全文获取类型
收费全文 | 1067篇 |
免费 | 413篇 |
国内免费 | 97篇 |
专业分类
化学 | 493篇 |
晶体学 | 177篇 |
力学 | 49篇 |
综合类 | 8篇 |
数学 | 59篇 |
物理学 | 791篇 |
出版年
2024年 | 4篇 |
2023年 | 7篇 |
2022年 | 55篇 |
2021年 | 42篇 |
2020年 | 41篇 |
2019年 | 33篇 |
2018年 | 32篇 |
2017年 | 55篇 |
2016年 | 73篇 |
2015年 | 51篇 |
2014年 | 45篇 |
2013年 | 145篇 |
2012年 | 79篇 |
2011年 | 80篇 |
2010年 | 71篇 |
2009年 | 93篇 |
2008年 | 71篇 |
2007年 | 81篇 |
2006年 | 69篇 |
2005年 | 53篇 |
2004年 | 61篇 |
2003年 | 61篇 |
2002年 | 23篇 |
2001年 | 35篇 |
2000年 | 35篇 |
1999年 | 30篇 |
1998年 | 24篇 |
1997年 | 29篇 |
1996年 | 19篇 |
1995年 | 14篇 |
1994年 | 13篇 |
1993年 | 9篇 |
1992年 | 9篇 |
1991年 | 9篇 |
1990年 | 5篇 |
1989年 | 5篇 |
1988年 | 5篇 |
1987年 | 3篇 |
1986年 | 2篇 |
1985年 | 1篇 |
1984年 | 2篇 |
1982年 | 2篇 |
1980年 | 1篇 |
排序方式: 共有1577条查询结果,搜索用时 375 毫秒
21.
Stefan G Ebbinghaus 《Journal of solid state chemistry》2004,177(3):817-823
Single crystals of the new compound La1.2Sr2.4RuO7, an oxide related to the hexagonal perovskites, were grown from a BaCl2 flux. The structure was solved by single crystal X-ray diffraction. La1.2Sr2.4RuO7 crystallizes in the space group with a=5.760(1) Å and c=18.273(3) Å. It is one of the rare examples of oxides with isolated RuO6-octahedra. The structure consists of alternating layers of RuO6-octahedra and trigonal (La,Sr)O6-prisms. These prisms are capped by one additional oxygen ion, which occupies a distorted position within the (La,Sr)O6-layers. La1.2Sr2.4RuO7 is the second member of the general [A2O][AnBn−1O3n] family of hexagonal perovskites with n=2 and the first ruthenate possessing this structure. XANES investigations, bond valence sum calculations and magnetic measurements show that ruthenium takes the oxidation state +5. Although the ruthenium ions have quite long distances, a medium strong antiferromagnetic interaction between these paramagnetic centers was observed. 相似文献
22.
Joowook Lee 《Analytica chimica acta》2005,545(1):27-32
We report linear sweep and square wave voltammetric studies on glucose oxidation at boron-doped diamond (BDD) electrodes in an alkaline medium in efforts to evaluate the techniques for electrochemically assaying glucose. The bare BDD electrode showed good linear responses to glucose oxidation for a concentration range from 0.5 to 10 mM glucose, which well encompasses the physiological range of 3-8 mM. The BDD electrodes did not experience interferences from ascorbic acid or uric acid during glucose detection. This method, when applied to real blood samples, gave results similar to those obtained by a commercial glucose monitor. 相似文献
23.
The pressure dependence of thelo-to phonons in InAs has been investigated by Raman scattering using the diamond anvil cell. Indium arsenide transforms, presumably
to the rock-salt structure at 70±1 kbar. The mode Grüneisen parameters for thelo-to phonons are γ
lo
=0.99±0.03, γ
to
=1.2±0.03 respectively. The effective charge,e*
T
, for InAs decreases slightly with pressure and this trend is in accordance with the behaviour of other III–V zinc blende
structured semiconductors: The structural phase transition is discussed in the light of theoretical calculations for phase
stability of III–V compounds, as well as recent high pressure x-ray diffraction studies. 相似文献
24.
Hassouni K. Leroy O. Farhat S. Gicquel A. 《Plasma Chemistry and Plasma Processing》1998,18(3):325-362
One-dimensional transport models of moderate-pressure H
2
and H
2
/CH
4
plasmas obtained in a diamond deposition microwave reactor are presented. These models describe the plasma as a thermochemically nonequilibrium flow with three different energy modes. The solution of the one-dimensional plasma transport equations enabled the estimation of plasma species concentrations and temperatures on the axis of the reactor. As far as pure H
2
plasmas are concerned, results showed that the model predictions of gas and vibration temperatures are in good agreement with experimental measurements. The model also yields a relatively good qualitative prediction of the variations of H-atom mole fraction with the power density absorbed by the plasma. The results obtained for H
2
/CH
4
discharges showed that the model prediction on the variations of H-atom mole fraction with methane percentage in the discharge is in good qualitative agreement with experimental results. They also showed that methane is rapidly converted to acetylene before reaching the discharge zone. The concentrations of neutral hydrocarbon species in the reactor are mainly governed by thermal chemistry. The addition of methane strongly affects the ionization kinetics of the plasma. Three major ions are generally obtained in H
2
/CH
4
plasmas: C
2
H
2
+
, C
2
H
3
+
, and C
2
H
5
+
. The relative predominance of these ions depends on the considered plasma region and on the discharge conditions. The ionic species concentrations are also mainly governed by chemistry, except very near the substrate surface. Finally the use of this transport model along with the surface chemistry model of Goodwin
(1)
enabled us to estimate the diamond growth rate for several discharge conditions. 相似文献
25.
A new class of monocrystalline diamond paste-based electrodes is proposed for the determination of chromium(III) at trace levels in vitamins. Three types of monocrystalline diamond—natural diamond 1 (natural diamond), synthetic diamond 50 (synthetic-1), and synthetic diamond 1 (synthetic-2)—were used for electrode construction. The linear concentration ranges are between 10–10 and 10–8; 10–9 and 10–7, and 10–10 to 10–8 mol L–1, with limits of detection of 10–12, 10–12, and 10–11 mol L–1, when natural diamond, synthetic-1, and synthetic-2, respectively, are used as electrode materials. For electrodes based on natural diamond and synthetic-1 it was found that Cr(III) yields a peak at about +0.275±0.015 V (vs. Ag/AgCl) within a predetermined positive potential range situated between +0.4 and +0.2 V, while for the electrode based on synthetic-2 the peaks are found at +0.300±0.015 V (vs. Ag/AgCl). The proposed method is reliable for the determination of chromium(III) at trace levels in two vitamin tablets (RSD<0.2%). 相似文献
26.
Sylvie Malo Antoine Maignan Sylvain Marinel Maryvonne Hervieu Kenneth R. Poeppelmeier Bernard Raveau 《Solid State Sciences》2005,7(12):1492
Recently, the ferroelectromagnet YMnO3 has been the focus of interest because it exhibits both antiferromagnetism (Néel temperature 80 K) and ferroelectricity (Curie temperature 914 K). There have been no reports of complete YMn1−xMxO3 solid solutions in which substitution of the foreign M cation preserves the hexagonal P63cm structure. In contrast there exist several homeotypic phases with the general formula, Ln1+nCunMO3+3n (n=1 (M=Ti), 2 (M=V) and 3 (M=Mo); Ln: lanthanide). Several YMn1−x(Cu3/4Mo1/4)xO3 compounds have been synthesized. The solid solution, from YMnO3 (x=0) to YCu3/4Mo1/4O3 (x=1) has been characterized by X-ray diffraction and transmission electron microscopy study. For 0<x<0.9, the compounds are found to crystallize in the non-centrosymmetric structure, space group P63cm, of YMnO3. The Mn-free end member, x=1, crystallizes in a complex multiple cell, the superstructure being associated to Cu3+/Mo6+ cationic ordering. Dilution of the Mn3+ magnetic array by the paramagnetic (Cu2+) and diamagnetic (Mo6+) cations is found to decrease the antiferromagnetic ordering temperature and it becomes undetectable for x0.5 compositions. 相似文献
27.
掺硼多晶金刚石膜的电化学性能研究 总被引:1,自引:0,他引:1
采用EACVD(Electron Assisted Chemical Vapor Deposition)方法制备了掺硼金刚石膜, 并用扫描电镜、拉曼光谱及霍尔效应等测试方法对其表面形貌、生长特性、载流子浓度以及导电性能进行了分析. 测试结果表明, 掺硼金刚石膜是由微米级晶粒组成的多晶膜, 其载流子浓度为4.88×1020 cm-3, 电阻率为0.03 Ω·cm, 是高品质金刚石膜. 用该金刚石膜制作电化学电极, 利用循环伏安法分别测量了金刚石膜电极在氯化钾空白底液、亚铁氰化钾溶液和左旋半胱氨酸溶液中的循环伏安曲线, 发现该金刚石膜电极在水溶液中具有宽的电化学窗口(约为3.7 V)和接近零的背景电流, 在生物制剂的检测中具有很高的灵敏度和良好的稳定性, 是一种理想的电化学电极材料. 相似文献
28.
《Electroanalysis》2004,16(21):1777-1784
The surface of boron‐doped diamond (BDD) electrode is modified by the polymer film for the first time. The cationic polymer film of N,N‐dimethylaniline (DMA) is electrochemically deposited on BDD electrode surface. This polymer (PDMA) film‐coated BDD electrode is used as a sensor which selectively detect dopamine (DA) in the presence of ascorbic acid (AA). This electrode also can detect both DA and its metabolite, 3,4‐dihydroxy phenyl acetic acid (DOPAC) in the presence of AA in the range of the physiological concentrations of these species. Favorable ionic interaction (i.e., electrostatic attraction) between the PDMA film and AA or DOPAC lowers their oxidation potentials and enhances the current response for AA and DOPAC compared to that at the bare electrode. The PDMA film also shows a hydrophobic interaction with DA and DOPAC. In cyclic voltammetric measurements, the PDMA film‐coated electrode can successfully separate the oxidation potentials for AA and DA coexisting in the same solution and the separation is about 200 mV. AA oxidizes at more negative potential than DA. In square‐wave voltammetry, the sensitivity of the PDMA film‐coated BDD electrode for DA in the presence of higher concentration of AA is higher than that of the PDMA film‐coated glassy carbon electrode. The hydrodynamic amperometric experiments confirm that the oxidation of AA is not affected by the oxidized product of DA and vice versa. So, unlike the bare electrode the catalytic oxidation of AA by the oxidized DA is eliminated at the PDMA film‐coated BDD electrode. The sensitivities of the modified electrode for AA, DA and DOPAC, which are present in the same solution with their physiological concentration ratios, are calculated to be 0.070, 0.363 and 0.084 μA μM?1, respectively. The modified electrode exhibits a stable and sensitive response to DA. 相似文献
29.
A novel carrier of ultradispersed diamond black powder (UDDBP) was used to support metallocene catalyst. Al2O3 was also used as carrier in order to compare with UDDBP. Supported catalysts for ethylene polymerization were synthesized by two different reaction methods. One way was direct immobilization of the metallocene on the support, the other was adsorption of MAO onto the support followed by addition of the metallocene. Four supported catalysts Cp2ZrCl2/UDDBP, Cp2ZrCl2/Al2O3, Cp2ZrCl2/MAO/UDDBP and Cp2ZrCl2/Al2O3/MAO were obtained. The content of the zirconium in the supported catalyst was determined by UV spectroscopy. The activity of the ethylene polymerization catalyzed by supported catalyst was investigated. The influence of Al/Zr molar ratio and polymerization temperature on the activity was discussed. The polymerization rate was also observed. 相似文献
30.