A model for crack formation during active solid pyrolysis of a char-forming solid: crack patterns; surface area generation; volatile mass efflux

A model is developed for the formation and propagation of cracks in a material sample that is heated at its top surface, pyrolyses, and then thermally degrades to form char. In this work the sample is heated uniformly over its entire top surface by a hypothetical flame (a heat source). The pyrolysis mechanism is described by a one-step overall reaction that is dependent nonlinearly on the temperature (Arrhenius form). Stresses develop in response to the thermal degradation of the material by means of a shrinkage strain caused by local mass loss during pyrolysis. When the principal stress exceeds a prescribed threshold value, the material forms a local crack. Cracks are found to generally originate at the surface in response to heating, but occasionally they form in the bulk, away from ever-changing material boundaries. The resulting cracks evolve and form patterns whose characteristics are described. Quantities examined in detail are: the crack spacing in the pyrolysis zone; the crack length evolution; the formation and nature of crack loops which are defined as individual cracks that have joined to form loops that are disconnected from the remaining material; the formation of enhanced pyrolysis area; and the impact of all of the former quantities on mass flux. It is determined that the mass flux from the sample can be greatly enhanced over its nominal (non-cracking) counterpart. The mass efflux profile qualitatively resembles those observed in Cone Calorimeter tests.     

Experimental and Theoretical Mechanistic Study on the Thermal Decomposition of 3,3-diphenyl-4-(trichloromethyl)-5-nitropyrazoline

The present paper is a continuation of comprehensive study regarding to synthesis and properties of pyrazoles and their derivatives. In its framework an experimental and theoretical studies of thermal decomposition of the 3,3-diphenyl-4-(trichloromethyl)-5-nitropyrazoline were performed. It was found, that the decompositions of the mentioned pyrazoline system in the solution and at the melted state proceed via completely different molecular mechanisms. These mechanisms have been explained in the framework of the Molecular Electron Density Theory (MEDT) with the computational level of B3LYP/6-31G(d). A Bonding Evolution Theory (BET) examination of dehydrochlorination of the 3,3-diphenyl-4-(trichloromethyl)-5-nitropyrazoline permits elucidation of the molecular mechanism. It was found, that on the contrary for most known HCl extrusion processes in solution, this reaction is realised via single-step mechanism.     

基于化学学科认知障碍突破的中考复习教学实践* ——以“二氧化碳的性质”为例

分析学生对二氧化碳的3个典型学科认知障碍,以“二氧化碳的捕捉”为情境,通过“尝试捕捉二氧化碳”“谁在捕捉二氧化碳”“捕捉背后的原理”等3个主要环节,实现对学科认知障碍的突破,展示了一种新的中考复习教学思路。     

Physical aging in amorphous poly(ethylene furanoate): Enthalpic recovery,density, and oxygen transport considerations

The current work utilizes three separate techniques to study the physical aging process in amorphous poly(ethylene furanoate) (PEF), which is a recently introduced engineering thermoplastic with enhanced properties compared to petroleum‐sourced poly(ethylene terephthalate). Differential scanning calorimetry aging experiments were conducted at multiple aging temperatures and times, and the resultant enthalpic recovery values compared to the theoretical maximum enthalpy loss evaluated from calculations involving extrapolation of the equilibrium liquid line. Density measurements reveal densification of the matrix for the aged versus unaged samples, and provide an estimate for the reduction in free volume for the aged samples. Complementary oxygen permeation and pressure‐decay sorption experiments provide independent verification of the free volume reduction mechanism for physical aging in glassy polymers. The current work provides the first detailed aging study for PEF. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 389–399     

Mono-Aryl/Alkylthio-Substituted (Hetero)acenes of Exceptional Thermal and Photochemical Stability by the Thio-Friedel–Crafts/Bradsher Cyclization Reaction

The highly substituted mono-aryl/alkylthio-(hetero)acenes prepared in this study have been found to be thermally more stable (T_decomp.=331–354 °C) than the known di-aryl/alkylthio-substituted acenes by an average of 25 °C. They are also much more photostable at 254 and 365 nm (in both argon and air) than the parent anthracene and other reported anthracenes. The most photostable aryl/alkylthio-anthracenes at 254 nm were found to be 60–70 (in air) and 130 (in argon) times more stable in solution than the unsubstituted anthracene, and much more stable than known EDG/EWG-substituted anthracenes (EDG=electron-donating group, EWG=electron-withdrawing group) with an extended aromatic core. Furthermore, the acenes showed significantly higher photostability at 365 nm in both air and argon. The anthracenes were obtained by the novel thio-Friedel–Crafts/Bradsher cyclization reaction of hitherto unknown [o-(1,3-dithian-2-yl)aryl](aryl)methyl thioethers. The developed approach provides a general access to mono-aryl/alkylthio-substituted (hetero)acene frameworks containing at least three fused (hetero)aromatic rings. The characteristic feature of this approach, which leads to highly substituted acenes, is that the substituents, unlike in other methods, may be introduced at an early stage of the synthesis. DFT and TD-DFT calculations confirmed the stabilizing role of the aryl/alkylthio substituent in the mono-aryl/alkylthio-substituted anthracenes, which are the most stable anthracenes prepared to date. Their high photostability is mainly due to the quenching of singlet oxygen by the acene and the quenching of the acene S₁ state by molecular oxygen.     

Intramolecular Hydroamination of Selenoalkynes to 2-Selenylindoles in the Absence of Catalyst

In this work, a series of 2-chalcogenylindoles was synthesized by an efficient methodology, starting from chalcogenoalkynes, including a previously unreported tellurium indole derivative. For the first time, these 2-substituted chalcogenylindoles were obtained in the absence of metal catalyst or base, under thermal conditions only. In addition, the results described herein represent a methodology with inverse regioselectivity for the chalcogen functionalization of indoles.     

掺镱双包层高功率光纤激光器输出特性研究

对线形腔掺镱双包层高功率光纤激光器的输出特性进行了研究 ,通过求解速率方程 ,得到了激光器泵浦阈值功率、输出光功率和斜率效率的表达式。分析了光纤长度、腔镜反射率和泵浦波长等因素对激光器阈值功率、输出光功率和斜率效率的影响 ,为高功率光纤激光器的优化设计提供了理论依据     

纵向泵浦Cr∶ Nd∶GSGG激光棒的热透镜效应研究

对纵向泵浦Cr∶Nd∶GSGG激光棒的热透镜效应进行了详细的理论分析。对温度分布的函数表达式 ,进行了讨论 ;分析了热引起的应力 ,得到了激光棒破裂的临界功率公式 ;最后对光学畸变进行了分析与讨论 ,推导了光程差计算公式     

新型的芯片间互连用CMOS/BiCMOS驱动器

从改善不同类型 IC芯片之间的电平匹配和驱动能力出发 ,设计了几例芯片间接口 (互连 )用 CMOS/Bi CMOS驱动电路 ,并提出了采用 0 .5 μm Bi CMOS工艺 ,制备所设计驱动器的技术要点和元器件参数。实验结果表明所设计驱动器既具有双极型电路快速、大电流驱动能力的特点 ,又具备 CMOS电路低压、低功耗的长处 ,因而它们特别适用于低电源电压、低功耗高速数字通信电路和信息处理系统。     

高性能调度技术中应用程序调度模型设计--地理空间信息网格调度技术的研究

地理空间信息网格调度技术，要比传统的高性能计算中的调度技术复杂，原因是如果将全部网格资源作为一个应用程序的调度和执行目标，必将导致通信延迟、成本昂贵、执行低效等。为此，综合考虑应用程序特性、机器特性等，研究设计了地理空间信息网格高性能调度技术中的应用程序调度模型，包括地理空间信息网格应用程序分析；资源特性分析；应用程序分解；性能预测；资源调度；机器选择；任务映射；任务调度；任务调度器和调度器管理模块。以实现为不同的应用程序匹配不同的计算资源，提高计算资源的利用率和应用程序的执行效率。