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181.
In terms of the Avrami equation, the effects of selected organic pigments on the kinetic parameters of the isothermal crystallization of coloured polyamide 6 were examined in the temperature range 468–478 K. It was found that B Blue and BB Red are active nucleating agents, which is acribed to their crystalline structure. G Orange slightly accelerates the crystallization of PA 6 at lower temperatures and concentrations, whereas in other conditions its effect is the opposite.The isothermal data were confirmed by the results of non-isothermal crystallization. The degree of supercooling corresponding to the peak of the DSC curve was the measured feature in this case.It was found that B Blue and BB Red reduce the free energy of formation of criticalsize nuclei by 20 and 12%, respectively, which is reflected in the rates of crystallization.
This work was supported by the Polish Academy of Science, goal 01.14. 相似文献
Zusammenfassung Mit Hilfe der Avrami Gleichung wurde der Einfluß einiger ausgewählter organischer Pigmente auf die kinetischen Parameter der isothermen Kristallisation gefärbter Polyamide 6 im Temperaturbereich 468–478 K untersucht. B Blue und BB Red erwiesen sich als aktive Keimbilder, was mit Hilfe ihrer kristallinen Struktur erklärt werden kann. Bei niedrigeren Temperaturen und geringeren Konzentrationen wird die Kristallisation von PA 6 durch G Orange leicht beschleunigt, unter anderen Bedingungen kann das Gegenteil beobachtet werden. Die isothermen Daten wurden durch die Ergebnisse bei nichtisothermer Kristallisation bekräftigt. In diesem Falle wurde das dem DSC Peak entsprechende Maß an Unterkühlung untersucht. Es wurde gefunden, daß B Blue und BB Red die freie Energie zur Bildung von Keimen kritischer Größe um 20 bzw. 12% herabsetzen, was sich in den Kristallisationsgeschwindigkeiten widerspiegelt.
, -6 468–478 . , , . , . . . , , , 20 12%, .
This work was supported by the Polish Academy of Science, goal 01.14. 相似文献
182.
The kinetics of the oxidation of promazine and chlorpromazine by hexaimidazolcobalt(III) were studied in the presence of a
large excess of cobalt(III) and H+ ions using u.v.–vis. spectroscopy ([CoIII] = (1–6) × 10−3 m, [ptz] = (2.5–10) × 10−5 m, [H+] = 0.05–0.8 m, I = 1.0 m (H+, Na+, Cl−), T = 333–353 K, l = 1 cm). In each case, the reversible reaction leads to formation of cobalt(II) species and a stable cationic radical. A
linear dependence of the pseudo-first-order rate constant (kobs) on [CoIII] with a non-zero intercept was established for both phenothiazine derivatives. A marked difference in the observed reaction
rate for promazine and chlorpromazine is associated with the difference in its ability to undergo oxidation and is consistent
with a trend in the redox potential changes for these reductants. The activation parameters for reactions studied were determined.
Mechanistic consequences of all the results are discussed. 相似文献
183.
Piotr Król Bożena Król Stanisław Pikus Maciej Kozak 《Colloid and polymer science》2006,285(2):169-175
Small angle X-ray scattering and differential scanning calorimetry methods were employed to characterise the internal order of structural phases present in polyurethane coatings obtained as a result of water evaporation from anionomer dispersions. Those anionomers were produced in the reaction of aromatic, cycloaliphatic and aliphatic diisocyanates with polyoxyethylene glycol, 2,2-bis-(hydroxymethyl)propionic acid and 1,6-hexamethylenediamine. The decisive effects were found from ionic and polar structures within the rigid urethane and urea segments on the ordered arrangement degree of the supermolecular structures in the obtained anionomers. That becomes apparent in differential scanning calorimetry thermograms and contributes to improved thermal stability of the produced polyurethane coatings. 相似文献
184.
W. Kołos 《Chemical physics letters》1976,39(3):416-417
The interaction energy between two hydrogen atoms in the D and D′ 1Πu states of the hydrogen molecule has been calculated for large internuclear distances (12 ? R ? 25 bohr). The variational method and a very flexible trial wave-function were used. The results indicate that for the states under consideration the Rayleigh-Schrödinger perturbation theory with the multipole expansion of the interaction hamiltonian gives reliable results only for R > 25 bohr i.e. in the region where the interaction energies are practically negligible. 相似文献
185.
Renata Wietecha Paweł Kościelniak Teresa Lech Tomasz Kielar 《Mikrochimica acta》2005,149(1-2):137-144
This study describes a simple, rapid and reliable method for simultaneous determination of selenium and arsenic in human hair by means of atomic fluorescence spectrometry combined with a hydride generation technique (HG-AFS). The procedure developed encompasses microwave digestion of a sample in the nitric acid environment only. The interferences caused by nitrous oxides are eliminated by removing a gas from above the digested solution with a stream of argon. The sample is then chemically treated in a flow-through hydride generation system and exposed to measurements in a double-channel atomic fluorescence spectrometer. The method permits determining both analytes in the linear range of 0.5–100µgL–1 with a detection limit equal to 0.2µgL–1, as well as with very good repeatability not exceeding 1% for Se and 2% for As. No mutual interferences from either of the analytes in the concentrations ranges matching the hair composition were found. The method was verified in terms of accuracy with the use of a reference material and then applied to the analysis of the natural samples of human hair. 相似文献
186.
Hołyst R Staniszewski K Patkowski A Gapiński J 《The journal of physical chemistry. B》2005,109(18):8533-8537
We observed a very unusual kinetic pathway in a separating C(12)E(6)/PEG/H(2)O ternary mixture. We let the mixture separate above the spinodal temperature (cloud point temperature) for some time and next cool it into a metastable region of a phase diagram, characterized by two minima of the Gibbs potential, one corresponding to the homogeneous mixture and one to the fully separated PEG-rich and C(12)E(6)-rich phases. Despite the fact that in the metastable region the thermodynamic equilibrium corresponds to the separated phases (global minimum of the Gibbs free energy), we observe perfect mixing of the initially separated phase. The homogeneous state, obtained in this way, does not separate, if left undisturbed. However, many cooling-heating cycles or full separation with visible meniscus above the cloud point temperature induce the phase separation in the metastable region. The metastable region can exist tens of degrees below the cloud point temperature. This effect is not observed in the binary mixture of C(12)E(6)/H(2)O. 相似文献
187.
188.
Andrzej Maączyński Marian Góral Barbara Wiśniewska-Gocłowska Adam Skrzecz David Shaw 《Monatshefte für Chemie / Chemical Monthly》2003,134(5):633-653
Summary. The evaluation of mutual solubility data for systems water with n-alkanes, isoalkanes, and cycloalkanes along the three phase line is reported and a formula for the prediction of solubility
of alkanes in water is developed. Then a cubic equation of state with an added term, which accounts for hydrogen bonding is
used for correlation of liquid–liquid equilibrium data and for prediction of solubility of water in hydrocarbons using alkane
in water solubility data. Comparison of the predicted and experimental solubilities is performed using all accessible experimental
data. With this approach it is possible to predict the solubilities of water in alkanes with good accuracy over the temperature
range up to about 20 K below critical temperature. Solubility of alkanes in water can also be calculated using experimental
data for solubility of water in alkanes but results of these calculations are more sensitive to experimental errors of the
data.
Corresponding author: E-mail: macz@ichf.edu.pl
Received August 5, 2002; accepted (revised) September 13, 2002
Published online March 13, 2003
RID="a"
ID="a" Dedicated to Prof. Dr. H. Gamsj?ger on the occasion of his 70th birthday anniversary 相似文献
189.
A. Małecki A. Małecka R. Gajerski B. Prochowska-Klisch A. Podgórecka 《Journal of Thermal Analysis and Calorimetry》1988,34(1):203-209
The mechanism of thermal decomposition of Co(NO3)2 · 2H2O was found to involve stages in which Co(NO3)3 and Co2O3 · H2O are formed both of which decompose to Co3O4. During the process, the total cobalt enters the +3 oxidation state, which is consistent with the results reported by Mehandjiev [2].
Zusammenfassung Es wurde gefunden, daß der Zersetzungsmechanismus von Co(NO3)2 · 2H2O Schritte umfaßt, bei denen Co(NO3)3 sowie Co2O3 · H2O gebildet werden, beides weiterzerfallend zu Co3O4. Während des Vorganges erreicht das Gesamtkobalt die Oxidationsstufe +3, was mit Ergebnissen von Mehandjiev übereinstimmt [2].
, , CO3O4. , .相似文献
190.
Sławomir J. Grabowski Andrzej J. Sadlej W. Andrzej Sokalski Jerzy Leszczynski 《Chemical physics》2006
The F3CCl?FH and F3CCl?FCH3 dimers, which feature the halogen–halogen contacts, are investigated at MP2/6–311++G(d,p) and MP2/aug–cc–pVDZ levels of approximation. The binding energies of these complexes are found to be comparable to those of the weak hydrogen bonds. In both complexes the Cl?F are found to be significantly shorter than the sum of the corresponding van der Waals radii. The C–Cl?F contacts are also found to exhibit certain deviation from linearity. However, the energy differences between linear and bent structures are very small and primarily accounted for by electrostatic interactions between remote parts of the dimer. This indicates a high conformational flexibility of the halogen–halogen contacts and may help to explain the diversity of structural features in crystals formed by halogen-containing molecules. In both dimers the halogen–halogen interaction leads to certain shortening of the C–Cl electron accepting bond. This is accompanied by a small increase of the C–Cl stretching frequency. Hence, the two investigated dimers can possibly be classified as the blue-shifting halogen–halogen contacts. 相似文献