Lifetime assessment of epoxies by the kinetics of thermal degradation

The kinetics of thermal degradation of 4,4′‐diaminodiphenylsulfone (DDS)‐cured glycidylethers (DGBA) and glycidylamines (TGDDM) have been studied by isothermal annealing. Thermal degradation proceeds via first‐order kinetics with activation energies of 138 (DGBA/DDS) and 95 kJ/mol (TGDDM/DDS). From these data the temperature‐dependent lifetime can be calculated. Based on the heat distortion temperature and 20 years' service as criteria, the upper service temperature is found to be around 115–120°C. In spite of the different activation energies and bond stabilities, only marginal differences in the upper allowed service temperatures between these resins were found. Only slight improvements can be expected by optimizing the cure conditions. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1881–1886, 2004     

Al2O3—Si3N4—ZrO2多相复合材料在燃煤MHD发电中的应用

采用Ａｌ２Ｏ３基料，添加第二相（ＺｒＯ２，Ｓｉ３Ｎ４）和纤维相（ＺｒＯ２，（ｆ），以热压法制成Ａｌ２Ｏ３－Ｓｉ３Ｎ４－ＺｒＯ２多相复合材料。研究表明，新材料在青静态和动态试验中表现出良好的综合性能：１０７３Ｋ时的高温电阴率ｐ＝１．２４×１７＾７Ω．ｃｍ；静态熔渣最大腐蚀速率Ｖｓ＝０．１６μｍ／ｈ；动态最大腐蚀速率Ｖｄ＝０．４４９μｍ／ｈ。与Ａｌ２Ｏ３陶瓷相比，室温抗弯强度提高９３％，抗热震临界...     

Two‐step consecutive reaction model and kinetic parameters relevant to the decomposition of Chinese forest fuels

Decomposition of some Chinese forest fuels has been studied by means of nonisothermal thermogravimetric analysis in oxidative and inert atmosphere at low heating rates. A comparison between thermogravimetric curves obtained in air and nitrogen shows that the existence of oxygen enhances the decomposition rate and changes the mechanisms of thermal degradation. After the water evaporation, two well‐defined decomposition stages have been observed in thermogravimetric curves obtained in air, which correspond to oxidative degradation of main components and oxidation of char formed. A kinetic model named “two‐step consecutive reaction model” is developed to describe the thermal degradation process of these materials in air, and there is a good agreement between the experimental and calculated thermogravimetric and derivative thermogravimetric curves. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 571–576, 2006     

Thermal Expansion of Solid Solutions in the ZrTiO4—In2O3—M2O5 (M = Sb, Ta) System

Axial and dilatometric thermal expansions and phase transformations were studied for solid solutions having the α-PbO₂ structure in the ZrTiO₄—In₂O₃—M₂O₅ (M = Sb, Ta) system with nominal formulas of Zr _x Ti _y In _z Sb _z O₄ and Zr _x Ti _y In _z Ta _z O₄ where x + y + 2 z = 2. With increased substitution of z , the cell volume increased, the difference in the b parameters at room temperature between those quenched from 1400° and 1000°C decreased, and the thermal expansion decreased. The axial thermal expansion of ZrTi _y In _z · Ta _z O₄ with z = 0.3 was almost identical with that of HfTiO₄, and those with z = 0.4 and z = 0.45 were smaller than that of HfTiO₄. Unit-cell volumes of these compound were compared with those of single oxides to make it clear that the unit-cell volume of ZrTiO₄ was small anomalously and to distinguish the normal and abnormal substitution systems. These results were explained by the working hypothesis proposed for these compounds.     

笼型γ-氨丙基倍半硅氧烷／环氧树脂非等温固化动力学

用动态DSC研究了笼型γ-氨丙基倍半硅氧烷／环氧树脂纳米杂化复合体系的固化过程、最佳配比与热稳定性能，并用Ozawa和Kissinger—Akahira—Sunose等转化率法研究了固化反应动力学。结果表明，该体系固化峰值温度为85℃，终了温度为118℃，最佳NH2与环氧基摩尔比为0．75，热分解最高起始温度为336-356℃。Ozawa法更适合本体系的动力学分析，固化反应表观活化能为71．0765kJ／mol，反应级数为0．9855级。     

The Kinetics of the Thermal Decomposition of Thermoplastic Polyurethane Elastomers under Thermoplastic Processing Conditions

A theoretical approach to the kinetics of the thermal decomposition of molten thermoplastic polyurethane elastomers, under conditions of thermoplastic processing, is described. On the basis of these considerations, the thermal decomposition in different instruments (melt index analyser and measuring extruder) can be described quantitatively and the various results can be compared. As a result, identical conditions of decomposition of the melt can be defined accurately, thus opening up the possibility of combining experimental values from different instruments. The fundamental kinetic equation obtained for the kinetics of the thermal decomposition of thermoplastic polyurethanes describes the decomposition reaction and the reverse reaction (formation reaction) – which is dependent on the system of measurement and processing – as a function of the molar mass (end‐group concentration) of the original product, determined from the velocity constants for the decomposition reaction and back reaction. The consideration of the limiting value for t → ∞ is in agreement with the equilibrium constant. Consequently, the development of physical characteristic functions of thermoplastic polyurethane elastomers – independent of the system of measurement – is possible.

Experimental values and calculated curves for the thermal decomposition of PUR‐Et in a melt index analyser.     

Thermal and crystallization characteristics of poly(ethylene terephthalate) with poly(oxybenzoate‐p‐trimethylene terephthalate) copolymer

Poly(ethylene terephthalate) (PET) was blended with two different poly(oxybenzoate‐p‐trimethylene terephthalate) copolymers, designated T28 and T64, with the level of copolymer varying from 1 to 15 wt %. All samples were prepared by solution blending in a 60/40 (by weight) phenol/tetrachloroethane solvent at 50°C. The crystallization behavior of the samples was studied by DSC. The results indicate that both T28 and T64 accelerated the crystallization rate of PET in a manner similar to that of a nucleating agent. The acceleration of PET crystallization rate was most pronounced in the PET/T64 blends with a maximum level at 5 wt % of T64. The melting temperatures for the blends are comparable to that of pure PET. The observed changes in crystallization behavior are explained by the effect of the physical state of the copolyester during PET crystallization as well as the amount of copolymer in the blends. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1599–1606, 2002     

超细CaCO3与金属氧化物M2O3对Al/AP/HTPB推进剂燃烧的催化协同效应研究

对超细及市售ＣａＣＯ３在低含量（≤１％）的情况下对丁羟推进剂燃烧性能的影响进行了研究，结果发现ＣａＣＯ３低含量时可提高推进剂的燃速且超细ＣａＣＯ３比市售ＣａＣＯ３的催化效率高。进一步研究了超细ＣａＣＯ３与金属氧化物Ｍ２Ｏ３组合对推进剂燃烧的催化作用，结果表明两者有协同效应，其组合的燃烧催化效果较各自单独使用的催化效果要好。     

Effects of the o‐aromatic ring in the molecular chain on the properties of polyester polyols

A series of liquid polyester polyols from adipic acid (AA), phthalic anhydride (PA), ethylene glycol, propanediol‐1,2, and trihydroxymethylpropane, varying in the molar ratio of PA to AA, were prepared. The effects of the o‐aromatic ring in the molecular chain, which came from PA, on the viscosity, glass‐transition temperature, and thermal degradation temperature of the polyester polyols were studied with viscometry, differential scanning calorimetry, and thermogravimetry. The intrinsic viscosity and glass‐transition temperature increased with the concentration of the o‐aromatic ring increasing. The temperature of the maximum thermal degradation rate for aliphatic polyester polyols was 434.20°C. Two steps of thermal degradation were found when there were o‐aromatic rings in the molecular chain. One thermal degradation temperature was 358.36–360.48°C, and the other was 412.85–427.18°C. Polyester polyols with o‐aromatic rings had higher stability at lower temperatures (<240.00°C). However, aliphatic polyester polyols had higher stability at higher temperatures (300.00–480.00°C). The activation energy and order of degradation were calculated from thermogravimetric curves. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1617–1624, 2002     

The influence of geometrical factors and feedstock on gasification in a high temperature fluidised bed

Results are presented for gasification of coal and char by means of air or air-steam mixtures in fluidised bed reactors of three different volumes. Two sizes of coal feedstock particles, 0.5-1.0 mm and 1.0-1.5 mm, and one size of char particles, 0.5-1.5 mm, were used. The calorific value of generated gas and the carbon conversion are presented as a function of particle residence time. For coal gasification higher carbon conversion has been obtained at the same particle residence time than for char gasification. For the steam gasification, a lower gas heating value of about 4 MJ/m³ (S.T.P.) was obtained.