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361.
Loon-seng Tan N. Venkatasubramanian 《Journal of polymer science. Part A, Polymer chemistry》1996,34(17):3539-3549
A series of novel benzocyclobutene (BCB)-pendanted polyamides (inherent viscosities: 0.20–0.69 dL/g) was synthesized from 3,5-diaminophenyl-4-benzocyclobutenyl ketone, and terephthaloyl, isophthaloyl, 4,4′-oxydibenzoyl chlorides, as well as 4,4′-(o-phenylenedioxy)dibenzoyl chloride. The DSC studies demonstrated that the BCB crosslinking exothermic transition occurred at nearly the same temperature (max. ∼︁ 275°C) for all the four polyamides, and they were thermally stable up to 380°C in helium, where the weight loss started to occur. TGA and DSC studies in air indicated that the polymers, in contrast to the model compound, showed evidence of oxidation just prior to or occurring simultaneously with the BCB crosslinking reaction. This could be attributed to the oxidation of the reactive diene generated from the ring-opening of the BCB competing with the process of two BCB pendant units approaching each other for crosslinking reaction. Preliminary examination of the BCB-pendanted polyamide regenerated from a methanesulfonic acid solution indicates that the BCB ring is quite stable (DSC evidence) in the strong acid medium. © 1996 John Wiley & Sons, Inc. 相似文献
362.
Aurica P. Chiriac Cristofor I. Simionescu 《Journal of polymer science. Part A, Polymer chemistry》1996,34(4):567-573
The effect of a continuous external magnetic field on the free radical polymerization of methyl methacrylate was studied with respect to some properties of the solvents used in the reaction. The studies were performed through dilatometric technique in and out a magnetic field of 0.25 T. Ten different solvents were used to underline the dependence between the magnetic field presence, the reaction medium, and the development of the polymerization process. The intervened magnetokinetic effects are attributed to the changes in the multiplicity of the radical pairs owing to the magnetic field influence. There is an interdependence among the viscosity and molar polarization of the solvents and the magnetic field effect. © 1996 John Wiley & Sons, Inc. 相似文献
363.
Hidemasa Azuma Yuzuru Katagiri Shinichi Yamabe 《Journal of polymer science. Part A, Polymer chemistry》1996,34(8):1407-1414
Transition states (TSs) of radical addition homopolymerization reactions of methyl acrylate, methyl methacrylate, dimethyl itaconate, and N-methyl itaconimide were examined with two-unit radical models using MOPAC (PM3 UHF) semiempirical method. Calculated activation energies (Eas) show good correlations with experimental values. Calculated activation entropies (−ΔS‡s) are found to be well proportional to Eas. The entropy terms play an important role as well as Ea in radical additions. Ea depends on the angle (θrs) between reaction points of radical and of monomer at TS. The bond length between reaction points at TS is constant regardless of monomers studied. The geometries and thermodynamical properties calculated here for TS indicate the importance of steric effects caused by substituted group(s) rather than electronic perturbation energies reported previously. © 1996 John Wiley & Sons, Inc. 相似文献
364.
365.
Tom Scherzer 《Journal of Polymer Science.Polymer Physics》1996,34(3):459-470
Rheo-optical FTIR spectroscopy was used for the first time to monitor molecular orientation phenomena in highly crosslinked epoxies. After studying the orientation behavior of epoxy/amine networks during uniaxial deformation above their glass transition temperature in a preceding article, this article deals with the rheo-optical characterization of the deformation process of those epoxy systems below Tg. The orientation behavior is influenced by the different molecular structure of the constituents and the free volume entrapped in the resins. Yield strain and tensile modulus are correlated with the slope of the orientation function. The orientation function was found to show an abrupt change of its slope in the yield point region. This phenomenon is discussed with respect to the mechanism of plastic deformation. © 1996 John Wiley & Sons, Inc. 相似文献
366.
Our SDFF for linear saturated hydrocarbon chains has been used to calculate the chain modulus of isolated and crystalline chains of n-alkanes of varying lengths. This has been done for static deformations and for the dynamic deformation in the longitudinal acoustic mode (LAM). Extrapolation to infinite chain length gives a common value of the room-temperature crystal modulus of 303 GPa (also obtained in an infinite chain calculation). Experimental Raman LAM measurements, corrected for chain-end interactions, give a modulus of 305 GPa, in excellent agreement. Problems with the experimental values obtained by inelastic neutron scattering and x-ray diffraction are discussed. © 1996 John Wiley & Sons, Inc. 相似文献
367.
Thierry Boxus Michle Deldime-Rubbens Patrick Mougenot Yves-Jacques Schneider Jacqueline Marchand-Brynaert 《先进技术聚合物》1996,7(7):589-598
Poly(ethylene terephthalate) (PET) films and track-etched microporous membranes naturally display, on their surfaces, reactive chain-ends, i.e. carboxyl and hydroxyl functions. These were assayed by suitable activation (reaction with carbodiimide and tosyl chloride, respectively), followed by coupling with 3H-lysine and liquid scintillation counting of the sample-associated radioactivity. Values ranging between 5 and 30 pmol/cm2 (open surface) of labeled end-groups were obtained, depending on the physico-chemical nature of the samples. Basic hydrolysis enriched the PET films with both types of endings (15–25 pmol/cm2). Reduction of films with the NaBH4-catechol complex in tetrahydrofuran enriched their surfaces with hydroxyl groups. However, this procedure was not readily applicable to the surface modification of membranes; we observed an erosion effect that was confirmed by scanning electron microscope analyses. In contrast with the reduction process, the oxidation with KMnO4 in 1.2N H2SO4 could be easily applied to the modification of either films or membranes; their surfaces were significantly enriched with carboxyl groups (15–50 pmol/cm2). This surface modification strategy has been used for the covalent coupling of adhesive proteins on PET membranes developed as supports for cell cultivation. 相似文献
368.
The epoxidation of styrene to styrene oxide at higher than 96% yield has been achieved by the catalysis by poly-(vinylbenzyl)acetylacetonate complexes of cobalt(II) or manganese(II) in the presence of isobutyraldehyde under an atmospheric pressure of molecular oxygen at room temperature. The kind of aldehyde and aldehyde/styrene molar ratio greatly influenced the reaction. The catalyst could be recycled, but after recycling for five times, the yield of styrene oxide decreased from 96.0% to 84.6%. 相似文献
369.
Edward A. Dietz 《Journal of separation science》1996,19(9):485-491
Gas chromatrography (GC) with sulfur chemiluminescence detection (SCD) is an outstanding combination for selectively determining trace concentrations of sulfur compounds in hydrocarbon samples. GC peaks can be identified by retention times when reproducible, automated injection techniques are used. However, as described in this work, analysts should be on the look out for retention shifting due to solvent effects from sample components. Three examples of retention shifting are presented: (1) thiophene by benzene; (2) methylthiophenes by toluene; and (3) dibenzothiophene by gas oil. Depending on samples and analysis conditions, retention shifts from a few hundredths to 1.5 min have been observed. Such retention shifts are likely to cause errors in peak identifications. Therefore, when using SCD, simultaneous FID monitoring is recommended as an aid in evaluating chromatograms for possible retention shifting due to solvent effects. 相似文献
370.
A capillary zone electrophoretic method with UV-scanning detection for the separation and identification of both free ligands and metal species is presented. The electrophoretic behavior of naturally occurring binding partners such as organic acids and amino acids was studied and compared with their metal-complexes. Copper(II) complexes of citrate and amino acids showed decreased electrophoretic mobilities and altered UV spectra. The optimized method was validated on ultrafiltered cow's milk and human milk samples. In cow's milk six low molecular weight substances, including citrate, orotate, and hippurate, could be separated. Metal supplementation with Cu(II), Ni(II), or Zn(II) decreased not only the citrate peak but also the orotate signal and in the case of copper(II) supplementation a new signal for the copper(II)-citrate complex appeared. In human milk samples various amino acids such as glutamate, phenylalanine, tyrosine, and tryptophan could be identified besides citrate. The electrophoretic mobilites and peak areas of the amino acids were also influenced by the metal supplementation. 相似文献