全文获取类型
收费全文 | 2749篇 |
免费 | 205篇 |
国内免费 | 369篇 |
专业分类
化学 | 1663篇 |
晶体学 | 12篇 |
力学 | 230篇 |
综合类 | 63篇 |
数学 | 591篇 |
物理学 | 764篇 |
出版年
2023年 | 34篇 |
2022年 | 68篇 |
2021年 | 117篇 |
2020年 | 73篇 |
2019年 | 48篇 |
2018年 | 56篇 |
2017年 | 59篇 |
2016年 | 93篇 |
2015年 | 90篇 |
2014年 | 115篇 |
2013年 | 176篇 |
2012年 | 135篇 |
2011年 | 178篇 |
2010年 | 146篇 |
2009年 | 181篇 |
2008年 | 173篇 |
2007年 | 189篇 |
2006年 | 183篇 |
2005年 | 149篇 |
2004年 | 122篇 |
2003年 | 126篇 |
2002年 | 94篇 |
2001年 | 88篇 |
2000年 | 66篇 |
1999年 | 73篇 |
1998年 | 79篇 |
1997年 | 69篇 |
1996年 | 43篇 |
1995年 | 35篇 |
1994年 | 36篇 |
1993年 | 30篇 |
1992年 | 26篇 |
1991年 | 12篇 |
1990年 | 21篇 |
1989年 | 15篇 |
1988年 | 19篇 |
1987年 | 12篇 |
1986年 | 13篇 |
1985年 | 13篇 |
1984年 | 9篇 |
1983年 | 4篇 |
1982年 | 12篇 |
1981年 | 6篇 |
1980年 | 7篇 |
1979年 | 7篇 |
1978年 | 4篇 |
1977年 | 2篇 |
1976年 | 5篇 |
1973年 | 4篇 |
1972年 | 4篇 |
排序方式: 共有3323条查询结果,搜索用时 78 毫秒
61.
62.
63.
Y. Marcus 《Journal of solution chemistry》1994,23(7):831-848
The water-structural contributions to the entropies and heat capacities of hydration of over 120 ions and the viscosity B-coefficients of nearly 80 aqueous ions are tabulated and correlated. B-coefficients for many more ions are predicted from this relationship and from their dependence on ionic size and charge. The structural entropies determine a unique scale of water structure making and breaking by the ions. 相似文献
64.
The thermodynamics of the conversion of aqueous glucose to fructose has been investigated using both heat conduction microcalorimetry
and high pressure liquid chromatography (HPLC). The reaction was carried out in both aqueous Tris/HCl buffer and in aqueous
phosphate buffer in the pH range 7–8 using the enzyme glucose isomerase and the cofactors CoCl2 and MgSO4. The temperature range over which this reaction was investigated was 298.15–358.15 K. We have found that the enthalpy of
reaction is independent of pH over the range investigated. A combined analysis of both the HPLC and microcalorimetric data
leads to the following results at 298 15 K:ΔG° = 349 ± 53 J mol-1, ΔH° = 2.78 ± 0.20 kJ mol-1, and ΔC
p
°
= 76 ± 30 J mol-1 K-1. The stated uncertainties are based upon an analysis of both the random and systematic errors inherent in the measurements.
Comparisons are made with literature data. The percent conversion of glucose to fructose has been calculated for the temperature
range 300–373.15 K. 相似文献
65.
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
66.
稀土高氯酸盐-谷氨酸配合物[Pr2(L-α-Glu)2(ClO4)(H2O)7](ClO4)3•4H2O的低温热容和热化学研究 总被引:1,自引:0,他引:1
合成了一种稀土高氯酸盐-谷氨酸配合物. 经TG/DTG、化学和元素分析、FTIR及与相关文献对比, 确定其组成为[Pr2(L-α-Glu)2(ClO4)(H2O)7](ClO4)3•4H2O, 纯度为99.0%以上. 利用显微熔点仪分析发现其没有熔点. 在78~370 K温区, 用精密绝热量热仪测量其低温热容, 在285~306 K温区发现一明显吸热峰, 归结为固-固相变过程. 通过相变温区三次重复热容测量, 得到相变温度Ttr、相变焓ΔtrHm和相变熵ΔtrSm分别为(297.158±0.280) K, (12.338±0.016) kJ•mol-1和(41.520±0.156) J•K-1•mol-1. 用最小二乘法将非相变温区的热容对温度进行拟合, 得到了热容随温度变化的两个多项式方程. 用此方程进行数值积分, 得到每隔5 K的舒平热容值和相对于273.15 K的热力学函数值. 根据TG/DTG结果, 推测了该配合物的热分解机理. 依据Hess定律, 选择1 mol•dm-3盐酸为量热溶剂, 利用等温环境溶解-反应量热计, 测定了该配合物的标准摩尔生成焓为: ΔfHm0=-(7223.1±2.4) kJ•mol-1. 相似文献
67.
Dispersion state and catalytic properties of vanadia species on the surface of V_2O_5/TiO_2 catalysts 总被引:1,自引:0,他引:1
The dispersion state and catalytic properties of anatase-supported vanadia species are studied by means of X-ray diffraction (XRD), laser Raman spectroscopy (LRS), H2 temperature-programmed reduction (TPR) and the selective oxidation of o-xylene to phthalic anhydride. The almost identical values of the experimental dispersion capacity of V2O5 on anatase and the surface vacant sites available on the preferentially exposed (001) plane of anatase suggest that the highly dispersed vanadium cations are bonded to the vacant sites on the surface of anatase as derived by the incorporation model. When the loading amount of V2O5 is far below its dispersion capacity, the dispersed vanadia species might mainly consist of isolated VOx species bridging to the surface through V-O-Ti bonds. With the increase of V2O5 loading the isolated vanadia species interact with their nearest neighbors (either isolated or polymerized vanadia) through bridging V-O-V at the expenses of V-O-Ti bonds, resulting in the increase of the ra 相似文献
68.
Guo-xiang Xu Lu Qi Bi-tao Yu Lei Wen Department of Applied Chemistry College of Chemistry Molecular Engineering Peking University Beijing China Department of Inorganic Nonmetal Materials School of Materials Science Engineering University of Science Technology Beijing Beijing China 《高分子科学》2006,(3):307-313
PVC disulfide (2SPVC) was synthesized by solution crosslink and its molecular structure was confirmed by infrared spectrum. 2SPVC's specific area is 36.1 m2·g-1 tested by stand BET method, and granularity experiment gives out the particle size of d0.5= 11.3μm. With SEM (Scanning Electron Microscope) experiment the surface morphology and particle shape of 2SPVC were observed. Cyclic voltammetry (scan rate: 0.5 mV·s-1) shows that 2SPVC experience an obvious S-S redox reaction in charge-discharge process. When 2SPVC was used as cathode material for secondary lithium battery in a 1 mol·L-1 solution of lithium bis(trifluoromethylsulfonyl) imide (Li(CF3SO2)2N) in a 5:45:50 volume ratio mixture of o-xylene (oxy), diglyme (DG) and dimethoxymethane (DME) at 30℃, the first discharge capacity of 2SPVC is about 400.3 mAh·g-1 which is very close to its theoretical value (410.5 mAh·g-1) at a constant discharge current of 15 mA·g-1. It can retain at about 346.1 mAh·g-1 of discharge capacity after 30 charge-discharge cycles. So 2SPVC is a very promising cathode candidate for rechargeable lithium batteries. 相似文献
69.
0引言为解决目前日益严重的汽车尾气排放对城市空气造成污染问题,作为绿色能源的锂离子电池已成为动力电池的首选对象。国际上,高容量、大功率锂离子电池早于1995年已开始研制。1996年,我国天津电源研究所也进行了大容量锂离子蓄电池及电池组的探索[1]。目前,锂离子电池的正极材料是制约其大规模推广应用的关键。现研究的正极材料主要包括具有层状结构的LiCoO2,LiN iO2和LiM nO2及具有尖晶石结构的LiM n2O4等。其中LiC oO2作为目前唯一已经商业化的正极材料具有理论容量高、可循环性能好等优点,但因Co资源的相对缺乏导致其价格高昂。… 相似文献
70.
《Thermochimica Acta》2003,401(2):169-173
The heat capacity and the heat content of gallium nitride were measured by calvet calorimetry (320-570 K) and by drop calorimetry (670-1270 K), respectively. The temperature dependence of the heat capacity in the form Cpm=49.552+5.440×10−3T−2.190×106T−2+2.460×108T−3 was derived by the least squares method. Furthermore, thermodynamic functions calculated on the basis of our experimental results and literature data on the molar entropy and the heat of formation of GaN are given. 相似文献