全文获取类型
收费全文 | 1282篇 |
免费 | 63篇 |
国内免费 | 42篇 |
专业分类
化学 | 299篇 |
晶体学 | 3篇 |
力学 | 41篇 |
综合类 | 9篇 |
数学 | 16篇 |
物理学 | 209篇 |
综合类 | 810篇 |
出版年
2024年 | 3篇 |
2023年 | 9篇 |
2022年 | 18篇 |
2021年 | 18篇 |
2020年 | 26篇 |
2019年 | 13篇 |
2018年 | 8篇 |
2017年 | 22篇 |
2016年 | 31篇 |
2015年 | 27篇 |
2014年 | 28篇 |
2013年 | 53篇 |
2012年 | 39篇 |
2011年 | 52篇 |
2010年 | 46篇 |
2009年 | 62篇 |
2008年 | 42篇 |
2007年 | 69篇 |
2006年 | 76篇 |
2005年 | 51篇 |
2004年 | 63篇 |
2003年 | 40篇 |
2002年 | 53篇 |
2001年 | 52篇 |
2000年 | 40篇 |
1999年 | 47篇 |
1998年 | 49篇 |
1997年 | 38篇 |
1996年 | 34篇 |
1995年 | 23篇 |
1994年 | 39篇 |
1993年 | 43篇 |
1992年 | 22篇 |
1991年 | 37篇 |
1990年 | 30篇 |
1989年 | 20篇 |
1988年 | 15篇 |
1987年 | 24篇 |
1986年 | 10篇 |
1985年 | 14篇 |
1983年 | 1篇 |
排序方式: 共有1387条查询结果,搜索用时 297 毫秒
41.
Powder‐XRD and 14N magic angle‐spinning solid‐state NMR spectroscopy of some metal nitrides
下载免费PDF全文
![点击此处可从《Magnetic resonance in chemistry : MRC》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Some metal nitrides (TiN, ZrN, InN, GaN, Ca3N2, Mg3N2, and Ge3N4) have been studied by powder X‐ray diffraction (XRD) and 14N magic angle‐spinning (MAS) solid‐state NMR spectroscopy. For Ca3N2, Mg3N2, and Ge3N4, no 14N NMR signal was observed. Low speed (νr = 2 kHz for TiN, ZrN, and GaN; νr = 1 kHz for InN) and ‘high speed’ (νr = 15 kHz for TiN; νr = 5 kHz for ZrN; νr = 10 kHz for InN and GaN) MAS NMR experiments were performed. For TiN, ZrN, InN, and GaN, powder‐XRD was used to identify the phases present in each sample. The number of peaks observed for each sample in their 14N MAS solid‐state NMR spectrum matches perfectly well with the number of nitrogen‐containing phases identified by powder‐XRD. The 14N MAS solid‐state NMR spectra are symmetric and dominated by the quadrupolar interaction. The envelopes of the spinning sidebands manifold are Lorentzian, and it is concluded that there is a distribution of the quadrupolar coupling constants Qcc's arising from structural defects in the compounds studied. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
42.
Xuelian Li 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(11):1703-1709
Aromatic‐aliphatic co‐polyurea has been synthesized from 4,4 prime‐diphenylmethane diisocyanate (MDI), m‐phenylene diamine (m‐PDA), and 1,6‐diaminohexane (HDA) in DMAc by solution polymerization. The chemical structure of the co‐polyurea has been characterized by 1H‐NMR. The thermal properties of the copolymers were measured by DSC and TGA. The co‐polyurea solutions were spun into fibers by means of wet spinning. The effects of coagulation conditions on the morphologies and mechanical properties of the co‐polyurea as spun fibers are discussed. 相似文献
43.
In this study a range of wholly aromatic copolyesters based on kink m‐acetoxybenzoic acid (m‐ABA) monomer (33 mol%) and equimolar‐linear p‐acetoxybenzoic acid (p‐ABA), hydroquinone diacetate (HQDA) and terephthalic acid (TPA) monomers (67 mol%) have been synthesized by melt polycondensation reaction process at 280°C and 260°C for different time intervals. Characterization of copolyesters were performed by solution viscosity measurement, wide–angle X‐ray diffraction (WAXD), differential scanning calorimetry (DSC), hot‐stage polarized light microscopy, proton‐nuclear magnetic resonance analysis (1H‐NMR). According to the results obtained, copolyesters showed thermotropic liquid crystalline behavior in an appropriate temperature range. The copolyesters were prepared in high yields. It was observed that the intrinsic viscosities of the copolyesters are increased regularly with increasing polymerization time and temperature. All the copolyesters were soluble in a trifluoroacetic acid/dichloromethane (30:70 v/v) except the copolyesters which were synthesized at 280°C in 5 h. According to the WAXD results; the degree of crystallinity of copolyesters were found to be between 5–15%. DSC and hot stage polarized light microscopy results showed that all the copolyesters are melt processable and a significant molecular interaction exist in a very broad temperature range (160°C and 165°C) in the nematic mesophase. The Tg values are increased with an increasing polycondensation reaction time and temperature and they were observed between 93–126°C. Fibers prepared by a hand‐spinning technique from the polymer melt exhibit well‐developed fibrillar structure parallel to the fiber axis. 相似文献
44.
Der‐Lii M. Tzou Lin‐Kai Ni Mei‐Man Chen Min‐Chuan Chiou Li‐Chou Chen Shan‐Te Hsu Kuo‐Lung Ku Chien‐Chung Cheng 《中国化学会会志》2013,60(9):1107-1112
Solid‐state Nuclear Magnetic Resonance (ss‐NMR) 13C single‐pulse excitation spectroscopy in combination with the magic‐angle spinning (MAS) technique was applied to a series of Phalaenopsis tissues, including the leaf, sheath, stem, and root, at different growth and spiking periods. Compared with{1H}/13C cross‐polarization MAS spectra, the 13C single‐pulse excitation MAS spectra displayed very distinct spectral patterns, recognizable as fingerprints of the tissues studied. 1Here, we demonstrate that solid‐state 13C single‐pulse excitation NMR spectroscopy provides a direct and robust analytical tool for studying the various tissues of Phalaenopsis in different growth and spiking induction periods. 相似文献
45.
Yao Wang Yang Zhang Yuedan Wang Rufeng Zhu Yuanli Chen Xue Liu Jia Xu Mufang Li Dong Wang 《Electroanalysis》2021,33(12):2406-2416
A cotton yarn biosensor based on electrochemical transistor functionalized with MWCNT and PANI was developed for the detection of urea. The transistors based on PANI/MWCNT/cotton yarns under optimized MWCNT concentration has been obtained, which exhibited high on/off current ratio, fast response time, and good operational stability. A transistor-based urea sensor was prepared from PANI/MWCNT/cotton yarns, which could monitor urea in the 1 nM–1 mM linear range with the correlation coefficient of 0.9716. Furthermore, the sensor showed superior reproducibility and high specificity. The practical applications of the proposed sensor were also confirmed. These results indicate the flexible transistor can be used as an efficient platform for biological detection in body fluids. 相似文献
46.
Flax-PP based thermally bonded roving (TBR) has a unique structure where the flax fibres remain twist-free and fully aligned along the roving axis. The present study describes an experimental investigation on the low velocity impact (LVI) behaviour of the TBR based woven fabric composites and compares the same with plain woven glass fabric reinforced PP composites (GRPC). Two different fabric architectures namely plain woven (PW) and unidirectional (UD) are fabricated using flax/PP based TBR. These TBR based woven fabrics and the glass fabric/PP sheets are consolidated in a compression moulding machine and the resultant composite-laminates are tested for their LVI behaviour. The impact test results revealed that the glass/PP composites absorb more energy and exhibit a higher peak load than both TBR based PW and UD fabric composites. However, the specific load and energy of all flax/PP composites are higher than the glass/PP composite. The damage tolerance of all composite laminates are evaluated by comparing their flexural strength before and after the impact. It is observed that the proportionate loss in flexural strength due to impact thrust is larger in case of glass/PP composites than all flax-PP composites. 相似文献
47.
In this study, Polystyrene based materials, PS, with tailored morphologies are prepared by solution blow spinning, SBS. It is demonstrated that this tailored morphology of PS can be designed through the choice of particular SBS processing conditions. Several SBS processing conditions, including solution concentration, gas pressure and solution feeding rate are changed to consider their individual and combined effects on the final polymer morphology. The morphology of the PS samples is inspected by scanning electron microscopy, SEM. This morphology is analyzed in terms of fiber diameter and relative amount of fibers respect to other morphological features such as lumps or fibers aggregates. Coupling the experimental analysis with the use of Box-Behnken method and the desirability function, particular values of parameters controlling the SBS processing conditions are able to be obtained in order to achieve certain morphologies of PS, in particular, maximum amount of fibers with the minimum diameter. Influence of PS morphology on hydrophobicity and the ability of oil absorption is studied by contact angle measurements. The use of Box-Behnken design together with the desirability function is revealed as a reliable and accurate method for designing polystyrene materials through the optimal election of SBS processing conditions for the production of the polymer with particular morphologies and therefore, with especial performance regarding adsorption and absorption of liquid wastes. SBS PS constituted by the maximum amount of fibers with the shortest diameters lead to superhydrophobic materials with the highest ability of oil absorption for the PS. 相似文献
48.
Yuanxin Li Jingjing Li Jing Sun Haonan He Bo Li Chao Ma Kai Liu Hongjie Zhang 《Angewandte Chemie (International ed. in English)》2020,59(21):8148-8152
Silk‐protein‐based fibers have attracted considerable interest due to their low weight and extraordinary mechanical properties. Most studies on fibrous proteins focus on the recombinant spidroins, but these fibers exhibit moderate mechanical performance. Thus, the development of alternative structural proteins for the construction of robust fibers is an attractive goal. Herein, we report a class of biological fibers produced using a designed chimeric protein, which consists of the sequences of a cationic elastin‐like polypeptide and a squid ring teeth protein. Remarkably, the chimeric protein fibers exhibit a breaking strength up to about 630 MPa and a corresponding toughness as high as about 130 MJ m?3, making them superior to many recombinant spider silks and even comparable to some native counterparts. Therefore, this strategy is a novel concept for exploring bioinspired ultrastrong protein materials through the development of new types of structural chimeric proteins. 相似文献
49.
Andrea Macrelli Nicol Simone Villa Andrea Lucotti David Dellasega Paolo Maria Ossi Matteo Tommasini 《Molecules (Basel, Switzerland)》2022,27(1)
The applications of SERS in therapeutic drug monitoring, or other fields of analytical chemistry, require the availability of sensitive sensors and experimental approaches that can be implemented in affordable ways. In this contribution, we show the production of cost-effective SERS sensors obtained by depositing Lee-Meisel Ag colloids on filter paper either by natural sedimentation or centrifugation. We have characterized the morphological and plasmonic features of the sensors by optical microscopy, SEM, and UV-Vis spectroscopy. Such sensors can be used to quantify by SERS the anti-epileptic drug Perampanel (in the concentration range 1 × 10−4–5 × 10−6 M) by spinning them during the micro-Raman measurements on the top of a custom device obtained from spare part hard disk drives. This approach minimizes laser-induced heating effects and allows averaging over the spatial non-uniformity of the sensor. 相似文献
50.
经由溶胶-凝胶法过程,应用静电纺丝机原理,以聚乙烯醇(PVA)和无机盐(LiMn2O4)为前驱物,制备出了含有LiMn2O4无机组分的复合纳米纤维,为复合无机纳米纤维的制备方式供给了一条新的思路。实验中系统地研究了PVA的浓度对其所形成的纤维描摹特征的影响。PVA水溶液用于纺丝的最好质量分数约为8.0%。在实验过程中,随着PVA质量分数的渐渐增加,其所形成纤维的直径也随之渐渐增大,而溶液的黏度也在逐步增大,这就使得溶剂挥发变得越来越难,小液珠的表面难以构成理想的“泰勒锥”,电压过小,样品溶液无法纺丝,在针头处成水滴状落在针头下方。电压过大则会在纤维丝上呈现念珠形态,阻碍样品电纺时的形貌。实验表明,在施加18kV的高电压,默认机器的其它设定条件下,依托不同质量分数的PVA溶液可制备出三种不同的纤维。 相似文献