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31.
Recent research has shown that a phase transformation of diamond to a different form of carbon is involved when diamonds are polished in the traditional fashion. The question as to how this phase transformation is activated and maintained to produce high wear rates is of great technological interest since it may radically change the way we view the processing of diamond. This paper describes the use of Raman spectroscopy to examine debris produced on the diamond polishing wheel, both during its preparation and during polishing. In addition, polished diamond surfaces were examined for the possible existence of non-diamond surface layers in an attempt to identify material removal mechanisms. Raman spectroscopy proves ideal for these analyses because its relatively high spatial resolution is well suited to the analysis of small wear features and debris particles, and because of the wealth of information it reveals about chemical structure. This level of structural information has been lacking in previous analyses of diamond polishing debris. In addition to the non-diamond carbon found in the wear debris, significant quantities of two iron oxides, magnetite (Fe3O4) and haematite (α-Fe2O3), were also found. An interesting observation was that a transformation from magnetite to haematite could be induced either by using high power laser excitation or by frictional heating during polishing. It is suggested that some of the Raman peaks previously attributed to lonsdaleite might better be explained by the presence of these oxides.  相似文献   
32.
The potential energy curves of the rare gas dimers He2, Ne2, and Ar2 have been computed using correlation consistent basis sets ranging from singly augmented aug-cc-pVDZ sets through triply augmented t-aug-cc-pV6Z sets, with the augmented sextuple basis sets being reported herein. Several methods for including electron correlation were investigated, namely Møller—Plesset perturbation theory (MP2, MP3 and MP4) and coupled cluster theory [CCSD and CCSD(T)]. For He2 CCSD(T)/d-aug-cc-pV6Z calculations yield a well depth of 7.35 cm-1 (10.58 K), with an estimated complete basis set (CBS) limit of 7.40 cm-1 (10.65 K). The latter is smaller than the 'exact' well depth (Aziz, R. A., Janzen, A. R., and Moldover, M. R., 1995, Phys. Rev. Lett., 74, 1586) by about 0.2 cm-1 (0.35 K). The Ne2 well depth, computed with the CCSD(T)/d-aug-cc-pV6Z method, is 28.31 cm-1 and the estimated CBS limit is 28.4 cm-1, approximately 1 cm-1 smaller than the empirical potential of Aziz, R. A., and Slaman, M., J., 1989, Chem. Phys., 130, 187. Inclusion of core and core—valence correlation effects has a negligible effect on the Ne2 well depth, decreasing it by only 0.04 cm-1. For Ar2, CCSD(T)/d-aug-cc-pV6Z calculations yield a well depth of 96.2 cm-1. The corresponding HFDID potential of Aziz, R. A., 1993, J. chem. Phys., 99, 4518 predicts of De of 99.7 cm-1. Inclusion of core and core-valence effects in Ar2 increases the well depth and decreases the discrepancy by approximately 1 cm-1.  相似文献   
33.
We study the diffusive dynamics of a hard-sphere fluid confined between parallel smooth hard walls. The position-dependent diffusion coefficient normal to the walls is larger in regions of high local packing density. High density regions also have the largest available volume, consistent with the fast local diffusivity. Indeed, local and global diffusivities as a function of the Widom insertion probability approximately collapse onto a master curve. Parallel and average normal diffusivities are strongly coupled at high densities and deviate from bulk fluid behavior.  相似文献   
34.
Density profiles are the most common measure of inhomogeneous structure in confined fluids, but their connection to transport coefficients is poorly understood. We explore via simulation how tuning particle-wall interactions to flatten or enhance the particle layering of a model confined fluid impacts its self-diffusivity, viscosity, and entropy. Interestingly, interactions that eliminate particle layering significantly reduce confined fluid mobility, whereas those that enhance layering can have the opposite effect. Excess entropy helps to understand and predict these trends.  相似文献   
35.
Contrary to some published reports, the vinyl esters of saturated fatty acids polymerize readily and rapidly. Vinyl oleate, when present in excess of 5%, and oxygen exert marked retarding effects. Techniques are described for the free-radical-initiated polymerization of the vinyl esters of caprylic, capric, lauric, myristic, palmitic, and stearic acids in bulk, dispersion, solution, and emulsion. Some data are given for polymerization in the presence of chain-transfer agents, such as carbon tetrachloride, dodecylmercaptan, and ethylbenzene. Conditions are reported for obtaining degrees of polymerization from about 2 (when chain-transfer agents are employed) to 10,000 (weight average). The weight average degree of polymerization increases markedly as the conversion increases, particularly above 80%. Even up to extremely high conversions, soluble polymers are obtained in most cases. Solubility characteristics, transition point data, molecular weights (osmometric and light-scattering), and isolation and purification techniques are also reported.  相似文献   
36.
As the human population continues to grow, there is a need for better management of our natural resources in order for our planet to be able to produce enough to sustain us. One important resource we must consider is marine fish populations. We use the tool of optimal control to investigate harvesting strategies for maximizing yield of a fish population in a heterogeneous, finite domain. We determine whether these solutions include no‐take marine reserves as part of the optimal solution. The fishery stock is modeled using a nonlinear, parabolic partial differential equation with logistic growth, movement by diffusion and advection, and with Robin boundary conditions. The objective for the problem is to find the harvest rate that maximizes the discounted yield. Optimal harvesting strategies are found numerically.  相似文献   
37.
A series of cyclometallated phenylpyridine platinum(II) complexes have been synthesised with a systematic variation in both the phenylpyridine and the ancillary ligand. Oxidation of one of the cyclometallated species leads to a number of isomeric platinum(IV) complexes, all of which eventually isomerize to a single compound. The route to these new compounds has been demonstrated to involve an initial slow oxidation followed by a rapid C-H activation to give doubly cyclometallated complexes. The solid state structures of a number of both the platinum(II) and the platinum(IV) species have been solved; many of the structures exhibited extended interactions that result in complex three dimensional packing.  相似文献   
38.
The tetra-n-butylammonium (TBA) salt of [(MeO)TiW(5)O(18)](3-) 1 was reacted with alcohols ROH to give primary, secondary and tertiary alkoxide derivatives [(RO)TiW(5)O(18)](3-) (R = Et 2, (i)Pr 3 and (t)Bu 4), whilst hydrolysis afforded [(mu-O)(TiW(5)O(18))(2)](6-) 5 rather than the hydroxo derivative (R = H). In reactions with (i)PrOH and (t)BuOH, impurity peaks observed at 1015 and 1020 ppm in the (17)O NMR spectra indicate alkoxide degradation and Ti=O bond formation via reactions analogous to those occurring at the surfaces of solid heteropolyacids. Aryloxides [(ArO)TiW(5)O(18)](3-) were prepared by reacting 1 with phenols ArOH (Ar = C(6)H(5) 6, C(6)H(4)Me-4 7, C(6)H(4)(t)Bu-4 8, C(6)H(4)OH-4 9, C(6)H(4)OH-3 10, C(6)H(3)(OH)(2)-3,5 11 and C(6)H(4)CHO-2 13). TiW(5)O(18) units were linked by reacting 1 with 9 to give [(mu-1,4-OC(6)H(4)O)(TiW(5)O(18))(2)](6-) 12. (17)O and (183)W NMR spectra are reported and X-ray crystal structures were obtained for TBA salts of anions 3-10 and 13, which showed that the titanium is six-coordinate in all cases. Reactions were monitored by (1)H NMR, including a 2D-EXSY study of methoxo exchange, and the slow rates observed are probably associated with the reluctance of titanium in these anions to achieve seven-coordination.  相似文献   
39.
The title compound, bis­(borato)­dodeca(tert‐butoxo)­octa­deca­lithium, [Li18(BO3)2(C4H9O)12], is formulated conveniently as [{(tBuOLi)3(Li3BO3)}2(tBuOLi)6]. A central 12‐membered ring and two outer six‐membered rings are formed by alternating Li+ cations and alkoxide O atoms. Sandwiched between the central ring and each of the outer rings is a planar array of three further Li+ cations surrounding a [BO3]3− anion. Thus, the mol­ecule consists of a cationic [Li18(OtBu)12]6+ cage encapsulating two borate anions. This compound is the first example of a structurally characterized polynuclear lithium borate, and a rare case of a lithium alkoxide cage with nuclearity greater than eight. All the alkoxide ligands are triply bridging, and the lithium ions have trigonal‐planar, trigonal‐pyramidal and fourfold coordination, all with major distortions from regular coordination geometry.  相似文献   
40.
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