首页 | 本学科首页   官方微博 | 高级检索  
文章检索
  按 检索   检索词:      
出版年份:   被引次数:   他引次数: 提示:输入*表示无穷大
  收费全文   1382篇
  免费   75篇
  国内免费   76篇
化学   643篇
晶体学   9篇
力学   206篇
综合类   8篇
数学   412篇
物理学   255篇
  2024年   3篇
  2023年   6篇
  2022年   6篇
  2021年   9篇
  2020年   27篇
  2019年   21篇
  2018年   35篇
  2017年   32篇
  2016年   38篇
  2015年   24篇
  2014年   21篇
  2013年   152篇
  2012年   39篇
  2011年   43篇
  2010年   56篇
  2009年   60篇
  2008年   84篇
  2007年   66篇
  2006年   70篇
  2005年   42篇
  2004年   65篇
  2003年   68篇
  2002年   56篇
  2001年   49篇
  2000年   45篇
  1999年   46篇
  1998年   41篇
  1997年   41篇
  1996年   34篇
  1995年   20篇
  1994年   30篇
  1993年   28篇
  1992年   24篇
  1991年   17篇
  1990年   13篇
  1989年   16篇
  1988年   15篇
  1987年   10篇
  1986年   7篇
  1985年   15篇
  1984年   11篇
  1983年   7篇
  1982年   13篇
  1981年   10篇
  1980年   4篇
  1979年   4篇
  1978年   6篇
  1977年   2篇
  1974年   1篇
  1973年   1篇
排序方式: 共有1533条查询结果,搜索用时 125 毫秒
101.
A manganese(II) complex with N,N′-bis(carboxymethyl)dithiooxamide (H4GLYDTO), [Mn(H2GLYDTO)(H2O)2]n, has been synthesized and characterized by elemental analysis and thermogravimetric analysis, as well as by infrared, electronic and EPR spectroscopy and magnetic susceptibility measurements. The crystal and molecular structure of this complex was determined by single-crystal X-ray structure analysis. The compound shows a 3D porous framework with alternate left- and right-handed helical channels where the manganese(II) ions have an octahedral environment. Variable temperature magnetic measurements reveal the existence of very weak antiferromagnetic interactions through the syn-anti carboxylate bridge, with an exchange parameter of J/k = −0.12 K.  相似文献   
102.
A repetitive potential cycling procedure was used to produce a specific multilayer hydrous oxide film on copper in base at 60 °C. Such a deposit undergoes reduction in a quasi-reversible manner at ca. −0.1 V (RHE), i.e. at a potential that is unrelated to Pourbaix data for copper but, as demonstrated previously, is of major significance with regard to the electrocatalytic behaviour of this electrode system. In accordance with the incipient hydrous oxide/adatom mediator model of electrocatalysis, an active surface state of the metal (Cu*) is assumed to be involved both in electrocatalysis and as a primary product in the hydrous oxide reduction reaction. While the latter process occurs very rapidly at −0.1 V, it is not usually reversible as it is accompanied by subsequent rapid loss of the active state of the metal. The same general approach was used previously to explain the hydrous oxide and electrocatalytic behaviour of a range of noble metals. Received: 28 August 1999 / Accepted: 11 November 1999  相似文献   
103.
The forward problem of electrical impedance tomography on unbounded domains can be studied by introducing appropriate function spaces for this setting. In this paper we derive the point‐wise asymptotic behaviour of weak solutions to this problem in the three‐dimensional case. Copyright © 2008 John Wiley & Sons, Ltd.  相似文献   
104.
105.
Main-chain biodegradable liquid crystal (LC) based on cholesteryl end-capped polycarbonate copolymers was investigated. The novel LC was synthesised through ring-opening copolymerisation of trimethylene carbonate with ε-caprolactone (CL) initiated by cholesterol, without adding any catalyst. The chemical structure of the resulting polymers was confirmed by 1H NMR. The liquid crystalline properties were validated by X-ray diffraction, differential scanning calorimetry and polarising optical microscopy. The results showed that the synthesised polycarbonate copolymers Chol-(TMCL)x + y exhibited liquid crystallinity in particular temperature ranges because of the incorporation of the cholesterol moieties. Furthermore, the effect of CL content on the mesomorphism properties of Chol-(TMCL)x+y was also investigated; the higher the CL content, the lower the mesomorphism properties. It might be attributed to the hindered orientation of LC caused by the crystallinity of the poly(ε-caprolactone) (PCL) segments in the polymer chain.  相似文献   
106.
ABSTRACT

High sensitivity of liquid crystals to the electric field makes them highly demanded and widely used in different applications. Despite the large number of the electro-optical research on the low-molar-mass liquid crystals electro-optics of the liquid crystalline (LC) polymers is much less studied. Herein, the comparative electro-optical behaviour of two nematic comb-shaped polyacrylates with phenylbenzoate mesogenic side groups was studied in detail. These two polyacrylates have completely the same structure of polymer backbone and spacer length but different in the direction of the ester group in the phenylbenzoate fragments. It was found that this difference predetermines their completely opposite electro-optical properties.

The influence of the electric field of different strength and frequency on the orientation of the mesogenic groups of these polymers is studied. It is shown that application of the electric field at temperatures above the glass transition temperature (~25°C) induces reorientation of the mesogenic groups along or perpendicular to the electric field direction depending in its turn on the ester group direction. For one of the polyacrylates an unusual textural transition is found; during cooling of the polymer sample under applied field at definite temperature a sharp change in the mesogen’s orientation from homeotropic to planar one is found. This electro-optical phenomenon is observed for the first time and probably associated with sharp change in sign of anisotropy of dielectric permittivity from positive (at high temperatures) to negative one (at lower temperatures). Kinetics of the electro-optical switching at different temperatures, influence of the molar masses of the polymer and frequency of the applied AC field on electro-optical behaviour of the polymers are studied. The possibility of the fixation of the electroinduced homeotropic alignment of the mesogenic groups by photopolymerisation of the diacrylate dissolved in the polymer is demonstrated.  相似文献   
107.
The purpose of this work is the formulation and application of a continuum thermodynamic approach to the phenomenological modeling of a class of engineering materials which can be dynamically formed using strong magnetic fields. This is carried out in the framework of a thermodynamic, internal-variable-based formulation in which the deformation, temperature and magnetic fields are in general coupled. This coupling takes the form of the Lorentz force as an additional supply of momentum, and the electromotive power as an additional supply of energy, in the material. In the current approach, the basic thermomechanical field relations for mass, momentum and moment of momentum are obtained from the total energy balance via invariance, and completed by Maxwells field equations. The constitutive formulation is based on the exploitation of the Müller-Liu entropy principle, here for the case of isotropic thermoelastic, viscoplastic material behaviour. The resulting reduced constitutive and field relations and restrictions are then applied to the modeling and simulation of high-speed electromagnetic forming of metal tubes and sheet metal. In this context, scaling arguments show that, over the relevant length- and timescales of engineering interest, the evolution of the magnetic field is diffusive in nature, and thermal conduction is negligible. Comparison of the simulation and experimental results for the final sheet metal form shows very good agreement.Received: 16 March 2004, Accepted: 6 May 2004, Published online: 17 September 2004PACS: 46.05. + b, 46.25.Hf, 46.35 + z Correspondence to: B. Svendsen  相似文献   
108.
Zusammenfassung Morphologische Untersuchungen an dem polymeren Mischsystem Phenolnovolakharz-Nitrilkautschuk haben gezeigt, daß diese Mischungen eine Struktur aufweisen, in der harte kugelige PF-Teilchen in einer Kautschukmatrix bzw. weiche Kautschukteilchen in einer Harzmatrix eingebettet sind. Mit Hilfe der morphologischen und mechanisch-dynamischen Untersuchungen wird versucht, das viskoelastische Verhalten von Polyblends mit der Van-der-Poel-Gleichung zu beschreiben. Es konnte gezeigt werden, daß bis zu ModulwertenGhart/Gweich ~ 100 eine gute Übereinstimmung mit der Van-der-Poel-Gleichung gefunden wird. Hohe Modulverhältnisse der harten Einlagerungskomponente zur weichen KomponentenGhart/Gweich ~ 1000, wie sie im kautschukelastischen Bereich auftreten, zeigen eine Übereinstimmung mit der Van-der-Poel-Gleichung nur bei einer Volumenkonzentration der harten EinlagerungskomponenteV f < 0,3. Diese Ergebnisse werden mit anderen bekannten theoretischen Überlegungen über den Zusammenhang zwischen Elastizitätsmodul und Zusammensetzung von Verbundwerkstoffen verglichen.Schlüsselwörter Phenolnovolakharz-Nitrilkautschuk-System, viskoelastisches Verhalten, Torsionspendel, Van-der-Poel-Gleichung
Summary Morphological investigations of the polymer compound-system novolak resin-nitril rubber (PF/NBR) have shown, that these mixtures exhibit structures, in which hard spherical particles are embedded in a rubber matrix, respectively soft rubber particles in a resin matrix.An attempt was made to describe the viscoelastic behaviour of these polyblends by means of morphological and dynamic-mechanical investigations with the relation given by Van der Poel.Up to ratios of the moduliGhard/Gsoft ~ 100 a good agreement with the Van-der-Poel equation was found. In the rubber elastic region at ratiosG hard/G soft ~ 1000 this agreement was found for volume concentrations of the phenolic componentV f ~ 0.3 only.The results are compared with other existing theories on the correlation between elastic modulus and composition of compound materials.
Mit 7 Abbildungen und 6 Tabellen  相似文献   
109.
Spruce sulphite cellulose (number average degree of polymerization 620) dissolved in an aqueous solution of 8% (w/w) LiOH*H2O and 12% (w/w) urea was methylated with dimethyl sulphate (DMS). By varying the reaction temperature between 22 and 50 °C, the molar ratio between 9 and 15 mol DMS per mol anhydroglucose unit, and the reaction time from 4 to 24 h, methyl cellulose (MC) with degree of substitution (DS) values in the range of 1.07 and 1.59 was prepared. The chemical structure of MC was analysed by FTIR and 1H NMR spectroscopy. The turbidity (given in nephelometric turbidity units, NTU) of the aqueous solution of MC reached an optimum of 10 NTU for a product obtained with 12 mol DMS/mol AGU at 50 °C. GPC measurements revealed polymer degradation to a certain extent. The intrinsic viscosity and the Huggins constant k of the MC samples increased with increasing DS value. The MC samples possess k values higher than 0.8, indicating association of the polymer chain. The zero-shear viscosity decreased with increase of both temperature and the amount of methylation agent due to the depolymerization. During the heating/cooling cycle (20-90 °C) of the aqueous solutions of MC, it was observed that samples synthesized at 22 °C with DS values lower than 1.3 did not undergo phase separation in aqueous solution. Phase separation hysteresis with a precipitation temperature up to 80 °C was obtained for aqueous solutions of MC with DS values between 1.07 and 1.66 synthesized at higher temperatures. The functionalization pattern determined by GLC of the corresponding partially methylated glucitol acetates is close to randomness and comparable with those of commercial MC samples.  相似文献   
110.
Surface initiated polymerization of N(isopropylacrylamide) (NIPAM) was performed by controlled radical polymerization on PET track-etched membranes presenting two different pore diameters (narrow pores: ∼80 nm and large pores: ∼330 nm). The opening and closing characteristics of the resulting PNIPAM-g-PET membranes were investigated by conductometric measurements carried out at different temperatures below and above the LCST of PNIPAM and in the presence of different salts. Depending on the membrane pore size, two types of permeation control mechanisms are observed. In large pore membranes, expanded PNIPAM chains conformations result in reduced effective pore size and therefore lower permeabilities relative to collapsed macromolecules chain conformations. In contrast, in narrow pore membranes, the expanded PNIPAM brush presents greater degrees of hydration in the surface layer and therefore gives rise to higher permeabilities than the collapsed conformation. In this situation, the overall permeability is thus comparable to that of a hydrogel membrane.  相似文献   
设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号