Self-Healing Anti-Atomic-Oxygen Phosphorus-Containing Polyimide Film via Molecular Level Incorporation of Nanocage Trisilanolphenyl POSS: Preparation and Characterization

Protection of polymeric materials from the atomic oxygen erosion in low-earth orbit spacecrafts has become one of the most important research topics in aerospace science. In the current research, a series of novel organic/inorganic nanocomposite films with excellent atomic oxygen (AO) resistance are prepared from the phosphorous-containing polyimide (FPI) matrix and trisilanolphenyl polyhedral oligomeric silsesquioxane (TSP–POSS) additive. The PI matrix derived from 2,2’-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride (6FDA) and 2,5-bis[(4-amino- phenoxy)phenyl]diphenylphosphine oxide (BADPO) itself possesses the self-healing feature in AO environment. Incorporation of TSP–POSS further enhances the AO resistance of the FPI/TSP composite films via a Si–P synergic effect. Meanwhile, the thermal stability of the pristine film is maintained. The FPI-25 composite film with a 25 wt % loading of TSP–POSS in the FPI matrix exhibits an AO erosion yield of 3.1 × 10−26 cm3/atom after an AO attack of 4.0 × 1020 atoms/cm2, which is only 5.8% and 1.0% that of pristine FPI-0 film (6FDA-BADPO) and PI-ref (PMDA-ODA) film derived from 1,2,4,5-pyromellitic anhydride (PMDA) and 4,4’-oxydianline (ODA), respectively. Inert phosphorous and silicon-containing passivation layers are observed at the surface of films during AO exposure.

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Atomic Oxygen-Resistant Polyimide Composite Films Containing Nanocaged Polyhedral Oligomeric Silsesquioxane Components in Matrix and Fillers

Nanomaterials ◽

10.3390/nano11010141 ◽

2021 ◽

Vol 11 (1) ◽

pp. 141

Author(s):

Yan Zhang ◽

Hao Wu ◽

Yi-dan Guo ◽

Yan-bin Yang ◽

Qiang Yu ◽

...

Keyword(s):

High Temperature ◽

Atomic Oxygen ◽

Composite Films ◽

Linear Thermal Expansion ◽

Polyhedral Oligomeric Silsesquioxane ◽

Low Earth Orbit ◽

Aromatic Diamine ◽

Self Healing ◽

Passivation Layers ◽

Oligomeric Silsesquioxane

For the development of spacecraft with long-servicing life in low earth orbit (LEO), high-temperature resistant polymer films with long-term atomic oxygen (AO) resistant features are highly desired. The relatively poor AO resistance of standard polyimide (PI) films greatly limited their applications in LEO spacecraft. In this work, we successfully prepared a series of novel AO resistant PI composite films containing nanocaged polyhedral oligomeric silsesquioxane (POSS) components in both the PI matrix and the fillers. The POSS-containing PI matrix film was prepared from a POSS-substituted aromatic diamine, N-[(heptaisobutyl-POSS)propyl]-3,5-diaminobenzamide (DABA-POSS) and a common aromatic diamine, 4,4′-oxydianline (ODA) and the aromatic dianhydride, pyromellitic dianhydride (PMDA) by a two-step thermal imidization procedure. The POSS-containing filler, trisilanolphenyl POSS (TSP-POSS) was added with the fixed proportion of 20 wt% in the final films. Incorporation of TSP-POSS additive apparently improved the thermal stability, but decreased the high-temperature dimensional stable nature of the PI composite films. The 5% weight loss temperature (T5%) of POSS-PI-20 with 20 wt% of DABA-POSS is 564 °C, and its coefficient of linear thermal expansion (CTE) is 81.0 × 10−6/K. The former is 16 °C lower and the latter was 20.0 × 10−6/K higher than those of the POSS-PI-10 film (T5% = 580 °C, CTE = 61.0 × 10−6/K), respectively. POSS components endowed the PI composite films excellent AO resistance and self-healing characteristics in AO environments. POSS-PI-30 exhibits the lowest AO erosion yield (Es) of 1.64 × 10−26 cm3/atom under AO exposure with a flux of 2.51 × 1021 atoms/cm2, which is more than two orders of magnitude lower than the referenced PI (PMDA-ODA) film. Inert silica or silicate passivation layers were detected on the surface of the PI composite films exposed to AO.

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Preparation and Properties of Intrinsically Atomic-Oxygen Resistant Polyimide Films Containing Polyhedral Oligomeric Silsesquioxane (POSS) in the Side Chains

Polymers ◽

10.3390/polym12122865 ◽

2020 ◽

Vol 12 (12) ◽

pp. 2865 ◽

Cited By ~ 1

Author(s):

Hao Wu ◽

Yan Zhang ◽

Yi-Dan Guo ◽

Hao-Ran Qi ◽

Yuan-Cheng An ◽

...

Keyword(s):

Atomic Oxygen ◽

Linear Thermal Expansion ◽

Polyhedral Oligomeric Silsesquioxane ◽

Tensile Modulus ◽

Low Earth Orbit ◽

Molecular Structures ◽

Polyimide Films ◽

Passivation Layers ◽

Pyromellitic Anhydride ◽

Oligomeric Silsesquioxane

The relatively poor atomic-oxygen (AO) resistance of the standard polyimide (PI) films greatly limits the wide applications in low earth orbit (LEO) environments. The introduction of polyhedral oligomeric silsesquioxane (POSS) units into the molecular structures of the PI films has been proven to be an effective procedure for enhancing the AO resistance of the PI films. In the current work, a series of POSS-substituted poly (pyromellitic anhydride-4,4′-oxydianiline) (PMDA-ODA) films (POSS-PI) with different POSS contents were synthesized via a POSS-containing diamine, N-[(heptaisobutyl-POSS)propyl]-3,5-diaminobenzamide (DABA-POSS). Subsequently, the effects of the molecular structures on the thermal, tensile, optical, and especially the AO-erosion behaviors of the POSS-PI films were investigated. The incorporation of the latent POSS substituents decreased the thermal stability and the high-temperature dimensional stability of the pristine PI-0 (PMDA-ODA) film. For instance, the PI-30 film with the DABA-POSS content of 30 wt% in the film exhibited a 5% weight loss temperature (T5%) of 512 °C and a coefficient of linear thermal expansion (CTE) of 54.6 × 10−6/K in the temperature range of 50–250 °C, respectively, which were all inferior to those of the PI-0 film (T5% = 574 °C; CTE = 28.9 × 10−6/K). In addition, the tensile properties of the POSS-containing PI films were also deteriorated, to some extent, due to the incorporation of the DABA-POSS components. The tensile strength (TS) of the POSS-PI films decreased with the order of PI-0 > PI-10 > PI-15 > PI-20 > PI-25 > PI-30, and so did the tensile modulus (TM) and the elongations at break (Eb). PI-30 showed the TS, TM, and Eb values of 75.0 MPa, 1.55 GPa, and 16.1%, respectively, which were all lower than those of the PI-0 film (TS = 131.0 MPa, TM = 1.88 GPa, Eb = 73.2%). Nevertheless, the incorporation of POSS components obviously increased the AO resistance of the PI films. All of the POSS-PI films survived from the AO exposure with the total fluence of 2.16 × 1021 atoms/cm2, while PI-0 was totally eroded under the same circumstance. The PI-30 film showed an AO erosion yield (Es) of 1.1 × 10−25 cm3/atom, which was approximately 3.67% of the PI-0 film (Es = 3.0 × 10−24 cm3/atom). Inert silica or silicate passivation layers were detected on the surface of the POSS-PI films after AO exposure, which efficiently prevented the further erosion of the under-layer materials.

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Preparation and Characterization of Transparent Polyimide Nanocomposite Films with Potential Applications as Spacecraft Antenna Substrates with Low Dielectric Features and Good Sustainability in Atomic-Oxygen Environments

Nanomaterials ◽

10.3390/nano11081886 ◽

2021 ◽

Vol 11 (8) ◽

pp. 1886

Author(s):

Yan Zhang ◽

Bo-han Wu ◽

Han-li Wang ◽

Hao Wu ◽

Yuan-cheng An ◽

...

Keyword(s):

Atomic Oxygen ◽

Composite Films ◽

Dissipation Factor ◽

Low Earth Orbit ◽

Nanocomposite Films ◽

Dielectric Parameters ◽

Low Dielectric ◽

Aerospace Applications ◽

Optically Transparent ◽

Order Of Magnitude

Optically transparent polyimide (PI) films with good dielectric properties and long-term sustainability in atomic-oxygen (AO) environments have been highly desired as antenna substrates in low earth orbit (LEO) aerospace applications. However, PI substrates with low dielectric constant (low-Dk), low dielectric dissipation factor (low-Df) and high AO resistance have rarely been reported due to the difficulties in achieving both high AO survivability and good dielectric parameters simultaneously. In the present work, an intrinsically low-Dk and low-Df optically transparent PI film matrix, poly[4,4′-(hexafluoroisopropylidene)diphthalic anhydride-co-2,2-bis(4-(4-aminophenoxy)phenyl)hexafluoropropane] (6FPI) was combined with a nanocage trisilanolphenyl polyhedral oligomeric silsesquioxane (TSP-POSS) additive in order to afford novel organic–inorganic nanocomposite films with enhanced AO-resistant properties and reduced dielectric parameters. The derived 6FPI/POSS films exhibited the Dk and Df values as low as 2.52 and 0.006 at the frequency of 1 MHz, respectively. Meanwhile, the composite films showed good AO resistance with the erosion yield as low as 4.0 × 10−25 cm3/atom at the exposure flux of 4.02 × 1020 atom/cm2, which decreased by nearly one order of magnitude compared with the value of 3.0 × 10−24 cm3/atom of the standard PI-ref Kapton® film.

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Property changes in materials due to atomic oxygen in the low Earth orbit

CEAS Space Journal ◽

10.1007/s12567-021-00376-2 ◽

2021 ◽

Author(s):

Aki Goto ◽

Kaori Umeda ◽

Kazuki Yukumatsu ◽

Yugo Kimoto

Keyword(s):

Photoelectron Spectroscopy ◽

Atomic Oxygen ◽

Surface Reactions ◽

Ccd Camera ◽

Polymeric Materials ◽

Thermal Control ◽

Polyimide Film ◽

Low Earth Orbit ◽

Earth Orbit ◽

Exposure Experiment

AbstractWe expect satellites at altitude below 300 km, very low Earth orbit (VLEO), making observations of the Earth at optical wavelength with increasingly higher resolution. The density of atomic oxygen (AO) at VLEO is significantly higher than that at LEO; severe degradation of spacecraft materials (polymers) due to the high-flux AO is a serious concern. To clarify VLEO environmental effects on spacecraft materials, we designed the Material Degradation Monitor (MDM) and MDM2 missions. The MDM is a material exposure experiment onboard the Super Low-Altitude Test Satellite (SLATS). It aims to understand reactions and degradation of polymeric materials depending on AO fluence in VLEO. In the MDM, samples of spacecraft material were exposed at altitude of 160–560 km; their degradation behaviors were observed optically by a CCD camera for 1.8 years. The MDM2 is a material exposure experiment onboard the International Space Station (ISS) and aims to correctly understand surface reactions and degradation of the same samples used in the MDM at a given AO fluence. In the MDM2, the samples were exposed at altitude of 400 km for 1 year and then returned to Earth for analysis. Based on the results from both missions, we will help in the molecular design of more-durable materials, and establish design standards for future VLEO satellites. This study aims to quantitatively understand the surface reactions and degradation of the 11 types of thermal control materials exposed on the ISS in the MDM2. Five types of multilayer insulation (MLI) films (three types of Si-containing AO protective materials (a silsesquioxane-(SQ-) containing coated polyimide film, two types of polysiloxane-block polyimide (BSF-30) films), an ITO-coated polyimide film, and a Beta Cloth), and flexible optical solar reflectors (flexible OSRs) were found to have a high durability against erosion by AO. This was determined by measuring their loss of mass and thermo-optical properties. The Ag/Inconel layer’s discoloration and peeling were observed for three types of FEP/Ag films as determined by the Ag layer’s oxidation by AO. Also, X-ray photoelectron spectroscopy (XPS) showed that reactions of the Si-containing materials, the SQ-coated polyimide film and the BSF-30 film, form a layer of silica that protects against AO. Even though the concentration of Si in the SQ-coating is the same or greater than in the BSF-30 film, the amount of the SQ-coating that reacted was larger than that of the BSF-30 film under the same AO fluence. Moreover, the effective ability of the UV-shielding coating, composed of ITO and CeO2 coated onto one of the BSF-30 films, was demonstrated by UV–Vis spectrometry. Its sufficient AO protection was confirmed by mass measurements, XPS analyses, and FE-SEM observations.

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Atomic oxygen effects on polymers containing silicon or phosphorus: Mass loss, erosion yield, and surface morphology

High Performance Polymers ◽

10.1177/0954008318814150 ◽

2018 ◽

Vol 31 (8) ◽

pp. 969-976 ◽

Cited By ~ 6

Author(s):

Wang Chunbo ◽

Jiang Haifu ◽

Tian Dongbo ◽

Qin Wei ◽

Chen Chunhai ◽

...

Keyword(s):

Surface Morphology ◽

Mass Loss ◽

Atomic Oxygen ◽

Low Earth Orbit ◽

Relative Order ◽

Oxygen Effects ◽

Arylene Ether ◽

Inorganic Coatings ◽

Oligomeric Silsesquioxane ◽

Surface Morphologies

The differences among polymers containing silicon or phosphorus, 20% polyhedral oligomeric silsesquioxane polyimide (20%-POSS-PI), 30% polysiloxane- block-polyimides (30%-PSX-PI), poly(siloxane imide) homopolymer (PSX-PI), and arylene ether phosphine oxide homopolymer (P-PPO), on mass loss, erosion yield, and surface morphology were elucidated. The tolerance against atomic oxygen (AO) was improved versus Kapton®H after introducing silicon or phosphorus to the polymers. The relative order of the mass loss was PSX-PI < P-PPO < 20%-POSS-PI < 30%-PSX-PI. In contrast, the erosion yields of 30%-PSX-PI, 20%-POSS-PI, and P-PPO decreased by orders of magnitude (PSX-PI declined by about two orders). The surface of Kapton®H was seriously eroded by AO exhibiting a “carpet-like” shape, and the roughness of the surface of Kapton®H became remarkable as the AO fluence increased. PSX-PI, P-PPO, 20%-POSS-PI, and 30%-PSX-PI at an AO fluence of 5.2 × 1020 atoms/cm2 had different surface morphologies, and the relative order of the surface roughness was PSX-PI < 30%-PSX-PI < 20%-POSS-PI < P-PPO. The 30%-PSX-PI and PSX-PI had minor mass losses and a smooth surface. This kind of material might replace inorganic coatings for applications in low earth orbit.

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Polymer-Single Wall Carbon Nanotube Composites for Potential Spacecraft Applications

MRS Proceedings ◽

10.1557/proc-706-z3.30.1 ◽

2001 ◽

Vol 706 ◽

Cited By ~ 17

Author(s):

Cheol Park ◽

Zoubeida Ounaies ◽

Kent A. Watson ◽

Kristin Pawlowski ◽

Sharon E. Lowther ◽

...

Keyword(s):

Electrical Conductivity ◽

Carbon Nanotube ◽

Composite Films ◽

Polymeric Materials ◽

Polymer Nanocomposite ◽

Weight Percent ◽

Nanocomposite Films ◽

Mechanical And Thermal Properties ◽

Single Wall Carbon Nanotube ◽

Single Wall Carbon

AbstractPolymer-single wall carbon nanotube (SWNT) composite films were prepared and characterized as part of an effort to develop polymeric materials with improved combinations of properties for potential use on future spacecraft. Next generation spacecraft will require ultra-lightweight materials that possess specific and unique combinations of properties such as radiation and atomic oxygen resistance, low solar absorptivity, high thermal emissitivity, electrical conductivity, tear resistance, ability to be folded and seamed, and good mechanical properties. The objective of this work is to incorporate sufficient electrical conductivity into space durable polyimides to mitigate static charge build-up. The challenge is to obtain this level of conductivity (10-8 S/cm) without degrading other properties of importance, particularly optical transparency. Several different approaches were attempted to fully disperse the SWNTs into the polymer matrix. These included high shear mixing, sonication, and synthesizing the polymers in the presence of pre-dispersed SWNTs. Acceptable levels of conductivity were obtained at loading levels less than one tenth weight percent SWNT without significantly sacrificing optical properties. Characterization of the nanocomposite films and the effect of SWNT concentration and dispersion on the conductivity, solar absorptivity, thermal emissivity, mechanical and thermal properties were discussed. Fibers and non-woven porous mats of SWNT reinforced polymer nanocomposite were produced using electrospinning.

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Nonlinear Phenomena in the Mass Loss of Polyimide Films under Hyperthermal Atomic Oxygen Beam Exposure

High Performance Polymers ◽

10.1088/0954-0083/13/4/301 ◽

2001 ◽

Vol 13 (4) ◽

pp. 225-234 ◽

Cited By ~ 23

Author(s):

Hiroshi Kinoshita ◽

Masahito Tagawa ◽

Kumiko Yokota ◽

Nobuo Ohmae

Keyword(s):

Mass Loss ◽

Atomic Oxygen ◽

Large Fraction ◽

Orbit Space ◽

Mass Gain ◽

Polyimide Film ◽

Low Earth Orbit ◽

Space Environment ◽

Nonlinear Phenomena ◽

Abstraction Reaction

Erosion phenomenon of polyimide film under the hyperthermal atomic oxygen beam exposure, which is a simulated low Earth orbit space environment, has been investigated. The polyimide film was spin-coated on a sensor crystal of a quartz crystal microbalance, and the mass of the film was measured under the atomic oxygen beam exposure. The spin-coated polyimide film which was exposed to a 4.7 eV atomic oxygen beam showed a mass gain at the beginning of the reaction and then steady-state mass loss followed. The experimental results of the mass change was analysed by the computational model, and the results showed that the carbon abstraction rate at the oxygen-adsorbed sites was two orders higher than that at the unoxidized polyimide surface. The computational results suggested that a large fraction of the carbon abstraction reaction occurred in the oxygen-adsorbed site through a Langmuir–Hinshelwood reaction mechanism.

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Monte Carlo Modeling of Atomic Oxygen Interaction with Protected Polymers for Projection of Materials Durability in Low Earth Orbit

MRS Proceedings ◽

10.1557/proc-278-41 ◽

1992 ◽

Vol 278 ◽

Cited By ~ 3

Author(s):

Bruce A. Banks ◽

Bruce M. Auer ◽

Sharon K. Rutledge ◽

Linda Gebauer ◽

Edward A. Sechkar

Keyword(s):

Monte Carlo ◽

Atomic Oxygen ◽

Protective Coatings ◽

Polymeric Materials ◽

Low Earth Orbit ◽

Earth Orbit ◽

Textured Surfaces ◽

Photovoltaic Array ◽

Defect Sites ◽

Oxygen Interaction

AbstractAtomic oxygen in low Earth orbit (LEO) readily attacks and oxidizes exposed spacecraft polymeric materials such as polyimide Kapton photovoltaic array blankets. The application of thin film silicon dioxide protective coatings can greatly extend the useful life of such materials in LEO. A Monte Carlo computational model has been developed which simulates atomic oxygen interaction with polymeric and protective coating materials for both ground laboratory and in-space experiments, allowing the determination of the geometrical shape of atomic oxygen attack of protected polymeric materials at defect sites in protective coatings. Modeling of attack of unprotected carbon-carbon composite materials predicts textured surfaces suitable for high emittance radiators. Results for fiberglass composites indicate loss of the matrix polymer leading to friable fibers. The computational modeling to project in-space performance based on ground laboratory testing predicts mass loss per fluence in space to be approximately one third that observed in plasma ashers.

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Improved atomic oxygen erosion resistance of the carbon fibre–epoxy interface with polyhedral oligomeric silsesquioxane

High Performance Polymers ◽

10.1177/0954008319896828 ◽

2020 ◽

Vol 32 (6) ◽

pp. 681-692 ◽

Cited By ~ 1

Author(s):

Dan Zhao ◽

Jinmei He ◽

Nan Zheng ◽

Yudong Huang

Keyword(s):

Carbon Fibre ◽

Photoelectron Spectroscopy ◽

Atomic Oxygen ◽

Erosion Resistance ◽

Polyhedral Oligomeric Silsesquioxane ◽

Low Earth Orbit ◽

Siloxane Oligomers ◽

Interlaminar Shear ◽

Oligomeric Silsesquioxane ◽

Atomic Oxygen Erosion

Polyhedral oligomeric silsesquioxane (POSS) was grafted onto the surface of carbon fibres (CFs) to fabricate carbon fibre/epoxy (CF/EP) composites with improved interlaminar shear strength (ILSS) and atomic oxygen (AO) erosion resistance. POSS-CF was prepared by reacting amine groups on the pretreated CF surface with the POSS to form a continuous uniform layer of siloxane oligomers. X-Ray photoelectron spectroscopy, scanning electron microscopy and Fourier transform infrared spectroscopy demonstrated that POSS was successfully grafted onto the CF surface. The ILSS and AO erosion resistance of the POSS-treated CFs and CF-EP interface were improved because a SiO2 passivation layer formed with AO exposure, especially with POSS-EP0409. This is an effective solution for enhancing the interfacial bonding force and interfacial AO erosion resistance for the low-Earth orbit environment.

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Silver nanowire loaded self-healing EVA films

Journal of Thermoplastic Composite Materials ◽

10.1177/0892705720962165 ◽

2020 ◽

pp. 089270572096216

Author(s):

Ayse Sezer Hicyilmaz ◽

Ayse Celik Bedeloglu

Keyword(s):

Healing Process ◽

Composite Films ◽

Ethylene Vinyl Acetate ◽

Nucleating Agent ◽

Optical Microscope ◽

Mechanical Tests ◽

Healing Time ◽

Silver Nanowire ◽

Nanocomposite Films ◽

Self Healing

In this study, ethylene vinyl acetate (EVA) transparent nanocomposite films, which heal easily with the inclusion of a low amount of silver nanowire (AgNw), were produced. For this purpose, first AgNw was homogeneously dispersed in the polymer solution and then, nanocomposite films were produced from the solutions by casting method. The thermal, mechanical and optical properties of the produced films were characterized. Self-healing properties of nanocomposite films were confirmed by optical microscopy and mechanical tests. Optical microscope results showed that the optimum recovery temperature was 130°C and the addition of a small amount (5% w/w) of AgNw reduced the recovery time of the scratch on EVA film reducing the healing time by 66.66% (from 15 minutes to 5 minutes). In addition, tensile test results supported the optical microscope results. DSC results showed that the regular crystal regions were formed in composite films due to the high thermal conductivity and nucleating agent effect of AgNw. On the other hand, DSC curves proved that the healing process was occurred via re-entanglement of the polymer chains by heat effect, while silver nanowire addition did not affect the mechanical strength and transparency of the films, significantly. AgNw-loaded-EVA-based self-healing transparent films can be used for applications such as tempered glass laminates, electrical cables, coatings, packages, especially to protect the product and reduce the cost of repair.

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