Influence of POSS Type on the Space Environment Durability of Epoxy-POSS Nanocomposites.

In order to use polymers at low Earth orbit (LEO) environment, they must be protected against atomic oxygen (AO) erosion. A promising protection strategy is to incorporate polyhedral oligomeric silsesquioxane (POSS) molecules into the polymer backbone. In this study, the space durability of epoxy-POSS (EPOSS) nanocomposites was investigated. Two types of POSS molecules were incorporated separately-amine-based and epoxy-based. The outgassing properties of the EPOSS, in terms of total mass loss, collected volatile condensable material, and water vapor regain were measured as a function of POSS type and content. The AO durability was studied using a ground-based AO simulation system. Surface compositions of EPOSS were studied using high-resolution scanning electron microscopy and X-ray photoelectron spectroscopy. It was found that with respect to the outgassing properties, only some of the EPOSS compositions were suitable for the ultrahigh vacuum space environment, and that the POSS type and content had a strong effect on their outgassing properties. Regardless of the POSS type being used, the AO durability improved significantly. This improvement is attributed to the formation of a self-passivated AO durable SiO2 layer, and demonstrates the potential use of EPOSS as a qualified nanocomposite for space applications.

The Effect of POSS Type on the Shape Memory Properties of Epoxy-Based Nanocomposites.

Thermally activated shape memory polymers (SMPs) can memorize a temporary shape at low temperature and return to their permanent shape at higher temperature. These materials can be used for light and compact space deployment mechanisms. The control of transition temperature and thermomechanical properties of epoxy-based SMPs can be done using functionalized polyhedral oligomeric silsesquioxane (POSS) additives, which are also known to improve the durability to atomic oxygen in the space environment. In this study, the influence of varying amounts of two types of POSS added to epoxy-based SMPs on the shape memory effect (SME) were studied. The first type contained amine groups, whereas the second type contained epoxide groups. The curing conditions were defined using differential scanning calorimetry and glass transition temperature (Tg) measurements. Thermomechanical and SME properties were characterized using dynamic mechanical analysis. It was found that SMPs containing amine-based POSS show higher Tg, better shape fixity and faster recovery speed, while SMPs containing epoxide-based POSS have higher crosslinking density and show superior thermomechanical properties above Tg. This work demonstrates how the Tg and SME of SMPs can be controlled by the type and amount of POSS in an epoxy-based SMP nanocomposite for future space applications.

Advances in Polyimide-Based Materials for Space Applications.

The space environment raises many challenges for new materials development and ground characterization. These environmental hazards in space include solar radiation, energetic particles, vacuum, micrometeoroids and debris, and space plasma. In low Earth orbits, there is also a significant concentration of highly reactive atomic oxygen (AO). This Progress Report focuses on the development of space-durable polyimide (PI)-based materials and nanocomposites and their testing under simulated space environment. Commercial PIs suffer from AO-induced erosion and surface electric charging. Modified PIs and PI-based nanocomposites are developed and tested to resist degradation in space. The durability of PIs in AO is successfully increased by addition of polyhedral oligomeric silsesquioxane. Conductive materials are prepared based on composites of PI and either carbon nanotube (CNT) sheets or 3D-graphene structures. 3D PI structures, which can expand PI space applications, made by either additive manufacturing (AM) or thermoforming, are presented. The selection of AM-processable engineering polymers in general, and PIs in particular, is relatively limited. Here, innovative preliminary results of a PI-based material processed by the PolyJet technology are presented.

3D Graphene-Infused Polyimide with Enhanced Electrothermal Performance for Long-Term Flexible Space Applications.

Polyimides (PIs) have been praised for their high thermal stability, high modulus of elasticity and tensile strength, ease of fabrication, and moldability. They are currently the standard choice for both substrates for flexible electronics and space shielding, as they render high temperature and UV stability and toughness. However, their poor thermal conductivity and completely electrically insulating characteristics have caused other limitations, such as thermal management challenges for flexible high-power electronics and spacecraft electrostatic charging. In order to target these issues, a hybrid of PI with 3D-graphene (3D-C), 3D-C/PI, is developed here. This composite renders extraordinary enhancements of thermal conductivity (one order of magnitude) and electrical conductivity (10 orders of magnitude). It withstands and keeps a stable performance throughout various bending and thermal cycles, as well as the oxidative and aggressive environment of ground-based, simulated space environments. This makes this new hybrid film a suitable material for flexible space applications.

Atomic-Oxygen-Durable and Electrically-Conductive CNT-POSS-Polyimide Flexible Films for Space Applications.

In low Earth orbit (LEO), hazards such as atomic oxygen (AO) or electrostatic discharge (ESD) degrade polymeric materials, specifically, the extensively used polyimide (PI) Kapton. We prepared PI-based nanocomposite films that show both AO durability and ESD protection by incorporating polyhedral oligomeric silsesquioxane (POSS) and carbon nanotube (CNT) additives. The unique methods that are reported prevent CNT agglomeration and degradation of the CNT properties that are common in dispersion-based processes. The influence of the POSS content on the electrical, mechanical, and thermo-optical properties of the CNT-POSS-PI films was investigated and compared to those of control PI and CNT-PI films. CNT-POSS-PI films with 5 and 15 wt % POSS content exhibited sheet resistivities as low as 200 Ω/□, and these resistivities remained essentially unchanged after exposure to AO with a fluence of ∼2.3 × 10(20) O atoms cm(-2). CNT-POSS-PI films with 15 wt % POSS content exhibited an erosion yield of 4.8 × 10(-25) cm(3) O atom(-1) under 2.3 × 10(20) O atoms cm(-2) AO fluence, roughly one order of magnitude lower than that of pure PI films. The durability of the conductivity of the composite films was demonstrated by rolling film samples with a tight radius up to 300 times. The stability of the films to thermal cycling and ionizing radiation was also demonstrated. These properties make the prepared CNT-POSS-PI films with 15 wt % POSS content excellent candidates for applications where AO durability and electrical conductivity are required for flexible and thermally stable materials. Hence, they are suggested here for LEO applications such as the outer layers of spacecraft thermal blankets.

Liquid phase deposition of a space-durable, antistatic SnO2 coating on Kapton.

Polyimides are widely used in thermal blankets covering the external surfaces of spacecrafts due to their space durability and their thermo-optical properties. However, they are susceptible to atomic oxygen (AO) erosion, the main hazard of low Earth orbit (LEO), and to electrical charging. This work demonstrates that liquid phase deposition (LPD) of 100 nm of tin oxide creates a protective coating on Kapton polyimide that has good adherence and is effective in preventing AO-induced surface erosion and in reducing electrical charging. The as-deposited tin oxide induces no significant changes in the original thermo-optical properties of the polymer and is effective in preventing electrostatic discharge (ESD). The durability of the oxide coating under AO attack was studied using oxygen RF plasma. The AO exposure did not result in any significant changes in surface morphology, thermo-optical, mechanical, and electrical properties of the tin oxide-coated Kapton. The erosion yield of tin oxide-coated Kapton was negligible after exposure to 6.4 × 10(20) O atoms·cm(-2) of LEO equivalent AO fluence, indicating a complete protection of Kapton by the LPD deposited coating. Moreover, the tin oxide coating is flexible enough so that its electrical conductivity stays within the desired range of antistatic materials despite mechanical manipulations. The advantages of liquid phase deposited oxides in terms of their not being line of site limited are well established. We now extend these advantages to coatings that reduce electrostatic discharge while still providing a high level of protection from AO erosion.

Reinforced carbon nanotubes as electrically conducting and flexible films for space applications.

Chemical vapor deposition (CVD)-grown entangled carbon nanotube (CNT) sheets are characterized by high electrical conductivity and durability to bending and folding. However, since freestanding CNT sheets are mechanically weak, they cannot be used as stand-alone flexible films. In this work, polyimide (PI) infiltration into entangled cup-stacked CNT (CSCNT) sheets was studied to form electrically conducting, robust, and flexible films for space applications. The infiltration process preserved CNTs' advantageous properties (i.e., conductivity and flexibility), prevented CNT agglomeration, and enabled CNT patterning. In particular, the CNT-PI films exhibited ohmic electrical conductance in both the lateral and vertical directions, with a sheet resistivity as low as 122 Ω/□, similar to that of as-grown CNT sheets, with minimal effect of the insulating matrix. Moreover, this high conductivity was preserved under mechanical and thermal manipulations. These properties make the reported CNT-PI films excellent candidates for applications where flexibility, thermal stability, and electrical conductivity are required. Particularly, the developed CNT-PI films were found to be durable in space environment hazards such as high vacuum, thermal cycling, and ionizing radiation, and hence they are suggested as an alternative for the electrostatic discharge (ESD) protection layer in spacecraft thermal blankets.

Transfer doping of single isolated nanodiamonds, studied by scanning probe microscopy techniques.

The transfer doping of diamond surfaces has been applied in various novel two-dimensional electronic devices. Its extension to nanodiamonds (ND) is essential for ND-based applications in many fields. In particular, understanding the influence of the crystallite size on transfer doping is desirable. Here, we report the results of a detailed study of the electronic energetic band structure of single, isolated transfer-doped nanodiamonds with nanometric resolution using a combination of scanning tunneling spectroscopy and Kelvin force microscopy measurements. The results show how the band gap, the valence band maximum, the electron affinity and the work function all depend on the ND's size and nanoparticle surface properties. The present analysis, which combines information from both scanning tunneling spectroscopy and Kelvin force microscopy, should be applicable to any nanoparticle or surface that can be measured with scanning probe techniques.