全文获取类型
收费全文 | 3078篇 |
免费 | 110篇 |
国内免费 | 259篇 |
专业分类
化学 | 2497篇 |
晶体学 | 14篇 |
力学 | 14篇 |
综合类 | 5篇 |
数学 | 4篇 |
物理学 | 913篇 |
出版年
2024年 | 10篇 |
2023年 | 77篇 |
2022年 | 27篇 |
2021年 | 45篇 |
2020年 | 47篇 |
2019年 | 45篇 |
2018年 | 33篇 |
2017年 | 37篇 |
2016年 | 80篇 |
2015年 | 57篇 |
2014年 | 75篇 |
2013年 | 184篇 |
2012年 | 200篇 |
2011年 | 223篇 |
2010年 | 138篇 |
2009年 | 211篇 |
2008年 | 191篇 |
2007年 | 196篇 |
2006年 | 226篇 |
2005年 | 187篇 |
2004年 | 146篇 |
2003年 | 155篇 |
2002年 | 91篇 |
2001年 | 81篇 |
2000年 | 69篇 |
1999年 | 66篇 |
1998年 | 81篇 |
1997年 | 56篇 |
1996年 | 45篇 |
1995年 | 39篇 |
1994年 | 42篇 |
1993年 | 44篇 |
1992年 | 29篇 |
1991年 | 44篇 |
1990年 | 33篇 |
1989年 | 28篇 |
1988年 | 18篇 |
1987年 | 18篇 |
1986年 | 8篇 |
1985年 | 6篇 |
1984年 | 9篇 |
1983年 | 6篇 |
1982年 | 3篇 |
1981年 | 5篇 |
1980年 | 6篇 |
1979年 | 11篇 |
1978年 | 4篇 |
1976年 | 5篇 |
1974年 | 4篇 |
1973年 | 2篇 |
排序方式: 共有3447条查询结果,搜索用时 15 毫秒
61.
A solid state copper(II) ion sensor is reported based on the application of electropolymerized undoped (neutral) polycarbazole
(PCz) and polyindole (PIn) modified electrodes. The new sensor shows high selectivity to Cu2+ ions with a detection limit of 10–5 M. PCz and PIn are formed respectively by the anodic oxidation of 50 mM carbazole and 5 mM indole monomers in dichloromethane
containing 0.1 M tetrabutylammonium perchlorate on a platinum electrode using a single compartment cell. Potentiostatic polymerization
of both the monomers are carried out at 1.3 V and 1.0 V vs. Ag/AgCl, respectively. Perchlorate ions were electrochemically
removed from the polymer films by applying – 0.2 V vs. Ag/AgCl. Polymer-coated electrodes are incubated in 1 M KCl solution
for 8 h followed by incubation in distilled water for 2 h before using as a metal ion sensor. The undoped PCz and PIn electrodes
were found to be highly selective and sensitive for Cu2+ ions with little selectivity for Pb2+ and negligible response towards Ag+, Hg2+, Cu+, Ni2+, Co2+, Fe2+, Fe3+ or Zn2+. Potentiometric responses for Cu2+ ions are recorded for both the sensor electrodes together with a double-junction Ag/AgCl reference electrode. Calibration
curves for Cu2+ are reported for both ion sensors. The polymer-modified electrodes were found to be stable for several weeks.
Electronic Publication 相似文献
62.
63.
A novel membrane sensor for selective monitoring of iodide, consisting of a triiodide‐ketoconazole ion pair complex dispersed in a PVC matrix, plasticized with a mixture of 2‐nitrophenyl octyl ether and dioctylphtalate with unique selectivity toward iodide ions, is described. The influence of membrane composition, pH of test solution and foreign ions on the electrode performance were investigated. The optimized membrane demonstrates a near‐Nernstian response for iodide ions over a wide linear range from 1.0 × 10?2 to 1.0 × 10?5 M, at 25 ± 1 °C. The electrode could be used over a wide pH range 3–10 and has the advantages of high selectivity, fast response time and good lifetime (over 4 months). It was successfully used as indicator electrode in potentiometric titrations and direct potentiometric assay of iodide ions. 相似文献
64.
The aim of this work is development of methodology for analysis of inorganic cations (sodium, ammonium, potassium, magnesium
and calcium) in fertilizer industry wastewater. Method development includes optimization of eluent flow rate and concentration
of eluent competing ion in order to obtain optimal separation within reasonable analysis time. For that purpose artificial
neural network retention model was developed and used in combination with normalized resolution product criteria function.
Developed artificial neural network retention model shows good predictive ability R2 ≥ 0.9983. The determined ion chromatographic parameters enable baseline separation of all components of interest. By performing
validation procedure and number of statistical tests it is shown that developed ion chromatographic method has superior performance
characteristic: linearity R2 ≥ 0.9984, recovery = 99.81% − 99.44%, repeatability RSD ≤ 0.52%. That result proves that proposed method can be used for
routine monitoring analysis in fertilizer industry. 相似文献
65.
Ion mobility spectrometry (IMS) is a proven technology for detection of vapor phase chemical warfare agents. The technology is suitable for field portable instrumentation due to its small size, high sensitivity, speed of analysis, and low power consumption. However, it suffers from a limited dynamic range and potential difficulties in identifying compounds in complex matrices. The use of gas chromatography (GC) coupled to IMS can overcome the difficulty of chemical identification in mixtures by separating the sample into individual components before detection. Using this approach, IMS technology has previously been adapted to detect biological aerosols using an open tube pyrolyzer and a short GC column (Py-GC-IMS). The open sample introduction tube of a Py-GC-IMS instrument would be a convenient configuration to accept aerosol particulates, and while viewed as needed for aerosol trapping, is not optimal for liquid chemical analyses. To examine the usefulness of an existing Py-GC-IMS system for analysis of chemicals in water, an existing open-port sample interface was replaced with a septum-equipped closed tube injector to contain analyte vapors resulting from liquid injection. Tributylphosphate (TBP) was used as a surrogate chemical warfare agent, and aqueous injections into both closed and open tube assemblies were performed. Sample introduction into the closed tube inlet was also accomplished using solid phase microextraction (SPME) preconcentration. The limit of detection for TBP using an open tube, closed tube, and closed tube configuration with SPME sample introduction was 0.980, 0.196, and 0.0098 mg/L, respectively. 相似文献
66.
Aigars Vītiņš Ģirts Vītiņš Jānis Krastiņš Ints Šteins Ilmārs Zālīte Andrejs Lūsis 《Journal of Solid State Electrochemistry》1998,2(5):299-307
Ceramic specimens have been obtained from the powder of ZrO2-7.5 mol% Y2O3 having a specific surface area of 30 m2/g synthesized in air plasma. The novelty of this research lies in the fact that the plasma process makes it possible to prepare
so-called nanopowders with a particle size less than 100 nm, possessing specific physical, chemical and technological properties.
The sintered density of the specimens was 94–96% of the theoretical value, 6.001 g/cm3. The X-ray diffraction pattern of the specimens corresponded to a face-centered cubic lattice. Impedance in the frequency
range of 100 Hz–15 MHz and d.c. polarization curves in a potential range of −10 to 10 mV were measured in the temperature
range 200–850 °C in heating and cooling cycles. The intragrain, the grain boundary and the total bulk conductivities, the
electrode polarization resistance and their activation energies were determined. The thermal stability of the studied system
was proved in three measurement series up to 600–850 °C in heating and cooling cycles. The results obtained have shown that
the conductivity of ZrO2-7.5 mol% Y2O3 ceramics is not solely a function of temperature, but also depends on the previous thermal state of the ceramics.
Received: 16 October 1997 / Accepted: 19 January 1998 相似文献
67.
The paper deals with the reconstruction of lipid bilayer membranes on a Au-covered polycarbonate membrane. Such a kind of like-biomembranes (namely mixed hybrid bilayer lipid membrane (MHBLM)) are characterised by appreciable long-term stability. Here we describe changes that have been made in the geometry of the experimental device in order to avoid artefacts and render membrane reproduction easier. Incorporation of valinomycin was performed to check the membrane and its stability: conductance and membrane potential following the changes of ion concentration were recorded. This new approach permits increase of successful trials and renders possible, when it breaks, easily formation of a new MHBLM on the same Au-covered polycarbonate membrane support. Finally, the stability shown by the MHBLM renders this system a promising tool for use under flowing conditions. 相似文献
68.
锂离子选择性微电极在生物体液中的响应 总被引:2,自引:0,他引:2
最近几年已报道了几种锂离子选择性电极.本文作者曾研制了以苯基膦酸二辛酯(DOPP)为溶剂,四苯硼酸盐为活性物质的PVC膜锂离子选择电极.本文在此基础上研制了锂离子选择性微电极,比较了以四苯硼酸钾(KTPB)及四苯硼酸钠(NaTPB)为活性物质的锂微电极的性能.同时考察了微电极在细胞内液、血清及生理盐液中对锂离子的响应特性. 相似文献
69.
Phosphate selective electrodes have been produced based upon rubbery membranes containing heterocylic macrocycles as sensors covalently bound to a cross-linked polystyrene-block–polybutadiene-block–polystyrene (SBS) polymer. The membranes were robust and the best HPO42−-selective membrane fabricated was composed of 7.1% (m/m) dicumyl peroxide, 28.3% (m/m) 2-nitrophenyloctylether, 9.8% (m/m) 3-(10-undecenyl)-1,5,8-triazacyclodecane-2,4-dione, 31.0% (m/m) SBS and 23.8% (m/m) PoleStar™ 200R (clay-based filler). The characteristics of this electrode were a linear Nernstian range of 3.9×10−3 to 1×10−6 mol dm−3 HPO42− with a limit of detection of 1.0×10−6 mol dm−3 HPO42−, a slope of −29.7±0.9 mV per activity decade and a pH range from 6 to 8. Selectivity coefficients for phosphate against various interfering anions (chloride, sulfate and nitrate) were determined. Response times were 2 min or under, stability of response and electrode lifetime in continuous use were also very satisfactory. The response behavior of HPO42−-ISEs based upon mobile and bound ionophores was comparable and suggests that mobility of the ionophore is not necessary to obtain a working ISE and that covalent binding of ionophores can be used to produce ISEs of increased stability and robustness. 相似文献
70.
Fine particle superacidic sulfated zirconia (SO42−/ZrO2, S-ZrO2) was synthesized by ameliorated method, and composite membranes with different S-ZrO2 contents were prepared by a recasting procedure from a suspension of S-ZrO2 powder and Nafion solution. The physico-chemical properties of the membranes were studied by ion exchange capacity (IEC) and liquid water uptake measurements, scanning electron microscopy (SEM) and X-ray diffraction (XRD) analysis, thermogravimetry–mass spectrometry (TG–MS) and Fourier transform infrared (FT-IR) spectroscopy. The results showed that the IEC of composite membrane increased with the content of S-ZrO2, S-ZrO2 was compatible with the Nafion matrix, the incorporation of the S-ZrO2 could increase the crystallinity and also improve the initial degradation temperature of the composite membrane. The performance of single cell was the best when the S-ZrO2 content was 15 wt.%, and achieved 1.35 W/cm2 at 80 °C and 0.99 W/cm2 at 120 °C based on H2/O2 and at a pressure of 2 atm, the performance of the single cell with optimized S-ZrO2 was far more than that of the Nafion at the same condition (e.g. 1.28 W/cm2 at 80 °C, 0.75 W/cm2 at 120 °C). The 15 wt.% S-ZrO2/Nafion composite membrane showed lower fuel cell internal resistance than Nafion membranes at high temperature and low relative humidity (RH). 相似文献