全文获取类型
收费全文 | 2355篇 |
免费 | 48篇 |
国内免费 | 158篇 |
专业分类
化学 | 2267篇 |
晶体学 | 46篇 |
力学 | 3篇 |
综合类 | 1篇 |
数学 | 2篇 |
物理学 | 242篇 |
出版年
2024年 | 3篇 |
2023年 | 1篇 |
2022年 | 4篇 |
2021年 | 17篇 |
2020年 | 10篇 |
2019年 | 20篇 |
2018年 | 18篇 |
2017年 | 39篇 |
2016年 | 32篇 |
2015年 | 37篇 |
2014年 | 34篇 |
2013年 | 151篇 |
2012年 | 46篇 |
2011年 | 67篇 |
2010年 | 48篇 |
2009年 | 116篇 |
2008年 | 173篇 |
2007年 | 191篇 |
2006年 | 183篇 |
2005年 | 158篇 |
2004年 | 188篇 |
2003年 | 130篇 |
2002年 | 132篇 |
2001年 | 91篇 |
2000年 | 101篇 |
1999年 | 102篇 |
1998年 | 86篇 |
1997年 | 73篇 |
1996年 | 58篇 |
1995年 | 65篇 |
1994年 | 56篇 |
1993年 | 51篇 |
1992年 | 41篇 |
1991年 | 7篇 |
1990年 | 6篇 |
1989年 | 4篇 |
1988年 | 3篇 |
1987年 | 9篇 |
1986年 | 3篇 |
1985年 | 4篇 |
1984年 | 1篇 |
1982年 | 1篇 |
1979年 | 1篇 |
排序方式: 共有2561条查询结果,搜索用时 281 毫秒
71.
Phase transition of water restrained by curdlan suspension
annealed at a temperature from 20 to 110°C was investigated by differential
scanning calorimetry (DSC). The melting temperature of water restrained by
annealed curdlan discontinuously decreased at around 60°C, while the amount
of bound water calculated from enthalpy of melting increased at 60°C,
regardless of water content. Using a highly sensitive DSC, curdlan suspension
with various concentrations was studied. It was found that an endothermic
transition was observed at ca. 58°C in a wide range of concentrations.
The transition observed at 60°C is thermo-reversible and both temperature
and transition enthalpy are constant even after gel formation. Well equilibrated
suspension at a temperature lower than 60°C formed no gel. 相似文献
72.
M. Salmerón Sánchez Y. Touzé A. Saiter J. M. Saiter J. L. Gómez Ribelles 《Colloid and polymer science》2005,283(7):711-720
The enthalpy relaxation of poly(hydroxyethyl methacrylate) (PHEMA), poly(ethyl methacrylate) (PEMA) and poly(ethyl acrylate) (PEA) networks, obtained by DSC, are compared. The temperature interval of the glass transition broadens in the sequence PEA-PEMA-PHEMA. The plots of the enthalpy loss during the annealing for 200 min at different temperatures below Tg show that the structural relaxation process also takes place in PHEMA in a broader temperature interval than in PEA or PEMA. The modelling of the structural relaxation process using a phenomenological model allows determining the temperature dependence of the relaxation times concluding that the fragility in PHEMA is significantly lower than in PEMA. Both features are ascribed to the connectivity of the polymer chains in PHEMA via hydrogen bonding. The role of the presence of the methyl group bonded to the main chain is analysed by comparing the results obtained in PEA and PEMA. 相似文献
73.
Summary The ordering behavior of quenched Cu-12 at% Mn was investigated by differential scanning calorimetry (DSC) under increasing temperature conditions. The ordering process can be better explained in terms of a homogeneous short-range-order (SRO) rather than a disperse-short-range-order (DSRO) model as for concentrated Cu-γMn solid solutions. At the employed high quench rates ordering is established in one stage here termed stage 1, assisted by excess vacancies. This stage obeys a first order kinetics law, being the effective activation energy consistent with a weighed average sum of the activation energy for migration of free and bound vacancies. An estimated solute-vacancy binding energy of 15 kJ mol-1 seems quite reasonable for this alloy together with the assessed activation energy for complex migration of 92.6 kJ mol-1. By adopting a first SRO order parameter based in quasi-chemical theory in pair approximation and using boundary values calculated from displayed features of DSC traces, the retained degree of quenched-in order at room temperature was calculated. This procedure also enabled to estimate an ordering energy of -2.7 kJ mol-1. The effect of quenching temperature demonstrate that for smaller vacancy sink densities, the retained degree of order at room temperature goes through a minimum. 相似文献
74.
Zouhair Asfari Rym Abidi Françoise Arnaud Jacques Vicens 《Journal of inclusion phenomena and macrocyclic chemistry》1992,14(2):163-169
The template synthesis of copper(II) phthalocyanine by the condensation of dicyanobenzene within the supercages of Cu(II) exchanged X and Y type zeolites was studied using differential scanning calorimetry. The exotherms for intrazeolite and surface complexation have been resolved. These thermal events exhibit a dependence on the copper loading and hydration level which has been interpreted as a pressure effect. 相似文献
75.
76.
[Ni(NH_2NHCO_2CN_3)_3](NO_3)_2·H_2O的制备、具体结构和热分解机理 总被引:4,自引:0,他引:4
由硝酸镍水溶液和肼基甲酸甲酯(NH_2NHCOOCH_3, MCZ)的水溶液反应,制备 出未见文献报道的配合物[Ni(MCZ)_3]-(NO_3)_2·H_2O。晶体结构测定结果表明, 该晶体属单斜晶系,P2_1/n空间群,晶体学参数为:a = 1.3681 (2) nm,b = 0. 8188 (1) nm,c = 1.6029 (4) nm,β = 92.16 (2)°,V = 1.7943 (6) nm~3, D_c = 1.744 g·cm~(-3),Z = 4,F(000) = 976,μ(Mo Kα) = 1.166 mm~(-1) 。结构采用全矩阵最小二乘法优化,除氢原子采用各向同性热参数外,其它非氢原 子均采用各向异性热参数修正,最终偏离因子R_1 = 0.0337,wR_2 = 0.0857。在 该配合物分子中,肼基甲酸甲酯作为双齿配体,由羰基氧原子和端基氮原子与Ni~ (2+)配位,形成五元平面螯合环,配合物分子中共有三个这样的螯合环,中心离子 为六配位八面体构型。配合物的外界是两个硝酸根离子和一个水分子,通过库仑力 和氢键与内界结合在一起。采用TG-DTG,DSC,IR等表征了标量化合物的热稳定性 。在程序升温条件下,该配合物的热分解过程是由一个弱的吸气热过程和三个较强 的连续的放热过程组成的,由TG-DTG和IR分析结果证明,在325 ℃时的最终分解产 物为NiO,得到了化合物的分解机理。 相似文献
77.
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
78.
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
79.
G. Vigier J. Tatibouet A. Benatmane R. Vassoille 《Colloid and polymer science》1992,270(12):1182-1187
Crystallization of poly(ethylene terephthalate) from the amorphous state has been studied in the temperature range 90°–120°C to characterize the amorphous phase when crystalline microstructure is developing. Small-angle x-ray scattering, scanning electron microscopy, and density measurements were used to investigate the morphology of semi-crystalline materials. Differential scanning calorimetry and dynamical mechanical spectroscopy experiments were carried out on amorphous, partially crystallized and crystallized specimens and, when structural relaxation is allowed (thermal treatments close to but below glass transition temperature), strong evidence is obtained for the existence of two different amorphous phases with different mobilities. 相似文献
80.
Clara Strandberg 《European Polymer Journal》2006,42(8):1855-1865
In an earlier study, we have shown that chemiluminescence (CL) and the total luminescence intensity (TLI) method are highly sensitive to oxidation in degradable PE. In this study, stabilised PE and PP were characterised with CL in an inert (TLI) and in an oxygen atmosphere (CL-OIT) and the results were compared to those obtained by the commonly used techniques, FT-IR (carbonyl index (CI)) and thermal analysis (DSC-OIT). PE was aged at a low temperature (80 °C) and PP was aged at temperatures between 60 and 120 °C. Non-Arrhenius behaviour was observed in the oxidation of PP. This showed the importance of aging at a low temperature to obtain realistic results. TLI and CI of stabilised PP and most of the stabilised PE gave comparable results with the same sensitivity for oxidation detection. This was in contrast to our previous results for degradable PE. However, TLI of unstabilised PE showed earlier oxidation detection than CI, which agreed with our earlier results. TLI of PE had a higher sensitivity than CL-OIT, and both TLI and CI of PP were sufficiently sensitive to detect the effect of aging at different temperatures, whereas DSC-OIT was not. 相似文献