全文获取类型
收费全文 | 1643篇 |
免费 | 250篇 |
国内免费 | 155篇 |
专业分类
化学 | 882篇 |
晶体学 | 21篇 |
力学 | 256篇 |
综合类 | 37篇 |
数学 | 79篇 |
物理学 | 773篇 |
出版年
2023年 | 23篇 |
2022年 | 41篇 |
2021年 | 67篇 |
2020年 | 68篇 |
2019年 | 47篇 |
2018年 | 37篇 |
2017年 | 69篇 |
2016年 | 74篇 |
2015年 | 68篇 |
2014年 | 57篇 |
2013年 | 182篇 |
2012年 | 103篇 |
2011年 | 89篇 |
2010年 | 83篇 |
2009年 | 84篇 |
2008年 | 67篇 |
2007年 | 100篇 |
2006年 | 96篇 |
2005年 | 67篇 |
2004年 | 55篇 |
2003年 | 64篇 |
2002年 | 55篇 |
2001年 | 61篇 |
2000年 | 49篇 |
1999年 | 40篇 |
1998年 | 50篇 |
1997年 | 35篇 |
1996年 | 25篇 |
1995年 | 37篇 |
1994年 | 38篇 |
1993年 | 24篇 |
1992年 | 13篇 |
1991年 | 12篇 |
1990年 | 18篇 |
1989年 | 6篇 |
1988年 | 7篇 |
1987年 | 6篇 |
1986年 | 7篇 |
1985年 | 3篇 |
1984年 | 5篇 |
1983年 | 1篇 |
1982年 | 2篇 |
1981年 | 2篇 |
1980年 | 1篇 |
1977年 | 3篇 |
1976年 | 1篇 |
1974年 | 1篇 |
1972年 | 1篇 |
1959年 | 1篇 |
1957年 | 2篇 |
排序方式: 共有2048条查询结果,搜索用时 718 毫秒
81.
采用密度泛函理论研究氮功能化对蒄类化合物几何构型、电子结构及载流子传输性质的影响. 结果表明, 引入杂N原子可以线性降低前线轨道能级, 增强电子注入能力与空气稳定性, 且邻位掺杂较迫位和均匀掺杂调节效果更为显著. 其中, 十二氮杂蒄(12ac)具有新颖的“碗状”构型和高的电子亲和势(3.45 eV), 是潜在的空气稳定电子传输材料构筑单元. 理论预测室温下2,6,10-三对甲氧基苯基-3,4,7,8,11,12-六甲氧基三氮杂蒄(3b)晶体的电子迁移率为0.242 cm2/V s, 预计是良好的电子传输材料, 值得进一步器件化研究. 相似文献
82.
重度原油注空气低温氧化过程研究(英文) 总被引:1,自引:0,他引:1
低温氧化反应对现场燃烧(ISC)技术点火的成功有十分重要的影响.采用高压氧化管,研究了不同温度压力下,新疆克拉玛依重度原油的低温氧化过程.结果表明,温度和压力的变化对低温氧化反应的放热程度、持续时间以及气体产物有明显影响.适合油样低温氧化反应的温度和压力分别为150℃和10MPa.此外,采用纯组分替代原油族组分进行低温氧化实验,研究低温氧化反应对原油族组分(饱和烃、芳香烃、胶质、沥青质)含量的影响.结果表明,原油所含族组分中,芳香烃组分最易被氧化,其含量由氧化前的19.17%减少到12.38%(150℃)和9.51%(250℃).随着低温氧化过程的进行,结构复杂的族组分(胶质、沥青质)的含量明显增加.实验数据对油藏实施注空气技术,以及该技术现场实施条件的确定有十分重要的指导意义. 相似文献
83.
Abstract Aromatics nitrate with NO2/air catalyzed by novel Brønsted acidic ionic liquids (ILs) without any volatile chlorinated organic solvent under mild conditions. The ILs employed were caprolactam based, [Caprolactam]X (X?=pTSO?, BSO?, BF4 ?, NO3 ?), which are of relatively lower cost and lower toxicity than traditional imidazolium‐based ILs. The nitration reactions were carried out at ?15 to ?0°C first, then at room temperature for a longer time with a little excessive NO2 (ca. 1.4 eqv.) for moderate yield (for toluene). The IL could be reused four times. 相似文献
84.
A new tetragonal phase of Lu11Sn10 is obtained from high temperature reaction of the pure elements in a welded tantalum tube. Its crystal structure was established by single-crystal X-ray diffraction. Lu11Sn10 crystallizes in the tetragonal space group I4/mmm (No.139) with a=11.2953(18), c=16.424(4), V=2095.5(7)3 , Z=4, Mr=3111.57, Dc=9.863 g/cm3 , μ=62.897 mm-1, F(000)=5124, and the final R=0.0348 and wR=0.0894 for 706 observed reflections with I>2σ(I). The structure of Lu11Sn10 may be derived from the Ho11Ge10 structural type. It is isostructural with Dy11Sn10 , featuring a three-dimensional (3D) framework composed of [Sn4] squares and [Sn2] dimers interlinked via Sn-Sn bonds with two types of one-dimensional (1D) tunnels along the c-axis, which are occupied by isolated Sn atoms, [Sn2] dimers and all the Lu atoms. Band structure calculation based on density functional theory method indicates that Lu11Sn10 is metallic. 相似文献
85.
Nick Alexandrou Murray Smith Richard Park Kevin Lumb Ken Brice 《International journal of environmental analytical chemistry》2013,93(4):257-280
Abstract The Accelerated solvent extraction (ASE) of PAHs (23 2- to 6-ring species) spiked onto glass fibre filters (GFFs) was studied as a function of variable extraction solvents, pressure, temperature and extraction times. Acceptable recoveries (85% ± 15%) were obtained for certain combinations of conditions and a tentative method (1500 psi, 150°C, 70:30 hexane:acetone mixture, 7 min heat-up time, 5 min static extraction time, 60% flush volume, 2 static cycles was selected for further testing. However, this method did not prove as effective as the traditional Soxhlet method of extraction when these parameters were used to extract native PAHs from ambient atmospheric particulate matter collected on a GFF by Integrated Atmospheric Deposition Network (IADN) sampling protocols. The extraction recovery study for spiked GFFs was repeated using slightly different extraction conditions: 2000 psi, 100°C, 70:30 hexane:acetone, 5 min heat-up time, 5 min static extraction time, 150% flush volume, 3 static cycles. When this method was applied to the extraction of native PAHs from ambient atmospheric particulate matter collected on GFFs, the results showed equivalent or better recoveries to that of the Soxhlet method. The total time of extraction was 25 min requiring only 30 mL of solvent. This ASE method is presently used to quantitatively determine PAHs in IADN particle-phase samples. 相似文献
86.
John L. Bove Paul Dalven 《International journal of environmental analytical chemistry》2013,93(3-4):189-196
An analytical technique is presented that determines the amount of airborne phthalates in a glass fiber filter. The methodology makes use of a GC/MS system that has been integrated with a dedicated mini-computer. 相似文献
87.
Richard J.C. Brown Kim E. Jarvis Benoit A. Disch Sharon L. Goddard 《International journal of environmental analytical chemistry》2013,93(3):335-348
Three different types of simple and low-cost calibration material for the measurement of the metals content of ambient particulate matter (PM) on filters using laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) have been compared: cellulose ester filters spiked with multi-element calibration solutions, pellets of compressed ambient particulate matter certified reference material (CRM), and powdered ambient particulate matter CRM adhered to a surface. Elements determined were As, Cd, Cr, Cu, Fe, Mn, Ni, Pb, V and Zn, each at approximate levels of 1000?ng per filter. Blank filters spiked with multi-elemental standards were found to be significantly more reproducible and repeatable than materials based on powdered reference materials. However, a comparison of these spiked filters with real samples of ambient PM showed that the analytical sensitivities obtained per mass of analyte were significantly different. It is concluded that the spiked filters could act as very effective quality control standards correcting, to within 1%, drifts in LA-ICP-MS measurements of up to 10%, or as indirect calibration materials supported by additional measurements using traditional wet chemical techniques. 相似文献
88.
Duc Hoai Do Christophe Walgraeve Samuel Fekadu Hayleeyesus Patrick De Wispelaere Jo Dewulf 《International journal of environmental analytical chemistry》2013,93(3):298-314
The effects of urban and indoor air pollution on human health are a major environmental concern for all, but not much has been researched in the developing world. Specifically, quantitative data on the occurrence of volatile organic compounds (VOCs) – main contributors to air pollution – in Asia and Africa are scarce compared to the availability of data in the developed world. This paper presents one of the first studies focusing on the analysis and occurrence of VOCs in Vietnam and Ethiopia, which constitutes part of the novelty of this work. A spectrum of 34 VOCs was measured at eight different urban sites in Ghent (Belgium), Hanoi (Vietnam), Jimma and Addis Ababa (Ethiopia) during three sampling campaigns from September 2008 to September 2010. Sampling was done in an active way by means of sorbent tubes filled with Tenax TA. The analysis was done by TD-GC-MS using internal standard calibration. Data were interpreted and compared in terms of (i) individual, subgroup and total VOCs concentration (TVOCs), (ii) indoor-to-outdoor (I/O) concentration ratios, (iii) source identification by diagnostic ratio and/or correlation coefficients, and (iv) ozone formation potential (OFP) at outdoor sites based on up-to-date maximum incremental reactivity (MIR). I/O concentration ratios varied between 0.2 and 30, with big differences noticed with respect to the type of VOC(s) considered and the type of outdoor sampling location. The highest TVOC concentrations were measured in street samples with maximum values of 54?µg/m3 in Ghent, 507?µg/m3 in Hanoi and 318?µg/m3 in Addis Ababa illustrating the large difference in ambient air quality levels. This is also reflected in the arithmetic mean OFP values (µg/m3) of 82, 1308 and 596 in Ghent, Hanoi and Addis Ababa, respectively. Results of this study could be helpful to support formulation of national policy with regard to ambient air quality. 相似文献
89.
Nga H. Nguyen Xuefei Leng Hao‐Jan Sun Virgil Percec 《Journal of polymer science. Part A, Polymer chemistry》2013,51(15):3110-3122
The efficient Cu(0) wire‐catalyzed single‐electron transfer‐living radical polymerization (SET‐LRP) of oligo(ethylene oxide) methyl ether methacrylate (OEOMA) in DMSO and binary mixtures of DMSO with H2O is reported. Addition of 10–80% H2O to DMSO resulted in an increase in the apparent rate constant of propagation ( ), corresponding to an increase in the polarity and extent of disproportionation. At higher H2O content, decreases, and in H2O is slightly lower than that in DMSO. This unexpected behavior was attributed to the physical inaccessibility of Cu(0) wire catalyst to the hydrophobic reactive centers of OEOMA and initiator which self‐assemble in H2O into micellar aggregates and vesicles. This hypothesis was confirmed by the faster polymerization in H2O than in DMSO during catalysis with Cu(0) nanoparticles generated by disproportionation of CuBr. SET‐LRP of OEOMA can be performed in protic and dipolar aprotic solvents in air by the addition of hydrazine hydrate. The polymerization exhibited no induction period and identical as in the degassed experiment, and led to polymers with narrow molecular weigh distribution. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 3110–3122 相似文献
90.
通过对正丁烷/氢气/空气混合物在Pt 催化表面的详细反应机理分析, 研究了氢气添加对正丁烷/空气混合物催化着火过程的影响. 研究发现, 在正丁烷/空气混合中添加氢气有助于正丁烷在更低的温度下实现催化着火, 而且不同的氢气添加量对混合物的着火温度和着火过程呈现不同的影响: 当氢气添加量较小时, 氢气的作用主要呈现为热影响; 而当氢气添加量较大时, 氢气的作用主要呈现为化学影响. 这些结果与实验结果是一致的. 本文进一步确定了发挥不同作用的氢气添加量的范围, 并分别对热作用和化学作用情况下的着火启动反应进行了动力学分析. 相似文献