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141.
142.
The solid‐state polymerization (SSP) reaction kinetics of poly(ethylene terephthalate) were investigated in connection with the initial precursor intrinsic viscosity (IV; molecular weight). Evaluations were performed with otherwise equivalent precursors melt‐polymerized to IVs of 0.50, 0.56, and 0.64 dL/g. The changes in the molecular weight and other properties were monitored as functions of the reaction times at solid‐state temperatures of 160–230°C. Precursors with higher initial molecular weights exhibited higher rates of SSP than those with lower initial values, as discussed in connection with the levels of crystallinity and the carboxyl and hydroxyl end‐group composition. Activation energies decreased at temperatures above 200°C, and this indicated a change in the SSP reaction mechanism. At temperatures of 200–230°C, similar activation energies were required for the polymerization of all three precursors. Lower temperature polymerizations, from 160 to 200°C, required higher activation energies for all precursors, with the 0.50‐IV material requirement almost twice as high as that calculated for the higher IV precursors. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 197–212, 2003 相似文献
143.
I. Hama T. Okamoto E. Hidai K. Yamada 《Journal of the American Oil Chemists' Society》1997,74(1):19-24
For the purpose of estimating the reaction mechanism of the direct ethoxylation of a fatty ester in the presence of an Al-Mg
composite oxide catalyst, a labeled fatty methyl ester C11H23CO18OCH3 containing 18O isotope was synthesized and directly ethoxylated. The product was evaluated by gas chromatography-mass spectrometry (GC-MS).
The GC-MS spectra showed that the 18O isotope label was present only in the methoxy group at the molecular end of the ethoxylated fatty methyl ester. This supports
the reaction mechanism of coordination anionic polymerization where the bond between the acyl and methoxy groups of the fatty
methyl ester molecule was broken, caused by the bifunctional effect of the acid-base active sites; an intermediate chemisorption
species was formed; and then ethylene oxide was addition-polymerized sequentially, in parallel. 相似文献
144.
145.
Two different methods of producing bi‐ and trimodal latices of a mixture of methyl methacrylate, butyl acrylate, and small amounts of acrylic acid were tested. It is shown that a combination of concentrating blends of seed particles by semibatch reaction, followed by a nucleation of small particles plus a second semibatch phase allowed us to obtain stable latices with solids contents over 65% and viscosities of below 2500 mPa s?1 with little coagulum formation. The key parameter in determining latex stability, coagulum formation, and viscosity appears to be the the particle size distribution, and especially its modification attributed to secondary nucleation. Because it is not possible to eliminate water‐soluble monomers from the polymerization recipe, secondary (homogeneous) nucleation must be minimized by careful addition of the free‐radical initiator and choice of monomer feed flow rates. The nucleation of the third population in the trimodal latices is best accomplished with a mixed surfactant system because renucleation by anionic surfactant alone leads to detrimental changes in the particle size distribution (PSD) resulting from excessive flocculation of particles. In addition, it was found that the viscosity of the final products was not sensitive to small changes in the ionic strength of the latex, although neutralization to a pH of 6 effectively doubles the final latex viscosity. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1916–1934, 2002; DOI 10.1002/app.10513 相似文献
146.
原位聚合法研制纳米胶囊相变材料 总被引:2,自引:0,他引:2
采用超声波工艺及细乳液原位聚合方法,研制了以聚苯乙烯为囊壁、正十八烷为囊芯的纳米胶囊相变材料;系统探讨了聚合反应各因素如引发剂、链转移剂、表面活性剂以及正十八烷/苯乙烯比等对乳胶粒子的形态、胶囊材料热性能的影响,对所研制的胶囊相变材料进行激光衍射粒度分析、透射电镜及差示扫描量热等表征.实验结果表明,在引发剂AIBN 0.5%(油相质量百分比,下同);链转移荆DD在T0.4%;复合乳化剂(SDS/OP10)总量2%,配比1:1及正十八烷/苯乙烯比=1:1条件下,胶囊呈球形均匀分布,聚苯乙烯囊壁能将正十八烷囊芯很好包裹住,其胶囊Z均直径124nm,相变焓可达124.4kJ·kg-1. 相似文献
147.
Continuous emulsion polymerizations of vinyl acetate were conducted at 50°C in a single continuous Couette–Taylor vortex flow reactor (CCTVFR) using sodium lauryl sulfate as emulsifier and potassium persulfate as initiator. The polymerization can be carried out very smoothly and stably, but the steady‐state monomer conversion attained in a CCTVFR is not as high as that in a plug flow reactor (PFR), but only slightly higher than that in a continuous stirred tank reactor (CSTR), even if the Taylor number is adjusted to an optimum value. Also, the effects of operating variables, such as the emulsifier, initiator, and monomer concentrations in the feed and the mean residence time on the kinetic behaviors were almost the same as those observed in a CSTR. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2755–2762, 2002 相似文献
148.
本文用纤维素材料经酸分解制备具有平衡聚合度(LODP)的微晶纤维素,再分散成超细纤维素胶体(准均相纤维素体系)。用扫描电镜(SEM)观察处理前后的纤维素颗粒尺寸,并比较它们和丙烯酰胺接枝共聚的反应速率、聚合转化率、接枝率、接技效率、聚丙烯酰胺支链的分子量及其分布的情况。 相似文献
149.
Styrene/hexadecane miniemulsions were polymerized at 50°C using a redox initiator. The miniemulsions and their corresponding latexes were characterized in terms of size, polymerization rate, and surface properties. The resulting data were analyzed to elucidate the miniemulsion stabilization and polymerization mechanisms. It was found that the free surfactant concentration exceeded the critical micelle concentration when large amounts of surfactant (60 mM sodium lauryl sulfate) were used, resulting in simultaneous micellar and droplet nucleation. Most surfactant was on the surface of the droplets (85%) or particles (95%). The fractional surface coverage was proportional to the surfactant concentration to the 0.55 power. Using a particle diameter equation, the number of particles was calculated to be proportional to the surfactant concentration to the 1.35 power. Through direct particle size measurements, a power of 1.38 was confirmed. The rate of polymerization was determined by reaction calorimetry to be proportional to the number of particles to the 0.59 power, in contrast to classical Smith–Ewart kinetics for conventional emulsions (1.0 power). The average number of radicals per particle was estimated from the rate and number data, and varied with the particle diameter to the 0.97 power. The observed kinetic dependencies were validated through an extension of Smith–Ewart theory. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3987–3993, 2003 相似文献
150.
超薄聚合物表面上滴状冷凝的传热研究 总被引:2,自引:0,他引:2
本文采用等离子体聚合和离子束动态混合注入技术在不同的基材(黄铜、紫铜、不锈钢和碳钢)上制备了聚六氟丙烯和聚四氟乙烯的超薄膜,并进行了垂直管外的水蒸汽的滴状冷凝实验。实验发现,对于不同的基材,表面制备的工艺参数对冷凝传热性能及维持滴状冷凝的寿命具有显著的影响。表面性能的测试和估算为预测给定蒸汽在某表面是否成滴提供了依据。 相似文献