Reaction kinetics modeling and thermal properties of epoxy–amines as measured by modulated‐temperature DSC. II. Network‐forming DGEBA + MDA

Reaction‐induced vitrification takes place in the network‐forming epoxy–amine system diglycidyl ether of bisphenol A (DGEBA) + methylenedianiline (MDA) when the glass‐transition temperature (T_g) rises above the cure temperature (T_cure). This chemorheological transition results in diffusion‐controlled reaction and can be followed simultaneously with the reaction rate in modulated‐temperature DSC (MTDSC). To predict the effect of T_cure and the NH/epoxy molar mixing ratio (r) on the reaction rate in chemically controlled conditions, a mechanistic approach was used based on the nonreversing heat flow and heat capacity MTDSC signals, in which the reaction steps of primary (E_1OH = 44 kJ mol^?1) and secondary amine (E_2OH = 48 kJ mol^?1) with the epoxy–hydroxyl complex predominating. The diffusion factor DF as defined by the Rabinowitch approach expresses whether the chemical reaction rate or the diffusion rate determines the overall reaction rate. A model based on the free volume theory together with an Arrhenius temperature dependency was used to calculate the diffusion rate constant in DF as a function of conversion (x) and T_cure. The relation between x, r, and T_g, needed in this model, can be predicted with the Couchman equation. An experimental approximation for DF is the mobility factor DF* obtained from the heat capacity signal at a modulation frequency of 1/60 Hz, normalized for the effect of the reaction heat capacity in the liquid state and the change in C_p in the glassy region with x and T_cure. In this way, an optimized set of diffusion parameters was obtained that, together with the optimized kinetic parameters set, can predict the reaction rate for different cure schedules and for stoichiometric and off‐stoichiometric mixtures. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2814–2833, 2004     

Restricted chain segment mobility in poly(amide) 6/clay nanocomposites evidenced by quasi-isothermal crystallization

Modulated temperature differential scanning calorimetry is used to explore the interactions between a poly(amide) 6 matrix and various types of clay reinforcement. During quasi-isothermal crystallization of the polymer/clay nanocomposites, an excess contribution is observed in the recorded heat capacity signal, due to reversible melting and crystallization. It is proposed that the magnitude of this excess contribution can be used to qualify the polymer/clay interfacial interaction, as it is directly linked to the segmental mobility of the polymer chains in the interphase region, where both the crystalline and amorphous polymer fractions are affected. It is shown that the interfacial interaction strongly depends on the type of clay filler used. These interactions play a key role in the development of specific material properties for the different types of nanocomposites. A simple interphase model for the poly(amide) 6/clay nanocomposites is proposed.     

Mechanical properties of recycled polyethylene ecocomposites filled with natural organic fillers

The use of natural organic fillers in addition to postconsumer recycled polymers is getting a growing interest during the last years; this is due to many advantages they can provide in terms of cost, aesthetic properties, environmental impact. In this work, several types of wood flour (differing each other with regard to production source and particle size) were added to a recycled polyethylene coming from films for greenhouses and the effects of filler type, content, and size were investigated. Investigation was then focused on the improvement of mechanical properties, through the addition of polar copolymers (ethylene‐co‐acrylic acid, ethylene‐vinyl acetate) and a maleic anhydride‐grafted‐grafted polyethylene (Licocene® PE MA 4351 TP), in order to try to overcome the poor adhesion between polar filler particles and nonpolar polymer chains. Investigation was also based on SEM micrographs. An overall positive influence of these additives was observed. Polym. Eng. Sci. 46:1131–1139, 2006. © 2006 Society of Plastics Engineers.     

解读"教育为人民服务"

党的十六大报告中明确了教育在现代化建设中的作用和地位 :“教育是发展科学技术和培养人才的基础 ,在现代化建设中具有先导性全局性作用 ,必须摆在优先发展的战略地位”。同时指出教育的功能是 :“全面贯彻党的教育方针 ,坚持教育为社会主义现代化建设服务 ,为人民服务 ,与生产劳动和社会实践相结合 ,培养德、智、体、美、劳全面发展的社会主义建设者和接班人”。十六大提出了一个新的教育理念 ,这就是教育为人民服务。1　“教育为人民服务”是“三个代表”重要思想在教育观念上的具体体现“为人民服务”是毛泽东同志在 1 944年为纪念一个…     

Composition and thermal properties of Rhea oil and its fractions

The rhea (Rhea americana) is a large running bird of the ratite family, native to South America. Oil extracted from rhea fat tissue is used in cosmetic manufacture. Here, the thermal behaviour and the fatty acid and triacylglycerol composition of Uruguayan rhea oil are studied. The results are compared with those obtained from two commercial samples of emu oil. The fatty acid profiles of emu and rhea oils are similar. Small variations are reflected in the non‐identical thermal behaviour of the oils. The solid content of both oils is fairly similar at room temperature. Thus, emu oil and rhea oil may replace one another in certain formulations, without resulting in important changes in physicochemical behaviour. The semisolid rhea oil was fractionated in two successive stages: an olein was obtained at 15 °C, which was refractionated at 10 °C. The thermogram of the olein obtained by cooling at 15 °C does not have the peak found at 34 °C in the thermogram of the original oil and is a softer product than the original oil. A further stage of fractionation of this olein produced a new liquid phase of slightly different thermal behaviour from that of the original olein. This product has a solid fat index around 7% at 15 °C and has melted completely at 20 °C. This second olein has more appropriate physical characteristics than those of the olein obtained from the first fractionation when used in liquid cosmetic formulations.     

The application of coherent optics to the study of adhesive joints. I. Speckle photography

A new technique of coherent optics, speckle photography, has been applied to the study of the behavior of adhesive joints under shear stress. This technique allows the determination of the in-plane motion by a point-by-point analysis with a sensitivity of about 3 μm. This property has been used to measure the interfacial displacement of model glass-glass joints bonded by different types of adhesive when submitted to shear. The experimental results permit direct verification of Volkersen's theory as well as the determination of the actual shear modull of the thin adhesive layer. The simplicity of use and interpretation of the technique of speckle photography should lead to significant application of this method in the future for the study of adhesive joints.     

In vitro comparison of hepatic metabolism of 9cis-11 trans and 10trans-12cis isomers of CLA in the rat

Hepatic metabolism of the two main isomers of CLA (9cis-11 trans, 10trans-12cisC_18∶2) was compared to that of oleic acid (representative of the main plasma FA) in 16 rats by using the in vitro method of incubated liver slices. Liver tissue samples were incubated at 37°C for 17h under an atmosphere of 95% O₂/5%CO₂ in a medium supplemented with 0.75 mM of FA mixture (representative of circulating nonesterified FA) and with 55 μM [1-¹⁴C]9cis-11 trans C_18∶2, [1-¹⁴C]10trans-12cis C_18∶2, or [1-¹⁴C]oleate. The uptake of CLA by hepatocytes was similar for both isomers (9%) and was three times higher (P<0.01) than for oleate (2.6%). The rate of CLA isomer oxidation was two times higher (49 and 40% of incorporated amounts of 9cis-11 trans and 10trans-12 cis, respectively) than that of oleate (P<0.01). Total oxidation of oleate and CLA isomers into [¹⁴CO₂] was low (2 to 7% of total oxidized FA) compared to the partial oxidation (93 to 98%) leading to the production of [¹⁴C] acid-soluble products. CLA isoemrs escaping from catabolism were both highly desaturated (26.7 and 26.8%) into conjugated 18∶3. Oleate and CLA isomers were mainly esterified into neutral lipids (30%). They were slowly secreted as parts of VLDL particles (<0.4% of FA incorporated into cells), the extent of secretion of oleate and of 10trans-12 cis being 2.2-fold higher than that of 9cis-11 trans (P<0.02). In conclusion, this study clearly showed that both CLA isomers were highly catabolized by hepatocytes, reducing their availability for peripheral tissues. Moreover, more than 25% of CLA escaping from catabolism was converted into conjugated 18∶3, the biological properties of which remain to be elucidated.     

巴豆酸乙烯酯的提取及聚合应用

巴豆酸乙烯酯存在于醋酸乙烯酯生产的工业废液中,在一定条件下聚合会形成环状结构。用于改性以聚醋酸乙烯酯为基础的乳胶漆无须引发剂和加热,只是简单混和即可使耐洗刷次数增加几倍,还可与其它乙烯基酯、氯乙烯、苯乙烯、马来酸酐等多种单体交联共聚。     

数字化微格教学系统在师范生培养过程中的应用研究

师范生的培养效果如何关乎到未来教师的教学能力,本文通过对当前我国师范生培养现状的分析,探讨如何应用数字化微格教学系统培养师范生的教学能力。