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101.
介绍氧弹分解-原子荧光法测定煤中汞含量的研究进展。影响该方法主要因素为称样量、氧气浓度、吸收剂、还原剂、煤种以及灰分含量。分别综述了各个因素对该方法的影响,可为相关标准的制定提供参考。该方法能够简单、经济、快速地测定煤中汞的含量,但是目前学者们对于该方法的相关研究还存在分歧,需要进一步的研究验证;同时,还需要注意以下几个研究方向:吸收剂和还原剂的选择对汞回收率的影响;吸收剂在密闭氧弹中对汞的回收率及吸收时间的研究;氧弹废气中汞含量的测定;煤种和灰分含量对汞含量测定的影响。 相似文献
102.
Bassan A Blomberg MR Siegbahn PE Que L 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(2):692-705
The reactivity of [HO-(tpa)Fe(V)=O] (TPA=tris(2-pyridylmethyl)amine), derived from O-O bond heterolysis of its [H(2)O-(tpa)Fe(III)-OOH] precursor, was explored by means of hybrid density functional theory. The mechanism for alkane hydroxylation by the high-valent iron-oxo species invoked as an intermediate in Fe(tpa)/H(2)O(2) catalysis was investigated. Hydroxylation of methane and propane by HO-Fe(V)=O was studied by following the rebound mechanism associated with the heme center of cytochrome P450, and it is demonstrated that this species is capable of stereospecific alkane hydroxylation. The mechanism proposed for alkane hydroxylation by HO-Fe(V)=O accounts for the experimentally observed incorporation of solvent water into the products. An investigation of the possible hydroxylation of acetonitrile (i.e., the solvent used in the experiments) shows that the activation energy for hydrogen-atom abstraction by HO-Fe(V)=O is rather high and, in fact, rather similar to that of methane, despite the similarity of the H-CH(2)CN bond strength to that of the secondary C-H bond in propane. This result indicates that the kinetics of hydrogen-atom abstraction are strongly affected by the cyano group and rationalizes the lack of experimental evidence for solvent hydroxylation in competition with that of substrates such as cyclohexane. 相似文献
103.
The geometries of the most stable isomers of gold telluride systems AuTe, Au2Te, and AuTe2 are determined using the MP2 method. The aspect of gold—telluride interaction, the electron correlation, and relativistic
effects on geometry and stability are investigated at the MP2 and CCSD(T) theoretical levels. The results show that the electron
correlation and relativistic effects are responsible not only for gold—gold attraction but also for additional gold—telluride
interaction. The gold—telluride interaction is strong enough to modify the known pattern of bare gold clusters. Both effects
are essential for determining the geometry and relative stability of this type of systems. 相似文献
104.
The application of Bacillus subtilis as a flocculant for fine coal has been reported here. Zeta-potential measurements showed that both the coal and bacteria had similar surface charge as a function of pH. Surface free energy calculations showed that the coal was hydrophobic while the bacterium was hydrophilic. The adhesion of the bacteria to coal and subsequent settling was studied in detail. Adhesion of bacteria to coal surface and subsequent settling of coal was found to be quick. Both adhesion and settling were found to be independent of pH, which makes the process very attractive for field applications. The presence of an electrolyte along with the bacterium was found to not only enhance adhesion of bacteria, but also produce a clear supernatant. Further, the settled fraction was more compact than with bacteria alone. Interaction energy calculations using the extended DLVO theory showed that the electrical forces along with the acid–base interaction energy play a dominant role in the lower pH range. Above pH 7, the acid–base interaction energy is the predominant attractive force and is sufficient enough to overcome the repulsive forces due to electrical charges to bring about adhesion and thus settling of fine coal. With increase in electrolyte concentration, the change in total interaction energy with pH is minimal which probably leads to better adhesion and hence settling. 相似文献
105.
The localized molecular orbitals and their energy levels for the clusters [Fe3S4(SH)3]2–, [(HS)3Fe3S4·Ni(PH3)]2–, [Mo3S4(OH2)9]4+, and [Mo3S4·Ni]4+ have been calculated by mean of the Edmiston-Ruedenberg energy localization technique under the CNDO/2 approximation in order to reveal the resemblance between [Fe3S4]+ and [Mo3S4]4+ in the geometrical configurations and the addition reactivities with heterometal atoms. It is shown that in these two cluster species with core {M
3(3-S)(-S)3} of similar structure (M = Mo, Fe) there exist three synergically connected three-centered two-electron (M-S-M) -bonds around the puckered six-membered {M3S3} rings on account of delocalization of a lone electron pair on each bridging S atom; these (M-S-M) -bonds are thus capable of forming cubane-like heterometal clusters with intruder metal atoms through the ( M) bonding. It is therefore seen that unlike the [Mo3S4]4+ with appreciable bonding between the Mo atoms, the extra d-electrons on the metal atoms in the [Fe3S4]+ cluster are localized on the Fe atoms, exhibiting an electronic structure significantly different from that of the [Mo3S4]4+ cluster. 相似文献
106.
The synthesis of goethite by oxidation of Fe2+in presence of metallic iron was undertaken in an aqueous medium containing indifferent salts such as Na2SO4, (NH4)2SO4, NaCl, and NH4Cl. Temperature and bubbling air rate were maintained, respectively, at 70°C and 1 L/min. The influence of anions and cations on the kinetics of each step of the process has been followed distinctly, the iron dissolution rate has been determined by the variation of the medium acidity, and the precipitation of goethite has been determined by gravimetric measurements. With respect to Cl−, the SO42−anion decreases the rate of the two reactions. NH4+acts as an inhibitor when it is present at low concentrations and as an accelerator for higher concentrations; the limit corresponding to the change of NH4+behavior depends on the nature of the counter ion. The reaction product is composed of pure goethite in the presence of sulfate salts, whereas a mixture of goethite and lepidocrocite, respectively, 60–70 and 40–30%, was observed in the presence of chloride salts. 相似文献
107.
A novel sensitive and simple method for rapid and selective extraction, preconcentration and determination of iron (as its
bathophenanthroline complex) and copper (as its neocuproine complex) using octadecyl silica cartridges and dual wavelength
spectrophotometry is presented. The dual wavelength method (533 nm for the iron-bathophenanthroline and 454 nm for the copper-neocuproine
as the analytical wavelength) is used to eliminate spectral interferences. Extraction efficiency and the influence of flow
rates of sample solution and eluent, pH, amount of neocuproine, bathophenanthroline and hydroxylamine hydrochloride, type
and least amount of eluent for elution of iron and copper complexes from cartridge, break-through volume and limit of detection
are evaluated. The effects of various cationic and anionic interferences on percent recovery of iron and copper are also studied.
Extraction efficiencies >95% are obtained by elution of cartridges with minimal amount of organic solvent. Iron and copper
were determined in the range of 3–100 ng mL−1. The limits of detection are 0.98 and 1.13 ng mL−1 for iron and copper, respectively. The proposed method is applied successfully to the determination of both analytes in river,
tap and well water samples.
Author for correspondence. E-mail: yyamini@modares.ac.ir
Received September 18, 2002; accepted December 12, 2002
Published online May 5, 2003 相似文献
108.
Kojima Kunihiko Miyazaki Mitsuharu Mizukami Fujio Maeda Kazuyuki 《Journal of Sol-Gel Science and Technology》1997,8(1-3):77-81
The structure of iron oxide was controlled by regulating the hydrolytic polymerization of aquo iron complexes with organic
polydentate ligands such as diols. Iron oxides were prepared by calcining the precursor polymers obtained from iron nitrate
nonahydrate and diols. When the diols were 1,2-pentanediol, 1,2-hexanediol and 1,2-octanediol, α-Fe2O3 with corundum structure appeared exclusively or as the main crystalline phase, in spite of the amount of diol used and the
calcination temperature. In the case of 1,2-decanediol and 1,2-dodecanediol, when five moles of the diols were used to one
mole of iron nitrate and the calcination temperatures were below 400°C, ψ-Fe2O3 with spinel structure appeared as the main phase and, when less than five moles of the diols were used, α-Fe2O3 appeared exclusively or as the main phase, irrespective of the calcination temperature. This tendency was also observed in
thin films. Thus, a transparent magnetic film composed of γ-Fe2O3 could be prepared by applying a benzene solution of the iron polymer, obtained with 5 equivalents of 1,2-decanediol, on quartz
and calcining the gel film at 350°C. 相似文献
109.
Complex systems of paramagnetic centres existing in demineralised flame coal (71.4 wt% C), medium-rank coal (85.6 wt% C) and
anthracite (94.9 wt% C) were analysed by electron paramagnetic resonance spectroscopy (EPR). Different groups of paramagnetic
centres were searched in macerals (exinite, vitrinite, inertinite) of coals with carbon contents of 73.8 wt% C and 85.6 wt%
C. Experimental EPR spectra were fitted by different superposition of theoretical lines. Total concentration of paramagnetic
centres both in coal and macerals increases with carbon content in the sample. Total concentration of paramagnetic centres
in macerals increases from exinite to inertinite. Four groups of paramagnetic centres were found in medium-rank coal, and
only two groups exist in flame coal and anthracite. The EPR spectrum of medium-rank coal is a superposition of two broad and
two narrow lines. Both broad and narrow, and two narrow lines were measured in EPR spectra of flame coal and anthracite, respectively.
Two types of paramagnetic centres with broad lines and one group with narrow lines exist in exinite and vitrinite from medium-rank
coal. Two narrow components were observed in EPR spectra of its inertinite. Two different broad electron paramagnetic resonance
signals were detected for macerals from low-coalificated coal. Paramagnetic centres systems of medium-rank coal samples reveal
the most complex character. Broad EPR lines were not observed for the higher coalificated samples, i.e., anthracite and inertinite
from medium-rank coal. Narrow lines do not occur in EPR spectra of low-coalificated macerals. Strong dipolar interactions
and fast spin-lattice relaxation processes are characteristic for paramagnetic centres with broad lines. Strong exchange interactions
and short spin-lattice relaxation time were measured for paramagnetic centres with the narrowest EPR signals. 相似文献
110.
Summary Thermomagnetometry has been applied to mineralized archaeological iron samples and samples from accelerated corrosion tests. It has successfully quantified the degree of corrosion, measured by the loss of iron, as well as the amount of magnetite formed and water held in the corrosion and adhered soil layers. Thermomagnetometry, thermogravimetric analysis and differential scanning calorimetry have been applied to the reported corrosion products from archaeological iron. Fourier transform infra-red and Raman spectroscopies and X-ray diffraction analyses were undertaken on the residues and at intermediate heating stages, where the thermal analyses indicated, to identify the reaction products. 相似文献