全文获取类型
收费全文 | 574篇 |
免费 | 42篇 |
国内免费 | 5篇 |
专业分类
化学 | 507篇 |
晶体学 | 3篇 |
力学 | 4篇 |
数学 | 75篇 |
物理学 | 32篇 |
出版年
2024年 | 1篇 |
2023年 | 7篇 |
2022年 | 6篇 |
2021年 | 10篇 |
2020年 | 22篇 |
2019年 | 18篇 |
2018年 | 8篇 |
2017年 | 8篇 |
2016年 | 24篇 |
2015年 | 28篇 |
2014年 | 36篇 |
2013年 | 40篇 |
2012年 | 61篇 |
2011年 | 73篇 |
2010年 | 47篇 |
2009年 | 30篇 |
2008年 | 39篇 |
2007年 | 31篇 |
2006年 | 20篇 |
2005年 | 17篇 |
2004年 | 11篇 |
2003年 | 10篇 |
2002年 | 12篇 |
2001年 | 6篇 |
2000年 | 8篇 |
1999年 | 6篇 |
1998年 | 3篇 |
1997年 | 7篇 |
1996年 | 2篇 |
1995年 | 1篇 |
1994年 | 3篇 |
1993年 | 1篇 |
1992年 | 4篇 |
1989年 | 1篇 |
1988年 | 1篇 |
1982年 | 1篇 |
1981年 | 4篇 |
1979年 | 1篇 |
1977年 | 3篇 |
1976年 | 2篇 |
1973年 | 2篇 |
1972年 | 2篇 |
1970年 | 2篇 |
1967年 | 1篇 |
1957年 | 1篇 |
排序方式: 共有621条查询结果,搜索用时 31 毫秒
11.
Pieter Bouckenooge Oliver Bauer Kathrin Eckhard Herman Terryn 《Surface and interface analysis : SIA》2020,52(4):174-184
In this paper, the behaviour of the industrial applied Ti/Zr conversion coating (CC) pretreatment on rolled automotive aluminium samples (AA5182) is analysed. Due to its nanometre lateral and depth resolution, Auger electron spectroscopy (AES) is used to analyse the CC distribution at surface cathodic intermetallic particles. As a result of its high surface sensitivity, the AES technique is very susceptible to differences in the top contamination layer thickness. It is demonstrated that AES point measurements performed on aluminium model samples coated with 1.5 and 3 nm of Ti (oxide) layer cannot differentiate the two-layer thicknesses if a difference in the top contamination thickness is not taken into account. A data analysis methodology is introduced, based on the ratio of normalized peak areas (enrichment ratios), to eliminate the effect of the contamination layer thickness. The experimental validation of the methodology is performed on the model samples, demonstrating errors of 2% on the enrichment ratios on similar samples with different contamination layer thicknesses, while the conventional spectra quantification results in errors of 49%. The methodology is also theoretically substantiated within certain constraints. By the use of the AES methodology, an enriched Ti and Zr deposition is confirmed at the cathodic intermetallic particles at the surface of the industrial no-rinse CC sprayed automotive aluminium sheet samples. 相似文献
12.
13.
14.
15.
Patricia Dähmlow Torsten Trittel Kathrin May Kirsten Harth Ralf Stannarius 《Liquid crystals》2018,45(7):993-1003
Elongated freely floating smectic bubbles are observed during their relaxation to equilibrium sphere shape. Unlike soap bubbles that perform weakly damped oscillations into equilibrium, this relaxation is overdamped in smectics by internal structure reorganisation processes. The bubble area reduction of centimetre-sized freely floating bubbles with few nanometres film thickness is recorded with high-speed optical imaging in microgravity and analysed quantitatively. We find a nearly linear reduction of the film area with time, driven by capillary forces and inhibited by smectic layer reorganisations. Characteristic times are in the milliseconds range, with little correlation to the film thickness and bubble size. Instead, the homogeneity of the films and the number and sizes of islands of excess layers that spontaneously form on the films appear to have crucial influence on the dynamics. The efficiency of this process sets the time scale of the film area shrinkage. We discuss the limitations of a minimalistic model that captures smectic layer reorganisation processes. 相似文献
16.
Owen S. Skinner Kathrin Breuker Fred W. McLafferty 《Journal of the American Society for Mass Spectrometry》2013,24(6):807-810
A conventional electron capture dissociation (ECD) spectrum of a protein is uniquely characteristic of the first dimension of its linear structure. This sequence information is indicated by summing the primary c m+ and z m+? products of cleavage at each of its molecular ion’s inter-residue bonds. For example, the ECD spectra of ubiquitin (M?+?nH)n+ ions, n?=?7–13, provide sequence characterization of 72 of its 75 cleavage sites from 1843 ions in seven c (1–7)+ and eight z (1–8)+? spectra and their respective complements. Now we find that each of these c/z spectra is itself composed of “charge site (CS)” spectra, the c m+ or z m+? products of electron capture at a specific protonated basic residue. This charge site has been H-bonded to multiple other residues, producing multiple precursor ion forms; ECD at these residues yields the multiple products of that CS spectrum. Closely similar CS spectra are often formed from a range of charge states of ubiquitin and KIX ions; this indicates a common secondary conformation, but not the conventional α-helicity postulated previously. CS spectra should provide new capabilities for comparing regional conformations of gaseous protein ions and delineating ECD fragmentation pathways. Figure
? 相似文献
17.
Kathrin Schreglmann Martina Hoeche Sibylle Steinbeiss Sandra Reinnicke Martin Elsner 《Analytical and bioanalytical chemistry》2013,405(9):2857-2867
Environmental degradation of organic micropollutants is difficult to monitor due to their diffuse and ubiquitous input. Current approaches—concentration measurements over time, or daughter-to-parent compound ratios—may fall short, because they do not consider dilution, compound-specific sorption characteristics or alternative degradation pathways. Compound-specific isotope analysis (CSIA) offers an alternative approach based on evidence from isotope values. Until now, however, the relatively high limits for precise isotope analysis by gas chromatography—isotope ratio mass spectrometry (GC-IRMS) have impeded CSIA of sub-microgram-per-liter scale micropollutant concentrations in field samples. This study presents the first measurements of C and N isotope ratios of the herbicide atrazine and its metabolite desethylatrazine at concentrations of 100 to 1,000 ng/L in natural groundwater samples. Solid-phase extraction and preparative HPLC were tested and validated for preconcentration and cleanup of groundwater samples of up to 10 L without bias by isotope effects. Matrix interferences after solid-phase extraction could be greatly reduced by a preparative HPLC cleanup step prior to GC-IRMS analysis. Sensitivity was increased by a factor of 6 to 8 by changing the injection method from large-volume to cold-on-column injection on the GC-IRMS system. Carbon and nitrogen isotope values of field samples showed no obvious correlation with concentrations or desethylatrazine-to-atrazine ratios. Contrary to expectations, however, δ 13 C values of desethylatrazine were consistently less negative than those of atrazine from the same sites. Potentially, this line of evidence may contain information about further desethylatrazine degradation. In such a case, the common practice of using desethylatrazine-to-atrazine ratios would underestimate natural atrazine degradation. 相似文献
18.
Peirong Chen Ly May Chew Aleksander Kostka Kunpeng Xie Martin Muhler Wei Xia 《Journal of Energy Chemistry》2013,22(2):312-320
Oxygen- and nitrogen-functionalized carbon nanotubes (OCNTs and NCNTs) were applied as metal-free catalysts in selective olefin hydrogenation. A series of NCNTs was synthesized by NH3 post-treatment of OCNTs. Temperature-programmed desorption, N2 physisorption, Raman spectroscopy, high-resolution transmission electron microscopy and X-ray photoelectron spectroscopy were employed to characterize the surface properties of OCNTs and NCNTs, aiming at a detailed analysis of the type and amount of oxygen- and nitrogen-containing groups as well as surface defects. The gas-phase treatments applied for oxygen and nitrogen functionalization at elevated temperatures up to 600 °C led to the increase of surface defects, but did not cause structural damages in the bulk. NCNTs showed a clearly higher activity than the pristine CNTs and OCNTs in the hydrogenation of 1,5-cyclooctadiene, and also the selectivity to cyclooctene was higher. The favorable catalytic properties are ascribed to the nitrogen-containing surface functional groups as well as surface defects related to nitrogen species. In contrast, oxygen-containing surface groups and the surface defects caused by oxygen species did not show clear contribution to the hydrogenation catalysis. 相似文献
19.
20.
Li Luo Kathrin Häfliger Dan Xie Markus Niederberger 《Journal of Sol-Gel Science and Technology》2013,65(1):28-35
Homogeneous transparent conducting Sn:ZnO films on fused silica substrates were prepared by dip-coating from nanoparticle dispersions, while the nanocrystalline Sn:ZnO particles with different dopant concentrations were synthesized by microwave-assisted non-aqueous sol–gel process using Sn(IV) tert-butoxide and Zn(II) acetate as precursors and benzyl alcohol as solvent. The dopant concentration had a great impact on the electrical properties of the films. A minimum resistivity of 20.3 Ω cm was obtained for a porous Sn:ZnO film with initial Sn concentration of 7.5 mol% after annealing in air and post-annealing in N2 at 600 °C. The resistivity of this porous film could further be reduced to 2.6 and 0.6 Ω cm after densified in Sn:ZnO and Al:ZnO reaction solution, respectively. The average optical transmittance of a 400-nm-thick Sn:ZnO film densified with Sn:ZnO after the two annealing steps was 91%. 相似文献