Flame-made compositions

Similarly to flame-made titanates, the precise control of the stoichiometry and material purity has an influence on the electronic properties of perovskite-type oxides such as LSC, LSCF, and BSCF. While conductivity is comparable with the highest reported in the literature (Figure 4.5), other unique properties are documented for these flame-made compositions. LSC, LSCF, and BSCF from a FSS process feature a pronounced shift of the temperature, at which the maximum conductivity is observed. The FSS process resulted in materials with an exceptional electronic conductivity, which may better match to a SOFC operated at intermediate or low temperatures. For example, LSCF cathodes based on flame-made nanopowders have shown polarization resistances in the range of 0.7 Q. cm at 592 °C [59], which are among the lowest reported for thick film layers of this material stoichiometry. Similar conclusions were drawn with respect to LSC-based cathodes, for which very low overpotentials were documented [60]. 

Pd-doped catalysts have been produced by USS [82]. The fingerprint of Pd adopting the octahedral coordination of Fe in LaFeo,95Pdo,o503 has been observed in the XANES spectra of the material prepared by spray synthesis (27m /g) similarly to the preparation by the amorphous citrate method (14m /g) [17,82]. In contrast, the flame-made material of the same composition (22m /g) exposed metallic Pd particles on LaFeOs similarly to preparation by solution combustion. The different nature of the Pd species obtained by changing the synthesis method dramatically influences their catalytic performance, since PdO nanoparticles exposed at the surface of the mixed oxide exhibit catalytic activity, whereas Pd—O species in the bulk of the mixed oxide are inactive, at least in the case of methane oxidation [27]. In contrast to LaFeOs, LaMnOs did not allow Pd to adopt the octahedral coordination irrespective of synthesis method. Therefore, the coordination of Pd strongly depends on both the composition of the perovskite-type oxide and the synthesis method. 

Jossen, R., Mueller, R., Pratsinis, S.E., Watson, M. and Akhtar, M.K. (2005) Morphology and composition of spray-flame-made yttria-stabilized zirconia nanoparticles. Nanotechnology, 16, S609-17. 

An example of a commercial semibatch polymerization process is the early Union Carbide process for Dynel, one of the first flame-retardant modacryhc fibers (23,24). Dynel, a staple fiber that was wet spun from acetone, was introduced in 1951. The polymer is made up of 40% acrylonitrile and 60% vinyl chloride. The reactivity ratios for this monomer pair are 3.7 and 0.074 for acrylonitrile and vinyl chloride in solution at 60°C. Thus acrylonitrile is much more reactive than vinyl chloride in this copolymerization. In addition, vinyl chloride is a strong chain-transfer agent. To make the Dynel composition of 60% vinyl chloride, the monomer composition must be maintained at 82% vinyl chloride. Since acrylonitrile is consumed much more rapidly than vinyl chloride, if no control is exercised over the monomer composition, the acrylonitrile content of the monomer decreases to approximately 1% after only 25% conversion. The low acrylonitrile content of the monomer required for this process introduces yet another problem. That is, with an acrylonitrile weight fraction of only 0.18 in the unreacted monomer mixture, the low concentration of acrylonitrile becomes a rate-limiting reaction step. Therefore, the overall rate of chain growth is low and under normal conditions, with chain transfer and radical recombination, the molecular weight of the polymer is very low. 

Fibers. The principal type of phenoHc fiber is the novoloid fiber (98). The term novoloid designates a content of at least 85 wt % of a cross-linked novolak. Novoloid fibers are sold under the trademark Kynol, and Nippon Kynol and American Kynol are exclusive Hcensees. Novoloid fibers are made by acid-cataly2ed cross-linking of melt-spun novolak resin to form a fuUy cross-linked amorphous network. The fibers are infusible and insoluble, and possess physical and chemical properties that distinguish them from other fibers. AppHcations include a variety of flame- and chemical-resistant textiles and papers as weU as composites, gaskets, and friction materials. In addition, they are precursors for carbon fibers. 

Neoprenes. Of the synthetic latices, a type that can be processed similarly to natural mbber latex and is adaptable to dipped product manufacture, is neoprene (polychloroprene). Neoprene latices exhibit poor initial wet gel strength, particularly in coagulant dipped work, but the end products can be made with high gum tensile strength, oil and aUphatic solvent resistance, good aging properties, and flame resistance. There are several types of neoprene latex, available at moderately high (ca 50 wt %) and medium soHds content. Differences in composition between the types include the polymer s microstmcture, eg, gel or sol, the type of stablizer, and the total soHds content (Table 22). 

Adiabatic flame temperatures agree with values measured by optical techniques, when the combustion is essentially complete and when losses are known to be relatively small. Calculated temperatures and gas compositions are thus extremely useful and essential for assessing the combustion process and predicting the effects of variations in process parameters (4). Advances in computational techniques have made flame temperature and equifibrium gas composition calculations, and the prediction of thermodynamic properties, routine for any fuel-oxidizer system for which the enthalpies and heats of formation are available or can be estimated. 

Most theories of droplet combustion assume a spherical, symmetrical droplet surrounded by a spherical flame, for which the radii of the droplet and the flame are denoted by and respectively. The flame is supported by the fuel diffusing from the droplet surface and the oxidant from the outside. The heat produced in the combustion zone ensures evaporation of the droplet and consequently the fuel supply. Other assumptions that further restrict the model include (/) the rate of chemical reaction is much higher than the rate of diffusion and hence the reaction is completed in a flame front of infinitesimal thickness (2) the droplet is made up of pure Hquid fuel (J) the composition of the ambient atmosphere far away from the droplet is constant and does not depend on the combustion process (4) combustion occurs under steady-state conditions (5) the surface temperature of the droplet is close or equal to the boiling point of the Hquid and (6) the effects of radiation, thermodiffusion, and radial pressure changes are negligible. 

In 1979, it was stated that poiybrominated aromatic ethers have received little attention (ref. 1). That statement is still applicable. Analyses to characterize this class of commercial flame retardants have been performed using UV (refs. 1-2), GC (refs. 1-6), and GC-MS (refs. 1-4). The bromine content of observed peaks was measured by GC-MS, but no identification could be made. The composition of poiybrominated (PB) diphenyl ether (DPE) was predicted from the expected relationship with polyhalogenated biphenyl, a class which has received extensive attention. NMR (refs. 3-6) was successfully used to identify relatively pure material which had six, or fewer, bromine atoms per molecule. A high performance liquid chromatography (HPLC) method described (ref. 1) was not as successful as GC. A reversed phase (RP) HPLC method was mentioned, but no further work was published. 

Sample Preparation. Liquid crystalline phases, i.e. cubic and lamellar phases, were prepared by weighing the components in stoppered test tubes or into glass ampoules (which were flame-sealed). Water soluble substances were added to the system as water solutions. The hydrophobic substances were dissolved in ethanol together with MO, and the ethanol was then removed under reduced pressure. The mixing of water and MO solutions were made at about 40 C, by adding the MO solution dropwise. The samples for the in vivo study were made under aseptic conditions. The tubes and ampoules were allowed to equilibrate for typically five days in the dark at room temperature. The phases formed were examined by visual inspection using crossed polarizers. The compositions for all the samples used in this work are given in Tables II and III. 

All hydrocarbon fire mechanisms and estimates will be affected by to some extent of flame stability features such as varying fuel composition as lighter constituents are consumed, available ambient oxygen supplies, ventilation patterns, and wind effects. Studies into these effects have generally not progressed to the level where precise estimations can be made without scale model tests or on site measurements. 

Unlike premixed flames, which have a very narrow reaction zone, diffusion flames have a wider region over which the composition changes and chemical reactions can take place. Obviously, these changes are principally due to some interdiffusion of reactants and products. Hottel and Hawthorne [5] were the first to make detailed measurements of species distributions in a concentric laminar H2-air diffusion flame. Fig. 6.5 shows the type of results they obtained for a radial distribution at a height corresponding to a cross-section of the overventilated flame depicted in Fig. 6.2. Smyth et al. [2] made very detailed and accurate measurements of temperature and species variation across a Wolfhard-Parker burner in which methane was the fuel. Their results are shown in Figs. 6.6 and 6.7. 

Continuous textile fibers are usually made by drawing molten glass though a bushing with many fine holes. In Fig. 2.20 glass marbles of controlled composition are fed into the melting pot, and primary filaments of glass are pulled into the jet flame. Typically, uniform-diameter fibers of between 4 and 20 micrometers are drawn at speeds in excess of 5000 feet per minute. 

Triple-base propellants are made by the addition of crystalUne nitroguanidine (NQ) to double-base propellants, similar to the way in which nitramine is added to CMDB propellants as described in the preceding section. Since NQ has a relatively high mole fraction of hydrogen within its molecular structure, the molecular mass of the combustion products becomes low even though the flame temperature is reduced. Table 4.13 shows the chemical composition, adiabatic flame temperature, and thermodynamic energy,/ as defined in Eq. (1.84), of a triple-base propellant at 10 MPa (NC 12.6% N). 

T. Shimizu, "Studies on Blue and Purple Flame Compositions Made With Potassium Perehlorate," Pyrotechnica VI, Pyrotechnica Publications, Austin, Texas, 1980. 

Binary mixtures of oxidizer with metallic fuel yield the highest flame temperatures, and the choice of oxidizer does not appear to make a substantial difference in the temperature attained. For compositions without metal fuels, this does not seem to be the case. Shimizu has collected data for a variety of compositions and has observed that potassium nitrate mixtures attain substantially lower flame temperatures than similar mixtures made with chlorate or perchlorate oxidizers. This result can be attributed to the substantially -endothermic decomposition of KNO 3 relative to the other oxidizers. Table 5.11 presents some of the Shimizu data [ 8]. 

Most explosive and pyrotechnic reactions produce significant quantities of smoke, and this visible phenomenon may or may not be desirable. Smoke can obscure colored flames, and therefore attempts are made to keep the production of smoke to a minimum in such mixtures. However, a variety of smoke-producing compositions are purposefully manufactured for use in daytime signalling and troop and equipment obscuration, as well as for amusement and entertainment purposes. 

Low-Explosive (LE). An explosive which when used in its normal manner deflagrates or burns rather than detonates that is the rate of advance of the reaction zone into the unreacted material is less than the velocity of sound in the unreacted material. LE s include propellants, certain primer mixtures, BkPdr, blasting explosives (See Ref 44, p B202-L), pyrotechnic compositions and delay compositions. Whether an explosive reacts as a high explosive or a low explosive depends on the manner in which it is initiated and confined. For example, a double base propellant when initiated in the usual manner acts as a LE. However, this material can be made to detonate if it is initiated by an intense shock. Conversely, a HE like TNT, can, under certain conditions be ignited by flame and will burn without detonation (Ref 40a, p 97)... 

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