全文获取类型
收费全文 | 5168篇 |
免费 | 340篇 |
国内免费 | 647篇 |
专业分类
化学 | 2634篇 |
晶体学 | 95篇 |
力学 | 321篇 |
综合类 | 15篇 |
数学 | 24篇 |
物理学 | 3066篇 |
出版年
2024年 | 10篇 |
2023年 | 60篇 |
2022年 | 93篇 |
2021年 | 107篇 |
2020年 | 100篇 |
2019年 | 96篇 |
2018年 | 115篇 |
2017年 | 210篇 |
2016年 | 240篇 |
2015年 | 190篇 |
2014年 | 315篇 |
2013年 | 410篇 |
2012年 | 272篇 |
2011年 | 383篇 |
2010年 | 264篇 |
2009年 | 366篇 |
2008年 | 331篇 |
2007年 | 373篇 |
2006年 | 302篇 |
2005年 | 247篇 |
2004年 | 248篇 |
2003年 | 200篇 |
2002年 | 166篇 |
2001年 | 142篇 |
2000年 | 132篇 |
1999年 | 98篇 |
1998年 | 96篇 |
1997年 | 94篇 |
1996年 | 81篇 |
1995年 | 54篇 |
1994年 | 51篇 |
1993年 | 47篇 |
1992年 | 48篇 |
1991年 | 36篇 |
1990年 | 33篇 |
1989年 | 29篇 |
1988年 | 14篇 |
1987年 | 12篇 |
1986年 | 14篇 |
1985年 | 7篇 |
1984年 | 12篇 |
1983年 | 7篇 |
1982年 | 15篇 |
1981年 | 10篇 |
1980年 | 11篇 |
1979年 | 4篇 |
1978年 | 6篇 |
1976年 | 2篇 |
1975年 | 1篇 |
1973年 | 1篇 |
排序方式: 共有6155条查询结果,搜索用时 62 毫秒
961.
When divalent metal chloride solutions of Mn, Fe, Co, Ni and Cd were mixed with potassium titanyl oxalate solution, mixed metal oxalates were obtained in the case of Fe, Co and Ni at room temperature in the pH range 1.5–3. In the case of manganese, heating was found to be necessary to induce precipitation and complete precipitation occurred at 80 °C. Mixed cadmium and titanyl oxalate precipitation was complete at a pH of 3 at room temperature. Various physico-chemical techniques were employed to characterize the as-dried oxalate precursors and the final MTiO3 oxide powders (M = Mn, Fe, Co, Ni and Cd) obtained on thermal decomposition. All these experimental results relating to the synthesis and characterizations of MTiO3 oxides are presented in this paper. The results suggest that the reaction of potassium titanyl oxalate and metal chloride solutions may not lead to the formation of a single molecular precursor by direct salt elimination reaction in the pH range 1.5–3. 相似文献
962.
AlF3包覆LiNi0.45Mn0.45Co0.10O2锂离子电池正极材料的结构表征和 电化学性能研究 总被引:2,自引:0,他引:2
通过共沉淀与固相反应法制备层状的LiNi0.45Mn0.45Co0.10O2, 并利用X射线衍射(XRD)和电子扫描显微镜(SEM)测定材料的结构和形貌. 在2.5~4.5 V范围内, 以0.1 C (28 mA8226;g-1)放电, LiNi0.45Mn0.45Co0.10O2正极材料的起始放电容量达到167.2 mAh8226;g-1, 但循环性能较差. 当采用AlF3包覆后, 材料的循环性能得到明显改善. 利用电化学阻抗谱(EIS)技术探索AlF3包覆对正极材料的电化学性能改善机理, 实验结果表明: AlF3包覆层能够阻止电解液对正极材料的溶解和侵蚀, 稳定其层状结构, 同时降低了电极界面阻抗. 因此AlF3包覆技术是一种改善LiNi0.45Mn0.45Co0.10O2材料电化学性能的有效方法和工具. 相似文献
963.
Post-blast detection of traces of explosives by means of Fourier transform infrared spectroscopy 总被引:1,自引:0,他引:1
A. Banas K. Banas M. Bahou H.O. Moser L. Wen P. Yang Z.J. Li M. Cholewa S.K. Lim Ch.H. Lim 《Vibrational Spectroscopy》2009,51(2):168-176
Samples obtained from debris after explosions of about 30 g of energetic materials were analyzed by means of Fourier transform infrared (FTIR) spectroscopy using both, Globar and synchrotron infrared radiation at the ISMI beamline of the Singapore synchrotron light source (SSLS). Low- and high-strength-of-explosion blasts were performed during each test run with the same explosive material. From the spectroscopic measurements, traces of unreacted explosives were found on more than 200 different materials that served as sample catchers in the explosions.The integrality of the experiments done confirmed that FTIR spectroscopy is a sufficiently sensitive method to detect traces of explosives in post-blast residues even of high-strength explosions. The method requires only a minimal amount of sample and enables accurate and very fast identification of the presence of explosive material. Finally, the synchrotron radiation infrared source provided one order of magnitude higher sensitivity compared to the conventional Globar source. 相似文献
964.
Infrared spectra of the title compounds with kröhnkite-type infinite octahedral–tetrahedral chains, K2Me(CrO4)2·2H2O (Me = Mg, Co, Ni, Zn, Cd), are presented in the regions of the uncoupled O–D stretching modes of matrix-isolated HDO molecules (isotopically dilute samples) and water librations. The strengths of the hydrogen bonds are discussed in terms of the respective OwO bond distances, the Me–water interactions (synergetic effect), the proton acceptor capability of the chromate oxygen atoms as deduced from Brown's bond valence sum of the oxygen atoms. The spectroscopic experiments reveal that hydrogen bonds of medium strength are formed in the chromates. The hydrogen bond strengths decrease in the order Cd > Zn > Ni > Co in agreement with the decreasing covalency of the respective Me–OH2 bonds in the same order, i.e. decreasing acidity of the water molecules. The infrared band positions corresponding to the water librations confirm the claim that the hydrogen bonds in K2Cd(CrO4)2·2H2O are stronger than those formed in K2Mg(CrO4)2·2H2O on one hand, and on the other—the hydrogen bonds in K2Ni(CrO4)2·2H2O are stronger than those in K2Co(CrO4)2·2H2O. 相似文献
965.
Four new Hofmann–3-phenylpropylamine (3PPA) type complexes with chemical formulae M(3PPA)2Ni(CN)4 (M = Ni, Co, Cd, and Pd) have been prepared and their vibrational spectra are reported in the region of 4000–60 cm−1. The vibrational bands arising from 3PPA ligand molecule, the polymeric sheet and metal–ligand bands of the compounds are assigned. The thermal behaviour of these complexes is also provided using the DTA and TGA along with the magnetic susceptibility data. The results indicate that the monodentate 3PPA ligand molecule bonds to the metal atom of |M–Ni(CN)4|∞ polymeric layers and hence the compounds are similar in structure to Hofmann-type complexes. 相似文献
966.
Harumi Sato Rumi Murakami Katsuhito Mori Yuriko Ando Isao Takahashi Isao Noda Yukihiro Ozaki 《Vibrational Spectroscopy》2009,51(1):132-135
Infrared reflection–absorption (IR-RAS) and transmission spectra were measured for poly(3-hydroxybutyrate) (PHB) thin films to explore its specific crystal structure in the surface region. As IR-RAS is sensitive to the vibration mode of perpendicular orientation of the surface, differences between IR-RAS and transmission spectra indicate an orientation of the lamella structure in the surface of PHB thin films. The relative intensity of the crystalline CO stretching band in the IR-RAS spectrum is significantly weaker than that in the transmission spectrum. It may be concluded that the transient dipole moment of the CO stretching mode of the crystalline state is not oriented perpendicular but nearly parallel to the substrate surface. On the other hand, the relative intensity of the band at 3009 cm−1 due to the C–H stretching mode of the C–HOC hydrogen bonding is similar between the IR-RAS and transmission spectra, suggesting that the C–H bond is oriented neither perpendicular nor parallel to the substrate surface but in an intermediate direction. Since the CO group of the C–HOC hydrogen bonding is oriented nearly parallel to the surface and its C–H group is in the intermediate direction, it is very likely that the C–HOC hydrogen bonding has a somewhat bent structure. These results are in good agreement with our previous conclusion that the C–HOC hydrogen bonding of PHB exists along the a-axis (not the b-axis) between the CH3 group of one helix and the CO group of another helix. 相似文献
967.
Hydrogen-bond structures in poly(2-hydroxyethyl methacrylate) (PHEMA) were investigated by infrared (IR) spectroscopy and quantum chemical calculations (QCC). A monomer of 2-hydroxyethyl methacrylate (HEMA) and model compounds of methyl acetate (MA) and methanol (MeOH) were also used. Evidences for OHOC and OHOH types of hydrogen-bonds were observed in an IR spectrum of a PHEMA solid. It was estimated from the present study that 47.3% of OH groups on the PHEMA side chain terminal are engaged in the OHOC type of hydrogen-bond, while the rest contributes to the OHOH type of hydrogen-bond. 相似文献
968.
H. Kudo S. Sudo T. Oka Y. Hama A. Oshima M. Washio T. Murakami 《Radiation Physics and Chemistry》2009,78(12):1067-1070
Ion-beam irradiation effects on polyimide, Kapton™, were studied with respect to optical and electronic properties. Stack films of Kapton™ (12.5 μm thick) were irradiated to various ion beams in air or vacuo at room temperature and subjected to ultraviolet–visible (UV–vis) spectroscopy, and change in absorbance and energy gap is discussed. The UV–vis absorption spectrum, which is assigned to the transition of electrons in benzene rings from π to π* orbital, upon He2+ (6 MeV/u) irradiation in air, shifted towards longer wavelength direction for all cases, and the shift was more obvious for higher linear energy transfer (LET) ion beams. The energy gap of the transition was estimated, and the H+ and He2+ ion beams caused little change in the transition energy gap Eg, while the heavier ions such as C6+ and Si14+ caused more significant decrease. This decrease is assumed to the structural changes around benzene rings, and the infrared spectroscopy revealed breakage in imide groups next to benzene ring in the repeating unit of polyimide. 相似文献
969.
乳酸-3-苯甲基-2,5-吗啉二酮共聚物的合成及共聚物组分分析 总被引:1,自引:0,他引:1
以苯丙氨酸为原料合成3-苯甲基-2,5-吗啉二酮(PMD),以辛酸亚锡为催化剂,研究PMD与丙交酯(LA)开环共聚得到乳酸-3-苯甲基-2,5-吗啉二酮共聚物,用IR、1H-NMR、DSC对共聚物进行分析表征,表明可得到含有苯丙氨酸的聚乳酸共聚物.利用红外定量分析法替代1H-NMR法测定共聚物中PMD的组分含量,以1671.53cm-1和870.82cm-1两波数处特征峰的吸光度比值,作标准工作曲线Y=0.05567X+0.1091,r=0.9993.比较了催化剂浓度、反应时间、温度对共聚物组分含量、共聚物特性黏数[η]的影响.结果表明,低催化剂浓度条件下(0.025mol%与0.1mol%),产物特性黏数[η]随反应时间的延长先增加然后下降;而在高催化剂浓度(0.2mol%)的条件下,因主链中形成了更多更稳定的酰胺键,产物特性黏数[η]10h内维持不变;随PMD加入量的增多,进入共聚物中的PMD组分也相应地呈线性增加,但因PMD的开环活性低于丙交酯,所以苯丙氨酸引入聚乳酸链段中比较困难,但在低投料比条件下(<20mol%),升高反应温度有利于PMD含量的增加;同样也因为PMD在共聚物中组分含量的增多,苯环的稳定性使共聚物[η]受催化剂浓度及温度的影响逐渐减弱. 相似文献
970.
A sol–gel titania poly(tetrahydrofuran) (poly-THF) coating was developed for capillary microextraction hyphenated on-line with high-performance liquid chromatography (HPLC). Poly-THF was covalently bonded to the sol–gel titania network which, in turn, became chemically anchored to the inner surface of a 0.25 mm I.D. fused silica capillary. For sample preconcentration, a 38-cm segment of the sol–gel titania poly-THF coated capillary was installed on an HPLC injection port as a sampling loop. Aqueous samples containing a variety of analytes were passed through the capillary and, during this process, the analytes were extracted by the sol–gel titania poly-THF coating on the inner surface of the capillary. Using isocratic and gradient elution with acetonitrile/water mobile phases, the extracted analytes were desorbed into the on-line coupled HPLC column for separation and UV detection. The sol–gel titania poly-THF coating was especially efficient in extracting polar analytes, such as underivatized phenols, alcohols, amines, and aromatic carboxylic acids. In addition, this coating was capable of extracting moderately polar and nonpolar analytes, such as ketones and polycyclic aromatic hydrocarbons. The sol–gel titania poly-THF coated capillary was also able to extract polypeptides at pH values near their respective isoelectric points. Extraction of these compounds can be important for environmental and biomedical applications. The observed extraction behavior can be attributed to the polar and nonpolar moieties in the poly-THF structure. This coating was found to be stable under extremely low and high pH conditions—even after 18 h of exposure to 1 M HCl (pH ≈0.0) and 1 M NaOH (pH ≈14.0). 相似文献