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   2627篇
  免费   176篇
  国内免费   458篇
化学   2846篇
晶体学   57篇
力学   14篇
综合类   44篇
数学   5篇
物理学   295篇
  2024年   3篇
  2023年   36篇
  2022年   43篇
  2021年   79篇
  2020年   94篇
  2019年   80篇
  2018年   78篇
  2017年   109篇
  2016年   108篇
  2015年   100篇
  2014年   106篇
  2013年   316篇
  2012年   159篇
  2011年   115篇
  2010年   106篇
  2009年   115篇
  2008年   122篇
  2007年   142篇
  2006年   135篇
  2005年   145篇
  2004年   122篇
  2003年   121篇
  2002年   102篇
  2001年   72篇
  2000年   52篇
  1999年   75篇
  1998年   66篇
  1997年   69篇
  1996年   64篇
  1995年   53篇
  1994年   43篇
  1993年   28篇
  1992年   38篇
  1991年   18篇
  1990年   17篇
  1989年   19篇
  1988年   19篇
  1987年   11篇
  1986年   16篇
  1985年   11篇
  1984年   4篇
  1982年   13篇
  1981年   6篇
  1980年   4篇
  1978年   6篇
  1977年   4篇
  1976年   4篇
  1975年   3篇
  1973年   3篇
  1972年   2篇
排序方式: 共有3261条查询结果,搜索用时 15 毫秒
131.
This study deals with the use of ethanol as washing solvent in the preparation of the silica gels from sodium silicate in order to enhance the textural properties, especially surface area. We here examined the effect of ethanol-washing on surface area, micro- and mesopore volume, and average pore size. The silica xerogels prepared from sodium silicate solution exhibited an extremely high surface area of 1139 m2/g by washing their hydrogels with ethanol. Compared to water-washed xerogels, ethanol-washed xerogels showed higher surface areas, total pore volumes, and larger average pore sizes. Unlike the surface area of water-washed xerogel, that of the ethanol-washed xerogel was not affected by the silica concentration of initial solution. This study indicates that the textural properties of sodium silicate-derived xerogels are further enhanced by using ethanol as washing solvent.  相似文献   
132.
Micellar systems are colloids with significant properties for pharmaceutical and food applications. They can be used to formulate thermodynamically stable mixtures to solubilize hydrophobic food-related substances. Furthermore, micellar formation is a complex process in which a variety of intermolecular interactions determine the course of formation and most important are the hydrophobic and hydrophilic interactions between surfactant–solvent and solvent–solvent. Glycols are organic compounds that belong to the group of alcohols. Among them, propane-1,2-diol (PG) is a substance commonly used as a food additive or ingredient in many cosmetic and hygiene products. The nature of the additive influences the micellar structure and properties of sodium dodecyl sulfate (SDS). When increasing the mass fraction of propane-1,2-diol in binary mixtures, the c.m.c. values decrease because propane-1,2-diol is a polar solvent, which gives it the ability to form hydrogen bonds, decreasing the cohesivity of water and reducing the dielectric constant of the aqueous phase. The values of ΔGm0 are negative in all mixed solvents according to the reduction in solvophobic interactions and increase in electrostatic interaction. With the rising concentration of cosolvent, the equilibrium between cosolvent in bulk solution and in the formed micelles is on the side of micelles, leading to the formation of micelles at a lower concentration with a small change in micellar size. According to the 1H NMR, with the addition of propylene glycol, there is a slight shift of SDS peaks towards lower ppm regions in comparison to the D2O peak. The shift is more evident with the increase in the amount of added propane-1,2-diol in comparison to the NMR spectra of pure SDS. Addition of propane-1,2-diol causes the upfield shift of the protons associated with hydrophilic groups, causing the shielding effect. This signifies that the alcohol is linked with the polar head groups of SDS due to its proximity to the SDS molecules.  相似文献   
133.
The effect of pressure on the dissociation constant of hydrofluoric acid was determined by using the indicator technique at 25°C at an ionic strength of 0.1m over a pressure range of 1 to 2000 atm. A value of 3.14 for pK a * at I =0 was obtained by extrapolation to zero ionic strength at 1 atm. The pressure dependence yielded a partial molar volume change of –9.6 cm3-mol–1 and a compressibility change of — 35×10–3 cm3-mol–1 –atm–1 for the dissociation. The dependence of ionic strength on the association constant K A * of NaF was studied at 25°C and 1 atm. Extrapolation to I=0 yielded a pK A * of –0.78. The pressure dependence of K A * gave a change of volume of 3.26 cm3-mol–1 and a change in compressibility of 6×10–3 cm3-mol–1-atm–1 for the formation of the ion pair.  相似文献   
134.
The solubilities of methane, ethane, propane, and n-butane were measured in aqueous solutions of sodium dodecylsulfate (NaDS) (0–0.1M) from 15 to 27°C. From these measurements the standard Gibbs energies, entropies, and enthalpies for the process of transferring the solute molecules from the gaseous phase into the solutions were calculated. An approximate relationship was found relating the volume fraction of the micelles to NaDS concentration.  相似文献   
135.
The Crystal Structures of the Vanadium Weberites Na2MIIVIIIF7 (MII ? Mn, Ni, Cu) and of NaVF4 At single crystals of the vanadium(III) compounds NaVF4 (a = 790.1, b = 531.7, c = 754.0 pm, β = 101.7°; P21/c, Z = 4), Na2NiVF7 (a = 726.0, b = 1031.9, c = 744.6 pm; Imma, Z = 4) and Na2CuVF7 (a = 717.6, b = 1043.5, c = 754.6 pm; Pmnb, Z = 4) X-ray structure determinations were performed, at Na2MnVF7 (a = 746.7, c = 1821.6 pm; P3221, Z = 6) a new refinement. NaVF4 crystallizes in the layer structure type of NaNbO2F2. The fluorides Na2MIIVF7 represent new orthorhombic (MII ? Ni; Cu) resp. trigonal (MII ? Mn) weberites. The average distances within the [VF6] octahedra of the four compounds are in good agreement with each other and with data of related fluorides (V? F: 193.3 pm). The differences between mean bond lengths of terminal and bridging F ligands are 5% in NaVF4, but less than 1% in the weberites. Details and data for comparison are discussed.  相似文献   
136.
催化湿式氧化中铜基催化剂的流失与控制   总被引:9,自引:0,他引:9  
 制备了催化湿式氧化处理有机废水用铜基催化剂,并用XRD,XRF和TG-DTG等手段对催化剂进行了表征,对催化剂及其前驱体的组成和结构进行了分析鉴定.结果表明,由类水滑石结构的前驱体焙烧得到的催化剂Cu-Al-Zn-O,其活性组分铜的流失得到了控制;在氧化降解苯酚、十二烷基苯磺酸钠和磺基水杨酸时,在初始氧分压0.5MPa和160~220℃的反应条件下,催化剂活性组分铜的流失量小于0.3mg/L.对催化剂活性组分不易流失的原因进行了理论解释和计算.  相似文献   
137.
Recently,theconformationofthecalixarenehasbeenshowntobeimportantincontrollingtheseIectivityofthereceptor.Forexample,sodiumioncouldbeboundverystronglybyesterderivativesofcalix[4]areneintheconeconformationl.Wehavefoundthatinthepresenceofcertainamountofsodiumion,microamountofReO4-canbequantitativelyextractedintol,2-dichloroethanebytheligandtetraethylp-tert-butylcalix[4]arenetetraacetate(L).ItshowsthatthepresenceofNa inaqueoussolutioncanpromotetheformationofhydrophobiccomplex[NaL] .ReO'-whichc…  相似文献   
138.
Farghaly OA 《Talanta》2004,63(2):497-501
A square wave adsorptive stripping voltammetric (SWAdSV) method for the indirect determination of trace amounts of magnesium with thiopentone sodium (TPS) as an electroactive ligand, at carbon paste mercury film electrode (CP-MFE) is proposed. It is observed that the increase of the square wave voltammetric cathodic peak current of TPS, under alkaline conditions, is linear with the increase of Mg concentration. Under optimum experimental conditions viz.; pH 10.75, 3×10−5 M TPS and 0.05 M phosphate buffer (Na2HPO4-NaH2PO4), a linear relation in the range 6×10−9 to 9×10−8 M Mg2+ (0.14-2.16 ppb), at 60 s deposition time, is obtained. The detection limit of Mg2+ is 0.14 ppb for 60 s deposition time with the relative standard deviation is 0.5% (n=5). The proposed method was successfully applied to the determination of magnesium in urine and tap water samples with satisfactory results. The data obtained are compared with the standard flame atomic absorption spectrophotometric method (FAAS).  相似文献   
139.
水/AOT/正庚烷微乳体系中磺酸根水化作用的FT—IR研究   总被引:1,自引:0,他引:1  
运用傅立叶变换红外光谱(FT-IR)对水/琥珀酸(乙基已基)磺酸钠(AOT)/正庚烷微乳体系中磺酸根的水化作用进行了研究.由于微乳体系中水分子与表面活性剂分子的相互作用,S=O对称伸缩振动的红外吸收峰向低频方向移动.体系中的加水量W0(水与AOT的摩尔比)由0.5增大至25时,磺酸根对称伸缩振动的红外吸收峰由1051.39cm-1向低频移动至1046.15cm-1.同时,由于Na 的不对称作用,AOT分子中磺酸根反对称伸缩振动分裂成两个吸收峰,分别位于正215cm-1及1245cm-1附近,两个劈裂峰的距离及各自的峰面积均随体系中加水量的变化而变化,应用二阶导数、傅立叶退卷积及曲线拟会等分辨率增强技术可更清楚地反映出这个二重峰的变化情况.固体AOT分子中碳酸根反对称伸缩振动分裂的两个峰之间频率的差值约为42cm-1,形成微乳液以后,这两个峰的差值变小,W0为20时,这两个峰频率的差值逐渐减小到29cm-1,这些变化与磺酸根的水化程度直接相关  相似文献   
140.
The conditions to fabricate the bulk porous specimens have been studied on account of sodium borosilicate (NBS) glasses. Glass composition, heat treatment at phase separation and TiO2 addition have been considered in this study. Original glass samples of composition in mol%: sample A: 9.19 Na2O - 23.58 B2O3 - 67.23 SiO2, sample B: 9.29 Na2O - 3.17 TiO2 - 23.82 B2O3 - 63.72 SiO2 were prepared by melting reagent grade chemicals (Na2CO3, HBO3, SiO2 and AgNO3) in platinum crucibles at 1480°C for 1 h in air. The melts were poured onto stainless steel plates and were annealed at 500°C for 0.5 h after cooling. Thus, obtained samples were phase separated at 700°C for 2, 15, 25 and 50 h to study their microstructure by scanning electron microscope (SEM). Besides the direct study of the microstructure by SEM, information on glass structural changes of samples are provided by measuring in situ changes by the optical transmittance thermal analysis. The isothermal measurements were carried out at 700, 720 and 740°C. The temperature of phase separation, the leaching and nucleator addition (TiO2), significantly influence the microstructure of the resulting leached product. TiO2 additive seems to suppress crystallization of cristobalite: especially at the extended above heat treatment phase separation runs. The phase-separated domains of glasses containing above 80 moles of SiO2 are so small that it is very hard to observe them by SEM. The glass composition in our case was selected in a way to have relatively large phase separated areas easily observed by SEM at magnification 20 000·. The influence of TiO2 is not too pronounced. It seems to suppress the cristobalite crystallization, especially of longer heating runs. The image analysis of leached glasses shows the prevailing content of the skeletal phase in a comparison to pores. The TiO2 content diminishes the content of the skeletal phase. This revised version was published online in July 2006 with corrections to the Cover Date.  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