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11.
Simple and convenient methods for determining surface chemical composition of lignocellulosic materials are described. The
methods are based on vapor phase fluorine surface derivatization with either trifluoro acetic anhydride (TFAA), tri-fluoro
ethanol (TFE) or pentafluorophenyl hydrazine (PFPH) and subsequent Electron Spectroscopy for Chemical Analysis (ESCA). Model
cellulosic surfaces with well defined functionalities were used to optimize the derivatization reaction conditions. Detection
and accessibility of surface hydroxyl functional groups were investigated in cotton and regenerated cellulose as models. Carboxymethyl
cellulose (CMC) was used as a model surface for detection and quantification of carboxylic acid groups. Theoretical conversion
curves for derivatization reactions were calculated and used to evaluate the extent of the reactions on the model surfaces.
It was found that the conversion was higher for the regenerated cellulose and CMC than for cotton. The protocols developed
using the model surfaces were applied to a case study on wood fibers with different degrees of complexity, namely dissolving
and chemithermomechanical (CTMP) pulp. Untreated and oxygen-plasma modified pulps were compared with respect to the surface
composition of functional groups. According to the derivatization reactions, functionalities containing oxygen were significantly
increased on the plasma-treated samples. The effect of the treatment was found to be dependent on the type of pulp. Fluorine
derivatization is shown to be an unambiguous method for clear assessment of the chemical functionalities of cellulosic surfaces. 相似文献
12.
İ. B. Özdemir 《Experiments in fluids》1997,22(4):271-280
This paper is concerned with an experimental investigation of the mixing inside the vortex ring formed by the gravity slumping
motion of a dense cloud in a less dense atmosphere. The dynamics of the spreading and instantaneous structures of the turbulent
flow were examined by visualization, single and multi-point measurements of velocity and concentration for two heavy gases,
carbondioxide (CO2) and dichlorodifluoromethane (CCl2F2), in a configuration in that heavy gas, initially trapped in a reservoir, was released with the rise of a shutter into calm
air of a sector-shaped dispersion channel.
Visualization of the cloud as a whole showed a spreading motion in which an advancing frontal structure was followed by a
stratified flow with a layer of dense fluid of higher velocities near the wall and, on top of it, a layer of dilute fluid
whose concentration is controlled by the mixing mechanisms within the head. During the course of spreading, there was always
a phase in which the head attained to a constant speed of advance, which occurred as 0.13 m/s for CO2 and 0.48 m/s for CCl2F2. It was interesting to observe for CO2 that the phase of constant speed took place in between two acceleration phases; the former was due to the initial slumping
of the cloud at the exit of the reservoir, and the latter was attributed to the collapse of the head on the transition to
the passive dispersion phase.
Instantaneous two-dimensional velocity field, measured with particle image velocimeter (PIV), showed that the cloud overran
the ambient air which caused the approaching dense fluid deflected away from the wall with significant vertical velocities
and downstream-moving separation, and the air trapped under the head resulted in the density inversion which introduced further
intricacy to the turbulent structure of the head. Instabilities at the upper free shear layer due to density and velocity
discontinuity rolled into periodic array of vortices which engulfed a considerable amount of air as they were convected backwards
over the head, but the incorporation of heavy and light fluids was completed with the appearance of microscales after the
collapse on the stratified layer. Analyses of the cloud head at different downstream locations also revealed that its size
remained unchanged when the speed of advance was constant, allowing the rate of change of the cloud volume being modeled with
the rate of spreading.
Contours of concentration obtained from digitized PIV pictures confirmed the kinematic features of the mixing revealed by
the velocity field and that the concentration values within the large structures were higher than those at the upper part
of the stratified layer. Motivated by the experimental observations, a semi-empirical analysis was presented to describe the
results and based on local values of the Richardson and Reynolds numbers.
Received: 4 October 1995 / Accepted: 4 July 1996 相似文献
13.
Solubility of carbon dioxide in aqueous solutions of sodium chloride: Experimental results and correlation 总被引:2,自引:0,他引:2
The solubility of carbon dioxide in aqueous solutions of sodium chloride was measured in the temperature range from 40 to 160°C, up to 6 mol-kg salt solutions and total pressures up to 10 MPa. Pitzer's(1) equations as well as the Chen and Evans(2) model were used to correlate the new data. Results are reported and compared to literature data and correlations. 相似文献
14.
The TG and DTA curves and diffractograms of powdered CeO2 samples irradiated with a CO2 laser beam with powers of 0.41–1.39 kW/cm2 are presented. The laser treatment induced structural changes and probably generation of a metastable phase. X-ray diffraction coupled with thermal analysis was used to establish the structural modifications in the irradiated samples after heating. 相似文献
15.
This study compared the fracture strength of Class II slot cavities restored with polymerizable restorative materials. Sixty, caries-free, posterior teeth were divided into five groups of 12 teeth. The Class II slot cavities were prepared. The teeth were restored with two packable composites (Filtek P60, Surefil), a microhybrid composite (Filtek Z250)and two ormocer (Definite, Admira). The restorations were then subjected to fracture resistance tests. The marginal ridges of the restorations were loaded at an angle of 13.5° to the long axis of the tooth in an Universal Testing Machine until failure. Analysis of mean forces indicated that, Filtek P60, Surefil and Filtek Z250 exhibited better performance than Definite and Admira. The tested resin composites differed in their mechanical properties. This study suggested that fracture behavior were highly influenced by the filler system. Overall, Filtek P60, Surefil, Filtek Z250, demonstrated good fracture resistance. Copyright © 2003 John Wiley & Sons, Ltd. 相似文献
16.
This preliminary study presents the experimental results concerning the concentrations of selected radionuclides (238U, 232K, 226Ra, 232Th) in Af?in-Elbistan, Çan, Çay?rhan, Erzurum, Göynük, Kangal, Orhaneli, Saray, Seyitömer, Soma, Tunçbilek, Yata?an and Yeniköy lignites, which are primarily utilized as fuel for thermal power plants in Turkey. Gamma-spectrometry of 39 representative lignite samples gave results with the following concentration ranges: 8 to 296 Bq/kg for 238U, 3 to 79 Bq/kg for 232Th, 17 to 360 Bq/kg for 40K, and 5 to 130 Bq/kg for 226Ra. The 238U results reported here are higher than other literature values for various world coals, earth's crust and world average. 相似文献
17.
G. Buchbauer H. Spreitzer B. Öckher C. Pretterklieber I. Piringer P. Wolschann 《Monatshefte für Chemie / Chemical Monthly》1995,126(4):467-472
Summary Guided by molecular modeling studies, the synthesis of the title compound is described. The organoleptic evaluation proved the predicted real sandal like odour of (Z)-dehydro-homo--santalol.
Aus den Diplomarbeiten von C.P. (1991), I.P. und B.Ö. (1992), Universität Wien 相似文献
18.
Schmitt C da Silva TP Bovay C Rami-Shojaei S Frossard P Kolodziejczyk E Leser ME 《Langmuir : the ACS journal of surfaces and colloids》2005,21(17):7786-7795
The electrostatic complexation between beta-lactoglobulin and acacia gum was investigated at pH 4.2 and 25 degrees C. The binding isotherm revealed a spontaneous exothermic reaction, leading to a DeltaHobs = -2108 kJ mol(-1) and a saturation protein to polysaccharide weight mixing ratio of 2:1. Soluble electrostatic complexes formed in these conditions were characterized by a hydrodynamic diameter of 119 +/- 0.6 nm and a polydispersity index of 0.097. The effect of time on the interfacial and foaming properties of these soluble complexes was investigated at a concentration of 0.1 wt % at two different times after mixing (4 min, referred as t approximately 0 h and t = 24 h). At t approximately 0 h, the mixture is mainly made of aggregating soluble electrostatic complexes, whereas after 24 h these complexes have already insolubilize to form liquid coacervates. The surface elasticity, viscosity and phase angle obtained at low frequency (0.01 Hz) using oscillating bubble tensiometry revealed higher fluidity and less rigidity in the film formed at t approximately 0 h. This observation was confirmed by diminishing bubble experiments coupled with microscopy of the thin film. It was thicker, more homogeneous and contained more water at t approximately 0 h as compared to t = 24 h (thinner film, less water). This led to very different gas permeability's of Kt approximately 0 h = 0.021 cm s(-1) and Kt=24 h) = 0.449 cm s(-1), respectively. Aqueous foams produced with the beta-lactoglobulin/acacia gum electrostatic complexes or coacervates exhibited very different stability. The former (t approximately 0 h) had a stable volume, combining low drainage rate and mainly air bubble disproportionation as the destabilization mechanism. By contrast, using coacervates aged for 24 h, the foam was significantly less stable, combining fast liquid drainage and air bubble destabilization though fast gas diffusion followed by film rupture and bubble coalescence. The strong effect of time on the air/water interfacial properties of the beta-lactoglobulin/acacia gum electrostatic complexes can be understood by their reorganization at the interface to form a coacervate phase that is more fluid/viscous at t approximately 0 h vs rigid/elastic at t = 24 h. 相似文献
19.
Chronoamperograms for gold in solutions containing 0.1 M thiourea, 0.5 M H2SO4, and catalytically active sulfide ions at the concentration c 1 from 1 × 10?5 to 4 × 10?5 M are obtained at different potentials with the aid of an automated setup intended for renewing the electrode surface directly in the solution by cutting off a thin surface layer of the metal. It is shown that the results of measurements of the current practically coincide at a constant value of the product c 1 t, where t is the time period elapsed after the renewal of the electrode surface. Such a coincidence testifies to a diffusion nature of processes that hamper accumulation of sulfide ions at the gold surface. This fact permitted the use of a procedure developed previously for the calculation of polarization curves at constant values of surface coverage θ by catalytically active ions. At θ = const, the voltammetric curves for gold in sulfide-containing thiourea solutions are shown to correspond to the Tafel equation. With the surface coverage increasing, the effective values of the exchange current i 0, transfer coefficient α, and anodic reaction order with respect to thiourea P a increase from the values i }~ 10?5 A cm?2, α }~ 0.12, and P a = 0.2, which are characteristic of pure solutions, to 2 × 10?4 A cm?2, α }~ 0.5, and P a = 1.1 (at θ }~ 0.5). An interpretation to the established regularities is given. 相似文献
20.
Breher F Rüegger H Mlakar M Rudolph M Deblon S Schönberg H Boulmaâz S Thomaier J Grützmacher H 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(3):641-653
The formation of adducts of the square-planar 16-electron complexes trans-[M(tropp(ph))(2)](+) and cis-[M(tropp(ph))(2)](+) (M=Rh, Ir; tropp(Ph)=5-diphenylphosphanyldibenzo[a,d]cycloheptene) with acetonitrile (acn) and Cl(-), and the redox chemistry of these complexes was investigated by various physical methods (NMR and UV-visible spectroscopy, square-wave voltammetry), in order to obtain some fundamental thermodynamic and kinetic data for these systems. A trans/cis isomerization cannot be detected for [M(tropp(ph))(2)](+) in non-coordinating solvents. However, both isomers are connected through equilibria of the type trans-[M(tropp(ph))(2)](+)+L<==>[ML(tropp(ph))(2)](n)<==>cis-[M(tropp(ph))(2)](+)+L, involving five-coordinate intermediates [ML(tropp(ph))(2)](n) (L=acn, n=+1; L=Cl(-), n=0). Values for K(d) (K(f)), that is, the dissociation (formation) equilibrium constant, and k(d) (k(f)), that is, the dissociation (formation) rate constant, were obtained. The formation reactions are fast, especially with the trans isomers (k(f)>1x10(5) m(-1) s(-1)). The reaction with the sterically more hindered cis isomers is at least one order of magnitude slower. The stability of the five-coordinate complexes [ML(tropp(ph))(2)](n) increases with Ir>Rh and Cl(-)>acn. The dissociation reaction has a pronounced influence on the square-wave (SW) voltammograms of trans/cis-[Ir(tropp(ph))(2)](+). With the help of the thermodynamic and kinetic data independently determined by other physical means, these reactions could be simulated and allowed the setting up of a reaction sequence. Examination of the data obtained showed that the trans/cis isomerization is a process with a low activation barrier for the four-coordinate 17-electron complexes [M(tropp(ph))(2)](0) and especially that a disproportionation reaction 2 trans/cis-[M(tropp(ph))(2)](0)-->[M(tropp(ph))(2)](+)+[M(tropp(ph))(2)](-) may be sufficiently fast to mask the true reactivity of the paramagnetic species, which are probably less reactive than their diamagnetic equilibrium partners. 相似文献