全文获取类型
收费全文 | 47096篇 |
免费 | 5161篇 |
国内免费 | 4540篇 |
专业分类
化学 | 40742篇 |
晶体学 | 671篇 |
力学 | 2569篇 |
综合类 | 300篇 |
数学 | 1402篇 |
物理学 | 11113篇 |
出版年
2024年 | 82篇 |
2023年 | 499篇 |
2022年 | 958篇 |
2021年 | 1126篇 |
2020年 | 1518篇 |
2019年 | 1406篇 |
2018年 | 1471篇 |
2017年 | 1924篇 |
2016年 | 2331篇 |
2015年 | 1987篇 |
2014年 | 2116篇 |
2013年 | 4358篇 |
2012年 | 3191篇 |
2011年 | 2890篇 |
2010年 | 2439篇 |
2009年 | 2875篇 |
2008年 | 2572篇 |
2007年 | 2840篇 |
2006年 | 2486篇 |
2005年 | 2197篇 |
2004年 | 1977篇 |
2003年 | 1688篇 |
2002年 | 1490篇 |
2001年 | 1171篇 |
2000年 | 1141篇 |
1999年 | 1024篇 |
1998年 | 910篇 |
1997年 | 777篇 |
1996年 | 775篇 |
1995年 | 718篇 |
1994年 | 607篇 |
1993年 | 507篇 |
1992年 | 447篇 |
1991年 | 407篇 |
1990年 | 305篇 |
1989年 | 264篇 |
1988年 | 275篇 |
1987年 | 244篇 |
1986年 | 166篇 |
1985年 | 133篇 |
1984年 | 141篇 |
1983年 | 49篇 |
1982年 | 99篇 |
1981年 | 64篇 |
1980年 | 34篇 |
1979年 | 39篇 |
1978年 | 17篇 |
1977年 | 9篇 |
1976年 | 9篇 |
1973年 | 10篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
921.
An evaluation of measurements of heat capacities by modulated differential scanning calorimetry, MDSC is presented. Heat capacities were obtained from 130 to 550 K by a non isothermal technique in which a periodic modulation was added to the linear heating rate. Effects of amplitude and period of modulation, sample weight, sample type, pan type, and cell imbalance are described. Results are compared with those obtained using the isothermal technique. Heat capacity could be measured well into the decomposition region and separated from the non reversing signal due to chemical reaction (degradation), thus allowing a precise detection of onsets of the thermal degradation. This additional information will aid in the interpretation of the degradation chemistry, a field vital for the petroleum-industry.Dedicated to Professor Bernhard Wunderlich on the occasion of his 65th birthdayPart of this paper was presented at the 23rd Conference of the North American Thermal Analysis Society, Toronto, Canada, September 25–28, 1994.The author (MVN) acknowledges the experimental assistance provided by J. Balogh of Exxon Research and Engineering Company, Linden. Helpful discussions with A. Boller of the University of Tennessee at Knoxville, Dr. Y. Jin, General Electrical, and Dr. S. Sauerbrunn formerly of TA Instruments are also acknowledged. 相似文献
922.
Summary A new procedure for derivatisation of inorganic mercury(II) to diphenylethynylmercury with simultaneous extraction into dichloromethane is proposed. The organomercury derivative is effectively analysed by HPLC using UV detection. The calibration curve is linear over three orders of magnitude (0.02–50 mg L–1 Hg); the detection limit is 0.1 ng Hg. A preliminary study of the effect of potential interfering agents, in particular Cu(II), Zn(II), Cd(II), Pb(II), and cysteine, and applications of the present methodology to real environmental samples are presented. 相似文献
923.
A method for the preconcentration of gold in natural waters at the sampling site using tributyl phosphate as a solid extractant [Se(TBP)] was developed as a preliminary step prior to the determination of gold by neutron activation and γ-spectrometry. The SE(TBP) was saturated with gaseous chlorine for extracting all gold species. In batch experiments gold was quantitatively retained on the SE(TBP) in 10 min. After extraction and washing, the SE(TBP) was ashed or back-extracted. Gold was quantitatively eluted with hot, neutral 0.025 M thiourea. The gold content of residues of ashing or eluents after evaporation was determined by neutron activation and γ-spectrometry. The detection limit for the overall procedure was 0.2 ng 1?1. The efficiency was tested on ‘equilibrated’ solutions prepared from river water and tracer solutions of gold. For comparison, the gold content of natural water samples was determined using preconcentration on activated charcoal. 相似文献
924.
氰乙基纤维素在二甲基甲酰胺、二甲基乙酰胺、二甲基亚砜、乙腈以及丙酮等溶剂中可以形成溶致性液晶。随浓度增加,溶液从各向同性状态经两相共存态转变成为完全的液晶态。升高温度到T_c,液晶相消失;降低温度到T′_c,液晶相再生成。T_c总大于T′_c。而且,浓度越高,过冷温度△T=T_c—T′_c越小。在各向同性,两相共存或完全的液晶状态,溶液平均折射率和消光度均与浓度呈线性关系。但在两相间相互转变时,即在C_1~*和C_2~*处,n-C和 A-C 曲线上出现转折点。高聚物与溶剂的相互作用参数X_(12)愈小,临界浓度C_1~*愈小。把描述大分子链柔顺性的参数f与X_(12)联系起来,可用 1956年 Flory的理论定性地解释溶剂对高聚物溶致性液晶形成的影响。 相似文献
925.
丁酸壳聚糖液晶的临界行为研究 总被引:6,自引:3,他引:6
用偏光显微镜法测定了丁酸壳聚糖在四种酸性溶剂中的临界浓度值.发现临界浓度值(v/v%)与溶剂的酸性无关,都是16%~17%.在以二氯乙酸为溶剂时,不同丁酰化程度的丁酸壳聚糖有相同的临界浓度.用DSC法测定了丁酸壳聚糖/二氯乙酸体系的临界温度,并绘制了相图.结果表明,浓度达60%(w/w%)后,临界温度基本不再变化,稳定在39℃左右. 相似文献
926.
G. Stringari Ivo Pancheri Frank Möller Osvaldo Failla 《Accreditation and quality assurance》1998,3(3):122-126
Chemical analyses of trace elements are affected by relatively high analytical errors due to the different steps of the laboratory
procedures: samples grinding, mineralisation and instrumental measurements. In the present communication, the influence of
the grinding phase on the global uncertainty of Pb, Cd, Ni and Cr determinations in plant samples by the classical method
of atomic absorption spectrometry/electrothermal atomisation (AAS-ETA) after dry ashing is quantified. Two grinding machines,
a planetary mill with balls and jars of agate versus a stainless steel grinder were compared by analysing leaf samples of
cucumber, strawberry, kiwivines, apple trees and grapevines from agricultural experimental plots under controlled conditions.
Variance components due to the difference between grinding methods and experimental plots were estimated. Further, the simultaneous
effects of the grinding methods on all considered metals have been evaluated by analysis of variance. With the stainless steel
grinder, on average, higher levels of the considered heavy metals were obtained (up to 67% of the mean values). On average,
the increments were similar for metals contained in steel (Ni and Cr) and those not contained (Pb and Cd). The true causes
of these differences need further investigation to determine whether the higher metal detection is due to possible contamination,
to a different grinding quality or to other reasons. Finally, the grinding methods did not seem to affect the combined uncertainty
of the analyses.
Received: 3 November 1997 · Accepted: 29 November 1997 相似文献
927.
About the Structure and Reactivity of Diammonium Hexafluoromanganate(IV) Electrolytic oxidation of an aqueous suspension of MnF2 containing NH4F, and subsequent crystallization in 40% HF yields yellow crystals of (NH4)2MnF6. It crystallizes in the hexagonal K2MnF6 type structure with the space group P63mc and a = 5.903; c = 9.565 Å; Z = 2. With in situ powder diffraction studies it is shown, that (NH4)2MnF6 is gradually reduced in a NH3 atmosphere between 30 and 230 °C to afford (NH4)3MnF6, (NH4)2MnF5, and finally NH4MnF3. (NH4)3MnF6, thereby, forms a hitherto unknown cubic (a = 9.082 Å) high temperature modification with the cryolite type structure. Under N2 the thermal decomposition of (NH4)2MnF6 proceeds via NH4MnF4 to yield MnF2. 相似文献
928.
E.?BertoloEmail author J.?A.?Kilner M.?Sahibzada 《Journal of Solid State Electrochemistry》2004,8(9):585-591
18O/16O isotope exchange depth profiling (IEDP) combined with secondary ion mass spectrometry (SIMS) has been used to measure the oxygen tracer diffusivity of SrCe0.95Yb0.05O3– between 800 °C and 500 °C at a nominal pressure of 200 mbar. The values of D* (oxygen tracer diffusion coefficient) and k (surface exchange coefficient) increase steadily with increasing temperature, and the activation energies are 1.13 eV and 0.96 eV, respectively. Oxygen ion conductivities have been calculated using the Nernst–Einstein equation. The transport number for oxide ions at 769 °C, the highest temperature studied, is only ~0.05. Moreover, SrCe0.95Yb0.05O3– has been studied using impedance spectroscopy under dry O2, wet O2 and wet H2 (N2/10% H2) atmospheres, over the range 850–300 °C. Above ~550 °C, SrCe0.95Yb0.05O3– shows higher conductivity in dry O2 than in wet O2 or wet H2; below that temperature the results obtained for the three atmospheres are comparable. Dry O2 shows the highest activation energy (0.77 eV); the activation energies for wet O2 and wet H2 are identical (0.62 eV).Abbreviations HTPC high-temperature proton conductor - IEDP isotope exchange depth profiling - SIMS secondary ion mass spectrometryPresented at the OSSEP Workshop Ionic and Mixed Conductors: Methods and Processes, Aveiro, Portugal, 10–12 April 2003 相似文献
929.
Ródenas-Torralba E Cava-Montesinos P Morales-Rubio A Cervera ML De La Guardia M 《Analytical and bioanalytical chemistry》2004,379(1):83-89
The aim of this study is to show the advantages of the emerging multicommutation methodology based on the use of solenoid valves for Te determination in milk by hydride generation atomic fluorescence spectrometry (HG-AFS). The delivery of a series of alternating sequential insertions of small volumes of samples and reagents gives rise to new hydrodynamic processes and exciting analytical potentials by controlling the time of flow through the on/off-switched solenoid valves. This drastically reduces the reagent consumption by a factor of 4 and the generation of effluents (590 mL h–1 instead of 750 mL h–1 generated by the continuous-mode measurement) and also provides an improvement in the laboratory productivity by an increase of the sample throughput (85 h–1 compared to 20 h–1 found in the continuous mode). So, multicommutation is an environmentally and economically sustainable alternative to the methodology based on continuous measurements. The multicommutation-based method developed was applied to tellurium determination in commercially available milk samples; a calibration range of 0.0–0.5 ng mL–1 and a detection limit of 0.20 ng L–1 with average relative standard deviation of 2.1% were found. Comparable results were obtained for a series of samples using both continuous and multicommutation HG-AFS modes. 相似文献
930.
A simple liquid chromatographic method was developed for the separation and quantification of voriconazole and its enantiomer
in drug substance. The separation was achieved on Chiral cel-OD (250 mm × 4.6 mm × 10 μm) using mobile phase consisting of
n-hexane and ethanol in the ratio 9:1 (v/v) with a flow rate of 1.0 mL min−1, at 27 °C column temperature and detection at 254 nm with an injection volume of 20 μL. Ethanol was used as diluent. The
method is capable of detecting the (2S, 3R) enantiomer down to 0.0075% and can quantify down to 0.021% with respect to sample concentration. The method is rapid and
the resolution achieved was about 3.0. This method can be employed for the quantification of (2S, 3R) enantiomer in voriconazole drug substance. 相似文献