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71.
Sorption of methanol,dimethyl carbonate,methyl acetate,and acetone vapors in CTA and PTMSP: General findings from the GAB Analysis
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Ondřej Vopička Kryštof Pilnáček Petr Číhal Karel Friess 《Journal of Polymer Science.Polymer Physics》2016,54(5):561-569
Sorption of vapors of four organic compounds in two glassy polymers, cellulose triacetate (CTA) and poly[(trimethylsilyl)propyne] (PTMSP), has been reported and analyzed in terms of Guggenheim‐Anderson‐De Boer (GAB) model. These two structurally and physicochemically different glassy polymers both independently showed that one sorption site was formed by about three monomeric units. This finding held true for vapors of all characterized compounds; that is, for methanol, for its derivatives dimethyl carbonate and methyl acetate, and for acetone. The “rule of three” might thus also be applicable to other sorbates and glassy polymers. Further, an original modification of the GAB model for the sorption of alcohols in PTMSP was derived and successfully tested. Overall, the analyses of the sorption isotherms, heats of sorption and diffusion coefficients supported the view that the sorption of vapors in glassy polymers has adsorptive nature. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 561–569 相似文献
72.
Roman Svoboda Pavel Čičmanec Jiří Málek 《Journal of Thermal Analysis and Calorimetry》2013,114(1):285-293
The applicability of the Kissinger equation for the evaluation of apparent activation energy corresponding to glass transition kinetics is examined. Theoretically simulated data based on the generally accepted Tool–Narayanaswamy–Moynihan model were used to represent relevant cases of structural relaxation behavior. The values of the apparent activation energy determined by the Kissinger equation were, despite the linearity of the dependencies, in major disagreement with the original values of ?h * used for the simulation of the source data. Furthermore, a large dependence of the ?h Kis * evaluation (performed using the Kissinger equation) on the thermal history of the glass was found. The latter represents an unacceptable systematic error in the methodology, implying the incorrectness of the Kissinger equation usage for the evaluation of “glass transition activation energy”. This study addresses the currently widespread (incorrect) usage of the Kissinger equation for the above-mentioned purpose. 相似文献
73.
Determination of Sulfide by Hematoxylin Multiwalled Carbon Nanotubes Modified Carbon Paste Electrode
This study investigates a new approach for the amperometric determination of sulfide using a hematoxylin multiwalled carbon nanotubes modified carbon paste electrode (HM‐MWCNTs/CPE). The experimental results show that HM‐MWCNTs/CPE significantly enhances the electrocatalytic activity towards sulfide oxidation. Cyclic voltammetric studies show that the peak potential of sulfide shifted from +400 mV at unmodified CPE to +175 mV at HM‐MWCNTs/CPE. The currents obtained from amperometric measurements at optimum conditions were linearly correlated with the concentration of sulfide. The calibration curve was obtained for sulfide concentrations in the range of 0.5–150×10?6 mol L?1. The detection limit was found to be 0.2×10?6 mol L?1 for the amperometric method. The proposed method was successfully applied to a river water sample in Pardubice, Czech Republic. 相似文献
74.
O. Rosskopfová M. Galamboš L. Pivarčiová M. Čaplovičová P. Rajec 《Journal of Radioanalytical and Nuclear Chemistry》2013,295(1):459-465
The sorption of nickel on synthetic hydroxyapatite was investigated using a batch method and radiotracer technique. The hydroxyapatite samples used in experiments were a commercial hydroxyapatite and hydroxyapatite of high crystallinity with Ca/P ratio of 1.563 and 1.688, respectively, prepared by a wet precipitation process. The sorption of nickel on hydroxyapatite was pH independent ranging from 4.5 to 6.5 as a result of buffering properties of hydroxyapatite. The adsorption of nickel was rapid and the percentage of Ni sorption on both samples of hydroxyapatite was >98 % during the first 15–30 min of the contact time for initial Ni2+ concentration of 1 × 10?4 mol dm?3. The experimental data for sorption of nickel have been interpreted in the term of Langmuir isotherm and the value of maximum sorption capacity of nickel on a commercial hydroxyapatite and hydroxyapatite prepared by wet precipitation process was calculated to be 0.184 and 0.247 mmol g?1, respectively. The sorption of Ni2+ ions was performed by ion-exchange with Ca2+ cations on the crystal surface of hydroxyapatite under experimental conditions. The competition effect of Co2+ and Fe2+ towards Ni2+ sorption was stronger than that of Ca2+ ions. NH4 + ions have no apparent effect on nickel sorption. 相似文献
75.
Kateřina Černovská Bedřich Košata Vladimíra Novotná Milada Glogarová 《Liquid crystals》2013,40(9):987-996
Several series of new benzofused thieno[3,2‐b]furan‐ and thieno[3,2‐b]thiophene‐based derivatives have been synthesized and their mesomorphic properties investigated. All the studied compounds exhibit a SmC* phase with very wide temperature interval. Additionally, some types of the compounds show the cholesteric, SmA or blue phase. In the ferroelectric SmC* phase we evaluated physical properties of relevance for possible applications. 相似文献
76.
Katarína Hroboňová Andrea Spevak Ľubica Spišská Jozef Lehotay Jozef Čižmárik 《Chemical Papers》2013,67(5):477-483
The molecularly imprinted polymers (MIPs) were synthesised and the influence of the type of porogen, the nature of sample solvent, and the binding capacity of material were tested by high-performance liquid chromatography (HPLC). Umbelliferone was used as the template for imprint formation. Methacrylic acid was used as the monomer and acetonitrile, ethanol, and chloroform as porogen. Non-imprinted polymers (NIPs) were prepared by the same procedure. The highest value of the specific binding capacity (269 μg of umbelliferone per 100 mg of polymer) was obtained for polymers prepared in chloroform as porogen and methanol/water (φ r = 1: 1) as the sample solvent. The group-selective MIP was used as sorbent for the SPE pre-treatment of umbelliferone from plant extracts prior to HPLC analysis. Analysis of the spiked samples showed good recoveries (> 77 %). The limit of detection, limit of determination, and repeatability of the method were also calculated. 相似文献
77.
The adsorption of CO and NO over VO x -SBA-15 mesoporous materials with different vanadium content was investigated by FT-IR spectroscopy. Vanadium complexes were reduced in situ by hydrogen atmosphere at 450 °C for 3 h. Spectra of reduced samples show increasing in intensity of silanol groups, caused by dissociation of V–O(Si) bonds and formation of new H–O(Si) bonds. Reduction occurs with formation of water. The band corresponds to overtone of V=O stretching modes decreases in intensity because of oxygen withdrawing from V=O species. Presence of V4+ and V3+ species was observed. Inspection of CO adsorbed IR spectra evidenced existence at least two different type of V3+–CO complexes on the silica surface differing in both stretching frequencies and complex stabilities. We did not found principal difference between spectra of absorbed CO at ?196 °C on the samples with different concentration of vanadium, probably because of relative low degree of reduction. As well as heterogeneity of surface V3+ and V4+ species was evidenced by adsorption of NO. Both V3+ and V4+ ions possess two effective coordinative vacancies and as a result can adsorb two NO molecules forming dinitrosyls. A part of V3+ cations forms only mononitrosyls characterize by band at 1724 cm?1. Results obtained after NO adsorption reveal existence of three different kinds of vanadium species. Probably two of them are isolated and associated vanadium sites. The third type of vanadium has different surrounding than other two types. It was demonstrated that NO is a better probe than CO for testing the oxidation and coordination state of reduced vanadium species. 相似文献
78.
Nature and population of Li+ cationic sites in MCM-22 zeolite and its pillared form (MCM-36) were investigated by means of adsorption of CO as a probe molecule. CO stretching frequency and adsorption heat were measured by FTIR spectroscopy and adsorption microcalorimetry. Intrazeolitic carbonyl complexes on Li+ cations in MCM-22 and MCM-36 are characterized by two main vibrational bands at 2,195 and 2,188 cm?1. Band at higher wavenumbers is ascribed to carbonyls on Li+ ions coordinated only to two oxygen atoms at the intersection of 10-ring channels and interacting with CO molecule by energy around 45 kJ mol?1. Band at 2,188 cm?1 was assigned to the carbonyls on Li+ cations located on top of 5 or 6-rings on the channel walls and coordinated to three or four oxygen atoms, interacting with CO molecule by energy 33–36 kJ mol?1. Effect of pillaring and layered form of zeolite on nature and population of Li+ cationic sites is also discussed, as well as the formation of dicarbonyl complexes. 相似文献
79.
In this paper we report the first chemoselective asymmetric hydrogenation of (1-bromo-1-alkenyl)boronic esters, which constitutes a new route to (α-bromoalkyl)boronic esters. The study demonstrates that excellent chemoselectivities along with full conversions can be obtained for hydrogenation of alkyl substituted derivatives with iridium–PˆN complexes. Moreover, acyclic alkyl derivatives afford (α-bromoalkyl)boronic esters in good enantioselectivities ranging from 64 to 73% ee. A cyclic alkyl derivative was obtained only in a nearly racemic form. The (1-bromo-1-alkenyl)boronic esters appear to be less reactive towards homogenous hydrogenation conditions than their chloro analogues as demonstrated by the higher catalyst loadings required to achieve full conversions for alkyl derivatives and lower conversions observed for the aryl substituted derivatives. 相似文献
80.
Rosana M. Turtos Stefan Gundacker Marco T. Lucchini Lenka Procházková Václav Čuba Hana Burešová Jan Mrázek Martin Nikl Paul Lecoq Etiennette Auffray 《固体物理学:研究快报》2016,10(11):843-847
The implementation of nanocrystal‐based composite scintillators as a new generation of ultrafast particle detectors is explored using ZnO:Ga nanopowder. Samples are characterized with a spectral‐time resolved photon counting system and pulsed X‐rays, followed by coincidence time resolution (CTR) measurements under 511 keV gamma excitation. Results are comparable to CTR values obtained using bulk inorganic scintillators. Bringing the ZnO:Ga nanocrystal's timing performance to radiation detectors could pave the research path towards sub‐20 ps time resolution as shown in this contribution. However, an efficiency boost when placing nanopowders in a transparent host constitutes the main challenge in order to benefit from sub‐nanosecond recombination times. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim) 相似文献