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Poly(arylene ether)s containing pendent ethynyl and substituted ethynyl groups and poly(arylene ether) copolymers containing pendent ethynyl and substituted ethynyl groups are readily prepared from bisphenols containing ethynyl and substituted ethynyl groups. The resulting polymers are cured up to 350 C to provide crosslinked poly(arylene ether)s with good solvent resistance, high strength and modulus.
This grant deals with several topics related to the dynamics of systems containing a compact object. Most of our research in 1994 dealt with systems containing Neutron Stars (NS's), but we also addressed systems containing a Black Hole (BH) or a White Dwarf (WD) in situations relevant to NS systems. Among the systems were isolated regular pulsars, Millisecond Pulsars (MSP's) that are either Single (SMP's) or in a binary (BMP's) Low Mass X-Ray Binaries (LMX's) and Cataclysmic Variables (CV's). We also dealt with one aspect of NS structure, namely NS superfluidity. A large fraction of our research dealt with irradiation-driven winds from companions. These winds turned out to be of some importance in the evolution of LMXB's and MSP's, be they SMP's or BMP's. While their role during LMXB evolution (i.e. during the accretion phase) is not yet clear, they may play an important role in turning BMP's into SMP's and also in bringing about the formation of planets around MSP's.
In an extension of previously reported work on ices containing CO, CO2, H2O, CH3OH, NH3, and H2, measurements of the physical and infrared spectral properties of ices containing molecules relevant to Jupiter's moon Io are presented. These include studies on ice systems containing SO2, H2S, and CO2. The condensation and sublimation behaviors of each ice system and surface binding energies of their components are discussed. The surface binding energies can be used to calculate the residence times of the molecules on a surface as a function of temperature and thus represent important parameters for any calculation that attempts to model the transport of these molecules on Io's surface. The derived values indicate that SO2 frosts on Io are likely to anneal rapidly, resulting in less fluffy, 'glassy' ices and that H2S can be trapped in the SO2 ices of Io during night-time hours provided that SO2 deposition rates are on the order of 5 micrometers/hr or larger.
This research has investigated the use of fuzzy logic, via the Matlab Fuzzy Logic Tool Box, to design optimized controller systems. The engineering system for which the controller was designed and simulate was the container crane. The fuzzy logic algorithm that was investigated was the 'predictive control' algorithm. The plant dynamics of the container crane is representative of many important systems including robotic arm movements. The container crane that was investigated had a trolley motor and hoist motor. Total distance to be traveled by the trolley was 15 meters. The obstruction height was 5 meters. Crane height was 17.8 meters. Trolley mass was 7500 kilograms. Load mass was 6450 kilograms. Maximum trolley and rope velocities were 1.25 meters per sec. and 0.3 meters per sec., respectively. The fuzzy logic approach allowed the inclusion, in the controller model, of performance indices that are more effectively defined in linguistic terms. These include 'safety' and 'cargo swaying'. Two fuzzy inference systems were implemented using the Matlab simulation package, namely the Mamdani system (which relates fuzzy input variables to fuzzy output variables), and the Sugeno system (which relates fuzzy input variables to crisp output variable). It is found that the Sugeno FIS is better suited to including aspects of those plant dynamics whose mathematical relationships can be determined.
Due to the difficulty in processing polyimides with high temperature stability and good solvent resistance, we have synthesized high performance polyimides with bicyclo(2.2.2)-oct-7-ene ring system which can easily be fabricated into films and fibers and subsequently converted to the more stable aromatic polyimides. In order to improve processability, we prepared two polyimides by reacting 1,4-phenylenediamine and 1,3phenylediamine with bicyclo(2.2.2)-7-octene-2,3,5,6-tetracarboxylic dianhydride. The polyimides were characterized by FTIR, FTNMR, solubility and thermal analysis. Thermogravimetric analysis (TGA) showed that the 1,4-phenylenediamine and 1,3-phenylenediamine containing polyimides were stable up to 460 and 379 C, respectively under nitrogen atmosphere. No melting transitions were observed for both polyimides. The 1,4-phenylenediamine containing polyimide is partially soluble in dimethyl sulfoxide, methane sulfonic acid and soluble in sulfuric acid at room temperature. The 1,3-phenylenediamine containing polyimide is partially soluble in dimethyl sulfoxide, tetramethyl urea, N,N-dimethyl acetamide and soluble in methane sulfonic acid and sulfuric acid.
The extreme temperatures anticipated for lubricated parts in advanced flight powerplants dictate the consideration of unconventional methods of lubrication such as solid lubricants and the reactive gases described in the present research. These halogen-containing "reactive" gases such as dichlorodifluoromethane, CF2Cl2, are among the most stable of organic molecules. The high "flash" temperatures generated at the contacting asperities as a result of frictional heat are sufficient to cause local decomposition of the halogen-containing gases. The active atoms thus released (e.g., chlorine) then react with the metal to be lubricated to form halides capable of effective lubrication. The presence of small amounts of a sulfur-containing gas (e.g., 1 percent sulfur hexafluoride, SF6) was found to catalyze the formation of metal halides. Friction and wear studies were made with a hemisphere (3/16-in. rad.) rider sliding in a circumferential path on the flat surface of a rotating disk (2 1/2-in. diam.). The specimens of corrosion-resistant 2 alloys were run in an atmosphere of the various gases with a load of 1200 grams, a sliding velocity of 120 feet per minute, and temperature from 75 to 1200 F. An effective lubricant for ferritic materials (M-1 tool steel) was CF2Cl2, but significant corrosion occurred above 600 F. Corrosion evaluation in CF2Cl2 suggested a number of nickel- and cobalt-base alloys for additional lubrication study. Several combinations of gases and these metals were found to lubricate to 1200 F without excessive corrosion. The gases were CF2Cl2 Plus 1 percent SF6, monobromotrifluoromethane CF3Br plus 1 percent SF6, dibromodifluoromethane CF2Br2, iodotrifluoromethane, CF3I, and I2. Careful selection of metals and gas are necessary for successful lubrication over specific temperature ranges. Optimum combinations give friction coefficients as low as 0.05 without
The Space Shuttle is connected to the mobile launch platform (MLP) by four aft skirt hold down studs on each solid rocket booster (SRB). Prior to lift-off, the frangible nuts inside the aft skirt blast containers are severed into two nut halves by two pyrotechnic booster cartridges. This action releases the Space Shuttle and allows the hold down studs to eject through the aft skirt bore and then down into the MLP. USBI has been tasked to upgrade the blast container for two specific reasons: (1) To eliminate lead for environmental concerns, and (2) To reduce the chance of nut recontact with the holddown stud. Nut recontact with the stud has been identified as a likely contributor to stud hang-ups. This upgrade will replace the lead liner with a unique open cell aluminum foam material, that has commercial and military uses. The aluminum foam used as an energy absorber is a proven design in many other aerospace/defense applications. Additional benefits of using the open cell, energy absorbent aluminum foam in place of the solid lead liner are: (A) Lead handling/exposure and possible contamination, along with hazardous waste disposal, will be eliminated; (B) Approximately 200 lbs. weight savings will be contributed to each Space Shuttle flight by using aluminum foam instead of lead; (C) The new aluminum liner is designed to catch all shrapnel from frangible nuts, thus virtually eliminating chance of debris exiting the HDP and causing potential damage to the vehicle; and (D) Using the lighter aluminum liner instead of lead, allows for easier assembly and disassembly of blast container elements, which also improves safety, operator handling, and the efficiency of operations.
The Space Shuttle is connected to the mobile launch platform (MLP) by four aft skirt hold down studs on each solid rocket booster (SRB). Prior to lift-off, the frangible nuts inside the aft skirt blast containers are severed into two nut halves by two pyrotechnic booster cartridges. This action releases the Space Shuttle and allows the hold down studs to eject through the aft skirt bore and then down into the MLP. USBI has been tasked to upgrade the blast container for two specific reasons: (1) To eliminate lead for environmental concerns, and (2) To reduce the chance of nut recontact with the holddown stud. Nut recontact with the stud has been identified as a likely contributor to stud hang-ups. This upgrade will replace the lead liner with a unique open cell aluminum foam material, that has commercial and military uses. The aluminum foam used as an energy absorber is a proven design in many other aerospace/defense applications. Additional benefits of using the open cell, energy absorbent aluminum foam in place of the solid lead liner are: (1) Lead handling / exposure and possible contamination, along with hazardous waste disposal, will be eliminated; (2) Approximately 200 lbs. weight savings will be contributed to each Space Shuttle flight by using aluminum foam instead of lead; (3) The new aluminum liner is designed to catch all shrapnel from frangible nuts, thus virtually eliminating chance of debris exiting the HDP and causing potential damage to the vehicle; (4) Using the lighter aluminum liner instead of lead, allows for easier assembly and disassembly of blast container elements, which also improves safety, operator handling, and the efficiency of operations.
As part of a program to develop high performance/high temperature adhesives and composite matrices for a Mach 2.4 high speed civil transport, imide oligomers containing phenylethynyl groups were investigated. Phenylethynyl groups were placed on the ends of oligomers of different molecular weights (1250, 2500 and 5000 g/mol), pendent along the backbone of oligomers and both pendent and terminal on oligomers. Many different compositions of phenylethynyl containing imide oligomers had been previously prepared and evaluated before selecting the composition based upon 3,3'.4,4'-biphenyltetracarboxcylic dianhydride (BPDA), 3.4'-oxydianiline (3,4'-ODA) and 1,3-bis(3-aminophenoxy)benzene (APB) for extensive work. 4-Phenylethynylphthalic anhydride (PEPA) was used to place phenylethynyl groups on the ends of the oligomers and 3,5-diamino-4'-phenylethynylbenzophenone (DPEB) was used to introduce pendent phenylethynyl groups along the oligomeric backbone. Upon heating above 300 C, the phenylethynyl groups react to provide chain extension, branching and cross linking. Several of these materials exhibited excellent properties as adhesives and composite matrices. The chemistry, processability and properties of the oligomers, the cured polymers, bonded specimens and composites from phenylethynyl containing oligomers are presented.
A flywheel testing facility is being constructed at the NASA Glenn Research Center. This facility is to be used for life cycle testing of various flywheel rotors. The lifecycle testing consists of spinning a rotor from a low rpm (approx. 20,000 ) to a high rpm (approx. 60,000) and then back to the low rpm. This spin cycle will model that which the rotor will see during use. To simulate the lifetime of the rotor, the spin cycle will be performed tens of thousands of times. A typical life cycle spin test is expected to last six months. During this time the rotor will be spun through a cycle every five minutes. The test will run continuously for the six month period barring a flywheel failure. Since it is not reasonable to have the surrounding area evacuated of personnel for the duration of the testing, the flywheel facility has to be designed to withstand a flywheel rotor failure and insure that there is no danger to any personnel in the adjacent buildings or surrounding areas. In order to determine if the facility can safely contain a flywheel rotor failure an analysis of the facility in conjunction with possible flywheel failure modes was performed. This analysis is intended as a worst case evaluation of the burst liner and vacuum tank's ability to contain a failure. The test chamber consists of a cylindrical stainless steel vacuum tank, two outer steel containment rings, and a stainless steel burst liner. The stainless steel used is annealed 302, which has an ultimate strength of 620 MPa (90,000 psi). A diagram of the vacuum tank configuration is shown. The vacuum tank and air turbine will be located below ground in a pit. The tank is secured in the pit with 0.3 m (12 in.) of cement along the base and the remaining portion of the tank is surrounded by gravel up to the access ports. A 590 kg (1300 lb.) bulkhead is placed on top of the pit during operation and the complete facility is housed within a concrete structure which has 7.5 cm (3 in.) thick walls. A cutaway of the facility is shown.
Polyimide-silica hybrids composed of an organic precursor containing a novel phenylethynyl imide silane and an inorganic precursor were evaluated as an adhesion-promoting interphase between surface-treated titanium alloy and a phenylethynyl-containing imide adhesive. The phenylethynyl groups present in the organic precursor, either as a pendent or end group, can bond chemically with a phenylethynyl-containing imide adhesive during processing, while the silane groups of the organic precursor would react chemically with the inorganic precursor. In addition, the inorganic precursor is able to react with the titanium alloy to form a stable bond with the metal oxide. Bond strength and durability were evaluated by single lap shear tests at various conditions. Lap shear specimens exhibited predominantly cohesive failure after a 3-d water boil with 92% retention of the initial room temperature strength. Morphology and chemical composition of the hybrid interphase were investigated with scanning electron microscopy, X-ray photoelectron spectroscopy, and Auger electron spectroscopy, which revealed development of a silicon-gradient, hybrid structure between the metal substrate and the adhesive.
The formation of pyruvaldehyde from triose sugars was catalyzed by poly-L-lysine contained in a small dialyzer (100 MWCO) suspended in a much larger triose substrate reservoir. The polylysine confined in the dialyzer functioned as a catalytic flow reactor that constantly brought in triose from the substrate reservoir by diffusion to offset the drop in triose concentration within the reactor caused by its conversion to pyruvaldehyde. A 400 mM solution of poly-L-lysine contained in a 0.35 ml dialyzer placed in a 120 ml solution of triose substrate (pH 5.5, 40 C) generated pyruvaldehyde 11 -times faster than an a control reaction without the catalytic dialyzer. However, since the catalytic dialyzer's volume was 343-times smaller than the control reaction, the synthetic intensity (rate/volume) of pyruvaldehyde synthesis within the catalytic dialyzer was 3400-times greater than that of the control reaction and substrate solution. A similar result was obtained using a dialyzer with a 500 MWCO value. Acting as a catalytic flow reactor the polylysine catalytic dialyzer synthesized about 3.5 molecules of pyruvaldehyde per lysine residue in 7 days -- an amount of triose equal to twice the weight of the catalyst. At 7 days the catalytic activity of polylysine was 16% of its initial value, a result indicating catalyst-poisoning caused by reaction of pyruvaldehyde with the e-amino groups of polylysine. The dialyzer method of catalyst containment was selected it provides a simple, flexible, and easily manipulated experimental system for studying the dynamics and evolutionary development of confined autocatalytic processes related to the origin of life under anaerobic conditions.
An improved understanding of the large-length-scale capillary flows arising in a low-gravity environment is critical to that engineering community concerned with the design and analysis of spacecraft fluids management systems. Because a significant portion of liquid behavior in spacecraft is capillary dominated it is natural to consider designs that best exploit the spontaneous character of such flows. In the present work, a recently verified asymptotic analysis is extended to approximate spontaneous capillary flows in a large class of cylindrical containers of irregular polygonal section experiencing a step reduction in gravitational acceleration. Drop tower tests are conducted using partially-filled irregular triangular containers for comparison with the theoretical predictions. The degree to which the experimental data agree with the theory is a testament to the robustness of the basic analytical assumption of predominantly parallel flow. As a result, the closed form analytical expressions presented serve as simple, accurate tools for predicting bulk flow characteristics essential to practical low-g system design and analysis. Equations for predicting corner wetting rates, total container flow rates, and transient surfaces shapes are provided that are relevant also to terrestrial applications such as capillary flow in porous media.
The objective of this research is to improve the atomic oxygen resistance of Kapton(TM), a polyimide (PI) made from pyromellitic acid dianhydride (PMDA) and 4,4'-oxydianiline (ODA), while retaining or enhancing the desirable properties of the pure polymer. Toward this end, zirconium-containing complexes and polymers were used to make composites and blends. Tetra(acetylacetonato)zirconium(IV), Zr(acac)4, which is commercially available, was identified as the best zirconium-containing complex for enhancing the atomic oxygen resistance of polyimide composites of the 10 complexes screened. Films prepared from the commercially available polyamic acid (PAA) of PMDA-ODA (DuPont) have good uniformity, flexibility, and tensile strength. A 24-layer 10% (mol) Zr(acac)4/PI composite film showed significant improvement (ca. 20 fold) of atomic oxygen resistance over the pure polyimide. However, 10% (mol) Zr(acac)4 represents an upper concentration limit, above which films undergo cracking upon thermal imidization. In order to increase the Zr complex concentration in PMDA-ODA PI films, while retaining good film properties, [Zr(adsp)2-PMDA]n coordination polymer [bis(4-amino-N,N'-disalicylidene- 1,2-phenylenediamino)zirconium(IV)-pyromellitic dianhydride] and [Zr(adsp)2-PMDA-ODA-PMDA]n terpolymer were synthesized and blended with commercial PAA, respectively. Several techniques were used to characterize the films made from the polymer containing Zr(acac)4. Plasma studies of films having 2% (mol) incremental concentrations of Zr in the Kapton up to 10% (mol) show that the overall rate of erosion is reduced about 75 percent.
Mussels collected from hydrocarbon seeps in the Gulf of Mexico grow with methane as sole carbon and energy source due to a symbiotic association with methane-oxidizing bacteria. Transmission electron micrographs of mussel gills show cells with stacked intracytoplasmic membranes similar to type I methanotrophic bacteria. Methanotrophs are known to synthesize several types of cyclic triterpenes, hopanoids and methyl sterols, as well as unique monounsaturated fatty acid, double bond positional isomers that serve as biomarkers for this group. Lipid analysis of dissected mussels demonstrated the presence of these biomarkers predominantly in the gill tissue with much smaller amounts in mantle and remaining body tissues. Gill tissue contained 1150 micrograms/g dry wt. of hopanepolyol derivatives and diplopterol while the mantle tissue contained only 17 micrograms/g. The C16 monounsaturated fatty acids (16:1) characteristic of type I methanotrophic membranes dominated the gill tissue making up 53% of the total while only 5% 16:1 was present in the mantle tissue. The methyl sterol distribution was more dispersed. The predominant sterol in all tissues was cholesterol with lesser amounts of other desmethyl and 4-methyl sterols. The gill and mantle tissues contained 3461 micrograms (17% methyl) and 2750 micrograms (5% methyl) sterol per gm dry wt., respectively. Methyl sterol accounted for 44% of the sterol esters isolated from the gill, suggesting active demethylation of the methanotrophic sterols in this tissue. The use of lipid biomarkers could provide an effective means for identifying host-symbiont relationships.
Phenylethynyl containing reactive additives were prepared from aromatic diamines containing phenylethynyl groups and various ratios of phthalic anhydride and 4-phenylethynylphthalic anhydride in glacial acetic acid to form the imide in one step or in N-methyl-2-pyrrolidinone to form the amide acid intermediate. The reactive additives were mixed in various amounts (10% to 90%) with oligomers containing either terminal or pendent phenylethynyl groups (or both) to reduce the melt viscosity and thereby enhance processability. Upon thermal cure, the additives react and become chemically incorporated into the matrix and effect an increase in crosslink density relative to that of the host resin. This resultant increase in crosslink density has advantageous consequences on the cured resin properties such as higher glass transition temperature and higher modulus as compared to that of the host resin.
Martian meteorite (shergottite) impact melt glasses that contain high concentrations of martian atmospheric noble gases and show significant variations in Sr-87/Sr-86 isotopic ratios are likely to contain Martian surface fines mixed with coarser regolith materials. The mixed soil constituents were molten due to shock at the time of meteoroid impact near the Martian surface and the molten glass got incorporated into the voids and cracks in some shergottite meteorites. Earlier, Rao et al. found large enrichments of sulfur (sulfate) during an electron-microprobe study of several impact melt glass veins and pods in EET79001,LithC thin sections. As sulfur is very abundant in Martian soil, these S excesses were attributed to the mixing of a soil component containing aqueously altered secondary minerals with the LithC precursor materials prior to impact melt generation. Recently, we studied additional impact melt glasses in two basaltic shergottites, Zagami and Shergotty using procedures similar to those described by Rao et al. Significant S enrichments in Zagami and Shergotty impact melt glass veins similar to the EET79001, LithC glasses were found. In addition, we noticed the depletion of the mafic component accompanied by the enrichment of felsic component in these impact melt glass veins relative to the bulk host rock in the shergottites. To explain these observations, we present a model based on comminution of basaltic rocks due to meteroid bombardment on martian regolith and mechanical fractionation leading to enrichment of felsics and depletion of mafics in the fine grained dust which is locally mobilized as a result of saltation and deflation due to the pervasive aeolian activity on Mars.
Protein crystals are grown in microgravity experiments inside the Space Shuttle during orbit. Such crystals are basically grown in a five-component system containing a salt, buffer, polymer, organic and water. During these experiments, a number of different polymeric containment materials must be compatible with up to hundreds of different PCG solutions in various concentrations for durations up to 180 days. When such compatibility experiments are performed at NASA/MSFC (Marshall Space Flight Center) simultaneously on containment material samples immersed in various solutions in vials, the samples are rather small out of necessity. DMA4 modulus was often used as the primary screening parameter for such small samples as a pass/fail criterion for incompatibility issues. In particular, the TA Instruments DMA 2980 film tension clamp was used to test rubber O-rings as small in I.D. as 0.091 in. by cutting through the cross-section at one place, then clamping the stretched linear cord stock at each end. The film tension clamp was also used to successfully test short length samples of medical/surgical grade tubing with an O.D. of 0.125 in.