全文获取类型
收费全文 | 3002篇 |
免费 | 85篇 |
国内免费 | 2篇 |
专业分类
化学 | 2005篇 |
晶体学 | 48篇 |
力学 | 88篇 |
数学 | 374篇 |
物理学 | 574篇 |
出版年
2023年 | 19篇 |
2022年 | 76篇 |
2021年 | 111篇 |
2020年 | 61篇 |
2019年 | 73篇 |
2018年 | 56篇 |
2017年 | 56篇 |
2016年 | 111篇 |
2015年 | 88篇 |
2014年 | 116篇 |
2013年 | 174篇 |
2012年 | 208篇 |
2011年 | 241篇 |
2010年 | 146篇 |
2009年 | 175篇 |
2008年 | 228篇 |
2007年 | 169篇 |
2006年 | 143篇 |
2005年 | 108篇 |
2004年 | 95篇 |
2003年 | 81篇 |
2002年 | 67篇 |
2001年 | 51篇 |
2000年 | 45篇 |
1999年 | 32篇 |
1998年 | 36篇 |
1997年 | 20篇 |
1996年 | 36篇 |
1995年 | 27篇 |
1994年 | 24篇 |
1993年 | 25篇 |
1992年 | 22篇 |
1991年 | 12篇 |
1990年 | 7篇 |
1989年 | 12篇 |
1988年 | 6篇 |
1987年 | 6篇 |
1986年 | 8篇 |
1985年 | 13篇 |
1984年 | 6篇 |
1983年 | 8篇 |
1982年 | 9篇 |
1981年 | 13篇 |
1980年 | 4篇 |
1979年 | 6篇 |
1978年 | 8篇 |
1976年 | 8篇 |
1973年 | 4篇 |
1961年 | 4篇 |
1953年 | 4篇 |
排序方式: 共有3089条查询结果,搜索用时 312 毫秒
41.
A major problem with spectrophotometric methods for nickel is cobalt interference, because many of the reagents for nickel also react with cobalt. In this work, the interference of cobalt in the determination of nickel using 2-(5-bromo-2-pyridylaxo)-5-diethylaminophenol (Br-PADAP) was eliminated by the use of derivative spectrophotometry, using the zero-crossing method for evaluation of the derivative signal. Br-PADAP reacts with nickel(II) in the presence of Triton X-100 to form a red complex with absorption maxima at 530 and 562 nm. The reactions parameters and the conditions for the measurements of the first-derivative signal were studied and the results demonstrated that using the derivative technique, Br-PADAP can be used for nickel determination with a selectivity higher than that of ordinary spectrophotometry and with a limit of detection of 0.2 ng ml(-1). The pH should be in the range 5.0-6.0 using an acetate buffer. The determination of nickel in the presence of cobalt was performed with conventional and derivative procedures, and the results demonstrated that only the derivative method should be used and, of the methods used for evaluation of the derivative signal, the zero-crossing method is the best. The proposed procedure was used for nickel determination in steels standards. The results demonstrated that the procedure has satisfactory accuracy and precision. Cobalt interference can be also eliminated by using dual-wave-length spectroscopy. 相似文献
42.
Xu X Mei S Ferreira JM Nishimura T Hirosaki N 《Journal of colloid and interface science》2004,277(1):111-115
Due to the steric barrier provided by the adsorption of the dispersant hypermer KD1 (a polyester/polyamine condensation polymer), stable and low-viscosity suspensions of SiC, Y(2)O(3), and Al(2)O(3) powder mixtures could be prepared in methyl ethyl ketone (MEK)/ethanol (E) solvent with solids loading as high as 60 vol%. The solvency of the dispersant in MEK/E decreased dramatically on cooling. Steady shear viscosity and oscillatory measurements were performed as a function of temperature for suspensions with different solids loading. The viscosity and elastic modulus of suspension increased with decreasing temperature and became more sensitive with the increase of solids loading. The suspensions with solids loading higher than 40 vol% could be solidified with decreasing temperature, but gelation temperature and gelation stiffness decreased with decreasing solids loading. The 60 vol% solid-loaded suspension was a stable and free-flowing fluid at 20 degrees C and gradually transformed to a very highly viscous and elastic system upon cooling to about 13 degrees C. Complete solidification occurred when the temperature was decreased to 5 degrees C. The gelation mechanism was mainly based on the collapse of the adsorbed layer as the temperature decreases, which induced incipient flocculation and formed a stiff network. The gelled body was further strengthened by separation of the dispersant from the suspension. 相似文献
43.
A.R. Sousa 《Polymer Degradation and Stability》2006,91(7):1504-1512
This work aims to analyze the effects of photodegradation on the stress cracking resistance of polystyrene. Injection moulded samples were exposed to the ultraviolet light for various times in the laboratory prior to solvent contact. The bars were then stressed in a tensile testing machine under the presence of butanol. During this period the stress relaxation was monitored and the ultimate properties were evaluated after selected periods of stress cracking. Complementary tests were done by size exclusion chromatography and by scanning electron microscopy. The results indicated that butanol causes significant modification in polystyrene, with extensive surface crazing as well as reduction in mechanical properties. This is intensified under higher mechanical stress. The previous degraded samples showed a higher level of stress relaxation and a greater loss in tensile strength in comparison to the undegraded ones. The synergist action of photodegradation and stress cracking in polystyrene may be a consequence of the chemical changes caused by oxidation like the formation of polar chemical groups and the reduction in molecular weight. 相似文献
44.
The purpose of this study is to investigate the influence of nickel, which is an alloying element in commonly used metallic biomaterials, on the biomaterials mineralization process. An electrochemical method was developed to quantify this metal ion in osteoblast-like cell culture medium (OST) by performing adsorptive cathodic stripping voltammetry (CSV) with dimethylglyoxime (DMG) at a mercury film microelectrode (MFM). The optimized analytical conditions and the square-wave CSV parameters for the analysis are: DMG concentration: 5.00 × 10−4 mol L−1; ammonium chloride buffer: 0.10 mol L−1 (pH 9.2); frequency: 50 Hz, amplitude 20 mV; step: 2 mV; adsorption time: 10 s, deposition potential: −0.70 V and reduction potential: −1.20 V. The limit of detection was 7.70 × 10−9 mol L−1 for an adsorption time of 10 s. The results achieved by CSV using the MFM were compared to those obtained by atomic absorption spectrometry (AAS) to ensure the reliability of the electrochemical method. The mineralization process was evaluated by biochemical and histochemical assays. 相似文献
45.
E. A. Guimares Costa F. De Brito Mota A. Ferreira Da Silva 《International journal of quantum chemistry》1992,41(3):517-524
The density of states is calculated for a random distribution of donor-pairs of hydrogenlike impurities in three- and two-dimensional systems. Recent investigations of the hydrogen molecule in the alternant–molecular–orbital approximation are here extended. We found that the lowest excited state 1Σu (i.e., H+H?), which is optically connected to the ground state, plays a relevant role in the absorption spectra of semiconductor systems. 相似文献
46.
Compared with chemical catalysis, enzymatic catalysis is a relatively new topic. Experimental work involving lipases deserves careful attention and accurate procedures still need to be implemented. A rapid but careful survey of published data immediately demonstrates that experiments performed under similar conditions with similar reagents have led to very different results. The aim of this work is to point out the importance of accurate and systematic procedures in order to ensure the reproducibility of experimental data. We strongly believe that different results found by different labs are due to problems detected in the procedures used. Quantification of the immobilisation efficiency of lipase on several supports through UV/visible methods and sampling methods used to obtain correct enzymatic activity values are specifically analysed. After a brief review which demonstrates the big discrepancies found in the literature, original data from Candida rugosa lipase adsorption on polypropylene powder and its use in the solvent-free synthesis of ethyl oleate are introduced in order to exemplify the difficulties found in these kinds of systems. Several procedures described in the literature are assayed and the accuracy of the results obtained is carefully analysed. The aim of the whole analysis performed is that it would be useful for any powdered solid to be used as a support for a lipase in a solvent-free system for any synthesis reaction, especially for those involving a volatile reagent. Throughout this contribution, special emphasis is placed on how catalytic reaction results using enzymes (free and immobilised) are reported so as to allow comparison between published data, something which is usually difficult since very different units are used and often complementary data are not included. 相似文献
47.
Ribeiro da Silva MD Gomes JR Gonçalves JM Sousa EA Pandey S Acree WE 《The Journal of organic chemistry》2004,69(8):2785-2792
The mean (N-O) bond dissociation enthalpies were derived for three 2-methyl-3-(R)-quinoxaline 1,4-dioxide (1) derivatives, with R = methyl (1a), ethoxycarbonyl (1b), and benzyl (1c). The standard molar enthalpies of formation in the gaseous state at T = 298.15 K for the three 1 derivatives were determined from the enthalpies of combustion of the crystalline solids and their enthalpies of sublimation. In parallel, accurate density functional theory-based calculations were carried out in order to estimate the gas-phase enthalpies of formation for the corresponding quinoxaline derivatives. Also, theoretical calculations were used to obtain the first and second N-O dissociation enthalpies. These dissociation enthalpies are in excellent agreement with the experimental results herewith reported. 相似文献
48.
Quassinoids from Picrasma crenata 总被引:1,自引:0,他引:1
From woods of Picrasma crenata, a new stereoisomer dihydronorneoquassin was obtained together with others well knowns dihydronorneoquassin, parain, alpha-neoquassin, beta-neoquassin and quassin. The structures were determined by spectroscopic data and chemical evidence. 相似文献
49.
Arthur de Sousa 《Microchemical Journal》1973,18(2):137-141
An indirect microdetermination of phosphate via EDTA titration is described, which can be applied to minerals, soils, fertilizers, biological samples, drugs and organo-phosphorus compounds. The method is based on the precipitation of phosphate as the very insoluble silver orthophosphate (Ksp = 1.3 × 10?20), dissolution of this precipitate in a solution of potassium cyanonickelate and titration of the nickel displaced by silver. The phosphate content is obtained indirectly by multiplying the number of ml of the titrant by a factor. The method takes about an hour after the phosphate is brought into solution. The accuracy is about 1% for samples containing 5–50 mg PO43? and about 3–5% for samples with 100 to 5000 μg PO43?. 相似文献
50.
Jo?o?Pedro?Ferreira Jo?o?Alexandre?Rodrigues Inês?Teodora?Elias?da?FonsecaEmail author 《Journal of Solid State Electrochemistry》2004,8(4):260-271
The electrochemical behaviour of copper in neutral buffered and non-buffered synthetic seawater and in pure chloride solutions has been studied by cyclic voltammetry, weight loss measurements, open circuit potential and scanning electron microscopy (SEM). Values of the repassivation potentials of Cu in non-buffered and buffered synthetic seawater, at 50 mV s–1, were 0.12 and 0.46 V vs. SCE, respectively. The sharpness, heights and location of the different peaks as well as their charges were shown to be influenced by the composition of the solution, buffering conditions, deoxygenation, polarization potential and time. High chloride concentrations lead to higher oxidation charges. The anodic and the cathodic charges were shown to increase as the chloride concentration increases. The open circuit potential transients of copper in non-deoxygenated, non-buffered synthetic seawater indicate pitting from the beginning of the exposure, while in buffered solutions the pitting appeared only after a quite long exposure period, i.e. after 40 days. Corrosion rates of Cu samples after 3 months of immersion were higher in solutions of pure chloride (0.5 M) than in synthetic seawater. After six months the differences were even more noticeable. SEM images have showed a somewhat higher density of pits on copper samples immersed in the chloride solution (0.5 M), in comparison with those in synthetic seawater. 相似文献