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   2665篇
  免费   177篇
  国内免费   471篇
化学   2896篇
晶体学   57篇
力学   14篇
综合类   44篇
数学   5篇
物理学   297篇
  2024年   4篇
  2023年   36篇
  2022年   57篇
  2021年   79篇
  2020年   94篇
  2019年   80篇
  2018年   78篇
  2017年   109篇
  2016年   109篇
  2015年   101篇
  2014年   107篇
  2013年   317篇
  2012年   151篇
  2011年   114篇
  2010年   106篇
  2009年   118篇
  2008年   124篇
  2007年   142篇
  2006年   132篇
  2005年   144篇
  2004年   125篇
  2003年   124篇
  2002年   102篇
  2001年   73篇
  2000年   59篇
  1999年   78篇
  1998年   70篇
  1997年   72篇
  1996年   65篇
  1995年   55篇
  1994年   43篇
  1993年   29篇
  1992年   38篇
  1991年   20篇
  1990年   19篇
  1989年   18篇
  1988年   20篇
  1987年   13篇
  1986年   17篇
  1985年   11篇
  1984年   4篇
  1982年   14篇
  1981年   5篇
  1980年   4篇
  1978年   6篇
  1977年   4篇
  1976年   4篇
  1975年   4篇
  1974年   3篇
  1973年   6篇
排序方式: 共有3313条查询结果,搜索用时 725 毫秒
111.
选用了变质程度不同的八种煤和三种不同分子量的聚对苯乙烯磺酸钠(PSS)添加剂,详细考查了该添加剂的分子量对水煤浆浆体性质的影响。结果发现,在考查PSS相对分子量的范围内(质均分子量为5.34×104~33.39×104),八种煤的水煤浆成浆性随着分子量的增大而增加,水煤浆成浆性与PSS添加剂的平均分子量的关系可归因于添加剂在煤粒上的吸附,分子量小的PSS在煤粒上的吸附量大于分子量大的PSS;PSS分子量的增加有利于水煤浆的流变性由胀性向假塑性转变;PSS分子量的增加使水煤浆的静态稳定性得到显著的改善。  相似文献   
112.
The alkali sodium ferrate (IV) Na4FeO4 has been prepared by solid-state reaction of sodium peroxide Na2O2 and wustite Fe1−xO, in a molar ratio Na/Fe=4, at 400°C under vacuum. Powder X-ray and neutron diffraction studies indicate that Na4FeO4 crystallizes in the triclinic system P−1 with the cell parameters= a=8.4810(2) Å, b=5.7688(1) Å, c=6.5622(1) Å, α=124.662(2)°, β=98.848(2)°, γ=101.761(2)° and Z=2. Na4FeO4 is isotypic with the other known phases Na4MO4 (M=Ti, Cr, Mn, Co and Ge, Sn, Pb). The solid solution Na4FexCo1−xO4 exists for x=0-1 and we have followed the evolution of the cell parameters with x to determine the lattice parameters of the triclinic cell of Na4FeO4. A three-dimensional network of isolated FeO4 tetrahedra connected by Na atoms characterizes the structure. This compound is antiferromagnetic below TN=16 K. At 2 K the magnetic cell is twice the nuclear cell and the magnetic structure is collinear (μFe=3.36(12) μB at 2 K). This black compound is highly hygroscopic. In water or on contact with the atmospheric moisture it is disproportionated in Fe3+ and Fe6+. The Mössbauer spectra of Na4FeO4 are fitted with one doublet (δ=− 0.22 mm/s, Δ=0.41 mm/s at 295 K) in the paramagnetic state and with a sextet at 8K. These parameters characterize Fe4+ high-spin in tetrahedral FeO4 coordination.  相似文献   
113.
Silver and gold organosols are easily prepared by transferring nanoparticles from aqueous phase into isooctane with high efficiency (>90%). Concentrations of sodium oleate and magnesium chloride have crucial effects on the transfer efficiency. Based on the UV-visible absorption spectra, TEM micrographs of nanoparticles, as well as molecular modeling calculation about the adsorption conformation of sodium oleate molecules, a possible phase transfer mechanism is proposed.  相似文献   
114.
Sodium salicylate (NaSal where Sal=2-hydroxybenzoate), when mixed with dibenzo-24-crown-8 (DB24C8) yields a bimetallic complex [NaSal]2DB24C8 in most polar organic media, while potassium salicylate (KSal) under similar conditions shows a tendency to yield 11 or 21 complexes depending upon medium or synthesis. However, the presence of both NaSal and KSal together results in a unique mixed cation complex of composition NaKSal2DB24C8. This product melts sharply (190-92°C) without decomposition, displays IR spectral characteristics comparable to those of [Na(Sal)]2DB24C8, and is stable in aqueous media as shown by the detectable cation effect on the UV absorption bands of Sal and DB24C8. Single crystal X-ray analysis of NaK(Sal)2DB24C8 reveals that the system represents a co-crystallization complex of individual (KSal)2DB24C8 and (NaSal)2DB24C8 molecules. The crystals are monoclinic,P21/c,a=19.976(2) Å,b=9.031(1) Å,c=25.541(5) Å,=122.065(9)°, Å3,T=298 K,Z=2+2, CuK =1.5418 Å, and 2 (2.5°–100°). FinalR factor for the 3012 observed reflections (F>3) is 0.092. Both the Na2- and K2-molecules possess crystallographic centers of symmetry with one metal and its associated anion on each side of the crown ring. However, the conformations of the crowns are very different in the two molecules, with the K2-crown being nearly planar and the Na2-crown being quite puckered. Four oxygen atoms from the DB24C8 (KO, 2.680–2.908 Å) and three carboxyl oxygen atoms (KO, 2.472–2.708 Å) from separate salicylate ions coordinate with each potassium. Three oxygens from the crown (NaO, 2.536–2.65 Å) and three carboxyl oxygens (NaO, 2.31–2.563 Å) coordinate with each sodium. The salicylate ions lie on opposite sides and nearly perpendicular (77.2°, Na2-molecule; 82.7° K2-molecule) to each crown but coordinate to both of the metal ions within a molecule. The K+K+ and Na+Na+ distances in the respective molecules are 3.95 and 3.34 Å. Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82044 (18 pages).  相似文献   
115.
Monolayer hydrate (MLH) NaxCoO2·y′H2O was obtained from superconducting bilayer hydrate (BLH) NaxCoO2·yH2O by partial extraction of H2O molecules between the CoO2 layers. Magnetization measurements indicated that electron densities in the CoO2 layer of the MLH phase remained unchanged after the water extraction. Nevertheless, superconductivity was completely suppressed in the MLH phase. This strongly suggests that the highly 2D nature in the BLH phase due to its thick insulating layers consisting of H2O molecules and Na+ ions plays an important role for inducing superconductivity.  相似文献   
116.
本文用自行建立的精密溶解层热装(?)测定了298.15K时,NH_4BPh_4、KBPH_4、RbBPh_4、CsBPh_4、TlBPh_4、AgBPh_4和HgPh_2七种沉淀反应的反应焓,由此计算了一价四苯硼酸盐的标准生成焓、熵及吉布斯自由能.  相似文献   
117.
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   
118.
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   
119.
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   
120.
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   
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