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101.
Thermal oxidation of sulfur vulcanized polyisoprene samples was studied by gravimetry and IR mapping of carbonyl groups (to determine the oxidized layer thickness (TOL)) at temperatures ranging from 60 to 150 °C in air. Oxidation appears noticeably lower than that for the starting non-vulcanized polyisoprene, revealing a stabilizing effect of sulfur-containing species. After a short period where mass loss presumably due to water evaporation predominates, the sample mass increases until a plateau corresponding to 6.3% (at 60 °C) to 0.5% (at 140 °C) mass gain. Practically no weight gain (∼0.1%) was observed at 150 °C. The mass uptake is due to oxygen grafting to the chains. TOL varies from about 4.6 mm (70 °C) to about 1 mm (150 °C).A kinetic model, derived from a mechanistic scheme of radical chain oxidation including stabilizing events due to hydroperoxide reduction by sulfur-containing groups and taking into account the diffusion-reaction coupling, was established and numerically resolved. The model predictions for mass changes and TOL values are in good agreement with experimental data. 相似文献
102.
D. Gabunia O. Tsagareishvili L. Gabunia G. Darsavelidze 《Journal of solid state chemistry》2006,179(9):2944-2948
Real structure and some physicomechanical characteristics of the samples of natural beta-rhombohedral boron B as well as of its 10B and 11B monoisotopes have been studied. It was shown that the influence of 10B and 11B isotopes on physicomechanical properties of boron had a different character. In particular, the samples enriched with 11B had high values of microhardness, shear modulus (SM) and elastic limit if compared to those of boron, while the samples enriched with 10B monoisotopes were characterized with high values of thermal expansion coefficient (TEC) and thermal conductivity; lattice parameters a and c increased by the sequence: 11B, B, 10B. It was established that TEC, thermal conductivity, microhardness, SM and shear elastic limit increased in all samples at annealing for 5 h at 1500 °C regardless of isotope content. 相似文献
103.
Summary Clenbuterol has been determined in urine by solidphase extraction on a C18 cartridge, diazotization of the eluate with nitrite, coupling of the diazonium ion with 1-(naphthyl)ethylenediamine, and
separation of the azo dye formed by HPLC with a C18 column and a micellar mobile phase containing 0.1 M sodium dodecyl sulphate, 12%n-butanol and 0.05 M citrate buffer, pH 3. Recoveries higher than 90% were obtained by mixing the samples with a 20% 0.2 M
NaOH before extraction. Limits of detection of 51 and 6.7 ng L−1 were obtained with spectrophotometric and thermal lens spectrometric detection, respectively; respective repeatabilities
were 3.1% (5 μg mL−1) and 5.6% (0.16 μg mL−1). 相似文献
104.
Y.V. PatelP.H. Parsania 《European Polymer Journal》2002,38(9):1827-1835
Solution and solid-state properties of poly(R,R′,4,4′-cyclohexylidene diphenylene diphenyl-4,4′-disulfonate) (PS-6: R=R′=H; PS-7: R=CH3, R′=H; PS-8: R=R′=Cl; PS-9: R=CH3, R′=Cl and PS-10: R=R′=Br) have been determined and discussed in terms of nature of the substituents. Ultrasonic velocity (2 MHz) and acoustical parameters of PS-7 and PS-9 solutions in chloroform, 1,2-dichloroethane and tetrahydrofuran (THF) at 30, 35 and 40 °C have been evaluated to understand the effect of methyl and chlorine groups, concentration, and temperature on molecular interactions. The data are interpreted in light of solvent-polymer and polymer-polymer interactions. Predominant solvation is observed in THF system and the least in chloroform system at all three temperatures. The structural change is observed above 2%. Both the polymers possess structure-forming tendency and it is supported by positive values of Sn.The densities of PS-7 and PS-9 determined by floatation method are in excellent agreement with calculated values but those determined by specific volume method differ remarkably from calculated values due to solvation effect. PS-7 and PS-9 possess respectively tensile strength of 38.4 and 1.1 N/mm2; electric strength of 16.2 and 25.0 kV/mm and volume resistivity of 5.7×1016 and 1.0×1017Ωcm. The low tensile strength of PS-9 is due to low molecular weight, rigid and brittle nature of the polymer chains. PS-6 to PS-9 are thermally stable up to about 349-379 °C while PS-10 up to about 279 °C and involved two-step degradation. DTA thermograms indicated Tg at about 204-226 °C. High activation energy indicated rigid nature of the polymer chains and the positive magnitudes of ΔS* indicated less ordered transition state. The nature of the substituents (CH3, Cl and Br) affected thermal, mechanical and electrical properties. 相似文献
105.
Marián Kucharík František Šimko Vladimír Danielik Miroslav Boča Roman Vasiljev 《Monatshefte für Chemie / Chemical Monthly》2007,138(12):1211-1215
Summary. The phase diagram of the system Na3AlF6–NaVO3 was determined by means of thermal analysis. The system is a simple binary eutectic one. The eutectic point was estimated
at x(NaVO3) = 0.975 and t
eut = 617°C. The XRD patterns of samples after thermal analysis revealed the presence of cryolite and NaVO3 only supporting the above assumption of a simple eutectic binary system. 相似文献
106.
CuM(II)Al ternary hydrotalcites (M(II) = Ni, Co and Mg) with a (Cu+M(II))/Al atomic ratio of 3.0 and Cu/M(II) atomic ratio of 5.0 were synthesized by coprecipitation under low supersaturation. Powder X-ray diffraction of the as-synthesized samples showed a pattern characteristic of hydrotalcite-like (HT-like) structure (JCPDS: 41-1428). Thermal analyses of these samples showed four stages of weight loss/heat change when recorded in nitrogen. Analysis of the evolved gases characterized the nature of these transformations. The thermoanalytical effects differed significantly especially for the high-temperature transformations, when the treatment was performed in oxygen. In situ powder X-ray diffraction of the samples was carried out to elucidate the phase evolution of these compounds. Surprisingly formation of CuO was noted at temperatures around 200°C well below the destruction of the layered network. The nature of the resulting phases varied with both the nature of the co-bivalent metal ion and the heating atmosphere. FT-IR spectroscopy confirmed the retention of carbonate ions at higher temperatures (above 700°C), although the concentration of carbonate anion (most likely unidentate) varied with the calcination temperature. The crystallinity of CuO increased significantly above 600°C, probably through dissociation of copper oxycarbonate. Significant differences in the thermal transformation temperatures (for the third and the fourth transformations) of these samples containing different co-bivalent metal ions were not observed. This suggests that an association of the co-bivalent metal ions and/or trivalent metal ion in this phase is unlikely. A plausible thermal evolution scheme of these hydrotalcites is proposed. 相似文献
107.
B. Sourd P. André J. Aubreton M.-F. Elchinger 《Plasma Chemistry and Plasma Processing》2007,27(1):35-50
In this paper, calculated values of the viscosity and thermal conductivity of atomic nitrogen, taking into account three species
(the ground and two excited states), are presented. The calculations, which assume that the temperature dependent probability
of occupation of the states is given by the Boltzmann factor, are performed for atmospheric-pressure in the temperature range
from 1,000 to 20,000 K. Six collision integrals are used in calculating the transport coefficients and we have introduced
new averaged collision integrals where the weight associated at each interacting species pair is the probable collision frequency.
The influence of the collision integral values and energy transfer between two different species is studied. These results
are compared which those of published theoretical studies. 相似文献
108.
The thermal decarboxylation of three dicarboxylic perfluoropolyether potassium salts of relatively short chain length has been investigated and the products and kinetics of the main reactions have been defined. From the rate constants and Arrhenius parameters data, the second decarboxylation appears to be quantitatively rather close to the first. 相似文献
109.
Summary Thermal field-flow fractionation separates polymers with high selectivity according to their Soret coefficient,S
τ, hence, according to their molar mass, and therefore consitutes an efficeint physicochemical tool for the determination of
the Soret coefficient of a given polymer in the carrier liquid from its retention time. However, the polymer concentration
in the sample influences the retention time and, hence, the value ofS
τ derived from it. An experimental study of the influence of sample concentration on retention,S
τ, and peak shape was performed for the polystyrene-decalin system over a relatively large temperature domain and for various
molar masses.
It is found that the retention time and the value ofS
τ increase with increasing sample concentration, the more so as the cold wall temperature is lower. This appears to be in contradiction
with the general non-equilibrium thermodynamic expression derived for polymer-solvent systems with positive second virial
coefficients, such as the present system over the temperature range investigated. There seems to be a temperature for which
the dependence ofS
τ on sample concentration vanishes. This temperature is about 375 K for the polystyrene-decalin system. As the sample concentration
increases, the peak barycentre and the standard deviation increases. As the peaks are fronting, the skewness is negative and
becomes more negative as the sample concentration increases. The peak skewness appears to be a good indicator of the onset
of sample concentration effects. The threshold concentration, for which these effects begin to become significant, decreases
with increasing molar mass. 相似文献
110.