全文获取类型
收费全文 | 2650篇 |
免费 | 94篇 |
国内免费 | 14篇 |
学科分类
数理化 | 2758篇 |
出版年
2023年 | 13篇 |
2022年 | 10篇 |
2021年 | 26篇 |
2020年 | 32篇 |
2019年 | 56篇 |
2018年 | 21篇 |
2017年 | 28篇 |
2016年 | 64篇 |
2015年 | 48篇 |
2014年 | 55篇 |
2013年 | 105篇 |
2012年 | 178篇 |
2011年 | 214篇 |
2010年 | 78篇 |
2009年 | 88篇 |
2008年 | 154篇 |
2007年 | 194篇 |
2006年 | 171篇 |
2005年 | 177篇 |
2004年 | 155篇 |
2003年 | 128篇 |
2002年 | 117篇 |
2001年 | 50篇 |
2000年 | 36篇 |
1999年 | 26篇 |
1998年 | 29篇 |
1997年 | 21篇 |
1996年 | 33篇 |
1995年 | 17篇 |
1994年 | 35篇 |
1993年 | 29篇 |
1992年 | 24篇 |
1991年 | 23篇 |
1989年 | 19篇 |
1988年 | 17篇 |
1987年 | 16篇 |
1986年 | 12篇 |
1985年 | 21篇 |
1984年 | 23篇 |
1983年 | 22篇 |
1982年 | 15篇 |
1981年 | 22篇 |
1980年 | 12篇 |
1978年 | 12篇 |
1977年 | 14篇 |
1976年 | 13篇 |
1975年 | 7篇 |
1974年 | 12篇 |
1973年 | 11篇 |
1971年 | 7篇 |
排序方式: 共有2758条查询结果,搜索用时 15 毫秒
1.
2.
Daria E. Lonsdale Geoffrey Johnston‐Hall Amanda Fawcett Craig A. Bell Carl N. Urbani Michael R. Whittaker Michael J. Monteiro 《Journal of polymer science. Part A, Polymer chemistry》2007,45(16):3620-3625
In this work, we propose that retardation in vinyl acetate polymerization rate in the presence of toluene is due to degradative chain transfer. The transfer constant to toluene (Ctrs) determined using the Mayo method is equal to 3.8 × 10?3, which is remarkably similar to the value calculated from the rate data, assuming degradative chain transfer (2.7 × 10?3). Simulations, including chain‐length‐dependent termination, were carried out to compare our degradative chain transfer model with experimental results. The conversion–time profiles showed excellent agreement between experiment and simulation. Good agreement was found for the Mn data as a function of conversion. The experimental and simulation data strongly support the postulate that degradative chain transfer is the dominant kinetic mechanism. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3620–3625, 2007 相似文献
3.
4.
This paper reviews the properties of the cathode ion flux generated in the vacuum arc. The structure and distribution of mass erosion from individual cathode spots and the characteristics of current carriers from the cathode region at moderate arc currents are described. An appreciable ion flux (~10% of total arc current) is emitted from the cathode of a vacuum arc. This ion flux is strongly peaked in the direction of the anode, though some ion flux may be seen even at angles below the plane of the cathode surface. The observed spatial distribution of the ion flux is expressed quite well as an exponential function of solid angle. The ion flux is quite energetic, with average ion potentials much larger than the arc voltage, and generally contains a considerable fraction of multiply-charged ions. The average ion potential and ion multiplicity increase significantly for cathode materials with higher arc voltages, but decrease with increasing arc current for a particular material. The main theories concerning ion acceleration in cathode spots are the potential hump theory (PH), which assumes that all ions are created at the same potential, and the gas dynamic theory (GD), which assumes that all ions are created with the same flow velocity. Experimental data on the potentials and energies of individual ions indicates that these theories in their original forms are not quite correct, however extensions or modifications of the PH and GD theories seem very likely to be able to predict correct values for the charge states, potentials, and energies of individual ions. 相似文献
5.
6.
Padma Gopalan Xuefa Li Mingqi Li Christopher K. Ober Chad P. Gonzales Craig J. Hawker 《Journal of polymer science. Part A, Polymer chemistry》2003,41(22):3640-3656
A modular approach has been developed for the synthesis of rod–coil block copolymers involving the initial preparation of a macroinitiator based on the rod block followed by the growth of the coil segment with living free-radical procedures. The key feature of this strategy is the utilization of an alkoxyamine group from the beginning of the synthesis, which serves as a solubilizing group and ensures that each rod block contains a single initiating fragment. Using this approach permits block copolymers based on insoluble biphenyl ester oligomers to be conveniently prepared with coil segments that range from styrenes to acrylates to 1,3-dienes. The tendency of the rod segments to crystallize is strongly dependent on the weight fraction of the rod segment and the chemical nature of the coil segment. Rod–coil molecules containing at least 25–35 wt % polystyrene or poly(n-butyl acrylate) coil segments show a two-dimensional hexagonal arrangement of rod aggregates, as characterized by transmission electron microscopy and small-angle X-ray scattering. Polyisoprene block copolymers exhibit a lamellar microstructure with short rigid domains in which the rod units lie in an interdigitated smectic C arrangement. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3640–3656, 2003 相似文献
7.
8.
Amanda J. Ziegler Craig C. McLauchlan Cyndi R. Sosnowski Albert W. Herlinger 《Acta Crystallographica. Section C, Structural Chemistry》2007,63(2):o132-o134
The title compound (H2DTMSP[EBP]), C14H36O6P2Si2, was crystallized by the slow evaporation of a solution in a 20:1 mixture of pentane and acetone. The H2DTMSP[EBP] molecule lies about an inversion center. In the solid state, the molecule exists in an anti configuration, with the molecular backbone C—C bond located on an inversion center. The compound exists in the solid state as hydrogen‐bonded infinite sheets in the ab plane, unlike the methylene analogue, which exists as hydrogen‐bonded infinite chains, demonstrating an `even–odd' effect of the length of the backbone alkyl chain. 相似文献
9.
Rachel K. O'Reilly Maisie J. Joralemon Craig J. Hawker Karen L. Wooley 《Journal of polymer science. Part A, Polymer chemistry》2006,44(17):5203-5217
Block copolymer micelles and shell cross-linked nanoparticles (SCKs) presenting Click-reactive functional groups on their surfaces were prepared using two separate synthetic strategies, each employing functionalized initiators for the controlled radical polymerization of acrylate and styrenic monomers to afford amphiphilic block copolymers bearing an alkynyl or azido group at the α-terminus. The first route for the synthesis of the azide-functionalized nanostructures was achieved via sequential nitroxide-mediated radical polymerization (NMP) of tert-butyl acrylate and styrene, originating from a benzylic chloride-functionalized initiator, followed by deprotection of the acrylic acids, supramolecular assembly of the block copolymer in water and conversion of the benzylic chloride to a benzylic azide. In contrast, the second strategy utilized an alkynyl-functionalized reversible addition fragmentation transfer (RAFT) agent directly for the RAFT-based sequential polymerization of tetrahydropyran acrylate and styrene, followed by selective cleavage of the tetrahydropyran esters to give the α-alkynyl-functionalized block copolymers. These Click-functionalized polymers, with the functionality located at the hydrophilic polymer termini, were then self-assembled using a mixed-micelle methodology to afford surface-functionalized “Clickable” micelles in aqueous solutions. The optimum degree of incorporation of the Click-functionalized polymers was investigated and determined to be ca. 25%, which allowed for the synthesis of well-defined surface-functionalized nanoparticles after cross-linking selectively throughout the shell layer using established amidation chemistry. Functionalization of the chain ends was shown to be an efficient process under standard Click conditions and the resulting functional groups revealed a more “solution-like” environment when compared to the functional group randomly inserted into the hydrophilic shell layer. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5203–5217, 2006 相似文献
10.
Olga Ordeig Craig E Banks Trevor J Davies F Javier del Campo Francesc Xavier Mu?oz Richard G Compton 《Analytical sciences》2006,22(5):679-683
Gold ultra-microelectrode arrays are used to explore the electrochemical oxidation of hydroxide ions and are shown to be analytical useful. Two types of ultra-microelectrode arrays are used; the first consist of 256 individual electrodes of 5 microm in radius, 170 of which are electrochemically active in a cubic arrangement which are separated from their nearest neighbour by a distance of 100 microm. The second array compromises 2597 electrodes of 2.5 microm in radius and of which 1550 of which are electrochemically active in a hexagonal arrangement separated by the nearest neighbour by 55 microm. Well defined voltammetric waves are found with peak currents proportional to the concentration of hydroxide ions in the range 50 microM to 1 mM. Detection limits of 20 microM using the 170 ultra-microelectrode and 10 microM with the 1550 ultra-microelectrode array are shown to be possible but with a higher sensitivity of 4 mA M(-1) observed using the 1550 ultra-microelectrode array compared to 1.2 mA M(-1) with the 170 ultra-microelectrode array. 相似文献