Chemische Zusammensetzung und Mikrostruktur polymerabgeleiteter Gläser und Keramiken im System Si–C–O. Teil 2: Charakterisierung der Gefügeausbildung mittels hochauflösender Durchstrahlungselektronenmikroskopie und Feinbereichsbeugung

Chemical Composition and Microstructure of Polymer‐Derived Glasses and Ceramics in the Si–C–O System. Part 2: Characterization of microstructure formation by means of high‐resolution transmission electron microscopy and selected area diffraction Liquid or solid silicone resins represent the economically most interesting class of organic precursors for the pyrolytic production of glass and ceramics materials on silicon basis. As dense, dimensionally stable components can be cost‐effectively achieved by admixing reactive filler powders, chemical composition and microstructure development of the polymer‐derived residues must be exactly known during thermal decomposition. Thus, in the present work, glasses and ceramics produced by pyrolysis of the model precursor polymethylsiloxane at temperatures from 525 to 1550 °C are investigated. In part 1, by means of analytical electron microscopy, the bonding state of silicon was determined on a nanometre scale and the phase separation of the metastable Si–C–O matrix into SiO₂, C and SiC was proved. The in‐situ crystallization could be considerably accelerated by adding fine‐grained powder of inert fillers, such as Al₂O₃ or SiC, which permits effective process control. In part 2, the microstructure is characterized by high‐resolution transmission electron microscopy and selected area diffraction. Turbostratic carbon and cubic β‐SiC precipitate as crystallization products. Theses phases are embedded in an amorphous matrix. Inert fillers reduce the crystallization temperature by several hundred °C. In this case, the polymer‐derived Si–C–O material acts as a binding agent between the powder particles. Reaction layer formation does not occur. On the investigated pyrolysis conditions, no crystallization of SiO₂ was observed.     

Processing and microstructure of non-oxide ceramic fibres

Research and development efforts on high-temperature, oxidation-resistant fibres have increased over the past decade due to the demand for light-weight, stiff and strong composite materials in aerospace applications. Varieties of ‘high-performance’, continuous, non-oxide fibres with low-density, high tensile strength and tensile modulus have been developed either from organic precursors or via chemical vapour deposition for fabrication of ceramic matrix composites. Fibres derived from polymer precursors (e.g. Nicalon, Tyranno, HPZ) are small in diameter (compared to CVD monofilaments) and are ideally suited for ceramic composites. Processing, microstructural stability and mechanical properties of these newly developed SiC and Si₃N₄ base fibres are briefly reviewed in this paper.     

Analytical pyrolysis as a tool for the study of plastic coals

The technique of analytical pyrolysis has been used to characterize 40 similar mid-rank western Kentucky coals of widely differing ASTM Gieseler plasticity. Certain pyrolysis/g.c. variables were shown to correlate well with both ASTM Gieseler and isothermal plasticity. Highly plastic coals were shown to exhibit certain characteristic peaks in the 450 °C pyrogram which were absent in the pyrogram of the non-plastic coals. Two coals, representing the two extremes in plasticity, were selected for further study. After extraction with solvents such as DMF the characteristic peaks were absent in the 450 °C pyrogram of the extraction residue of the highly plastic coal. These peaks were also shown to decrease with increasing severity of air oxidation of the plastic coal. This technique appears to be a useful tool for the analysis of mid-rank plastic coals and supports the view that the substances contained in the bitumen fraction of these coals are involved in the development of the plastic state.     

On the suitability of agricultural by-products for the manufacture of granular activated carbon

An investigation of several agricultural by-products revealed that their suitability for activated carbon production is not determined by general material-specific features (elemental composition) but by type-specific features. A coarse-cellular structure (as in wood), which is indicated by porosities of the raw materials higher than 35% is disadvantageous. A specific change in the properties of cokes (porosity, density, hardness) is possible by varying the conditions of pyrolysis. By rapid heating in the pyrolysis step, for instance, macroporous residues are produced. Temperature and burnoff have the greatest influence on the quality of the activated carbon during the activation step. Of the investigated materials, coconut shells yield granular activated carbon of the highest quality. The following order of suitability of raw materials for activated carbon production was established: coconut shells> peach stones> plum stones> hazelnut shells> walnut shells> cherry stones.     

Thermal degradation of poly(dimethylsilylene) and poly(tetramethyldisilylene‐co‐styrene)

Thermal degradation of poly(dimethylsilylene) homopolymer (PDMS) and poly(tetramethyldisilylene‐co‐styrene) copolymer (PTMDSS) was investigated by pyrolysis‐gas chromatography and thermogravimetry (TG). PDMS decomposes by depolymerization, producing linear and cyclic oligomeric products, whereas PTMDSS decomposes by random degradation along the chain resulting in each monomeric product and various other combination products. The homopolymer was found to be much less stable than the copolymer. The decomposition mechanisms leading to the formation of various products are shown. The kinetic parameters of thermal degradation were evaluated by different integral methods using TG data. The activation energies of decomposition (E) for the homopolymer and the copolymer are found to be 122 and 181 kJ/mol, respectively, and the corresponding values of order of reaction are 1 and 1.5. The observed difference in the thermal stability and the values of the kinetic parameters for decomposition of these polymers are explained in relation with the mechanism of decomposition. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Evaporation and Evolution of Suspended Solution Droplets at Atmospheric and Reduced Pressures

Thermal history and solute precipitation behavior of suspended solution droplets of sodium chloride (NaCl), magnesium sulphate (MgSO₄), and zirconium hydroxychloride (ZrO(OH)Cl) evaporating at atmospheric and reduced pressures are studied. Experimental measurements on the variation of droplet diameter, solution concentration, and temperature during the evaporation period are presented and discussed. The results of solute precipitation behavior in solution droplets observed under an optical microscope are displayed and discussed. Results indicate that reducing the pressure (∼ 33 kPa) results in a change in the solution droplet evaporation rate, but the thermal histories of a particular solution droplet are similar at the atmospheric and reduced pressures. At atmospheric and reduced pressures used in this study, the d² law for solution droplets is valid at early stages of the evaporation and before the solute precipitation initiates. Drying of MgSO₄ and ZrO(OH)Cl solution droplets results in the formation of spherical particles, whereas drying of spherical NaCl solution droplets results in the formation of cubic particles.     

Pyrolysis of tertiarybutylphosphine at low pressure

The pyrolysis of tertiarybutylphosphine (TBP) has been studied in the low pressure conditions used for chemical beam epitaxy (CBE). The pyrolysis studies were carried out in low pressure reactors of two different configurations, one of which is a cracker cell designed for use in a CBE system. The reaction products were studied using a quadrupole mass spectrometer. The products observed are accounted for by a reaction mechanism involving homolysis of the parent TBP molecule to produce PH₂ and C₄H₉ radicals. These undergo subsequent reactions to form the stable products C₄H₈, PH₃ and H₂, with smaller amounts of P and P₂ being produced. The production of the sub-hydride PH₂ using this cracker cell design indicates that the use of partially cracked TBP may be a promising technique for reducing the amount of carbon incorporated into the growing epitaxial layer.     

Sodium silicate as a coke inhibitor during naphtha pyrolysis

Rates of coke formation during steam pyrolysis of naphtha have been investigated in a jet-stirred reactor both for sodium silicate coated and uncoated Inconel 600 surfaces in the temperature range of 1078–1108 K. Coke formation rates were significantly reduced on sodium silicate coated plates due to the passivation of the metal surface. However, the coking rates gradually increased with successive decokings of the coated surface.     

热带城市垃圾典型组分的热解特性研究

对热带城市垃圾的几种典型组分进行了热解实验，得到了它们的失重曲线，通过对失重曲线进行分析，得到了这几种典型组分的热解规律，并通过建立热解动力学模型，求出了其中两种组分的活化能E和频率因子A。     

Thermal degradation of cinnamoylated poly(vinyl alcohol)

Thermogravimetry and pyrolysis in combination with gas chromatography and infrared spectroscopy were the experimental techniques applied to the thermal degradation of cinnamoylated poly(vinyl alcohol) samples, constituted from vinyl alcohol-vinyl cinnamate photocrosslinkable copolymers. The thermal decomposition products include gases, liquids and solids. The gases are formed from saturated and unsaturated volatile hydrocarbons C₁? C₄, carbon monoxide and carbon dioxide. The liquid fraction includes aromatic hydrocarbons and some oxygenated organic compounds. The solid product identified in the greatest amount was cinnamic acid. The content in the thermal decomposition products varies considerably both with copolymer composition and temperature.