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Paciorek, K. L.

Publications and source records attributed to Paciorek, K. L..

16 records
All sourcesNASA NTRSDOE OSTI
NASA NTRS1987

Improved perfluoroalkylether fluid development

The objective of this program was to optimize and scale up the linear perfluoroalkylether stabilization process and to provide test data regarding the fluids' thermal oxidative stability in the presence of metal alloys. The stabilization of Fomblin Z-25 was scaled up to 300 g of fluid. The modified fluid was stable at 316 C in oxygen in the presence of M-50 alloy for more than 24 hrs but less than 40 hrs; the amount of volatiles produced after 24 hrs was 5.5 mg/g. In the presence of Ti(4Al,4Mn) alloy, under the above conditions, following an exposure of 24 hrs, the amount of volatiles formed was 6.2 mg/g; 56 hrs exposure yielded 13.9 mg/g. The commercial fluid at 288 C (in oxygen) in the presence of M-50 after 15 hrs of exposure decomposed extensively, 342 mg/g; in the presence of Ti(4Al,4Mn) alloy after only 8 hrs at 288 C, the amount of volatiles was 191 mg/g. Formulation of the commercial fluid with C2PN3 additive was not as effective as the stabilization processing. All the perfluoroalkylether fluids studied were stable in nitrogen at 343 C. The thermal oxidative stability in the absence of metal alloys varied, with Aflunox exhibiting the best behavior. All the fluids were degraded in oxygen at 316 C during 24 hrs exposure to Ti(4Al,4Mn) alloy with the exception of a perfluoroalkylether substituted triazine and the modified Z-25.

Paciorek, K. L.↗
NASA NTRS1983

Thermal oxidative degradation reactions of perfluoroalklethers

The objective of this contract was to investigate the mechanisms operative in thermal and thermal oxidative degradation of Fomblin Z and hexafluoropropene oxide derived fluids and the effect of alloys and additives upon these processes. The nature of arrangements responsible for the inherent thermal oxidative instability of the Fomblin Z fluids has not been established. It was determined that this behavior was not associated with hydrogen end-groups or peroxy linkages. The degradation rate of these fluids at elevated temperatures in oxidizing atmospheres was found to be dependent on the surface/volume ratio. Once a limiting ratio was reached, a steady rate appeared to be attained. Based on elemental analysis and oxygen consumption data, -CF2OCF2CF2O-, not -CF2CF2O-, is one of the major arrangements present. The action of the M-50 and Ti(4 Al, 4 Mn) alloys was found to be much more drastic in the case of Fomblin Z fluids than that observed for the hexalfuoropropane oxide derived materials. The effectiveness of antioxidation/anticorrosion additives, P-3 and phospha-s-triazine, in the presence of metal alloys was very limited at 316 C; at 288 C the additives arrested almost completely the fluid degradation. The phospha-s-triazine appeared to be at least twice as effective as the P-3 compound; it also protected the coupon better. The Ti(4 Al, 4 Mn) alloy degraded the fluid mainly by chain scission processes; this took place to a much lesser degree with M-50.

Paciorek, K. L.↗
NASA NTRS1981

Synthesis of perfluoroalkylene dianilines

The objective of this contrast was to optimize and scale-up the synthesis of 2,2-bis(4-aminophenyl)-hexafluoropropane and 1,3-bis(4-aminophenyl)hexafluoropropane, as well as to explore avenues to other perfluoroalkyl-bridged dianilines. Routes other than Friedel-Crafts reaction leading to 2,2-bis(4-aminophenyl)hexafluoropropane were investigated. The processes utilizing bisphenol-AF were all unsuccessful; reactions aimed at the production of 4-(hexafluoro-2-halo-isopropyl)aniline from the hydroxyl intermediate failed to yield the desired products. Tailoring the conditions of the Friedel-Crafts reaction of 4-(hexafluoro-2-hydroxyisopropyl)aniline, aniline, and aluminum chloride by using hydrochloride salts and selecting optimum reagent ratios, reaction times, and temperature resulted in approx. 20% yield of pure crystallized 2,2-bis(4-aminophenyl)hexafluoropropane in 0.2 mole reaction batches. Yields up to approx. 40% were realized in small, approx. 0.01 mole, batches. The synthesis of 1,3-bis(4-aminophenyl)hexafluoropropane starting with perfluoroglutarimidine was reinvestigated. The yield of the 4-step reaction sequence giving 1,3-bis(4-acetamidophenyl)hexafluoropropane was raised to 44%. The yield of the subsequent hydrolysis process was improved by a factor of approx. 2. Approaches to prepare other perfluoroalkyl-bridged dianilines were unsuccessful. Reactions reported to proceed readily with trifluoromethyl substituents failed when longer chain perfluoroalkyl groups were employed.

Paciorek, K. L.↗
NASA NTRS1981

Thermal oxidative degradation reactions of perfluoroalkylethers

The mechanisms operative in thermal oxidative degradation of Fomblin Z and hexafluoropropene oxide derived fluids and the effect of alloys and additives upon these processes are investigated. The nature of arrangements responsible for the inherent thermal oxidative instability of the Fomblin Z fluids is not established. It was determined that this behavior is not associated with hydrogen end groups or peroxy linkages. The degradation rate of these fluids at elevated temperatures in oxidizing atmospheres is dependent on the surface/volume ratio. Once a limiting ratio is reached, a steady rate appears to be attained. Based on elemental analysis and oxygen consumption data, CF2OCF2CF2O2, no. CF2CF2O, is one of the major arrangements present. The action of the M-50 and Ti(4 Al, 4 Mn) alloys is much more drastic in the case of Fomblin Z fluids than that observed for the hexafluoropropene derived materials. The effectiveness of antioxidation anticorrosion additives, P-3 and phospha-s-triazine, in the presence of metal alloys is very limited at 316 C; at 288 C the additives arrested almost completely the fluid degradation. The phospha-s-triazine appears to be at least twice as effective as the P-3 compound; it also protected the coupon better. The Ti(4 Al, 4 Mn) alloy degraded the fluid mainly by chain scission processes this takes place to a much lesser degree with M-50.

Paciorek, K. L.↗
NASA NTRS1980

Phosphazene diamines

The synthesis of a specific phosphazene diamine was optimized, other phosphorus-containing diamines were prepared, and their effect upon certain characteristics of epoxy resins, prepared via reaction with MY 720, in particular, char yield at elevated temperatures was evaluated. The synthesis of the phosphazene diamine resulting from the interaction of methylenedianline with 4,4'-bis(diphenylphosphino)biphenyl was simplified into a one step process giving 77 percent yield of the pure product. Using this procedure, a related diamine containing bis(diphenylphosphino)methane was obtained in a 70 percent yield. Preparation of another class of phosphorus containing amines based upon p-aminophenyldiphenyl-phosphine was unsuccessful; the inability to produce p-aminophenylithlum was responsible for this failure. Seven epoxy resins employing Araldite MY 720, diaminodiphenylsulfone, and two of the phosphorus containing diamines were prepared, characterized, and their char yield capacity at elevated temperatures assessed. Based on these investigations, the resins containing phosphorus appear to exhibit significantly better char formation characteristics than materials hardened using conventional amines, without impairing the other properties measured.

Paciorek, K. L.↗
NASA NTRS1978

Preparation of linear hydroxy substituted polyphosphazenes

The synthesis of partially hydroxy-substituted phosphazene prepolymers amenable to processing into cellular, flexible polyurethane foams was investigated. Factors determined include (1) the environment of the hydroxyl group; (2) the ease of the hexachlorocyclotriphosphazene polymerization; (3) the nature of the nonreactive substituents; and (4) the mode of introduction of the hydroxyl entity. The specific approaches taken, the rationale of the selections made, and the results are discussed.

Paciorek, K. L.↗
NASA NTRS1978

Synthesis of perfluoroalkylene aromatic diamines

Analogues of methylene dianilines were synthesized, in which the methylene group between the two aromatic nuclei was replaced by various perfluoroalkylene linkage. The hydrolytic thermal, and thermal oxidative stabilities of PMR Polyimides derived from these diamines were determined. Three types of PMR Polyimide discs were fabricated from the dimethyl ester of 3,3', 4,4'-benzophenonetetracarboxylic acid, the methyl ester of 5-norbornene-2,3-dicarboxylic acid, and one of the following three diamines: methyl dianiline, 1,3-bis(4-aminophenyl)hexafluoropropane, and 2,2-bis(4-aminophenyl)hexafluoropropane. The polyimide based on 2,2-bis(4-aminophenyl)hexafluoropropane exhibited the best hydrolytic, thermal, and thermal oxidative stability as determined by moisture uptake and thermogravimetric analysis.

Paciorek, K. L.↗
NASA NTRS1977

Cross Linking and Degradation Mechanisms in Model Sealant Candidates

Model compounds were investigated as to which type of heterocyclic ring is the most advantageous for curing sealants based on perfluoroalkylether chains. The relative thermal, thermal oxidative, hydrolytic, and fuel stability of potential crosslinks were determined. Specifically substituted materials were synthesized and evaluation of their stabilities in air, inert atmosphere, water, and Jet-A fuel at 235 and 325 C was made. Three heterocyclic ring systems were considered, namely, triazine, 1,2,4- and 1,3,4-oxadiazoles.

Paciorek, K. L.↗
NASA NTRS1976

Flame retardant polyphosphazenes

Three processes for the preparation of polyphosphazenes were investigated: (1) the reaction of bisphosphines with diazides, (2) the condensation of bisdichlorophosphoranes with diamines; and (3) the treatment of bisphosphines with diamines in the presence of carbon tetrachloride followed by base dehydrohalogenation. All products obtained were of low molecular weight; the degree of polymerization did not exceed twelve repeating units. However, several compositions exhibited good thermal stability. No weight loss was observed up to 390 C when heated in air at 5 C/min. Treatment of bisphosphines with either an excess of a diazide or an excess of a diamine in the presence of carbon tetrachloride resulted in the production of difunctional phosphazenes which were respectively, azido and amino terminated. The reaction of these azido terminated extended monomers with bisphosphines did not produce high molecular weight materials. The bis-aminophosphazene prepared for the first time under this contract was successfully incorporated into a polyimide.

Paciorek, K. L.↗
NASA NTRS1975

Flame resistant nontoxic polymer development

A number of homopolymers, copolymers, and terpolymers were synthesized employing styrene and four derivatives of diphenyl-p-styrylphosphine. The various polymeric compositions were prepared by two processes, (1) monomer bulk polymerizations and (2) substitution of preformed polydiphenyl-p-styrylphosphine. Results indicate that the majority of the compositions exhibit superior melting and flame retardant characteristics as compared to polystyrene, but are inferior in molding and film forming capability. Terpolymerization appears to result in the materials with the best overall combination of properties. Toxicological evaluation of three representative basic compositions in the form of molded washers showed that no mortalities occurred among the test animals exposed to the products of the oxidative thermal decomposition of the three materials.

Paciorek, K. L.↗
NASA NTRS1975

Syntheses and degradations of fluorinated heterocyclics

The relative stability of two ring systems, the triazine rings and 1,2,4-oxadiazoles, which offer potential crosslinks useful for curing perfluoroalkyl ether elastomers, has been investigated. Tris (perfluoro-n-heptyl)-s-triazine, the perfluoroether substituted-s-triazine, 1,4-bis/(5-perfluoro-n-heptyl)-1,2,4-oxadiazolyl/benzene, its perfluoroalkyl ether substituted analog, and 3,5-bis-(perfluoro-n-heptyl)-1,2,4-oxadiazole were synthesized and subjected to thermal and oxidative degradation at 235 and 325 C and to hydrolytic degradation at 235 C. The perfluoroalkyl ether substituted triazine and 3,5-bis(perfluoro-n-heptyl)-1,2,4-oxadiazole were found to be stable under all conditions investigated.

Paciorek, K. L.↗
NASA NTRS1974

Crosslinking and degradation mechanisms in model sealant candidates

Heterocyclic ring systems were investigated, triazines and 1,2,4-oxadiazoles. Only a limited effort was extended to the preparation of triazoles. Compounds, n-perfluoroheptyl-s-triazine, a perfluoroether substituted triazine, C3F7OCF(CF3)CF2OCF(CF3) 3C3N3,1,4-bus (5-perfluoro-n-heptyl)-1,2,4-oxadiazolyl -benzene, its perfluoroalkylether substituded analogue, and 3,5-bis(perfluoro-n-heptyl)-1,2,4-oxadiazole were synthesized and characterized. To eliminate the effect due to a tertiary fluorine present in branched materials, the pure n-alkyl-compounds were prepared. The main starting material, perfluoro-n-octanonitrile, was obtained from commercially available perfluoro-n-octanoic acid via a three step synthesis.

Paciorek, K. L.↗
NASA NTRS1973

Flame retardant polyphosphazenes

Six polyphosphazene compositions were prepared by reaction of three bis-tertiary phosphines with two phenyl-s-triazine derived diazides. All six polyphosphazenes produced were completely characterized, four of them were furthermore subjected to isothermal gravimetric analysis, smoke density measurements, flammability and oxidative thermal degradation testing. The results of the characterization studies indicate that only low molecular weight oligomers, possibly of a cyclic structure, were obtained in the polymerization reactions. Despite this, however, two of the materials showed no weight loss after 96 hr at 200 C, one did not autoignite at 500 C in air, and all four self extinguished when exposed to a flame as soon as contact between flame and resin was lost. The only toxic decomposition products to be concerned about were found to be hydrogen cyanide and benzene. Under the conditions employed it was proven, however, that the quantities of toxic products are greatly reduced if no ignition takes place, e.g., if thermal decomposition proceeds at a sufficiently low rate.

Paciorek, K. L.↗
NASA NTRS1971

Fundamental ignition study for material fire safety improvement, part 2

The autoignition behavior of polymeric compositions in oxidizing media was investigated as well as the nature and relative concentration of the volatiles produced during oxidative decomposition culminating in combustion. The materials investigated were Teflon, Fluorel KF-2140 raw gum and its compounded versions Refset and Ladicote, 45B3 intumenscent paint, and Ames isocyanurate foam. The majority of the tests were conducted using a stagnation burner arrangement which provided a laminar gas flow and allowed the sample block and gas temperatures to be varied independently. The oxidizing atmospheres were essentially air and oxygen, although in the case of the Fluorel family of materials, due to partial blockage of the gas inlet system, some tests were performed unintentionally in enriched air (not oxygen). The 45B3 paint was not amenable to sampling in a dynamic system, due to its highly intumescent nature. Consequently, selected experiments were conducted using a sealed tube technique both in air and oxygen media.

Paciorek, K. L.↗
NASA NTRS1970

Fundamental ignition study for material fire safety improvement, part 1

The investigation of preignition, ignition, and combustion characteristics of Delrin (acetate terminated polyformaldehyde) and Teflon (polytetrafluoroethylene) resins in air and oxygen are presented. The determination of ignition limits and their dependence on temperature and the oxidizing media, as well as the analyses of the volatiles produced, were studied. Tests were conducted in argon, an inert medium in which only purely pyrolytic reactions can take place, using the stagnation burner arrangement designed and constructed for this purpose. A theoretical treatment of the ignition and combination phenomena was devised. In the case of Delrin the ignition and ignition delays are apparently independent of the gas (air, oxygen) temperatures. The results indicate that hydrogen is the ignition triggering agent. Teflon ignition limits were established in oxygen only.

Paciorek, K. L.↗