Additives to reduce susceptibility of thermosets and thermoplastics to erosion from atomic oxygen

Polymeric materials have many attractive features such as light weight, high strength, and broad applicability in the form of films, fibers, and molded objects. In low earth orbit (LEO), these materials, when exposed on the exterior of the spacecraft, have the serious disadvantage of being susceptible to erosion by atomic oxygen (AO). AO is the most common chemical species at LEO altitudes. AO can be an extremely efficient oxidizing agent as was apparent from the extensive erosion of organic films exposed in STS missions. The mechanism for erosion involves the reaction of oxygen atoms at the surface of the substrate to form small molecular species. The susceptibility of polymeric materials varies with their chemical composition. Films with silicon atoms incorporated in the molecular structures have large coefficients of thermal expansion. This limits their utility. In an alternative approach additives were sought that mix physically and form a protective oxide layer when the film is exposed to AO. A large number of organic compounds containing silicon, germanium, or tin atoms were screened. Most were found to have very limited solubility in the polyetherimide (Ultem) films that were being protected from AO. However, one, bis(triphenyl tin) oxide, (BTO), is miscible in Ultem up to about 25 percent. Films of Ultem polyimide containing up to 25 wt percent BTO were prepared by evaporation of solvent from a solution of Ultem and BTO. The effects of AO on these films were simulated in the oxygen atmosphere of a radio frequency glow-discharge chamber. In the second part of this study, atoms were incorporated in epoxy resins. Experiments are in progress to measure the resistance of films of the cured epoxy to AO in the discharge chamber

Space environmental effects on polymeric materials

Two of the major environmental hazards in the Geosynchronous Earth Orbit (GEO) are energetic charged particles and ultraviolet radiation. The charged particles, electrons and protons, range in energy from 0.1 to 4 MeV and each have a flux of 10 to the 8th sq cm/sec. Over a 30 year lifetime, materials in the GEO will have an absorbed dose from this radiation of 10 to the 10th rads. The ultraviolet radiation comes uninhibited from the sun with an irradiance of 1.4 kw/sq m. Radiation is known to initiate chain sission and crosslinking in polymeric materials, both of which affect their structural properties. The 30-year dose level from the combined radiation in the GEO exceeds the threshold for measurable damage in most polymer systems studied. Of further concern is possible synergistic effects from the simultaneous irradiation with charged particles and ultraviolet radiation. Most studies on radiation effects on polymeric materials use either electrons or ultraviolet radiation alone, or in a sequential combination

The effects of the interaction of polymeric materials with the space environment

Polymeric materials in low earth orbit will be exposed to a harmful environment mainly due to atomic oxygen and ultraviolet radiation. In geosynchronous earth orbit, the major hazards to such materials are energetic charged particles and ultraviolet radiation. The progress of studies on the effects of these hazards on a polyetherimide, a polyimide, and an epoxy adhesive is presented

Preparation, Fabrication, and Evaluation of Advanced Polymeric and Composite Materials

The thesis titles are given below: physical and mechanical behavior of amorphous poly(arylene ether-co-imidasole)s and poly(arylene ether-co-imidasole) modification epoxies; the requirements of patentability as applied to the chemical arts; fabrication of thermoplastic polymer composite ribbon; blend of reactive diluents with phenylethynyl-terminated arylene ether oligomers; the synthesis, characterization, and application of ether-containing polyimides; the synthesis of reflective and electrically conductive polyimide films via an in-situ self-metalization procedure using silver (I) complexes; the thermal cure of phenylethynyl terminated polyimides and selected model compounds; and the synthesis, characterization, and molecular modeling of cyclic arylene ether oligomers

The effects of atomic oxygen on polymeric materials

At the altitudes of low-earth orbit (LEO), atomic oxygen (AO) is the most abundant chemical species. This strong oxidizing agent reacts with virtually any organic material that is not already fully oxidized. Erosion by AO can be extensive and jeopardizes any protective coatings, thermal blankets, adhesives, and structural composites exposed on the exterior of satellites in LEO. Researchers prepared and tested organic materials for their susceptibility to AO using a commercial plasma asher which approximately simulates the oxygen effects in LEO. Experiments were performed on a polyimide, a polysulfone, and two epoxy adhesives into which low molecular-weight additives have been dissolved. Incorporated in the molecular structure of these additives are elements such as silicon whose nonvolatile oxides, which are formed on exposure to AO, remain as a coating on the surface to create a barrier between the remainder of the organic material and the AO. We find that the additives protect the materials, but the low solubility of some limit their utility. Concurrent studies are underway to measure the effect of the additives on the thermal expansion coefficients of the materials. Tows of aramid fibers, which are important components in the proposed tether satellite systems, have been eroded in the asher. The results which show that the square root of the mass remaining decreases linearly with the time of exposure (see the figure) are consistent with a constant rate of surface erosion. The tensile strength of these eroded tows decreases with time of exposure also; additional measurements are in progress

P-V-T Properties of Polyimides and Model Imide Compounds

Aromatic polyimides are used as matrix resins in advanced composites, as high strength films, and as high-temperature adhesives, owing in part to their unusual thermal and chemical stability. The polyimides' desirable qualities of very high softening temperatures and negligibly small solubilities in and low permeabilities by most solvents have limited the kinds of fundamental studies that can be performed on these systems. Consequently, relationships between the molecular structure of polyimides and their bulk properties are not as well understood as might be expected given their widespread applications. In particular, the intermolecular forces in polyimides that play a critical role determining their densities, solubilities, viscosities, moduli, glass transitions, etc. are less well characterized for polyimides than for other widely used polymeric materials. The purpose of the present study is to obtain experimental data for establishing parameters that characterize the intermolecular forces in polyimides. We report here our studies on tractable low molecular-weight imides that contain the same structural features that are present in polyimide materials. We have measured equation-of-state properties and dipole moments for a variety of such systems in the liquid state. Both pure compounds and binary mixtures have been studied

Polyimide-Clay Composite Materials for Space Application

The introduction of nanometer-sized clay particles into a polyimide matrix has been shown to enhance the physical properties of specific polymer systems. The clay comprises large stacked platelets of the oxides of aluminum and silicon. These sheets have long dimensions on the order of tenths of a micrometer and thicknesses of several nanometers. Homogeneous dispersion of the clay platelets in the polymer matrix is necessary to achieve those enhancements in polymer properties. Natural montmorillonite with the empirical formula Na0.33Mg0.33Al1.67(OH)2(Si4O10) contains exchangeable inorganic cations. The clay lamellae stack together with the positive sodium ions situated between the surfaces of the individual sheets to balance negatively charged oxygen atoms that are on the surfaces of the sheets. These surface charges contribute to strong electrostatic forces which hold the sheets together tightly. Exfoliation can be accomplished only with unusual measures. In preparing clay nanocomposites, we have taken two steps to try to reduce these interlamellar forces in order to promote the separation (exfoliation) of the sheets and the dispersion of the individual clay particles throughout the organic polymer matrix. In the first step, some of the surface Na(+) ions are replaced with Li(+) ions. Unlike sodium cations, the lithium cations migrate into the interior of the lamellae when the system is heated. Their departure from the surface reduces the surface charge and therefore the attractive forces between the sheets. The loss of alkali metal cations from the surface can be measured as the cation exchange capacity (CEC) of the clay. For example, we found that the CEC of montmorillonite clay was reduced by almost two thirds by treating it with lithium ions and heating to 250 C for 24 hr. Lesser heating has a smaller effect on the CEC. X-ray diffraction measurements show that the d-spacing decreased from ca. 1.34 to 0.97 nm, apparently a consequence of a collapse of the clay layers. We observed that the d-spacing can be varied by altering the heat treatment. In the second part of our effort to reduce the interlamellar forces, the remaining inorganic surface cations were replaced by the trimethylphenylammonium ion (TMPA), the biphenyltrimethylammonium ion (BTMA), or the tetraphenylphosphonium ion (TPP)

Shielding materials for highly penetrating space radiations

Interplanetary travel involves the transfer from an Earth orbit to a solar orbit. Once outside the Earth's magnetosphere, the major sources of particulate radiation are solar cosmic rays (SCR's) and galactic cosmic rays (GCR's). Intense fluxes of SCR's come from solar flares and consist primarily of protons with energies up to 1 GeV. The GCR consists of a low flux of nuclei with energies up to 10(exp 10) GeV. About 70 percent of the GCR are protons, but a small amount (0.6 percent) are nuclei with atomic numbers greater than 10. High energy charged particles (HZE) interact with matter by transferring energy to atomic electrons in a Coulomb process and by reacting with an atomic nucleus. Energy transferred in the first process increases with the square of the atomic number, so particles with high atomic numbers would be expected to lose large amounts of energy by this process. Nuclear reactions produced by (HZE) particles produce high-energy secondary particles which in turn lose energy to the material. The HZE nuclei are a major concern for radiation protection of humans during interplanetary missions because of the very high specific ionization of both primary and secondary particles. Computer codes have been developed to calculate the deposition of energy by very energetic charged particles in various materials. Calculations show that there is a significant buildup of secondary particles from nuclear fragmentation and Coulomb dissociation processes. A large portion of these particles are neutrons. Since neutrons carry no charge, they only lose energy by collision or reaction with a nucleus. Neutrons with high energies transfer large amounts of energy by inelastic collisions with nuclei. However, as the neutron energy decreases, elastic collisions become much more effective for energy loss. The lighter the nucleus, the greater the fraction of the neutron's kinetic energy that can be lost in an elastic collision. Thus, hydrogen-containing materials such as polymers are most effective in reducing the energy of neutrons. Once neutrons are reduced to very low energies, the probability for undergoing a reaction with a nucleus (the cross section) becomes very high. The product of such a reaction is often radioactive and can involve the release of a significant amount of energy. Thus, it is important to provide protection from low energy neutrons during a long duration space flight. Among the light elements, lithium and boron each have an isotope with a large thermal neutron capture cross section, Li-6 and B-10. However, B-10 is more abundant in the naturally-occurring element than Li-6, has a thermal neutron capture cross section four times that of Li-6, and produces the stable products, He-4 and Li-7 in the interaction while Li-6 produces radioactive tritium (H-3). Thus, boron is the best light-weight material for thermal neutron absorption in spacecraft. The work on this project was focused in two areas: computer design where existing computer codes were used, and in some cases modified, to calculate the propagation and interactions of high energy charged particles through various media, and materials development where boron was incorporated into high performance materials

Candidate gene analysis of femoral neck trabecular and cortical volumetric bone mineral density in older men.

In contrast to conventional dual-energy X-ray absorptiometry, quantitative computed tomography separately measures trabecular and cortical volumetric bone mineral density (vBMD). Little is known about the genetic variants associated with trabecular and cortical vBMD in humans, although both may be important for determining bone strength and osteoporotic risk. In the current analysis, we tested the hypothesis that there are genetic variants associated with trabecular and cortical vBMD at the femoral neck by genotyping 4608 tagging and potentially functional single-nucleotide polymorphisms (SNPs) in 383 bone metabolism candidate genes in 822 Caucasian men aged 65 years or older from the Osteoporotic Fractures in Men Study (MrOS). Promising SNP associations then were tested for replication in an additional 1155 men from the same study. We identified SNPs in five genes (IFNAR2, NFATC1, SMAD1, HOXA, and KLF10) that were robustly associated with cortical vBMD and SNPs in nine genes (APC, ATF2, BMP3, BMP7, FGF18, FLT1, TGFB3, THRB, and RUNX1) that were robustly associated with trabecular vBMD. There was no overlap between genes associated with cortical vBMD and trabecular vBMD. These findings identify novel genetic variants for cortical and trabecular vBMD and raise the possibility that some genetic loci may be unique for each bone compartment

Time to Osteoporosis and Major Fracture in Older Men

For older men who undergo bone mineral density (BMD) testing, the optimal osteoporosis screening schedule is unknown. Time-to-disease estimates are necessary to inform screening intervals