首页 | 本学科首页   官方微博 | 高级检索  
文章检索
  按 检索   检索词:      
出版年份:   被引次数:   他引次数: 提示:输入*表示无穷大
  收费全文   9840篇
  免费   983篇
  国内免费   909篇
化学   4072篇
晶体学   136篇
力学   3928篇
综合类   129篇
数学   662篇
物理学   2805篇
  2024年   19篇
  2023年   81篇
  2022年   364篇
  2021年   426篇
  2020年   323篇
  2019年   213篇
  2018年   207篇
  2017年   313篇
  2016年   388篇
  2015年   329篇
  2014年   427篇
  2013年   634篇
  2012年   454篇
  2011年   608篇
  2010年   420篇
  2009年   535篇
  2008年   505篇
  2007年   596篇
  2006年   587篇
  2005年   484篇
  2004年   486篇
  2003年   415篇
  2002年   349篇
  2001年   301篇
  2000年   324篇
  1999年   257篇
  1998年   221篇
  1997年   207篇
  1996年   210篇
  1995年   155篇
  1994年   124篇
  1993年   131篇
  1992年   108篇
  1991年   100篇
  1990年   73篇
  1989年   52篇
  1988年   60篇
  1987年   56篇
  1986年   36篇
  1985年   26篇
  1984年   25篇
  1983年   13篇
  1982年   26篇
  1981年   24篇
  1980年   4篇
  1979年   8篇
  1977年   6篇
  1976年   9篇
  1973年   3篇
  1957年   3篇
排序方式: 共有10000条查询结果,搜索用时 373 毫秒
81.
采用电沉积-热解法在3Cr25Ni7N合金表面制备了Y2O3薄膜,并研究了薄膜处理对合金在1000℃空气中的抗高温氧化性能的影响。氧化动力学曲线、SEM及XRD分析结果表明,Y2O3薄膜处理使合金表面氧化膜以尖晶石结构为主,氧化膜致密,有效地抑制了Cr2O3的挥发反应,且氧化膜与基体的附着性好,因此合金在高温下的抗氧化性能得到提高,这与氧化钇薄膜在较低温度下抗高温氧化性能提高的机制是不同的。在不同温度下,Y2O3薄膜处理均可以有效提高合金的抗高温氧化性能。  相似文献   
82.
Tschmelak J  Proll G  Gauglitz G 《Talanta》2005,65(2):313-323
Certain contaminants at trace concentrations in surface waters can have dramatic effects on the hormonal system of organisms in the aquatic environment. Therefore, immunoanalytical methods at a very low limit of detection (LOD) and a low limit of quantification (LOQ) are becoming more and more important for environmental analysis and especially for monitoring drinking water quality. Environmental monitoring of antibiotics, hormones, endocrine disrupting chemicals, and pesticides in real water samples (e.g. surface, ground or drinking water) with difficult matrices places high demands on chemical analysis. Biosensors have suitable characteristics such as efficiency in allowing very fast, sensitive, and cost-effective detection. Here we describe an assay optimization process with a fully automated immunoassay for estrone which resulted in a LOD below 0.20 ng L−1 and a LOQ below 1.40 ng L−1. In contrast to common analytical methods such as GC-MS or HPLC-MS, the biosensor used requires no sample pre-treatment and pre-concentration. The very low validation parameters for estrone are the result of the continuous optimization of the immunoassay. The basis of our sensitive assay is the antibody with a high affinity constant towards estrone. During the optimization process, we reduced the amount of antibody per sample and improved the chip surface modification. Finally, this proceeding led to a calibration routine with an amount of antibody of only 3.0 ng per sample (sample volume: 1.0 mL). The reduction of the amount of antibody per sample results in better validation parameters (LOD, LOQ, and IC50), but this reduction leads to the current device-related limitation of the River Analyser (RIANA).For some endocrine disrupting compounds, no effect levels (NOELs) in the lower nanogram per liter range are reported. This defines the challenge, which analytical methods have to compete with and our RIANA instrument with its improved sensitivity for the detection of a single hormone in the lower nanogram per liter range is a powerful tool in aquatic analytics in addition to the common analytical methods.  相似文献   
83.
A novel sorbent, dihydroxylated polymethylmethacrylate (DHPMM), coated on hollow-fiber membrane, is used for the polymer-coated hollow-fiber microextraction of trace amounts of natural and synthetic estrogens, such as diethylstilbestrol, estrone, 17beta-estradiol and 17alpha-ethynylestradiol, in aqueous samples. In this procedure, estrogens were extracted using the functionalized polar DHPMM polymer with derivatization using N-methyl-N-(trimethylsilyl)trifluoroacetamide followed by gas chromatography-mass spectrometric analysis. The detection limits for estrogens in aqueous sample were between 0.03 and 0.8 ng l(-1) and the calibration curves were linear over the concentration range 0.05-10 microgl(-1) and had correlation coefficients of >0.994. The relative standard deviations (RSDs) were <15% (n = 3). This simple, accurate, sensitive and selective analytical method is applicable to the determination of trace amounts of estrogens in reservoir and potable water samples.  相似文献   
84.
钇对Ti-1100高温钛合金热稳定性和蠕变行为的影响   总被引:3,自引:1,他引:3  
量了Ti1100和Ti1100/01%Y(质量分数)高温钛合金在600℃/100h空气中暴露后的拉伸性能及在600℃/150MPa/100h条件下的蠕变性能,利用透射电镜观察了合金室温及蠕变后的组织。结果表明,Ti1100合金加入01%的Y后,由于原始β晶粒得到细化,明显改善了其热稳定性;固溶在基体中的硅原子阻碍位错滑移和攀移,使蠕变中的回复过程难于实现;稀土还抑制α2相的长大,所形成的氧化物也阻碍位错的运动。这些均有利于提高Ti1100合金的抗蠕变性能。  相似文献   
85.
Abstract

A novel hydrolysis-resistant superabsorbent composite was prepared via the solution polymerization based on acrylic acid (AA) and sodium bentonite (SBT) as monomers, tetraallylammonium bromine (TAAB) as crosslinker and ammonium persulfate (APS) as initiator. The mechanism of polymerization and the structure of the superabsorbent polymer (SAP) were studied by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (X-ray), and scanning electron microscopy (SEM). The reaction conditions such as different mass ratios of APS to AA, TAAB to AA, SBT to AA, neutralization degree of AA were optimized by orthogonal experiment, and the influence of each reaction condition on the capacity of water absorption at 150?°C was investigated via single-factor controlled experiment. The hydrolysis resistance and swelling kinetics of the SAP were studied in different solutions at 150?°C. Compared to traditional SAPs, the SAP synthesized with TAAB as crosslinker performed a more excellent hydrolysis resistance and water absorbency capacity at high temperatures. The water absorbency in distilled water or 0.1?mol L?1 NaCl solution could reach 392.6 and 145.2?g g?1at 150?°C, respectively. The SAP maintaining high swelling capacity in the pH range of 5–9 indicated its wide application values in the acidic or alkaline environment at high temperature. In addition, the SAP exhibited good reusability which could still retain about 73% of its initial water absorbency after reswelling six times at 150?°C.  相似文献   
86.
The applicability of thermal lens spectrometry (TLS) for quantification and routine determination of hexavalent chromium was investigated by using a collinear dual beam thermal lens spectrometer. In aqueous solutions the LOD of 0.1 μg l−1 was obtained for Cr(VI) by using 160 mW laser power. The performance of the technique was verified by the determination of hexavalent chromium in standard reference water samples (NIST SRM 1643a and NIST SRM 1643c) and comparing the results for Cr(VI) in CCA (Cr, Cu, As)-treated timber extracts to concentrations obtained by atomic absorption spectrometry (AAS). Good agreement between the TLS results and reported values for Cr(VI) in SRMs as well as AAS results for Cr(VI) in CCA-treated timbers confirmed that TLS is a reliable and accurate analytical technique applicable for the determination of Cr(VI) in aqueous solutions at concentration levels 0.5–100 μg l−1.  相似文献   
87.
Chaozhang Huang 《Talanta》2007,73(2):274-281
Mesoporous titanium dioxide as a novel solid-phase extraction material for flow injection micro-column preconcentration on-line coupled with ICP-OES determination of trace metals (Co, Cd, Cr, Cu, Mn, Ni, V, Ce, Dy, Eu, La and Yb) in environmental samples was described. Possessing a high adsorption capacity towards the metal ions, mesoporous titanium dioxide has found to be of great potential as an adsorbent for the preconcentration of trace metal ions in samples with complicated matrix. The experimental parameters including pH, sample flow rate, volume, elution and interfering ions on the recovery of the target analytes were investigated, and the optimal experimental conditions were established. Under the optimized operating conditions, a preconcentration time of 90 s and elution time of 18 s with enrichment factor of 10 and sampling frequency of 20 h−1 were obtained. The detection limits of this method for the target elements were between 0.03 and 0.36 μg L−1, and the relative standard deviations (R.S.D.s) were found to be less than 6.0% (n =7, c =5 ng mL−1). The proposed method was validated using a certified reference material, and has been successfully applied for the determination of the afore mentioned trace metals in natural water samples and coal fly ash with satisfactory results.  相似文献   
88.
This paper mainly deals with the design and synthesis of a novel styrene-butadieneblock copolymer. When this copolymer is used in the tread portion of tyres, it can improvewet skid resistance and reduce rolling resistance without sacrificing its general physical-mechanical properties. The visco-elastic curve of tire tread using the novel copolymer asits rubber portion was showed. Reactivity ratios for two monomers in the polymerizingsystem were calculated. The diagrams of differelitial, integral and finite difference calculithroughout the whole molecular chain were presented. The influence of the micro- andmacro-structure of the copolymer chain on wet skid resistance and rolling resistance wasdiscussed  相似文献   
89.
Residual stress in the epoxy plate during a rapid cooling process was measured by the layer removal method and calculated by the linear thermoviscoelastic theory considering specific volume relaxation. The relaxations of the tensile modulus and specific volume were measured by an Instron thermomechanical analyzer. When the starting temperature of the cooling process was near the glass transition temperature of the cured epoxy, the residual stress in the epoxy plate was smaller than when the starting temperature was higher than the glass transition temperature. However, the transient stress in the cured epoxy plate was higher when the starting temperature was near the glass transition temperature than when the starting temperature was higher than the glass transition temperature. The quenched epoxy plate was compressed in the direction parallel to the surface and expanded in the thickness direction.  相似文献   
90.
The cellular mechanism based on P-glycoprotein (PGP) for its drug pump function has become very important in multidrug resistance (MDR) research. A method has been established to characterize PGP on single K562 cell by coupling capillary electrophoresis with laser induced fluorescence detection. A permeable intact cell after the immunoassay binding with fluorescence labeling antibody was injected into the capillary and directly separated without lysis. It was found that once 5-10 optional cells were detected in batch, the PGP amount on this cell line could be outlined and calculated clearly. The PGP amount on K562 MDR cell line is 3.88 times higher than that on K562 sensitive cell line. These two cell lines with immunoassay binding were also analyzed by injection of multi-cells in order to improve the throughput. A resistance factor so called multidrug resistance multiple (MRM) was introduced to evaluate the MDR difference between cell lines. The MRM values of the cell line K562 measured by single cell analysis are well correlated with those by flow cytometry, which also prove the validity of our method in single cell analysis for the possibility of cancer diagnosis, pharmacokinetics and drug screening in future.  相似文献   
设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号