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21.
Anionic copolymerizations of styrene (M1) with excess 1-(4-dimethyl-aminophenyl)-1-phenylethylene (M2) were conducted in benzene at 25°C for 24h, using sec-butyllithium as initiator. Narrow molecular weight distribution copolymers with M?;n = 16.1 × 103 g/mol (M?w/M?n = 1.04) and 38.2 × 103g/mol (M?w/M?n = 1.05), and 24 and 38 moles of M2 per macromolecule, respectively, were characterized by size exclusion chromatography, 1H NMR spectroscopy and DSC. The monomer reactivity ratio, r1 = 5.6, was obtained from the copolymer composition at complete consumption of M1, assuming that the rate constant k22 =0,i.e. r2 =0. The polymers exhibited Tg values of 128 and 119°C, respectively, which correspond to an estimated Tg = 217°C for the hypothetical homopolymer of M2. 相似文献
22.
Cis-1,4-polybutadiene (PB) in a 0.5% solution of a solvent mixture of dichloromethane and 1,2-dibromoethane or tetrahydrofuran was quantitatively brominated with elemental bromine at 0°C under careful exclusion of oxygen to head-to-head poly(vinyl bromide). Partially brominated PB has a structure of random or block sequences of butadiene units in the polymer depending on the bromination solvent but shows no stereospecificity in the CHBrCHBr-dyads. Partially brominated PB with block structure showed a microphase-separated morphology over a wide range of composition. Microphase separation is less pronounced for the more random structure of butadiene units. I.r and 13C n.m.r. spectroscopy of the partially brominated PB was used to follow the progress of the bromination. 相似文献
23.
Melting and crystallization behaviour of elastoplastic semicrystalline copolymers: poly(ether ester)
The melting and crystallization behaviour of an elastoplastic semi-crystalline poly(etherester) has been studied by differential scanning calorimetry. The shape of the melting endotherm is strongly dependent on heating rate and annealing time and results from the sum of simultaneous melting and crystallization phenomena. Samples prepared by different techniques, i.e. by solvent evaporation or by melt extrusion, behave very differently owing to specific crystal morphologies. By applying the Hoffman-Weeks plot, the equilibrium melting temperature has been extrapolated. The Avrami treatment allows the calculation of the index n and of the rate constant K from the isothermal kinetic data. 相似文献
24.
The effect of a range of organic additives on the thermal stability of poly(vinyl chloride), both with and without a chloroparaffin extender, was studied using a number of experimental techniques. Of the additives used the best overall balance was provided by pentaerythritol, which increased stability when the extender was present and had no effect when it was absent. The congo red test emerged as the most suitable technique, being consistent and inexpensive and able to screen several additives simultaneously. Isothermal differential thermal analysis correlated with the congo red test but required more expensive equipment, was time-consuming and demanded good mixing of the poly(vinyl chloride) compound to give reproducible results. Thermogravimetry was not sufficiently sensitive and the heat stability test was the least useful of all. 相似文献
25.
Thermodynamic parameters have been determined for the interaction of methyl orange and poly(vinylpyrrolidone) in aqueous solutions containing tris, tris and hydrochloric acid, or water only. Enthalpy changes were determined by use of a flow microcalorimeter. Free energy changes were calculated from the results of equilbrium dialysis studies. The results are interpreted in terms of the behaviour of poly(vinylpyrrolidone) in these systems. Analysis of data shows that the hydrophobic interactions in the systems are in the order: tris > wateronly > tris-HC1. 相似文献
26.
An outline of the characteristics of PEEK and the versatility of its compositional forms (micro and macro composites) are given to illustrate its wide potential for success in engineering applications. Although it is necessary to have particular tabulations of mechanical properties for engineering design, these are seldom available and consequently it is argued that an understanding of stiffness, toughness and strength properties are required to fully exploit available manufacturer's data and thus develop the full potential of PEEK and its composites. Stiffness characteristics are considered in terms of a modulus function which is dependent on time under load and temperature. In its composite forms, whether reinforced with short or continuous fibres, stiffness anistropy can be both considerable and complex, but some empirical ground-rules are apparent. For continuous fibre composites even in the form of complex lay-ups, it is also possible to attempt some stiffness prediction from certain pseudo-elastic constants. Toughness of PEEK and its composites is described in terms of both comparative and intrinsic properties. Instrumented falling weight impact data, particularly as a function of temperature enable some insight into ductile-brittle transitions for the unreinforced material, but crack initiation and crack propagation processes for the various fibre reinforced forms. Intrinsic toughness is described in terms of linear elastic fracture mechanics theory. Strength properties are described for static and dynamic loading configurations. In particular, PEEK and its composites are evaluated for increasing test severities for strength characteristics; stress concentration, loading form and test temperature are considered. 相似文献
27.
C. N. Cacaval E. C. BuruianÎ D. Rou E. Rusu G. E. Grigoriu V. Brboiu 《Polymer International》1985,17(4):343-346
Thermogravimetry and pyrolysis in combination with gas chromatography and infrared spectroscopy were the experimental techniques applied to the thermal degradation of cinnamoylated poly(vinyl alcohol) samples, constituted from vinyl alcohol-vinyl cinnamate photocrosslinkable copolymers. The thermal decomposition products include gases, liquids and solids. The gases are formed from saturated and unsaturated volatile hydrocarbons C1? C4, carbon monoxide and carbon dioxide. The liquid fraction includes aromatic hydrocarbons and some oxygenated organic compounds. The solid product identified in the greatest amount was cinnamic acid. The content in the thermal decomposition products varies considerably both with copolymer composition and temperature. 相似文献
28.
The syntheses of polyenynes as model compounds for poly(diacetylene)s (PDAs) are described. Variation of properties (UV–VIS, Raman, NMR and bond geometries) as a function of the chain length was investigated. After extrapolation to infinite chain length these data were compared to those for PDAs. From UV–VIS spectra a value of λ = 551 nm (2.25 eV) was calculated corresponding to the electronic transition of a single polyenyne chain. This energy is located at the low energy end of a yellow PDA solution spectrum. From Raman scattering v(C?C) = 2108–2128 cm?1 and v(C?C) = 1505–1532 cm?1 were calculated after extrapolation. Similarly sp-C13C NMR data yielded a shift of δ = 100 ppm. These data are almost identical to data known for yellow PDA solutions. Bond geometries are almost identical to those of poly(diacetylene)s and theoretical data. 相似文献
29.
The effects of α‐form and β‐form nuclei on polymorphic morphology of poly(butylene adipate) (PBA) upon recrystallization from the molten state up to various Tmax values were examined by differential scanning calorimetry (DSC), wide‐angle X‐ray diffraction (WAXD) and polarized light microscopy (PLM). In this study, PBA with complex melting and polymorphism behaviour was used as a model for examining different types and extents of residual nuclei. As the PBA initially containing the sole α‐crystal was brought to a molten state of various Tmax, the extents of trace α‐form crystal nuclei varied and were dependent on Tmax. Furthermore, it did not matter whether, initially, the PBA contained α‐ or β‐form crystals (or both) because only a single type of α‐nuclei could be left upon treatment to the molten liquid state at Tmax. Therefore, only the α‐crystal in PBA had ‘memory capacity’ in the molten liquid state while the β‐crystal did not. This was so because the latter had been completely transformed into the solid state prior to being heated into a liquid. PBA crystallized before α‐nuclei could be packed into α‐crystal, regardless of the crystallization temperature (Tc). For recrystallization from molten PBA without any nuclei, the crystalline polymorphism was correspondingly influenced by Tc. Copyright © 2005 Society of Chemical Industry 相似文献
30.
Novel diols containing imide groups were prepared via condensation of aromatic dianhydrides with 5‐amino‐1‐naphthol. The diimide–dinaphthols prepared were characterized by conventional methods and used to synthesize new poly(urethane–imide)s (PUIs). All the polymers were characterized and their physical properties, such as solubility, solution viscosity, thermal stability, and thermal behaviour were studied. The polymers obtained showed more thermal stability than typical polyurethanes because of the presence of the imide groups. Copyright © 2003 Society of Chemical Industry 相似文献