Amy L. Brunsvold

Atomic Oxygen Effects on POSS Polyimides in Low Earth Orbit

Kapton polyimde is extensively used in solar arrays, spacecraft thermal blankets, and space inflatable structures. Upon exposure to atomic oxygen in low Earth orbit (LEO), Kapton is severely eroded. An effective approach to prevent this erosion is to incorporate polyhedral oligomeric silsesquioxane (POSS) into the polyimide matrix by copolymerizing POSS monomers with the polyimide precursor. The copolymerization of POSS provides Si and O in the polymer matrix on the nano level. During exposure of POSS polyimide to atomic oxygen, organic material is degraded, and a silica passivation layer is formed. This silica layer protects the underlying polymer from further degradation. Laboratory and space-flight experiments have shown that POSS polyimides are highly resistant to atomic-oxygen attack, with erosion yields that may be as little as 1% those of Kapton. The results of all the studies indicate that POSS polyimide would be a space-survivable replacement for Kapton on spacecraft that operate in the LEO environment.

Crossed beams and theoretical studies of the O(3P)+CH4→H+OCH3 reaction excitation function

The excitation function for the reaction, O(3P)+CH4-->H+OCH3, has been measured in a crossed molecular beams experiment and determined with direct dynamics calculations that use the quasiclassical trajectory method in conjunction with a recently developed semiempirical Hamiltonian. Good agreement is found between experiment and theory, enabling us to address two fundamental issues for the O(3P)+CH4 reaction that arise for all O(3P)+saturated hydrocarbon reactions: (1) the importance of triplet excited states that correlate adiabatically to ground-state reactants and products and (2) the importance of intersystem crossing processes involving the lowest singlet surface [corresponding to reaction with O(1D)]. Our results indicate that the first excited triplet surface contributes substantially to the cross section when the collision energy exceeds the reaction barrier (approximately 2 eV) by more than 0.5 eV. Although triplet-singlet crossings may occur at all energies, we have found that their effect on the excitation function is negligible for the collision energies studied-up to 1.5 eV above threshold.

Erosion of Kapton ® H by Hyperthermal Atomic Oxygen

Organic polymers are subject to erosion from ambient atomic oxygen in low Earth orbit. The linearity of the O-atom fluence dependence of Kapton ® H erosion and the dependence of Kapton H erosion yield on surface temperature have been investigated. Sample exposures were performed with a pulsed beam containing hyperthermal O atoms that were generated with a laser detonation source. After exposure, samples were removed from the chamber in which the exposures were performed, and postexposure analyses were performed: etch depth (profilometry) and surface topography (atomic force microscopy). A systematic set of exposures, which eroded room-temperature Kapton H from 1.4 to 25 μm, showed that the erosion yield of Kapton H is linearly dependent on O-atom fluence. This result helps validate the use of Kapton H mass loss (or erosion depth) as a linear measure of the O-atom fluence of a materials exposure. The erosion of Kapton H was strongly temperature dependent. At lower temperatures (<100◦C), the erosion yield appeared to be independent of sample temperature. However, above 100◦C, the erosion yield exhibited an Arrhenius-like temperature dependence, with an apparent activation energy of 0.31 eV. These observations suggest that O-atom-induced erosion of Kapton H proceeds through direct, nonthermal, gas-surface reactions and through reactions that depend on surface temperature.

Erosion of FEP Teflon and PMMA by VUV Radiation and Hyperthermal O or Ar Atoms

A combination of beam-surface-scattering, quartz-crystal-microbalance, and surface-recession experiments was conducted to study the effects of various combinations of O atoms [in the O((3)P) ground state], Ar atoms, and vacuum ultraviolet (VUV) light on fluorinated ethylene-propylene copolymer (FEP) Teflon and poly(methyl methacrylate) (PMMA). A laser-breakdown source was used to create hyperthermal beams containing O and O(2) or Ar. A D(2) lamp provided a source of VUV light. O atoms with 4 eV of translational energy or less did not react with a pristine FEP Teflon surface. Volatile O-containing reaction products were observed when the O-atom energy was higher than 4.5 eV, and the signal increased with the O-atom energy. Significant erosion of FEP Teflon ( approximately 20% of Kapton H) was observed when it was exposed to the hyperthermal O/O(2) beam with an average O-atom energy of 5.4 eV. FEP Teflon and PMMA that were exposed to VUV light alone exhibited much less mass loss. Collision-induced dissociation by hyperthermal Ar atoms also caused mass loss, similar in magnitude to that caused by VUV light. There were no observed synergistic effects when VUV light or Ar bombardment was combined with O/O(2) exposure. For both FEP Teflon and PMMA, the erosion yields caused by simultaneous exposure to O/O(2) and either VUV light or Ar atoms could be approximately predicted by adding the erosion yield caused by O/O(2), acting individually, to the erosion yield caused by the individual action of either VUV light or Ar atoms.

Properties and improved space survivability of POSS (polyhedral oligomeric silsesquioxane) polyimides

Kapton polyimide (PI) is widely used on the exterior of spacecraft as a thermal insulator. Atomic oxygen (AO) in lower earth orbit (LEO) causes severe degradation in Kapton resulting in reduced spacecraft lifetimes. One solution is to coat the polymer surface with SiO 2 since this coating is known to impart remarkable oxidation resistance. Imperfections in the SiO 2 application process and micrometeoroid / debris impact in orbit damage the SiO 2 coating, leading to erosion of Kapton. A self passivating, self healing silica layer protecting underlying Kapton upon exposure to AO may result from the nanodispersion of silicon and oxygen within the polymer matrix. Polyhedral oligomeric silsesquioxane (POSS) is composed of an inorganic cage structure with a 2:3 Si:O ratio surrounded by tailorable organic groups and is a possible delivery system for nanodispersed silica. A POSS dianiline was copolymerized with pyromellitic dianhydride and 4, 4′-oxydianiline resulting in POSS Kapton Polyimide. The glass transition temperature (Tg) of 5 to 25 weight % POSS Polyimide was determined to be slightly lower, 5 – 10 %, than that of unmodified polyimides (414 °C). Furthermore the room temperature modulus of polyimide is unaffected by POSS, and the modulus at temperatures greater than the Tg of the polyimide is doubled by the incorporation of 20 wt % POSS. To simulate LEO conditions, POSS PI films underwent exposure to a hyperthermal O-atom beam. Surface analysis of exposed and unexposed films conducted with X-ray photoelectron spectroscopy, atomic force microscopy, and surface profilometry support the formation of a SiO 2 self healing passivation layer upon AO exposure. This is exemplified by erosion rates of 10 and 20 weight % POSS PI samples which were 3.7 and 0.98 percent, respectively, of the erosion rate for Kapton H at a fluence of 8.5 × 10 20 O atoms cm -2 . This data corresponds to an erosion yield for 10 wt % POSS PI of 4.8 % of Kapton H. In a separate exposure, at a fluence of 7.33 × 10 20 O atoms cm -2 , 25 wt % POSS Polyimide showed the erosion yield of about 1.1 % of that of Kapton H. Also, recently at a lower fluence of 2.03 × 10 20 O atoms cm -2 , in going from 20 to 25 wt % POSS PI the erosion was decreased by a factor of 2 with an erosion yield too minor to be measured for 25 wt % POSS PI.

Dynamics of Hyperthermal Collisions of O(3P) with CO

The dynamics of O(3P) + CO collisions at a hyperthermal collision energy near 80 kcal mol-1 have been studied with a crossed molecular beams experiment and with quasi-classical trajectory calculations on computed potential energy surfaces. In the experiment, a rotatable mass spectrometer detector was used to monitor inelastically and reactively scattered products as a function of velocity and scattering angle. From these data, center-of-mass (c.m.) translational energy and angular distributions were derived for the inelastic and reactive channels. Isotopically labeled C18O was used to distinguish the reactive channel (16O + C18O 16OC + 18O) from the inelastic channel (16O + C18O 16O + C18O). The reactive 16OC molecules scattered predominantly in the forward direction, i.e., in the same direction as the velocity vector of the reagent O atoms in the c.m. frame. The c.m. translational energy distribution of the reactively scattered 16OC and 18O was very broad, indicating that 16OC is formed with a wide range of internal energies, with an average internal excitation of approximately 40% of the available energy. The c.m. translational energy distribution of the inelastically scattered C18O and 16O products indicated that an average of 15% of the collision energy went into internal excitation of C18O, although a small fraction of the collisions transferred nearly all the collision energy into internal excitation of C18O. The theoretical calculations, which extend previously published results on this system, predict c.m. translational energy and angular distributions that are in near quantitative agreement with the experimentally derived distributions. The theoretical calculations, thus validated by the experimental results, have been used to derive internal state distributions of scattered CO products and to probe in detail the interactions that lead to the observed dynamical behavior.

Beam-Surface Scattering Studies of the Individual and Combined Effects of VUV Radiation and Hyperthermal O, O2, or Ar on FEP Teflon Surfaces

Beam-surface scattering experiments were used to probe products that scattered from FEP Teflon surfaces during bombardment by various combinations of atomic and molecular oxygen, Ar atoms, and vacuum ultraviolet (VUV) light. A laser-breakdown source was used to create hyperthermal (translational energies in the range 4-13 eV) beams of argon and atomic/molecular oxygen. The average incidence energy of these beams was tunable and was controlled precisely with a synchronized chopper wheel. A filtered deuterium lamp provided a source of VUV light in a narrow-wavelength range centered at 161 nm. Volatile products that exited the surfaces were monitored with a rotatable mass spectrometer detector. Hyperthermal O atoms with average translational energies above approximately 4 eV may react directly with a pristine FEP Teflon surface, and the reactivity appears to increase with the translational energy of the incident O atoms. VUV light or highly energetic collisions of O2 or Ar may break chemical bonds and lead to the ejection of volatile products; the ejection of volatile products is enhanced when the surface is subjected to VUV light and energetic collisions simultaneously. Exposure to VUV light or to hyperthermal O2 or Ar may increase the reactivity of an FEP Teflon surface to O atoms.

Hyperthermal Ar atom scattering from a C"0001… surface

Experiments and simulations on the scattering of hyperthermal Ar from a C(0001) surface have been conducted. Measurements of the energy and angular distributions of the scattered Ar flux were made over a range of incident angles, incident energies (2.8-14.1 eV), and surface temperatures (150-700 K). In all cases, the scattering is concentrated in a narrow superspecular peak, with significant energy exchange with the surface. The simulations closely reproduce the experimental observations. Unlike recent experiments on hyperthermal Xe scattering from graphite [Watanabe et al., Eur. Phys. J. D 38, 103 (2006)], the angular dependence of the energy loss is not approximated by the hard cubes model. The simulations are used to investigate why parallel momentum conservation describes Xe scattering, but not Ar scattering, from the surface of graphite. These studies extend our knowledge of gas-surface collisional energy transfer in the hyperthermal regime, and also demonstrate the importance of performing realistic numerical simulations for modeling such encounters.

Unusual Mechanisms Can Dominate Reactions at Hyperthermal Energies: An Example from O(3P) + HCl → ClO + H

An unusual mechanism in the reaction, O(3P) + HCl --> ClO + H, dominates at hyperthermal collision energies. This mechanism applies to collision geometries in which the H atom in the HCl molecule is oriented toward the reagent O atom. As the Cl-O bond forms, the H atom experiences a strong repulsive force from both the O and Cl atoms. The ClO product scatters forward with respect to the initial velocity of the O atom, and the H atom scatters backward. This mechanism accounts for more than half the reactive trajectories at energies >110 kcal mol-1, but it does not involve motion near the minimum energy path, which favors an SN2-like reaction mechanism where the H atom is oriented away from the reagent O atom during the collision.

Space Survivability of Main‐Chain and Side‐Chain POSS‐Kapton Polyimides

Kapton® polyimde (PI) is extensively used in solar arrays, spacecraft thermal blankets, and space inflatable structures. Upon exposure to atomic oxygen (AO) in low Earth orbit (LEO), Kapton® is severely degraded. An effective approach to prevent this erosion is chemically bonding polyhedral oligomeric silsesquioxane (POSS) into the polyimide matrix by copolymerization of POSS‐diamine with the polyimide monomers. POSS is a silicon and oxygen cage‐like structure surrounded by organic groups and can be polymerizable. The copolymerization of POSS provides Si and O in the polymer matrix on the nano level. During POSS polyimide exposure to atomic oxygen, organic material is degraded and a silica passivation layer is formed. This silica layer protects the underlying polymer from further degradation. Ground‐based studies and MISSE‐1 and MISSE‐5 flight results have shown that POSS polyimides are resistant to atomic‐oxygen attack in LEO. In fact, 3.5 wt% Si8O11 main‐chain POSS polyimide eroded about 2 μm during the...