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151.
152.
Simple two-parameter Hückel and Pitzer equations were used for the calculation of the activity coefficients of aqueous hydrochloric acid at 25°C up to a molality of 2.0 mol-kg–1. The data obtained by Harned and Ehlers(12,13) from galvanic cells without liquid junction were used in the analysis and the parameters obtained were compared to those obtained from all reliable data presented in the literature for HCl at this temperature. A good agreement between the parameters was always observed. The activity coefficients obtained by the new equations were compared to those suggested by Robinson and Stokes,(8) Hamer and Wu,(1) and Pitzer and Mayorga,(9) and good agreement was also found. The data from the most important literature data sets for HCl were also predicted using the new activity coefficient equations, and the magnitude of the resulting errors was close to the precision of the measurements, the errors forming an almost random pattern for all data sets. 相似文献
153.
SAPO-5,-11和-34分子筛模板剂的脱除及其结构的热致变化 总被引:2,自引:0,他引:2
用水热法合成了SAPO-5,-11和-34硅磷酸铝类分子筛。并对经不同温度焙烧处理的样品进行表征,结果表明:分子筛中模块剂的热分解过程与其结构和孔大小有较大的关系。在SAPO-5和SAPO-34分子筛中,外部联接的T-O-T键的反对称伸缩振动峰(1240cm~(-1)-1038cm~(-1))和其对称伸缩振动(734cm~(-1)-600cm~(-1))及双环的变形振动(600-500cm~(-1))的吸收峰对样品的结晶度比较敏感。但在SAPO-11中,分子筛骨架中T-O-T反对称伸缩振动(1225cm~(-1)和1038cm~(-1))随结晶度的下降而基本保持不变,但内四面体(TO_4)的对称伸缩振动,反对称伸缩振动峰及T-O弯曲振动峰随样品焙烧温度的升高而减弱并分裂。红外吸收带向低频方向移动。SEM-EDAX结果表明:随样品焙烧温度的升高,结晶度下降,分子筛晶形变得不规则,晶面越来越粗糙,但结晶度的下降并非由于其中PO_4四面体的热分解所引起,而是由外部联结的T-O-T键的断裂,双环被破坏及骨架元素间的重排所引起。 相似文献
154.
J. Howard Rytting Danny R. McHan Takeru Higuchi David J. W. Grant 《Journal of solution chemistry》1986,15(8):693-703
Henry's law constants have been determined for -butyrolactone (BL), ethyl acetate (EA), and 2-methyl-3-pentanol (MEP) in mixtures of iso-octane (ISO) and toluene (TOL), for BL, EA, TOL, and ISO in cinnamaldehyde (CIN) and for TOL and ISO in each other and in BL. From these data and published vapor pressures, the activity coefficients at infinite dilution and the standard molar Gibbs free energy of transfer, G
2
0
of the solutes from dilute solution in ISO to dilute solution in each solvent medium have been calculated. The different behavior patterns of BL and EA are attributed to differences in their abilities to exist in different conformations possessing different dipole moments. For polar solutes, G
2
0
decreases with increasing polarizability of the solvent and with increasing dipole moment of the solute, suggesting increased contributions from dipole-induced dipole (Debye) interactions. The sigmoidal plot of G
2
0
against the change in pair potential energy calculated from the classical expressions suggests that G
2
0
seriously underestimates the strength of the Debye interactions in comparison with the London interactions. 相似文献
155.
Bernhard Wunderlich 《Thermochimica Acta》2003,403(1):1-13
Linear, flexible macromolecules are long recognized as phase structures limited to micrometer and nanometer dimensions with covalent bonds crossing the interfaces. This special, usually non-equilibrium structure leads to unique properties and a multitude of changes for different thermal and mechanical histories. Analyses that enable the study of these properties are temperature-modulated calorimetry and related techniques which allow the separation of equilibrium and non-equilibrium responses. Research on these topics is reviewed and combined to a model for the nanophases. The new approach to the complex nanophase systems yields a better understanding of the relationship between structure and thermodynamic properties. Special emphasis is placed on the size and surface effects on the glass and melting transitions, the development of rigid-amorphous phases, and the reversible melting within the globally metastable structure. 相似文献
156.
Andrea Szép András Szabó Nikoletta Tóth Péter Anna György Marosi 《Polymer Degradation and Stability》2006,91(3):593-599
The effects of non-treated (MMT), organophilic (OMM), and olefin/silicone polymer intercalated (IMM) montmorillonites on the thermal stability of ethylene-vinyl acetate copolymer (EVA) and on the flammability of magnesium hydroxide filled EVA were studied. The influence of various treatments on the delamination of montmorillonites in EVA was detected by rheological measurements and by Raman microscopy. The latter was a unique method for rapid detection of the dispersion also in highly filled EVA. Enhancement of thermo-oxidative stability of EVA and flame-retarded EVA could be observed by thermal analysis in the presence of variously treated montmorillonites. The flame-retardant efficiency of magnesium hydroxide was improved by simultaneous application of MMT and IMM. The increased performance of magnesium hydroxide was explained by the rheological effect of the IMM, catalytic effect of MMT and chemical interactions of montmorillonites with the metal hydroxide. 相似文献
157.
158.
Wei-Shih Yang 《Journal of statistical physics》1987,49(1-2):1-32
The grand canonical ensemble of a two-dimensional Coulomb system with±1 charges is proved to have screening phenomena in its high-temperature region. The Coulomb potential in a finite region is assumed to be (–)–1, where
is the Laplacian with zero boundary conditions on. The hard-core condition is not assumed. The model is set up by separating (–)–1 into a shortrange part and a long-range part depending on a parameter. The self-energies are subtracted only for the short-range part and therefore a choice of is a choice of subtraction of self-energies. The method of proof is in general the same as that of Brydges-Federbush Debye screening, except that here a modification for the short-range part of the potentials is needed. 相似文献
159.
Using Gawedzki and Kupiainen's rigorous block spin transformation method, we study critical phenomena in 4 spin systems in four dimensions. In Part I of this work we investigate in detail the renormalization group trajectory of the system not exactly at the critical point. 相似文献
160.
R. Der 《Journal of statistical physics》1987,46(1-2):349-389
The various approaches to nonequilibrium statistical mechanics may be subdivided into convolution and convolutionless (time-local) ones. While the former, put forward by Zwanzig, Mori, and others, are used most commonly, the latter are less well developed, but have proven very useful in recent applications. The aim of the present series of papers is to develop the time-local picture (TLP) of nonequilibrium statistical mechanics on a new footing and to consider its physical implications for topics such as the formulation of irreversible thermodynamics. The most natural approach to TLP is seen to derive from the Fourier-Laplace transform
) of pertinent time correlation functions, which on the physical sheet typically displays an essential singularity at z= and a number of macroscopic and microscopic poles in the lower half-plane corresponding to long- and short-lived modes, respectively, the former giving rise to the autonomous macrodynamics, whereas the latter are interpreted as doorway modes mediating the transfer of information from relevant to irrelevant channels. Possible implications of this doorway mode concept for socalled extended irreversible thermodynamics are briefly discussed. The pole structure is used for deriving new kinds of generalized Green-Kubo relations expressing macroscopic quantities, transport coefficients, e.g., by contour integrals over current-current correlation functions obeying Hamiltonian dynamics, the contour integration replacing projection. The conventional Green-Kubo relations valid for conserved quantities only are rederived for illustration. Moreover,
may be expressed by a Laurent series expansion in positive and negative powers ofz, from which a rigorous, general, and straightforward method is developed for extracting all macroscopic quantities from so-called secularly divergent expansions of
as obtained from the application of conventional many-body techniques to the calculation of
. The expressions are formulated as time scale expansions, which should rapidly converge if macroscopic and microscopic time scales are sufficiently well separated, i.e., if lifetime (memory) effects are not too large. 相似文献