Isothermal crystallization kinetics of poly(3‐hydroxybutyrate)/layered double hydroxide nanocomposites

Poly(3‐hydroxybutyrate) (PHB)/layered double hydroxides (LDHs) nanocomposites were prepared by mixing PHB and poly(ethylene glycol) phosphonates (PEOPAs)‐modified LDH (PMLDH) in chloroform solution. Both X‐ray diffraction data and TEM micrographs of PHB/PMLDH nanocomposites indicate that the PMLDHs are randomly dispersed and exfoliated into the PHB matrix. In this study, the effect of PMLDH on the isothermal crystallization behavior of PHB was investigated using a differential scanning calorimeter (DSC) and polarized optical microscopy. Isothermal crystallization results of PHB/PMLDH nanocomposites show that the addition of 2 wt % PMLDH into PHB induced more heterogeneous nucleation in the crystallization significantly increasing the crystallization rate and reducing their activation energy. By adding more PMLDH into the PHB probably causes more steric hindrance of the diffusion of PHB, reducing the transportation ability of polymer chains during crystallization, thus increasing the activation energy. The correlation among crystallization kinetics, melting behavior and crystalline structure of PHB/PMLDH nanocomposites can also be discussed. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3337–3347, 2006     

Assessing contaminated hydrogen peroxide for safe storage and transportation using the FTAI

Hydrogen peroxide is a very versatile oxidizing agent, and it is also environmentally compatible considering that the products of its exothermic decomposition are oxygen and water.When kept in a clean temperature-controlled environment, the self-reaction (decomposition) rate is extremely low. However, it is well known that even a small amount of contamination will dramatically increase the reaction rate. This paper describes the use of the fast thermal activity interpreter (FTAI) instrument to examine the chemical reactivity of commercially available 50% hydrogen peroxide at two different temperatures (30 and 40°C) both with and without contamination. The results show that at 30°C a small amount of rust (330 ppm) increases the reaction rate of 50% hydrogen peroxide by a factor of 50. When the temperature is increased to 40°C, the reaction rate is further increased by almost a factor of four. The implication for reactivity management is that at this contamination level most practical vessel sizes would require emergency venting capability. An evaluation was then performed to determine the emergency venting requirement for the safe transportation or storage of the contaminated hydrogen peroxide. It was determined that for quantities of the material less than 5 gallons, conventional breather vents would be sufficient to accommodate the gas evolved. However, for larger quantities, a safety relief device would be needed. For example, for a 400-gallon tote bin at 40°C the required minimum vent area is estimated to be 4.3 in², corresponding to a minimum vent diameter of 2.3 inches.     

高压下碱卤晶体的三参量等温状态方程

 由等温体积弹性模量的定义及其与压强关系的假设出发，导出了一个新的适用于高压下碱卤晶体的三参量等温状态方程。计算了室温下NaCl晶体在0～30 GPa压强范围内、CsCl晶体在0～40 GPa压强范围内的相对体积以及NaCl晶体在0～30 GPa压强范围内的等温体积弹性模量，计算结果与实验值一致。对等温体积弹性模量及其对压强的一阶、二阶导数与压强的关系进行了讨论，指出压强趋于无穷大时的等温体积弹性模量是常数。     

La-Fe-M(M=Al, Si)化合物磁热性能研究进展

介绍了La-Fe-M(M=AI,Si)化合物在磁热性能研究方面的最新进展。具有NaZn13型晶体结构,含高浓度Fe的La-Fe—M(M=AI,Si)化合物为良好的软磁材料;用少量的Co替代化合物中Si,Al元素可以将化合物的居里温度提高至室温;对La(Fe1-yCoy)xSi13-x化合物,适量的Si,Co组合可使化合物在室温产生可与Gd5Si2Ge2比拟的磁热效应;加入适量的间隙原子H,也可使La(FexSi1-x)13在室温的磁热性能远远大于金属Gd;对含Si量低及含Si量高的La(FexSi1-x)13化合物在相转变点附近由温度和磁场诱导相变的本质做了详细阐述。     

Thermal and structure analysis of FeSO4·H2O-BaO2 mixtures

Investigations on the thermal decomposition of FeSO₄·H₂O-BaO₂ mixtures were carried out under isothermal conditions by using simultaneously solid electrolyte cell (EMF-method). Evoked interactions producing oxygen in the temperature range 553-673 K were established by means of a solid electrolyte oxygen analyzer. Based on Mössbauer spectroscopy data and X-ray analysis it was proved that these reactions were associated with the release of oxygen from barium peroxide, oxidation of ferrosulphate-monohydrate to FeOHSO₄, and formation of barium ferrites such as BaFe₂O₄ and BaFe₁₂O₁₉.     

Development of a new analytical method for the evaluation of hazards from slow decomposition of waste streams and process solutions

A wide variety of liquid streams are generated as part of the process research and development effort. Frequently these streams are drummed off, either as intermediates that must be held for processing or as wastes that must be sent off-site for disposal. Because of the long times and low concentrations often involved, current thermoanalytical techniques were inadequate to detect the potential of streams to generate gas. A custom-made apparatus, the gas evolution test cell (GETC), was developed in the Merck Research Laboratories to measure the gas generation potential of various streams under precisely defined conditions, is the key innovation for the development of a quantitative gas-generation test method.     

环氧乙烷和环氧丙烷共聚体系的等温结晶和熔融

环氧乙烷（ＥＯ）和环氧丙烷（ＰＯ）共聚体系的等温结晶前期符合Ａｖｒａｍｉ方程。ＰＯ组分含量增加，Ａｖｒａｍｉ指数ｎ值由１．８到２．４，体系的结晶生长速率与共聚体系的组成和结晶度有关，ＥＯ／ＰＯ共聚体系的平衡熔点随ＰＯ含量的增加而降低。随Ｔｃ增大，△Ｈｍ与△Ｓｍ呈线性降低。     

A novel approach to study the isothermal behaviour of substances after 0.01–1 s from the chemical process initiation

New modifications of a contact heater are suggested for investigating thermal decomposition processes, as well as for determining kinetic characteristics of substances under conditions of intense heating to a fixed constant temperature.

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Zusammenfassung Zur Untersuchung von thermischen Zersetzungsprozessen und der Bestimmung der Reaktionskinetik von Substanzen bei intensivem Erhitzen auf vorgegebene konstante Temperaturen wird eine neue Abart von Kontakterhitzern beschrieben.

     

尼龙66/蒙脱土复合材料结晶行为的研究

在密炼机中采用熔融共混法制备蒙脱土重量分数为 2 5 %、4 5 %的尼龙 6 6 /蒙脱土复合材料 .通过DSC法对非等温结晶行为及在 2 2 8～ 2 4 0℃范围内的等温结晶行为进行研究 ,并与纯尼龙 6 6进行比较 .从其等温和非等温结晶行为的研究表明 ,蒙脱土起成核剂的作用 ,它的填入使尼龙 6 6结晶速率提高 ,但填料与基体间的相互作用使其链段运动困难 ,结晶活化能提高 ;在研究的填料含量变化范围内 ,结晶行为变化不大 ,并且找到该复合材料在 2 2 8～ 2 34℃范围结晶对温度的不敏感区 ;对非等温结晶过程分析 ,刘结平 莫志深方程是适用的 ,而Ozawa方程则是不适用的 .