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Carbon Nanotube – Polysiloxane Nanocomposites for Ablative Thermal Protection Systems

Ultra-high temperature resins (UHTR) such as polysiloxane possess excellent characteristics for ablation including low thermal conductivity, lightweight composition, high thermal resistance, and the ability to form a durable char layer. To enhance its mechanical strength, the aerospace industry utilizes fiber reinforcement, such as carbon fiber reinforced polysiloxane (CF-polysiloxane), due to its high strength-to-weight ratio. Carbon nanotubes (CNTs) have advantages over microfibers including higher specific strength, lower density, and customizable thermal conductivity. Their nano-scale dimensions allow for a more homogenous material compared to traditional microfibers. Conventional methods of incorporating CNTs into resins often have structural defects such as voids, CNT agglomerations, and randomly dispersed CNTs, resulting in marginal improvements in properties. A novel approach known as bulk nanocomposite laminating (BNL) has been introduced involving CNT densification, resin polymer infiltration, and pressurized curing to achieve a high packing density exceeding 35% by volume. Characterization and testing to simulate re-entry conditions is performed with a sample of CNT-polysiloxane nanocomposite cured onto a CF-polysiloxane backing. These samples are subjected to ablation by an oxyacetylene flame while collecting temperature data to evaluate thermal protection properties.

Palak B Patel↗

Surface characterization of LDEF materials

The NASA Long Duration Exposure Facility (LDEF), a passive experimental satellite, was placed into low-Earth orbit by the Shuttle Challenger in Apr. 1984. The LDEF spent an unprecedented 69 months in space. The flight and recovery of the LDEF provided a wealth of information on the longterm space environmental effects of a variety of materials exposed to the low-Earth orbit environment. Surface characterization of LDEF materials included polymers, composites, thermal control paints, and aluminum. X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES), scanning electron microscopy (SEM), and contact angle analysis were used to document changes in both the surface composition and surface chemistry of these materials. Detailed XPS analysis of the polymer systems, such as Kapton, polyimide polysiloxane copolymers, and fluorinated ethylene propylene thermal blankets on the backside of the LDEF revealed significant changes in both the surface composition and surface chemistry as a result of exposure to the low-Earth orbit environment. Polymer systems such as Kapton, polyimide polysiloxane copolymers, and polysulfone showed a common trend of decreasing carbon content and increasing oxygen content with respect to the control sample. Carbon 1s curve fit XPS analysis of the composite samples, in conjunction with SEM photomicrographs, revealed significant ablation of the polymer matrix resin to expose the carbon fibers of the composite during exposure to the space environment. Surface characterization of anodized aluminum tray clamps, which were located at regular intervals over the entire LDEF frame, provided the first results to evaluate the extent of contamination with respect to position on the LDEF. The XPS results clearly showed that the amount and state of both silicon and fluorine contamination were directly dependent upon the position of the tray clamp on the LDEF.

Wightman, J. P.↗

Processing and Characterization of Basalt Fiber Reinforced Ceramic Composites for High Temperature Applications Using Polymer Precursors

The development of high temperature structural composite materials has been very limited due to the high cost of the materials and the processing needed. Polymer Derived Ceramics (PDCs) begin as a polymer matrix, which allows a shape to be formed prior to the cure, and is then pyrolized in order to obtain a ceramic with the associated thermal and mechanical properties. The two PDCs used in this development are polysiloxane and polycarbosilane. Basalt fibers are used for the reinforcement in the composite system. The use of basalt in structural and high temperature applications has been under development for over 50 years, yet there has been little published research on the incorporation of basalt fibers as a reinforcement in composites. Continuous basalt fiber reinforced PDCs have been fabricated and tested for the applicability of this composite system as a high temperature structural composite material.

High Temperature Composites↗

Tailoring Silicon Oxycarbide Glasses for Oxidative Stability

Blackglas(Trademark) polysiloxane systems produce silicon oxycarbide glasses by pyrolysis in inert atmosphere. The silicon oxycarbides evidence oxidative degradation that limits their lifetime as composite matrices. The present study characterizes bonding rearrangements in the oxycarbide network accompanying increases in pyrolysis temperature. It also addresses the changes in susceptibility to oxidation due to variations in the distribution of Si bonded species obtained under different processing conditions. The study is carried out using Si-29 nuclear magnetic resonance (NMR) spectroscopy and a design of experiments approach to model the oxidation behavior. The NMR results are compared with those obtained by thermogravimetric analysis (TGA). Samples pyrolyzed under inert conditions are compared to those pyrolyzed in reactive ammonia environments.

Hurwitz, F. I.↗

Poly(aryl ethers) and related polysiloxane copolymer molecular coatings: Preparation and radiation degradation

The radiation degradation of poly(arylene ether sulfones) and related materials is studied. These basic studies are important both as a means to developing stronger, more stable matrix resins for composite materials, as well as to improve the data base in regard to chemical structure-physical property relationships. Thirty homo and copolymers were synthesized, at least partially characterized and, in several cases suitable film casting techniques were developed. Four samples were chosen for initial radiation degradation. Poly(dimethyl siloxane) soft bocks/segments can preferentially migrate to the surface of copolymer films. Since siloxanes are utilized as thermal control coatings, this form of 'molecular' coating is of interest. The chemistry for preparing such copolymers with any of the polymers described was demonstrated.

Mcgrath, J. E.↗

Processing and Characterization of Basalt Fiber Reinforced Ceramic Composites for High Temperature Applications Using Polymer Precursors

The development of high temperature structural composite materials has been very limited due to the high cost of the materials and the processing needed. Ceramics can take much higher temperatures, but they are difficult to produce and form in bulk volumes. Polymer Derived Ceramics (PDCs) begin as a polymer matrix, allowing a shape to be formed, to be cured, and be pyrolized in order to obtain a ceramic with the associated thermal and mechanical properties. The two PDCs used in this development are polysiloxane and polycarbosilane. Polysiloxanes contain a silicon oxycarbide backbone when pyrolized up to 1000degC. Polycarbosilane, an organosilicon polymer, contain a silicon-carbon backbone; around 1200degC, -SiC begins to crystallize. The use of basalt in structural and high temperature applications has been under development for over 50 years, yet there has been little published research on the incorporation of basalt fibers as a reinforcement in composites. Basalt is a naturally occurring material found in volcanic rock. Continuous basalt fiber reinforced PDCs have been fabricated and tested for the applicability of this composite system as a high temperature structural composite material. Testing for this included thermal and mechanical testing per ASTM standard tests.

High Temperature Composites↗

Processing and Characterization of Basalt Fiber Reinforced Ceramic Composites for High Temperature Applications Using Polymer Precursors

The development of high temperature structural composite materials has been very limited due to the high cost of the materials and the processing needed. Ceramics can take much higher temperatures, but they are difficult to produce and form in bulk volumes. Polymer Derived Ceramics (PDCs) begin as a polymer matrix, allowing a shape to be formed and cured and then to be pyrolized in order to obtain a ceramic with the associated thermal and mechanical properties. The two PDCs used in this development are polysiloxane and polycarbosilane. Polysiloxanes contain a silicon oxycarbide backbone when pyrolized up to 1000C. Polycarbosilane, an organosilicon polymer, contain a silicon-carbon backbone; around 1200C, beta-SiC begins to crystallize. The use of basalt in structural and high temperature applications has been under development for over 50 years, yet there has been little published research on the incorporation of basalt fibers as a reinforcement in composites. Basalt is a naturally occurring material found in volcanic rock. Continuous basalt fiber reinforced PDCs have been fabricated and tested for the applicability of this composite system as a high temperature structural composite material. Thermal and mechanical testing includes oxyacetylene torch testing and three point bend testing.

Ceramic Matrix Composites↗

Processing and Characterization of Basalt Fiber Reinforced Ceramic Composites for High Temperature Applications Using Polymer Precursors

The development of high temperature structural composite materials has been very limited due to the high cost of the materials and the processing needed. Ceramics can take much higher temperatures, but they are difficult to produce and form in bulk volumes. Polymer Derived Ceramics (PDCs) begin as a polymer matrix, allowing a shape to be formed and cured and then to be pyrolized in order to obtain a ceramic with the associated thermal and mechanical properties. The two PDCs used in this development are polysiloxane and polycarbosilane. Polysiloxanes contain a silicon oxycarbide backbone when pyrolized up to 1000 deg C. Polycarbosilane, an organosilicon polymer, contain a silicon-carbon backbone; around 1200 deg C, Beta-SiC begins to crystallize. The use of basalt in structural and high temperature applications has been under development for over 50 years, yet there has been little published research on the incorporation of basalt fibers as a reinforcement in composites. Basalt is a naturally occurring material found in volcanic rock. Continuous basalt fiber reinforced PDCs have been fabricated and tested for the applicability of this composite system as a high temperature structural composite material. Thermal and mechanical testing includes oxyacetylene torch testing and three point bend testing.

Polymer Derived Ceramics↗

Atomic Oxygen Durability Evaluation of a UV Curable Ceramer Protective Coating

The exposure of most silicones to atomic oxygen in low Earth orbit (LEO) results in the oxidative loss of methyl groups with a gradual conversion to oxides of silicon. Typically there is surface shrinkage of oxidized silicone protective coatings which leads to cracking of the partially oxidized brittle surface. Such cracks widen and branch crack with continued atomic oxygen exposure ultimately allowing atomic oxygen to reach any hydrocarbon polymers under the silicone coating. A need exists for a paintable silicone coating that is free from such surface cracking and can be effectively used for protection of polymers and composites in LEO. A new type of silicone based protective coating holding such potential was evaluated for atomic oxygen durability in an RF atomic oxygen plasma exposure facility. The coating consisted of a UV curable inorganic/organic hybrid coating, known as a ceramer, which was fabricated using a methyl substituted polysiloxane binder and nanophase silicon-oxo-clusters derived from sol-gel precursors. The polysiloxane was functionalized with a cycloaliphatic epoxide in order to be cured at ambient temperature via a cationic UV induced curing mechanism. Alkoxy silane groups were also grafted onto the polysiloxane chain, through hydrosilation, in order to form a network with the incorporated silicon-oxo-clusters. The prepared polymer was characterized by H-1 and Si-29 NMR, FT-IR, and electrospray ionization mass spectroscopy. The paper will present the results of atomic oxygen protection ability of thin ceramer coatings on Kapton H as evaluated over a range of atomic oxygen fluence levels.

Banks, Bruce A.↗