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1.
In this work, the kinetics and mechanism of free-radical polymerisation of glycidyl methacrylate (GMA) using potassium peroxydisulphate
(PDS) as water soluble initiator in the presence of synthesized 1, 4-Bis (tributyl methyl ammonium) benzene dichloride (TBMABDC)
as multi-site phase transfer catalyst (MPTC) was studied. The polymerisation reactions were carried out under inert and unstirred
conditions at constant temperature of 60 ± 1°C in cyclohexane/water biphase media. The role of concentrations of monomer,
initiator, catalyst and volume fraction of aqueous phase, solvent polarity and temperature on the rate of polymerisation (Rp)
was ascertained. The order with respect to monomer and initiator was found to be unity. The order with respect to catalyst
was found to be 0.51. The rate of polymerisation is independent of ionic strength and pH of the medium. However, an increase
in the polarity of solvent has slightly increased the Rp value. Based on the results obtained, a suitable kinetic scheme has
been proposed to account for the experimental observations and its significance discussed. 相似文献
2.
Alkyl radicals produced in the indirect reduction of alkyl halides or alkyldimethylsulfonium salts by electrochemically generated aromatic radical anions couple fast with the latter and alkylated or dialkylated dihydro compounds are formed. Rate constants measured for the coupling reaction between on one hand methyl, primary, secondary and tertiary alkyl radicals as well as benzyl and cumyl radicals and on the other hand a wide spectrum of electrochemically generated aromatic radical anions are found to be about 1×109 M−1 s−1. Previous measurements of coupling rate constants for primary alkyl radicals have been re-evaluated since they were affected by the presence of an SN2 reaction occurring between the alkyl halides used as radical precursors and the aromatic radical anions. New experiments are also included using alkyldimethylsulfonium salts as precursors in order to prevent such SN2 artefacts. It is concluded that sterical hindrance does not play a significant role for the radical-radical anion coupling reactions. In general the rate constants for the coupling reactions are all close to 109 M−1 s−1. 相似文献
3.
4.
The process of ozonation of glyoxal in aqueous solution has been studied by following its chemical and kinetic evolution. Results show that the oxidative process leads to formation of carboxylic functions and carbon dioxide according to a constant selectivity ratio at varying conversion degree.. Comparison between the oxygen amounts of reaction products and the corresponding ozone consumptions reveals that molecular oxygen takes part in the reaction process. System behavior is explained on the basis of radical reaction mechanism. 相似文献
5.
A novel two-stage fluidised-bed/fixed-bed reactor was designed to investigate the effects of volatile-char interactions on the volatilisation of alkali and alkaline earth metallic (AAEM) species during the pyrolysis of Victorian brown coal at 900 °C. With the two-stage reactor configuration, the AAEM-free volatiles generated from the pyrolysis of the H-form coal in the fluidised bed came into direct contact with the char from NaCl-loaded or Na-form coals in the fixed bed. The results indicated that the interactions between the volatiles, especially free radicals in the volatiles, and the char particles enhanced the volatilisation of Na from the char drastically. However, such radical-char interactions resulted in little volatilisation of Mg and Ca, indicating the importance of valence of the AAEM species. The degree of the volatile-char interactions was also related to the ageing of the char and the chemical form of AAEM species in the coal substrate. The volatiles interacted more strongly with the nascent char than the aged char, indicating that the AAEM species existed in the aged char in more stable forms than in the nascent char. 相似文献
6.
Copolymers of 1,1-diphenylethylene (DPE) behave in a very special way in radical polymerization. Particularly, the behavior of MMA-DPE copolymers in radical polymerization is investigated. The results reveal that the semiquinoid structure of the precursor polymer identified in a previous contribution is activated by the attack of free radicals and thus, in a second stage polymerization with a second monomer, block copolymers are formed. The block copolymer yield depends strongly on the ratio between the amount of DPE-containing precursor polymer and the initiator and monomer concentration used in the second stage. The mechanism proposed is able to explain at least qualitatively all experimental results including the restriction of this mode of control of radical polymerization to the formation of diblock copolymers only. 相似文献
7.
The contribution of ozone and hydroxyl radical to the formation of bromate ion was investigated in a continuous flow reactor. Experiments were conducted under a wide range of ozone dose (0.7 ~ 3.8 mgL), pH (6.5 ~ 8.5), and t-butanol concentration (0 ~ 0.5 mM). The formation of bromate ion was found to depend on radical reaction pathway, because the amount of bromate ion formed increased with pH and decreased with t-butanol, a radical scavenger, even when dissolved ozone concentrations were almost the same. In fact, the amount of bromate ion formed was reduced by 90% in the presence of t-butanol. Furthermore, the formation of bromate ion occurred even when dissolved ozone was not significantly detected in the presence of organic matter (TOC of 1 mgCL). The second-order reaction rate constant of hydroxyl radical with bromide ion, k HO,Br? of 1.7 × 109 (M?1s?1), was obtained on the assumption that the reactions of bromide ion and t-butanol with hydroxyl radical were competitive with each other in the presence of t-butanol and that the formation of bromate ion depended on the reaction of bromide ion with hydroxyl radical. Therefore, it is concluded that the reaction of bromide ion with hydroxyl radical dominated in the overall reaction from bromide ion to bromate ion in the continuous flow reactor. 相似文献
8.
9.
J. Rafael Sendra 《Journal of Symbolic Computation》2011,46(9):1030-1038
We present algorithms for parametrizing by radicals an irreducible curve, not necessarily plane, when the genus is less than or equal to 4 and the curve is defined over an algebraically closed field of characteristic zero. In addition, we also present an algorithm for parametrizing by radicals any irreducible plane curve of degree d having at least a point of multiplicity d−r, with 1≤r≤4 and, as a consequence, every irreducible plane curve of degree d≤5 and every irreducible singular plane curve of degree 6. 相似文献
10.