Ionic Polyimides: New High Performance Polymers for Additive Manufacturing
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Enrique Jackson↗
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Some effects of composition on friction and wear of graphite-fiber-reinforced polyimide liners in plain spherical bearings
Oscillating, plain spherical bearings with graphite-fiber-reinforced polyimide (GFRPI) liners were tested for friction and wear from 25 to 315 C. A condensation polymer was compared with an addition polymer, and a high-modulus fiber was compared with a lower cost, low-modulus fiber. All polymer-fiber combinations gave friction coefficients from 0.05 to 0.18 and low wear. Adding CdO and CdI2 reduced the wear of degassed bearings in dry air. These additives were not needed when the bearing liners contained adsorbed moisture. Although, at 25 C, MoS2 reduced the friction and wear of the base composite at unit loads above 70,000,000 N/m squared (10,000 psi), it had no beneficial effect at lighter loads.
Sliney, H. E.↗
MISSE PEACE Polymers Atomic Oxygen Erosion Results
Forty-one different polymer samples, collectively called the Polymer Erosion and Contamination Experiment (PEACE) Polymers, have been exposed to the low Earth orbit (LEO) environment on the exterior of the International Space Station (ISS) for nearly 4 years as part of Materials International Space Station Experiment 2 (MISSE 2). The objective of the PEACE Polymers experiment was to determine the atomic oxygen erosion yield of a wide variety of polymeric materials after long term exposure to the space environment. The polymers range from those commonly used for spacecraft applications, such as Teflon (DuPont) FEP, to more recently developed polymers, such as high temperature polyimide PMR (polymerization of monomer reactants). Additional polymers were included to explore erosion yield dependence upon chemical composition. The MISSE PEACE Polymers experiment was flown in MISSE Passive Experiment Carrier 2 (PEC 2), tray 1, on the exterior of the ISS Quest Airlock and was exposed to atomic oxygen along with solar and charged particle radiation. MISSE 2 was successfully retrieved during a space walk on July 30, 2005, during Discovery s STS-114 Return to Flight mission. Details on the specific polymers flown, flight sample fabrication, pre-flight and post-flight characterization techniques, and atomic oxygen fluence calculations are discussed along with a summary of the atomic oxygen erosion yield results. The MISSE 2 PEACE Polymers experiment is unique because it has the widest variety of polymers flown in LEO for a long duration and provides extremely valuable erosion yield data for spacecraft design purposes.
deGroh, Kim, K.↗
Curable polyphosphazenes
Class of polyphosphazene polymers can be cured at moderate temperatures by action of moisture. In addition, polymers maintain flexibility when exposed to low temperatures.
Reynard, K. A.↗
Final Report
This cooperative agreement explored the novel polymerization of vinylsilane, alone and in combination with other alkenylsilanes, alkylsilanes, and/or crosslinking agents, using dimethyltitanocene as homogeneous catalyst. The reactions were found to be initiated photochemically under mild conditions, and no hydrogen gas was evolved when alkenylsilanes were polymerized. The polymers were found to have predominately a carbosilane-type backbone containing -SiH2-CH2-CH2-Si and -SiH2-CH(CH3)-Si type linkages. The mechanism of polymerization was found to be step-growth. Despite the relatively low molecular weight of the polymer (M(sub n) - 500 and M(sub W) - 1500), pyrolysis resulted in conversion to C-rich SiC ceramic in high char yields (-60%). Copolymerization with methylsilane resulted in higher chars and more crystalline polymer. Addition of crosslinking agents such as polybutadiene or methyltrivinylsilane increased the viscosity of the polymer produced and enabled application as coatings to fiber toes.
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Development of an Unstructured, Three-Dimensional Material Response Design Tool
A preliminary verification and validation of a new material response model is presented. This model, Icarus, is intended to serve as a design tool for the thermal protection systems of re-entry vehicles. Currently, the capability of the model is limited to simulating the pyrolysis of a material as a result of the radiative and convective surface heating imposed on the material from the surrounding high enthalpy gas. Since the major focus behind the development of Icarus has been model extensibility, the hope is that additional physics can be quickly added. The extensibility is critical since thermal protection systems are becoming increasing complex, e.g. woven carbon polymers. Additionally, as a three-dimensional, unstructured, finite-volume model, Icarus is capable of modeling complex geometries as well as multi-dimensional physics, which have been shown to be important in some scenarios and are not captured by one-dimensional models. In this paper, the mathematical and numerical formulation is presented followed by a discussion of the software architecture and some preliminary verification and validation studies.
Material Response Model↗
Development of a Three-Dimensional, Unstructured Material Response Design Tool
A preliminary verification and validation of a new material response model is presented. This model, Icarus, is intended to serve as a design tool for the thermal protection systems of re-entry vehicles. Currently, the capability of the model is limited to simulating the pyrolysis of a material as a result of the radiative and convective surface heating imposed on the material from the surrounding high enthalpy gas. Since the major focus behind the development of Icarus has been model extensibility, the hope is that additional physics can be quickly added. This extensibility is critical since thermal protection systems are becoming increasing complex, e.g. woven carbon polymers. Additionally, as a three-dimensional, unstructured, finite-volume model, Icarus is capable of modeling complex geometries. In this paper, the mathematical and numerical formulation is presented followed by a discussion of the software architecture and some preliminary verification and validation studies.
Thermal Protection System↗
Phosphorus-containing imide resins
Cured polymers of bis and tris-imides derived from tris(m-aminophenyl) phosphine oxides by reaction with maleic anhydride or its derivatives, and addition polymers of such imides, including a variant in which a monoimide is condensed with a dianhydride and the product is treated with a further quantity of maleic anhydride prior to curing are disclosed and claimed. Such polymers are flame resistant. Also disclosed are an improved method of producing tris(m-aminophenyl) phosphine oxides from the nitro analogues by reduction with hydrazine hydrate using palladized charcoal or Raney nickel as the catalyst and fiber reinforced cured resin composites.
Varma, I. K.↗
Thermomechanical behavior of a polynorbornadiene
A high-temperature linear amorphous hydrocarbon polymer synthesized cationically from 2,5-norbornadiene was studied thermomechanically with respect to physical transitions and stability in nitrogen. The glass transition temperature was determined to be 320 C (at less than 1 cps), which is probably the highest known for a linear hydrocarbon addition polymer. The thermomechanical technique of torsional braid analysis, together with thermogravimetric analysis, differential thermal analysis, infrared analysis, and solubility studies, was used to investigate the sequential events of the glass transition and degradation. The polymer is of particular interest since it is a high-temperature plastic which in the bulk form would probably need to be processed at high speeds in the vicinity of the glass transition temperature in an inert atmosphere. The presence of tertiary hydrogen atoms should render it amenable to degradation by the earth's environment.
Roller, M. B.↗
Combustion of a polymer (PMMA) sphere in microgravity
Polymer combustion is a highly complicated process where chemical reactions may occur not only in the gas phase, but also in the condensed phase as well as at the solid-gas interphase. The chemistry depends strongly on the coupling between the condensed phase and gas phase phenomena. For some polymers, additional complications arise due to the formation of char layers. For others, the behavior of the condensed phase involves swelling, bubbling, melting, sputtering, and multi-stage combustion. Some of these features bear resemblance to the phenomena observed in coal particle combustion. In addition to its relevance to spacecraft fire safety, the combustion of polymeric materials is related to many applications including solid and hybrid rocket propulsion, and of recent interest, waste incineration . The burning rate is one of the most important parameters used to characterize the combustion of polymers. It has been used to rank the polymer flammability under the same experimental conditions and to evaluate various modes of inhibiting polymer flammability. The main objective of this work is to measure the burning rates of a polymeric material in low gravity. Because of inherent logistical difficulties involved in microgravity experiments, it is impossible to examine a wide spectrum of polymeric materials. It is desirable to investigate a polymer whose combustion is less complicated, and yet will lead to a better understanding of the burning characteristics of other more complicated materials. Therefore, a typical non-charring polymer is selected for use in this experimental study. PMMA (polymethylmethacrylate) has been chosen because its thermo-physical properties are well characterized. Although the combustion of PMMA has been extensively studied in 1G experiments, only a limited amount of work has been conducted in low gravity. A spherical sample geometry is chosen in this study because it is the simplest configuration in terms of the microgravity hardware design requirements. Furthermore, a burning PMMA sphere in microgravity represents a one-dimensional flame with overall combustion characteristics expected to be analogous to the combustion of a liquid fuel droplet, a field with many well-developed theories and models. However, differences can also be expected such as the flame-front standoff ratios and the condensed phase processes occurring during combustion.
Yang, Jiann C.↗
Fully plasma-sprayed compliant backed ceramic turbine seal
A seal with a high temperature abradable lining material which encircles the tips of turbine blades in turbomachinery was designed. The seal is directed to maintaining the minimum operating clearances between the blade tips and the lining of a high pressure turbine. A low temperature easily decomposable material in powder form is blended with a high temperature oxidation resistant metal powder. The two materials are simultaneously deposited on a substrate formed by the turbine casing. Alternately, the polymer powder may be added to the metal powder during plasma spraying. A ceramic layer is then deposited directly onto the metal-polymer composite. The polymer additive mixed with the metal is then completely volatilized to provide a porous layer between the ceramic layer and the substrate. Thermal stresses are reduced by the porous structure which gives a cushion effect. No brazing is required by using only plasma spraying for depositing both the powders of the metal and polymer material as well as the ceramic powder.
Bill, R. C.↗
Antimisting kerosene atomization and flammability
Various parameters found to affect the flammability of antimisting kerosene (Jet A + polymer additive) are investigated. Digital image processing was integrated into a technique for measurement of fuel spray characteristics. This technique was developed to avoid many of the error sources inherent to other spray assessment techniques and was applied to the study of engine fuel nozzle atomization performance with Jet A and antimisting fuel. Aircraft accident fuel spill and ignition dynamics were modeled in a steady state simulator allowing flammability to be measured as a function of airspeed, fuel flow rate, fuel jet Reynolds number and polymer concentration. The digital imaging technique was employed to measure spray characteristics in this simulation and these results were related to flammability test results. Scaling relationships were investigated through correlation of experimental results with characteristic dimensions spanning more than two orders of magnitude.
Fleeter, R.↗
Thermal expansion and swelling of cured epoxy resin used in graphite/epoxy composite materials
The paper presents results of experiments in which the thermal expansion and swelling behavior of an epoxy resin system and two graphite/epoxy composite systems exposed to water were measured. It was found that the cured epoxy resin swells by an amount slightly less than the volume of the absorbed water and that the swelling efficiency of the water varies with the moisture content of the polymer. Additionally, the thermal expansion of cured epoxy resin that is saturated with water is observed to be more than twice that of dry resin. Results also indicate that cured resin that is saturated with 7.1% water at 95 C will rapidly increase in moisture content to 8.5% when placed in 1 C water. The mechanism for this phenomenon, termed reverse thermal effect, is described in terms of a slightly modified free-volume theory in conjunction with the theory of polar molecule interaction. Nearly identical behavior was observed in two graphite/epoxy composite systems, thus establishing that this behavior may be common to all cured epoxy resins.
Adamson, M. J.↗
Viscous flow drag reduction; Symposium, Dallas, Tex., November 7, 8, 1979, Technical Papers
The symposium focused on laminar boundary layers, boundary layer stability analysis of a natural laminar flow glove on the F-111 TACT aircraft, drag reduction of an oscillating flat plate with an interface film, electromagnetic precipitation and ducting of particles in turbulent boundary layers, large eddy breakup scheme for turbulent viscous drag reduction, blowing and suction, polymer additives, and compliant surfaces. Topics included influence of environment in laminar boundary layer control, generation rate of turbulent patches in the laminar boundary layer of a submersible, drag reduction of small amplitude rigid surface waves, and hydrodynamic drag and surface deformations generated by liquid flows over flexible surfaces.
Hough, G. R.↗
Fully plasma-sprayed compliant backed ceramic turbine seal
A seal having a high temperature abradable lining material encircling the tips of turbine blades in turbomachinery is discussed. The minimum operating clearances between the blade tips and the lining of a high pressure turbine are maintained. A low temperature easily decomposable material, such as a polymer, in powder form is blended with a high temperature oxidation resistant metal powder. The two materials are simultaneously deposited on a substrate formed by the turbine casing. Alternately, the polymer powder may be added to the metal powder during plasma spraying. A ceramic layer is then deposited directly onto the metal polymer composite. The polymer additive mixed with the metal is then completely volatilized to provide a porous layer between the ceramic layer and the substrate.
Bill, R. C.↗
Influence of liquid water and water vapor on antimisting kerosene (AMK)
Experiments have been performed to evaluate the compatibility of liquid water and water vapor with antimisting kerosenes (AMK) containing polymer additive FM-9 developed by Imperial Chemical Industries. This effort consists of the determination of water solubility in AMK, influence of water on restoration (degradation) of AMK, and effect of water on standard AMK quality control methods. The principal conclusions of this investigation are: (1) the uptake of water in AMK critically depends upon the degree of agitation and can be as high as 1300 ppm at 20 C, (2) more than 250 to 300 ppm of water in AMK causes an insoluble second phase to form. The amount of this second phase depends on fuel temperature, agitation, degree of restoration (degradation) and the water content of the fuel, (3) laboratory scale experiments indicate precipitate formation when water vapor comes in contact with cold fuel surfaces at a much lower level of water (125 to 150 ppm), (4) precipitate formation is very pronounced in these experiments where humid air is percolated through a cold fuel (-20 C), (5) laboratory tests further indicate that water droplet settling time is markedly reduced in AMK as compared to jet A, (6) limited low temperature testing down to -30 C under laboratory conditions indicates the formation of stable, transparent gels.
Yavrouian, A. H.↗
Phosphorus-containing imide resins
Bis- and tris-imides derived from tris (m-aminophenyl) phosphine oxides by reaction with maleic anhydride or its derivatives, and addition polymers of such imides, including a variant in which a mono-imide is condensed with a dianhydride and the product is treated with a further quantity of maleic anhydride. Such monomers or their oligomes may be used to impregnate fibers and fabrics which when cured, are flame resistant. Also an improved method of producing tris (m-aminophenyl) phosphine oxides from the nitro analogues by reduction with hydrazine hydrate using palladized charcoal or Raney nickel as the catalyst is described.
Varma, I. K.↗
Shearing stability of lubricants
Shearing stabilities of lubricating oils containing a high mol. wt. polymer as a viscosity index improver were studied by use of ultrasound. The oils were degraded by cavitation and the degradation generally followed first order kinetics with the rate of degradation increasing with the intensity of the ultrasonic irradiation and the cumulative energy applied. The shear stability was mainly affected by the mol. wt. of the polymer additive and could be determined in a short time by mechanical shearing with ultrasound.
Shiba, Y.↗