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41.
Summary The reaction order with respect to TiCl4 was investigated in the quasiliving polymerization of styrene using a 1-phenylethyl chloride/TiCl4/Bu2O initiating system in mixture of 1,2-dichloroethane and n-hexane (55:45 v/v) at -15 °C. It was found out that the reactions order with respect to TiCl4 was closer to 1. A mechanistic scheme to explain the kinetic behavior of quasiliving styrene polymerization in 1-phenylethyl chloride/TiCl4/Bu2O is proposed.  相似文献   
42.
Summary Quasiliving cationic polymerization of styrene was obtained in the system 2-phenyl-2-propano-/AlCl3·OBu2/Bu2O in a mixture of 1,2-dichloroethane and n-hexane (55:45 viv) at -15 °C. The molecular weights of the polymers (Mn) increased in direct proportion to the monomer conversion. However, the experimental Mns are essentially higher than theoretical ones, indicating that slow initiation relative to propagation takes place. The molecular weight distributions were broad (Mw/Mn2.5), probably due to the slow initiation and slow exchange between reversibly terminated and propagating species.  相似文献   
43.
The activated anionic ring-opening polymerization of ε-caprolactam initiated by 0.35 mol% of combined initiator, i.e., equimolar mixture of magnesium di(ε-caprolactamate) (CL2Mg) with magnesium halides (MgCl2, MgBr2, and MgI2) as well as of ε-caprolactam magnesium bromide (CLMgBr) in the presence of 0.35 mol% of N-acetyl-ε-caprolactam as an activator has been investigated in the temperature range 140–200 °C. It was found that the reaction rate increased while the apparent activation energy decreased in the following series: CL2Mg/MgCl2 < CL2Mg/MgBr2 ~ CLMgBr < CL2Mg/MgI2. In addition, the poly(ε-caprolactam)s prepared with CL2Mg/MgX2 (MgX2 = MgCl2, MgBr2, and MgI2) are characterized by slightly higher thermal stability than polymers obtained with CLMgBr as initiator. These observations were explained in terms of the coordination of Lewis acids (MgX2, where X = Cl, Br, and I) with imide carbonyl of N-acyllactam end groups leading to the increase of their reactivity and stability.  相似文献   
44.
Polymers filled with low amounts of layered silicate dispersed at nanoscale level are most promising materials characterized by a combination of chemical, physical and mechanical properties that cannot be obtained with macro‐ or microscopic dispersions of inorganic fillers. Polymer layered silicate nanocomposites can be obtained by insertion of polymer molecules in the galleries between the layers of phyllosilicate. Here, hydrated alkaline or alkaline earth metal cations are hosted which neutralize the negative charge resulting from isomorphous substitutions of Mg or Al cations within the silicate. Insertion of polymer molecules to prepare “intercalation hybrids” can be carried out by replacing the water hydration molecules in the galleries by polymers containing polar functional groups, using the so called ion‐dipole method. A more general technique involves compatibilization of the silicate by intercalation of an organic molecule, typically an organic alkylammonium salt, that replaces the cations in the interlayer galleries to form an organically modified layered silicate (OLS). The aliphatic chain of the OLS favors the intercalation of any type of polymer. Intercalated or delaminated polymer‐silicate hybrids are obtained depending on whether the stack organization of the silicate layers is preserved or is lost, with single sheets being distributed in the polymer matrix. The methods currently used for preparing polymer layered silicate (PLS) nanocomposites are: in situ polymerization, from polymer solution, or from polymer melt. Although PLS nanocomposites have been known for a long time, it is the possibility of preparing them by melt intercalation of OLS in processing that is boosting the present interest in these materials and their properties. So far PLS nanocomposites have been characterized by X‐ray diffractometry, transmission electron microscopy, differential scanning calorimetry, and NMR. Published results on PLS nanocomposites are reviewed concerning their characterization and properties with particular reference to fire retardant behavior.  相似文献   
45.
Akzo Nobel Chemicals has recently introduced on the market an aromatic oligomeric phosphate (BDP) based on Bisphenol A. This product shows higher thermal and hydrolytic stability than other aryl phosphates. It provides similar or better fire retardant performance than an oligomeric phosphate (RDP) based on resorcinol. Fire retardant formulations with BDP based on polycarbonate/ABS plastic (PC/ABS) blend, polyphenylene oxide/high impact polystyrene (PPO/HIPS) blend, and HIPS alone show similar or better physical properties than those obtained with RDP. Upon thermal decomposition of the fire retarded polymers containing BDP, phosphorus tends to accumulate in the solid residue, a result which indicates that the primary fire retardant action of BDP is likely to occur in the condensed phase.  相似文献   
46.
A molecule of the photoreceptor Ca2+-binding protein recoverincontains four potential EF-hand Ca2+-binding sites, of whichonly two, the second and the third, are capable of binding calciumions. We have studied the effects of substitutions in the second,third and fourth EF-hand sites of recoverin on its Ca2+-bindingproperties and some other characteristics, using intrinsic fluorescence,circular dichroism spectroscopy and differential scanning microcalorimetry.The interaction of the two operating binding sites of wild-typerecoverin with calcium increases the protein's thermal stability,but makes the environment around the tryptophan residues moreflexible. The amino acid substitution in the EF-hand 3 (E121Q)totally abolishes the high calcium affinity of recoverin, whilethe mutation in the EF-hand 2 (E85Q) causes only a moderatedecrease in calcium binding. Based on this evidence, we suggestthat the binding of calcium ions to recoverin is a sequentialprocess with the EF-hand 3 being filled first. Estimation ofCa2+-binding constants according to the sequential binding schemegave the values 3.7 x 106 and 3.1 x 105 M–1 for thirdand second EF-hands, respectively. The substitutions in theEF-hand 2 or 3 (or in both the sites simultaneously) do notdisturb significantly either tertiary or secondary structureof the apo-protein. Amino acid substitutions, which have beendesigned to restore the calcium affinity of the EF-hand 4 (G160D,K161E, K162N, D165G and K166Q), increase the calcium capacityand affinity of recoverin but also perturb the protein structureand decrease the thermostability of its apo-form.  相似文献   
47.
Electronic and structural properties of antiphase boundaries in group III-V semiconductor compounds have been receiving increased attention due to the potential to integration of optically-active III-V heterostructures on silicon or germanium substrates. The formation energies of {110}, {111}, {112}, and {113} antiphase boundaries in GaAs and GaP were studied theoretically using a full-potential linearized augmented plane-wave density-functional approach. Results of the study reveal that the stoichiometric {110} boundaries are the most energetically favorable in both compounds. The specific formation energy γ of the remaining antiphase boundaries increases in the order of γ{113} ≈ γ{112} < γ{111}, which suggests {113} and {112} as possible planes for faceting and annihilation of antiphase boundaries in GaAs and GaP.  相似文献   
48.
Shape memory alloys (SMA) suffer from the same impairing mechanisms experienced during cycling loading by classic alloys. Moreover, SMA fatigue behavior is greatly influenced by thermomechanical cycling through the zone of thermoelastic phase transformation, which is the basis of shape memory and superelasticity effects. Since the fatigue resistance of any material can be improved by an appropriate thermomechanical treatment, in the present work combined differential scanning calorimetry and microhardness testing were used to determine an optimum annealing temperature for the cold-worked Ni-50.1%Ti alloy. The optimization is based on the assumption that latent heat of transformation is proportional to the mechanical work generated by SMA upon heating, while material hardness is related to the yield stress of the material. It is supposed that an optimum trade-off in these two properties guarantees the best dimensional and functional stability of SMA devices. The level and stability of the mechanical work generated by the material during low-cycle fatigue testing are considered criteria for the material performance and thus of the validity of the proposed optimization procedure.  相似文献   
49.
Some features of microdistribution of copper-based binary alloys and their components have been studied. If the codeposition rate of the more electropositive component (copper) is at least partially controlled by diffusion, antilevelling takes place for the alloy as a whole. Considerable enrichment of the deposit with respect to the more electropositive component is observed on micropeaks, provided the electrodeposition rate of the more electronegative component is nearly constant at all points of the microprofile (electrodeposition of Cu-Ni alloy from pyrophosphate solution). If the more electropositive component produces a depolarizing effect on the deposition of the more electronegative component, microdistribution of the latter also becomes non-uniform in spite of the absence of diffusion control (Cu-Cd and Cu-Zn alloys). In this case an overall alloy microdistribution shows stronger antilevelling; however, the composition of the deposit becomes more uniform over the microprofile.  相似文献   
50.
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