ALBERT

Description: Polyimide-silica hybrids composed of an organic precursor containing a novel phenylethynyl imide silane and an inorganic precursor were evaluated as an adhesion-promoting interphase between surface-treated titanium alloy and a phenylethynyl-containing imide adhesive. The phenylethynyl groups present in the organic precursor, either as a pendent or end group, can bond chemically with a phenylethynyl-containing imide adhesive during processing, while the silane groups of the organic precursor would react chemically with the inorganic precursor. In addition, the inorganic precursor is able to react with the titanium alloy to form a stable bond with the metal oxide. Bond strength and durability were evaluated by single lap shear tests at various conditions. Lap shear specimens exhibited predominantly cohesive failure after a 3-d water boil with 92% retention of the initial room temperature strength. Morphology and chemical composition of the hybrid interphase were investigated with scanning electron microscopy, X-ray photoelectron spectroscopy, and Auger electron spectroscopy, which revealed development of a silicon-gradient, hybrid structure between the metal substrate and the adhesive.

Description: In this presentation, polyimide-silica hybrids using novel phenylethynyl imide silanes are reported. The phenylethynyl group is present in the organic precursor as either a pendent or an end group to bond chemically with the polyimide adhesive containing phenylethynyl groups during processing, while the silane group of the organic precursor would chemically react with the inorganic precursor through oxane bond formation. The chemical compositions of these novel hybrids were examined using X-ray mapping modes of scanning electron microscopy (SEM), which revealed a silicon gradient interphase between the high surface energy substrate and the polyimide adhesive. Novel aromatic phenylethynyl imide silanes (APEISs) and pendent phenylethynyl imide oligomeric disilanes (PPEIDSs) have been synthesized, and sol-gel solutions containing the new silanes, a phenylethynyl terminated imide oligomer (PETI-5), and an inorganic precursor were formulated to develop a gradient hybrid interphase between a titanium alloy and the adhesive. Two different sol-gel systems were investigated to develop organic-inorganic hybrids. Hybrid I was composed of an organic precursor containing both phenylethynyl and silane groups (PPEIDS) and an inorganic precursor. Functional group concentrations were controlled by the variation of the molecular weight of the imide backbone of PPEIDS. Hybrid II was composed of organic and inorganic precursors and a coupling agent containing both phenylethynyl and silane groups. Morphology and chemical composition of the hybrid interphase between the inorganic substrate and the adhesive were investigated, and the bond strength and durability were evaluated using lap shear tests at various conditions. The assessment of how the bonding at an interface is affected by various sol-gel solution compositions and environments is reported.

Description: High-speed commercial aircraft require a surface treatment for titanium (Ti) alloy that is both environmentally safe and durable under the conditions of supersonic flight. A number of pretreatment procedures for Ti alloy requiring multi-stages have been developed to produce a stable surface. Among the stages are, degreasing, mechanical abrasion, chemical etching, and electrochemical anodizing. These treatments exhibit significant variations in their long-term stability, and the benefits of each step in these processes still remain unclear. In addition, chromium compounds are often used in many chemical treatments and these materials are detrimental to the environment. Recently, a chromium-free surface treatment for Ti alloy has been reported, though not designed for high temperature applications. In the present study, a simple surface treatment process developed at NASA/LaRC is reported, offering a high performance surface for a variety of applications. This novel surface treatment for Ti alloy is conventionally achieved by forming oxides on the surface with a two-step chemical process without mechanical abrasion. This acid-followed-by-base treatment was designed to be cost effective and relatively safe to use in a commercial application. In addition, it is chromium-free, and has been successfully used with a sol-gel coating to afford a strong adhesive bond after exposure to hot-wet environments. Phenylethynyl containing adhesives were used to evaluate this surface treatment with sol-gel solutions made of novel imide silanes developed at NASA/LaRC. Oxide layers developed by this process were controlled by immersion time and temperature and solution concentration. The morphology and chemical composition of the oxide layers were investigated using scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and Auger electron spectroscopy (AES). Bond strengths made with this new treatment were evaluated using single lap shear tests.

Description: The durability of titanium (Ti) alloys bonded with high temperature adhesives such as polyimides has failed to attain the level of performance required for many applications. The problem to a large part is attributed to the instability of the surface treatment on the Ti substrate. Although Ti alloy adhesive specimens with surface treatments such as chromic acid anodization, Pasa-Jell, Turco, etc. have provided high initial mechanical properties, these properties have decreased as a function of aging at ambient temperature and faster, when aged at elevated temperatures or in a hot-wet environment. As part of the High Speed Civil Transport program where Ti honeycomb sandwich structure must perform for 60,000 hours at 177 C, work was directed to the development of environmentally safe, durable Ti alloy surface treatments.

Description: Tailoring the solar absorptivity (alpha(sub s)) and thermal emissivity (epsilon(sub T)) of materials constitutes an innovative approach to solar energy control and energy conversion. Numerous ceramic and metallic materials are currently available for solar absorbance/thermal emittance control. However, conventional metal oxides and dielectric/metal/dielectric multi-coatings have limited utility due to residual shear stresses resulting from the different coefficient of thermal expansion of the layered materials. This research presents an alternate approach based on nanoparticle-filled polymers to afford mechanically durable solar-absorptive and thermally-emissive polymer nanocomposites. The alpha(sub s) and epsilon(sub T) were measured with various nano inclusions, such as carbon nanophase particles (CNPs), at different concentrations. Research has shown that adding only 5 wt% CNPs increased the alpha(sub s) and epsilon(sub T) by a factor of about 47 and 2, respectively, compared to the pristine polymer. The effect of solar irradiation control of the nanocomposite on solar energy conversion was studied. The solar irradiation control coatings increased the power generation of solar thermoelectric cells by more than 380% compared to that of a control power cell without solar irradiation control coatings.

Description: Polymer-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(exp -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.