全文获取类型
收费全文 | 2721篇 |
免费 | 227篇 |
国内免费 | 543篇 |
专业分类
化学 | 1606篇 |
晶体学 | 21篇 |
力学 | 910篇 |
综合类 | 70篇 |
数学 | 108篇 |
物理学 | 776篇 |
出版年
2024年 | 9篇 |
2023年 | 25篇 |
2022年 | 74篇 |
2021年 | 80篇 |
2020年 | 87篇 |
2019年 | 81篇 |
2018年 | 73篇 |
2017年 | 107篇 |
2016年 | 122篇 |
2015年 | 118篇 |
2014年 | 131篇 |
2013年 | 255篇 |
2012年 | 151篇 |
2011年 | 227篇 |
2010年 | 170篇 |
2009年 | 181篇 |
2008年 | 200篇 |
2007年 | 148篇 |
2006年 | 189篇 |
2005年 | 150篇 |
2004年 | 120篇 |
2003年 | 116篇 |
2002年 | 102篇 |
2001年 | 79篇 |
2000年 | 77篇 |
1999年 | 68篇 |
1998年 | 68篇 |
1997年 | 45篇 |
1996年 | 47篇 |
1995年 | 35篇 |
1994年 | 31篇 |
1993年 | 19篇 |
1992年 | 27篇 |
1991年 | 18篇 |
1990年 | 12篇 |
1989年 | 10篇 |
1988年 | 8篇 |
1987年 | 7篇 |
1986年 | 3篇 |
1985年 | 3篇 |
1984年 | 2篇 |
1983年 | 2篇 |
1982年 | 8篇 |
1980年 | 2篇 |
1979年 | 1篇 |
1978年 | 1篇 |
1973年 | 1篇 |
1959年 | 1篇 |
排序方式: 共有3491条查询结果,搜索用时 15 毫秒
101.
The adsorption and inhibition effect of xanthione (XION) on mild steel in 0.5 M H2SO4 at 303–333 K were studied using gravimetric and UV–visible spectrophotometric methods. The results obtained show that XION acts as an effective corrosion inhibitor for mild steel in sulphuric acid and inhibition efficiency reaches 98.0% at a very low inhibitor concentration of 10 μM. Inhibition efficiency was found to increase with increase in XION concentration but decreased with temperature suggesting physical adsorption mechanism. Arrhenius law and its transition equation lead to estimate the activation parameters of the corrosion process. XION inhibits the corrosion of mild steel effectively at moderate temperature and adsorbs according to the Langmuir isotherm. Thermodynamic parameters governing the adsorption process have been calculated and discussed. The UV–visible absorption spectra of the solution containing the inhibitor after the immersion of mild steel specimen indicate the formation of a XEN–Fe complex. Attempt to correlate the molecular structure to quantum chemical indices was made using density functional theory (DFT). 相似文献
102.
Stir bar sorptive extraction (SBSE) and thermal desorption (TD)–gas chromatography–mass spectrometry (GC–MS) have been optimized for the determination of five organic booster biocides (Chlorothalonil, Dichlofluanid, Sea-Nine 211, Irgarol 1051 and TCMTB) in seawater samples. The parameters affecting the desorption and absorption steps were investigated using 10 mL seawater samples. The optimised conditions consisted of an addition of 0.2 g mL−1 KCl to the sample, which was extracted with 10 mm length, 0.5 mm film thickness stir bars coated with polydimethylsiloxane (PDMS), and stirred at 900 rpm for 90 min at room temperature (25 °C) in a vial. Desorption was carried out at 280 °C for 5 min under 50 mL min−1 of helium flow in the splitless mode while maintaining a cryotrapping temperature of 20 °C in the programmed-temperature vaporization (PTV) injector of the GC–MS system. Finally, the PTV injector was ramped to a temperature of 280 °C and the analytes were separated in the GC and detected by MS using the selected-ion monitoring (SIM) mode. The detection limits of booster biocides were found to be in the range of 0.005–0.9 μg L−1. The regression coefficients were higher than 0.999 for all analytes. The average recovery was higher than 72% (R.S.D.: 7–15%). All these figures of merit were established running samples in triplicate. This simple, accurate, sensitive and selective analytical method may be used for the determination of trace amounts of booster biocides in water samples from marinas. 相似文献
103.
The protection power of the cationic surfactant decylammonium acetate (DAA) in seawater has been studied to define the perfect conditions have to be found for using it as a corrosion inhibitor for copper surface. The adsorption isotherm of this surfactant on copper surface has been determined at different interval times at 30°C. The given isotherms have, in general, similar shapes exhibiting a Languimirian L-shape. The corrosion measurement has been determined according to weight loss method. The study declines that cationic DAA, in seawater, protects well the copper surface against corrosion when added with low concentrations, while high concentrations show bad inhibition efficiency. ICP spectroscopic analysis assures this result where high Cu% has been obtained in the presence of high DAA concentration. 相似文献
104.
Salah Abd El Wanees Sabry Hamed Seda 《Journal of Dispersion Science and Technology》2013,34(12):1813-1826
AbstractThe kinetics of H2 production during Zn corrosion in 0.5?M HCl without and with various additives of N,N'-bis-(1-hydroxyphenylimine)-2,5-thiophenedicarboxaldehyde (HPTD) was studied using gasometry and electrochemical techniques. The surface of the corroded Zn samples was investigated using SEM and Optical Profilometry. The rate of H2 production (RHP) increased with the immersion time and temperature. Presence of HPTD mitigated RHP due to an adsorption process. The electrochemical impedance spectroscopy showed that HPTD had a good inhibitive effect. Polarization data proved that HPTD acted as a surface-active mixed-type inhibitor. Some thermodynamic parameters were deduced and discussed. Theoretical calculations were also conducted to corroborate the capability of HPTD to protect Zn surface from corrosion process. 相似文献
105.
苯基硫脲对6063铝合金表面化学镀镍层电化学性能的影响 总被引:1,自引:0,他引:1
采用极化曲线及交流阻抗技术研究了不同浓度的苯基硫脲(稳定剂)对6063铝合金表面镍层的电化学性能的影响。极化曲线结果表明,镀液中加入苯基硫脲后的镀镍层比基体铝合金具有更正的腐蚀电位(Ecorr)、小孔(点)腐蚀电位(Epit)及更低的腐蚀电流(icorr)。为了解释镍层的电化学性能,建立了等效电路模型,并拟合出了表面电阻(Rcoat)及电容(Qcoat),电荷转移电阻(Rct)及双电层电容(Qdl)等腐蚀参数。交流阻抗研究结果表明,加入6~10 mg/L苯基硫脲后的镀镍层具有较高的表面电阻(Rcoat)、电荷转移电阻(Rct)及较低的表面电容与双电层电容(Qcoat与Qdl)。镀镍层的交流阻抗谱及极化曲线的测试结果表明,制备的镀层具有较好的耐腐蚀性能,并且相互吻合。采用扫描电子显微镜及能谱对化学镀镍层的表面形貌及成份进行了分析。结果显示,表面处于较均匀的状态,磷元素的质量分数超过10%。 相似文献
106.
Electroless Ni–P and Ni–P–TiCN composite coatings have been deposited successfully on Al substrates. Scanning electron microscopy (SEM) and energy dispersive X‐ray (EDX) techniques were applied to study the surface morphology and the chemical composition of the deposited films. Moreover, X‐ray diffraction (XRD) proved that Ni–P and Ni–P–TiCN deposits have amorphous structures. The properties of Ni–P–TiCN/Al composite films such as hardness, corrosion resistance and electrocatalytic activity were examined and compared with that of Ni–P/Al film. The results of hardness measurements reveal that the presence of TiCN particles with Ni–P matrix improves its hardness. Additionally, the performance against corrosion was examined using Tafel lines and electrochemical impedance spectroscopy techniques in both of 0.6 M NaCl and a mixture of 0.5 M H2SO4 with 2 ppm HF solutions. The results indicate that the incorporation of high dispersed TiCN particles into Ni–P matrix led to a positive shift of the corrosion potential and an increase in the corrosion resistance for all aluminum substrates after their coating with Ni–P–TiCN. In addition, Ni–P–TiCN/Al electrodes showed a higher electrochemical catalytic activity and stability toward methanol oxidation in 0.5 M NaOH solution compared with that of Ni–P/Al. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
107.
The adsorption and corrosion inhibition behavior of synthesized Schiff base-based cationic gemini surfactant bis[p-(N,N,N-tetradecyldimethylammonium bromide)benzylidene]thiourea (14-S-14) on mild steel in 20% formic acid in the temperature range of 30°C to 60°C was evaluated using weight loss measurements, solvent analysis of iron ions and potentiodynamic polarization measurements. The synthesized inhibitor was characterized using Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance spectroscopy (NMR), and thin layer chromatography (TLC). The surface morphology of the corroded mild steel specimen was evaluated using scanning electron microscopy (SEM), energy dispersive x-ray analysis (EDAX), and atomic force microscopy (AFM). Thermodynamic/kinetic parameters were calculated to elaborate the adsorption and corrosion inhibition mechanism of the inhibitor. The inhibition efficiency of the compound was found to vary with inhibitor concentration, immersion time, and temperature. The adsorption of the compound on the steel surface was found to obey Langmuir adsorption isotherm. 相似文献
108.
The corrosion inhibition of mild steel in hydrochloric acid solution in the presence of three different molecular weights of polyvinyl alcohol (PVA) designated as PVA-I, PVA-II, and PVA-III corresponding to 14,000, 72,000, and 125,000 g mol?1, respectively, was investigated using electrochemical impedance spectroscopy, linear polarization resistance (LPR), and potentiodynamic polarization techniques at 25°C. It was found that PVA of different molecular weights inhibited the corrosion of mild steel in the acid environment. Inhibition efficiency (η%) increases with increase in concentration of the polymers. LPR measurements clearly show that inhibition efficiency increases with increasing molecular weight in the order PVA-III > PVA-II > PVA-I. Polarization curves indicate that PVA functions as a mixed inhibitor affecting both the anodic metal dissolution and cathodic hydrogen evolution partial reactions of the corrosion process. The experimental data obtained fitted well into Langmuir adsorption isotherm model. Physical adsorption mechanism is proposed from the thermodynamic (free energy of adsorption) parameters obtained. 相似文献
109.
Mahendra Yadav Sushil Kumar Rajesh Ranjan Sinha Sumit Kumar 《Journal of Dispersion Science and Technology》2014,35(12):1751-1763
Imidazole derivatives, namely, 1-((1-(piperazinomethyl)-1H-benzoimidazol-2-yl)methyl)-2-phenylhydrazine (PBIP), and 1-((1-(morpholinomethyl)-1H-benzoimidazol-2-yl)methyl)-2-phenylhydrazine (MBIP) were synthesized and investigated as inhibitors for mild steel corrosion in 15% HCl solution using weight loss, potentiodynamic polarization, and electrochemical impedance spectroscopy (EIS) techniques. It was found that the inhibition efficiency of both the inhibitors increases with increase in concentration of inhibitors and decreases with increase in temperature. The inhibitors, PBIP and MBIP, show corrosion inhibition efficiency of 92.6% and 91.4% at 300 ppm concentration, respectively, at 303 K. Polarization studies showed that both the studied inhibitors were of mixed type in nature. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) were performed for surface study of uninhibited and inhibited mild steel samples. The semi-empirical AM1 method was employed for theoretical calculations. 相似文献
110.
Headspace stir bar sorptive extraction followed by thermal desorption and gas chromatography with mass spectrometry to determine musk fragrances in sludge samples without sample pretreatment 总被引:1,自引:0,他引:1 下载免费PDF全文
Laura Vallecillos Marta Pedrouzo Eva Pocurull Francesc Borrull 《Journal of separation science》2014,37(11):1322-1329
A direct, simple and solvent‐free method based on headspace stir bar sorptive extraction and thermal desorption gas chromatography with mass spectroscopy was developed to determine 13 musk fragrances (six polycyclic musks, three nitro musks and four macrocyclic musks) in sludge without sample treatment. The optimal headspace stir bar sorptive extraction conditions were achieved when a polydimethylsiloxane stir bar was exposed for 45 min in the headspace of a 10 mL vial filled with 100 mg of sludge mixed with 0.2 mL of water stirred at 750 rpm at 80°C. The stir bar was then desorbed in the thermal desorption gas chromatography and mass spectrometry system, obtaining limits of detection between 5 and 30 ng/g. The method applicability was tested with sewage sludge from two urban wastewater treatment plants and from a potable water treatment plant. Results showed galaxolide and tonalide to be the most abundant musk fragrances found in wastewater treatment plants with maximal concentrations of 9240 and 7500 ng/g, respectively. Maximum concentration levels between 35 and 635 ng/g were found for musk ketone, musk moskene, traseolide, phantolide and celestolide in this kind of samples. Concentrations below the limits of quantitation of phantolide, galaxolide, tonalide and musk ketone were found in sludge from a potable water treatment plant. 相似文献