全文获取类型
收费全文 | 2836篇 |
免费 | 254篇 |
国内免费 | 273篇 |
专业分类
化学 | 1812篇 |
晶体学 | 16篇 |
力学 | 282篇 |
综合类 | 14篇 |
数学 | 76篇 |
物理学 | 1163篇 |
出版年
2024年 | 4篇 |
2023年 | 32篇 |
2022年 | 58篇 |
2021年 | 57篇 |
2020年 | 60篇 |
2019年 | 79篇 |
2018年 | 69篇 |
2017年 | 94篇 |
2016年 | 103篇 |
2015年 | 82篇 |
2014年 | 120篇 |
2013年 | 249篇 |
2012年 | 111篇 |
2011年 | 178篇 |
2010年 | 137篇 |
2009年 | 172篇 |
2008年 | 168篇 |
2007年 | 172篇 |
2006年 | 168篇 |
2005年 | 168篇 |
2004年 | 126篇 |
2003年 | 106篇 |
2002年 | 97篇 |
2001年 | 86篇 |
2000年 | 87篇 |
1999年 | 88篇 |
1998年 | 59篇 |
1997年 | 81篇 |
1996年 | 57篇 |
1995年 | 54篇 |
1994年 | 45篇 |
1993年 | 40篇 |
1992年 | 16篇 |
1991年 | 26篇 |
1990年 | 13篇 |
1989年 | 10篇 |
1988年 | 8篇 |
1987年 | 12篇 |
1986年 | 11篇 |
1985年 | 5篇 |
1984年 | 6篇 |
1983年 | 6篇 |
1982年 | 12篇 |
1981年 | 11篇 |
1979年 | 5篇 |
1978年 | 3篇 |
1977年 | 4篇 |
1976年 | 2篇 |
1975年 | 2篇 |
1974年 | 2篇 |
排序方式: 共有3363条查询结果,搜索用时 46 毫秒
101.
Silica sol-gel films were prepared by dipping, starting from an acid catalyzed solution of methyltriethoxysilane (MTES) and tetraethoxysilane (TEOS). Silver metal nanoparticles were produced in the silica layer by introducing in the sol-gel precursor solution AgNO3 or AgClO4·H2O. The silver ions were thermally reduced in air at 800°C, giving an intense yellow coating film. The silver metal particles were observed by transmission electron microscopy and X-ray diffraction. The diameter of the silver particles was found to be about 10 nm. Absorption measurements in the UV-Vis were used to evaluate the volume fraction of silver colloids embedded in the silica layer. 相似文献
102.
合成形态、大小及结构可人为调控的无机材料是现代材料科学的重要研究方向[1]. 借助于各类有机添加剂及模板剂的调控作用, 可利用溶液合成方法制备出形貌与结构受到有效调控的无机粒子[2,3]. 室温固态化学反应已被成功地应用于多种无机纳米粒子[4]及纳米线[5]的合成, 并显示出高效、节能、无污染和操作简便等优点, 因而在材料合成领域具有应用前景[6]. 相似文献
103.
Olaf Evers Erich Hdicke Gregor Ley 《Colloids and surfaces. A, Physicochemical and engineering aspects》1994,90(2-3):135-147
The self-consistent mean field model of Scheutjens and Fleer is used to model spherical aggregates of homopolymers and monomer—polymer particles in solution. For homopolymer aggregates we found that the chain ends are preferentially located at the exterior side of the polymer/solvent interface. The distribution of the end segments may be an important parameter in latex film formation. For monomer—polymer particles a “core-shell” structure is found with an extended core containing a monomer—polymer mixture and a thin shell a few nanometres thick strongly enriched with monomer. The monomer-enriched shell seems to function as a solvating envelope for the dangling chain ends. These results are compared with other simulations based on a single chain in a spherical-cavity model. 相似文献
104.
105.
表面引发原子转移自由基聚合方法合成Fe3O4/PMMA复合纳米微粒 总被引:7,自引:1,他引:7
采用表面引发原子转移自由基聚合方法合成了核壳结构的磁性高分子纳米微粒. 作为聚合反应引发剂的3-氯丙酸, 首先与油酸修饰的Fe3O4纳米微粒表面的部分油酸置换, 然后在Fe3O4纳米微粒表面引发甲基丙烯酸甲酯聚合, 合成的纳米复合材料用TEM, FTIR, XRD和DSC表征. 磁性测试结果表明, 所制备的磁性高分子纳米微粒仍具有超顺磁性, 但由于聚合物的存在, 其饱和磁化强度降低. 相似文献
106.
Gutiérrez-Dabán A Fernández-Espinosa AJ Ternero-Rodríguez M Fernández-Alvarez F 《Analytical and bioanalytical chemistry》2005,381(3):721-736
The size distribution of polycyclic aromatic hydrocarbons (PAH) was determined for airborne particles from a large city with high vehicular traffic. The analytical method was optimised and validated using NIST standard reference material (SRM 1649a Urban Dust). The 16 priority PAH listed in the US-EPA were Soxhlet-extracted from filtered particulate matter and then fractionated using on-column chromatography. The aromatic fraction was quantified by gas chromatography-mass spectrometry. Real samples of particles collected in Seville (Spain) were analysed using the validated method. Values for the total concentration of PAH in the air, as well as the concentrations of each PAH in six particle-size ranges were obtained. Values of the PAH in TSP, PM10, PM2.5 and PM1 were assessed. 相似文献
107.
N,N-Diethyldithiocarbamate functionnalized 1,4-polyisoprenes were prepared from 1,4-polyisoprenes (natural or synthetic). The syntheses were performed by nucleophilic addition of N,N-diethyldithiocarbamate salts upon oxirane rings of epoxidized units according to a SN2 mechanism with ring opening. Studies on model molecules of epoxidized 1,4-polyisoprene units (1,2-epoxy-1-methylcyclohexane and 4,5-epoxy-4-methyloctane) were previously achieved to develop the procedure. The best yields were obtained at low temperature in polar medium, and more especially in water with sodium N,N-diethyldithiocarbamate (DEDT-Na) as reagent. A diastereospecific addition was noted when reaction was performed in water with DEDT-Na. Afterwards, the developed procedure was successfully generalized to epoxidized synthetic polyisoprenes and epoxidized natural rubber (in THF, then in latex medium). Excellent results were obtained in latex medium with epoxidized natural rubber (ENR) latices. As with the models, a diastereospecific addition of sodium N,N-diethyldithiocarbamate trihydrate onto epoxidized 1,4-polyisoprene units of ENR was observed at the condition to bring the latex medium to pH 8 before introduction of DEDT-Na. Influence of temperature, drc, and DEDT-Na concentration were successively examined to determine the best conditions of the addition on ENR latices. 相似文献
108.
Capek I 《Advances in colloid and interface science》2002,99(2):77-162
The principal subject discussed in the current paper is the radical polymerization in the aqueous emulsions of unsaturated monomers (styrene, alkyl (meth)acrylates, etc.) stabilized by non-ionic and ionic/non-ionic emulsifiers. The sterically and electrosterically stabilized emulsion polymerization is a classical method which allows to prepare polymer lattices with large particles and a narrow particle size distribution. In spite of the similarities between electrostatically and sterically stabilized emulsion polymerizations, there are large differences in the polymerization rate, particle size and nucleation mode due to varying solubility of emulsifiers in oil and water phases, micelle sizes and thickness of the interfacial layer at the particle surface. The well-known Smith-Ewart theory mostly applicable for ionic emulsifier, predicts that the number of particles nucleated is proportional to the concentration of emulsifier up to 0.6. The thin interfacial layer at the particle surface, the large surface area of relatively small polymer particles and high stability of small particles lead to rapid polymerization. In the sterically stabilized emulsion polymerization the reaction order is significantly above 0.6. This was ascribed to limited flocculation of polymer particles at low concentration of emulsifier, due to preferential location of emulsifier in the monomer phase. Polymerization in the large particles deviates from the zero-one approach but the pseudo-bulk kinetics can be operative. The thick interfacial layer can act as a barrier for entering radicals due to which the radical entry efficiency and also the rate of polymerization are depressed. The high oil-solubility of non-ionic emulsifier decreases the initial micellar amount of emulsifier available for particle nucleation, which induces non-stationary state polymerization. The continuous release of emulsifier from the monomer phase and dismantling of the non-micellar aggregates maintained a high level of free emulsifier for additional nucleation. In the mixed ionic/non-ionic emulsifiers, the released non-ionic emulsifier can displace the ionic emulsifier at the particle surface, which then takes part in additional nucleation. The non-stationary state polymerization can be induced by the addition of a small amount of ionic emulsifier or the incorporation of ionic groups onto the particle surface. Considering the ionic sites as no-adsorption sites, the equilibrium adsorption layer can be thought of as consisting of a uniform coverage with holes. The de-organization of the interfacial layer can be increased by interparticle interaction via extended PEO chains--a bridging flocculation mechanism. The low overall activation energy for the sterically stabilized emulsion polymerization resulted from a decreased barrier for entering radicals at high temperature and increased particle flocculation. 相似文献
109.
The synthesis and comprehensive characterization of a purely sterically stabilized latex with narrow size distribution is
reported. By use of non-ionic initiators no chemically bound surface charges are generated. Stabilization of the particles
is achieved through use of a non-ionic surfactant having a double bond in the hydrophobic part which is chemically bound to
the surface. Analysis of the latex particles thus generated by transmission electron microscopy, disc centrifugation, and
small-angle X-ray scattering (SAXS) reveals that the size distribution is narrow (standard deviation between 6 and 10%). SAXS
furthermore demonstrates that the surfactant is located in a thin layer on the surface. The interaction of the particles is
purely repulsive as shown by the analysis of the turbidity of the latex. The systems obtained herein may serve as model systems
of water-borne purely sterically stabilized colloid particles.
Received: 23 December 1997 Accepted: 18 May 1998 相似文献
110.
Conidia of Aspergillus niger were immobilized in calcium alginate gel for the production of citric acid. First, the type of the preactivation medium,
together with the preactivation period, was investigated. It was found that A. niger requires a 2-d preactivation period at a 0.05 g/L NH4NO3 concentration. Second, preactivated cells were used to determine the effects of nitrogen concentration and the flow rate
of oxygen and air on the production of citric acid. Maximum citric acid production was attained with medium containing 0.01
g/L of NH4NO3. The rate of citric acid production in the nitrogenous medium was 33% higher when oxygen was used instead of air during the
production phase. This corresponds to an increase of 85% when compared to production when neither oxygen nor air was fed into
the system. In the nonnitrogenous medium citric acid concentration remained similar regardless of the use of air or oxygen.
However, in the nonnitrogenous production medium, citric acid production was not influenced considerably when oxygen was used
instead of air. The advantage of using immobilized cells is that production is achieved easily in the continuous system. Therefore,
citric acid production was also tested using a packed-bed bioreactor, and an increase in productivity by a factor of 22 was
achieved compared to the batch system. 相似文献