全文获取类型
收费全文 | 325篇 |
免费 | 25篇 |
国内免费 | 9篇 |
专业分类
化学 | 213篇 |
晶体学 | 7篇 |
力学 | 12篇 |
数学 | 70篇 |
物理学 | 57篇 |
出版年
2022年 | 4篇 |
2021年 | 2篇 |
2020年 | 6篇 |
2019年 | 5篇 |
2018年 | 6篇 |
2017年 | 5篇 |
2016年 | 12篇 |
2015年 | 18篇 |
2014年 | 19篇 |
2013年 | 26篇 |
2012年 | 8篇 |
2011年 | 12篇 |
2010年 | 13篇 |
2009年 | 16篇 |
2008年 | 27篇 |
2007年 | 17篇 |
2006年 | 11篇 |
2005年 | 4篇 |
2004年 | 8篇 |
2003年 | 13篇 |
2002年 | 11篇 |
2001年 | 8篇 |
2000年 | 4篇 |
1999年 | 4篇 |
1998年 | 7篇 |
1997年 | 6篇 |
1996年 | 6篇 |
1995年 | 6篇 |
1994年 | 5篇 |
1993年 | 3篇 |
1992年 | 6篇 |
1991年 | 3篇 |
1990年 | 3篇 |
1988年 | 3篇 |
1987年 | 5篇 |
1986年 | 4篇 |
1985年 | 3篇 |
1984年 | 2篇 |
1983年 | 2篇 |
1982年 | 5篇 |
1981年 | 4篇 |
1978年 | 2篇 |
1976年 | 3篇 |
1975年 | 2篇 |
1972年 | 2篇 |
1971年 | 3篇 |
1970年 | 4篇 |
1968年 | 2篇 |
1966年 | 2篇 |
1900年 | 1篇 |
排序方式: 共有359条查询结果,搜索用时 31 毫秒
351.
B. B. Koleva T. M. Kolev V. Simeonov T. Spassov M. Spiteller 《Journal of inclusion phenomena and macrocyclic chemistry》2008,61(3-4):319-333
Colloid suspensions in nematic liquid crystal were employed for the first time in 2004 as a tool for the partial orientation of solids, to be examined by linearly polarized IR-(IR-LD) spectroscopy. It has been found is found that a partial orientation (15–20%) of suspended particles, is adequate for the recording of reasonable linearly polarized IR-spectra is achieved when: 5 ± 1% by weight of the given solid compound (organic, inorganic, transition metal complex or glass) with particle size within the limits 0.3–0.9 μm is mixed with a nematic liquid crystal substance (ZLI 1695, ZLI 1538 or MLC 6815) suitable for IR spectroscopy and the slightly viscous suspension obtained is phase pressed between two KBr-plates. These latter are roughened in one direction prior to use with fine sandpaper (C800) (size 5 μm). Then, the KBr-plattes and pressed suspension are moved repeatedly with 3 μm/s for 100 times. The optimal cell thickness is 100 μm. If mathematical procedures are used for polarized IR-spectra interpretation, then it is possible to perform structural elucidation of the embedded compounds, independently of their melting point, crystalline or amorphous state, and the quality of the monocrystals or polycrystalline of the e sample. The method permits the study of organic and inorganic compounds, transition metal complexes and glasses. Here we will discuss the fundamental questions concerning the above state such as the morphology of the suspended particles, the particle size, the influence of the physical chemistry properties of liquid crystal medium on the degree of orientation of suspended particles; the velocity of the shearing of the suspension, the degree of the roughening of the KBr-plates and their effects on the degree of orientation, the influence of the space group on the orientation parameter, the nature and balance of the forces acting on the suspended particles; their degree of orientation, the mathematical model used. Conventional and linearly polarized IR-spectroscopy and electron microscopy are used for elucidation of these points. Statistical approaches have also been applied in order to estimate the impact of the experimental parameters (size, velocity, thickness) on the IR-signal for each of the 13 systems studied. An experimental design of the type involving full factorial design on two levels of variation of the input factors is presented. 相似文献
352.
Koleva BB Kolev T Seidel RW Tsanev T Mayer-Figge H Spiteller M Sheldrick WS 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2008,71(2):695-702
A distortion of the aromatic character and stabilization of the imino-form as a result of the protonation of 4-dimethylaminopyridine was established by IR-, UV- and 1H NMR-spectral analysis of 4-diaminopyridinium hydrogensquarate. Quantum chemical calculations were carried out at MP2 and B3LYP levels of theory and a 6-311++G** basis set with a view to determining the changes in geometrical parameters and IR-spectroscopic characteristics resulting from Npy protonation. Linear-dichroic IR-spectroscopy coupled with the orientation techniques of solid samples as liquid crystal suspensions and melted solid polycrystalline films was applied for the identification of the IR-bands, characteristic for the structural fragments of the neutral and imino-form of the pyridine derivative. The spectral results were compared with the structure, obtained by a single crystal X-ray analysis. The salt contains dimmers of hydrogensquarate anions and Npy protonated cations of which the former are stabilized by strong intermolecular OH...O interactions (2.552 angstroms and 143.1(2) degrees). The 4-diaminopyridinium cation interacts with the anion through moderate NH...O bonds (2.729 angstroms and 165.0(0) degrees ). Individual cations are pi-pi stacked with their neighbors at a distance of 3.406 angstroms. 相似文献
353.
Smith JN V White G White MI Bernstein R Hochrein JM 《Journal of the American Society for Mass Spectrometry》2012,23(9):1579-1592
Aged materials, such as polymers, can exhibit modifications to their chemical structure and physical properties, which may render the material ineffective for its intended purpose. Isotopic labeling was used to characterize low-molecular weight volatile thermal-oxidative degradation products of nylon 6.6 in an effort to better understand and predict changes in the aged polymer. Headspace gas from aged (up to 243 d at 138?°C) nylon 6.6 monomers (adipic acid and 1,6-hexanediamine) and polymer were preconcentrated, separated, and detected using cryofocusing gas chromatography mass spectrometry (cryo-GC/MS). Observations regarding the relative concentrations observed in each chromatographic peak with respect to aging time were used in conjunction with mass spectra for samples aged under ambient air to determine the presence and identity of 18 degradation products. A comparison of the National Institute of Standards and Technology (NIST) library, unlabeled, and isotopically labeled mass spectra (C-13 or N-15) and expected fragmentation pathways of each degradation product were used to identify the location of isotopically labeled atoms within the product's chemical structure, which can later be used to determine the exact origin of the species. In addition, observations for unlabeled nylon 6.6 aged in an O-18 enriched atmosphere were used to determine if the source of oxygen in the applicable degradation products was from the gaseous environment or the polymer. Approximations for relative isotopic ratios of unlabeled to labeled products are reported, where appropriate. 相似文献
354.
Crystallographic and transport properties of nominally undoped and Sn-doped InGaAsN layers grown by low-temperature LPE have been studied and related to the growth conditions.In the case of lattice matching, flat and uniform mirror-like layers of 8–10 μm in thickness are obtained. The compositions of the layers under study have been determined by combination of X-ray microanalysis and X-ray diffraction methods to be In0.035Ga0.065As0.086N0.014. The lattice mismatch between layer and substrate Δal/as calculated from X-ray diffraction curves is less than?7×10?4 for all samples. The layers grown at lower epitaxy temperatures exhibit the highest crystalline quality, better lattice match and better homogeneity. This is in good agreement with the results of morphological study by atomic force microscopy which show root mean-square surface roughness of 0.18 nm for the best layers.CV and Hall measurements reveal that intentionally undoped InGaAsN layers are n-type with free carrier concentration about one order of magnitude higher in comparison to layers not containing nitrogen and high electron mobility values over 2000 cm2/Vs. A dramatic reduction in the free carrier concentration and slightly increase in mobility are observed for Sn-doped InGaAsN layers. 相似文献
355.
The syntheses of an important class of hitherto unreported novel pyrazoles are described. The regioselective synthesis of 1,3,4,5-tetrasubstituted pyrazoles was achieved by the Huisgen cyclization of nitrile imines with a trisubstituted bromoalkene. The substituted bromoalkene functions as an alkyne synthon which was used to construct 5,5-disubstituted bromopyrazoline intermediates that undergo aromatization to the analogous pyrazoles through the loss of HBr. The cycloaddition regioselectivity was confirmed through single X-ray crystal data of one of the pyrazoles. 相似文献
356.
357.
358.
Gregory F. Meyers Michael T. Dineen Edward O. Shaffer II Ted Stokich Jr. Jang‐hi Im 《Macromolecular Symposia》2001,167(1):213-226
Scanning probe microscopy (SPM) techniques are used to characterize surfaces related to the processing of benzocyclobutene (BCB) dielectric thin films. Thermally cured resins and photodefineable resins are sold under the trade name CYLCOTENETM1) for electronic applications. TappingMode AFM (TMAFM) imaging is used to follow changes in adhesion promoter morphology upon baking to help explain adhesion performance. Power spectral density (PSD) analysis of TMAFM images of plasma treated BCB surfaces are unique and can be used to ‘fingerprint’ processes. Selective oxidation of the BCB surface can be used to fabricate a phase imaging standard for TMAFM. Near surface modulus of the BCB materials is 3.6 ± 0.2 GPa and the hardness is 0.38 ± 0.2 GPa measured by depth‐sensing nanoindentation. Creep recovery of indents can be used to qualitatively distinguish between thermal and photocureable materials. A heated tip in a scanning thermal microscope can induce the thermal curing of BCB over micron sized areas. Local thermal analysis with the same probe allows the measurement of the changes in the glass transition, Tg, at the surface with cure temperature. 相似文献
359.
Manish K. Saraf Louis M. Wojcinski II Karen A. Kennedy Sylvain Gerard Paul A. Charpentier Joseph M. DeSimone George W. Roberts 《Macromolecular Symposia》2002,182(1):119-129
The surfactant-free precipitation polymerization of vinylidene fluoride (VF2) in supercritical carbon dioxide was studied in a continuous stirred autoclave. The polymerization temperature ranged from 65 to 85°C, the average residence time in the reactor varied from 10 to 50 min., and the pressure was between 210 and 305 bar. Diethyl peroxydicarbonate was used as the initiator. The fractional conversion of monomer varied from 7 to 26%, the number-average molecular weight of the polymer was between about 14,000 and 79,000, and the weight-average molecular weight was between about 21,000 and 700,000. In many cases, the polymer exhibited a bimodal molecular-weight distribution, especially at high monomer concentrations. 相似文献