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.     

Characterization of new Pt(IV)–thiazole complexes: Analytical,spectral, molecular modeling and molecular docking studies and applications in two opposing pathways

New thiazole derivatives were synthesized and fully characterized, then coordinated with PtCl₄ salt. Also, the newly synthesized Pt(IV) complexes were investigated analytically (elemental and thermogravimetric analyses), spectrally (infrared, UV–visible, mass, ¹H NMR, ¹³C NMR, X‐ray diffraction) as well as theoretically (kinetics, modeling and docking). The data extracted led to the establishment of the best chemical and structural forms. Octahedral geometry was the only formula proposed for all complexes, which is favorable for d⁶ systems. The molecular ion peaks from mass spectral analysis coincide with all analytical data, confirming the molecular formula proposed. X‐ray diffraction (XRD) and scanning electron microscopy (SEM) allowed discrimination of features between crystalline particles and other amorphous morphology. By applying Gaussian09 as well as HyperChem 8.2 programs, the best structural forms were obtained, as well as computed significant parameters. Computed parameters such as softness, hardness, surface area and reactivity led us towards application in two opposing pathways: tumor inhibition and oxidation activation. The catalytic oxidation for CO was conducted over PtO₂, which was yielded from calcination of the most reactive complex. The success of catalytic role for synthesized PtO₂ was due to its particulate size and surface morphology, which were estimated from XRD patterns and SEM images, respectively. The antitumor activity was tested versus HCT‐116 and HepG‐2 cell lines. Mild toxicity was recorded for two of the derivatives and their corresponding complexes. This degree of toxicity is more favorable in most cases, due to exclusion of serious side effects, which is coherently attached with known antitumor drugs.     

Nb(iPrNPMe2)3Fe–PMe3: A potential high reactivity heterobimetallic catalyst for acetylene cycloadditions

Alkynes cycloaddition reactions are powerful tools for constructing cyclic molecules with optimal atom efficiency, but these reactions cannot proceed at ambient temperature without transition-metal catalysts. In this work, a heterobimetallic complex featuring an Nb–Fe triple bond, Nb(ⁱPrNPMe₂)₃Fe–PMe₃, has been evaluated as the potential catalyst for acetylene cycloaddition, using density functional theory. The calculated results show that the singlet-state (i.e. ground-state) Nb(ⁱPrNPMe₂)₃Fe–PMe₃ can be applied to benzene synthesis, but is not suitable for cyclobutadiene. Benzene can be obtained easily at room temperature and is the unique product on the singlet potential surface. The irradiation of infrared-red light can drive the excitation of singlet Nb(ⁱPrNPMe₂)₃Fe–PMe₃ to its triplet state. Both benzene and cyclobutadiene can be formed on the triplet reaction potential surface due to their low energy barriers. Therefore, Nb(ⁱPrNPMe₂)₃Fe–PMe₃ is a potential high reactivity heterobimetallic catalyst for the cyclotrimerization of alkynes. In the reaction process, the catalytic active site of Nb(ⁱPrNPMe₂)₃Fe–PMe₃ moves from niobium to iron.     

碳纳米管阵列、捆束的三步升温工艺制备及其形貌与结构

使用结构简单的单温炉设备，通过三步升温热解二茂铁、三聚氰氨混合物方法，在二氧化硅、多晶陶瓷基底上分别合成了碳纳米管阵列、碳纳米管捆束.使用扫描电子显微镜、透射电子显微镜、电子能量损失谱和x射线光电子能谱对合成样品进行了结构和成分分析.结果显示：两种基底上合成的纳米管均为多壁纯碳管；生长于光滑二氧化硅表面的碳纳米管具有高度取向性和一致的外径，长度为10—40μm.碳纳米管采取催化剂顶端生长模式并展示出类杯状形貌；生长于粗糙多晶陶瓷表面的碳纳米管捆束随机取向，碳纳米管直径为15—80nm，长度在几百微米，展示 关键词： 碳纳米管 热解法 三步升温工艺     

The synthesis of azo compounds from nitro compounds using lead and triethylammonium formate

Aromatic nitro compounds were reduced to the corresponding symmetrically substituted azo compounds using lead as catalyst and triethylammonium formate as hydrogen donor. Various azo compounds containing additional reducible substituents including halogens, nitrile, acid, phenol, ester, methoxy functions, etc, have been synthesized in a single step by the use of this reagent. The conversion is reasonably fast, clean, high yielding and occurs at room temperature in methanol.     

纳米KMn8O16粉体的室温固相合成与表征

室温或近室温固相反应要求绿色化、清洁化[1,2]。我们以KMnO4和MnCl2·4H2O为原料,用室温固相氧化还原反应制备氧化锰粉体时,得到了一种对H2O2分解具有较高催化活性的纳米KMn8O16粉体,用XRD、SEM、IR等技术对其进行了表征,发现研磨时间对粉体性能有显著影响。1　实验部分1 1　粉体的制备按摩尔比(2∶3)准确称取一定量的分析纯KMnO4和MnCl2·4H2O,分别置于玛瑙研钵中充分研细,再混合研磨,固相反应立即发生,体系颜色逐渐加深,并有刺激性气体产生,充分研磨后70℃恒温12h,固相产物依次经水洗至中性、醇洗、抽滤,真空干燥得黑色粉…     

一类催化反应中的非线性奇摄动边值问题的渐近解

本文研究了催化反应非线性奇摄动边值问题．利用微分不等式理论和方法，得到了问题的解的任意次近似渐近估计．     

A thermoanalytical study of the formation and activation of novel copper-carbon catalysts

Simultaneous DSC-TG and DTA-TG were used to investigate the calatytic effect of the metal on the thermal decomposition of a cellulose matrix containing small copper particles. The techniques were also used to demonstrate the effect of the metal particles on the subsequent activation of the carbon matrix, a process which develops the pore structure necessary to expose the metal particles to the gas phase. Temperature programmed desorption was used to study the initial mass loss found on activation. To quantify the catalytic effect of the copper particles on the activation process an estimate was made of the activation energy of the catalysed and uncatalysed reactions. The work gives valuable information on the processes involved in the preparation of a new range of metal-carbon catalysts. In celebration of the 60^th birthday of Dr. Andrew K. Galwey     

木质装饰板材贫氧条件下燃烧和热解特性研究

本文利用热重差热分析仪,在各种不同的氧气浓度下对落叶松、红木和红松样品进行实验。通过对TG、DTG和DTA曲线的分析,样品干燥基要经历两个失重过程,第一个失重过程主要是纤维素和半纤维素的热解,第二个失重过程主要是木质素的炭化分解和燃烧。在各氧气浓度条件下,热解失重的第一个阶段TG和DTG曲线差异很小;在各样品失重的第二个阶段,随着氧气浓度的增加,TG和DTG曲线左移,反应结束的温度明显降低。氧气能使木质素的炭化物氧化并进而可能使其着火燃烧,从而使反应进程加快。当氧气浓度大于6.32%时,各样品DTA曲线上均有两个明显放热峰,并且随着氧气浓度的增加,DTA曲线放热峰越尖锐,放热峰面积越大,说明氧气浓度越大,在两阶段失重过程中更多的挥发分物质和固体炭化物参与燃烧。     

Flame Temperature Effect on the Structure of SiC Nanoparticles Grown by Laser Pyrolysis

Small SiC nanoparticles (10 nm diameter) have been grown in a flow reactor by CO₂ laser pyrolysis from a C₂H₂ and SiH₄ mixture. The laser radiation is strongly absorbed by SiH₄ vibration. The energy is transferred to the reactive medium and leads to the dissociation of molecules and the subsequent growth of the nanoparticles. The reaction happens with a flame. The purpose of the experiments reported in this paper is to limit the size of the growing particles to the nanometric scale for which specific properties are expected to appear. Therefore the effects of experimental parameters on the structure and chemical composition of nanoparticles have been investigated. For a given reactive mixture and gas velocity, the flame temperature is governed by the laser power. In this study, the temperature was varied from 875°C to 1100°C. The chemical analysis of the products indicate that their composition is a function of the temperature. For the same C/Si atomic ratio in the gaseous phase, the C/Si ratio in the powder increases from 0.7 at 875°C up to 1.02 at 1100°C, indicating a growth mechanism limited by C₂H₂ dissociation. As expected, X-ray diffraction has shown an improved crystallisation with increasing temperature. Transmission electron microscopy observations have revealed the formation of 10 nm grains for all values of laser power (or flame temperature). These grains appear amorphous at low temperature, whereas they contain an increasing number of nanocrystals (2 nm diameter) when the temperature increases. These results pave the way to a better control of the structure and chemical composition of laser synthesised SiC nanoparticles in the 10 nm range.