Pyrolytic properties

Complex pyrolysis chemistry takes place in the conversion system of any conventional solid-fuel combustion system. The pyrolytic properties of biomass are controlled by the chemical composition of its major components, namely cellulose, hemicellulose, and lignin. Pyrolysis of these biopolymers proceeds through a series of complex, concurrent and consecutive reactions and provides a variety of products which can be divided into char, volatile (non-condensible) organic compounds (VOC), condensible organic compounds (tar), and permanent gases (water vapour, nitrogen oxides, carbon dioxide). The pyrolysis products should finally be completely oxidised in the combustion system (Figure 14). Emission problems arise as a consequence of bad control over the combustion system. 

Polycyclomethylsilazane (PCMS). Polysilazanes containing organic groups on the silicon backbone atoms are more typical as preceramic polymers, especially those substituted with methyl groups [7-12]. Polymers consisting of the monomeric units -[MeSiHNH]- are "isomeric" to the N-methylsilazanes discussed above. Comparison between the pyrolytic properties of the two is, Aerefore, of great interest. 

Figure 5-1 shows the thermal decomposition behavior of representative hinder resins when heated in the air atmosphere. As the figure shows, the final thermal decomposition end temperature differs according to the type of binder, and acrylic polymer has the best pyrolytic properties. When copper is used as a wiring material in LTCCs, the thermal decomposition behavior of the binder must be borne in mind particularly since a low oxygen concentration atmosphere is used and even after firing, binder tends to remain as residue in the ceramic [3]. 

An interesting question that arises is what happens when a thick adsorbed film (such as reported at for various liquids on glass [144] and for water on pyrolytic carbon [135]) is layered over with bulk liquid. That is, if the solid is immersed in the liquid adsorbate, is the same distinct and relatively thick interfacial film still present, forming some kind of discontinuity or interface with bulk liquid, or is there now a smooth gradation in properties from the surface to the bulk region This type of question seems not to have been studied, although the answer should be of importance in fluid flow problems and in formulating better models for adsorption phenomena from solution (see Section XI-1). 

Other techniques include oxidative, steam atmosphere (33), and molten salt (34) pyrolyses. In a partial-air atmosphere, mbber pyrolysis is an exothermic reaction. The reaction rate and ratio of pyrolytic filler to ok products are controlled by the oxygen flow rate. Pyrolysis in a steam atmosphere gives a cleaner char with a greater surface area than char pyroly2ed in an inert atmosphere however, the physical properties of the cured compounded mbber are inferior. Because of the greater surface area, this pyrolytic filler could be used as activated carbon, but production costs are prohibitive. Molten salt baths produce pyroly2ed char and ok products from tine chips. The product characteristics and quantities depend on the salt used. Recovery of char from the molten salt is difficult. 

Mechanical Properties. The hexagonal symmetry of a graphite crystal causes the elastic properties to be transversely isotropic ia the layer plane only five independent constants are necessary to define the complete set. The self-consistent set of elastic constants given ia Table 2 has been measured ia air at room temperature for highly ordered pyrolytic graphite (20). With the exception of these values are expected to be representative of... 

Wei and Robbins [10] have reviewed much of the work performed on the thermal physical properties of CBCF. Fhe emissivity parallel to the fibers was 0.8 over the temperature range from 1000 to 1800 °C. This value is higher than the emissivity of c-direction pyrolytic graphite (0.5-0.6), but is close to values for graphite and dense carbon-carbon composite (0.8-0.95). 

Bokros, J.C., Deposition, structure, and properties of pyrolytic carbon, Chem. Phys. Carbon, 1969,5, 1 IIS. 

Property Conventional electro-graphite Glassy or harp carbon Pyrolytic carbon ... 

Graphite is commonly produced by CVD and is often referred to as pyrolytic graphite. It is an aggregate of graphite crystallites, which have dimensions (L ) that may reach several hundred nm. It has a turbostratic structure, usually with many warped basal planes, lattice defects, and crystallite imperfections. Within the aggregate, the crystallites have various degrees of orientation. When they are essentially parallel to each other, the nature and the properties of the deposit closely match that of the ideal graphite crystal. 

H-BN is produced by hot-pressing the powder or by CVD. The processes impart different properties. The hot-pressed material shows less anisotropy than the CVD BN, since the powder grains are randomly oriented. CVD BN is usually a turbostratic boron nitride with warped basal planes and lattice defects. It is also known as pyrolytic boron nitride or PBN.1 11 " ]... 

The layer of titanium and ruthenium oxides usually is applied to a titanium substrate pyrolytically, by thermal decomposition (at a temperature of about 450°C) of an aqueous or alcoholic solution of the chlorides or of complex compounds of titanium and rathenium. The optimum layer composition corresponds to 25 to 30 atom % of ruthenium. The layer contains some quantity of chlorine its composition can be written as Ruq 2sTio 750(2- c)Cl r At this deposition temperature and Ru-Ti ratio, the layer is a poorly ordered solid solution of the dioxides of ruthenium and titanium. Chlorine is completely eliminated from the layer when this is formed at higher temperatures (up to 800°C), and the solid solution decomposes into two independent phases of titanium dioxide and ruthenium dioxide no longer exhibiting the unique catalytic properties. 

Savinova ER, Lebedeva NP, Simonov PA, Kryukova GN. 2000. Electrocatalytic properties of platinum anchored to the surface of highly oriented pyrolytic graphite. Russ J Electrochem. 36 (9) 952-959. 

One potential solution to these problems, suggested some 20 years ago by Chantrell and Popper (1), involves the use of inorganic or organo-metallic polymers as precursors to the desired ceramic material. The concept (2) centers on the use of a tractable (soluble, meltable or malleable) inorganic precursor polymer that can be shaped at low temperature (as one shapes organic polymers) into a coating, a fiber or as a matrix (binder) for a ceramic powder. Once the final shape is obtained, the precursor polymer can be pyrolytically transformed into the desired ceramic material. With careful control of the pyrolysis conditions, the final piece will have the appropriate physical and/or electronic properties. 

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