全文获取类型
收费全文 | 3347篇 |
免费 | 365篇 |
国内免费 | 662篇 |
专业分类
化学 | 3671篇 |
晶体学 | 38篇 |
力学 | 28篇 |
综合类 | 9篇 |
物理学 | 628篇 |
出版年
2024年 | 9篇 |
2023年 | 27篇 |
2022年 | 62篇 |
2021年 | 89篇 |
2020年 | 111篇 |
2019年 | 96篇 |
2018年 | 105篇 |
2017年 | 123篇 |
2016年 | 134篇 |
2015年 | 143篇 |
2014年 | 163篇 |
2013年 | 351篇 |
2012年 | 220篇 |
2011年 | 243篇 |
2010年 | 180篇 |
2009年 | 207篇 |
2008年 | 198篇 |
2007年 | 196篇 |
2006年 | 179篇 |
2005年 | 186篇 |
2004年 | 152篇 |
2003年 | 160篇 |
2002年 | 102篇 |
2001年 | 87篇 |
2000年 | 94篇 |
1999年 | 73篇 |
1998年 | 73篇 |
1997年 | 85篇 |
1996年 | 43篇 |
1995年 | 43篇 |
1994年 | 52篇 |
1993年 | 27篇 |
1992年 | 23篇 |
1991年 | 12篇 |
1990年 | 20篇 |
1989年 | 17篇 |
1988年 | 17篇 |
1987年 | 33篇 |
1986年 | 38篇 |
1985年 | 60篇 |
1984年 | 25篇 |
1983年 | 24篇 |
1982年 | 36篇 |
1981年 | 30篇 |
1980年 | 18篇 |
1979年 | 6篇 |
1978年 | 2篇 |
排序方式: 共有4374条查询结果,搜索用时 0 毫秒
91.
Hydrogen species in both SiO2 and Rh/SiO2 catalysts pretreated in different atmospheres (H2, O2, helium or air) at different temperatures (773 or 973 K) were investigated by means of 1H MAS NMR. In SiO2 and O2-pretreated catalysts, a series of downfield signals at -7.0, 3.8-4.0, 2.0 and 1.5-1.0 were detected. The first two signals can be attributed to strongly adsorbed and physisorbed water and the others to terminal silanol (SiOH) and SiOH under the screening of oxygen vacancies in SiO2 lattice, respectively. Besides the above signals, both upfield signal at -110 and downfield signals at 3.0 and 0.0 were also detected in H2-pretreated catalyst, respectively. The upfield signal at -110 originated from the dissociative adsorption of H2 over rhodium and was found to consist of both the contributions of reversible and irreversible hydrogen. There also probably existed another dissociatively adsorbed hydrogen over rhodium, which was known to be p hydrogen and in a unique form of "delocalized hydrogen". It wa 相似文献
92.
Mokoena Emma M. Datye Abhaya K. Coville Neil J. 《Journal of Sol-Gel Science and Technology》2003,28(3):307-317
DL-tartaric acid was used as a template for the formation of silica nanotubes and spheres by the sol-gel method from tetraethylorthosilicate (TEOS) as silica source. The reactions were carried out in ethanol/water mixtures in the presence of aqueous ammonia, between 0°C and 75°C, using both stirred and non-stirred conditions. TEM and SEM images show that the yield and microstructure of the silica is influenced by the synthetic conditions (temperature, ammonia (aq) concentration, gelation time, solvent mixture). It was observed that the chiral form of the tartaric acid used and the diffusion of TEOS to the template determines the eventual silica structure. 相似文献
93.
纳米银掺杂二氧化硅复合颗粒的制备及表征 总被引:2,自引:0,他引:2
0引言金属纳米颗粒因其粒子尺寸小(1 ̄100nm),比表面积大,表面原子数多,表面能和表面张力随粒径的下降急剧增大而具有量子尺寸效应[1]、小尺寸效应[2]、表面效应[3]及宏观量子隧道效应[4]等,从而出现了不同于常规固体的新奇特性,如:光学性质、磁性质以及电磁学性质[5],使其在催化、信息存储及非线性光学等领域展示了广阔的应用前景[6]。虽然制备金属纳米颗粒的方法有很多[6],但是由于纳米尺寸的金属颗粒具有较高的表面能,容易发生聚集,所以如何保持其稳定性依旧是比较困难的问题。随着纳米科技的发展,人们正尝试用各种方法来解决这个问题:如… 相似文献
94.
Summary The effect of silanol groups on three types of octadecylmodified column gels using heat-treated silicas by calcination has been studied by high-performance liquid chromatography. After heat-treating at 180°C, 500°C and 950°C, the silicas treated with octadecyldimethylchlorosilane were used for the measurement of physical and chemical analysis. From elemental carbon analysis data, the reactive silanol group concentrations, OH(s), were determined to be 2.0 in the 180°C treated silica, 2.1 in the 500°C treated silica and 1.6 in the 950°C treated silica, respectively (original silica: mean pore diameter 116 Å, specific surface area 298 m2/g, pore volume 1.22 ml/g, particle size 5.0 m). The separation factors, , of pyridine versus phenol were measured to be 0.79 on 180°C treated silica, 0.91 on 500°C treated silica and 1.98 on 950°C treated silica, using acetonitrile-water mixtures as the eluent. And then, on the basis of the physico-chemical and chromatographic data, the three types of octadecyl modified column gels using heat-treated silicas by calcination have been compared. 相似文献
95.
Pereira J.C.G. Catlow C.R.A. Price G.D. Almeida R.M. 《Journal of Sol-Gel Science and Technology》1997,8(1-3):55-58
Density Functional Theory is used to study water, methanol, ethanol, TMOS, and TEOS molecules and the most important silica
clusters participating in sol-gel processes. Calculated bond lengths, bond angles and electric dipole moments compare well
with experimental data. The energy of these molecules is reported and used to discuss the energetics of the hydrolysis and
condensation reactions. Molecular Dynamics is employed to simulate liquid water, methanol, ethanol, TMOS, TEOS and experimental
sol-gel solutions. Calculated densities and enthalpies of vaporisation compare well with experimental data. Preliminary results
are presented for MD simulations of sol-gel solutions. 相似文献
96.
4-Amino-3-hydroxy-2-(2-chlorobenzene)-azo-1-naphthalene sulfonic acid (AHCANSA) was used as a chelating modifier to improve the reactivity of the silica gel surface in terms of selective binding and extraction of heavy metal ions. The surface coverage values were found to be 0.488 and 0.473mmolg–1 for the newly modified physically adsorbed silica gel phase (I) and chemically immobilized-AHCANSA phase (II), respectively. The modified silica gel phases (I, II) were tested for stability in different acidic buffer solutions (pH 1–6) and found to be highly resistant to hydrolysis and leaching by buffer solutions above pH 2. The application of these two phases as solid extractors for a series of mono-, di-, and tri-valent metal ions from aqueous solutions was also performed with different controlling factors such as the pH value of metal ion solutions and equilibrium shaking time. The mmolg–1 metal capacity values determined by silica gel phases (I, II) were found to confirm high affinity and selectivity characters for binding with heavy metal ions such as Cr3+, Ni2+, Cu2+, Zn2+, Cd2+ and Pb2+ in a range of 0.250–0.483. The tested alkali and alkaline earth metals, Na+, K+, Mg2+ and Ca2+, were found to exhibit little interaction and binding ability with the modified silica gel phases. The selectivity characters incorporated into the modified silica gel phases were further utilized and applied in solid phase extraction and pre-concentration of trace concentration levels (1.0µgmL–1 and 2.00–2.50ngmL–1) from real seawater samples. The percentage recovery values determined for Cr3+, Cu2+, Zn2+, Cd2+ and Pb2+ were found to be in the range of 95.2–98.1±2.0–5.0%, and the pre-concentration recovery values for the same tested heavy metal ions were found to be in the range of 92.5–97.1±3.0–6.0% for the two newly modified silica gel phases with a pre-concentration factor of 500.Received December 20, 2002; accepted May 14, 2003
published online September 1, 2003 相似文献
97.
采用温和条件下的溶胶-凝胶技术,成功制备了阴离子交换-反相混合模式硅胶基质毛细管电色谱整体柱。通过调整反应液中不同前体的比例,优化了整体柱的制备条件。通过扫瞄电镜,对柱床进行了表征和分析。实验发现,所制备的整体柱电渗流的方向和大小可随流动相pH值的改变而改变,在酸性和中性条件下,具有从阴极流向阳极的电渗流;当流动相pH值升至约7.5时,电渗流方向发生了反转(由阳极流向阴极)。在优化的实验条件下,用所制备的整体柱对所考察的酸性(中性)化合物实现了快速分离,并获得了高达160,000N/m的柱效。 相似文献
98.
Jacob G. Reynolds 《Silicon Chemistry》2007,3(5):267-269
The Partial Charge Model was developed to predict the hydroxylation, polymerization, and precipitation of ions. The purpose
of this study is to evaluate the Partial Charge Model for describing the polymerization of silica in aqueous solutions. The
Partial Charge Model predicts the stability of ions and complexes based on the assumption that the stable species will have
the same electronegativity as the mean electronegativity of the solution. The silica system was chosen for model validation
because of the rare availability of self-consistent thermodynamic data on many dissolved but polymerized silicate anions,
including both linear and cyclical species. The electronegativity of each species was calculated using the Partial Charge
Model and the results were plotted against the stability constants for the ions. The silicate anions segregated into groups
on the plot based on the number of charges per silicon atom in the polymer. Plots of the log of the stability constant versus
the change in electronegativity produced a linear relationship for the silica polymers containing one negative charge per
silicon atom, which resulted in an r
2 of 0.9978. Thus, the Partial Charge Model successfully describes the thermodynamics of silica polymerization in aqueous solution
for species that are sufficiently alike, but was not accurate for all silica species. 相似文献
99.
The paper presents the results of testing
the thermal stability and flammability of butadiene-acrylonitrile rubber vulcanizates
with different contents of combined acrylonitrile: Perbunan NT 1845 and Perbunan
NT 3945 from Bayer, containing unmodified and bromine- or iodine-modified
silica. The test results were obtained with the use of a derivatograph, measurements
of flammability by the method of oxygen index, in air and also with the use
of a cone calorimeter. The effect of the modification on the zeta potential
was also examined.
A considerable reduction in the flammability
of nitrile rubber vulcanizates filled with silica can be obtained by the modification
of filler with bromine or iodine. All the vulcanizates containing modified
silica are self-extinguishing. An appropriate filling of NBR 39 vulcanizates
with bromine-modified silica makes it possible to obtain non-flammable polymeric
materials. They neither ignite nor glow under the action of a flame source
for 30 s.
The findings can be a rational basis for the synthesis
of modified silica that can act as active filler and effective flame-retardant
agent at the same time. 相似文献
100.
M. G. Ferreira Da Silva J. M. Fernàndez Navarro 《Journal of Sol-Gel Science and Technology》1994,2(1-3):895-901
The effect of thermal treatment on the structural incorporation of Cr2O3 in xCr2O3·(100 – x)SiO2 and 5R
n
O·xCr2O3·(95 – x)SiO2 (where x=0.01–1 mol.% and R=Li, Na and Ca) gel glasses was studied by optical absorption spectrophotometry, DTA-TG, XRD and electron microscopy.Samples heat treated at 60°C have green color due to the presence of Cr3+ in octahedral coordination. The optical transmission, and color (yellow, orange or ambar), of the samples heat treated between 200 and 700°C prove that Cr3+ (octahedrally coordinated) and Cr6+ (tetrahedrally coordinated) are both present. Segregation of Cr2O3 take place at temperatures above 800°C.In reducing conditions the gel glasses were green due to the presence of a high content of Cr3+ ions. Samples containing Li or Na show crystalline phases at temperatures below 850°C. 相似文献