Shelf Life of PMR Polyimide Monomer Solutions and Prepregs Extended

PMR (Polymerization of Monomeric Reactants) technology was developed in the mid-1970's at the NASA Glenn Research Center at Lewis Field for fabricating high-temperature stable polyimide composites. This technology allowed a solution of polyimide monomers or prepreg (a fiber, such as glass or graphite, impregnated with PMR polyimide monomers) to be thermally cured without the release of volatiles that cause the formation of voids unlike the non-PMR technology used for polyimide condensation type resins. The initial PMR resin introduced as PMR 15 is still commercially available and is used worldwide by aerospace industries as the state-of-the-art resin for high-temperature polyimide composite applications. PMR 15 offers easy composite processing, excellent composite mechanical property retention, a long lifetime at use temperatures of 500 to 550 F, and relatively low cost. Later, second-generation PMR resin versions, such as PMR II 50 and VCAP 75, offer improvements in the upper-use temperature (to 700 F) and in the useful life at temperature without major compromises in processing and property retention but with significant increases in resin cost. Newer versions of nontoxic (non-methylene dianiline) PMR resins, such as BAX PMR 15, offer similar advantages as originally found for PMR 15 but also with significant increases in resin cost. Thus, the current scope of the entire PMR technology available meets a wide range of aeronautical requirements for polymer composite applications

Screening of High Temperature Organic Materials for Future Stirling Convertors

Along with major advancement of Stirling-based convertors, high temperature organics are needed to develop future higher temperature convertors for much improved efficiencies as well as to improve the margin of reliability for the current SOA (State-of-the-Art) convertors. The higher temperature capabilities would improve robustness of the convertors and also allow them to be used in additional missions, particularly ones that require a Venus flyby for a gravity assist. Various organic materials have been employed as essential components in the convertor for their unique properties and functions such as bonding, potting, sealing, thread locking, insulation, and lubrication. The Stirling convertor radioisotope generators have been developed for potential future space applications including Lunar/Mars surface power or a variety of spacecraft and vehicles, especially with a long mission cycle, sometimes up to 17 years, such as deep space exploration. Thus, performance, durability, and reliability of the organics should be critically evaluated in terms of every possible material structure-process-service environment relations based on the potential mission specifications. The initial efforts in screening the high temperature candidates focused on the most susceptible organics, such as adhesive, potting compound, O-ring, shrink tubing, and thread locker materials in conjunction with commercially available materials. More systematic and practical test methodologies that were developed and optimized based on the extensive organic evaluations and validations performed for various Stirling convertor types were employed to determine thermal stability, outgassing, and material compatibility of the selected organic candidates against their functional requirements. Processing and fabrication conditions and procedures were also optimized. This report presents results of the three-step candidate evaluation processes, their application limitations, and the final selection recommendations

Lightweight, Durable, and Multifunctional Electrical Insulation Material Systems for High Voltage Applications

Newly developed multilayer structures of well-known polymer insulation materials significantly improved dielectric breakdown voltage, VB, or dielectric strength, K, if well-bonded, when compared to those of single material insulations or the commercial SOA systems, such as Teflon-Kapton-Teflon (TKT), at the same overall thickness. To date, the greatest improvement of the new structures from a few candidate materials, including various types of Kapton PIs and PFA or PET as bond layer (BL), was about 61% higher than that of the Kapton PI alone films, 40.1 vs. 24.9 kV, which was translated to 86.3% decrease in insulation thickness, thus significant volume and weight reduction of the final system. However, it was of interest to note that most improvements of the multilayer structures occurred at thicker overall thicknesses, above ~ 0.15 mm. Extensive analyses also showed that K of the multilayer structures increased with (i) decreasing individual layer thickness regardless of material type, (ii) increasing total accumulated thickness of PI or overall PI/BL ratio, and (iii) increasing number of interface or total number of layers, but only above the aforementioned overall thickness limit. Increases in VB of the multilayer structures were directly correlated with damage evolution and failure mode. With further material-design-process optimizations of the multilayer structures, it was expected to achieve other multifunctionalities, such as high partial discharge (PD) resistance, improved durability, EMI shielding, and high thermal dissipation in addition to high dielectric strength. These new structures can be used in various high voltage and high temperature applications, such as future hybrid or all electric aircraft wiring and power transmission as well as many other non-aerospace high power cables, electronic parts and components, printed circuit board, and so forth. The multilayer insulation system can be easily processed and manufactured with various conductor types via calendaring, compression-molding, stamping, laminating, vacuum-bagging and autoclaving, or 3D printing, even for complex 3-D components. Based on their unique structural configurations and potential capabilities, the new insulation system was identified as micro-multilayer multifunctional electrical insulation (MMEI). Patent application of the MMEI concept and current design configurations was filed for a 1-year provisional application (OAI-58834, Serial No.: 62/659,234), pending conversion to a U.S. utility application. This paper presents details of the MMEI structures, their dielectric performance analyses, potential mechanisms, and commercial scaleup feasibility assessment

Selective Clay Placement within a Silicate Clay-Epoxy Blend Nanocomposite and the Effect on Physical Properties

Many epoxy systems under consideration for composite pressure vessels are composed of toughened epoxy resins. In this work, epoxy blends containing both rigid aromatic and flexible aliphatic components were prepared, to model toughened systems, and determine the optimum route of silicate addition. Compositions were chosen such that both glassy and rubbery resins were obtained at room temperature. The physical properties of the nanocomposites varied with T(g) and silicate placement, however, nanocomposite T(g)s were observed which exceeded that of the base resin by greater than 10 C. The tensile strength of the glassy resin remained constant or decreased on the dispersion of clay while that of the rubbery material doubled. Selectively placing the clay in the aliphatic component of the rubbery blend resulted in a greater than 100% increase in material toughness

Thermal Properties of Lunar Regolith Simulants

Various high temperature chemical processes have been developed to extract oxygen and metals from lunar regolith. These processes are tested using terrestrial analogues of the regolith. But all practical terrestrial analogs contain H2O and/or OH-, the presence of which has substantial impact on important system behaviors. We have undertaken studies of lunar regolith simulants to determine the limits of the simulants to validate key components for human survivability during sustained presence on the Moon. Differential Thermal Analysis (DTA) yields information on phase transitions and melting temperatures. Thermo-Gravimetric Analysis (TGA) with Fourier Transform Infrared (FTIR) analysis provides information on evolved gas species and their evolution temperature profiles. The DTA and TGA studies included JSC-1A fine (Johnson Space Center Mare Type 1A simulant), NU-LHT-2M (National Aeronautics and Space Administration (NASA)-- United States Geological Survey (USGS)--Lunar Highlands Type 2M simulant) and its proposed feedstocks: anorthosite; dunite; high quality (HQ) glass and the norite from which HQ glass is produced. As an example, the DTA and TGA profiles for anorthosite follow. The DTA indicates exothermic transitions at 355 and 490 C and endothermic transitions at 970 and 1235 C. Below the 355 C transition, water is lost accounting for approximately 0.1 percent mass loss. Just above 490 C a second type of water is lost, presumably bound in lattices of secondary minerals along with other volatile oxides. Limited TGA-FTIR data is available at the time of this writing. For JSC-1A fine, the TGA-FTIR indicates at least two kinds of water are evolved in the 100 to 500 and the 700 to 900 C ranges. Evolution of carbon dioxide types occurs in the 250 to 545, 545 to 705, and 705 to 985 C ranges. Geologically, the results are consistent with the evolution of "water" in its several forms, CO2 from break down of secondary carbonates and magmatic, dissolved gas and glass recrystallizatio

Diels-Alder Trapping of Photochemically Generated o-Quinodimethane Intermediates: An Alternative Route to Photocured Polymer Film Development

Photolysis of o-methylphenyl ketones generates bis-o-quinodimethane intermediates that can be trapped in situ by dienophiles through Diels-Alder cycloadditions. This well-known photochemical process is applied to a series of six new photoreactive monomers containing bis-(o-methylphenyl ketone) functionalities combined with diacrylate and triacrylate ester monomers for the development of acrylic ester copolymer blends. Irradiation of cyclohexanone solutions of the bis-(o-methylphenyl ketone)s and acrylate esters produce thin polymer films. Solid state 13C NMR data indicated 47- 100% reaction of the bis-(o-methylphenyl ketone)s, depending on experimental conditions, to yield the desired products. DSC and TGA analyses were performed to determine the glass transition temperature, T,, and onset of decomposition, Td, of the resulting polymer films. A statistical Design of Experiments approach was used to obtain a systematic understanding of the effects of experimental variables on the extent of polymerization and the final polymer properties

Low-melt Viscosity Polyimide Resins for Resin Transfer Molding (RTM) II

A series of polyimide resins with low-melt viscosities in the range of 10-30 poise and high glass transition temperatures (Tg s) of 330-370 C were developed for resin transfer molding (RTM) applications. These polyimide resins were formulated from 2,3,3 ,4 -biphenyltetracarboxylic dianhydride (a-BPDA) with 4-phenylethynylphthalic anhydride endcaps along with either 3,4 - oxyaniline (3,4 -ODA), 3,4 -methylenedianiline, (3,4 -MDA) or 3,3 -methylenedianiline (3,3 -MDA). These polyimides had pot lives of 30-60 minutes at 260-280 C, enabling the successful fabrication of T650-35 carbon fiber reinforced composites via RTM process. The viscosity profiles of the polyimide resins and the mechanical properties of the polyimide carbon fiber composites will be discussed

Lightweight, Durable, and Multifunctional Electrical Insulation Material Systems for High Voltage Applications

Newly developed multilayer structures of well-known polymer insulation materials significantly improved dielectric breakdown voltage, VB, or dielectric strength, K, if well-bonded, when compared to those of single material insulations or the commercial SOA systems, such as Teflon-Kapton-Teflon (TKT), at the same overall thickness. To date, the greatest improvement of the new structures from a few candidate materials, including various types of Kapton PIs and PFA or PET as bond layer (BL), was about 61% higher than that of the Kapton PI alone films, 40.1 vs. 24.9 kV, which was translated to 86.3% decrease in insulation thickness, thus significant volume and weight reduction of the final system. However, it was of interest to note that most improvements of the multilayer structures occurred at thicker overall thicknesses, above ~ 0.15 mm. Extensive analyses also showed that K of the multilayer structures increased with (i) decreasing individual layer thickness regardless of material type, (ii) increasing total accumulated thickness of PI or overall PI/BL ratio, and (iii) increasing number of interface or total number of layers, but only above the aforementioned overall thickness limit. Increases in VB of the multilayer structures were directly correlated with damage evolution and failure mode. With further material-design-process optimizations of the multilayer structures, it was expected to achieve other multifunctionalities, such as high partial discharge (PD) resistance, improved durability, EMI shielding, and high thermal dissipation in addition to high dielectric strength. These new structures can be used in various high voltage and high temperature applications, such as future hybrid or all electric aircraft wiring and power transmission as well as many other non-aerospace high power cables, electronic parts and components, printed circuit board, and so forth. The multilayer insulation system can be easily processed and manufactured with various conductor types via calendaring, compression-molding, stamping, laminating, vacuum-bagging and autoclaving, or 3D printing, even for complex 3-D components. Based on their unique structural configurations and potential capabilities, the new insulation system was identified as micro-multilayer multifunctional electrical insulation (MMEI). Patent application of the MMEI concept and current design configurations was filed for a 1-year provisional application (OAI-58834, Serial No.: 62/659,234), pending conversion to a U.S. utility application. This paper presents details of the MMEI structures, their dielectric performance analyses, potential mechanisms, and commercial scaleup feasibility assessment

Interfacial Strength and Physical Properties of Functionalized Graphene - Epoxy Nanocomposites

The toughness and coefficient of thermal expansion of a series of functionalized graphene sheet - epoxy nanocomposites are investigated. Functionalized graphene sheets are produced by splitting graphite oxide into single graphene sheets through a rapid thermal expansion process. These graphene sheets contain approx. 10% oxygen due to the presence of hydroxide, epoxide, and carboxyl functional groups which assist in chemical bond formation with the epoxy matrix. Intrinsic surface functionality is used to graft alkyl amine chains on the graphene sheets, and the addition of excess hardener insures covalent bonding between the epoxide matrix and graphene sheets. Considerable improvement in the epoxy dimensional stability is obtained. An increase in nanocomposite toughness is observed in some cases

Evaluation of Nanomaterial Approaches to Damping in Epoxy Resin and Carbon Fiber/Epoxy Composite Structures by Dynamic Mechanical Analysis

Vibration mitigation in composite structures has been demonstrated through widely varying methods which include both active and passive damping. Recently, nanomaterials have been investigated as a viable approach to composite vibration damping due to the large surface available to generate energy dissipation through friction. This work evaluates the influence of dispersed nanoparticles on the damping ratio of an epoxy matrix. Limited benefit was observed through dispersion methods, however nanoparticle application as a coating resulting in up to a three-fold increase in damping