全文获取类型
收费全文 | 82267篇 |
免费 | 459篇 |
国内免费 | 417篇 |
专业分类
化学 | 27069篇 |
晶体学 | 846篇 |
力学 | 6813篇 |
数学 | 32633篇 |
物理学 | 15782篇 |
出版年
2021年 | 48篇 |
2019年 | 56篇 |
2018年 | 10465篇 |
2017年 | 10277篇 |
2016年 | 6136篇 |
2015年 | 939篇 |
2014年 | 388篇 |
2013年 | 550篇 |
2012年 | 3966篇 |
2011年 | 10730篇 |
2010年 | 5736篇 |
2009年 | 6129篇 |
2008年 | 6785篇 |
2007年 | 8960篇 |
2006年 | 419篇 |
2005年 | 1514篇 |
2004年 | 1730篇 |
2003年 | 2161篇 |
2002年 | 1132篇 |
2001年 | 286篇 |
2000年 | 344篇 |
1999年 | 209篇 |
1998年 | 239篇 |
1997年 | 186篇 |
1996年 | 267篇 |
1995年 | 159篇 |
1994年 | 138篇 |
1993年 | 150篇 |
1992年 | 102篇 |
1991年 | 123篇 |
1990年 | 94篇 |
1989年 | 97篇 |
1988年 | 105篇 |
1987年 | 106篇 |
1986年 | 102篇 |
1985年 | 115篇 |
1984年 | 115篇 |
1983年 | 86篇 |
1982年 | 100篇 |
1981年 | 93篇 |
1980年 | 92篇 |
1979年 | 116篇 |
1978年 | 103篇 |
1977年 | 89篇 |
1976年 | 73篇 |
1975年 | 68篇 |
1974年 | 59篇 |
1973年 | 68篇 |
1972年 | 53篇 |
1914年 | 49篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
991.
Danielle Giron S. Monnier M. Mutz P. Piechon T. Buser F. Stowasser K. Schulze M. Bellus 《Journal of Thermal Analysis and Calorimetry》2007,89(3):729-743
Adequate very sensitive quantification methods are needed for the development and are also now required for the monitoring
of undesirable solid form(s) as routine tests. The pre-requisite for quantitation are selectivity, sensitivity and most important
the purity of standards and their proper storage, what is a challenge for metastable forms.
Several analytical techniques are available such as X-ray diffraction, spectroscopy, thermal analysis and microcalorimetry.
The different steps of the validation of the analytical methods and problems to be solved are discussed. Examples illustrate
the different techniques and compare their possible advantages and limits. The relative standard deviation of measurements
should allow for checking the homogenization procedure of mixtures for calibration. The validation should be carried out following
ICH guidelines for validation of analytical methods. Comparison of different techniques in adequate concentration range add
confidence in the analytical results. 相似文献
992.
The hydrolysis of ethyl formate catalysed by hydrochloric acid was studied at three temperatures in water-acetone media and in water media containing different concentrations of sodium nitrate. The effect of various ionic strengths and dielectric constants upon the rate of acid hydrolysis of ethyl formate is presented from the point of electrostatics and the results were compared to like effects upon the acid hydrolysis of ethyl acetate and methyl propionate. Neither the dielectric constant effect nor the salt effect lends itself readily to theoretical interpretation. It was assumed that a partial explanation of these anomalous results might be in the extrapolation of the acid radical to the simplest carboxylic acid. This suggestion was supported somewhat by the trends towards less adherance to the electrostatic theory at certain temperatures in the series methyl propionate, ethyl acetate and ethyl formate. 相似文献
993.
Andrzej Czerwiński Iwona Kiersztyn Michał Grdeń 《Journal of Solid State Electrochemistry》2003,7(6):321-326
The effect of temperature on hydrogen and deuterium electrosorption into a palladium LVE (limited-volume electrode) has been
investigated. A decrease in hydrogen capacity (H/Pd ratio) with increasing temperature has been observed. Temperature strongly
influences the plots of measured H(D)/Pd values vs. potential scan rate. In addition, hydrogen absorption was found to be
dependent on the composition of the surrounding electrolyte solution. These results have confirmed the hypothesis that two
different mechanisms of hydrogen desorption from the palladium electrode take place, namely electrochemical oxidation and
non-electrochemical recombination. Further, the ratio between the rate constants for these two processes has been found to
change with temperature.
Electronic Publication 相似文献
994.
Summary The thermal behavior of KH2PO4, NaH2PO4 and Na2HPO4 under non-isothermal conditions using TG method with different heating rates was studied. The values of the reaction rate were processed by means of Friedmans differential-isoconversional method. A dependence of the activation energy vs. conversion was observed. Therefore a procedure based on the compensation effect (suggested by Budrugeac and Segal) was applied. A less speculative data processing protocol was offered by the non-parametric kinetics method suggested by Serra, Nomen and Sempere. Three steps were observed by non-isothermal heating: a dehydration, a dimerization and a polycondensation. The differences in the intimate reaction mechanism are determined by the initial number of water molecules. 相似文献
995.
Employing hot tungsten filament to thermal dissociate molecular hydrogen,we generated gas phase atomic hydrogen under ultra-high vacuum(UHV)conditions and investigated its interaction with Pt(111) surface.Thermal desorption spectroscopy(TDS)results demonstrate that adsorption of molecular hy- drogen on Pt(111)forms surface Had species whereas adsorption of atomic hydrogen forms not only surface Had species but also bulk Had species.Bulk Had species is more thermal-unstable than surface Had species on Pt(111),suggesting that bulk Had species is more energetic.This kind of weakly- adsorbed bulk Had species might be the active hydrogen species in the Pt-catalyzed hydrogenation reactions. 相似文献
996.
Acetonitrile and [D3]acetonitrile in the vicinal region of a planar AgX fiber contain linear dipole–dipole linked oligomers as shown by 1) comparison of infrared band intensity ratios in the gaseous and condensed phases and 2) remarkable plots of absorbance (C? N stretch) versus time during evaporation from an AgX planar fiber element. The plots (CH3CN 2252 cm?1, CD3CN 2262 cm?1) reveal the presence of octamers, hexamers, tetramers, and dimers along with some heptamer, trimer, and monomer structures. A novel isotope effect arises from the somewhat smaller size of the CD3CN resulting in an increase in the CN band intensity. The organized oligomers may be termed pseudocrystals and are the main components responsible for absorption intensity in the infrared spectrum of acetonitrile, on the AgX planar fiber or in an IR cell. 相似文献
997.
Ahmad Shaabani Abbas Rahmati Soheila Naderi 《Monatshefte für Chemie / Chemical Monthly》2007,138(6):553-557
Summary. Reaction of triphenylphosphine and an electron deficient acetylenic ester in the presence of strong N–H acid such as alkyl
and aryl sulfamides or acetamide produces phosphorous ylides at room temperature in CH2Cl2. The aryl sulfamide phosphoranes undergo a smooth transformation reaction in boiling toluene and produce iminophosphoranes. 相似文献
998.
[reaction: see text] The synthesis of four bioactive analogues of the somatostatin (SRIF-14) mimetic, beta-d-glucoside (+)-2, in which the C1 indole side chain is replaced with indole surrogates, has been achieved. These congeners, possessing the naphthyl, benzothiophene, benzyl, and benzofuran substituents, were predicted to satisfy the electrostatic requirements of the tryptophan binding pocket of SRIF. Unlike the previously described C4 picolyl and pyrazinyl congeners, these ligands bind the hSST4 receptor. 相似文献
999.
Crown ethers were reacted with HN-proton-donor molecules to obtain crystalline molecular host-guest complexes. It was found that complexes with crown ethers of different structure are formed, depending on the linear dimensions and mode of steric shielding of active centers of the proton-donor molecules.Translated from Zhurnal Obshchei Khimii, Vol. 74, No. 12, 2004, pp. 2030–2033.Original Russian Text Copyright © 2004 by Wang, Ganin.This revised version was published online in April 2005 with a corrected cover date. 相似文献
1000.
Soonam Park Feng Liao John M. Larson Steven L. Girshick Michael R. Zachariah 《Plasma Chemistry and Plasma Processing》2004,24(3):353-372
A molecular beam mass spectrometry system for in situ measurement of the concentration of gas phase species including radicals impinging on a substrate during thermal plasma chemical vapor deposition (TPCVD) has been designed and constructed. Dynamically controlled substrate temperature was achieved using a variable thermal contact resistance method via a backside flow of an argon/helium mixture. A high quality molecular beam with beamtobackground signal greater than 20 was obtained under film growth conditions by sampling through a small nozzle (75 m) in the center of the substrate. Mass discrimination effects were accounted for in order to quantify the species measurements. We demonstrate that this system has a minimum detection limit of under 100 ppb. Quantitative measurements of hydrocarbon species (H, H2, C, CH3, CH4, C2H2, C2H4) using Ar/H2/CH4 mixtures and silicon species (Si, SiH, SiH2, SiCl, SiCl2, Cl, HCl) using Ar/H2/SiCl4 mixtures were obtained under thermal plasma chemical vapor deposition conditions. 相似文献