全文获取类型
收费全文 | 80622篇 |
免费 | 5207篇 |
国内免费 | 3949篇 |
专业分类
化学 | 22877篇 |
晶体学 | 280篇 |
力学 | 4530篇 |
综合类 | 617篇 |
数学 | 8429篇 |
物理学 | 12687篇 |
综合类 | 40358篇 |
出版年
2024年 | 249篇 |
2023年 | 732篇 |
2022年 | 1698篇 |
2021年 | 1812篇 |
2020年 | 1719篇 |
2019年 | 1637篇 |
2018年 | 1502篇 |
2017年 | 1977篇 |
2016年 | 2405篇 |
2015年 | 2447篇 |
2014年 | 3942篇 |
2013年 | 4488篇 |
2012年 | 4851篇 |
2011年 | 4670篇 |
2010年 | 3769篇 |
2009年 | 4438篇 |
2008年 | 4311篇 |
2007年 | 5225篇 |
2006年 | 4577篇 |
2005年 | 4162篇 |
2004年 | 3796篇 |
2003年 | 3243篇 |
2002年 | 2632篇 |
2001年 | 2300篇 |
2000年 | 2052篇 |
1999年 | 1925篇 |
1998年 | 1641篇 |
1997年 | 1522篇 |
1996年 | 1380篇 |
1995年 | 1317篇 |
1994年 | 1184篇 |
1993年 | 985篇 |
1992年 | 955篇 |
1991年 | 817篇 |
1990年 | 765篇 |
1989年 | 623篇 |
1988年 | 577篇 |
1987年 | 397篇 |
1986年 | 243篇 |
1985年 | 186篇 |
1984年 | 133篇 |
1983年 | 63篇 |
1982年 | 101篇 |
1981年 | 65篇 |
1980年 | 51篇 |
1979年 | 77篇 |
1978年 | 35篇 |
1977年 | 16篇 |
1976年 | 23篇 |
1957年 | 8篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
981.
A novel conjugation-elongated bis(ethylenedithio)tetraselenafulvalene (BETS) type donor, 2,5-bis(4,5-ethylenedithio-1,3-diselenol-2-ylidene)-2,3,4,5-tetrahydrothiophene (BEDT-HBDST) and its magnetic and non-magnetic anion salts, (BEDT-HBDST)2MX4 (MX4−=FeCl4−, GaCl4−, FeBr4− and GaBr4−), were prepared. These four salts are isostructural and belong to the space group of P2/c. They showed semiconducting behavior with small activation energies (59-64 meV). The band structures of these salts are quasi one-dimensional and there is a midgap between the upper band and the lower band, since the degree of dimerization is significant in the stacking direction. The MX4− ions are located between the donor columns and near to the ethylenedithio moieties of the donor molecules. The magnetic susceptibilities of the FeCl4− and FeBr4− salts follow the Curie-Weiss law with Curie constants of 4.6 and 4.8 emu K mol−1 (sum of the spins of S=5/2 and S=1/2) and negative Weiss temperatures of θ=−1.2 and −4.9 K, respectively, revealing a weak antiferromagnetic interaction of 3d spins of the FeCl4− and FeBr4− anions. The Fe?Fe (6.66-7.60 Å), Cl?Cl (4.81-4.82 Å) and Br?Br (4.74-4.77 Å) distances in the crystal structures of these salts are significantly long. Therefore, the direct magnetic interaction between the 3d spins of the nearest neighboring Fe3+ ions appears to be not readily accessible. 相似文献
982.
A reversed-phase ion-pair HPLC with indirect photometric detection for the simultaneous determination of sulfite, sulfate, hydroxymethanesulfonate (HMS), and other inorganic anions in atmospheric water has been developed. Separations were accomplished in less than 10 min in a cetylpyridinium-coated C18 column with 0.5 mM potassium hydrogen phthalate-0.015% triethanolamine-3% methanol at pH 7.9 as mobile phase. Quantitation was carried out by the peak area method, with detection limits in the pmol range. UV light absorption responses were linear over a wide concentration range from several hundred μmoles to the detection limits of each anion. The application of the method provides a rapid and efficient technique for the quantitative determination of sulfur and other inorganic species in atmospheric liquids. 相似文献
983.
叙述了同步辐射白光全反射X射线荧光分析的实验装置,给出了几种标准物质TXRF实验的检出限,并对实验结果进行了讨论。 相似文献
984.
On the Hydrates M(HSeO3)2 · 4H2O (M = Mg, Co, Ni, Zn) – Crystal Structures, IR, Raman, and Thermoanalytical Investigations From aqueous solutions of M(HSeO3)2 single crystals of Mg(HSeO3)2 · 4H2O and of the hitherto unknown compounds Co(HSeO3)2 · 4H2O, Ni(HSeO3)2 · 4H2O and Zn(HSeO3)2 · 4H2O could be obtained. The crystal structures, X-ray powder, IR, Raman and thermoanalytical (DTA, TG, Raman heating) data are presented and discussed. The crystal data of the isotypic compounds are: monoclinic, space group C2/c, Z = 4, Mg: a = 1 464.6(2), b = 755.3(1), c = 1 099.9(1) pm, β = 126.59(1)°, V = 0.9769(1) nm3, Co: a = 1 462.5(2), b = 756.5(2), c = 1 102.2(2) pm, β = 126.53(1)°, V = 0.9798(2) nm3, Ni: a = 1 452.2(2), b = 751.0(1), c = 1 091.5(1) pm, β = 126.28(1)°, V = 0.9595(1) nm3, Zn: a = 1 468.3(2), b = 755.8(1), c = 1 103.1(1) pm, β = 126.79(1)°, V = 0.9804(2) nm3. The crystal structures consist of hexagonal packed [M(HSeO3)2 · 2H2O]n chains of [MO4(H2O)2] octahedra linked by Se atoms. They contain trigonal pyramidal SeO2OH?ions with “free” hydroxyl groups and also “free” molecules of water of crystallization. The hydroxyl groups build strong H-bonds (O? H …? O distances: 265–268 pm). The IR spectra show AB doublett bands in the OH stretching mode region of the hydroxyl groups. The water molecules of crystallization are linked to planar (H2O)4 tetramers by H-bonds with unusually short O? H …? O bond distances of 271–273 pm. DTA and TG measurements indicate that thermal decomposition results in the direct formation of the respective diselenite MSe2O5. Raman heating measurements show under quasi static conditions the intermediate formation of the anhydrous hydrogen selenites. 相似文献
985.
J. O. Hill 《Journal of Thermal Analysis and Calorimetry》1994,42(2-3):607-621
The research in thermal analysis and calorimetry, conducted by the author over the period 1964 to 1993, is summarised and concisely reviewed. The major investigations have focussed on thermal analysis studies of coordination compounds, particularly the metal dithiocarbamate complexes. A significant solution calorimetric study of some metal dithiocarbamate complexes has also been undertaken. DSC has been applied to determine the sublimation enthalpies of many metal dithiocarbamate and metal pentane-2,4-dionate complexes and solution calorimetry has been applied to study the thermochemistry of the latter group of complexes. Thermal analysis investigations of several inorganic molten salt systems have been initiated. Thermometric titrimetry has been applied to study metal-macrocyclic ligand systems in aqueous media and particularly those systems of environmental significance. Temperature calibration standards for TMA have been proposed and TMA has been applied to study the mechanical properties of several common inorganic compounds. DTA has been applied to study a wide variety of phenols and has subsequently been applied as an analytical technique to determine the components of solid state phenol mixtures. Thermometric titrimetry has been applied to determine the phenolic content of wines. A comprehensive thermal analysis study of Australian brown coal has been undertaken, involving the DSC determination of coal specific energy, a TG/DTA study of the coal pyrolysis and combustion processes and a TG/DTA and EGA study of the cation catalytic effect on the coal pyrolysis process. Thermal analysis and calorimetric techniques have been extensively publicised and promoted by the publication of specialist reviews, the presentation of symposia review papers and the oral presentation of short courses, particularly in the SE Asian region. This review essentially reveals the diversity of possible application of thermal analysis and calorimetric techniques and the primary significance of thermodynamic data in the fundamental rationalisation of chemical phenomena. 相似文献
986.
J. Escribano R. Masegosa D. Nava M. G. Prolongo Catalina Salom 《Journal of Thermal Analysis and Calorimetry》2006,83(3):675-679
The
mineral sabugalite (HAl)0.5[(UO2)2(PO4)]2⋅8H2O, has been studied using a combination of energy
dispersive X-ray analysis, X-ray diffraction, dynamic and controlled rate
thermal analysis techniques. X-ray diffraction shows that the starting material
in the thermal decomposition is sabugalite and the product of the thermal
treatment is a mixture of aluminium and uranyl phosphates. Four mass loss
steps are observed for the dehydration of sabugalite at 48°C (temperature
range 39 to 59°C), 84°C (temperature range 59 to 109°C), 127°C
(temperature range 109 to 165°C) and around 270°C (temperature range
175 to 525°C) with mass losses of 2.8, 6.5, 2.3 and 4.4%, respectively,
making a total mass loss of water of 16.0%. In the CRTA experiment mass loss
stages were found at 60, 97, 140 and 270°C which correspond to four dehydration
steps involving the loss of 2, 6, 6 and 2 moles of water. These mass losses
result in the formation of four phases namely meta(I)sabugalite, meta(II)sabugalite,
meta(III)sabugalite and finally uranyl phosphate and alumina phosphates. The
use of a combination of dynamic and controlled rate thermal analysis techniques
enabled a definitive study of the thermal decomposition of sabugalite. While
the temperature ranges and the mass losses vary due to the different experimental
conditions, the results of the CRTA analysis should be considered as standard
data due to the quasi-equilibrium nature of the thermal decomposition process.
The online version of the original article can be found at 相似文献
987.
This research applies semiconductor photocatalysts, which are formed by metal ion exchange on the surface of kaolinite catalyst with cations, to the study of photocatalytic degradation of 4‐chlorophenol. The analysis results of catalyst properties shows that, after sintering at 400 °C, kaolinite catalyst has a particle size of between 10–100 nm indicating the nano level of synthesized catalysts. Under the same condition, kaolinite‐Ag/Zn catalyst works better in degradation efficiency than single kaolinite‐Ag and kaolinite‐Zn catalysts. Kaolinite‐Zn catalyst declines in degradation efficacy after 150 minutes and performs poorer than the other three types of kaolinite catalysts. In the experiments of different amounts of catalysts, when the concentration exceeds 0.1 wt%, utilization of light energy and degradation efficiency will be reduced due to shielding effect. When at different pH values, the higher the pH value, the more OH‐will be released and that is beneficial for reaction with substances and the increase of reaction rate. Finally multivariate analysis proves that there is one determining factor that influences the photocatalytic degradation of 4‐chlorophenol in kaolinite catalysts, named as “the factor with intermediates competition degree,” the one affecting the 4‐CP degradation at different weight percentages that is referred to as the “shielding effect factor.” 相似文献
988.
Oxide ceramic masses react to simple shearing with hardening (peptisation: increase in the shear stress with the shear deformation).
In the present study the correlation between the increase in the shear stress and the porosity, agglomeration processes and
the type of flow are analysed. For this purpose oxide ceramic masses are tested in a shear device especially developed for
pastes and analysed by rheometric experiments, NMR methods and particle size analysis. The results support the hypothesis
that structural changes (hardening, increase in the mean porosity) of the material during the peptisation mainly depend on
the magnitude and not on the kind of the energy input and thus of the type of flow. The fraction of bound (more generally,
the immobilised) water increases with the shear displacement. Also crushing of primary particles could be observed. Both the
crushing of solid particles causing an increased solid surface and the formation of a three-dimensional gel structure are
microscopic effects capable of resulting in the binding or retaining water. On a macroscopic scale these phenomena cause hardening.
Magnetic resonance imaging visualises flow-induced agglomerates, which form owing to the shear flow and increase the porosity
averaged over the whole sample. After the shear experiment rolls of paste can be seen which indicate that the general assumption
of a plane shear flow in the shear device is not warrantable.
Received: 19 July 2001 Accepted: 25 October 2001 相似文献
989.
Summary A method is reported for the determination of dibutyltin (DBT), diphenyltin (DPhT), tributyltin (TBT), and triphenyltin (TPhT)
species at the nanogram per litre concentration level in natural water samples. Analytes were isolated from samples by solid-phase
extraction and analysed both off-line and on-line by reversed-phase high-performance liquid chromatography with post-column
derivatization and fluorimetric detection. Several SPE cartridges and eluents were evaluated; C18 enrichment and elution with a mixture of methanol, acetic acid, and water was found most suitable. Preconcentration factors
up to 250 can be achieved when a 500-mL sample is processed. Detection limits, recovery rates, and the precision of the whole
process have been determined. The method has been applied to the determination of organotin species in spiked natural water
samples collected on the NW Mediterranean coast. Recovery rates range from 75 to 110% and detection limits are at the low
ng L−1 level (1–3 ng Sn L−1 for DPhT, DBT, and PhT and 40 ng Sn L−1 for TBT when 250 mL spiked sea water is processed.) 相似文献
990.