全文获取类型
收费全文 | 2278篇 |
免费 | 264篇 |
国内免费 | 368篇 |
专业分类
化学 | 2165篇 |
晶体学 | 176篇 |
力学 | 41篇 |
综合类 | 4篇 |
数学 | 11篇 |
物理学 | 513篇 |
出版年
2023年 | 21篇 |
2022年 | 24篇 |
2021年 | 52篇 |
2020年 | 77篇 |
2019年 | 55篇 |
2018年 | 35篇 |
2017年 | 71篇 |
2016年 | 109篇 |
2015年 | 99篇 |
2014年 | 93篇 |
2013年 | 254篇 |
2012年 | 93篇 |
2011年 | 109篇 |
2010年 | 128篇 |
2009年 | 124篇 |
2008年 | 143篇 |
2007年 | 159篇 |
2006年 | 174篇 |
2005年 | 169篇 |
2004年 | 146篇 |
2003年 | 113篇 |
2002年 | 103篇 |
2001年 | 65篇 |
2000年 | 60篇 |
1999年 | 51篇 |
1998年 | 44篇 |
1997年 | 33篇 |
1996年 | 48篇 |
1995年 | 59篇 |
1994年 | 46篇 |
1993年 | 48篇 |
1992年 | 30篇 |
1991年 | 17篇 |
1990年 | 17篇 |
1989年 | 7篇 |
1988年 | 5篇 |
1987年 | 3篇 |
1986年 | 4篇 |
1985年 | 5篇 |
1984年 | 8篇 |
1983年 | 1篇 |
1982年 | 4篇 |
1981年 | 4篇 |
排序方式: 共有2910条查询结果,搜索用时 31 毫秒
31.
The ultrasound-assisted crystallization process has promising potentials for improving process efficiency and modifying crystalline product properties. In this work, the crystallization process of fotagliptin benzoate methanol solvate (FBMS) was investigated to improve powder properties and downstream desolvation/drying performance. The direct cooling/antisolvent crystallization process was conducted and then optimized with the assistance of ultrasonic irradiation and seeding strategy. Direct cooling/antisolvent crystallization and seeding crystallization processes resulted in needle-like crystals which are undesirable for downstream processing. In contrast, the ultrasound-assisted crystallization process produced rod-like crystals and reduced the crystal size to facilitate the desolvation of FBMS. The metastable zone width (MSZW), induction time, crystal size, morphology, and process yield were studied comprehensively. The results showed that both the seeding and ultrasound-assisted crystallization process (without seeds) can improve the process yield and the ultrasound could effectively reduce the crystal size, narrow the MSZW, and shorten the induction time. Through comparing the drying dynamics of the FBMS, the small rod-shaped crystals with a mean size of 9.6 μm produced by ultrasonic irradiation can be completely desolvated within 20 h, while the desolvation time of long needle crystals with an average size of about 157 μm obtained by direct cooling/antisolvent crystallization and seeding crystallization processes is more than 80 h. Thus the crystal size and morphology were found to be the key factors affecting the desolvation kinetics and the smaller size produced by using ultrasound can benefit the intensification of the drying process. Overall, the ultrasound-assisted crystallization showed a full improvement including crystal properties and process efficiency during the preparation of fotagliptin benzoate desolvated crystals. 相似文献
32.
33.
34.
《Journal of polymer science. Part A, Polymer chemistry》2018,56(14):1554-1563
A new class of amphiphilic polymers carrying two pendant docosyl (C22) chains, located at periodic intervals that are separated by PEG chains of varying lengths, was synthesized via a simple melt‐transesterification polymerization, using dimethyl, 2,5‐didocosyloxyterephthalate as one of the monomers. DSC, variable temperature FT‐IR, and WAXS studies demonstrated that immiscibility between the pendant docosyl units and the backbone PEG segments drives their self‐segregation; this results in the crystallization of the pendant docosyl segments and the generation of a lamellar morphology with the alkyl segments and the PEG chains occupying alternate layers. Based on the study of model criss‐cross amphiphiles that resemble the polymer repeat unit, it is postulated that the chains reconfigure such that both the docosyl chains fold to one side of the terephthalate unit while the PEG segments form a loop on the other side; these chains then organize in a bilayer to form the lamellar structure. The simplicity of the synthesis and the rather unique properties of these polymers suggests that such a design could be translated to develop other interesting functional materials that could exploit the immiscibility‐driven microphase separation for the generation of sub‐10 nm domains; these could have potential applications, such as in membranes, solid polymer electrolyte formulations, and so forth. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 1554–1563 相似文献
35.
Abstract An optical autoclave for phase studies on mixtures in the temperature range from 80 to 373 K and for pressures up to 200 MPa is described. The cell is fitted with sapphire windows and employs magnetic stirring. Measurements are performed according to the synthetical (e.g. by visual observation) or analytical method (e.g. by sampling and online gaschromatography). Results for the crystallization and fluid phase equilibria of the binary systems nitrogen + trifluoromethane and argon + trifluoromethane from 110 K to 230 K and up to 200 MPa are presented and discussed in comparison with other N2- and CHF3-systems. 相似文献
36.
Toshimitsu Ichimori Shinichi Yamazaki Kunio Kimura 《Journal of polymer science. Part A, Polymer chemistry》2013,51(20):4301-4308
Composition control of aromatic poly(thioester‐amide) was examined by the reaction‐induced phase separation during polymerization of S‐acetyl‐4‐mercaptobenzoic acid (AMBA) and p‐acetylaminobenzoic acid (AABA) in aromatic solvent. The poly(thioester‐amide)s were obtained as precipitates and their yields became lower at the middle range of the content of AMBA in feed (χf). The contents of p‐mercaptobenzoyl (MB) moiety (χp) in the precipitates prepared without shearing were in good agreement with the χf values. In contrast to this, the χp values of the precipitates prepared at χf of 50–70 mol % under shearing were much lower than the χf values. The reaction rate of AMBA increased with shearing, whereas that of AABA was unchanged by shearing. This shearing effect on the reaction rates accelerated to form the homo‐oligomers. The solubility of MB oligomers enhanced by shearing, whereas that of p‐benzamide oligomers did not enhance owing to the strong interaction through hydrogen bonding. The MB oligomers were inhibited to be precipitated, resulting in the lower χp values than the χf values. The composition could be controlled by the application of the shearing to the heterogeneous polymerization. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 4301–4308 相似文献
37.
《Journal of Macromolecular Science: Physics》2013,52(3-4):709-715
An unexpected type of primary crystal nucleation is described, involving spinodal decomposition (SD) type microphase separation due to the orientation fluctuations of rigid segments prior to crystal nucleation. This type of mechanism was found by the present authors about 10 years ago, and recently, it was theoretically revealed by Olmsted et al. to be one of three types of primary crystal nucleation: the well-known homogeneous crystal nucleation directly from the liquid–crystal coexistence domain, which occurs at higher temperatures above the binodal temperature T b , crystal nucleation after binodal microphase separation between T b and spinodal temperature T s , and that after SD below T s . The detailed experimental results for the spinodal-type crystal nucleation, especially the temperature dependence of characteristic wavelength in SD, are explained as well. 相似文献
38.
We report the inverse Meyer–Neldel (MN) rule in the thermally activated crystallization of a hybrid composite of phenol formaldehyde using two experimental approaches. In the first experiment, the annealing time dependence of the pre-exponential factor K 0 and the activation energy of crystallization E c were studied. In the second experiment, the annealing temperature dependence of the same parameters was investigated. We observed the inverse Meyer–Neldel rule between the pre-exponential factor K 0 and the activation energy of crystallization E c in both cases. 相似文献
39.
S. J. Guerrero A. Keller P. L. Soni P. H. Geil 《Journal of Macromolecular Science: Physics》2013,52(2):161-166
The main body of the present work is a summary of the extensive account in Ref. 1 to which we have to refer the reader for most of the details. Additional material is being included where explicitly stated. 相似文献
40.
《Current Applied Physics》2015,15(3):319-325
Pd is one of the metals suitable for inducing low-temperature crystallization in Ge. However, it is not clear how residual Pd atoms are integrated into the Ge lattice. Therefore, time-differential γ–γ perturbed angular correlations (TDPAC) technique using the 100Pd(→100Rh) nuclear probe produced by recoil implantation has been applied to study the hyperfine interactions of this probe in single-crystalline undoped Ge. A Pd-vacancy complex aligned along the <111> crystallographic direction with a unique interaction frequency of 8.4(5) Mrad/s has been identified. This complex was measured to have a maximum relative fraction of about 76(4)% following annealing at 350 °C. Further annealing at higher temperatures reduced this fraction, possibly via dissociation of the complex. Calculations suggest dissociation energy of 1.94(5) eV for the complex. DFT calculations performed in this work are in reasonable good agreement with the experimental values for the electric-field gradient of the defect complex in Ge and Si for comparison. The calculations predict a split-vacancy configuration with the Pd on a bond-centred interstitial site having a nearest-neighbour semi-vacancy on both sides (V-PdBI-V) in Ge and Si. 相似文献