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51.
Charged polypeptides containing sulfonate groups were prepared by transesterification of poly(γ‐methyl L ‐glutamate) with isethionic acid. The coil–helix transition of the sulfonated polypeptides was investigated in aqueous alcohols. Marked counter‐ion specificity was observed for helix formation: Li+ < Na+ < Cs+ ≦ Rb+ ≦ K+; this was different to that for poly(L ‐glutamate) (PLG): Cs+ ? K+ < Li+ < Na+. Specific helix stabilization by counter‐ion mixing, which has been found for the PLG system, was not observed for the sulfonated polypeptides. The counter‐ion‐ and solvent‐specific helix formation is discussed and compared with that in PLG. © 2001 Society of Chemical Industry 相似文献
52.
Houran Shafiee Shotaro Beppu Shuhei Iwasaki Akihiro Tagaya Yasuhiro Koike 《Polymer Engineering and Science》2015,55(6):1330-1338
The intrinsic birefringence Δn0 and photoelastic coefficient C of poly(methyl methacrylate), poly(2,2,2‐trifluroethyl methacrylate), poly(phenyl methacrylate), and poly(2,2,3,3,3‐pentafluorophenyl methacrylate) were determined. We categorized these methacrylate polymers into four birefringence‐types, even though their molecular structures differed only by the substituents on the side chains. Based on the results of Δn0 and C, novel polymers that exhibit neither orientational nor photoelastic birefringence, i.e., zero–zero‐birefringence polymers, were designed and synthesized by quaternary copolymerization system. Furthermore, we confirmed that the mechanisms of orientational birefringence and photoelastic birefringence generation were different in these methacrylate polymers. The conformation of the repeat unit of the polymers was nearly constant during the generation of orientational birefringence. In contrast, the conformation of the repeat unit of the polymers changed during the generation of photoelastic birefringence in the glassy state. These findings demonstrated the reasonability of evaluating orientational and photoelastic birefringence separately, as well as the adequacy of the classification of polymers into four birefringence‐types. Given these results and the fact that zero–zero‐birefringence polymers could be prepared successfully by four‐birefringence type monomers, we demonstrated the reasonability of the method for designing the zero–zero‐birefringence polymers. POLYM. ENG. SCI., 55:1330–1338, 2015. © 2015 Society of Plastics Engineers 相似文献
53.
Effects of Atmospheric Composition on the Molecular Structure of Synthesized Silicon Oxycarbides 下载免费PDF全文
Masaki Narisawa Fuji Funabiki Akihiro Iwase Fumihiro Wakai Hideo Hosono 《Journal of the American Ceramic Society》2015,98(10):3373-3380
The dependence of silicon oxycarbides' chemical composition and molecular structure on their reaction conditions was tested by varying the atmosphere under which pyrolysis was performed. To obtain the silicon oxycarbides, densely cross‐linked silicone resin particles with an averaged diameter of 2 μm were pyrolyzed in various atmospheres of H2, Ar, and CO2, in the temperature range 700°C–1100°C. The residual mass of resin after pyrolysis was almost constant at 700°C, although their apparent colors varied distinctly. The sample obtained from the H2 atmosphere was white, whereas that obtained from the CO2 atmosphere was dark brown. Fourier‐transform infrared (FT‐IR) spectra of the residues suggested that the Si–O–Si network evolution was accelerated in the CO2 atmosphere. Beyond 800°C, the chemical compositions of the compounds obtained from a H2 atmosphere increasingly approached near‐stoichiometric SiO2–xSiC composition with increasing the pyrolysis temperature. Compounds from a CO2 atmosphere approached a composition of SiO2–xC with no free SiC as the pyrolysis temperature increased. In the products from an Ar atmosphere, SiO2–xSiC–yC compositions were typically obtained. The observed effects of the pyrolysis atmosphere on the resulting chemical compositions were analyzed in terms of thermodynamic calculations. Electron spin resonance (ESR) spectra revealed broad and intense signals from products obtained from either Ar or CO2. Estimating from the signal intensity, the residual spin concentrations were in the range 1018–1019 g?1. Meanwhile, the spectra from the samples obtained in H2 showed weak and sharp signals with estimated spin concentrations ranging from 1016–1017 g?1. This signal attenuation may have been due to the hydrogen capping of dangling bond formed during pyrolysis. 相似文献
54.
Preparation of porous membranes by selective decomposition of adamantane unit in ABA‐type triblock copolymer 下载免费PDF全文
The mechanism of pore formation by selective decomposition of adamantane unit in an ABA‐type triblock copolymer derived from 4,4‐(hexafluoroisopropylidene)diphthalic anhydride‐2,3,5,6‐tetramethyl‐1,4‐phenylenediamine (6FDA‐TeMPD) and poly(2‐methyl‐2‐adamantylmethacrylate) (PMAdMA) was investigated on this basis. This study aims to developing a novel method of material design for high‐precision gas separation membranes and application to electric devices by improving dielectric constant. Scanning electron microscopy images showed that the membrane structure changed considerably after heating; the difference increased with the increase in adamantane content. Interestingly, the internal structure of Block(36 mol%6FDA‐TeMPD/64 mol%PMAdMA) membrane was almost unchanged although its surface structure was changed. These results suggest that the mechanism of formation of porous membrane involves the decomposition of adamantane unit from surface. In addition, more adamantane units inside the membrane were discharged to the surface of the membrane through a path formed by decomposed adamantane units. POLYM. ENG. SCI., 56:1191–1200, 2016. © 2016 Society of Plastics Engineers 相似文献
55.
Dr. Tomoya Hirano Dr. Takashi Fujiwara Dr. Hideaki Niwa Michitake Hirano Kasumi Ohira Yusuke Okazaki Shin Sato Dr. Takashi Umehara Dr. Yuki Maemoto Prof. Akihiro Ito Prof. Minoru Yoshida Prof. Hiroyuki Kagechika 《ChemMedChem》2018,13(15):1530-1540
The histone methyltransferase SET7/9 methylates not only histone but also non‐histone proteins as substrates, and therefore, SET7/9 inhibitors are considered candidates for the treatment of diseases. Previously, our group identified cyproheptadine, used clinically as a serotonin receptor antagonist and histamine receptor (H1) antagonist, as a novel scaffold of the SET7/9 inhibitor. In this work, we focused on dibenzosuberene as a substructure of cyproheptadine and synthesized derivatives with various functional groups. Among them, the compound bearing a 2‐hydroxy group showed the most potent activity. On the other hand, a 3‐hydroxy group or another hydrophilic functional group such as acetamide decreased the activity. Structural analysis clarified a rationale for the improved potency only by tightly restricted location and type of the hydrophilic group. In addition, a SET7/9 loop, which was only partially visible in the complex with cyproheptadine, became more clearly visible in the complex with 2‐hydroxycyproheptadine. These results are expected to be helpful for further structure‐based development of SET7/9 inhibitors. 相似文献
56.
Sun-Chan Jeong Ichiro Katayama Hirokane Kawakami Yutaka Watanabe Hironobu Ishiyama Nobuaki Imai Yoshikazu Hirayama Hiroari Miyatake Masao Sataka Satoru Okayasu Hiroyuki Sugai Shin-Ichi Ichikawa Katsuhisa Nishio Shinichi Mitsuoka Takamitsu Nakanoya Masahito Yahagi Takanori Hashimoto Kazunori Takada Mamoru Watanabe Tomoko Ishikawa Akihiro Iwase 《Journal of Phase Equilibria and Diffusion》2005,26(5):472-476
For the effective use of short-lived radioactive beams, soon to be available at the Tokai Radioactive Ion Accelerator Complex, the authors have developed a radiotracer method for diffusion studies in solids. The experimental test was performed by the measurement of the diffusion coefficients of Li in a sample of the compound βLiAl using an α-emitting radiotracer of 8Li (T1/2=0.84 s). It was found that the time-dependent yields of the α particles from the diffusing 8Li that was initially implanted in the sample could be used as a measure of the diffusivity of the tracer in a nondestructive way. The method was applied to measure the self-diffusion coefficients of Li in βLiGa, and for investigating how the Li diffusion in the Li ionic conductors is affected by the concentration of atomic defects (i.e., the existence of the atomic vacancies of Li and the defects in Ga sites that are replaced by Li). 相似文献
57.
High‐tension multiannealing (HTMA) was applied to improve the tensile properties of poly(p‐phenylene sulfide) fibers, which was furthermore applied to the fibers produced and improved with the zone‐drawing and zone‐annealing treatments. The HTMA treatment was repeatedly applied to the fibers under the conditions of a 250°C temperature and an applied tension of between 201.0 and 188.0 MPa. As a result, at the 13th treatment the degree of crystallinity increased to 40%. On the other hand, the orientation factor of crystallites increased dramatically to 0.982 during the zone‐drawing treatment, but increased only slightly during the subsequent treatments of zone annealing and HTMA. The finally obtained fiber had a tensile modulus of 10.4 GPa and a tensile strength of 0.73 GPa. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 1569–1576, 2000 相似文献
58.
In this study, we aimed to reduce the cure time, and to lower the cure temperature of the benzoxazine compound. Therefore, curing reaction of benzoxazine with bisoxazoline or epoxy resin using the latent curing agent and the properties of the cured resins were investigated. The cure behavior of benzoxazine with bisoxazoline or epoxy resin using the latent curing agent was monitored by differential scanning calorimetry and measurements for storage modulus (G′). The properties of the cured resin were estimated by mechanical properties, electrical insulation, water resistance, heat resistance, and flame resistance. As a result, it was confirmed that by using the latent curing agent, cure time of benzoxazine and bisoxazoline or epoxy resin was reduced, and cure temperature was lowered. And it was found that the curing reaction using phenol‐novolac based benzoxazine (Na) as the benzoxazine compound could proceed more rapidly than that using bisphenol‐A based benzoxazine (Ba) as the benzoxazine compound. However, the cured resins from Ba and bisoxazoline or epoxy resin using the latent curing agent showed good heat resistance, flame resistance, and mechanical properties compared with those from Na and bisoxazoline or epoxy resin using the latent curing agent. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009 相似文献
59.
Takehiko Sakamoto Hiroyuki Morishima Akihiro Yoshida Shuichi Naito 《Catalysis Letters》2009,131(3-4):419-424
Successively impregnated Pt–Mo/Al2O3 and Pt–Fe/Al2O3 catalysts exhibited large enhancement effect in H2 formation rate of liquid phase methanol reforming. Added Mo oxide forms monolayer on Al2O3 and facilitates the higher dispersion of Pt particles. In the case of Fe, formation of some surface bimetallic clusters between Pt and Fe was confirmed by XAS analysis, which causes the enhancement effect of H2 formation in MeOH–H2O reaction. 相似文献
60.
Akihiro Orita Shoko Tanabe Tatsuhiko Ono Junzo Otera 《Advanced Synthesis \u0026amp; Catalysis》2010,352(9):1419-1423
Fluorous distannoxanes (XRf2SnOSnRf2X)2⋅n H2O (Rf=C6F13C2H4) ( 1 : X=C8F17SO3, n=10; 4 : X=Cl, n=0) ( 1 ) catalyze the Mukaiyama aldol reaction and the allylation of aldehydes with tetraallyltin at room temperature in fluorous/organic biphasic solvent systems, in which the reactions proceed more rapidly than in a single organic or fluorous solvent. Due to the unique surface activity of 1 , the catalyst, organic substrate(s), and reagent(s) are distributed in both organic and fluorous phases to facilitate smooth reactions. Upon dilution with toluene after the reaction, the catalyst concentrates to the fluorous phase, while the organic substances migrate to the organic phase to effect facile catalyst recovery and recycling. By virtue of such a unique solvophilicity, a new version of fluorous biphase technology has been developed. 相似文献