全文获取类型
收费全文 | 3933篇 |
免费 | 567篇 |
国内免费 | 610篇 |
专业分类
化学 | 3848篇 |
晶体学 | 135篇 |
力学 | 110篇 |
综合类 | 45篇 |
数学 | 7篇 |
物理学 | 965篇 |
出版年
2024年 | 3篇 |
2023年 | 51篇 |
2022年 | 76篇 |
2021年 | 127篇 |
2020年 | 171篇 |
2019年 | 167篇 |
2018年 | 139篇 |
2017年 | 173篇 |
2016年 | 225篇 |
2015年 | 190篇 |
2014年 | 217篇 |
2013年 | 366篇 |
2012年 | 278篇 |
2011年 | 222篇 |
2010年 | 210篇 |
2009年 | 222篇 |
2008年 | 233篇 |
2007年 | 249篇 |
2006年 | 231篇 |
2005年 | 241篇 |
2004年 | 207篇 |
2003年 | 173篇 |
2002年 | 166篇 |
2001年 | 99篇 |
2000年 | 83篇 |
1999年 | 72篇 |
1998年 | 80篇 |
1997年 | 84篇 |
1996年 | 72篇 |
1995年 | 44篇 |
1994年 | 39篇 |
1993年 | 37篇 |
1992年 | 34篇 |
1991年 | 27篇 |
1990年 | 16篇 |
1989年 | 16篇 |
1988年 | 20篇 |
1987年 | 11篇 |
1986年 | 6篇 |
1985年 | 2篇 |
1984年 | 3篇 |
1983年 | 1篇 |
1982年 | 4篇 |
1981年 | 3篇 |
1980年 | 6篇 |
1979年 | 4篇 |
1978年 | 5篇 |
1976年 | 2篇 |
1973年 | 2篇 |
1972年 | 1篇 |
排序方式: 共有5110条查询结果,搜索用时 15 毫秒
21.
The kinetics of noble metal nanoparticle formation in bottom-up syntheses are important for controlling and optimizing these methods. Hence, experimental probes that are easily accessible to most laboratories are also of interest. We collected kinetic curves for the formation of silver nanoparticles in a modified Turkevich method with citrate acting as the reducing and stabilizing agent by (i) measuring the change in silver nanoparticle surface plasmon resonance by UV-visible spectroscopy, a somewhat indirect method, and then also by (ii) measuring the change in silver ion concentration by ion-selective electrode potentiometry and/or atomic absorption spectroscopy, two more direct methods. The resulting sigmoidal kinetic curves were curvefitted with the Finke-Watzky two-step kinetic model of slow, continuous nucleation and fast autocatalytic growth to extract average rate constants. We found that the kinetic curves obtained by following the change in silver ion concentration were apparent mirror images of those constructed by following the change in nanoparticle surface plasmon resonance, and that their respective curvefits displayed the same sigmoidal characteristics. The resultant values of the rate constants for nucleation and growth overlapped within experimental error between the methods and showed similar trends over the range of citrate concentrations studied. The use of multiple probes in this work to follow the kinetics of nanoparticle formation helps fill a need for the comparison and evaluation of different methods available to scientists, particularly those considered easily accessible. 相似文献
22.
Diana Gonzalez Joseph T. Golab Andrew J. Cigler James A. Kaduk 《Acta Crystallographica. Section C, Structural Chemistry》2020,76(7):706-715
The crystal structures of a new polymorph of dipotassium hydrogen citrate, 2K+·HC6H5O72?, and potassium rubidium hydrogen citrate, K+·Rb+·HC6H5O72?, have been solved and refined using laboratory powder X‐ray diffraction and optimized using density functional techniques. In the new polymorph of the dipotassium salt, KO7 and KO8 coordination polyhedra share corners and edges to form a three‐dimensional framework with channels parallel to the a axis and [111]. The hydrophobic methylene groups face each other in the channels. The un‐ionized carboxylic acid group forms a strong charge‐assisted hydrogen bond to the central ionized carboxylate group. The hydroxy group forms an intermolecular hydrogen bond to a different central carboxylate group. In the potassium rubidium salt, the K+ and Rb+ cations are disordered over two sites, in approximately 0.72:0.28 and 0.28:0.72 ratios. KO8 and RbO9 coordination polyhedra share corners and edges to form a three‐dimensional framework with channels parallel to the a axis. The un‐ionized carboxylic acid group forms a strong charge‐assisted hydrogen bond to an ionized carboxylate group. The hydroxy group forms an intermolecular hydrogen bond to the central carboxylate group. Density functional theory (DFT) calculations on the ordered cation structures suggest that interchange of K+ and Rb+ at the two cation sites changes the energy insignificantly. 相似文献
23.
针对有机合成过程中碳及碳化物的残余,传统方法中普遍使用除碳的工艺,而很少有文章针对非晶碳的结构和形貌进行表征。为此,本文采用高尿素含量的前驱盐体系,通过在氮气保护气氛中煅烧获得AlN粉体。采用X射线衍射分析、红外和拉曼光谱分析、扫描电子显微镜和透射电子显微镜对850~1 500 ℃温度范围内煅烧获得产物的结构和形貌进行表征,对AlN合成过程中含碳产物结构形貌的变化,以及AlN和含碳产物之间相互的依存生长关系进行分析。结果表明,AlN生长的过程中伴随着无定形碳的石墨化转变,AlN颗粒的形貌也受含碳残余产物形貌的影响而出现有规律的变化。 相似文献
24.
Cover Picture: One‐Step Synthesis of Silver Nanoparticle‐Decorated Hydroxyapatite Nanowires for the Construction of Highly Flexible Free‐Standing Paper with High Antibacterial Activity (Chem. Eur. J. 32/2016) 下载免费PDF全文
25.
采用磁控溅射技术在聚甲基丙烯酸甲酯(PMMA)树脂基托表面沉积一层纳米银(Ag NPs)涂层.研究了纳米银改性PMMA树脂基托的机械性能,为改性材料的临床应用提供理论基础.根据国际标准ISO2409:2007描述的划格法对涂层与基底的附着力强度进行测试,各组试件的接触角采用静态液滴法测量,三点弯曲法检测试件的弯曲强度.结果显示,各组涂层与PMMA基底材料结合良好,各组试件的表面润湿性变化不大,其中PMMA-Ag NPs80s组疏水性略有提高,各组试件的弯曲强度均符合国家标准. 相似文献
26.
A novel method based on plastic processing and equipment for preparing ultra-fine metal fibers and particles is reported. With this new method, metal fibers and particles can both be produced on the same equipment and the surfaces of the fibers and particles can be protected from oxidation by the polymers or solvents during the preparation process. Metal-alloy powders with lower melt point were filled into polymer by an extruder, followed by a die-drawing process at a temperature lower than the melt temperature of the metal alloy. Metal fibers or particles were obtained after the polymer matrix was washed away. Metal alloy fibers can be obtained when a polymer that strongly interacts with metal alloy, such as a special polyvinyl alcohol with a low alcoholysis degree, is used as the polymer matrix. Metal-alloy particles can be obtained when a polymer with weak interaction with metal alloy, such as polyethylene (PE), is used as the polymer matrix. Based on the principle of this new method, it is possible to produce finer or even nano-sized metal fibers and particles with higher melting points. 相似文献
27.
Aleksandar Kremenovi Predrag Vuli 《Acta Crystallographica. Section C, Structural Chemistry》2014,70(3):256-259
The X‐ray powder diffraction pattern that corresponds to the disordered state of kalsilite (potassium aluminium orthosilicate), KAlSiO4, is investigated. The directionality of (Al,Si)O4 tetrahedra within single six‐membered tetrahedral ring building units (S6R) could not be defined. With equal probability for the directionality of each tetrahedra within one S6R [free apex pointing up (U) or down (D)], an undefined sequence of U and D directionalities is needed to describe the S6R building units. The extinction conditions of disordered kalsilite are also different compared to ordered kalsilite within the space group P63. In disordered kalsilite, h0l and hhl reflections with l = 2n + 1 are systematically absent. 相似文献
28.
29.
A neutron powder diffraction study on lithium titanate Li2TiO3 was performed at low temperatures. The monoclinic β-phase has been found to be stable over the whole investigated range of temperatures (4 K–300 K). A smooth and nonlinear increase of the lattice parameters has been observed upon heating and correlated to the behavior of interatomic distances. Lithium diffusion pathways in Li2TiO3 were estimated theoretically on the basis of the obtained structural data using bond-valence modeling. Experimentally diffusion pathways were evaluated by analysis of the negative nuclear scattering densities at 1073 K, which were reconstructed using a maximum entropy method. Although the bond-valence mismatch map indicated a possible Li diffusion either in ab plane or along c direction, analysis of the experimental data revealed that Li migration is thermodynamically less feasible in latter case. 相似文献
30.
Dr. Martin Schmidt Prof. Albert Masson Prof. Hai‐Ping Cheng Prof. Catherine Bréchignac 《Chemphyschem》2015,16(4):855-865
Adsorption and coadsorption studies on free silver clusters show that nitrogen physisorbs like rare gases, whereas oxygen chemisorbs with similarities and differences to bulk silver surfaces. Silver nanoparticles activate, or even dissociate adsorbed oxygen molecules. The global electron configurations of the adsorbent and adsorbate dominate the stability at small clusters. This is more important than geometry and site effects. Due to electronic shell effects and electron pairing, the activation of oxygen strongly varies with size. At more than 40 free electrons in the complex, such quantum effects start to blur. The size dependence becomes smoother and general trends govern the reactivity, which is driven by the interaction between the charge state of the nanoparticle and the charge transfer of the reaction. 相似文献