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961.
Schwarz H 《Angewandte Chemie (International ed. in English)》2003,42(37):4442-4454
Gas-phase experiments provide information which, in conjunction with results from electronic structure calculations, help to unravel the critical role relativistic effects play in many areas of transition-metal chemistry. Examples include the thermochemical data of gold halides in different oxidation states, the fascinating structural properties of gold(I) complexes, the dramatic effects of ligands on the ionization energy of gold, or the binding in cationic metal-carbene complexes. Furthermore, in the context of methane functionalization, special emphasis is paid to the chemistry of cationic metal-carbene complexes, and at uncovering the mechanistic details of important carbon-heteroatom coupling reactions. It is the interplay of conducting experiments of "isolated" molecules under well-defined conditions with reliable electronic structure calculations that has considerably improved our understanding of the role relativistic effects play in the context of transition-metal chemistry, catalysis, and beyond. 相似文献
962.
963.
采用射频反应溅射法在玻璃衬底上制备Zn3N2薄膜,然后向真空室中通入纯氧气进行热氧化制备ZnO薄膜.利用X射线衍射、扫描电子显微镜、霍尔效应测量、透射光谱和光致发光光谱等表征技术,研究了氧化温度和氧化时间对ZnO薄膜的结晶质量、电学性质和光学性能的影响.研究结果显示,450℃下氧化2h后的样品中除含有ZnO外,还有Zn3N2成分,500℃下氧化2h可以制备出电阻率为0.7Ωcm,空穴载流子浓度为1017cm-3,空穴迁移率为0.9cm2/Vs的具有c轴择优取向的p型ZnO薄膜.此时的ZnO薄膜具有良好的光学特性,紫外可见光范围内透过率为85%,处于紫外区域的激子复合产生的发光峰很强,且半高宽较窄,而处于可见光部分来自于深能级发射的绿色发光峰很弱.这种工艺制备的ZnO薄膜质量较好,有利于实现在短波长光电器件方面的应用. 相似文献
964.
Hongyan Sun S.I. Yang G. Jomaas C.K. Law 《Proceedings of the Combustion Institute》2007,31(1):439-446
Laminar flame speeds were accurately measured for CO/H2/air and CO/H2/O2/helium mixtures at different equivalence ratios and mixing ratios by the constant-pressure spherical flame technique for pressures up to 40 atmospheres. A kinetic mechanism based on recently published reaction rate constants is presented to model these measured laminar flame speeds as well as a limited set of other experimental data. The reaction rate constant of CO + HO2 → CO2 + OH was determined to be k = 1.15 × 105T2.278 exp(−17.55 kcal/RT) cm3 mol−1 s−1 at 300-2500 K by ab initio calculations. The kinetic model accurately predicts our measured flame speeds and the non-premixed counterflow ignition temperatures determined in our previous study, as well as homogeneous system data from literature, such as concentration profiles from flow reactor and ignition delay time from shock tube experiments. 相似文献
965.
The aim of this work is to study the effects of duty ratio on the growth mechanism of the ceramic coatings on Ti-6Al-4V alloy prepared by pulsed single-polar MPO at 50 Hz in NaAlO2 solution. The phase composition of the coatings was studied by X-ray diffraction, and the morphology and the element distribution in the coating were examined through scanning electron microscopy and energy dispersive spectroscopy. The thickness of the coatings was measured by eddy current coating thickness gauge. The corrosion resistance of the coated samples was examined by linear sweep voltammetry technique in 3.5% NaCl solution. The changes of the duty ratio (D) of the anode process led to the changes of the mode of the spark discharge during the pulsed single-polar MPO process, which further influenced the structure and the morphology of the ceramic coatings. The coatings prepared at D = 10% were composed of a large amount of Al2TiO5 and a little γ-Al2O3 while the coatings prepared at D = 45% were mainly composed of α-Al2O3 and γ-Al2O3. The coating thickness and the roughness were both increased with the increasing D due to the formation of Al2O3. The formation of Al2TiO5 resulted from the spark discharge due to the breakdown of the oxide film, while the formation of Al2O3 resulted from the spark discharge due to the breakdown of the vapor envelope. The ceramic coatings improved the corrosion resistance of Ti-6Al-4V alloy. And the surface morphology and the coating thickness determined the corrosion resistance of the coated samples prepared at D = 45% was better than that of the coated samples prepared at D = 10%. 相似文献
966.
Improvement of corrosion properties of microarc oxidation coating on magnesium alloy by optimizing current density parameters 总被引:2,自引:0,他引:2
The microstructure, composition and corrosion performance of oxide coatings formed on AM60B alloy using microarc oxidation techniques at different waveforms of applied current densities were investigated within this study. It is found that the use of optimizing current density waveforms, i.e. decaying freely current density in the later stage and stepped decreasing current density, significantly improved the microstructure of oxide coatings compared with the constant current density mode, which are connected with changes in behaviors of spark discharges on the surface in oxidation process. The optimal waveform of current density is showed to be decaying freely current density in the later stage, which results in sealing the originally formed large micropores. The optimisation of the microstructure results in a significant improvement of the corrosion resistance of oxide coating. 相似文献
967.
Physicochemical, surface and catalytic properties of pure and doped CuO/Fe2O3 system were investigated using X-ray diffraction (XRD), energy dispersive X-ray analysis (EDX), nitrogen adsorption at −196 °C and CO-oxidation by O2 at 80-220 °C using a static method. The dopants were Li2O (2.5 mol%) and CoO (2.5 and 5 mol%). The results revealed that the increase in precalcination temperature from 400 to 600 °C and Li2O-doping of CuO/Fe2O3 system enhanced CuFe2O4 formation. However, heating both pure and doped solids at 600 °C did not lead to complete conversion of reacting oxides into CuFe2O4. The promotion effect of Li2O dopant was attributed to dissolution of some of dopant ions in the lattices of CuO and Fe2O3 with subsequent increase in the mobility of reacting cations. CoO-doping led also to the formation of mixed ferrite CoxCu1−xFe2O4. The doping process of the system investigated decreased to a large extent the crystallite size of unreacted portion of Fe2O3 in mixed solids calcined at 600 °C. This process led to a significant increase in the SBET of the treated solids. Doping CuO/Fe2O3 system with either Li2O or CoO, followed by calcination at 400 and 600 °C decreased its catalytic activity in CO-oxidation by O2. However, the activation energy of the catalyzed reaction was not much affected by doping. 相似文献
968.
This paper reports physical properties of porous silicon and oxidized porous silicon, manufactured by anodisation from heavily p-type doped silicon wafers as a function of experimental parameters. The growth rate and refractive index of the layers were studied at different applied current densities and glycerol concentrations in electrolyte. When the current density varied from 5 to 100 mA/cm2, the refractive index was between 1.2 and 2.4 which corresponded to a porosity range from 42 to 85%. After oxidation, the porosity decreased and was between 2 and 45% for a refractive index range from 1.22 to 1.46. The thermal processing also induced an increase in thickness which was dependent on the initial porosity. This increase in thickness was more important for the lowest porosities. Lastly, the roughness of the porous layer/silicon substrate interface was studied at different applied current densities and glycerol concentrations in solution. Roughness decreased when the current density or glycerol concentration increased. Moreover, roughness was also reduced by thermal oxidation. 相似文献
969.
CdS/TiO2/漂珠复合光催化剂制备及其降解高效氯氰菊酯研究 总被引:2,自引:0,他引:2
采用溶胶-凝胶-浸渍法制备了Cds/TiO2/漂珠复合光催化剂,通过SEM,XRD对其结构进行了表征.以高效氯氰菊酯(BEC)杀虫剂的光催化降解为模型反应,研究了CdS/TiO2/漂珠的光催化性能,探讨了影响催化剂活性的因素及采用太阳光作光源处理BEC的可行性.结果表明,CdS/TiO2/漂珠投加量为3 000mg·L-1,初始浓度为45 mg·L-1、初始pH为6.5,通气量为200 mL·min-1时间为60 min,BEC降解率分别为92.1%(125W高压汞灯)和79.3%(5 W紫外灯),采用太阳光照射300 min,BEC降解率可达93.4%.BEC的降解反应遵从L-H动力学模型,测得反应速率常数9.80 mg·(L·min)-1,吸附常数4.36×10-3 L·mg-1. 相似文献
970.
Influence of pretreatment methods on adsorption and catalytic characteristics of toluene over heterogeneous palladium based catalysts 总被引:1,自引:0,他引:1
The adsorption and catalytic characteristics of heterogeneous palladium based catalyst and its modified catalysts with gases (air and hydrogen) and acidic aqueous solution (HCl) were studied for evaluating the influence of pretreatment methods for toluene. The structural and energetic adsorption properties of the parent and pretreated catalysts were analyzed by means of nitrogen adsorption isotherms and gravimetric methods. The light-off curve and the XPS investigation were used for analyzing the catalytic activity and the surface state of palladium. It was clearly shown from the experimental results that hydrogen pretreated catalysts having metallic surface state exhibited the highest adsorption capacity and catalytic activity compared to that of parent and modified catalysts. The adsorption equilibrium data for toluene were obtained at three different temperatures and correlated successfully with the two-site Langmuir molecular isotherm model (L2m). It was also found that the palladium phase has more adsorption affinity for toluene molecules than the alumina support. The isosteric heat of adsorption calculated by using the Clausius-Clapeyron equation significantly changed with the coverage and the lateral interactions between the adsorbate-adsorbate molecules control the system. Furthermore, comparative analysis of the adsorption energy distribution revealed that the parent and its modified catalysts have different types of surface energetic heterogeneities. 相似文献