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61.
《Journal of separation science》2003,26(5):402-408
When nitrated polynuclear aromatic hydrocarbons (NPAH) were recognised as long‐term toxic compounds and were also identified in several anthropogenic emissions and among the by‐products of photochemical smog they became objects of investigation in ambient air in both polluted and clean environments. In Italy the first investigations focussing on atmospheric NPAH were performed in the early eighties and encompassed both the canyon streets and dwelling areas of Rome. Because NPAH were indicated as markers of vehicle emission, new investigations were performed in other cities and also in rural and (nominally) unpolluted locations. In general, the first measurements of NPAH were episodic and could not be assumed to be strictly representative of the sites investigated. In contrast, nowadays consistent data bases on NPAH have been built up and are discussed in the technical literature, so that both neat concentrations and the yearly timed variation of the most important NPAH congeners have been measured in Italian air. Although concentrations of NPAH in air are usually much lower than those of PAH, owing to their very high potency in inducing mutations and tumours NPAH are regarded as having an important health impact on populations living in Italian urban areas. In this regard the genotoxicity of atmospheric aerosols is partly associated with nitrofluoranthenes and nitropyrenes whereas nitronaphthalenes and methylnitronaphthalenes seem to contribute to that of the gaseous organic fraction. Several civic and regional administrations are introducing control of atmospheric NPAH among ways of improving air quality in cities. 相似文献
62.
Correlated multivariate processes have a dependence structure which must be taken into account when estimating the covariance matrix. The natural estimator of the covariance matrix is introduced and is shown that to be biased under the dependence structure. This bias is studied under two different asymptotic models, namely increasing the domain by increasing the number of observations, and increasing the number of observations in the fixed domain. Using the first asymptotic model, we quantify the convergence rate of the bias and of the covariance between the components of the estimated covariance matrix. The second asymptotic model serves to derive a fast and accurate bias correction. As shown, under mild hypotheses, the asymptotic normality of the estimated covariance matrix holds and can be used to test whether the bias is significant, for example, in the sense that the eigenvectors of the estimated and true covariance matrices are significantly different. 相似文献
63.
Biological transformation of volatile organic compounds is one of the key factors that influence contaminant-plume evolution
and thus natural attenuation. In this study we investigate the effect of biological transformation on the transport of contaminants
in the aqueous and gaseous phases. The analysis includes the study of the effect of density-driven advection of contaminants
in the gaseous phase on multiphase and multispecies flow, fate and transport modeling in the subsurface. Trichloroethylene
(TCE) and its two byproducts, dichloroethylene and vinyl chloride, are analyzed as the target contaminants. Our results indicate
that density-driven advection of the gaseous phase, which is initiated by evaporation of TCE as a nonaqueous phase liquid,
increases the downward and also the lateral migration of TCE within the unsaturated zone. This process also influences the
location of high-concentration zones of the byproducts of TCE in the unsaturated and the saturated zones. Biotransformation
of TCE contributes to the reduction of dissolved TCE plume development as expected. The daughter byproducts, which are introduced
into the subsurface system, show distinct transport patterns as they are affected by their independent degradation kinetics
and density-driven advection. These observations, which are based on our simulation results for biotransformation and transport
of TCE and its byproducts, are useful in evaluating the natural attenuation processes, its potential health hazards and also
the evaluation of potential plume development at contaminated sites. 相似文献
64.
Investigation on ultrafast thrid—order optical nonlinearity of metal(dmit)2/mnt)2 Charge transfer complexes
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We have investigated the transient third-order optical nonlinearity of the solutions of Metal(dmit)2/(mnt)2 salts in acetone by employing femtosecond optical Kerr gate measurement at 830nm wavelength.An order of enhancement on the second-order hyperppolarizability is found for the above salts with central atoms of Cu and Ni.We have suggested an explanation for the enhancement based on the extension of electronic conjugation by the entring Cu or Ni atom. 相似文献
65.
66.
Brad M. Rosen Virgil Percec 《Journal of polymer science. Part A, Polymer chemistry》2007,45(21):4950-4964
Atom transfer radical polymerization (ATRP) and single electron‐transfer living radical polymerization (SET‐LRP) both utilize copper complexes of various oxidation states with N‐ligands to perform their respective activation and deactivation steps. Herein, we utilize DFT (B3YLP) methods to determine the preferred ligand‐binding geometries for Cu/N‐ligand complexes related to ATRP and SET‐LRP. We find that those ligands capable of achieving tetrahedral complexes with CuI and trigonal bipyramidal with axial halide complexes with [CuIIX]+ have higher energies of stabilization. We were able to correlate calculated preferential stabilization of [CuIIX]+ with those ligands that perform best in SET‐LRP. A crude calculation of energy of disproportionation revealed that the same preferential binding of [CuIIX]+ results in increased propensity for disproportionation. Finally, by examining the relative energies of the basic steps of ATRP and SET‐LRP, we were able to rationalize the transition from the ATRP mechanism to the SET‐LRP mechanism as we transition from typical nonpolar ATRP solvents to polar SET‐LRP solvents. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4950–4964, 2007 相似文献
67.
Meng F. Q. Lu M. K. Yang Z. H. Zeng H. 《Journal of Thermal Analysis and Calorimetry》1998,52(2):609-613
The thermal behavior of two new non-linear optical (NLO) materials, urea-(D) tartaric acid (UDT) and urea-(DL) tartaric acid
(UDLT) were studied by using DSC, TG and TMA. The results show that: 1) The two crystals have different melting points but
similar decomposition temperatures due to the influences of intermolecular forces, which is attributed to the stereo effects
of (D)-tartaric and (DL)-tartaric acid molecules; 2) There was only thermal expansion and no thermal contraction when the
UDT and UDLT crystals were heated; 3) There was no phase transition within the measured temperature range; 4) The thermal
expansion of the UDT and UDLT crystals shows a small anisotropy; 5) The specific heats of UDT and UDLT change linearly with
temperature in the measured temperature range and the value for UDT is 1.321 J g-1 K-1 at 320 K while the specific heat of
UDLT is 1.357 J g-1 K-1 at the same temperature.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
68.
N. V. Sotskaya O. V. Dolgikh E. I. Ryabinina 《Russian Journal of Electrochemistry》2005,41(8):866-873
The rate of anodic oxidation of the hypophosphite ion on alloys Ni-P, Ni-B, and Ni-Mo-P is studied as a function of their composition and structure. The organic compounds that are customarily used to stabilize electrolytes of electroless nickel plating are shown to come useful when controlling composition of the Ni-P coatings at the expense of their different influence on the rates of partial processes of deposition of the alloy components. The formation of catalytic activity of such coatings is affected mostly by a structural factor. With alloys Ni-P, Ni-B, and Ni-Mo-P, whose composition was varied by altering the concentration of the source of the alloying component, dependence of catalytic activity of the surface on the composition is defined mainly by an electronic factor.__________Translated from Elektrokhimiya, Vol. 41, No. 8, 2005, pp. 972–980.Original Russian Text Copyright © 2005 by Sotskaya, Dolgikh, Ryabinina. 相似文献
69.
一种新型有机电致微腔结构的双模发射 总被引:4,自引:4,他引:0
采用结构Glass/DBR/ITO/NPB/NPB:Alq/Alq/Al制作了有机微腔电致发光器件。将空穴传输材料与发光材料以一定比例混合作为发光层,为了便于对比,在不改变有机层的膜厚的情况下同时制作了传统的异质结微腔器件,发现两种器件的发光光谱有很大不同,器件的复合效率与传统的异质结器件相比也得到了很大提高,这是因为将两种有机材料混合能消除界面势垒,提高器件的复合效率,从而提高了器件的发光性能,实现了微腔双模发射,且两个模式的半峰全宽分别为8nm和12nm。通过进一步优化器件结构可以实现微腔白光发射。 相似文献
70.
Lubomír Kubáček 《Mathematica Slovaca》2007,57(1):59-82
In some situations estimates of unknown parameters must be corrected by additional measurements. It is in principle no problem
to calculate the corrected estimates, however, it is of more interest to find formulae for correction itself. The formulae
enable us to design an additional experiment and to judge its usefulness.
The aim of the paper is to find such formulae for several situations.
Supported by the grant of the Council of Czech Government MSM 6 198 959 214. 相似文献