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羰基铑催化剂由于其加氢性能较弱,在羰基化反应的研究中,通常仅作为烯烃氢甲酰化制醛的催化剂。产物中得不到醇。本文则报道了以Rh_2(AcO)_4和Rh_6(CO)_16为催化剂,在一个反应器内进行烯烃氢甲酰化,加氢制醇的研究。系统考察了Rh/Pbu_3/EtOH催化体系受各种反应条件的影响。在最佳反应条件下,烯烃转化率达100%。对醇选择性亦在99.5%以上,正异构比在2以上.为烯烃一步制醇建立了铑系催化新体系。文中并利用红外光谱测定了反应过程的催化剂物种.实验证明,由烯烃一步制醇是由烯烃首先进行氢甲酰化反应,然后由生成的醛进一步加氢成醇的一个串联反应过程。前一步骤反应速度较快,2h内可使95%以上的烯烃转化为醛,后面由醛加氢成醇则进行缓慢,在100—120℃下,至少22h,才能使醛全部转化为醇。 相似文献
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以激光介质的第一主应力为评判标准,依据Griffith微裂纹理论作为断裂临界应力,基于已报道的断裂实验数据和3维、瞬态的有限元计算,建立了预测一定泵浦参数下钕玻璃断裂可能性的Weibull统计模型,同时分析了影响介质泵浦极限的其它因素。结果表明:材料的抛光工艺决定了介质的断裂应力;对于短脉冲大能量方式工作的钕玻璃介质,基于美国2 0世纪9 0年代的抛光水平,1 Hz以下低重频时应优先考虑18 kW.cm-2的泵浦饱和极限,10 Hz以上高重频时应优先考虑介质的断裂极限。 相似文献
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In this paper, we introduce the notion of Euclidean module and weakly Euclidean ring. We prove the main result that a commutative ring R is weakly Euclidean if and only if every cyclic R-module is Euclidean, and also if and only if End( R M) is weakly Euclidean for each cyclic R-moduleM. In addition, some properties of torsion-free Euclidean modules are presented. 相似文献
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A detailed master equation simulation has been carried out for the thermal unimolecular decomposition of C6H10 in a shock tube. At the highest temperatures studied experimentally [J. H. Kiefer and J. N. Shah, J. Phys. Chem., 91, 3024 (1987)], the average thermal vibrational energy is greater than the reaction threshold and therefore 〈ΔE〉 (up and down steps) is positive for molecules at that energy, rather than negative; the converse is true at lower temperatures. The calculated incubation time, in which the decomposition rate constant rises to 1/e of its steady state value, is found to be only weakly dependent on temperature (at constant pressure) between 1500 K and 2000 K and to depend almost exclusively on 〈ΔE〉d (down steps, only), and not on collision probability model. Simulations of the experimental data show the magnitude of 〈ΔE〉d depends weakly on assumed collision probability model, but is nearly independent of temperature. The second moment 〈ΔE〉½ is found to be independent of both temperature and transition probability model. The experimental data are not very sensitive to the possible energy-dependence of 〈ΔE〉d for a wide range of assumptions. It is concluded that the observed experimental “delay times” probably can be identified with the incubation time; further experiments are desirable to test this possibility and obtain more direct measures of the incubation time. 相似文献
6.
Jichun Li 《Numerical Methods for Partial Differential Equations》2006,22(4):884-896
By using a special interpolation operator developed by Girault and Raviart (finite element methods for Navier‐Stokes Equations, Springer‐Verlag, Berlin, 1986), we prove that optimal error bounds can be obtained for a fourth‐order elliptic problem and a fourth‐order parabolic problem solved by mixed finite element methods on quasi‐uniform rectangular meshes. Optimal convergence is proved for all continuous tensor product elements of order k ≥ 1. A numerical example is provided for solving the fourth‐order elliptic problem using the bilinear element. © 2005 Wiley Periodicals, Inc. Numer Methods Partial Differential Eq, 2006 相似文献
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Three hydroxamic acid ligands (HL1 = acetohydroxamic acid; HL2 = benzohydroxamic acid; HL3 = N-phenylbenzohydroxamic acid), have been used to synthesize series of mono- or dialkyltin(IV) complexes, which include (i) the carboxyl acid hybrid five-coordinated dialkyltin complexes (C4H9)2SnL1L4 (1), [(CH3)2SnL2L5]·0.5C6H6 (2), (HL4 = acetic acid; HL5 = benzoic acid); (ii) the six-coordinated mono-n-butyltin complexes (C4H9)SnL1·Cl2·H2O (3), (C4H9)SnL2·Cl2·H2O (4), [(C4H9)SnL3·Cl2·H2O]·H2O (5), [(C4H9Sn)2(L3)2·Cl2·(OCH3)2] (6); and (iii) the alkali metal-mingled seven-coordinated mono-n-butyltin complexes [(C4H9Sn)3L2Na]+·Cl−·(CH3CH2)2O (7), [(C4H9Sn)3L2K]+·Cl−·CH2Cl2 (8). All complexes were characterized by elemental analyses, IR, 1H, 13C, 119Sn NMR and X-ray single crystal diffraction. In these complexes, hydroxamic acids present bidentate coordination modes with the carbonyl O atom and the hydroxyl O atom binding to tin center. In complexes 1-6, each tin atom is coordinated by one hydroxamic acid ligand. However, in complexes 7 and 8, tin atom is surrounded by three hydroxamic acid ligands, and all hydroxyl O atoms of the ligands also bind to the alkali metal center (Na or K). This kind of organotin(IV) framework containing one alkali metal is found for the first time. Furthermore, the supramolecular structures of 1, 3, 4 and 6 have been found to consist of 1D linear molecular chains formed by intermolecular N-H···X or C-H···X (X = O, N or Cl) hydrogen bonds. For complex 2, an interesting macrocyclic tetramer has been built by the intermolecular N-H···O hydrogen bonds. Fascinatingly, two unique symmetric dimeric structures are recognized in complexes 7 and 8, which is individually bridged by intermolecular N-H···Cl and N-H···O hydrogen bonds. In addition, for 8, the dimeric cycles have been further connected into a 1D supramolecular chain. 相似文献
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<正>Diffraction efficiency of volume Bragg grating,whose period is in the same order as the incident wavelength, is related to the polarization direction of the incident linear polarized beam.When two linearly polarized recording beams with the same polarization direction are used for recording volume Bragg gratings in a photopolymer with diffusion amplification,the azimuth of polarization of the reconstruction beam influences the diffraction efficiency of the grating.When the probe beam is linearly polarized and oriented orthogonally to the grating vectors,the±1-order diffraction beams are also linearly polarized with polarization direction parallel to that of the probe beam.According to the results,a two-dimensional nonspatial optical filter consisting of the volume Bragg gratings would achieve significantly higher efficiency. 相似文献
10.
Zhang J Meng L Zhao D Fei Z Lu Q Dyson PJ 《Langmuir : the ACS journal of surfaces and colloids》2008,24(6):2699-2704
A facile method for the fabrication of dendritic gold nanoparticles (NPs) by use of an ionic polymer template has been developed. In situ generation of an imidazolium-based (cationic) polymer, poly[1-methyl-3-(4-vinylbenzyl)imidazolium], with AuCl4- counteranions is achieved by addition of HAuCl4 into a solution containing poly[1-methyl-3-(4-vinylbenzyl)imidazolium chloride]. Subsequent reduction with NaBH4 in water or in a mixture of ethanol and water affords various NPs depending on the conditions, including large dendritic gold NPs that have been analyzed by transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDS), and selected area electron diffraction (SAED). The structures of the dendritic gold NPs were found to depend on the ethanol concentration. Scanning electron microscopy (SEM) images of the ionic polymer reveal that the solvent used to deposit the polymer strongly influences its structure and may be correlated to the structure of the resulting NPs. 相似文献