全文获取类型
收费全文 | 2647篇 |
免费 | 113篇 |
国内免费 | 7篇 |
专业分类
化学 | 2059篇 |
晶体学 | 7篇 |
力学 | 40篇 |
数学 | 384篇 |
物理学 | 277篇 |
出版年
2023年 | 21篇 |
2022年 | 20篇 |
2021年 | 93篇 |
2020年 | 71篇 |
2019年 | 76篇 |
2018年 | 37篇 |
2017年 | 42篇 |
2016年 | 109篇 |
2015年 | 96篇 |
2014年 | 102篇 |
2013年 | 168篇 |
2012年 | 195篇 |
2011年 | 201篇 |
2010年 | 153篇 |
2009年 | 115篇 |
2008年 | 169篇 |
2007年 | 151篇 |
2006年 | 137篇 |
2005年 | 137篇 |
2004年 | 131篇 |
2003年 | 102篇 |
2002年 | 99篇 |
2001年 | 34篇 |
2000年 | 42篇 |
1999年 | 31篇 |
1998年 | 25篇 |
1997年 | 25篇 |
1996年 | 30篇 |
1995年 | 21篇 |
1994年 | 22篇 |
1993年 | 18篇 |
1992年 | 18篇 |
1991年 | 7篇 |
1990年 | 6篇 |
1989年 | 5篇 |
1988年 | 7篇 |
1987年 | 10篇 |
1986年 | 7篇 |
1985年 | 7篇 |
1984年 | 2篇 |
1983年 | 5篇 |
1981年 | 3篇 |
1980年 | 2篇 |
1979年 | 1篇 |
1978年 | 1篇 |
1977年 | 2篇 |
1976年 | 2篇 |
1975年 | 3篇 |
1974年 | 2篇 |
1970年 | 2篇 |
排序方式: 共有2767条查询结果,搜索用时 92 毫秒
991.
Claudia Aparicio Libor Machala Zdenek Marusak 《Journal of Thermal Analysis and Calorimetry》2012,110(2):661-669
The thermal decomposition of Prussian blue (iron(III) hexacyanoferrate) under inert atmosphere of argon was monitored by thermal analysis from room temperature up to 1000?°C. X-ray powder diffraction and 57Fe M?ssbauer spectroscopy were the techniques used for phase identification before and after sample heating. The decomposition reaction is based on a successive release of cyanide groups from the Prussian blue structure. Three principal stages were observed including dehydration, change of crystal structure of Prussian blue, and its decomposition. At 400?°C, a monoclinic Prussian blue analogue was identified, while at higher temperatures the formation of various polymorphs of iron carbides was observed, including an orthorhombic Fe2C. Increase in the temperature above 700?°C induced decomposition of primarily formed Fe7C3 and Fe2C iron carbides into cementite, metallic iron, and graphite. The overall decomposition reaction can be expressed as follows: Fe4[Fe(CN)6]3·4H2O????4Fe?+?Fe3C?+?7C?+?5(CN)2?+?4N2?+?4H2O. 相似文献
992.
Antonio Greco Alfonso Maffezzoli Emanuela Calò Claudia Massaro Roberto Terzi 《Journal of Thermal Analysis and Calorimetry》2012,109(3):1493-1502
The objective of this work is to study the sintering behavior of polyamide 6 (PA6) powders and PA6 nanocomposites by means of thermomechanical (TMA) and dimensionless analysis in view of its technological application in rotational molding. TMA analysis was used to monitor the bulk density evolution of PA6 powders and PA6 nanocomposites when heated above the melting temperature. Experimental TMA results indicate that the sintering of PA6 and PA6 nanocomposites occurs in two different steps, namely powder coalescence and void removal. Furthermore, TMA analysis showed that relevant degradation phenomena occur during the sintering of PA6 and PA6 nanocomposites, leading to gas formation in the molten polymer. The suitability of these materials in rotational molding was then assessed by defining a processing window, as the temperature difference between the endset sintering and the onset degradation. The heating rate dependence of the processing window was explained by means of dimensionless analysis, showing that powder coalescence is influenced by the viscosity evolution of the matrix, whereas void removal is influenced by the gas diffusivity inside the molten matrix. Therefore, the diffusion activation energy correlates the endset sintering temperature to the heating rate. On the other hand, the onset degradation temperature depends on the heating rate, due to the characteristic activation energy of the degradation process. Accordingly, the width of the processing window mainly depends on the values of the activation energies for diffusivity and degradation. The width of the processing window for neat PA6 was found to be too narrow to candidate this polymer for rotational molding. The addition of nanofiller causes a narrowing of the processing window, whereas the PA6 matrix modified with a thermal stabilizer showed a sufficiently broad processing window, compatible for use in rotational molding. 相似文献
993.
Lattanzi A De Fusco C Russo A Poater A Cavallo L 《Chemical communications (Cambridge, England)》2012,48(11):1650-1652
A dramatic enhancement of the diastereo- and enantioselectivity in the nitro-Michael addition reaction organocatalysed by a commercially available α,α-L-diaryl prolinol was disclosed when performing the reaction in unconventional hexafluorobenzene as a medium. DFT calculations were performed to clarify the origin of stereoselectivity and the role of C(6)F(6). 相似文献
994.
Water-stable MIL-101 microcrystals adhere well to polysulfone (PSF) and yield a very robust mixed-matrix MIL-101-PSF membrane for the O(2)/N(2) separation with a selectivity of 5-6 and an unsurpassed O(2) permeability increase by a factor of four to above 6 barrer for MIL-101 loadings of 24%. 相似文献
995.
Hunger K Buschhaus L Schmeling N Staudt C Pfeifer A Kleinermanns K 《Physical chemistry chemical physics : PCCP》2012,14(13):4538-4547
Copolyimide membranes are established materials for the separation of gaseous and liquid mixtures. Cross-linking of the polymer strands improves the physical and chemical stability. The photo-cross-linking of a 6FDA-ODA/6FDA-DABA 4?:?1 copolyimide membrane containing maleimide side groups as linker was investigated by FTIR spectroscopy. IR absorption spectra of the copolyimide backbone, 3-hydroxypropyldimethyl maleimide and the copolyimide functionalized with 3-hydroxypropyldimethyl maleimide were measured before and after different irradiation times and compared to each other. For band assignment a normal mode analysis was performed. The backbone of the polymer and the maleimide linker can be well distinguished due to their different spectral band positions. Only the films containing a maleimide moiety perform a photoreaction, the polymer backbone does not interfere. Based on the difference spectra and the results of the DFT calculations it was shown that the trans- and the cis-cycloadduct as well as the previously suggested 2-2'-adduct without a cyclobutane ring are formed upon UV irradiation. Evidence for an oxetane-like photoproduct was not found. Different time constants for the increase of the product bands were observed. The cycloadduct accumulates with a shorter time constant (τ = 2 to 5 min) than the 2-2'-adduct (τ = 75 min). The yield of the photo-cross-linking reaction was determined by spectral deconvolution and kinetic fitting of several marker bands. For the copolyimide synthesized in this work, a maximum value of 6% was reached. The stiffness of the copolyimide backbone inhibits further photo-cross-linking. 相似文献
996.
Gnahm M Berger C Arkhipova M Kunkel H Pajkossy T Maas G Kolb DM 《Physical chemistry chemical physics : PCCP》2012,14(30):10647-10652
Five hexaalkylguanidinium-based ionic liquids have been synthesised, and based on their cyclic voltammograms the most suited one, N,N-dibutyl-N',N'-diethyl-N',N'-dimethylguanidinium bis(trifluoromethylsulfonyl)imide, has been chosen for electrochemical studies. The surface interaction of this room-temperature ionic liquid with single crystalline gold surfaces (Au(100) and Au(111)) has been investigated using cyclic voltammetry, impedance spectroscopy and in situ scanning tunnelling microscopy (STM). The interfacial capacitance was found to be very low; STM measurements revealed the hex-reconstruction and herringbone reconstruction for Au(100) and for Au(111), respectively, at negative potentials; that is, at these potentials no hints for ad-structures of the cation could be found. 相似文献
997.
Chu MK Chen J Gordijo CR Chiang S Ivovic A Koulajian K Giacca A Wu XY Sun Y 《Lab on a chip》2012,12(14):2533-2539
We have developed glucose-responsive implantable microdevices for closed-loop delivery of insulin and conducted in vivo testing of these devices in diabetic rats. The microdevices consist of an albumin-based bioinorganic membrane that utilizes glucose oxidase (GOx), catalase (CAT) and manganese dioxide (MnO(2)) nanoparticles to convert a change in the environmental glucose level to a pH stimulus, which regulates the volume of pH-sensitive hydrogel nanoparticles and thereby the permeability of the membrane. The membrane is integrated with microfabricated PDMS (polydimethylsiloxane) structures to form compact, stand-alone microdevices, which do not require tethering wires or tubes. During in vitro testing, the microdevices showed glucose-responsive insulin release over multiple cycles at clinically relevant glucose concentrations. In vivo, the microdevices were able to counter hyperglycemia in diabetic rats over a one-week period. The in vitro and in vivo testing results demonstrated the efficacy of closed-loop biosensing and rapid response of the 'smart' insulin delivery devices. 相似文献
998.
The synthesis of layered donor/acceptor-materials based on perylenes (1a–c) and ter(thiophen)es (2a, 2b), ordered by hydrogen bonding moieties is reported. Based on the successful (selective) chlorination of 3,4:9,10-perylene tetracarboxylic dianhydride (3) to obtain a perylene derivative with only four chlorine atoms, subsequent functionalization with different hydrogen-bonding moieties is achieved via the azide/alkyne click reaction as proven by extensive ESI-TOF measurements. The perylene- (1a–c) and terthiophene- (2a, 2b) compounds are useful as acceptor and donor parts, respectively, in organic solar cells as proven via UV–vis and fluorescence measurements. Charge transfer between donor and acceptor parts (2a/1b) was determined as 41% via fluorescence resonance energy transfer (FRET), proving the association of the two components via the attached hydrogen bonding moieties. These measurements indicate that the mixture 2a/1b displays large potential for use as a layered ordered material with controlled spacings for organic solar cells based on a thereby facilitated charge-transfer. 相似文献
999.
Complex Eu(AlH(4))(2) and Sr(AlH(4))(2) hydrides have been prepared by a mechanochemical metathesis reaction from NaAlH(4) and europium or strontium chlorides. The crystal structures were solved from powder X-ray diffraction data in combination with solid-state (27)Al NMR spectroscopy. The thermolysis pathway was analyzed in detail, allowing identification of new intermediate EuAlH(5)/SrAlH(5) compounds. Rehydrogenation experiments indicate that the second decomposition step is reversible. 相似文献
1000.
A Abbotto C Coluccini E Dell'orto N Manfredi V Trifiletti MM Salamone R Ruffo M Acciarri A Colombo C Dragonetti S Ordanini D Roberto A Valore 《Dalton transactions (Cambridge, England : 2003)》2012,41(38):11731-11738
The first examples of thiocyanate-free thiophene-substituted Ru(ii) cyclometalated complexes, based on thiophene-derived 2-(2,4-difluorophenyl)pyridine ligands, are presented and investigated as photosensitizers in DSCs. Upon thiophene substitution the complexes presented enhanced optical properties compared to the reference dye with no thiophene substitution. DSCs based on the dithienyl-derived dye showed power conversion efficiencies up to 5.7%, more than twice that containing the complex without the thiophene substitution. 相似文献