全文获取类型
收费全文 | 49912篇 |
免费 | 15730篇 |
国内免费 | 87篇 |
专业分类
化学 | 58281篇 |
晶体学 | 63篇 |
力学 | 2151篇 |
数学 | 3491篇 |
物理学 | 1743篇 |
出版年
2024年 | 372篇 |
2023年 | 4094篇 |
2022年 | 1474篇 |
2021年 | 2538篇 |
2020年 | 4687篇 |
2019年 | 2393篇 |
2018年 | 2321篇 |
2017年 | 642篇 |
2016年 | 5665篇 |
2015年 | 5600篇 |
2014年 | 5052篇 |
2013年 | 5337篇 |
2012年 | 3457篇 |
2011年 | 1358篇 |
2010年 | 3600篇 |
2009年 | 3520篇 |
2008年 | 1313篇 |
2007年 | 1036篇 |
2006年 | 394篇 |
2005年 | 365篇 |
2004年 | 281篇 |
2003年 | 246篇 |
2002年 | 243篇 |
2001年 | 119篇 |
1997年 | 144篇 |
1996年 | 145篇 |
1995年 | 183篇 |
1994年 | 121篇 |
1993年 | 232篇 |
1992年 | 115篇 |
1988年 | 132篇 |
1985年 | 125篇 |
1984年 | 135篇 |
1983年 | 128篇 |
1982年 | 160篇 |
1981年 | 177篇 |
1980年 | 219篇 |
1979年 | 202篇 |
1978年 | 222篇 |
1977年 | 329篇 |
1976年 | 376篇 |
1975年 | 467篇 |
1974年 | 489篇 |
1973年 | 294篇 |
1972年 | 374篇 |
1971年 | 357篇 |
1970年 | 541篇 |
1969年 | 416篇 |
1968年 | 457篇 |
1967年 | 116篇 |
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
141.
Xe(OTeF5)2 reacts with Sb(OTeF5)3 under the formation of [Xe2(OTeF5)3]+[Sb(OTeF5)6]-. From SO2ClF solution a yellow solvate [F5TeOXe]+·SO2ClF· [Sb(OTeF5)6]- is formed with the crystal data: a = 1028.1(1), b = 1040.9(1), c = 1780.2(3) pm, α = 98.07(1), β = 97.68(1), γ = 105.82(1)°, space group . The O-Xe···O fragment is essentially linear (176.1(2)°), and the two Xe-O distances are quite different 197.1(4) and 242.6(4) pm. 相似文献
142.
Dr. Wojciech Puacz 《Mikrochimica acta》1982,77(3-4):271-275
Summary An accurate and simple indirect method of flame emission spectrometric determination of small quantities of elemental sulphur is described. The method is based on the reduction of elemental sulphur by means of sodium borohydride and oxidation of the resulting boron-sulphur compounds to sulphate by means of hydrogen peroxide. The determinations can be carried out in the presence of methanol, acetone, dimethylformamide, toluene and benzene. The detection limit of the reported method is 1 ppm of sulphur.
Presented at the 8th International Microchemical Symposium, Graz, August 25–30, 1980. 相似文献
Indirekte etnissionsspektroskopische Bestimmungsmethode für Spuren elementaren Schwefels. I.
Zusammenfassung Eine genaue und einfache, indirekte, emissionsspektroskopische Methode zur Bestimmung geringer Mengen elementaren Schwefels wurde ausgearbeitet. Sie besteht in der Reduktion des elementaren Schwefels mit Hilfe von Natriumborhydrid und in der Oxydation der entstehenden Bor-Schwefel-Verbindung zu Sulfat mit Hilfe von Wasserstoffperoxid. Die Analyse wurde in Methanol, Aceton, Dimethylformamid, Toluol und Benzol durchgeführt. Die Erfassungsgrenze beträgt 1 ppm Schwefel.
Presented at the 8th International Microchemical Symposium, Graz, August 25–30, 1980. 相似文献
143.
Dr. A. R. Haly 《Colloid and polymer science》1963,189(1):43-50
Summary The present position of theoretical investigation of the water-content versus relative humidity isotherm is briefly indicated. Previous workers have anticipated an effect on equilibrium water-content arising from the mechanical properties of the keratin network. Such an effect is reported for supercontracted wool fibres and for reduced and S-methylated fibres, for which an increased saturation water-content is observed. In the case of S-methyl wool, saturation water-content shows little or no dependence on the number of disulphide cross-links, however it does depend on the number of S-methyl groups present. The results are considered in terms ofFlory-Huggins solution theory, and it is indicated that this theory can be usefully applied for relative humidities in excess of 85%. In normal wool solution absorption is permitted only in the noncrystalline component, but in supercontracted wool or S-methyl wool takes place in both components. Even when saturation water-content is greatly increased the isotherm is not appreciably changed below 85% R. H., indicating that no additional sites for strong binding of water become available; apparently all such sites are accessible in normal wool at approximately 85% relative humidity.
Zusammenfassung Der gegenwärtige Stand theoretischer Untersuchungen für den isothermen Wassergehalt gegen relative Feuchtigkeit ist kurz kritisch dargelegt. Die bisherigen Bearbeiter haben einen Einfluß auf das Gleichgewicht des Wassergehaltes seitens der mechanischen Eigenschaften des Keratinnetzwerkes angenommen. Ein solcher Effekt wird für superkontrahierte Wollfasern und für solche, reduziert und mit Schwefelmethyl behandelt, mitgeteilt, für die eine erhöhte Wassersättigung zu beobachten ist. Im Fall der schwefelmethylierten Wolle zeigt die Sättigung geringe oder keine Abhängigkeit von der Zahl der Disulfidvernetzungen, sie hängt jedoch von der Zahl der Schwefel-Methylgruppen ab. Diese Resultate werden mit derFlory-Huggins-Lösungstheorie betrachtet, und es zeigt sich, daß diese Theorie gut für relative Feuchtigkeiten größer als 85% angewendet werden kann. In normaler Wolle ist Lösungsabsorption nur in den nichtkristallinen Anteilen möglich, aber in superkontrahierter oder schwefelmethylierter Wolle findet sie auch in den Kristalliten statt. Auch wenn der Sättigungswert der Isotherme gegen Ende stark beeinflußt wird, ändert sich der Verlauf der Isotherme unterhalb 85% r. F. nicht. Das zeigt, daß kerne zusätzlichen Plätze für starke Wasserbindungen entstehen. Offensichtlich sind alle diese Plätze in normaler Wolle bei etwa 85% r. F. zugänglich.相似文献
144.
HgI2 crystallizes under ambient conditions from various solvents and by sublimation into three concomitant polymorphs whose colors are red, orange, and yellow. The orange and yellow phases are metastable and transform into the red phase when touched. A phase transition from red to yellow occurs at 400 K. The reverse transition from yellow to red shows a huge hysteresis. We established that the structures of the metastable yellowM phase (determined by single‐crystal X‐ray diffraction) and the high‐temperature yellowHT phase (determined by powder synchrotron X‐ray diffraction and second‐harmonic generation) are different, albeit closely related. Both show analogous packings of I? Hg? I molecules, which are straight in the first and bent with an angle of ca. 160° in the second. The red and orange phases are tetrahedral semiconductor structures that sublime even at room temperature. The growth of the yellowM phase from 2‐chloroethanol and the kinetics of the reconstructive phase transition red to yellowHT and back were studied by optical microscopy, Raman spectroscopy in solution, luminescence, and powder synchrotron X‐ray diffraction as a function of time at various temperatures. Both yellow phases grow by accretion of HgI2 molecules, present in the solution or liberated from the red crystals, on the surface of the crystal. In contrast, the reverse transformation from yellow to red occurs in the bulk of the crystal, presumably by migration of Hg in the packing of I and subsequent rearrangement of I. The displacement parameters of Hg in both structures are considerably larger than those of I and apparently not dominated by disorder effects. 相似文献
145.
Walrand J Lengelé M Blanquet G 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2004,60(14):3299-3303
Using diode-laser spectroscopy, the intensities of 58 lines of the v(1) + v(1/2) - v(1/2) band and 36 lines of the 2v(1) - v(1) band of OCS have been measured. The corresponding band strengths S(0)(v) and the vibrational transition dipoles micro(v) have been derived through least squares fitting of these individual intensities. The band strengths values have been determined with a precision better than 2.5%. 相似文献
146.
Iterative extended Hükel calculations for all valence electrons and iterative PPP calculations in the variable electronegativity formalism for -electrons were performed on benzene, pyridine, fluorobenzene, and the pyrylium ion. The charge distributions for all compounds were found more uniform and plausible with the iteration procedures than without. Polarization effects from the-electrons were found to be of importance for the -electrons. The lone-pair picture of the highest occupied MO in pyridine is preserved in the iterative extended Hückel method, and two lone-pairs were obtained on the fluorine atom of fluorobenzene. The results indicate that this atom is not hybridized.
Sponsored in part by King Gustaf VI Adolfs 70-Years Fund for Swedish Culture, Knut and Alice Wallenberg's Foundation, and in part by the Swedish National Research Council. 相似文献
Zusammenfassung Benzol, Pyridin, Fluorbenzol und Pyriliumion wurden mit einer iterativen EH-Methode und einer iterativen PPP-VE-Methode berechnet. Es zeigte sich, daß Ladungsverteilungen bei Benutzung des Iterationsverfahrens besser beschrieben werden. Polarisationseffekte der-Elektronen auf die -Elektronen stellen sich als wichtig heraus. Auch in der IEH-Methode bleibt das oberste besetzte MO des Pyridins ein einsames Elektronenpaar. Am Fluoratom im Fluorbenzol werden zwei einsame-Elektronenpaare erhalten. Die Resultate führen zu der Annahme, daß dieses Atom nicht hybridisiert ist.
Resumé Des calculs par les méthodes itératives de Hückel étendu pour tous les électrons de valence et de PPP avec électronégativité variable pour les électrons ont été effectués pour le benzène, la pyridine, le fluorobenzène et l'ion pyrylium. Les distributions de charge pour tons ces composés sont plus uniformes et plus plausibles avec les procédés itératis que sans. Les électrons ont un effet de polarisation important sur les électrons . La plus haute orbitale occupée dans la pyridine reste identifiable comme la paire libre dans la méthode de Hückel étendue, et l'on obtient deux paires libres sur l'atome de fluor du fluorobenzène. Cet atome n'est pas hybride.
Sponsored in part by King Gustaf VI Adolfs 70-Years Fund for Swedish Culture, Knut and Alice Wallenberg's Foundation, and in part by the Swedish National Research Council. 相似文献
147.
Contributions to the Chemistry of Transition Metal Alkyl Compounds. XLIII. Tetrakis(alkoxycarbonylmethyl)titanium Compounds Organotitanium(IV) compounds of the type (ROCOCH2)4Ti (R ? C2H5, i-C3H7, t-C4H9, C6H5, C6H5CH2) were obtained by reactions of ROCOCH2Li derivatives with TiCl4 at low temperature. The compounds which decompose only above 90°C were characterized by the hydrolysis products, anaerobic reactions with iodine, and the i.r. spectra. The bond conditions are discussed. 相似文献
148.
Empirical solvent parameters of silica surfaces are determined by means of solvatochromic dyes, e.g., Cu(tmen) (acac)+ ClO
4
–
/B(C6H5)
4
–
, Fe(phen)2(CN)2, and Michlers Ketone dissolved in 1,2-dichloroethane or cyclohexane. The values obtained by UV/VIS-measurements are compared with both the polarity scales of Kamlet and Taft and with Gutmann's donor and acceptor numbers. Kamlet and Taft's -parameter (the hydrogen-bond donation capacity of a solvent) is determined independently by means of salicylideneaniline. The * of silica is determined using 5-N,N-dimethylamino-5-nitro-2,2-bithiophene and the complex of tetracyanoethylene with Michlers Ketone, respectively. Further on the reliabilities of the obtained Kamlet-Taft parameters , , and * are checked by comparism with experimental and calculated values of theE
T(30)-parameter of silica by means of multi-parameter regression analysis. The surface properties of silica are influenced mainly by HBD-properties (75%) and dipolarity/polarizability * (20%), but hardly by the HBA-properties (<5%). UV/VIS-measurements were carried out in a special equipment with glass fiber optics, A drawing of the apparatus is given. 相似文献
149.
At sufficiently high concentrations of methanol and of alkali salts in aqueous silica dispersions, the negative -potentials of the particles are decreased. This effect is more pronounced with lithium than with other alkali cations, and it is independent on the anion. The NMR spectra indicate lithium adsorption on silica from mixed solvents, but not in the absence of alcohol.Supported by a contract with the XMX Corporation, Burlington, Massachusetts, USA 相似文献
150.
Prof. Dr. Hans Sachs 《Journal of Geometry》1992,43(1-2):148-165
According to H. BRAUNER a flag space is a three-dimensional affine space with an absolute {,f,F}, wheref is a line in the plane of infinity andF a point onf. A cyclide is a surface of order 4 that intersects only atf. A STROMMER-cyclide is a cyclide generated by translation of a circle in an isotropic plane. In this paper we proof that all STROMMER-cyclides can be generated by translation of an isotropic circle along a divergent Newton-parabola or a conic in a full isotropic plane. We give normal-forms and CAD-pictures of these surfaces. Finaly some geometrical results about STROMMER-cyclides are developed.
Herrn o.Prof. Dr. Gy. Strommer zum 70. Geburtstag gewidmet. 相似文献
Herrn o.Prof. Dr. Gy. Strommer zum 70. Geburtstag gewidmet. 相似文献