全文获取类型
收费全文 | 25606篇 |
免费 | 2152篇 |
国内免费 | 858篇 |
专业分类
化学 | 22543篇 |
晶体学 | 79篇 |
力学 | 332篇 |
综合类 | 42篇 |
数学 | 1400篇 |
物理学 | 4220篇 |
出版年
2023年 | 178篇 |
2022年 | 350篇 |
2021年 | 462篇 |
2020年 | 810篇 |
2019年 | 686篇 |
2018年 | 604篇 |
2017年 | 744篇 |
2016年 | 1112篇 |
2015年 | 988篇 |
2014年 | 1183篇 |
2013年 | 1889篇 |
2012年 | 1311篇 |
2011年 | 1397篇 |
2010年 | 1189篇 |
2009年 | 1408篇 |
2008年 | 1370篇 |
2007年 | 1439篇 |
2006年 | 1261篇 |
2005年 | 1076篇 |
2004年 | 1048篇 |
2003年 | 938篇 |
2002年 | 1662篇 |
2001年 | 512篇 |
2000年 | 380篇 |
1999年 | 401篇 |
1998年 | 380篇 |
1997年 | 298篇 |
1996年 | 273篇 |
1995年 | 261篇 |
1994年 | 208篇 |
1993年 | 199篇 |
1992年 | 188篇 |
1991年 | 122篇 |
1990年 | 70篇 |
1989年 | 69篇 |
1988年 | 66篇 |
1985年 | 119篇 |
1984年 | 151篇 |
1983年 | 121篇 |
1982年 | 182篇 |
1981年 | 134篇 |
1980年 | 122篇 |
1979年 | 128篇 |
1978年 | 115篇 |
1977年 | 156篇 |
1976年 | 120篇 |
1975年 | 133篇 |
1974年 | 170篇 |
1973年 | 137篇 |
1972年 | 83篇 |
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
71.
Thermotropic copolyester fibers of oxynaphthoate and oxybenzoate have been subjected to conditions that promote solid-state polymerization as well as annealing. The annealing process causes the crystals to perfect with a simultaneous increase in heat of fusion and melting temperature. Solid-state polymerization, a reaction rate-controlled process, causes the polymer viscosity average molecular weight to increase by chain extension from about 14,000 g/mole to more than 87,000 g/mole with a simultaneous impressive increase in tenacity from about 10 g/d (1.2 GPa) to almost 30 g/d (3.7 GPa). To understand the changes in mechanical properties, we have modeled the fiber structure as short rod-like molecules poorly bonded to a continuous matrix of parallel molecules. Lengthening of the reinforcing molecules facilitates better transfer of load from matrix to molecules, resulting in higher tenacity fibers. © 1994 John Wiley & Sons, Inc. 相似文献
72.
Duygu Avci Aylin Ziylan Albayrak 《Journal of polymer science. Part A, Polymer chemistry》2003,41(14):2207-2217
Two phosphorus‐containing acrylate monomers were synthesized from the reaction of ethyl α‐chloromethyl acrylate and t‐butyl α‐bromomethyl acrylate with triethyl phosphite. The selective hydrolysis of the ethyl ester monomer with trimethylsilyl bromide (TMSBr) gave a phosphonic acid monomer. The attempted bulk polymerizations of the monomers at 57–60 °C with 2,2′‐azobisisobutyronitrile (AIBN) were unsuccessful; however, the monomers were copolymerized with methyl methacrylate (MMA) in bulk at 60 °C with AIBN. The resulting copolymers produced chars on burning, showing potential as flame‐retardant materials. Additionally, α‐(chloromethyl)acryloyl chloride (CMAC) was reacted with diethyl (hydroxymethyl)phosphonate to obtain a new monomer with identical ester and ether moieties. This monomer was hydrolyzed with TMSBr, homopolymerized, and copolymerized with MMA. The thermal stabilities of the copolymers increased with increasing amounts of the phosphonate monomer in the copolymers. A new route to highly reactive phosphorus‐containing acrylate monomers was developed. A new derivative of CMAC with mixed ester and ether groups was synthesized by substitution, first with diethyl (hydroxymethyl)phosphonate and then with sodium acetate. This monomer showed the highest reactivity and gave a crosslinked polymer. The incorporation of an ester group increased the rate of polymerization. The relative reactivities of the synthesized monomers in photopolymerizations were determined and compared with those of the other phosphorous‐containing acrylate monomers. Changing the monomer structure allowed control of the polymerization reactivity so that new phosphorus‐containing polymers with desirable properties could be obtained. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2207–2217, 2003 相似文献
73.
The morphology of blends of styrenic polymers in a matrix of 75% Nylon-6 prepared in a Brabender Plasti-Corder was examined by scanning electron microscopy. Styrene/acrylonitrile copolymers (SAN) form smaller particles as the AN level increases owing to the corresponding decrease in the SAN–polyamide interfacial tension. Various styrenic polymers containing functional groups, maleic anhydride or oxazoline type, that can react with Nylon-6 during melt processing were added to the SAN phase which also led to a decrease in the particle size owing to the graft copolymer formed in situ. The effects of functional group type, amount of functional groups per chain, amount of functional polymer added, and the miscibility of the styrene/maleic anhydride (SMA) and SAN copolymers on the morphology of the styrenic phase in the Nylon-6 matrix are described. © 1992 John Wiley & Sons, Inc. 相似文献
74.
Nicolas Meyer Mohamad Nasser Eddine Christelle Delaite Guy Hurtrez Philippe Dumas 《Journal of polymer science. Part A, Polymer chemistry》2003,41(21):3329-3335
The reactions of polystyryllithium and potassium on dimethoxymethyl 1,1‐diphenylethylene derivatives were studied in different solvents. In a polar medium, A3 and A6 star types were formed according to the stoichiometry, whereas in a nonpolar medium, hyperbranched structures were synthesized. Extensions of an already proposed mechanism in polar and nonpolar media were examined. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3329–3335, 2003 相似文献
75.
Yi Liu David D. Díaz Adrian A. Accurso K. Barry Sharpless Valery V. Fokin M. G. Finn 《Journal of polymer science. Part A, Polymer chemistry》2007,45(22):5182-5189
1,2,3‐Triazole‐based polymers generated from the Cu(I)‐catalyzed cycloaddition between multivalent azides and acetylenes are effective adhesive materials for metal surfaces. The adhesive capacities of candidate mixtures of azide and alkyne components were measured by a modified peel test, using a customized adhesive tester. A particularly effective tetravalent alkyne and trivalent azide combination was identified, giving exceptional strength that matches or exceeds the best commercial formulations. The addition of Cu catalyst was found to be important for the synthesis of stronger adhesive polymers when cured at room temperature. Heating also accelerated curing rates, but the maximum adhesive strengths achieved at both room temperature and high temperature were the same, suggesting that crosslinking reaches the same advanced point in all cases. Polytriazoles also form adhesives to aluminum, but copper is bound more effectively, presumably because active Cu(I) ions may be leached from the surface to promote crosslinking and adhesion. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5182–5189, 2007 相似文献
76.
Yoshitomo Ono Naoyuki Kawashima Hiroto Kudo Tadatomi Nishikubo Takabumi Nagai 《Journal of polymer science. Part A, Polymer chemistry》2007,45(14):2978-2988
The ring‐opening copolymerization of a glycidyl ester derivative having a benzophenone group and the donor–acceptor norbornadiene (D‐A NBD) dicarboxylic acid, 5‐(4‐methoxyphenyl)‐1,4,6,7,7‐pentamethyl‐2,5‐norbornadiene‐2,3‐dicarboxylic acid, monoglycidyl ester derivatives with D‐A NBD dicarboxylic anhydride using tetraphenylphosphonium bromide as a catalyst proceeded smoothly to give novel self‐photosensitizing NBD polymers in good yields. The molecular weight of these polyesters was about 4,000, and lower than that of analogous NBD polymers having no benzophenone group. All the synthesized NBD polymers isomerized smoothly to the corresponding quadricyclane (QC) polymers upon UV irradiation in tetrahydrofuran (THF) solution and in the film state. The rate of the photoisomerization of the D‐A NBD moieties in these polymers was higher than that of the D‐A NBD moieties in the polymer having no photosensitizing group. Furthermore, the rate of the photoisomerization of the D‐A NBD moieties in these polymers was also higher than that of the NBD polymer with low molecular weight photosensitizer in dilute solution. The photo‐irradiated polymers having QC moieties released thermal energies of 146–180 J/g. The D‐A NBD moieties contained in these NBD polymers possessed fair to good fatigue resistance. The degradation of the NBD moieties in these polymers was 15–30% after 50 repeated cycles of interconversion. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2978–2988, 2007 相似文献
77.
Ilaria Fratoddi Chiara Battocchio Alessandra L. Groia Maria V. Russo 《Journal of polymer science. Part A, Polymer chemistry》2007,45(15):3311-3329
The reactivity of square planar palladium(II) and platinum(II) complexes in trans or cis configuration, namely trans or cis‐[dichlorobis(tributylphosphine)platinum(II)] and trans‐[dichlorobis(tributylphosphine)palladium(II)] with 1,1′‐bis(ethynyl) 4,4′‐biphenyl, DEBP, leading to π‐conjugated organometallic oligomeric and polymeric metallaynes, was investigated by a systematic variation of the reaction conditions. The formation of polymers and oligomers with defined chain length [? M(PBu3)2 (C?C? C6H4? C6H4? C?C? )]n (n = 3–10 for the oligomers, n = 20–50 for the polymers) depends on the configuration of the precursor Pt(II) and Pd(II) complexes, the presence/absence of the catalyst CuI, and the reaction time. A series of model reactions monitored by XPS, GPC, and NMR 31P spectroscopy showed the route to modulate the chain growth. As expected, the nature of the transition metal (Pt or Pd) and the molecular weight of the polymers markedly influence the photophysical characteristics of the polymetallaynes, such as optical absorption and emission behavior. Polymetallaynes with nanostructured morphology could be obtained by a simple casting procedure of polymer solutions. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3311–3329, 2007 相似文献
78.
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
79.
Ioannis K. Argyros 《Journal of Mathematical Analysis and Applications》2004,298(2):374-397
We provide a local as well as a semilocal convergence analysis for two-point Newton-like methods in a Banach space setting under very general Lipschitz type conditions. Our equation contains a Fréchet differentiable operator F and another operator G whose differentiability is not assumed. Using more precise majorizing sequences than before we provide sufficient convergence conditions for Newton-like methods to a locally unique solution of equation F(x)+G(x)=0. In the semilocal case we show under weaker conditions that our error estimates on the distances involved are finer and the information on the location of the solution at least as precise as in earlier results. In the local case a larger radius of convergence is obtained. Several numerical examples are provided to show that our results compare favorably with earlier ones. As a special case we show that the famous Newton-Kantorovich hypothesis is weakened under the same hypotheses as the ones contained in the Newton-Kantorovich theorem. 相似文献
80.
Jan Hamhalter 《International Journal of Theoretical Physics》2004,43(10):2101-2111
We summarize and deepen recent results on the interplay between properties of states and the structure of von Neumann algebras. We treat Jauch–Piron states and the concept of independence in noncommutative probability theory. 相似文献