SEARCH · Search NASA
Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.
Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.
Relative toxicity data on the pyrolysis products of a variety of thermoplastic and thermoset polymers are presented. The data are presented in terms of time to incapacitation and time to death with a fixed sample weight of 1.0 g, and in terms of the apparent lethal concentration required to produce 50 percent mortality within a fixed exposure period of 30 min.
Various samples of cellular polymers were evaluated for toxicity of pyrolysis gases, using the screening test method developed at the University of San Francisco. The cellular polymer samples included polyimide, polymethacrylimide, polybismaleimide, polyurethane, polyisocyanurate, polyethylene, polychloroprene, polyvinyl chloride, polystyrene, polysiloxane, and polyphosphazene. The cellular polymers exhibited varying levels of toxicity under these test conditions. Among the rigid cellular polymers, times to death were shortest with the imide type foams and longest with polyvinyl chloride and polystyrene. Among the flexible cellular polymers, times to death were shortest with polyimide and polyester, and longest with polychloroprene and polysiloxane. Increased char yield was not necessarily associated with reduced toxicity.
The toxicity of the pyrolysis gases from some samples of polyurethane flexible foams appears to have decreased with age, while other samples seem to exhibit no significant change with age in this respect. The changes observed were greater than could be accounted for by variations in the material, or test variations or artifacts.
Silicon epitaxy analysis of silane produced in the Process Development Unit operating in a completely integrated mode consuming only hydrogen and metallurgical silicon resulted in film resistivities of up to 120 ohms cm N type. Preliminary kinetic studies of dichlorosilane disproportionation in the liquid phase have shown that 11.59% SiH4 is formed at equilibrium after 12 minutes contact time at 56 C. The fluid-bed reactor was operated continuously for 48 hours with a mixture of one percent silane in helium as the fluidizing gas. A high silane pyrolysis efficiency was obtained without the generation of excessive fines. Gas flow conditions near the base of the reactor were unfavorable for maintaining a bubbling bed with good heat transfer characteristics. Consequently, a porous agglomerate formed in the lower portion of the reactor. Dense coherent plating was obtained on the silicon seed particles which had remained fluidizied throughout the experiment.
Comparison of the char yield after occurrence of a flash fire in the pyrolysis gases from various materials indicates that increased char yield appears to be associated with reduced flash-fire propensity for certain types of materials. For certain other materials, flash-fire propensity appears to be independent of char yield. The mechanisms of thermal decomposition and char formation may be more important factors in flash-fire propensity than the quantitative degree of char formation.
Swiss Webster male mice which had survived near-lethal concentrations of pyrolysis gases from a variety of polymeric materials were killed two weeks after exposure, and the lungs, heart, liver, kidney, and spleen were examined. Microscopic examination revealed no significant effects on the liver, kidney, and spleen, while the effect on lungs could not be determined because of the high level of pathology in both experimental and control animals. The polymeric materials which were pyrolyzed were polyethylene, ABS, polycarbonate, polyaryl sulfone, polyether sulfone, polyphenylene sulfide, modified polyphenylene oxide, chlorinated polyvinyl chloride, polyvinylidene fluoride, and fluorene polycarbonate. It is suggested that tissue specimens should be examined 24 or 48 hr after exposure rather than 2 wks after exposure, since the 2 wk period permits healing to occur.
Nine samples of synthetic polymers were evaluated for toxicity of pyrolysis gases, using the toxicity screening test method developed at the University of San Francisco. The materials were polyoxymethylene, polyethylene (five samples), polypropylene, polymethyl methacrylate, and polystyrene. Of the five polyethylene samples, three contained known levels of chlorine. These test results were combined with earlier data to provide a comparison of 25 samples of synthetic polymers. Polyoxymethylene appeared to exhibit the greatest toxicity, and polystyrene the least toxicity, under these particular test conditions
A sample of polypropylene was evaluated for toxicity of pyrolysis gases, using the toxicity screening test method developed at the University of San Francisco. The gases from this sample appeared to be equivalent or less toxic than the gases from a sample of polyethylene under these particular test conditions. Carbon monoxide appeared to be the principal toxicant.
Twenty-three samples of flexible foams and twelve samples of rigid foams were evaluated for toxicity of pyrolysis gases, using the USF toxicity screening test method. Polychloroprene among the flexible foams, and polystyrene among the rigid foams, appeared to exhibit the least toxicity under these particular test conditions.
Large silicon particles result from controlled pyrolysis of silane. Mixture of 1 percent silane in nitrogen pyrolyzed at 300 degrees C to generate aerosol of silicon seed particles.
Silicon deposition on silicon seed particles by silane pyrolysis in a fluidized-bed reactor is investigated as a low-cost, high-throughput method to produce high-purity polysilicon for solar-cell applications. Studies of fines, particles 0.1-10 microns diam, initiated from homogeneous decomposition in the reactor were conducted using 2 and 6-in-diam fluidized beds. The studies show functional dependences of fines elutriation on silane feed concentration, temperature, gas velocity, and bubble size. The observation that the fines elutriation is generally below 10 percent of the silicon-in-silane feed is attributed to scavenging by large particles in an environment of less free space for homogeneous nucleation. Preliminary results suggest that, with proper conditions and distributor design, high-silane-concentration (over 50 percent SiH4 in H2) feed may be used.
The development of silicon carbide-silicon nitride fibers (SiC-Si3N4) by the pyrolysis of polycarbosilazane precursors is reviewed. Precursor resin, which was prepared by heating tris(N-methylamino)methylsilane or tris(N-methylamino)phenylsilane to about 520 C, was drawn into fibers from the melt and then made unmeltable by humidity conditioning at 100 C and 95 percent relative humidity. The humidity treated precursor fibers were pyrolyzed to ceramic fibers with good mechanical properties and electrical resistivity. For example, SiC-Si3N4 fibers derived from tris(N-methylamino)methylsilane had a tensile rupture modulus of 29 million psi and electrical resistivity of 6.9 x ten to the 8th power omega-cm, which is ten to the twelfth power times greater than that obtained for graphite fibers.
Thermogravimetric analysis data are presented on the unmeltable polycarbosilazane precursor of silicon carbide-silicon nitride fibers, over the room temperature-1000 C range in a nitrogen atmosphere, in order to establish the weight loss at various temperatures during the precursor's pyrolysis to the fiber material. The fibers obtained by this method are excellent candidates for use in applications where the oxidation of carbon fibers (above 400 C) renders them unsuitable.
An ideal backmixed reactor model (CSTR) and a fluidized bed bubbling reactor model (FBBR) were developed for silane pyrolysis. Silane decomposition is assumed to occur via two pathways: homogeneous decomposition and heterogeneous chemical vapor deposition (CVD). Both models account for homogeneous and heterogeneous silane decomposition, homogeneous nucleation, coagulation and growth by diffusion of fines, scavenging of fines by large particles, elutriation of fines and CVD growth of large seed particles. At present the models do not account for attrition. The preliminary comparison of the model predictions with experimental results shows reasonable agreement. The CSTR model with no adjustable parameter yields a lower bound on fines formed and upper estimate on production rates. The FBBR model overpredicts the formation of fines but could be matched to experimental data by adjusting the unkown jet emulsion exchange efficients. The models clearly indicate that in order to suppress the formation of fines (smoke) good gas-solid contacting in the grid region must be achieved and the formation of the bubbles suppressed.
The three steps in pyrolytic carbon formation are: (1) gaseous hydrocarbon polymerization and aromatic formation; (2) gas-phase condensation and surface adsorption/impingement of polyaromatic hydrocarbon; and (3) final dehydration to carbon. The structure of the carbon in the various stages of formation is examined. The apparatuses and experimental procedures for the pyrolysis of methane in a 60 cm long quartz reactor tube at temperatures ranging from 1400-1600 K are described. The percentage of carbon converted and its density are calculated and tabularly presented. The results reveal that dense carbon formation is maximized and soot eliminated by this procedure. It is observed that conversion efficiency depends on the composition of the inlet gas and conversion increases with increasing temperature. Based on the experimental data a three-man carbon reactor subsystem (CRS) is developed; the functions of the Sabatier Methanation Reactor, two carbon formation reactors and fluid handling components of the CRS are analyzed. The CRS forms 16 kg of carbon at a rate of 0.8 kg/day for 20 days in a two percent volume density quartz wool packing at temperature of 1500-1600 K.
Changes in the degree of isomerization of steranes and triterpanes during kerogen pyrolysis in the absence or presence of minerals are described. Kerogen from a Monterey Formation diatomite core sample was pyrolyzed under reduced pressure at 300 C for 2-1000 hrs in the presence or absence of calcite, illite, and montmorillonite. It is observed that the extent of isomerization of biomakers in C-20 in 14 alpha(H), 17 alpha(H)-steranes, at C-22 in 17 alpha(H), 21 beta(H)-hopanes and of 17 beta(H), 21 beta(H)-hopanes correlates to early diagenetic stages in rock extracts from sedimentary basins, and faster isomerization for steranes and triterpanes in the bitumen then for those in the kerogen structure are detected. The effects of the minerals on the isomerization reactions are examined; calcite inhibits, and illite and montmorillonite catalyze the reactions.
The development of silicon carbide-silicon nitride fibers (SiC-Si3N4) by the pyrolysis of polycarbosilazane precursors is reviewed. Precursor resin, which was prepared by heating tris(N-methylamino)methylsilane or tris(N-methylamino)phenylsilane to about 520 C, was drawn into fibers from the melt and then made unmeltable by humidity conditioning at 100 C and 95 percent relative humidity. The humidity treated precursor fibers were pyrolyzed to ceramic fibers with good mechanical properties and electrical resistivity. For example, SiC-Si3N4 fibers derived from tris(N-methylamino)methylsilane had a tensile rupture modulus of 29 million psi and electrical resistivity of 6.9 x ten to the 8th power omega-cm, which is ten to the twelfth power times greater than that obtained for graphite fibers.
Adherent, abrasion-resistant coat deposited with existing equipment. Carbon formed and deposited as coating on copper substrate by pyrolysis of hydrocarbon oil in electrical-arc discharges. Technique for producing carbon deposits on copper accomplished with electrical-discharge-machining equipment used for cutting metals. Applications for new coating technique include the following: solar-energy-collecting devices, coating of metals other than copper with carbon, and carburization of metal surfaces.