全文获取类型
收费全文 | 3301篇 |
免费 | 127篇 |
国内免费 | 513篇 |
专业分类
化学 | 3158篇 |
晶体学 | 19篇 |
力学 | 24篇 |
综合类 | 19篇 |
数学 | 4篇 |
物理学 | 717篇 |
出版年
2024年 | 3篇 |
2023年 | 70篇 |
2022年 | 52篇 |
2021年 | 63篇 |
2020年 | 95篇 |
2019年 | 94篇 |
2018年 | 63篇 |
2017年 | 64篇 |
2016年 | 71篇 |
2015年 | 85篇 |
2014年 | 102篇 |
2013年 | 172篇 |
2012年 | 239篇 |
2011年 | 199篇 |
2010年 | 147篇 |
2009年 | 207篇 |
2008年 | 213篇 |
2007年 | 248篇 |
2006年 | 197篇 |
2005年 | 174篇 |
2004年 | 164篇 |
2003年 | 151篇 |
2002年 | 100篇 |
2001年 | 111篇 |
2000年 | 118篇 |
1999年 | 122篇 |
1998年 | 94篇 |
1997年 | 84篇 |
1996年 | 78篇 |
1995年 | 64篇 |
1994年 | 54篇 |
1993年 | 56篇 |
1992年 | 50篇 |
1991年 | 43篇 |
1990年 | 30篇 |
1989年 | 26篇 |
1988年 | 10篇 |
1987年 | 5篇 |
1986年 | 4篇 |
1985年 | 4篇 |
1984年 | 1篇 |
1983年 | 1篇 |
1982年 | 2篇 |
1981年 | 1篇 |
1980年 | 5篇 |
1979年 | 2篇 |
1978年 | 1篇 |
1973年 | 1篇 |
1966年 | 1篇 |
排序方式: 共有3941条查询结果,搜索用时 15 毫秒
11.
Corrosion-related defects of pure iron were investigated by measuring Doppler broadening energy spectra (DBES) of positron annihilation and positron annihilation lifetime (PAL). Defect profiles of the S-parameter from DBES as a function of positron incident energy up to 30 keV (i.e. ∼1 μm depth) were analyzed. The DBES data show that S-parameter increases as a function of positron incident energy (mean depth) after corrosion, and the increase in the S-parameter is larger near the surface than in the bulk due to corrosion. Furthermore, information on defect size from PAL data as a function of positron incident energy up to 10 keV (i.e. ∼0.2 μm depth) was analyzed. In the two-state trapping model, the lifetime τ2 = 500 ps is ascribed to annihilation of positrons in voids with a size of the order of nanometer. τ1, which decreases with depth from the surface to the bulk, is ascribed to the annihilation of positrons in dislocations and three-dimensional vacancy clusters. The corroded samples show a significant increase in τ1 and the intensity I2, and near the surface the corroded iron introduces both voids and large-size three-dimensional vacancy clusters. The size of vacancy clusters decreases with depth. 相似文献
12.
C. Jeyaprabha 《Applied Surface Science》2005,252(4):966-975
The inhibitor performance of chemically synthesized water soluble poly(aminoquinone) (PAQ) on iron corrosion in 0.5 M sulphuric acid was studied in relation to inhibitor concentration using potentiodynamic polarization and electrochemical impedance spectroscopy measurements. On comparing the inhibition performance of PAQ with that of the monomer o-phenylenediamine (OPD), the OPD gave an efficiency of 80% for 1000 ppm while it was 90% for 100 ppm of PAQ. PAQ was found to be a mixed inhibitor. Besides, PAQ was able to improve the passivation tendency of iron in 0.5 M H2SO4 markedly. 相似文献
13.
J.D. Desai 《Applied Surface Science》2006,252(6):2251-2258
Iron oxide thin films have been obtained by spray pyrolysis using 100% methanolic and ethanolic solutions of iron tri-chloride. The films were deposited onto ITO-coated glass substrates. The preparative conditions have been optimized to obtain compact, pin-hole-free and smooth thin films which are adherent to the substrate. The structural, morphological and compositional characterizations have been carried out by X-ray diffraction, scanning electron microscopy and energy dispersive X-ray analysis. The films deposited using ethanolic solution results into pure hematite; α-Fe2O3 thin films, however, films deposited using methanolic solution consists of hematite and maghemite-c phases of iron oxide. The films are nanocrystalline with particle size of 30-40 nm. The optical absorbance of the film was of the order of 105 cm−1. The optical band gap of films was found to be 2.26 and 2.20 eV for the films deposited using methanolic and ethanolic solutions, respectively. 相似文献
14.
We investigated iron and cobalt films with 20% carbon concentration with nanocrystalline structure. One of the aims of this work is to analyze the physical nature of high-speed structural self-assembling as often happens in explosive crystallization processes in these films. 相似文献
15.
Fumie Takei Daisuke Kodama Sugiko Nakamura Kiyotaka Onitsuka Shigetoshi Takahashi 《Journal of polymer science. Part A, Polymer chemistry》2006,44(1):585-595
Aryl isocyanides bearing free‐base and metallo‐porphyrins were prepared and polymerized with a Pd–Pt μ‐ethynediyl complex as the initiator to give polymers with narrow polydispersity indices. The molecular weights of the resulting polymers were precisely controlled by the initial feed ratio of the porphyrin monomer to the initiator. The UV–VIS spectra suggested that the porphyrin pendants are regularly arranged to form stacked columns. Metallo‐porphyrin polymers were also prepared by reacting free‐base porphyrin polymers with metal salts. The successive reactions of free‐base and zinc‐porphyrin monomers resulted in the formation of diblock polymers. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 585–595, 2006 相似文献
16.
过氧化物模拟酶在介体型生物传感器方面应用初探 总被引:2,自引:0,他引:2
meso-四(4-磺基苯)卟啉锰(Ⅲ)作为过氧化物模拟酶可催化H_2O_2与K_4Fe(CN)_6反应。电流响应与H_2O_2浓度在3.0×10~(-4)~1.0×10~(-3)mol/L范围内呈线性关系。重现性和回收率良好。抗坏血酸和DL-半胱氨酸干扰严重。 相似文献
17.
A method for the direct determination of volatile and non-volatile nickel and vanadium compounds in crude oil without previous treatment using direct solid sampling graphite furnace atomic absorption spectrometry is proposed. The crude oil samples were weighed directly onto solid sampling platforms using a microbalance and introduced into a transversely heated solid sampling graphite tube. In previous work of our group losses of volatile nickel and vanadium compounds have been detected, whereas other nickel and vanadium compounds were thermally stable up to 1300 and 1600 °C, respectively. In order to avoid this problem different chemical modifiers (conventional and permanent) have been investigated. With 400 μg of iridium as permanent modifier, the signal started to drop already after two atomization cycles, possibly because of an interaction of nickel (which is a catalyst poison) with iridium. Twenty micrograms of palladium applied in each determination was found to be optimum for both elements. The palladium was deposited on the platform and submitted to a drying step at 150 °C for 75 s. After that the sample was added onto the platform and submitted to the furnace program. The influence of sample mass on the linearity of the response and on potential measurement errors was also investigated using four samples with different nickel content. For the sample with the lowest nickel concentration the relationship between mass and integrated absorbance was found to be non-linear when a high sample mass was introduced. It was suspected that the modifier had not covered the entire platform surface, which resulted in analyte losses. This problem could be avoided by using 40 μL of 0.5 g L−1 Pd with 0.05% Triton X-100. Calibration curves were established with and without modifier, with aqueous standards, oil-in-water emulsions and the certified reference material NIST SRM 1634c (trace metals in residual fuel oil). The sensitivity for aqueous standards and emulsions was close to that for SRM 1634c, making possible the use of aqueous standards for calibration. The limits of detection and quantification obtained for nickel and vanadium under this condition were found to be 0.02 and 0.06 μg g−1, respectively, for both elements, based on 10 mg of sample. Nickel and vanadium were determined in the samples with (total Ni and V) and without the use of Pd (thermally stable compounds), and the concentration of volatile compounds was calculated by difference. The results were compared with those obtained by high-resolution continuum source graphite furnace atomic absorption spectrometry by emulsion technique; no significant differences were found for total Ni and V at the 95% confidence level according to a Student's t-test. 相似文献
18.
Georgiy B. Shul’pin Camilla C. Golfeto Lidia S. Shul’pina 《Tetrahedron letters》2005,46(27):4563-4567
The H2O2-FeCl3-bipy system in acetonitrile efficiently oxidises alkanes predominantly to alkyl hydroperoxides. Turnover numbers attain 400 after 1 h at 60 °C. It has been assumed that bipy facilitates proton abstraction from a H2O2 molecule coordinated to the iron ion (these reactions are stages in the catalytic cycle generating hydroxyl radicals from the hydrogen peroxide). Hydroxyl radicals then attack alkane molecules finally yielding the alkyl hydroperoxide. 相似文献
19.
meso-四(4-磺酸苯基)卟啉与Co(Ⅱ)的显色反应的研究 总被引:3,自引:0,他引:3
本文研究了弱酸性介质中钴(Ⅱ)与TPPS4的显色反应条件。实验发现胺类化合物质子化后,不参与成络反应,而均能使TPPS4试剂的吸光度大大降低,从而提高了测定的灵敏度,Co(Ⅱ)-TPPS4络合比为1:1,ε_(426)=3.54×10 ̄5,钴含量在0~5.0μg/25mL范围内呈线性,并用于烟草、茶叶中痕量钴的测定,得到了满意的结果。 相似文献
20.
Atsushi Ikeda Masaru Kawaguchi Yoshio Suzuki Tsukasa Hatano Munenori Numata Seiji Shinkai Akio Ohta Makoto Ohta 《Journal of inclusion phenomena and macrocyclic chemistry》2000,38(1-4):163-170
The calixarene-fullerene interaction,which causes only a slight change in the absorptionspectra, has been substantiated by calorimetricmeasurements: the H° values arecomparable with those obtained from the associationconstants estimated by a spectroscopic method. Furthermore, we determined the association constantbetween homooxacalix[3]arene and [60]fullerenederivatives with a porphyrin moiety by fluorescencespectra. 相似文献