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A series of polyimides derived from a newly synthesized diamine, namely, 4,4-bis(4-aminophenoxy)-2,2-dimethylbiphenyl (BAPD), were developed and characterized. Their physical and thermal properties were compared to polyimides based on'commercially available 2,2-bis(4-(4-aminophenoxy)phenyl)propane (BAPP).
2,5-Bis(perfluoro-n-heptyl)-, 2-perfluoroalkylether-5-perfluoro-n- heptyl- , and 2 , 5-bisperfluoroalkylether-1,3,4-oxadiazoles were synthesized and characterized. 2,5-Bis(perfluoro-n-heptyl)-1,3,4-oxadiazole was thermally and hydrolytically stable at 325 C; however, in the presence of air, degradation took place at 235 C. The perfluoroalkylether analogue exhibited thermal and hydrolytic stability at 325 C; it was found to be unaffected by jet-A fuel and air at 235 C. At 325 C in air some degradation occurred as evidenced by volatiles production, oxygen consumption, and 96% starting material recovery.
As part of a program to develop high-performance/high-temperature structural resins for aeronautical applications, imide oligomers containing pendent and terminal phenylethynyl groups were prepared, characterized and the cured resins evaluated as composite matrices. The oligomers were prepared at a calculated number-average molecular weight of 5000 g/mol and contained 15-20 mol% pendent phenylethynyl groups. In previous work, an oligomer containing pendent and terminal phenylethynyl groups exhibited a high glass transition temperature (approximately 313 C), and laminates therefrom exhibited high compressive properties, but processability, fracture toughness, microcrack resistance and damage tolerance were less than desired. In an attempt to improve these deficiencies, modifications in the oligomeric backbone involving the incorporation of 1,3-bis(3-aminophenoxy)benzene were investigated as a means of improving processability and toughness without detracting from the high glass transition temperature and high compressive properties. The amide acid oligomeric solutions were prepared in N-methyl-2-pyrrolidinone and were subsequently processed into imide powder, thin films, adhesive tape and carbon fiber prepreg. Neat resin plaques were fabricated from imide powder by compression moulding. The maximum processing pressure was 1.4 MPa and the cure temperature ranged from 350 to 371 C for 1 h for the mouldings, adhesives, films and composites. The properties of the 1,3-bis(3-aniinophenoxy)benzene modified cured imide oligomers containing pendent and terminal phenylethynyl groups are compared with those of previously prepared oligomers containing pendent and terminal phenylethynyl groups of similar composition and molecular weight.
Because of its high reactivity, atomic oxygen causes surface erosion on polymeric materials. although the reaction efficiency depends on the chemical structure of the polymer. We have found an organotin compound, bis(triphenyltin) oxide (BTO), which has an unusually high solubility in solutions of a number of commercial high performance polymers. Films of these polymers containing BTO showed a substantial reduction in erosion by atomic oxygen when compared with films of the pure material. Analysis has shown that in the presence of atomic oxygen, erosion of the exposed surfaces of the BTO-containing films leaves a residual protective tin oxide coating . Since the additive is uniformly distributed throughout the polymeric material, any break or puncture in the protective coating is "healed" by the material below. Samples were exposed to the environment of the low earth orbit (LEO) on two Space Shuttle flights, STS-46, in June of 1992, and STS-51 in September of 1993. The analysis of these samples has been reported previously. For both flights, the samples were small (1.3 cm and 1.9 cm respectively) thus limiting the scope of analysis. In the research under this cooperative agreement, films of a polyetherimide, were exposed to the LEO environment on Space Shuttle flight STS-85 in August of 1997 as part of the Evaluation of Space Environment and Effects on Materials (ESEM) experiment. The polyetherimide chosen is available commercially as Ultem, registered to the General Electric Company. Films of pure Ultem, Ultem with 10% BTO by mass, and Ultem with 20% BTO by mass were exposed in the ram direction for 40 hours during STS-85. Ultem has a Tg of 215 deg C and is soluble in common chlorinated solvents. Granules of the polymer were dried at 120 deg C, but otherwise were used as received. Films were cast on a glass plate from a solution of the polymer in a 60/40 (w/w) mixture of chloroform and 1,1,2,2-tetrachloroethane. The plate was placed in a dust-free box for at least 24 hours to allow much of the solvent to evaporate, and then was moved to a vacuum oven and slowly heated from 20 to 220 deg C over a period of two weeks to completely remove all solvent. Each exposed sample was 7.6 cm long and 2.2 cm wide and about 0.025 mm thick. The structures of Ultem and bis(triphenyltin) oxide are shown.
As part of an ongoing effort to develop materials for resin transfer molding (RTM) of high performance/high temperature composites, a new phenylethynyl containing imide designated as PETI-375 has been under evaluation. PETI-375 was prepared using 2,3,3 ,4 - biphenyltetracarboxylic dianhydride (a-BPDA), 1,3-bis(4-aminophenoxy)benzene and 2,2 - bis(trifluoromethyl)benzidine and endcapped with 4-phenylethynylphthalic anhydride. This material exhibited a stable melt viscosity of 0.1-0.4 Pa sec at 280 C. High quality, void-free laminates were fabricated by high temperature RTM using unsized T-650 carbon fabric and evaluated. After curing for 1 hour at 371 C, the laminates exhibited a glass transition temperature of approx. 375 C by thermomechanical analysis. The laminates were essentially void and microcrack free as evidenced by optical microscopic examination. The chemistry, physical, and composite properties of PETI-375 will be discussed.
Unique, self-metallized films were investigated for deployable reflector antenna applications at L-band. Polyamic acid resins or soluble polyimides were doped with metal complexes, cast into films, and thermally cured. Each resulting film had a metallic layer on one side, adhering unfailingly to the polymer. Metallization was successful for silver or palladium in 3,3',4,4'-benzophenonetetracarboxylic acid dianhydride (BTDA) and 4,4'- oxydianiline and for gold in BTDA and 2,2-bis[4-(4- aminophenoxy)phenyl]hexafluoropropane (4-BDAF) or the space durable polyimide, 2,2-bis(3,4-dicarboxyphenyl)- hexafluoropropane dianhydride and 4-BDAF (LaRCCP1). Reflectivity, transmissivity, and emissivity were determined, using an HP 8510 Vector Network Analyzer, to within 0.001 precision and accuracy. A custom-made test fixture/positioner, a thru-reflect-line calibration, and calculated reflection coefficients were used. The Ag film proved most suitable for further study, with 0.9957 reflectivity and 0.0042 emissivity. The Pd films were 0.89 reflective and 0.11 emissive; both Au films tested entirely transmissive. Transmission and scanning electron micrographs, S-parameters, and power coefficients are shown.
Polyphenylquinoxalines are prepared by the nucleophilic displacement reaction of di(hydroxyphenyl)quinoxaline monomers with activated aromatic dihalides or dinitro compounds. The reactions are carried out in polar aprotic solvents during alkali metal bases at elevated temperatures under nitrogen. The di(hydroxyphenyl)quinoxaline monomers are prepared either by reacting stoichiometric quantities of aromatic bis(o-diamines) with a hydroxybenzil or by reacting o-phenylenediamine with a dihydroxybenzil or bis(hydroxyphenylglyoxylyl)benzene.
Polyphenylquinoxalines are prepared by the nucleophilic displacement reaction of di(hydroxyphenyl)quinoxaline monomers with activated aromatic dihalides or dinitro compounds. The reactions are carried out in polar aprotic solvents using alkali metal bases at elevated temperatures under nitrogen. The di(hydroxyphenyl)quinoxaline monomers are prepared either by reacting stoichiometric quantities of aromatic bis(o-diamines) with a hydroxybenzil or by reacting o-phenylenediamine with a dihydroxybenzil or bis(hydroxyphenylglyoxylyl)benzene.
We employ molecular dynamics (MD) simulation and experiment to investigate the structure, thermodynamics, and transport of N-methyl-N-butylpyrrolidinium bis(trifluoromethylsufonyl)imide ([pyr14][TFSI]), N -methyl-N-propylpyrrolidinium bis(fluorosufonyl)imide ([pyr13][FSI]), and 1-ethyl-3-methylimidazolium boron tetrafluoride ([EMIM][BF4]), as a function of Li-salt mole fraction (0.05 xLi+ 0.33) and temperature (298 K T 393 K). Structurally, Li+ is shown to be solvated by three anion neigh- bors in [pyr14][TFSI] and four anion neighbors in both [pyr13][FSI] and [EMIM][BF4], and at all levels of xLi+ we find the presence of lithium aggregates. Pulsed field gradient spin-echo NMR measurements of diffusion and electrochemical impedance spectroscopy measurements of ionic conductivity are made for the neat ionic liquids as well as 0.5 molal solutions of Li-salt in the ionic liquids. Bulk ionic liquid properties (density, diffusion, viscosity, and ionic conductivity) are obtained with MD and show excellent agreement with experiment. While the diffusion exhibits a systematic decrease with increasing xLi+, the contribution of Li+ to ionic conductivity increases until reach- ing a saturation doping level of xLi+ 0.10. Comparatively, the Li+ conductivity of [pyr14][TFSI] is an order of magnitude lower than that of the other liquids, which range between 0.1-0.3 mScm. Our transport results also demonstrate the necessity of long MD simulation runs ( 200 ns) required to converge transport properties at room T. The differences in Li+ transport are reflected in the residence times of Li+ with the anions (Li), which are revealed to be much larger for [pyr14][TFSI] (up to 100 ns at the highest doping levels) than in either [EMIM][BF4] or [pyr13][FSI]. Finally, to comment on the relative kinetics of Li+ transport in each liquid, we find that while the net motion of Li+ with its solvation shell (vehicular) significantly contributes to net diffusion in all liquids, the importance of transport through anion exchange (hopping) increases at high xLi+ and in liquids with large anions.
Ionic liquid epoxide monomers capable of reacting with cross-linking agents to form polymers with high tensile and adhesive strengths. Ionic liquid epoxide monomers comprising at least one bis(glycidyl) N-substituted nitrogen heterocyclic cation are made from nitrogen heterocycles corresponding to the bis(glycidyl) N-substituted nitrogen heterocyclic cations by a method involving a non-nucleophilic anion, an alkali metal cation, epichlorohydrin, and a strong base.
Ionic liquid electrolytes have been proposed as a means of improving the safety and cycling behavior of advanced lithium batteries; however, the properties of these electrolytes under high lithium doping are poorly understood. Here, we employ both polarizable molecular dynamics simulation and experiment to investigate the structure, thermodynamics and transport of three potential electrolytes, N-methyl-N-butylpyrrolidinium bis(trifluoromethylsufonyl)imide ([pyr14][TFSI]), N- methyl-N-propylpyrrolidinium bis(fluorosufonyl)imide ([pyr13][FSI]), and 1-ethyl-3-- methylimidazolium boron tetrafluoride ([EMIM][BF4]), as a function of Li (-) salt concentration and temperature. Structurally, Li(+) is shown to be solvated by three anion neighbors in [pyr14][TFSI] and four anion neighbors in both [pyr13][FSI] and [EMIM][BF4], and at all levels of xLi we find the presence of lithium aggregates. Furthermore, the computed density, diffusion, viscosity, and ionic conductivity show excellent agreement with experimental data. While the diffusion and viscosity exhibit a systematic decrease and increase, respectively, with increasing xLi, the contribution of Li(+) to ionic conductivity increases until reaching a saturation doping level of xLi 0.10. Comparatively, the Li(+) conductivity of [pyr14][TFSI] is an order of magnitude lower than that of the other liquids, which range between 0.1-0.3 mScm. The differences in Li(+) transport are reflected in the residence times of Li(+) with the anions, which are revealed to be much larger for [pyr14][TFSI] (up to 100 ns at the highest doping levels) than in either [EMIM][BF4] or [pyr13][FSI]. Finally, we comment on the relative kinetics of Li(+) transport in each liquid and we present strong evidence for transport through anion exchange (hopping) as opposed to the net motion of Li(+) with its solvation shell (vehicular).
Ionic liquid electrolytes have been proposed as a means of improving the safety and cycling behavior of advanced lithium batteries; however, the properties of these electrolytes under high lithium doping are poorly understood. Here, we employ both polarizable molecular dynamics simulation and experiment to investigate the structure, thermodynamics and transport of three potential electrolytes, N-methyl-Nbutylpyrrolidinium bis(trifluoromethylsufonyl)imide ([pyr14][TFSI]), N- methyl-Npropylpyrrolidinium bis(fluorosufonyl)imide ([pyr13][FSI]), and 1-ethyl-3-- methylimidazolium boron tetrafluoride ([EMIM][BF4]), as a function of Li-salt concentration and temperature. Structurally, Li(+) is shown to be solvated by three anion neighbors in [pyr14][TFSI] and four anion neighbors in both [pyr13][FSI] and [EMIM][BF4], and at all levels of x(sub Li) we find the presence of lithium aggregates. Furthermore, the computed density, diffusion, viscosity, and ionic conductivity show excellent agreement with experimental data. While the diffusion and viscosity exhibit a systematic decrease and increase, respectively, with increasing x(sub Li), the contribution of Li(+) to ionic conductivity increases until reaching a saturation doping level of x(sub Li) is approximately 0.10. Comparatively, the Li(+) conductivity of [pyr14][TFSI] is an order of magnitude lower than that of the other liquids, which range between 0.1 - 0.3 mS/cm. The differences in Li(+) transport are reflected in the residence times of Li(+) with the anions, which are revealed to be much larger for [pyr14][TFSI] (up to 100 ns at the highest doping levels) than in either [EMIM][BF4] or [pyr13][FSI]. Finally, we comment on the relative kinetics of Li(+) transport in each liquid and we present strong evidence for transport through anion exchange (hopping) as opposed to the net motion of Li(+) with its solvation shell (vehicular).
Ionic liquid electrolytes have been proposed as a means of improving the safety and cycling behavior of advanced lithium batteries; however, the properties of these electrolytes under high lithium doping are poorly understood. Here, we employ both polarizable molecular dynamics simulation and experiment to investigate the structure, thermodynamics and transport of three potential electrolytes, N-methyl-N-butylpyrrolidinium bis(trifluoromethylsufonyl)imide ([pyr14][TFSI]), N- methyl-N-propylpyrrolidinium bis(fluorosufonyl)imide ([pyr13][FSI]), and 1-ethyl-3-- methylimidazolium boron tetrafluoride ([EMIM][BF4]), as a function of Li (-) salt concentration and temperature. Structurally, Li(+) is shown to be solvated by three anion neighbors in [pyr14][TFSI] and four anion neighbors in both [pyr13][FSI] and [EMIM][BF4], and at all levels of xLi we find the presence of lithium aggregates. Furthermore, the computed density, diffusion, viscosity, and ionic conductivity show excellent agreement with experimental data. While the diffusion and viscosity exhibit a systematic decrease and increase, respectively, with increasing xLi, the contribution of Li(+) to ionic conductivity increases until reaching a saturation doping level of xLi 0.10. Comparatively, the Li(+) conductivity of [pyr14][TFSI] is an order of magnitude lower than that of the other liquids, which range between 0.1-0.3 mScm. The differences in Li(+) transport are reflected in the residence times of Li(+) with the anions, which are revealed to be much larger for [pyr14][TFSI] (up to 100 ns at the highest doping levels) than in either [EMIM][BF4] or [pyr13][FSI]. Finally, we comment on the relative kinetics of Li(+) transport in each liquid and we present strong evidence for transport through anion exchange (hopping) as opposed to the net motion of Li(+) with its solvation shell (vehicular).
Given the expressed NASA opinion that there is no perceived increase in astronaut fracture prevalence to warrant using Bis prophylactically, we surveyed the entire astronaut corps for evidence associating fracture incidence with spaceflight duration. Aim was to acquire fracture data to support the use of Bis to prevent spaceflight-induced changes in bone as a mitigation strategy for fracture risk.
Preparation of poly-organometallosiloxane polymers from reactions between bis-dialkylamino metal derivatives and silanediols
Synthesis of some Schiff bases by amine, carbonyl, and bis exchange reactions
Isomeric Schiff base polymers synthesis by bis- Schiff-base exchange reaction from appropriate pairs selected from monomers, noting thermal stabilities
Schiff base cross-links effect on synthesis of polymeric azomethines produced by bis exchange reactions, carbonyl and amine