Path to achieving molecular dispersion in a dense reactive mixture

A uniform dispersion of reactants is necessary to achieve a complete reaction involving multicomponents. In this study, we have examined the role of plasticizer in the reaction of two seemingly unlikely reactants: a highly crystalline hexamethylenetetramine (HMTA) and a strongly hydrogen bonded phenol formaldehyde resin. By combining information from NMR, infrared spectroscopy and differential scanning calorimetry, we were able to determine the role of specific intermolecular interactions necessary for the plasticizer to dissolve the highly crystalline HMTA and to plasticize the phenol formaldehyde resin in this crosslinking reaction. The presence of the plasticizer increased the segmental mobility, disrupted the hydrogen bonded matrix, and freed the hydroxyl units, which further increased the solubility of the HMTA. Both the endothermic and exothermic transitions are accounted for in the calorimetric data obtained. For the first time, it is possible to obtain the effective molar ratio of each component needed to complete the crosslinking reaction efficiently. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1519–1526     

DFT mechanistic study of the H2‐assisted chain transfer copolymerization of propylene and p‐methylstyrene catalyzed by zirconocene complex

DFT computations have been performed to investigate the mechanism of H₂‐assisted chain transfer strategy to functionalize polypropylene via Zr‐catalyzed copolymerization of propylene and p‐methylstyrene (pMS). The study unveils the following: (i) propylene prefers 1,2‐insertion over 2,1‐insertion both kinetically and thermodynamically, explaining the observed 1,2‐insertion regioselectivity for propylene insertion. (ii) The 2,1‐inserion of pMS is kinetically less favorable but thermodynamically more favorable than 1,2‐insertion. The observation of 2,1‐insertion pMS at the end of polymer chain is due to thermodynamic control and that the barrier difference between the two insertion modes become smaller as the chain length becomes longer. (iii) The pMS insertion results in much higher barriers for subsequent either propylene or pMS insertion, which causes deactivation of the catalytic system. (iv) Small H₂ can react with the deactivated [Zr]?pMS?PP_n facilely, which displace functionalized pMS?PP_n chain and regenerate [Zr]? H active catalyst to continue copolymerization. The effects of counterions are also discussed. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 576–585     

Measured and Predicted Solubility Phase Diagrams of Quaternary Systems LiBr-NaBr-MgBr2-H2O and LiBr-KBr-MgBr2-H2O at 298.15 K

The stable phase equilibria of quaternary systems LiBr-NaBr-MgBr₂-H₂O and LiBr-KBr-MgBr₂-H₂O at 298.15 K were studied by both experimental measurement(isothermal solution saturation method) and theoretical prediction(Pitzer model). The solubilities of the saturated solution have been determined experimentally and two stable phase diagrams and relevant water diagrams of the two quaternary systems were obtained. Results show that quaternary system LiBr-NaBr-MgBr₂-H₂O is hydrate II type as NaBr and NaBr·2H₂O coexistence. Its phase diagram consists of only one invariant point, four univariant curves, and five crystallization fields. The quaternary system LiBr-KBr-MgBr₂-H₂O is a complex type as the double salt KBr·MgBr₂·6H₂O formed. In addition to this double salt, the three single salts LiBr·2H₂O, KBr and MgBr₂·6H₂O also crystallize. In this paper, the solubilities of phase equilibria in above quaternary systems were also calculated by the Pitzer's electrolyte solution model. All the needed parameters can be obtained from the literature or be fitted by experimental data. On the Basis of the experimental and calculated results, the phase diagram of the quaternary system was plotted for comparison. It shows that the calculation results are consistent with the experimental ones.     

A new molecular rectifier device and some research in its processing

Organic materials of D-π-A type MR-X (MR-1: p-dimethylaminophenylethenetrica-rbonitrile and MR-2: p-diphenylaminophenylethene tricarbonitrile) were designed and synthesized. The device with a sandwich structure shows good rectificative phenomena. The highest rectification ratio 10000 was achieved in device Cu/MR-1/Ag, and about 100 in other device M/MR-X/M (M: Cu, Ag). It has been found that rectificative phenomena exist only in the atmosphere-liquid interface region by means of liquid adsorption, and electric field could help form the oriented molecular film. __________ Translated from Journal of Fudan University (Natural Science), 2005, 44(4) (in Chinese)     

Nd2Fe14B化合物磁晶各向异性起源的理论研究

本文根据Nd₂Fe₁₄B化合物中存有少量巡游电子的基本实验事实,提出了在Nd₂Fe₁₄B中配位子所产生的晶场和巡游电子所产生的电场共同造成了Nd离子磁晶各向异性的理论模型。提出并解决了计算巡游电子同中心Nd离子相互作用的理论方法。在同时考虑Nd离子所受配位子的晶场和巡游电子的电场的作用情况下,用单离子模型计算了Nd₂Fe₁₄B中Nd离子所产生的磁晶各向异性及其随温度的变化。所 关键词：     

四气门发动机可变涡流稀薄燃烧特性研究

本文研究了可变涡流对四气门发动机稀薄燃烧特性的影响情况。在稀薄燃烧情况下,发动机负荷大小对CO和HC排放的影响不大,对NOx排放的影响主要表现在对13～17空燃比范围内NOx排放的影响,负荷越大,NOx排放越大;对空燃比小于13或大于17以后的NOx排放影响较小。阀片位置对发动机排放特性的影响较小,对发动机的燃油经济性存在一定影响,这是因为不同阀片位置的进气涡流比不同所致,同时也表明较强的涡流运动对燃油经济性更有利。涡流运动在不同转速条件下对发动机燃油经济性的影响情况不同,它更有利于改善低速条件下的燃油经济性。