with HCl etherate. The rhodacycles thus obtained are stable to air and moisture in the solid state and the acceptor‐substituted compounds are even stable to air and moisture in solution. The photophysical properties of the rhodacyclopentadienes are highly unusual in that they exhibit, exclusively, fluorescence between 500–800 nm from the S1 state, with quantum yields of Φ=0.01–0.18 and short lifetimes (τ=0.45–8.20 ns). The triplet state formation (ΦISC=0.57 for 2 a ) is exceptionally slow, occurring on the nanosecond timescale. This is unexpected, because the Rh atom should normally facilitate intersystem crossing within femto‐ to picoseconds, leading to phosphorescence from the T1 state. This work therefore highlights that in some transition‐metal complexes, the heavy atom can play a more subtle role in controlling the photophysical behavior than is commonly appreciated. 相似文献
84.
Kay Hettrich Manfred Pinnow Bert Volkert Lars Passauer Steffen Fischer 《Cellulose (London, England)》2014,21(4):2479-2488
Novel nanoscaled cellulose particles were prepared using high-pressure homogenization of aqueous media contenting treated cellulose samples in a Microfluidizer® processor (MF). Here, we present the generation of spherical cellulose nanoparticles as an extension of previously published reports of nano fibrillated cellulose. Although MF treatment of unmodified cellulose yields nanofibrils which are reported in several publications, in the current work different kinds of pretreatments were proven to be necessary to obtain spherical structured cellulose nanoparticles. One such treatment may be the decrystallization of cellulose regenerating it from N-methylmorpholine-N-oxid-monohydrate (NMMNO*H2O). Nanocellulose was then obtained by a subsequent high-pressure mechanical treatment of the precipitate in aqueous dispersion. Decrystallization was also realized by grinding cellulose in a planetary ball mill. The resulting amorphous intermediates were characterized by Raman spectroscopy. Another approach tested was hydrolysis and subsequent mechanical treatment using an Ultra-Turrax® and MF. Another alternative was given by the mechanical treatment of aqueous dispersions of low substituted cellulose derivatives such as carboxymethyl cellulose and oxidized cellulose without any further hydrolysis. 相似文献
85.
Andrew Marais Mikael S. Magnusson Thomas Joffre Erik L. G. Wernersson Lars Wågberg 《Cellulose (London, England)》2014,21(6):3941-3950
Polyelectrolytes have been used extensively in the papermaking industry for various purposes. Although recent studies have shown that polyamines can be efficient dry-strength additives, the mechanism governing the strength enhancement of paper materials following the adsorption of polyamines onto pulp fibres is still not well understood. In this study, the effect of the adsorption of polyallylamine hydrochloride (PAH) onto the surface of unbleached kraft pulp fibres was investigated on both the fibre and the network scale. Isolated fibre crosses were mechanically tested to evaluate the impact of the chemical additive on the interfibre joint strength on the microscopic scale and the effect was compared with that previously observed on the paper sheet scale. X-ray microtomography was used to understand structural changes in the fibrous network following the adsorption of a polyamine such as PAH. Using image analysis methods, it was possible to determine the number of interfibre contacts (or joints) per unit length of fibre as well as the average interfibre joint contact area. The results showed that the median interfibre joint strength increased by 18 % upon adsorption of PAH. This can be achieved both by a larger molecular contact area in the contact zones and by a stronger molecular adhesion. The addition of the polymer also increased the number of efficient interfibre contacts per sheet volume. This combination of effects is the reason why polyamines such as PAH can increase the dry tensile strength of paper materials. 相似文献
86.
Henriette N. Tobiesen Dr. Lars A. Leth Marc V. Iversen Dr. Line Næsborg Dr. Søren Bertelsen Prof. Dr. Karl Anker Jørgensen 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(42):18648-18652
The first stereoselective, near-equimolar, and metal-free oxidative bioconjugation of amino acids and oligopeptides to aldehydes is presented. Based on a newly developed organocatalytic oxidative concept, the C-terminal and side-chain carboxylic acid functionalities of amino acids and oligopeptides are shown to couple in a stereoselective manner to α-branched aldehydes catalyzed by a chiral primary amine and a quinone as oxidizing agent. The oxidative coupling generally proceeds in high yield. For aspartic acid, selective coupling of the side-chain, or the C-terminal carboxylic acid, is demonstrated depending on the protection strategy. The stereoselective, oxidative bioconjugation concept is extended to a series of oligopeptides where coupling to carboxylic acid functionalities is presented. Bioorthogonal linker molecules for further functionalization are obtained by merging the oxidative coupling strategy with the click concept. It is demonstrated that the configuration of the new stereocenter is determined exclusively by the organocatalyst. 相似文献
87.
Dr. Kang Cheng Lars I. van der Wal Dr. Hideto Yoshida Jogchum Oenema Dr. Justine Harmel Dr. Zhaorong Zhang Dr. Glenn Sunley Dr. Jovana Zečević Prof. Krijn P. de Jong 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(9):3620-3628
Improving product selectivity by controlling the spatial organization of functional sites at the nanoscale is a critical challenge in bifunctional catalysis. We present a series of composite bifunctional catalysts consisting of one-dimensional zeolites (ZSM-22 and mordenite) and a γ-alumina binder, with platinum particles controllably deposited either on the alumina binder or inside the zeolite crystals. The hydroisomerization of n-heptane demonstrates that the catalysts with platinum particles on the binder, which separates platinum and acid sites at the nanoscale, leads to a higher yield of desired isomers than catalysts with platinum particles inside the zeolite crystals. Platinum particles within the zeolite crystals impose pronounced diffusion limitations on reaction intermediates, which leads to secondary cracking reactions, especially for catalysts with narrow micropores or large zeolite crystals. These findings extend the understanding of the “intimacy criterion” for the rational design of bifunctional catalysts for the conversion of low-molecular-weight reactants. 相似文献
88.
Lars Müller Santina Hoof Matthias Keck Christian Herwig Prof. Dr. Christian Limberg 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(51):11851-11861
The design of biomimetic model complexes for the cysteine dioxygenase (CDO) and cysteamine dioxygenase (ADO) is reported, where the 3-His coordination of the iron ion is simulated by three pyrazole donors of a trispyrazolyl borate ligand (Tp) and protected cysteine and cysteamine represent substrate ligands. It is found that the replacement of phenyl groups—attached at the 3-positions of the pyrazole units in a previous model—by mesityl residues has massive consequences, as the latter arrange to a more spacious reaction pocket. Thus, the reaction with O2 proceeds much faster and afterwards the first structural characterization of an iron(II) η2-O,O-sulfinate product became possible. If one of the three Tp-mesityl groups is placed in the 5-position, an even larger reaction pocket results, which leads to yet faster rates and accumulation of a reaction intermediate at low temperatures, as shown by UV/Vis and Mössbauer spectroscopy. After comparison with the results of investigations on the cobalt analogues this intermediate is tentatively assigned to an iron(III) superoxide species. 相似文献
89.
Long Yang Ralf Steinbock Alexej Scheremetjew Rositha Kuniyil Lars H. Finger Antonis M. Messinis Lutz Ackermann 《Angewandte Chemie (International ed. in English)》2020,59(27):11130-11135
A ruthenium‐catalyzed electrochemical dehydrogenative annulation reaction of imidazoles with alkynes has been established, enabling the preparation of various bridgehead N‐fused [5,6]‐bicyclic heteroarenes through regioselective electrochemical C?H/N?H annulation without chemical metal oxidants. Novel azaruthenabicyclo[3.2.0]heptadienes were fully characterized and identified as key intermediates. Mechanistic studies are suggestive of an oxidatively induced reductive elimination pathway within a ruthenium(II/III) regime. 相似文献
90.
Grzegorz Greczynski Lars Hultman 《Angewandte Chemie (International ed. in English)》2020,59(13):5002-5006
X‐ray photoelectron spectroscopy (XPS) is an indispensable technique in modern materials science for the determination of chemical bonding as evidenced by more than 10 000 XPS papers published annually. A literature survey reveals that in the vast majority of cases an incorrect referencing of the binding energy scale is used, neglecting warnings that have been formulated from the early days of the technique. Consequences for the data reliability are disastrous and decades of XPS work require revisiting. The purpose of this Viewpoint is to highlight the existing problems, review the criticism and suggest ways forward. 相似文献