Strips of nickel-titanium (NiTi) shape memory alloy (SMA) and carbon fiber-reinforced polymer matrix composite (PMC) were bonded together via thin film adhesives. Tensile and lap shear tests were conducted to confirm the deformation of SMAs and to evaluate the adhesive strength between the SMA and PMC. Scanning electron microscopy (SEM) was used to examine interfacial bonding after failure. ABAQUS models were generated to show the effects of enhanced bond strength and stress distribution. Results revealed that the addition of thin film adhesives increased the average adhesive strength between SMA and PMC while halting shape memory effect within the pullout specimen.

Shape Memory Alloy (SMA) was placed within Polymer Matrix Composite (PMC) panels alongside film adhesives to examine bonding. Double cantilever beam (DCB) testing was performed using ASTM D5528. C-scanning was performed before testing, modal acoustic emissions (MAE) were monitored during testing, and microscopy performed post-test. Data was analyzed using modified beam theory (MBT), compliance calibration (CC) and modified compliance calibration (MCC) methods. Fracture toughness for control specimens was higher than previously reported due to fiber-bridging. Specimens with SMAs and adhesives stabilized crack propagation. Results revealed SMA-bridging; a phenomenon mimicking fiber-bridging which increased the load and fracture toughness of SMA specimens.

Tensile tests of Nickel-titanium (NiTi) shape memory alloys (SMA) embedded within carbon fiber reinforced polymer matrix composite (CFRP/PMC) laminates were evaluated with simultaneous monitoring of modal acoustic emissions (MAE). Three different layup configurations utilizing two different thin film adhesives were applied to bond the materials. Ultimate tensile strengths, strains, and moduli were obtained along with cumulative AE energy of events and specimen failure location. Scanning electron microscopy was used to examine the break areas of the specimens post-test. Microscopy was used to validate failure locations revealed from MAE analysis. A unique finding within this research showed that 90° plies in the outer ply gave the strongest acoustic signals as well as the cleanest fracture of the specimens tested. Overlapping 0° ply layers surrounding the SMA was found to be the best scenario to prevent failure of the specimen itself.

A novel series of ablative composites containing a hyperbranched polyazomethine synthesized inside a carbon fiber preform (HyPAZA) were prepared, which have similar density to phenolic impregnated carbon ablators (approximate to 0.3g/cc). A novel method of synthesizing strong hyperbranched polyazomethine thermosets has been developed, enabling polyazomethines to be studied in ablators for the first time. Several formulations of HyPAZA perform better than the phenolic impregnated carbon ablator in terms of polymer char yield, composite mechanical strength, CO2 laser ablation tests at heat fluxes of 550 and 1100W/cm2, and small-scale arcjet testing at a heat flux of 400W/cm2. Char yields of hyperbranched polyazomethines were as high as 79% at 1000 degrees C by thermogravimetric analysis. This is one of the highest char yields ever reported for a fully organic polymer. Some HyPAZA composites are over 10 times stronger than the carbon fiber preform, as determined by compression tests. Specimens were also tested in an arcjet facility at 400W/cm2. Several formulations exhibited better performance than the phenolic impregnated carbon ablator in terms of ablation rate by a factor of 1.2 to 1.7. In addition, HyPAZA composites impregnated with aerogel show a lower rate of increase of back wall temperature, and therefore a lower thermal conductivity.

Polyimide gels are produced by cross-linking anhydride capped polyamic acid oligomers with aromatic triamine in solution and chemically imidizing. The gels are then supercritically dried to form nanoporous polyimide aerogels with densities as low as 0.14 g/cm(3) and surface areas as high as 512 m(2)/g. To understand the effect of the polyimide backbone on properties, aerogels from several combinations of diamine and dianhydride, and formulated oligomer chain length are examined. Formulations made from 2,2'-dimethylbenzidine as the diamine shrink the least but have among the highest compressive modulus. Formulations made using 4,4'-oxydianiline or 2,2'dimethylbenzidine can be fabricated into continuous thin films using a roll to roll casting process. The films are flexible enough to be rolled or folded back on themselves and recover completely without cracking or flaking, and have tensile strengths of 4-9 MPa. Finally, the highest onset of decomposition (above 600 °C) of the polyimide aerogels was obtained using p-phenylene diamine as the backbone diamine with either dianhydride studied. All of the aerogels are suitable candidates for high-temperature insulation with glass transition temperatures ranging from 270-340 °C and onsets of decomposition from 460-610 °C.

Combinations of rigid and flexible aromatic diamines were used to tailor the properties of octa(aminophenyl)-silsesquioxane (OAPS) cross-linked polyimide aerogels. 2,2'-Dimethylbenzidine (DMBZ) or p-phenylenediamine (PPDA) was used in combination with the more-flexible diamine, 4,4'-oxydianiline (ODA). The amount of rigid diamine was varied from 0% to 100% of the total diamines in the backbone. The resulting aerogels vary in density, shrinkage, porosity, surface area, mechanical and thermal properties (depending on the type of diamine and the proportions of rigid diamine to flexible diamine used). Replacing ODA with PPDA increases shrinkage that occurs during gelation and processing, while increasing the DMBZ fraction decreases shrinkage. Replacing ODA with 50 mol % of DMBZ maintains the flexibility of thin films, while the moisture resistance of the aerogels is greatly improved.

We report the first synthesis of polyimide aerogels cross-linked through a polyhedral oligomeric silsesquioxane, octa(aminophenyl)silsesquioxane (OAPS). Gels formed from polyamic acid solutions of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), bisaniline-p-xylidene (BAX) and OAPS were chemically imidized and dried using supercritical CO(2) extraction to give aerogels having density around 0.1 g/cm(3). The aerogels are greater than 90 % porous, have high surface areas (230 to 280 m(2)/g) and low thermal conductivity (14 mW/m-K at room temperature). Notably, the polyimide aerogels cross-linked with OAPS have higher modulus than polymer reinforced silica aerogels of similar density and can be fabricated as both monoliths and thin films. Thin films of the aerogel are flexible and foldable making them an ideal insulation for space suits, and inflatable structures for habitats or decelerators for planetary re-entry, as well as more down to earth applications.

Reinforcing silica aerogels by conformally coating the nanoskeleton with a polymer has been demonstrated to be an effective way to improve mechanical properties. In addition, the mesoporosity and low thermal conductivity is maintained, making this robust form of aerogel an enabling material for a variety of aerospace applications. However, the process for making the aerogels can be quite long, involving production of the gel, solvent exchanges, and diffusion of monomer, followed by more solvent exchanges and supercritical fluid extraction. This paper for the first time compares a synthetic scheme that shortens the process to make epoxy reinforced aerogels by eliminating monomer diffusion and half of the solvent washes to the previously described diffusion-controlled process. The ethanol-soluble epoxy monomers are included in the initial step of the sol-gel process without interfering with gelation of the starting silanes. Notably, properties of aerogels made using a low amount of amine reactive sites have properties similar to those previously reported that used the longer diffusion controlled process, whereas higher amounts of amine sites produce less desirable monoliths with much higher density and lower surface areas.

Cross-linking silica aerogels with organic groups has been shown to improve the strength over un-cross-linked aerogels by as much as 2 orders of magnitude. Previous cross-linking chemistry has been developed using solvents specifically chosen to dissolve the monomers and accommodate the reaction temperature. Because the process of making the aerogels requires so much solvent, it is of interest to consider less toxic solvents such as ethanol to increase safety and enhance scale up. To this end, two different epoxy precursors with suitable solubility in ethanol were evaluated as cross-linkers for silica gels prepared from (3-aminopropyl)triethoxysilane and tetraethylorthosilicate. In addition, 1,6-bis(trimethoxysilyl)hexane (BTMSH) was used as an additive in the underlying silica structure to add flexibility to the aerogels. It was found that the ethanol-derived aerogels exhibited more shrinkage than those prepared from other solvents but that including BTMSH in the aerogels significantly reduced this shrinkage. Inclusion of BTMSH also imparted the ability of the aerogel monoliths to recover elastically when compressed up to 50% strain. In addition, optimized cross-linked aerogels prepared in this study have mechanical properties comparable to those using other more undesirable solvents and cross-linkers.

Silica aerogels are desirable materials for many applications that take advantage of their light weight and low thermal conductivity. Addition of a conformal polymer coating which bonds with the amine decorated surface of the silica network improves the strength of the aerogels by as much as 200 times. Even with vast improvement in strength they still tend to undergo brittle failure due to the rigid silica backbone. We hope to increase the flexibility and elastic recovery of the silica based aerogel by altering the silica back-bone by incorporation of more flexible hexane links. To this end, we investigated the use of 1,6-bis(trimethoxysilyl)hexane (BTMSH), a polysilsesquioxane precursor3, as an additional co-reactant to prepare silica gels which were subsequently cross-linked with di-isocyanate. Previously, this approach of adding flexibility by BTMSH incorporation was demonstrated with styrene cross-linked aerogels. In our study, we varied silane concentration, mol % of silicon from BTMSH and di-isocyanate concentration by weight percent to attempt to optimize both the flexibility and the strength of the aerogels.

Lightweight materials with excellent thermal insulating properties are highly sought after for a variety of aerospace and aeronautic applications. (1) Silica based aerogels with their high surface area and low relative densities are ideal for applications in extreme environments such as insulators for the Mars Rover battery. (2) However, the fragile nature of aerogel monoliths prevents their widespread use in more down to earth applications. We have shown that the fragile aerogel network can be cross-linked with a di-isocyanate via amine decorated surfaces to form a conformal coating. (3) This coating reinforces the neck regions between secondary silica particles and significantly strengthens the aerogels with only a small effect on density or porosity. Scheme 1 depicts the cross-linking reaction with the di-isocyanate and exhibits the stages that result in polymer cross-linked aerogel monoliths.

Organic materials are an essential part of the Advanced Stirling Convertor (ASC) construction as adhesives, potting, wire insulation, lubrication coatings, bobbins, bumpers, insulators, thread lockers. Since a long lifetime of such convertors to be used in the Advanced Stirling Radioisotope Generator (ASRG), sometimes up to 17 years, is required in various space applications such as Mars rovers, deep space missions, and lunar surface power, performance, durability and reliability of those organics should be critically evaluated in every possible material-process-fabricationservice environment relations. The objective of this study was to evaluate, validate, and recommend organics for use in ASCs. Systematic and extensive evaluation methodologies were developed and conducted for various organic materials. The overall efforts dealing with organics materials for the last several years are summarized in the key areas, e.g., process-fabrication optimization, adhesive bonding integrity, outgassing, thermal stability, and durability.

We have previously reported cross-linking the mesoporous silica structure of aerogels with di-isocyanates, styrenes or epoxies reacted with amine decorated silica surfaces. These approaches have been shown to significantly increase the strength of aerogels with only a small effect on density or porosity. Herein, we examine the effect of including up to 5% (w/w) carbon nanofibers in the silica backbone before cross-linking. The addition of 5% carbon nanofibers to the lowest density aerogels studied triples the compressive modulus and the tensile stress at break is increased five-fold with no density penalty. The carbon fiber also improves the strength of the initial hydrogels before cross-linking, which may have implications in manufacturing.