全文获取类型
收费全文 | 711篇 |
免费 | 10篇 |
国内免费 | 108篇 |
专业分类
化学 | 627篇 |
晶体学 | 2篇 |
力学 | 8篇 |
综合类 | 1篇 |
数学 | 106篇 |
物理学 | 85篇 |
出版年
2024年 | 1篇 |
2023年 | 20篇 |
2022年 | 5篇 |
2021年 | 14篇 |
2020年 | 22篇 |
2019年 | 20篇 |
2018年 | 17篇 |
2017年 | 41篇 |
2016年 | 30篇 |
2015年 | 28篇 |
2014年 | 45篇 |
2013年 | 51篇 |
2012年 | 25篇 |
2011年 | 46篇 |
2010年 | 34篇 |
2009年 | 54篇 |
2008年 | 47篇 |
2007年 | 43篇 |
2006年 | 26篇 |
2005年 | 35篇 |
2004年 | 22篇 |
2003年 | 28篇 |
2002年 | 22篇 |
2001年 | 24篇 |
2000年 | 27篇 |
1999年 | 23篇 |
1998年 | 6篇 |
1997年 | 14篇 |
1996年 | 3篇 |
1995年 | 10篇 |
1994年 | 6篇 |
1993年 | 11篇 |
1992年 | 5篇 |
1991年 | 2篇 |
1990年 | 3篇 |
1988年 | 1篇 |
1986年 | 3篇 |
1985年 | 2篇 |
1984年 | 4篇 |
1983年 | 3篇 |
1982年 | 1篇 |
1981年 | 2篇 |
1980年 | 3篇 |
排序方式: 共有829条查询结果,搜索用时 62 毫秒
1.
2.
3.
《Thermochimica Acta》2004,411(1):53-60
The aim of this work was to understand the crystallization process of terfenadine in solution.Cooling of saturated solutions prepared at 50 °C at different temperatures, evaporating the solvent from nearly saturated solutions at a certain temperature, and exposing ethanol solutions of terfenadine to water vapour atmosphere were the techniques used for obtaining terfenadine specimens. The characterization of these specimens was carried out by thermal microscopy, differential thermal analysis, thermogravimetry and powder X-ray diffraction. Crystalline phases, amorphous solids, and solvates were identified. For the solvents used in the present study, the crystallinity degree of terfenadine decreases from ethanol-water to ethanol and from this to methanol. Decreasing the temperature promotes the formation of amorphous solid material; at low temperatures, methanol and ethanol solvates are also formed.Desolvation, following the terfenadine aggregation process in solution accounts for the different behaviour found for the solvents and for the effect of temperature on the structure. The role of the solvent as structure-mediator is explained on the grounds of the values previously published for the enthalpy of solution of terfenadine in the solvents under study. 相似文献
4.
A simple and novel method was developed to successfully synthesize N-succinyl-O-carboxymethylchitosan (NSOCMCS) using N-acylation of chitosan with succinic anhydride. The NSOCMCS structure was characterized by Fourier transform infrared and
1H nuclear magnetic resonance. The aggregation behaviors of NSOCMCS were studied using fluorescence spectroscopy, dynamic light
scattering, and atomic force microscopy techniques. The critical aggregation concentration of NSOCMCS in water was determined
to be 0.2–0.3 mg/ml. The apparent hydrodynamic radium of an NSOCMCS aggregate was dependent on the concentration. The aggregates
demonstrated a much swollen association conformation in aqueous solution. The possible aggregation mechanisms for the NSOCMCS
in water are discussed. Moreover, a driving force to form an open aggregation morphology was revealed in this study. Aggregation
behaviors are important physicochemical properties of NSOCMCS, which impact the potential application in the biomedical field. 相似文献
5.
Jing Liu Ji-jun Wang Ting Li Yong Zhou De-yan Shen Yun Huang Shou-ke Yan State Key Laboratory of Polymer Physics Chemistry Institute of Chemistry The Chinese Academy of Sciences Beijing China Physics Department Peking University Beijing China 《高分子科学》2007,(2):207-215
Aggregation process of isotactic poly(methyl methacrylate) (i-PMMA) has been studied extensively for many years, and considerable progress has been made in both experimental and theoretical studies. They are, however, seldom sustained by real-space observations of the underlying morphology. In this paper, the aggregation process of i-PMMA in concentrated acetone solutions and the fractal structure of the resulting three-dimensional clusters were characterized on the basis of real-space AFM observations of their two-dimensional projection. It was found that spherical multiple-chain particles formed upon collapse and aggregation of the involving chains as a whole during quenching the solution to room temperature. By keeping the solution at room temperature, the initially formed particles stick together upon contact to form larger particles through reassembling very slowly. The succeeding collision of the enlarged spherical particles leads to the formation of small clusters. These newly formed small clusters grow when they meet with other clusters or single Brownian particles. This leads to the formation of large clusters with fractal dimension of 1.95$±0.05, which suggest a reaction-limited cluster aggregation of i-PMMA in a concentrated acetone solution. This is in accordance with the conclusion obtained by light scattering measurements. 相似文献
6.
R. Sakamoto 《Colloid and polymer science》1984,262(10):788-792
Solvent effects on the phase separation of poly(-benzyl L-glutamate) to liquid crystal and isotropic solution have been observed in various helicogenic solvents. The temperature-composition phase diagrams have been determined for each solution. The critical concentrations,
2
*
, at which the phase separation occours have been compared in various solvents. In dimethylformamide in which the polymer is molecularly dispersed, the observed
2
*
value has agreed with that calculated by Flory's theory. In some solvents in which the polymer aggregates in a head-to-tail mode such as chloroform, the observed
2
*
values have been considerably small. It is assumed that the polymer aggregates behave as longer particles than the original particles. In dioxane in which the polymer aggregates highly both in a head-to-tail and a side-by-side modes, the
2
*
value has been a little larger than that in chloroform. In this case the relationship between the aggregation and the liquid crystal formation is so complicated that further investigation is necessary. In aromatic solvents such asm-cresol that dissolves the polymer almost molecularly, the
2
*
is smaller than that in dimethylformamide. Therefore, the intermolecular interactions between the phenyl groups in the side groups of the polymer and those in solvent molecules must be considered.The author is grateful to Mr. K. Sano and Mr. M. Watanabe for their observation of the liquid crystal formation. 相似文献
7.
团聚纳米SiO_2在苯乙烯乳液聚合过程中的再分散过程及机理 总被引:2,自引:3,他引:2
用二氧化硅 (SiO2 )存在下的乳液聚合法制备了聚苯乙烯 (PSt) 纳米SiO2 复合材料 ,研究了苯乙烯(St)乳液聚合过程中团聚纳米SiO2 的解离与再分散过程及分散的机理 .发现商品纳米SiO2 粒子以团聚体形式存在 ,团聚体大小远超出纳米级范围 .随聚合时间的延长 ,St的转化率逐渐增加 ,而PSt SiO2 复合微胶囊的粒径逐渐减小 ,反应 12 0min后 ,转化率和复合微胶囊粒子的粒径趋于稳定 .透射电镜 (TEM)也显示PSt SiO2 复合微胶囊粒子具有海岛结构 ,而SiO2 粒子的粒径在纳米范围内 ,表明在乳液聚合过程中SiO2 团聚体被逐渐解离 ,并重新分散到纳米尺度 .红外光谱研究发现 ,在乳液聚合过程中 ,除生成PSt均聚物外 ,还在纳米SiO2 表面生成了PSt接枝共聚物 ,改善了无机纳米粒子与聚合物之间的界面相容性 .聚合过程中的反应热和剪切搅拌是团聚体被解离和重新分散的主要原因 ,而生成的聚合物起到隔离作用 相似文献
8.
Molecular mobility in thermotropic polyesters and side-chain polymers with different struc-ture of mesogens and spacers has been studied by dielectrical method in dilutesolutions. The results made it possible to establish the multiplicity of dielectric relaxationtransitions which reflects the small- and large-scale types of molecular motion. It was shownthat dielectric relaxation processes occurring in accordance with local mechanism (relaxationtimes 10~(-9)--10~(-7)s. and the activation energy 10--50kJ/mol) are due to the mobility of kineticchain elements of different length within a monomer units. It was found that the dielectricrelaxation process connected with a large-scale form of molecular motion (relaxation times10~(-5)--10~(-6)s. and the activation energy 100kJ/mol) did not depend on the molecular massbut was infiuenced by factors changing the conformational state of the macromolecule. It isestablished tha the cooperative reorientation mobility of associated mesogenic fragments isthe source of the large-scale process. 相似文献
9.
Sandra Ristori Grard Gebel Giacomo Martini 《Colloids and surfaces. A, Physicochemical and engineering aspects》1993,80(2-3):113-120
The aggregation properties of ammonium perfluorooctanoate (NH4-PFO) in concentrated aqueous phases have been investigated by magnetic resonance techniques and have been compared with the aggregation properties in dilute solutions. Magnetic resonance methods indicated that NH4-PFO—water systems with surfactant concentrations below 45% (w/w) behaved as isotropic purely micellar solutions in the temperature range 285–340 K. For higher concentrations the system exhibited a rather complex structure, having both isotropic and anisotropic components. The nematic nature of the anisotropic fraction was demonstrated by 19F NMR studies. The 19F NMR and EPR of nitroxides (TempTMA+, 5- and 16-DXSA) inserted as paramagnetic probes into the concentrated NH4-PFO—water systems allowed us to establish that the lamellar phase could be mechanically oriented between quartz slides. The EPR investigation also gave details concerning the dynamics of both the oriented and non-oriented structures. 相似文献
10.