全文获取类型
收费全文 | 62975篇 |
免费 | 6068篇 |
国内免费 | 4739篇 |
专业分类
化学 | 30042篇 |
晶体学 | 656篇 |
力学 | 3920篇 |
综合类 | 566篇 |
数学 | 10496篇 |
物理学 | 28102篇 |
出版年
2024年 | 94篇 |
2023年 | 546篇 |
2022年 | 1420篇 |
2021年 | 1439篇 |
2020年 | 1588篇 |
2019年 | 1504篇 |
2018年 | 1368篇 |
2017年 | 1514篇 |
2016年 | 1896篇 |
2015年 | 1684篇 |
2014年 | 2361篇 |
2013年 | 4269篇 |
2012年 | 2781篇 |
2011年 | 3119篇 |
2010年 | 2537篇 |
2009年 | 3732篇 |
2008年 | 3903篇 |
2007年 | 4553篇 |
2006年 | 3945篇 |
2005年 | 3061篇 |
2004年 | 2630篇 |
2003年 | 2802篇 |
2002年 | 3061篇 |
2001年 | 2376篇 |
2000年 | 2217篇 |
1999年 | 1891篇 |
1998年 | 1808篇 |
1997年 | 1165篇 |
1996年 | 1085篇 |
1995年 | 908篇 |
1994年 | 930篇 |
1993年 | 712篇 |
1992年 | 747篇 |
1991年 | 495篇 |
1990年 | 476篇 |
1989年 | 359篇 |
1988年 | 334篇 |
1987年 | 314篇 |
1986年 | 287篇 |
1985年 | 249篇 |
1984年 | 258篇 |
1983年 | 144篇 |
1982年 | 201篇 |
1981年 | 201篇 |
1980年 | 131篇 |
1979年 | 154篇 |
1978年 | 134篇 |
1977年 | 120篇 |
1976年 | 75篇 |
1973年 | 63篇 |
排序方式: 共有10000条查询结果,搜索用时 11 毫秒
1.
Padavattan Govindaswamy Patrick J. Carroll Yurij A. Mozharivskyj Mohan Rao Kollipara 《Journal of Chemical Sciences》2006,118(4):319-326
The reaction of [{(η5-C5Me5)M(μ-Cl)Cl}2] {where M = Rh (1), Ir (2)} with functionalized phosphine viz., diphenyl-2-pyridylphosphine (PPh2Py) in dichloromethane solvent yield neutral ϰ1-P-coordinated rhodium and iridium complexes [(η5-C5Me5)RhCl2(κ1-P-PPh2Py)]3 and [(η5-C5Me5) IrCl2(ϰ1-P-PPh2Py)]4. Reaction of complexes 1 and 2 with the ligand PPh2Py in methanol under reflux give bis-substituted complexes such as [(η5-C5Me5)RhCl(ϰ1-P-PPh2Py)2]+
5 and [(η5-C5Me5)IrCl(ϰ1-P-PPh2Py)2]+
6, whereas stirring in methanol at room temperature gives P-, N-chelating complexes of the type [(η5-C5Me5)RhCl(ϰ2-P-N-PPh2Py)]+ 7 and [(η5-C5Me5)IrCl(ϰ2-P-N-PPh2Py)]+
8. Neutral ϰ1-P-coordinated complexes [(η5-C5Me5)RhCl2(ϰ1-P-PPh2Py)]3 and [(η5-C5Me5)IrCl2(ϰ1-P-PPh2Py)]4 easily undergo conversion to the cationic P-, N-chelating complexes [(η5-C5Me5)RhCl(ϰ2-P-N-PPh2Py)]+
7 and [(η5-C5Me5) IrCl(ϰ2-P, N-PPh2Py)]+
8 on stirring in methanol at room temperature. These complexes are characterized by FT-IR and FT-NMR spectroscopy as well as
analytical methods. The molecular structures of the representative complexes [(η5-C5Me5)RhCl2(ϰ1-P-PPh2Py)]3, [(η5-C5Me5)IrCl2(ϰ1-P-PPh2Py)]4 and hexafluorophosphate salt of complex [(η5-C5Me5)IrCl(ϰ2-P-PPh2Py)2]+
6 are established by single-crystal X-ray diffraction methods 相似文献
2.
LYNDA D. RODWELL EDWARD B. BARBIER CALLUM M. ROBERTS TIM R. McCLANAHAN 《Natural Resource Modeling》2002,15(4):453-486
ABSTRACT. The excessive and unsustainable exploitation of our marine resources has led to the promotion of marine reserves as a fisheries management tool. Marine reserves, areas in which fishing is restricted or prohibited, can offer opportunities for the recovery of exploited stock and fishery enhancement. In this paper we examine the contribution of fully protected tropical marine reserves to fishery enhancement by modeling marine reserve‐fishery linkages. The consequences of reserve establishment on the long‐run equilibrium fish biomass and fishery catch levels are evaluated. In contrast to earlier models this study highlights the roles of both adult (and juvenile) fish migration and larval dispersal between the reserve and fishing grounds by employing a spawner‐recruit model. Uniform larval dispersal, uniform larval retention and complete larval retention combined with zero, moderate and high fish migration scenarios are analyzed in turn. The numerical simulations are based on Mombasa Marine National Park, Kenya, a fully protected coral reef marine reserve comprising approximately 30% of former fishing grounds. Simulation results suggest that the establishment of a fully protected marine reserve will always lead to an increase in total fish biomass. If the fishery is moderately to heavily exploited, total fishery catch will be greater with the reserve in all scenarios of fish and larval movement. If the fishery faces low levels of exploitation, catches can be optimized without a reserve but with controlled fishing effort. With high fish migration from the reserve, catches are optimized with the reserve. The optimal area of the marine reserve depends on the exploitation rate in the neighboring fishing grounds. For example, if exploitation is maintained at 40%, the ‘optimal’ reserve size would be 10%. If the rate increases to 50%, then the reserve needs to be 30% of the management area in order to maximize catches. However, even in lower exploitation fisheries (below 40%), a small reserve (up to 20%) provides significantly higher gains in fish biomass than losses in catch. Marine reserves are a valuable fisheries management tool. To achieve maximum fishery benefits they should be complemented by fishing effort controls. 相似文献
3.
The development of the poly(3‐hydroxybutyrate) (PHB) morphology in the presence of already existent poly(vinylidene fluoride) (PVDF) spherulites was studied by two‐stage solidification with two separate crystallization temperatures. PVDF formed irregular dendrites at lower temperatures and regular, banded spherulites at elevated temperatures. The transition temperature of the spherulitic morphology from dendrites to regular, banded spherulites increased with increasing PVDF content. A remarkable amount of PHB was included in the PVDF dendrites, whereas PHB was rejected into the remaining melt from the banded spherulites. When PVDF crystallized as banded spherulites, PHB could consequently crystallize only around them, if at all. In contrast, PHB crystallized with a common growth front, starting from a defined site in the interfibrillar regions of volume‐filling PVDF dendrites. It formed by itself dendritic spherulites that included a large number of PVDF spherulites. For blends with a PHB content of more than 80 wt %, for which the PVDF dendrites were not volume‐filling, PHB first formed regular spherulites. Their growth started from outside the PVDF dendrites but could later interpenetrate them, and this made their own morphology dendritic. These PHB spherulites melted stepwise because the lamellae inside the PVDF dendrites melted at a lower temperature than those from outside. This reflected the regularity of the two fractions of the lamellae because that of those inside the dendrites of PVDF was controlled by the intraspherulitic order of PVDF, whereas that from outside was only controlled by the temperature and the melt composition. The described morphologies developed without mutual nucleating efficiency of the components. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 873–882, 2003 相似文献
4.
Mao‐Chuan Yuan Ping‐I Shih Chen‐Han Chien Ching‐Fong Shu 《Journal of polymer science. Part A, Polymer chemistry》2007,45(14):2925-2937
We have synthesized a blue‐light‐emitting polyfluorene (PF) derivative ( PF‐CBZ‐OXD ) that presents bulky hole‐transporting carbazole and electron‐transporting oxadiazole pendent groups functionalized at the C‐9 positions of alternating fluorene units. The results from photoluminescence and electrochemical measurements indicate that both the side chains and the PF main chain retain their own electronic characteristics in the copolymer. An electroluminescent device incorporating this polymer as the emitting layer was turned on at 4.5 V; it exhibited a stable blue emission with a maximum external quantum efficiency of 1.1%. Moreover, we doped PF‐CBZ‐OXD and its analogue PF‐TPA‐OXD with a red‐light‐emitting iridium phosphor for use as components of phosphorescent red‐light emitters to investigate the effect of the host's HOMO energy level on the degree of charge trapping and on the electrophosphorescent efficiency. We found that spectral overlap and individual energy level matching between the host and guest were both crucial features affecting the performance of the electroluminescence devices. Atomic force microscopy measurements indicated that the dipolar nature of PF‐CBZ‐OXD , in contrast to the general nonpolarity of polydialkylfluorenes, provided a stabilizing environment that allowed homogeneous dispersion of the polar iridium triplet dopant. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2925–2937, 2007 相似文献
5.
We derive a test problem for evaluating the ability of time-steppingmethods to preserve the statistical properties of systems inmolecular dynamics. We consider a family of deterministic systemsconsisting of a finite number of particles interacting on acompact interval. The particles are given random initial conditionsand interact through instantaneous energy- and momentum-conservingcollisions. As the number of particles, the particle density,and the mean particle speed go to infinity, the trajectory ofa tracer particle is shown to converge to a stationary Gaussianstochastic process. We approximate this system by one describedby a system of ordinary differential equations and provide numericalevidence that it converges to the same stochastic process. Wesimulate the latter system with a variety of numerical integrators,including the symplectic Euler method, a fourth-order Runge-Kuttamethod, and an energyconserving step-and-project method. Weassess the methods' ability to recapture the system's limitingstatistics and observe that symplectic Euler performs significantlybetter than the others for comparable computational expense. 相似文献
6.
Jenn‐Long Liu 《国际流体数值方法杂志》2004,44(12):1299-1315
This paper presents a relaxation algorithm, which is based on the overset grid technology, an unsteady three‐dimensional Navier–Stokes flow solver, and an inner‐ and outer‐relaxation method, for simulation of the unsteady flows of moving high‐speed trains. The flow solutions on the overlapped grids can be accurately updated by introducing a grid tracking technique and the inner‐ and outer‐relaxation method. To evaluate the capability and solution accuracy of the present algorithm, the computational static pressure distribution of a single stationary TGV high‐speed train inside a long tunnel is investigated numerically, and is compared with the experimental data from low‐speed wind tunnel test. Further, the unsteady flows of two TGV high‐speed trains passing by each other inside a long tunnel and at the tunnel entrance are simulated. A series of time histories of pressure distributions and aerodynamic loads acting on the train and tunnel surfaces are depicted for detailed discussions. Copyright © 2004 John Wiley & Sons, Ltd. 相似文献
7.
Ibrahim Erol 《Journal of polymer science. Part A, Polymer chemistry》2004,42(13):3157-3169
A new type of methacrylate monomer, [2‐oxo‐2‐(4‐acetyl) phenyl amino] ethylene methacrylate (APEMA), was synthesized. The oxime, 2,4‐dinitrophenylhydrazone, and thiosemicarbazone derivatives of poly{[2‐oxo‐2‐(4‐acetyl) phenyl amino] ethylene methacrylate} [poly(APEMA)] were prepared with hydroxylamine hydrochloride, 2,4‐dinitrophenylhydrazine, and thiosemicarbazone hydrochloride, respectively. The radical homopolymerization of APEMA was performed at 65 °C in a 1,4‐dioxane solution with benzoyl peroxide as an initiator. The monomer and its homopolymer were characterized with Fourier transform infrared and NMR techniques. The thermal stabilities of poly(APEMA) and its derivatives were investigated with thermogravimetric analysis and differential scanning calorimetry. The ultraviolet stability of the polymers were compared. The solubility and inherent viscosity of the polymers were also determined. The number‐average and weight‐average molecular weights and polydispersity index of the polymers were determined with gel permeation chromatography. The antibacterial and antifungal effects of the monomer and the polymer and its derivatives were also investigated on various bacteria and fungi. The activation energies of the thermal degradation of the polymers were calculated with the Ozawa method. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3157–3169, 2004 相似文献
8.
H. Kaczmarek J. Kowalonek Z. Klusek S. Pierzgalski S. Datta 《Journal of Polymer Science.Polymer Physics》2004,42(4):585-602
The photooxidative degradation of blends (in a full range of compositions) of amorphous poly(vinyl chloride) (PVC) with semicrystalline poly(ethylene oxide) (PEO) in the form of thin films is investigated using absorption spectroscopy (UV–visible and Fourier transform infrared) and atomic force microscopy (AFM). The amount of insoluble gel formed as a result of photocrosslinking is estimated gravimetrically. It is found that the PVC/PEO blendsí susceptibility to photooxidative degradation differs from that pure of the components and depends on the blend composition and morphology. Photoreactions such as degradation and oxidation are accelerated whereas dehydrochlorination is retarded in blends. The photocrosslinking efficiency in PVC/PEO blends is higher than in PVC; moreover, PEO is also involved in this process. AFM images showing the lamellar structure of semicrystalline PEO in the blend lead to the conclusion that the presence of PVC does not disturb the crystallization process of PEO. The changes induced by UV irradiation allow the observation of more of the distinct PEO crystallites. This is probably caused by recrystallization of short, more mobile chains in degraded PEO or by partial removal of the less stable amorphous phase from the film surface. These results confirm previous information on the miscibility of PVC with PEO. The mechanism of the interactions between the components and the blend photodegradation are discussed. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 585–602, 2004 相似文献
9.
Atomic force microscopy (AFM) has been used to visualize the plastic deformation mechanisms that are responsible for the yielding of semicrystalline polymers of low degree of crystallinity (<50%). Indeed, AFM, if operated in suitable conditions, is able to image both the amorphous and the crystalline phases. Polyamide 6 films have been drawn at temperatures T < 160 °C. Postmortem AFM observations show that, at yield, shear bands nucleate and propagate in the amorphous phase. They cross the crystalline lamellae and run over the whole surface of the sample. By crossing the lamellae, they form nanoblocks of uniform size. Neither the size of the nanoblocks nor the angle between the tensile axis and the shear bands can be explained in terms of crystal plasticity. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 687–701, 2004 相似文献
10.
A. Zubeldia M. Larraaga P. Remiro I. Mondragon 《Journal of Polymer Science.Polymer Physics》2004,42(21):3920-3933
The microstructure and fracture behavior of epoxy mixtures containing two monomers of different molecular weights were studied. The variation of the fracture toughness by the addition of other modifiers was also investigated. Several amounts of high‐molecular‐weight diglycidyl ether of bisphenol A (DGEBA) oligomer were added to a nearly pure DGEBA monomer. The mixtures were cured with an aromatic amine, showing phase separation after curing. The curing behavior of the epoxy mixtures was investigated with thermal measurements. A significant enhancement of the fracture toughness was accompanied by slight increases in both the rigidity and strength of the mixtures that corresponded to the content of the high‐molecular‐weight epoxy resin. Dynamic mechanical and atomic force microscopy measurements indicated that the generated two‐phase morphology was a function of the content of the epoxy resin added. The influence of the addition of an oligomer or a thermoplastic on the morphologies and mechanical properties of both epoxy‐containing mixtures was also investigated. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3920–3933, 2004 相似文献