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排序方式: 共有95条查询结果,搜索用时 31 毫秒
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R B Timmons 《Photochemistry and photobiology》1970,12(3):219-230
Abstract— The gas phase photochemical reactions of SO2 induced by 3130 Å radiation have been studied in the presence of added alkanes or added CO. The quantum yields obtained in the reactions with the low molecular weight alkanes employed are lower than those obtained by previous workers. The quantum yields were found to be pressure dependent increasing slowly with increasing pressure. A stoichiometric ratio of one SO2 removed per molecule of hydrocarbon consumed was observed only under experimental conditions of [SO2] < [RH]. For reaction mixtures where [SO2] < [RH] the ratio of [SO2]/[RH] reacted always exceeded unity. The quantum yields decreased slightly with increasing temperature. In all the alkane reaction systems studied, the deposition of viscous, nonvolatile reaction products was observed. In the experiments with added CO, the quantum yields were computed with respect to the rate of CO2 formation. At 25°C and equal pressures of SO2 and CO, φco2 was observed to be 0.005 and it decreased slightly with increasing temperature. The results obtained are interpreted in terms of the sulfoxidation of the alkanes and the oxidation of CO proceeding by way of a 3SO2 reaction intermediate. 相似文献
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Cotton FA Daniels LM Murillo CA Timmons DJ Wilkinson CC 《Journal of the American Chemical Society》2002,124(31):9249-9256
Full characterization of the first homologous series of dimolybdenum paddlewheel compounds having electronic configurations of the types sigma(2)pi(4)delta(x), x = 2, 1, 0, and Mo-Mo bond orders of 4, 3.5, and 3, respectively, has been accomplished with the guanidinate-type ligand hpp (hpp = the anion of 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidine). Essentially quantitative oxidation of Mo(2)(hpp)(4), 1, by CH(2)Cl(2) gives Mo(2)(hpp)(4)Cl, 2. The halide in 2 can be replaced by reaction with TlBF(4) to produce Mo(2)(hpp)(4)(BF(4)), 3. Further oxidation of 2 by AgBF(4) produces Mo(2)(hpp)(4)ClBF(4), 4. The change from bond order 4 (in 1) to 3.5 in Mo(2)(hpp)(4)Cl is accompanied by an increase in the Mo-Mo bond length of 0.061 to 2.1280(4) A. A further increase of 0.044 A in the Mo-Mo distance to 2.172(1) A is observed as the bond order decreases to 3 in 4. At the same time, the Mo-N distances decrease smoothly as the oxidation state of the Mo atoms increases. Electrochemical studies have shown two chemically reversible processes at very negative potentials, E(1)(1/2)= -0.444 V and E(2)(1/2)= -1.271 V versus Ag/AgCl. These correspond to the processes Mo(2)(6+/5+) and Mo(2)(5+/4+), respectively. The latter potential is displaced by over 1.5 V relative to those of the Mo(2)(formamidinate)(4) compounds and the first one has never been observed in such complexes. Thus, in surprising contrast to previously observed behavior of the dimolybdenum unit, when it is surrounded by the very basic guanidinate ligand hpp, there is an extraordinary stabilization of the higher oxidation numbers of the molybdenum atoms. 相似文献
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Wang Jenn-Henn Chen Xiaolan Chen Jin-Jian Calderon Jose G. Timmons Richard B. 《Plasmas and Polymers》1997,2(4):245-260
The use of a variable duty cycle pulsed RF plasma is shown to provide film chemistry control during polymerization of saturated (CH2Br2) and unsaturated (CH2=CHCH2Br) bromine containing monomers. With both monomers, the degree of bromine atom retention in the films is observed to increase in a progressive fashion as the RF duty cycle employed during plasma polymerization is decreased. The film deposition rates, when expressed in terms of thickness per Joule of RF energy input, increase rapidly as the RF duty cycles are reduced. Additionally, the film morphology is observed to become increasingly smooth with decreasing RF duty cycles during deposition, as illustrated with the allyl bromide monomer. The film chemistry controllability of this study is demonstrated with monomers possessing the relatively weak C-Br bond. As such, the present work represents an important extension of the pulsed plasma polymerization approach to include retention of a labile bond during film formation. The introduction of reactive surface functional groups, at controlled densities, provides additional molecular tailoring possibilities via subsequent chemical derivatization processes. 相似文献
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J.J. Bernstein S. FellerA. Ramm J. NorthJ. Maldonis M. MescherW. Robbins R. StonerB. Timmons 《Solid State Ionics》2011,198(1):47-49
Cesium containing glass with solid metal electrodes was used as a Cs atom source in a high vacuum system. A silver anode provides an injection source of highly mobile ions which sweep Cs to the cathode surface, from which they evaporate into the vacuum. Cathode metallization with finger patterns was used leaving bare glass for Cs evaporation. Laser absorption measurements show Cs vapor generation synchronous with an applied DC voltage. 相似文献
8.
Todd Timmons 《Historia Mathematica》2004,31(4):102
Mathematics in the United States developed slowly over its first one hundred years. Before the appearance of successful mathematics journals, American mathematicians depended on science journals to publish their work. Three journals, the Transactions of the American Philosophical Society, the Memoirs of the American Academy of Arts and Sciences, and the American Journal of Science and Arts, played pivotal roles in the development of a mathematics publication community. 相似文献
9.
Marcos Ghislandi Luis Antonio Sanchez de A. Prado Alejandra de la Vega Oyerviedes Hans Wittich Karl Schulte Ana Barros‐Timmons 《Journal of polymer science. Part A, Polymer chemistry》2008,46(10):3326-3335
Vapor‐grown carbon nanofibers (CNFs) were oxidized and functionalized for atom transfer radical polymerization (ATRP) of tert‐butyl acrylate (t‐BA) from the surface of the CNFs. The materials were characterized by solubility tests, Fourier‐transform infrared (FTIR) spectroscopy, Raman spectroscopy, thermogravimetric analysis (TGA), X‐ray diffraction (XRD), and scanning electron microscopy. The FTIR and electron microscopy results suggest that ATRP process was successfully used to graft poly(tert‐butyl acrylate) (poly(t‐BA)) chains from the surface of the fibers. Raman results strongly indicate the partial degradation of the graphitic layer of CNFs because of the chemical treatments. TGA results suggest that the presence of poly(t‐BA) leads to a decrease of the initial degradation temperature of the fibers. XRD and electron microscopy results indicate that the microstructure of fibers was not destroyed because of the oxidation and functionalization processes. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3326–3335, 2008 相似文献
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