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Nickel has been found to be an effective cathode material and catalyst for reductive destruction of chlorinated solvents in contaminated water. This study investigated reductive dechlorination of carbon tetrachloride (CT) at a nickel rotating disk electrode using chronoamperometry and electrochemical impedance spectroscopy. Chronoamperometry experiments were performed to determine rates of CT reduction as a function of the electrode potential, pH, CT concentration, and temperature. The reaction products of CT dechlorination were 95 +/- 4% methane and 4.1 +/- 2.5% chloroform. Only trace levels of methylene chloride and chloromethane were produced, indicating that sequential hydrogenolysis was not the predominant pathway for methane production. Electrochemical impedance spectroscopy showed that the rate-limiting step for methane production was the transfer of the first electron to a physically adsorbed CT molecule. The temperature independence of the electron transfer coefficient and the decreasing activation energy with decreasing electrode potential indicated that the rate-limiting step involved an outer-sphere electron transfer. At neutral pH values, oxides inactivated much of the electrode surface for both CT reduction and hydrogen evolution. At lower pH values, oxide dissolution served to increase the electroactive surface area of the disk electrode. Anson analysis and kinetic modeling showed that CT adsorption to electroactive sites was a nonlinear function of the CT concentration and was in equilibrium with the bulk solution. CT dechlorination rates on nickel electrodes were 16 times slower than those on iron electrodes under similar conditions. However, CT reactions at nickel surfaces produced predominantly methane as the first detectable product, while reduction at iron surfaces produced chloroform. These results suggest that, although nickel is not a catalyst for the rate-limiting step for CT dechlorination, it may serve a catalytic role in subsequent reaction steps. 相似文献
64.
This research investigated an electrochemical method for inactivating contaminated stockpiles of the biocidal agent, triclosan. The goal of the electrolysis was to produce products that were amenable to treatment in conventional activated sludge treatment systems. Triclosan oxidation in electrochemical cells with boron doped diamond (BDD) film anodes was investigated in aqueous solutions at a pH value of 12. Chronoamperometry experiments showed that direct oxidation of triclosan occurred at potentials below those for H2O, Cl-, or OH- oxidation. Measurable rates of triclosan oxidation began at potentials above 0.4 V with respect to the standard hydrogen electrode (SHE), while potentials of 0.5, 1.3, and 1.8 V were required to obtain measurable oxidation rates of H2O, Cl-, and OH-, respectively. At anode potentials below 2 V, the dominant electrode reaction involved direct triclosan oxidation, while indirect oxidation was the dominant pathway at higher potentials. However, cyclic voltammetry experiments showed that direct oxidation of triclosan resulted in the formation of a passivating film on the electrode that could only be removed by oxidation at potentials above 3 V. Direct triclosan oxidation showed a very weak potential dependence, suggesting that its oxidation was limited by chemical dependent factors rather than by an outer-sphere electron transfer reaction. Organic triclosan oxidation products consisted primarily of chlorinated acetic acids and chlorinated phenolic compounds. Although the byproducts of triclosan oxidation became increasingly less reactive with increasing electrolysis time, triclosan could be completely oxidized to CO2 at current densities above 2 mA/cm2. Microtox testing indicated that residual triclosan accounted for nearly all the toxicity in the treated water, despite the fact that chlorinated byproduct concentrations were significantly higher than those of triclosan itself. 相似文献
65.
A 12-mo longitudinal study of 88 newly hired nurses and junior accountants (mean age of all Ss 24 yrs) tested a series of assumptions from the authors' (see record 1981-31481-001) investment model concerning the determinants of job satisfaction, job commitment, and turnover. In general, greater job satisfaction resulted from high job rewards and low job costs; whereas strong job commitment was produced by high rewards, low costs, poor alternative quality, and large investment size. Whereas the impact of job rewards on satisfaction and commitment remained relatively constant, job costs seemed to exert an increasingly powerful influence over time. Investment size also exerted greater impact on job commitment with the passage of time. Just prior to their leaving, the job commitment of Ss who left was best predicted by a combination of rewards, costs, and alternatives. Ss who stayed and those who left differed from one another with regard to changes over time in each investment model factor—those who left experienced greater decline in rewards, increase in costs, increase in alternative quality, and decrease in investment size than those who stayed. Turnover appeared to be mediated by a decline over time in degree of job commitment. (28 ref) (PsycINFO Database Record (c) 2010 APA, all rights reserved) 相似文献
66.
PJ Hofschire EP Todd RL Varco EL Kaplan JE Edwards 《Canadian Metallurgical Quarterly》1976,69(3):439-440
We report an unusual case in which an apparently normal upper lobe of the right lung was supplied by major systemic arterial and pulmonary arterial vessels. The anomalous artery arose from the descending aorta. Following interruption of this vessel, the machinery-like murmur previously present disappeared. 相似文献
67.
Circular dichroism and Fourier transform infrared spectroscopy of bovine alphaS2-casein both report a 24 to 32% content of alpha-helix. A consensus of sequence based predictions for alpha-helix suggests a Lys77-Gln91 helix within the sequence (Ser61-Arg125). This motif is repeated at (Ser143-Leu207), and this region contains a longer Thr145-Leu177 predicted alpha-helix. A short, seven-member alpha-helix may also organize the N-terminal peptide that precedes the first phosphoserine [-Srp-]3 cluster. As was found for other caseins studied by these spectroscopic methods, a high degree of extended beta-sheet (approximately 30%) and turns (25 to 30%) are predicted for alphaS2-casein. 相似文献
68.
This study uses social capital theory and social network analysis to explore how relations in an online academic communication network impact the overall structure of that network. Social network analysis is a particularly advantageous methodological tool for linking changes in microlevel choices to macrolevel structural alterations. Results indicate the online communication network’s structure exists independent of changes in communication ties. Specifically degree centrality, betweenness centrality, and clique formation indicated communication ties are initiated and discontinued over a 7-month timeframe. However, the dynamic nature of the microlevel communication choices does not mirror the quasi-stable structure of the online network. Results provide avenues for future research. 相似文献
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70.
K Rithidech VP Bond EP Cronkite MH Thompson JE Bullis 《Canadian Metallurgical Quarterly》1995,92(4):1152-1156
In an effort to identify the precise role of a deletion at regions D-E of mouse chromosome 2 [del2(D-E)] during the development of radiation-induced myeloid leukemia, we conducted a serial sacrifice study in which metaphase chromosomes were examined by the G-banding technique. Such metaphase cells were collected from x-irradiated mice during the period of transformation of some of the normal hematopoietic cells to the fully developed leukemic phenotype. A group of 250 CBA/Ca male mice (10-12 weeks old) were exposed to a single dose of 2 Gy of 250-kilovolt-peak x-rays; 42 age-matched male mice served as controls. Groups of randomly selected mice were sacrificed at 20 hr, 1 week, and then at intervals of 3 months up to 24 months after x-irradiation. Slides for cytogenetic, hematological, and histological examination were prepared for each animal at each sacrifice time. An expansion of cells with lesions on one copy of chromosome 2 was evident in 20-25% of treated mice at each sacrifice time. The majority of such lesions were translocations at 2F or 2H, strongly suggesting hypermutability of these sites on mouse chromosome 2. No lesions were found in control mice. The finding leads to the possibility that genomic lesions close to 2D and 2E are aberrants associated with radiation leukemogenesis, whereas a single clone of cells with a del2(D-E) may lead directly to overt leukemia. The data also indicate that leukemic transformation arises from the cumulative effects of multiple genetic events on chromosome 2, reinforcing the thesis that multiple steps of mutation occur in the pathogenesis of cancer. 相似文献