Development of high thermal conductivity polymeric materials for spacecraft use Final report, 1 Jul. 1966 - 31 May 1969
High thermal conductivity polymeric materials for spacecraft applications using phenyl compounds
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High thermal conductivity polymeric materials for spacecraft applications using phenyl compounds
High temperature polymer matrix composites are attractive materials for space transporation propulsion systems because of their low density and high specific strength. However, the relatively poor stability and processability of these materials can render them unsuitable for many of these applications. New polymeric materials have been developed under the Propulsion Research and Technology Program through the use of novel resin chemistry and nanotechnology. These new materials can significantly enhance the durability and weight and improve the processability and affordability of propulsion components for advanced space transportation systems.
High thermal conductivity polymeric materials for spacecraft electronic equipment use
Relative toxicity data for a large number of natural and synthetic polymeric materials are presented which were obtained by 11 pyrolysis and three flaming-combustion test methods. The materials tested include flexible and rigid polyurethane foams, different kinds of fabrics and woods, and a variety of commodity polymers such as polyethylene. Animal exposure chambers of different volumes containing mice, rats, or rabbits were used in the tests, which were performed over the temperature range from ambient to 800 C with and without air flow or recirculation. The test results are found to be sensitive to such variables as exposure mode, temperature, air flow and dilution, material concentration, and animal species, but relative toxicity rankings appear to be similar for many methods and materials. It is concluded that times to incapacitance and to death provide a more suitable basis for relative toxicity rankings than percent mortality alone, that temperature is the most important variable in the tests reported, and that variables such as chamber volume and animal species may not significantly affect the rankings.
Brief description of an engineering test program to determine the effects of the space environment on polymeric materials
The governing differential equations are developed to model the thermomechanical behavior of chemically decomposing, polymeric materials. These equations account for thermal and gaseous diffusion through a poroelastic, transversely isotropic solid. The Bubnov-Galerkin finite element method is applied to the governing equations to cast the coupled set into a single matrix equation. A method for solving these equations simultaneously at each time step is discussed.
A previously developed formulation for modeling the thermomechanical behavior of chemically decomposing, polymeric materials is verified by simulating the response of carbon phenolic specimens during two high temperature tests: restrained thermal growth and free thermal expansion. Plane strain and plane stress models are used to simulate the specimen response, respectively. In addition, the influence of the poroelasticity constants upon the specimen response is examined through a series of parametric studies.
Apparatus for determining volatile condensable material present in polymeric products
Various polymeric materials, including synthetic polymers and cellulosic materials, were evaluated at different temperatures, heating rates and air flow rates for thermophysical and toxicological responses. It is shown that char yields appeared to be a function of air access as much as of the chemical structure of the material. It is stated that the sensitivity of the apparent thermal stability of some materials to air access is so marked that thermogravimetric studies in oxygen-free atmospheres may be a consistently misleading approach to comparing synthetic polymers intended to increase fire safety. Toxicity also appeared to be a function of temperature and air access as much as of the chemical structure of the material. Toxicity of the gases evolved seemed to increase with increasing char yield for some polymers.
This document contains extended abstracts and presentation transcripts from a workshop on microgravity studies of organic and polymeric materials held in Huntsville, Alabama, April 27, 1993.
Techniques are discussed for limiting or controlling the degradation products (outgassing) of polymeric materials in the space environment. One technique, now ASTM E-595-77, is used to screen out those materials which lose greater than 1% Total Mass Loss when in vacuum for 24 hours at 125 C and which have more than 0.10% Collected Volatile Condensable Materials condensing on a collector surface at 25 C. Examples of silicone materials which are high and low in outgassing are given. The numerous mechanical motions in spacecraft experiments require liquid lubricants which also might degrade in space. Labyrinth seals and barrier films are utilized to limit the degradation of or from these lubricants. A recoverable in-flight experiment has been proposed for making definitive measurements of how effective these techniques are in limiting the amounts and escape paths of outgassed molecules.
Four research and development areas are considered for further exploration in the quest of more flame-resistant polymeric materials. It is suggested that improvements in phenolphthalein polycarbonate processability may be gained through linear free energy relationship correlations. Looped functionality in the backbone of a polymer leads to both improved thermal resistance and increased solubility. The guidelines used in the pyrolytic carbon production constitute a good starting point for the development of improved flame-resistant materials. Numerous organic reactions requiring high temperatures and the techniques of protected functionality and latent functionality constitute the third area for exploration. Finally, some well-known organic reactions are suggested for the formation of polymers that were not made before.
This cooperative agreement was intended to investigate the effects of a space environment on the properties of polymeric materials. In addition, efforts have been made to understand and investigate environment simulation techniques and test methodology. The results identified the changes in the properties of six aerospace structural adhesives, three neat high polymers, and two fiber-reinforced polymers, as caused by exposure to four simulated space environmental conditions. Significant property changes occurred for several of the systems as a result of one or more of the exposures. A summary of the research follows a list of related publications and presentations.
Some of the primary purposes of this work are to study important technologies, particularly involving thin films, relevant to organic and polymeric materials for improving applicability to optical circuitry and devices and to assess the contribution of convection on film quality in unit and microgravity environments. Among the most important materials processing techniques of interest in this work are solution-based and by physical vapor transport, both having proven gravitational and acceleration dependence. In particular, PolyDiAcetylenes (PDA's) and PhthaloCyanines (Pc's) are excellent NonLinear Optical (NLO) materials with the promise of significantly improved NLO properties through order and film quality enhancements possible through microgravity processing. Our approach is to focus research on integrated optical circuits and optoelectronic devices relevant to solution-based and vapor processes of interest in the Space Sciences Laboratory at the Marshall Space Flight Center (MSFC). Modification of organic materials is an important aspect of achieving more highly ordered structures in conjunction with microgravity processing. Parallel activities include characterization of materials for particular NLO properties and determination of appropriation device designs consistent with selected applications. One result of this work is the determination, theoretically, that buoyancy-driven convection occurs at low pressures in an ideal gas in a thermalgradient from source to sink. Subsequent experiment supports the theory. We have also determined theoretically that buoyancy-driven convection occurs during photodeposition of PDA, an MSFC-patented process for fabricating complex circuits, which is also supported by experiment. Finally, the discovery of intrinsic optical bistability in metal-free Pc films enables the possibility of the development of logic gate technology on the basis of these materials.
Apparent lethal concentrations for 50 per cent of the test animals within a 30-min exposure period (ALC/50/) were determined for seventeen samples of polymeric materials, using the screening test method. The materials evaluated included resin-glass composites, film composites, and miscellaneous resins. ALC(50) values, based on weight of original sample charged, ranged from 24 to 110 mg/l. Modified phenolic resins seemed to exhibit less toxicity than the baseline epoxy resins. Among the film composites evaluated, only flame modified polyvinyl fluoride appeared to exhibit less toxicity than the baseline polyvinyl fluoride film.
Polymer electrolyte membranes that conduct hydroxide ions have potential use in fuel cells. A variety of polystyrene-based quaternary ammonium hydroxides have been reported as anion exchange fuel cell membranes. However, the hydrolytic stability and conductivity of the commercially available membranes are not adequate to meet the requirements of fuel cell applications. When compared with commercially available membranes, polystyrene-imidazolium alkaline membrane electrolytes are more stable and more highly conducting. At the time of this reporting, this has been the first such usage for imidazolium-based polymeric materials for fuel cells. Imidazolium salts are known to be electrochemically stable over wide potential ranges. By controlling the relative ratio of imidazolium groups in polystyrene-imidazolium salts, their physiochemical properties could be modulated. Alkaline anion exchange membranes based on polystyrene-imidazolium hydroxide materials have been developed. The first step was to synthesize the poly(styrene-co-(1-((4-vinyl)methyl)-3- methylimidazolium) chloride through a free-radical polymerization. Casting of this material followed by in situ treatment of the membranes with sodium hydroxide solutions provided the corresponding hydroxide salts. Various ratios of the monomers 4-chloromoethylvinylbenzine (CMVB) and vinylbenzine (VB) provided various compositions of the polymer. The preferred material, due to the relative ease of casting the film, and its relatively low hygroscopic nature, was a 2:1 ratio of CMVB to VB. Testing confirmed that at room temperature, the new membranes outperformed commercially available membranes by a large margin. With fuel cells now in use at NASA and in transportation, and with defense potential, any improvement to fuel cell efficiency is a significant development.
Simulated Venusian atmosphere effects on polymeric plastic and rubber materials, comparing with high temperature air and nitrogen exposures
Polymer degradation under aggressive environmental stressors often develops heterogeneities due to diffusion-limited reaction phenomena. This is well established for diffusion-limited oxidation (DLO), which is known to occur for most polymeric materials at elevated temperatures but has been less summarized for the conditions of diffusion-limited hydrolysis (DLH). Here, an overview of hydrolysis for several materials and a computational model, analogous to the underlying equations for DLO, able to define this diffusion-reaction system is presented. A systematic study of the influence of various parameters, such as water diffusivity, reaction rate and order, and a more in-depth focus on residual isocyanate hydrolysis in a polymeric methylene diphenyl diisocyanate (pMDI) based polyurethane (PU) foam is given. For this system, we present experimental data for model ‘input’ parameters and discuss predictions for different conditions. We conceptually compare the behavior of diffusion-limited oxidation to that of diffusion-limited hydrolysis (DLH). With the mathematical framework and key material properties presented herein, any DLH phenomena following Fickian diffusion behavior can be understood, modeled, and predicted.