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941.
Yasunori Yoshida Takashi Nakano Hidetsugu Tanaka Terunori Fujita 《Israel journal of chemistry》2002,42(4):353-359
This contribution reports the catalytic behavior of bis(pyrrolide-imine)Ti complexes 1 and 2 , [2-(RNCH)-C4H3N]2TiCl2 ( 1 , R = Ph; 2 , R = cyclohexyl), and bis(phenoxy-imine)Ti complex 3 , [2-(Ph-NCH)-3-t Bu-C6H3O]2TiCl2 for the copolymerization of ethylene with propylene, 1-hexene, or norbornene. An inspection of the X-ray structures of complexes 1–3 suggested that complexes 1 and 2 with pyrrolide-imine ligands would provide more space for olefin polymerization than complex 3 with phenoxy-imine ligands. In addition, DFT calculations also showed that active species derived from complexes 1 and 2 possess higher electrophilicity of the Ti center compared to that from complex 3 . Complexes 1 and 2 on activation with methylalumoxane (MAO) had higher affinity for propylene and 1-hexene and incorporated higher amounts of propylene ( 1 ; 30.5 mol%, 2 ; 23.4 mol%) and 1-hexene ( 1 ; 1.9 mol%, 2 ; 1.7 mol%) than complex 3 (propylene; 4.5 mol%, 1-hexene; 0.4 mol%). The incorporation levels of propylene and 1-hexene displayed by complexes 1 and 2 were lower than those for Cp2TiCl2 (propylene; 41.6 mol%, 1-hexene; 5.1 mol%) under identical conditions. In contrast, complexes 1 and 2 exhibited higher incorporation ability for norbornene and produced copolymers with much higher norbornene contents ( 1 ; 32.0 mol%, 2 ; 26.5 mol%) than Cp2TiCl2 (1.2 mol%) under the same conditions. Additionally, complex 3 also promoted higher norbornene incorporation (4.3 mol%) than Cp2TiCl2 and provided a copolymer with extremely narrow molecular weight distribution (Mw/Mn 1.14). A correlation exists between electrophilicity of the Ti center in active species and norbornene incorporation. 相似文献
942.
Takashi Fujikawa Hiroshi Kimura Kazuyuki Kiriyama Kazuhiko Hagiwara 《Catalysis Today》2006,111(3-4):188-193
Cosmo Oil has successfully developed a new CoMo HDS catalyst, C-606A, for production of ultra-low sulfur diesel fuels. This catalyst was prepared by an impregnation method using a solution containing Co, Mo, P, and citric acid on a HY-Al2O3. The resulting catalyst air-dried only without calcination. The HDS activity was measured with straight-run light gas oil feedstocks under industrial hydrotreating conditions. C-606A had a three times higher HDS activity compared with the conventional CoMoP/Al2O3 catalyst. Commercial operation with C-606A has successfully demonstrated high performance. This catalyst has superior activity, which enables <10-ppm sulfur content in products in a commercial hydrotreater designed to produce 500-ppm sulfur diesel fuels. 相似文献
943.
The photocatalytic oxidation of CO into CO2 with oxidants such as NO, N2O and O2 proceeded efficiently on a Mo/SiO2 with high Mo dispersion under UV light irradiation. It was found that the reaction rate greatly depended on the kind and concentration of the oxidant. Photoluminescence investigations reveal the close relationship between the reaction rate and the relative concentration of the photo-excited Mo6+-oxide species, i.e. charge transfer–excited–triplet state (Mo5+–O−)*, under steady-state reaction conditions. Moreover, the photocatalytic oxidation of CO with O2 in excess H2 was carried out to test suitability for applications to supplying pure H2. This reaction was seen to proceed efficiently on Mo/SiO2 with a high CO conversion of 100% and CO selectivity of 99% after 180 min under UV light irradiation, showing higher photocatalytic performance than TiO2 (P-25) photocatalyst. UV–vis, XAFS, photoluminescence and FT-IR investigations revealed that the high reactivity of the charge transfer–excited–triplet state (Mo5+–O−)*, with CO as well as the high reactivity of the photoreduced Mo-oxide species (Mo4+-species) with O2 to produce the original Mo-oxide species (Mo6+O2−), played a crucial role in the reactions. 相似文献
944.
Reactive blending has been usually utilized to stabilize morphology and to improve the properties of multi-component polymer blends by generating copolymers in situ at the interface. However, the present study on blends composed of poly(butylene terephthalate) (PBT) and functionalized styrene-acrylonitrile random copolymer (SAN) demonstrates another possibility for this method, i.e. tailoring morphology and thereby controlling the properties of polymer blends. By varying reaction conditions it was demonstrated that blends could be formed having the same ratio of [PBT]/[SAN] but which possessed completely different microstructural forms: a sea-island morphology with and without micelles, a corded dispersed phase morphology, and a highly oriented, layer-like morphology. 相似文献
945.
Preparation and properties of poly(methylmethacrylate)-silica hybrid materials incorporating reactive silica nanoparticles 总被引:1,自引:0,他引:1
In this study, poly(methylmethacrylate) (PMMA)-based hybrid materials were prepared from reactive silica nanoparticles. These nanoparticles were obtained by the reaction of 2-(methacryloyloxy)ethyl isocyanate with colloidal silica dispersed in ethyl acetate, and they were copolymerized in various ratios with methyl methacrylate. Dynamic mechanical analysis (DMA), thermogravimetric analysis (TGA) and visible spectrometry were performed to evaluate the physical properties of the resulting hybrid materials. The PMMA-silica hybrid copolymers maintained high transparency, and their storage elastic modulus and surface hardness increased with increasing silica content. Moreover, in comparison with PMMA, the hybrid copolymers had greater heat resistance and lower volume contraction. 相似文献
946.
Hiroko Kosugi Takashi Kojima Kiyomi Kikugawa 《Journal of the American Oil Chemists' Society》1991,68(1):51-55
The thiobarbituric acid (TBA) reactivity of oxidized methyl linoleate, soybean oil, sesame oil, lard, chicken oil and sardine
oil was characterized by using four different methods with 0.01% butylated hydroxytoluene (BHT). Optimal pH for the reactivity
of most of the oxidized samples was 3–4, and that of some samples was above 5. Introduction of 2 mMt-butyl hydroperoxide (t-Bu00H) or 0.2 mM ferric ion in the reaction markedly enhanced the reactivity. Introduction of 0.2 mM ethylenediamine tetraacetic
acid suppressed the reactivity. The characteristics of the TBA-reactivity of the samples were similar to those of alkadienals
or alkenals. The most preferable method for the estimation of the TBA-reactive substances of the oxidized fats and oils was
that using solvents at pH 3.5 with introduction of BHT, andt-Bu00H or ferric ion. 相似文献
947.
Prevention of catalyst deactivation in carbon monoxide methanation on a highly active Ni-based composite catalyst has been investigated. The composite catalyst, Ni-La2O3-Ru supported on silica, has greater activity than that of a Ni catalyst, but the decrease of the catalyst activity with reaction time is greater than that of the Ni catalyst, especially when the CO conversion is low. The reason for this behaviour is found in the relation between the amount of surface-carbon species and the degree of deactivation. When the CO methanation reaction is operated at above the temperature of complete CO conversion, catalyst deactivation is avoided. At such high temperatures the amount of surface-carbon species is small. The catalyst deactivation is considerably suppressed with a low concentration, e.g. 1–3 kPa, of additional CO2 or CO2 + H2O. The cause of this suppression is considered to be the renewal of the covered surface with the carbon-species by the competitive adsorption of these additives. 相似文献
948.
Multiple melting behavior of poly(butylene-2,6-naphthalate) (PBN) was studied with X-ray analysis and differential scanning calorimetry (DSC). Double endothermic peaks L and H attributed to the α-form crystal modification, a small peak attributed to the β-form crystal modification, and a new shoulder peak S at a lower temperature of peak H appeared in the DSC melting curves. Wide-angle X-ray diffraction patterns of the samples isothermally crystallized at 200 and 220 °C were obtained at a heating rate of 1 K min−1, successively. In this heating process, change of crystal structure and increase of quantity of the β-form crystallites could not be observed up to the final melting. With increasing temperature, the diffraction intensity decreased gradually and then increased distinctly before a steep decrease due to the final melting. The X-ray analysis clearly proved the melt-recrystallization during heating. The β-form crystal modification was formed during slow heating process in the high temperature region. 相似文献
949.
Yomi?WatanabeEmail author Praphan?Pinsirodom Toshihiro?Nagao Takashi?Kobayashi Yutaka?Nishida Yoshiaki?Takagi Yuji?Shimada 《Journal of the American Oil Chemists' Society》2005,82(11):825-831
Acid oil is a by-product in the neutralization step of vegetable oil refining and is an alternative source of biodiesel fuel.
A model substrate of acid oil, which is composed of TAG and FFA, was used in experiments on the conversion to FAME by immobilized
Candida antarctica lipase. FFA in the mixture of TAG/FFA were efficiently esterified with methanol (MeOH), but the water generated by the esterification
significantly inhibited methanolysis of TAG. We thus attempted to convert a mixture of TAG/FFA to FAME by a two-step process
comprising methyl esterification of FFA and methanolysis of TAG by immobilized C. antarctica lipase. The first reaction was conducted at 30°C in a mixture of TAG/FFA (1∶1, wt/wt) and 10 wt% MeOH using 0.5 wt% immobilized
lipase, resulting in efficient esterification of FFA. The reaction mixture after 24 h was composed of 49.1 wt% TAG, 1.3 wt%
FFA, 49.1 wt% FAME, and negligible amounts of DAG and MAG (<0.5 wt%). The reaction mixture was then dehydrated and used as
a substrate for the second reaction, which was conducted at 30°C in a solution of the dehydrated mixture and 5.5 wt% MeOH
using 6 wt% immobilized lipase. The activity of the lipase increased gradually when the reaction was repeated by transferring
the enzyme to a fresh substrate mixture. The activity reached a maximum after 6 cycles, and the content of FAME achieved was
>98.5 wt% after a 24-h reaction. The immobilized lipase was very stable in the first-and second-step reactions and could be
used for >100 d without significant loss of activity. 相似文献
950.