全文获取类型
收费全文 | 1319篇 |
免费 | 26篇 |
国内免费 | 325篇 |
专业分类
化学 | 1575篇 |
晶体学 | 2篇 |
力学 | 4篇 |
综合类 | 2篇 |
数学 | 3篇 |
物理学 | 84篇 |
出版年
2023年 | 115篇 |
2022年 | 14篇 |
2021年 | 15篇 |
2020年 | 26篇 |
2019年 | 26篇 |
2018年 | 21篇 |
2017年 | 33篇 |
2016年 | 21篇 |
2015年 | 14篇 |
2014年 | 30篇 |
2013年 | 150篇 |
2012年 | 50篇 |
2011年 | 72篇 |
2010年 | 56篇 |
2009年 | 79篇 |
2008年 | 100篇 |
2007年 | 101篇 |
2006年 | 107篇 |
2005年 | 78篇 |
2004年 | 76篇 |
2003年 | 42篇 |
2002年 | 48篇 |
2001年 | 45篇 |
2000年 | 41篇 |
1999年 | 47篇 |
1998年 | 32篇 |
1997年 | 22篇 |
1996年 | 20篇 |
1995年 | 20篇 |
1994年 | 26篇 |
1993年 | 27篇 |
1992年 | 16篇 |
1991年 | 12篇 |
1990年 | 13篇 |
1989年 | 23篇 |
1988年 | 18篇 |
1987年 | 11篇 |
1986年 | 2篇 |
1983年 | 3篇 |
1982年 | 4篇 |
1980年 | 2篇 |
1979年 | 1篇 |
1975年 | 1篇 |
1974年 | 1篇 |
1973年 | 2篇 |
1972年 | 1篇 |
1971年 | 1篇 |
1968年 | 2篇 |
1967年 | 2篇 |
1966年 | 1篇 |
排序方式: 共有1670条查询结果,搜索用时 183 毫秒
1.
In this study, parenchyma cellulose, which was extracted from maize stalk pith as an abundant source of agricultural residues, was applied for preparing cellulose nanoparticles (CNPs) via an ultrasound-assisted etherification and a subsequent sonication process. The ultrasonic-assisted treatment greatly improved the modification of the pith cellulose with glycidyltrimethylammonium chloride, leading to a partial increase in the dissolubility of the as-obtained product and thus disintegration of sheet-like cellulose into nanoparticles. While the formation of CNPs by ultrasonication was largely dependent on the cellulose consistency in the cationic-modified system. Under the condition of 25% cellulose consistency, the longer sono-treated duration yielded a more stable and dispersible suspension of CNP due to its higher zeta potential. Degree of substitution and FT-IR analyses indicated that quaternary ammonium salts were grafted onto hydroxyl groups of cellulose chain. SEM and TEM images exhibited the CNP to have spherical morphology with an average dimeter from 15 to 55 nm. XRD investigation revealed that CNPs consisted mainly of a crystalline cellulose Ι structure, and they had a lower crystallinity than the starting cellulose. Moreover, thermogravimetric results illustrated the thermal resistance of the CNPs was lower than the pith cellulose. The optimal CNP with highly cationic charges, good stability and acceptable thermostability might be considered as one of the alternatively renewable reinforcement additives for nanocomposite production. 相似文献
2.
Alexander Zeller 《Journal of organometallic chemistry》2006,691(21):4379-4385
The ethylene polymerization reaction of a neutral nickel catalyst was studied by DFT calculations at the Becke3LYP/6-31G(d) level of theory. As in related cases a β-agostic bond stabilizes the nickel alkyl ground states. Transition states for the insertion of the olefin show a distinct α-agostic interaction, which has not been observed for late metal polymerization catalysts before. An ethylene-alkyl complex was identified as the resting state of the reaction. The overall barrier height of the reaction amounts to 17.54 kcal/mol, which slightly increases to 17.60 kcal/mol for the polymerization of deuterated ethylene. Therefore, a small positive kinetic isotope effect (kH/kD = 1.09) can be calculated, which is caused by the α-agostic interaction in the transition state. A comparison to other late metal based polymerization systems reveals that the ethylene coordination step of highly active catalysts is significantly lower in energy compared to catalysts which are only moderately active. 相似文献
3.
Pulse radiolysis with kinetic spectroscopic detection was applied to study the kinetics of the first steps of radiation induced polymerization of cyclohexyl acrylate and cyclohexyl methacrylate in cyclohexane solvent. The reactions were initiated by cyclohexyl radicals produced in the radiolysis of the solvent. The transient absorption spectra of the -carboxyalkyl type radicals produced in addition reaction show maxima around 300 nm. This shifts to longer wavelength with time after the pulse. This phenomenon was explained by the oligomerization reaction. From the kinetic curves average rate coefficients of termination for the oligomer radicals (2kt) were determined as a function of time elapsed after the electron pulse. The values obtained were compared with those calculated for other (acrylate and methacrylate type) monomers. 相似文献
4.
Grishin D. F. Semyonycheva L. L. Telegina E. V. Smirnov A. S. Nevodchikov V. I. 《Russian Chemical Bulletin》2003,52(2):505-507
Organometallic compounds Cp2TiCl2, (EtC5H4)2NbCl2, and (PriC5H4)2WCl2 were assessed as additives that control polymer chain growth in the polymerization of methyl methacrylate. In the presence of compounds mentioned in amounts comparable with that of the initiator, a uniform process with no gel-effect occured and respective linear increase in the molecular weight of the polymer up to high degrees of the monomer conversion was observed. 相似文献
5.
Summary The solubility parameters of cationic surfactants were obtained using the inverse gas chromatographic technique. The surfactants
didodecyl dimethyl ammonium bromide, dioctadecyl dimethyl ammonium bromide and dodecyl pyridinium chloride were used as stationary
phase and retention data of different probe solutes were measured at different temperatures. The results were analysed by
the combination of Flory-Huggins and Hildebrand theories, and the solubility parameters of the surfactants were obtained in
a range of temperatures between 80–120°C. 相似文献
6.
7.
T. Hayashita T. Kurosawa T. Miyata K. Tanaka M. Igawa 《Colloid and polymer science》1994,272(12):1611-1619
The cationic azo-surfactants possessing different spacers and tail alkyl chain lengths have been synthesized by azocoupling ofp-alkylaniline orop-ethoxyaniline with phenol, followed by alkylation and quaternalization with dibromoalkane and trimethylamine, respectively. These surfactants showed a good solubility in water. A reversibletrans-cis isomerization of the azosurfactants by photoirradiation was assessed by UV-Vis absorption spectra. Due to a difference in HLB between thetrans- andcis-surfactants, the observed critical micelle concentration (CMC) values and the electric conductivity of the surfactant solution at above the CMC were significantly affected by the photoinducedtrans-cis isomerization. The azo-surfactants bearing moderate alkyl chain lengths such as surfactants 6 (R2=C2H4, R3=C4H9) and 9 (R2=C4H8, R3=C2H5) were found to be effective to achieve large CMC changes (3.6 mmol/L for 6 and 5.9 mmol/L for 9) by UV-light irradiation. The replacement of the tail chain species also affected the photoresponsive function. The surfactant 12, possessingp-ethoxy group as the tail chain, was found to form a stable micelle aggregation as compared with the structurally related surfactant 10 having ethyl unit as its tail group, but it exhibited a large CMC change (5.3 mmol/L) by UV-light irradiation. 相似文献
8.
Historical perspectives for the chemistry of diene complexes of early transition metals developed at Osaka University in the period after 1970s were reviewed briefly and personally. Preparative chemistry of this field commenced from the magnesium-diene 1:1 compounds and quickly extended to almost all the early transition metals. By the studies operated together with other researchers, unique features of these diene complexes, especially their bonding and structure, selective reactions, and catalysis performances are described. 相似文献
9.
《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
10.
高分子阳离子絮凝剂用于炼油废水处理研究 总被引:15,自引:0,他引:15
用聚二甲基二烯丙基氯化铵型高分子阳离子絮凝剂处理炼油废水考察了险油和化学耗氧量的动态变化规律。对产生的浮渣性质及滤饼的成份进行了研究。并且与聚合铝的处理效果进行对照。研究结果表明,HCA除油和化学耗管氧量的性能优于PAC,HCA产生的浮渣是PAC的三分之一,而浮渣中的含油量则是PAC的三倍。 相似文献