全文获取类型
收费全文 | 5249篇 |
免费 | 845篇 |
国内免费 | 436篇 |
专业分类
化学 | 2692篇 |
晶体学 | 37篇 |
力学 | 409篇 |
综合类 | 82篇 |
数学 | 2280篇 |
物理学 | 1030篇 |
出版年
2024年 | 11篇 |
2023年 | 62篇 |
2022年 | 154篇 |
2021年 | 245篇 |
2020年 | 242篇 |
2019年 | 218篇 |
2018年 | 180篇 |
2017年 | 210篇 |
2016年 | 266篇 |
2015年 | 211篇 |
2014年 | 342篇 |
2013年 | 409篇 |
2012年 | 354篇 |
2011年 | 344篇 |
2010年 | 307篇 |
2009年 | 331篇 |
2008年 | 277篇 |
2007年 | 322篇 |
2006年 | 257篇 |
2005年 | 232篇 |
2004年 | 218篇 |
2003年 | 232篇 |
2002年 | 168篇 |
2001年 | 139篇 |
2000年 | 100篇 |
1999年 | 82篇 |
1998年 | 70篇 |
1997年 | 73篇 |
1996年 | 63篇 |
1995年 | 60篇 |
1994年 | 56篇 |
1993年 | 20篇 |
1992年 | 25篇 |
1991年 | 30篇 |
1990年 | 20篇 |
1989年 | 19篇 |
1988年 | 28篇 |
1987年 | 12篇 |
1986年 | 13篇 |
1985年 | 30篇 |
1984年 | 23篇 |
1983年 | 12篇 |
1982年 | 13篇 |
1981年 | 7篇 |
1980年 | 13篇 |
1979年 | 6篇 |
1978年 | 6篇 |
1977年 | 8篇 |
1976年 | 3篇 |
1959年 | 2篇 |
排序方式: 共有6530条查询结果,搜索用时 312 毫秒
101.
Wojciech Paszkowicz 《Analytica chimica acta》2006,566(1):81-98
Genetic algorithms represent a powerful global-optimisation tool applicable in solving tasks of high complexity in science, technology, medicine, communication, etc. The usual genetic-algorithm calculation scheme is extended here by introduction of a quadratic self-learning operator, which performs a partial local search for randomly selected representatives of the population. This operator is aimed as a minor deterministic contribution to the (stochastic) genetic search. The population representing the trial solutions is split into two equal subpopulations allowed to exhibit different mutation rates (so called asymmetric mutation). The convergence is studied in detail exploiting a crystallographic-test example of indexing of powder diffraction data of orthorhombic lithium copper oxide, varying such parameters as mutation rates and the learning rate. It is shown through the averaged (over the subpopulation) fitness behaviour, how the genetic diversity in the population depends on the mutation rate of the given subpopulation. Conditions and algorithm parameter values favourable for convergence in the framework of proposed approach are discussed using the results for the mentioned example. Further data are studied with a somewhat modified algorithm using periodically varying mutation rates and a problem-specific operator. The chance of finding the global optimum and the convergence speed are observed to be strongly influenced by the effective mutation level and on the self-learning level. The optimal values of these two parameters are about 6 and 5%, respectively. The periodic changes of mutation rate are found to improve the explorative abilities of the algorithm. The results of the study confirm that the applied methodology leads to improvement of the classical genetic algorithm and, therefore, it is expected to be helpful in constructing of algorithms permitting to solve similar tasks of higher complexity. 相似文献
102.
N. SanzJ. Zaccaro L. DelmotteC. Le Luyer A. Ibanez 《Journal of solid state chemistry》2002,165(1):25-34
Organic nanocrystals of N-4-nitrophenyl-l-prolinol (NPP) have been grown in sol-gel matrices prepared from silicon alkoxide precursors. Our process is based on the control of the nucleation and growth kinetics of the dye in the pores of dense gels. Nanocomposites gel-glasses are obtained with a high optical quality due to the small size of the nanocrystals (10-20 nm). Differential scanning calorimetry experiments evidenced clearly the melting point of NPP nanocrystals, which is registered 51°C above that of NPP powder. Micro-Raman and solid state NMR spectroscopies allowed us to demonstrate that our nanocrystallization process does not chemically modify NPP molecules. We specified also the nature of interactions existing between the NPP nanocrystals and the xerogels. These strong interactions, which explain the important increase of the melting point of the nanocrystals in comparison to the NPP powder, are hydrogen bonds between nitro groups of NPP and uncondensed silanol functions of the silicate network. 相似文献
103.
Synthesis of silanized polyether urethane hybrid systems. Study of the curing process through hydrogen bonding interactions 总被引:1,自引:0,他引:1
Different types of silanized polyurethanes (SPUR) were prepared in two ways: the first type (a), by reacting a polyether diol with an isocyanatesilane and the second type (b) by reacting it with diisocyanate (IPDI) and afterwards with aminosilane. These systems are able to cure with atmospheric moisture and, as a consequence, a tridimensional hybrid structure is formed where the inorganic and organic phases are bonded with covalent bonds. The evolution of the curing process in both systems has been monitored by means of Fourier transform infrared spectroscopy, through the changes observed in the carbonyl stretching vibration region. The results obtained show that the SPURs of kind (b) present stronger hydrogen bonding interactions as a consequence of urea groups present in the final structure. Moreover, given the proximity of both urethane and urea groups to alkoxysilane end groups, during the alkoxysilane curing process these groups are forced to approximate themselves even further and therefore the reticulation process leads to an increase of the self association of urethane and urea groups.Finally, DSC has been used to measure Tg values of the systems studied before and after the curing process. The obtained results have confirmed the main conclusions obtained in FTIR analysis. 相似文献
104.
Immobilized copper(Ⅱ) in organic-inorganic hybrid materials catalyzed Ar-N coupling of arylboronic acids with imidazoles has been developed. Arylboronic acids reacted with imidazoles smoothly in the presence of a 3-(2-aminoethylamino)propyl functionalized silica gel immobilized copper(Ⅱ) catalyst (10 mol%) in methanol without any additives and bases. The reactions generated the corresponding cross-coupling products in good yields. Furthermore, silica-supported copper can be recovered and recycled by a simple filtration procedure and used for five consecutive trials without decreases in activity. 相似文献
105.
由正硅酸乙酯水解制得的SiO2溶胶,在以γ—甲基丙烯酰氧丙基三甲氧基硅烷(TMSPM)为偶联剂的体系中,经溶胶-凝胶法制备了透明的光固化聚氨酯丙烯酸酯杂化材料[(PUA—TMSPM)/SiO2]。研究了盐酸浓度对(PUA-TMSPM)/SiO2结构与性能的影响。结果表明:随着pH值减小,硅溶胶体系和(PUA-TM-SPM)/SiO2杂化体系的热稳定性增大;盐酸摩尔分数XHCl的增加使(PUA-TMSPM)/SiO2光固化膜表面的两相界面结合更紧密,涂层变得更致密,并导致膜的硬度和耐磨性提高。 相似文献
106.
YU Biao HUI Yong-ZhengState Key Laboratory of Bio-organic Natural Products Chemistry Shanghai Institute of Organic Chemistry Chinese Academy of Sciences Shanghai China 《中国化学》1996,14(2):171-179
Three types of single-chain hydrocarbon fluorocarbon hybrid bolaamphiphiles were synthesized.They readily formed different kinds of organized supramolecular assemblies,including vesicles,tapes,and micellar fibers,in aqueous solution.The aggregates morphology was characterized by transmission electron microscopy (TEM) after negative staining.The superstructures of these aggregates seemed to be determined by the geometry and the head group's properties of the corresponding amphiphiles. 相似文献
107.
Masaya Kawasumi 《Journal of polymer science. Part A, Polymer chemistry》2004,42(4):819-824
The first successful example of a polymer‐clay hybrid was nylon‐clay hybrid (NCH), which is a nano‐meter‐sized composite of nylon‐6 and 1‐nm‐thick exfoliated aluminosilicate layers of the clay mineral. NCH was found and developed at Toyota Central Research and Development Laboratories over 17 years ago. The NCH containing a few weight percentages of clay exhibits superior properties such as high modulus, high strength, and good gas‐barrier properties. The key for the discovery of NCH was the polymerization of a nylon monomer in the interlayer space of the clay. This highlight presents the development of NCH from its discovery to its commercialization. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 819–824, 2004 相似文献
108.
Zaharescu M. Jitianu A. Brăileanu A. Madarász J. Novák CS. Pokol G. 《Journal of Thermal Analysis and Calorimetry》2003,71(2):421-428
Hybrid materials with different amounts of organics permanently bound on the inorganic network obtained in the TEOS-MTEOS
(tetraethoxysilan-methyltriethoxysilan) system are used for obtaining coatings with different optical and mechanical properties.
To study the thermal stability of the mentioned materials, compositions with different molar ratios of the precursors were
prepared. The influence of the solvent and water amounts on the gelation process was also investigated. The gels obtained
were characterised by IR spectrometry and their decomposition temperatures were determined by DTA/TG. Thermal stability of
the gels is rather influenced by their composition than the conditions of the gelation process.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
109.
Tao Miao 《Tetrahedron letters》2007,48(1):95-99
The immobilization of copper in organic-inorganic hybrid materials catalyzing the Ullmann reaction has been described. Phenols reacted with aryl iodides, aryl bromides and aryl chlorides smoothly in the presence of a 3-(2-aminoethylamino)propyl functionalized silica gel immobilized copper catalyst. The protocol involved the use of DMSO as the solvent, and potassium fluoride as the base. The reactions generated the corresponding cross-coupling products in good to excellent yields. Furthermore, the silica-supported copper could be recovered and recycled by a simple filtration of the reaction solution and used for 10 consecutive trials without loss of its reactivity. 相似文献
110.
Jeong Hwan Kim Ji Hoon Ko Byeong-Soo Bae 《Journal of Sol-Gel Science and Technology》2007,41(3):249-255
Multi-scale hybrid nanocomposites containing both ∼15 nm silica colloids and ∼2 nm oligosiloxanes in a methacryl polymer matrix
were newly designed and fabricated. Colloidal silica sols were dispersed in methacryl oligosiloxanes nano-hybrid resins synthesized
by sol-gel reaction of methacryloxypropylmethoxysilane and diphenylsilanediol. On the basis of TEM and SANS analyses, it was
confirmed that the silica colloids were compatibly dispersed and different sizes of colloidal silica and oligosiloxanes co-exist
in the solutions. Multi-scale hybrid nanocomposites fabricated by UV and thermal curing with incorporation of silica colloids
in the nano-hybrid materials show enhanced mechanical and thermal characteristics. 相似文献