全文获取类型
收费全文 | 11464篇 |
免费 | 2091篇 |
国内免费 | 2968篇 |
专业分类
化学 | 12909篇 |
晶体学 | 174篇 |
力学 | 371篇 |
综合类 | 63篇 |
数学 | 202篇 |
物理学 | 2804篇 |
出版年
2024年 | 38篇 |
2023年 | 194篇 |
2022年 | 386篇 |
2021年 | 535篇 |
2020年 | 773篇 |
2019年 | 564篇 |
2018年 | 515篇 |
2017年 | 583篇 |
2016年 | 745篇 |
2015年 | 697篇 |
2014年 | 804篇 |
2013年 | 1343篇 |
2012年 | 966篇 |
2011年 | 987篇 |
2010年 | 790篇 |
2009年 | 826篇 |
2008年 | 796篇 |
2007年 | 762篇 |
2006年 | 639篇 |
2005年 | 588篇 |
2004年 | 580篇 |
2003年 | 464篇 |
2002年 | 340篇 |
2001年 | 286篇 |
2000年 | 219篇 |
1999年 | 194篇 |
1998年 | 180篇 |
1997年 | 135篇 |
1996年 | 106篇 |
1995年 | 110篇 |
1994年 | 80篇 |
1993年 | 81篇 |
1992年 | 33篇 |
1991年 | 32篇 |
1990年 | 28篇 |
1989年 | 16篇 |
1988年 | 18篇 |
1987年 | 15篇 |
1986年 | 11篇 |
1985年 | 11篇 |
1984年 | 11篇 |
1983年 | 10篇 |
1982年 | 7篇 |
1981年 | 7篇 |
1980年 | 5篇 |
1979年 | 7篇 |
1977年 | 1篇 |
1976年 | 2篇 |
1972年 | 1篇 |
1971年 | 1篇 |
排序方式: 共有10000条查询结果,搜索用时 16 毫秒
71.
U.Deva Priyakumar 《Tetrahedron letters》2004,45(12):2495-2498
A novel preference for planar tetracoordination was observed over the conventional tetrahedral arrangement in a new series of C5H2, C5H4, C5H41+/2+ and related compounds. The stability of these molecules is assessed with the ring-opening barriers, HOMO-LUMO gap, singlet-triplet energy differences and nucleus independent chemical shift values. 相似文献
72.
73.
采用微波电子回旋共振等离子体化学气相沉积(MWPECRCVD)方法,使用不同的源气体(CHF3CH4,CHF3C2H2,CHF3C6H6)体系制备了aC∶F∶H薄膜.由于CH4,C2H2,C6H6气体在等离子体中的分解反应不同导致了薄膜的沉积速率和结构上的差异.红外吸收谱的结果表明,用C6H6CHF3作为源气体沉积的薄膜中几乎不含H,而用C2H2CHF3所沉积的薄膜中的含氟量最高,其相应的CF振动峰位向高频方向偏移.薄膜的真空退火结果表明,aC∶F∶H薄膜的热稳定性除了取决于薄膜的CC键浓度外,还与CC键
关键词:
氟化非晶碳膜
电子回旋共振化学气相沉积
红外吸收光谱 相似文献
74.
Electrochemical oxidation of thio/carbohydrazide and their hydrazone derivatives Benzaldehyde thiocarbohydrazone [BTCH] diacetylene
thiocarbohydrazone [DATCH] have been studied in Brit-ton Robinson buffer in aqueous and nonaqueous media at a glassy carbon
electrode. The effects of pH, sweep rate, concentration, temperature and surfactants have been studied. The complex bis (carbo/thiocabohydrazide) Zn(II) chloride was also subjected to voltammetric analysis in order to understand the reactivity
both in free and metal bound states. The reaction conditions were optimized for the determination of above compounds in micrograms
quantities by differential pulse voltammetry, analytical utility of this investigation is also highlighted. 相似文献
75.
采用循环伏安法,对SPEPt电极以及SPEAu-Pt电极上还原态CO2的电化学氧化行为研究表明,此类电极的电化学特性与光滑Pt电极一致:CO2在氢原子吸附电位区0~250mV(vs.RHE)处,可与电极上化学吸附的氢反应,生成还原态的CO2,通过线性扫描,还原态CO2即发生一不可逆电化学氧化过程(阳极剥离).在SPEPt系列及SPEAu-Pt系列上CO2的电化学行为表明,当SPEPt系列上Pt的载量为2.5mL的0.01mol·L-1H2PtCl6的Pt时,对还原态CO2的电催化活性最好,当Pt的载量相同时,在SPEAu-Pt上,催化剂对还原态CO2的电化学氧化行为比SPEPt电极更强,这是由于预先沉积的Au对后沉积的Pt有调制作用. 相似文献
76.
《Electroanalysis》2006,18(22):2218-2224
This article deals with the development of a method for the determination of osmium at a carbon paste electrode (CPE) modified with cationic surfactants of the quaternary ammonium salt type; namely, cetyltrimethylammonium bromide (CTAB) and 1‐(ethoxycarbonyl)‐pentadecyltrimethyl‐ammonium bromide (Septonex); both being added in situ and serving for preconcentration of osmium via its hexachloroosmate(IV) anion. The proper electrochemical detection was performed by cathodic scanning in the differential pulse voltammetric mode. Optimization studies concerning important experimental parameters also included a specially performed potentiometric titration, helping to define the actual stoichiometry for the ion‐pairing process, the main principle and driving force of the accumulation step. In a chloride/acetate buffer based supporting medium and with Septonex as the modifier of choice, the reduction signal for osmium was found to be proportional to the Os(IV) concentration in a range from 5×10?9 to 5×10?7 mol L?1 with a limit of detection close to 5×10?9 mol L?1 (with preconcentration for 60 s). The method capable to determine Os(IV) in the presence of both Pt(IV) and Ir(III) was tested on model solutions as well as with real sample of industrial waste water (spiked with the analyte); both yielding the recovery rates within 88–99%. 相似文献
77.
Hyeong Taek Ham Yeong Suk Choi Mu Guen Chee In Jae Chung 《Journal of polymer science. Part A, Polymer chemistry》2006,44(1):573-584
This work is to make carbon nanotubes dispersible in both water and organic solvents without oxidation and cutting nanotube threads. Polystyrene‐singlewall carbon nanotube (PS‐SWNT) composites were prepared with three different methods: miniemulsion polymerization, conventional emulsion polymerization, and mixing SWNT with PS latex. The two factors, crosslinking and surface coverage of PS are important factors for the mechanical and electrical properties, including dispersion states of SWNT in various solvents. The PS‐SWNT composite prepared via a conventional emulsion polymerization showed SWNT bundles entirely covered with PS, whereas the PS‐SWNT composite prepared via a miniemulsion polymerization showed SWNT partially covered with crosslinked PS nanoparticles. The method of mixing SWNTs with PS latex did not show the well dispersed state of carbon nanotubes because PS was not crosslinked and was dissolved in a solvent, and nanotubes separated from PS precipitated. So the PS nanoparticle‐SWNT composite had lower electrical resistance, and higher mechanical strength than the other composites made by the latter two methods. As the amount of SWNT increases, the bare surface area of SWNT increases and the electrical conductivity increases in the composite made by the miniemulsion polymerization. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 573–584, 2006 相似文献
78.
Tzong‐Ming Wu Shih‐Hsiang Lin 《Journal of polymer science. Part A, Polymer chemistry》2006,44(21):6449-6457
Size‐controllable polypyrrole (PPy)/multiwalled carbon nanotube (MWCNT) composites have been synthesized by in situ chemical oxidation polymerization directed by various concentrations of cationic surfactant cetyltrimethylammonium bromide (CTAB). Raman spectra, FTIR, SEM, and TEM were used to characterize their structure and morphology. These results showed that the composites are core (MWCNT)–shell (PPy) tubular structures with the thickness of the PPy layer in the range of 20–40 nm, depending on the concentration of CTAB. Raman and FTIR spectra of the composites are almost identical to those of PPy alone. The electrical conductivities of these composites are 1–2 orders of magnitude higher than those of PPy without MWCNTs. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6449–6457, 2006 相似文献
79.
Alberto Giaconia Giuseppe Filardo Onofrio Scialdone Alessandro Galia 《Journal of polymer science. Part A, Polymer chemistry》2006,44(13):4122-4135
A laboratory‐scale continuous reaction system using a stirred tank reactor was assembled in our laboratory to study the dispersion polymerization of vinyl monomers in supercritical carbon dioxide (scCO2). The apparatus was equipped with a suitable downstream separation section to collect solid particles entrained in the effluent stream from the reactor, whose monomer concentration could be measured online with a gas chromatograph. The dispersion polymerization of methyl methacrylate in scCO2 was selected as a model process to be investigated in the apparatus. The experiments were performed at 65 °C and 25 MPa with 2,2′‐azobisisobutyronitrile as the initiator and a reactive polysiloxane macromonomer as a surfactant to investigate the effect of the mean residence time of the reaction mixture on the monomer conversion, polymerization rate, polymer molecular weight, and particle size distribution. The results were compared with those obtained in batch polymerizations carried out under similar operative conditions. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4122–4135, 2006 相似文献
80.
The solubility and diffusion coefficient of carbon dioxide in intermediate‐moisture starch–water mixtures were determined both experimentally and theoretically at elevated pressures up to 16 MPa at 50 °C. A high‐pressure decay sorption system was assembled to measure the equilibrium CO2 mass uptake by the starch–water system. The experimentally measured solubilities accounted for the estimated swollen volume by Sanchez–Lacombe equation of state (S‐L EOS) were found to increase almost linearly with pressure, yielding 4.0 g CO2/g starch–water system at 16 MPa. Moreover, CO2 solubilities above 5 MPa displayed a solubility increase, which was not contributed by the water fraction in the starch–water mixture. The solubilities, however, showed no dependence on the degree of gelatinization (DG) of starch. The diffusion coefficient of CO2 was found to increase with concentration of dissolved CO2, which is pressure‐dependent, and decrease with increasing DG in the range of 50–100%. A free‐volume‐based diffusion model proposed by Areerat was employed to predict the CO2 diffusivity in terms of pressure, temperature, and the concentration of dissolved CO2. S‐L EOS was once more used to determine the specific free volume of the mixture system. The predicted diffusion coefficients showed to correlate well with the measured values for all starch–water mixtures. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 607–621, 2006 相似文献