Abstract
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 SiO2 since this coating is known to impart remarkable oxidation resistance. Imperfections in the SiO2 application process and micrometeoroid / debris impact in orbit damage the SiO2 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 SiO2 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 × 1020 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 × 1020 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 × 1020 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.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
Explore related subjects
Discover the latest articles, news and stories from top researchers in related subjects.References
de Groh, K. K., Banks, B. A., “Techniques for Measuring Low Earth Orbital Atomic Oxygen Erosion of Polymers,” 2002 Symposium and Exhibition sponsored by the Society for the Advancement of Materials and Process Engineering, Long Beach, CA, May 12-16, 2002.
Koontz S. L., Leger L. J., Visentine J. T., Hunton D. E., Cross J. B., and Hakes C. L., “EOIM-III Mass Spectroscopy and Polymer Chemistry: STS 46, July - August 1992,” Journal of Spacecraft and Rockets, Vol. 32, No. 3, 1995, pp. 483–495.
de Groh, K. K., and Banks, B. A., “Automic-Oxygen Undercutting of Long Duration Exposure Facility Aluminized-Kaption Multilayer Insulation,” Journal of Spacecraft and Rockets, Vol. 31, No., 4. 1994, pp. 656–664.
Banks B. A., Rutledge S. K., de Groh K. K., Mirtich M. J., Gebauer L., Olle R., and Hill C. M., “The Implication of the LDEF Results on Space Freedom Power System Materials, “Proceedings of the 5th International Symposium on Material in a Space Environment”, Cannes-Mandelieu, France, 1991, p. 137
Tennyson R. C., “Protective Coatings for Spacecraft Materials, “Surface and Coatings Technology”, 68/69 (1994) 519–527. p.45.
Gilman J.W., Schlitzer D. S., Lichtenhan J. D., “Low Earth Orbit Resistant Siloxane Copolymers,” Journal of Applied Polymer Science, Vol. 60, p. 591–596. (1996)
Grobner J. and Kerr J. B., “Ground-Based Determination of the Spectral Ultraviolet Extraterrestrial Soalar Irradiance: Providing a Link Between Space-Based and Ground-Based Solar UV Measurements,” Journal of Grophysical Research-Atmospheres,” 2001. 106(D7): p. 7211–7217.
Mather P.T., Jeon H.G., Romo-Uribe A., Haddad T.S., and Lichtenhan J.D., “Mechanical Relaxation and Microstructure of Poly(Norbornyl- POSS) Copolymers,” Macromolecules, 1999. 32(4): p. 1194–1203.
Wright M. E., Schorzman D. A., Feher F.J., and Jin R. Z., “Synthesis and Thermal Curing of Aryl-Ethynyl-Terminated coPOSS Imide Oligomers: NewInorganic/Organic Hybrid Resins,” Chemistry of Materials. 2003, 15, 264–268
Feher F.J., Nguyen F., Soulivong D., and Ziller J.W., “A New Route to Incompletely Condensed Silsesquioxanes: Acid- Mediated Cleavage and Rearrangement of (c-C6H11)(6)Si6O9 to C-2-[(c-C6Hn)(6)Si6O8X2],” Chemical Communications, 1999(17): p. 1705–1706.
Feher F.J., Terroba R., and Ziller J.W., “A New Route to Incompletely-Condensed Silsesquioxanes: Base- Mediated Cleavage of Polyhedral Oligosilsesquioxanes,” Chemical Communications, 1999(22): p. 2309–2310.
Feher F.J., Soulivong D., and Eklund A.G., “Controlled Cleavage of R8Si8O12 Frameworks: A Revolutionary New Method for Manufacturing Precursors to Hybrid Inorganic-Organic Materials,” Chemical Communications, 1998(3): p. 399–400.
Blanski R.L., Phillips S. H., Chaffee K., Lichtenhan J. D.,, Lee A., and Geng H.P., “The Preparation and Properties of Organic/Inorganic Hybrid Materials by Blending POSS into Organic Polymers,” Polymer Preprints, 2000. 41(1): p. 585.
Amy L. Brunsvold, Timothy K. Minton, Irina Gouzman, Eitan Grossman, and Rene Gonzalez The Journal of High Performance Polymers, Special Edition, Publication, 2004, 16(2), p.303–318.
Gonzalez R. I., “Synthesis and In-Situ Atomic Oxygen Erosion Studies of Space-Survivable Hybrid Organic/Inorganic POSS Polymers,” Ph.D. Dissertation, Chem Eng Department, University of Florida, 2002. http://purl.fcla.edu/fcla/etd/UFE1000127
Gonzalez R. I., Phillips S. H., Hoflund G. B., “In Situ Oxygen-Atom Erosion Study of polyhedral oligomeric silsesquioxane-Siloxane Copolymer,” Journal of Spacecraft and Rockets, 2000, 37(4), p.463–467.
Minton T. K., and Garton D. J., “Dynamics of Atomic-Oxygen-Induced Polymer Degradation in Low-Earth Orbit,” in Advanced Series in Physical Chemistry: Chemical Dynamics in Extreme Environments, edited by R. A. Dressler (World Scientific, Singapore, 2001), pp. 420–489.
Dooling D. and Finckenor M. M., “Material Selection Guidelines to Limit Atomic Oxygen Effects on Spacecraft Surfaces, NASA/TP - 1999-209260, p.
Garton D J, Minton T K, Maiti B, Troya D, and Schatz G C 2003 Journal of Chemical Physics 1181585-8
Diego Troya and George C. Schatz, J. Chem. Phys., 120, 7696–7707 (2004).
Cornelius, C.J. and E. Marand, Polymer 2002; 43: 2385.
Mauritz, K.A. and M. Warren, Macromolecules 1989; 22: 1730.
Matos, M.C., L.M. Ilharco and R.M. Almeida J Non-Cryst Solids 1992; 147,148: 232–7.
Cowie J.M.G. Polymers: chemistry and physics of modern materials. 2nd Ed. New York, Blackie/Chapman & Hall, 1994.
Menard K.P. Dynamic Mechanical Analysis: A Practical Introduction New York: CRC Press, 1999.
Adrova, N.A., M.I. Bessonov, L.A. Laius and A.P. Rudakov Polyimides: A New Class of Heat-resistant Polymers Jerusalem: IPST Press, 1969
Acknowledgments
The authors would like to thank Mr. Scott Barker for performing the dynamic mechanical thermal testing. This work was financially supported by the Air Force Office of Scientific Research (Grant No. F49620-01-1-0276) and from the Air Force Office of Scientific Research through a Multiple University Research Initiative (Grant No. F49620-01-100335).
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Tomczak, S.J., Marchant, D., Svejda, S. et al. Properties and Improved Space Survivability of POSS (Polyhedral Oligomeric Silsesquioxane) Polyimides. MRS Online Proceedings Library 851, 487–498 (2004). https://doi.org/10.1557/PROC-851-NN9.1
Published:
Issue Date:
DOI: https://doi.org/10.1557/PROC-851-NN9.1