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排序方式: 共有999条查询结果,搜索用时 93 毫秒
1.
Yuanyuan Chen Jian Peng Tian Sheng Ruixuan Qin Shuqi Dai Zaifa Shi Zichao Tang Laisen Wang Qinghua Zhang Bin Han Liping Sun Jun Xu Jian Weng 《Advanced functional materials》2021,31(42):2104246
Radicals are closely related to human life and health and have been widely used in biology, chemistry, functional materials, etc. However, the high reactivity, disorder, and short half-lives limit their wide applications. Therefore, it remains a great challenge to prepare stable and ordered radicals. Herein, radicals are prepared with protective umbrellas (diethylmethyleneamine, DEMA) that are integrated on the surface of 2D layered materials to isolate water and oxygen and enhance the stability of radicals. Taking 2D black phosphorus (BP) as an example: triethylamine reacts with dichloromethane to form quaternary ammonium salts with further Hoffmann elimination to produce DEMA radicals that could react with one electron of a lone pair electrons in P on the surface of BP to produce P radicals, which shows a prolonged half-life of 21 days at room temperature. First-principle calculations and electron paramagnetic resonance fitting confirm that the steric hindrance constructed by dense DEMA passivation layer acts as a protective umbrella and the 2D coupling of P radicals and other P atoms in 2D BP plane to enhance the stability and strong superexchange interaction of P radicals. Furthermore, it is a general strategy to produce stable radicals integrated on the 2D plane. 相似文献
2.
自由基是食品在发生氧化过程中形成的高度反应性中间体,针对食品体系中自由基的检测可以用来评价食品的氧化程度。电子自旋共振技术(Electron Spin Resonance,ESR)可以提供有用的结构信息使自由基被识别,ESR已成功检测不同食品中存在的自由基。本文介绍了ESR技术在不同食品体系中检测自由基的应用,分析了自旋捕获在ESR检测食品中自由基的效果,阐述了ESR检测技术在预测食品氧化稳定性方面发挥的作用。ESR技术可以为食品体系中自由基的跟踪、评定及食品氧化稳定性的预测提供理论依据。 相似文献
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Fei Xu Xiangli Shi Qingzhu Zhang Wenxing Wang 《International journal of molecular sciences》2015,16(8):18714-18731
The chlorothiophenoxy radicals (CTPRs) are key intermediate species in the formation of polychlorinated dibenzothiophenes/thianthrenes (PCDT/TAs). In this work, the formation of CTPRs from the complete series reactions of 19 chlorothiophenol (CTP) congeners with H and OH radicals were investigated theoretically by using the density functional theory (DFT) method. The profiles of the potential energy surface were constructed at the MPWB1K/6-311+G(3df,2p)//MPWB1K/6-31+G(d,p) level. The rate constants were evaluated by the canonical variational transition-state (CVT) theory with the small curvature tunneling (SCT) contribution at 600–1200 K. The present study indicates that the structural parameters, thermal data, and rate constants as well as the formation potential of CTPRs from CTPs are strongly dominated by the chlorine substitution at the ortho-position of CTPs. Comparison with the study of formation of chlorophenoxy radicals (CPRs) from chlorophenols (CPs) clearly shows that the thiophenoxyl-hydrogen abstraction from CTPs by H is more efficient than the phenoxyl-hydrogen abstraction from CPs by H, whereas the thiophenoxyl-hydrogen abstraction from CTPs by OH is less impactful than the phenoxyl-hydrogen abstraction from CPs by OH. Reactions of CTPs with H can occur more readily than that of CTPs with OH, which is opposite to the reactivity comparison of CPs with H and OH. 相似文献
5.
Shensong Wang Zheng Wu Jie Chen Jiangping Ma Jingshi Ying Shouchen Cui Shigang Yu Yongming Hu Jinhe Zhao Yanmin Jia 《Ceramics International》2019,45(9):11703-11708
In this work, the hydrothermally-synthesized sodium niobate nanowires were used to decompose Rhodamine B dye solution through the piezo-catalytic effect. With the sodium niobate catalyst, a high piezo-catalytic degradation ratio of ~80% was achieved under the excitation of vibration for the Rhodamine B dye solution (~5?mg/l). These active species in the catalytic process, hydroxyl radicals and superoxide radicals with the strong oxidation ability, were also observed, which confirmed the key role of piezoelectric effect for piezo-catalysis. The piezo-catalysis of sodium niobate nanowires provides a high-efficiency and reusable tool in application in depredating the dye wastewater. 相似文献
6.
在先进飞行器发动机中,吸热碳氢燃料在进入燃烧室之前会发生热裂解反应,生成未反应燃料和小分子裂解产物的混合物(称为裂解态燃料)。本工作研究了在1300~1800 K、0.1~3.0 MPa和当量比为1.0的条件下,不同的裂解转化率、裂解压力、点火压力和自由基对正癸烷裂解着火特性的影响。通过采用一种精确的组合机理,从理论上计算了流动反应器中3.0和5.0 MPa下正癸烷裂解组分,与文献中的实验结果吻合较好。结果表明,正癸烷在3 MPa和5 MPa下裂解的出口转化率分别为46.2%和58.8%,裂解产物分布一致,但乙烯的含量随着压力的升高明显的降低,而烷烃含量随着压力的增大而增加。尽管自由基总体含量很低,但在3 MPa条件下裂解产物中的自由基浓度依然高于5 MPa条件下。对于点火延迟时间的计算结果则表明,裂解态正癸烷的点火延迟时间随着转化率的增大而延长,且在5 MPa下随着转化率的变化更明显。相同转化率下,5 MPa下的裂解态正癸烷的点火延迟时间比3 MPa下更短。此外,与无自由基的裂解正癸烷相比,裂解正癸烷中自由基的存在可以加速着火过程,转化率小于40%时,着火延迟时间缩短15%以上。 相似文献
7.
目的:制备北沙参多糖及其铁配合物,对其理化性质、结构特征和生物活性进行研究。方法:采用水提醇沉法制备北沙参多糖,经三氯化铁共热合成得到多糖铁配合物,利用紫外-可见光谱、红外光谱、高效阴离子交换色谱、透射电镜、差热-热重联用热分析仪等对多糖及其铁配合物的理化性质和结构特征进行测定,并考察其清除羟自由基和对α-葡萄糖苷酶的抑制作用。结果:北沙参多糖的提取率为18.4%,是由葡萄糖和甘露糖组成,其物质的量比为1.00:4.25,制备得到的多糖铁配合物中铁离子质量分数为19.31%,是以聚合的β-FeOOH微核为核心,多糖在其表面配合形成的多糖铁(Fe~(3+))表面配合物。结果表明,北沙参多糖及其铁配合物均具有清除羟自由基和对α-葡萄糖苷酶的抑制作用,且经铁修饰后的多糖对羟自由基清除作用和对α-葡萄糖苷酶的抑制能力明显增强。结论:北沙参多糖经铁修饰后,对羟自由基清除作用和对α-葡萄糖苷酶的抑制能力均得到提高。 相似文献
8.
9.
The aim of this study was to evaluate the influence of chemical and physical processes at the resin-composite and composite-cement interface as a function of the resin composite's water exposure on the bond strength (BS) between these two components. The free-radical concentration was studied using electron paramagnetic resonance (EPR), while the chemical changes at the resin composite's surface were studied using attenuated total-reflection FTIR spectroscopy (ATR-FTIR). The free-radical concentration in the studied samples dropped to 10% in 24 h, indicating that prolonged BS values do not correlate with the free-radical concentration. An alternative bonding mechanism between the resin composite and the composite cement was proposed, based on the formation of an interpenetrating polymer network (IPN) layer at the interface. As proven using ATR-FTIR spectroscopy, changes occurred at the resin composite's surface as a consequence of water exposure, comprising the diffusion of water molecules into the resin composite. These changes reduced the diffusion rate of the composite cement's phosphorus-containing monomers into the resin composite, as shown by the linescan SEM-EDS analysis of phosphorus, thus reducing the thickness of the IPN layer at the interface and consequently reducing the BS between both components.This study reveals that the concentration of free radicals at the surface of the resin composite is only relevant immediately after the polymerisation to the bond strength between the resin composite and the composite cement. Therefore, an alternative explanation is given by applying the theory of the formation of a gradient IPN at the interface between the resin composite and the adhesive cement by changes in the rate of diffusion of the adhesive cement's monomers into the resin composite as a function of the resin composite's exposure to water. 相似文献
10.
The influence of different types of iron salts (i.e., ferrous or ferric cations with sulphate, nitrate or chloride anions) on the reaction between coarse thermomechanical pulp and acid hydrogen peroxide (Fenton chemistry) was studied when the initial pH was 3.2 and 5.3. Also, ferric ions chelated with EDTA or EDG at different molar ratios were compared with ferrous sulphate when the initial pH was extended from about 3 to 8. Different anions of ferric ion salt gave a similar catalytic effect. At an initial pH of 7–8, the ferric-EDTA catalyzed reaction resulted in similar or higher hydrogen peroxide consumption and more detectable hydroxyl radicals than the ferrous sulphate catalyzed reaction, but less reaction with the pulp was indicated. Between pH 5–8, using Fe-EDG as a catalyst gave higher hydrogen peroxide consumption and more detectable hydroxyl radicals than if using ferrous sulphate; however, the measured effect on the pulp was similar or less. 相似文献