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At least 163 records · Page 9

Lithium Polymer Electrolytes and Solid State NMR

Research is being done at the Glenn Research Center (GRC) developing new kinds of batteries that do not depend on a solution. Currently, batteries use liquid electrolytes containing lithium. Problems with the liquid electrolyte are (1) solvents used can leak out of the battery, so larger, more restrictive, packages have to be made, inhibiting the diversity of application and decreasing the power density; (2) the liquid is incompatible with the lithium metal anode, so alternative, less efficient, anodes are required. The Materials Department at GRC has been working to synthesize polymer electrolytes that can replace the liquid electrolytes. The advantages are that polymer electrolytes do not have the potential to leak so they can be used for a variety of tasks, small or large, including in the space rover or in space suits. The polymers generated by Dr. Mary Ann Meador's group are in the form of rod -coil structures. The rod aspect gives the polymer structural integrity, while the coil makes it flexible. Lithium ions are used in these polymers because of their high mobility. The coils have repeating units of oxygen which stabilize the positive lithium by donating electron density. This aids in the movement of the lithium within the polymer, which contributes to higher conductivity. In addition to conductivity testing, these polymers are characterized using DSC, TGA, FTIR, and solid state NMR. Solid state NMR is used in classifying materials that are not soluble in solvents, such as polymers. The NMR spins the sample at a magic angle (54.7') allowing the significant peaks to emerge. Although solid state NMR is a helpful technique in determining bonding, the process of preparing the sample and tuning it properly are intricate jobs that require patience; especially since each run takes about six hours. The NMR allows for the advancement of polymer synthesis by showing if the expected results were achieved. Using the NMR, in addition to looking at polymers, allows for participation on a variety of other projects, including aero-gels and carbon graphite mat en als. The goals of the polymer electrolyte research are to improve the physical properties of the polymers. This includes improving conductivity, durability, and expanding the temperature range over which it is effective. Currently, good conductivity is only present at high temperatures. My goals are to experiment with different arrangements of rods and coils to achieve these desirable properties. Some of my experiments include changing the number of repeat units in the polymer, the size of the diamines, and the types of coil. Analysis of these new polymers indicates improvement in some properties, such as lower glass transition temperature; however, they are not as flexible as desired. With further research we hope to produce polymers that encompass all of these properties to a high degree.

Berkeley, Emily R.↗

The industrial processing of unidirectional fiber prepregs

Progress made in the industrial processing of preimpregnated composites with unidirectional fibers is discussed, with particular emphasis on applications within the aerospace industry. Selection of industrial materials is considered. Attention is given to the conditions justifying the use of composites and the properties required of industrial prepregs. The hardening cycle is examined for the cases of nonmodified and polymer modified resins, with attention given to the stabilization of flow, the necessary changes of state, viscosity control, and the elimination of porosity. The tooling necessary for the fabrication of a laminated plate is illustrated, and the influence of fabrication and prepreg properties on the mechanical characteristics of a laminate are indicated. Finally, the types of prepregs available and the processing procedures necessary for them are summarized.

Laird, B.↗

Low coefficient of thermal expansion polyimides containing metal ion additives

Polyimides have become widely used as high performance polymers as a result of their excellent thermal stability and toughness. However, lowering their coefficient of thermal expansion (CTE) would increase their usefulness for aerospace and electronic applications where dimensional stability is a requirement. The incorporation of metal ion-containing additives into polyimides, resulting in significantly lowered CTE's, has been studied. Various metal ion additives have been added to both polyamic acid resins and soluble polyimide solutions in the concentration range of 4-23 weight percent. The incorporation of these metal ions has resulted in reductions in the CTE's of the control polyimides of 12 percent to over 100 percent depending on the choice of additive and its concentration.

Stoakley, D. M.↗

Polyimides That Contain Cyclobutene-3,4-Dione Moieties

Linear aromatic polyimides containing cyclobutene-3,4,-dione moieties synthesized in experiments. Polymers exhibit high thermal and thermo-oxidative stabilities, making them useful in structural components exposed to hot and/or oxidative environments, as in jet engines and on outer surfaces of supersonic aircraft. Electrons in cyclobutene-3,4-dione moieties readily excited to states of higher energy upon exposure to ultraviolet light, giving rise to electronic properties with potential utility in photovoltaic, photoconductive, and/or photoemissive devices.

St. Clair, Terry L.↗

Development of DMBZ-15 High-Glass-Transition-Temperature Polyimides as PMR-15 Replacements Given R&D 100 Award

PMR-15, a high-temperature polyimide developed in the mid-1970s at the NASA Lewis Research Center,1 offers the combination of low cost, easy processing, and good high-temperature performance and stability. It has been recognized as the leading polymer matrix resin for carbon-fiber-reinforced composites used in aircraft engine components. The state-of-the-art PMR-15 polyimide composite has a glass-transition temperature (Tg) of 348 C (658 F). Since composite materials must be used at temperatures well below their glass-transition temperature, the long-term use temperatures of PMR-15 composites can be no higher than 288 C (550 F). In addition, PMR-15 is made from methylene dianiline (MDA), a known liver toxin. Concerns about the safety of workers exposed to MDA during the fabrication of PMR-15 components and about the environmental impact of PMR-15 waste disposal have led to the industry-wide implementation of special handling procedures to minimize the health risks associated with this material. These procedures have increased manufacturing and maintenance costs significantly and have limited the use of PMR-15 in commercial aircraft engine components.

Chuang, Kathy↗

Improved high temperature resistant matrix resins

The objective was to develop organic matrix resins suitable for service at temperatures up to 644 K (700 F) and at air pressures up to 0.4 MPa (60 psia) for time durations of a minimum of 100 hours. Matrix resins capable of withstanding these extreme oxidative environmental conditions would lead to increased use of polymer matrix composites in aircraft engines and provide significant weight and cost savings. Six linear condensation, aromatic/heterocyclic polymers containing fluorinated and/or diphenyl linkages were synthesized. The thermo-oxidative stability of the resins was determined at 644 K and compressed air pressures up to 0.4 MPa. Two formulations, both containing perfluoroisopropylidene linkages in the polymer backbone structure, exhibited potential for 644 K service to meet the program objectives. Two other formulations could not be fabricated into compression molded zero defect specimens.

Chang, G. E.↗

Atomic-oxygen induced structural changes in polyphosphazene films and coatings

Various polymers were exposed to atomic oxygen O(3P) and comparisons made of their stability. The rates of reaction and mass removal for polyphosphazenes exposed to atomic oxygen were found to be significantly lower than for other polymers evaluated in this study. Surface analysis of polyphosphazene films indicated that O(3P) induces rearrangements in the phosphorus-nitrogen backbone of the polymer, resulting in cross-linking and cleavage of some pendant groups that are then replaced by oxygen.

Fewell, Larry L.↗

Nonlinear optical polymers for electro-optic signal processing

Photonics is an emerging technology, slated for rapid growth in communications systems, sensors, imagers, and computers. Its growth is driven by the need for speed, reliability, and low cost. New nonlinear polymeric materials will be a key technology in the new wave of photonics devices. Electron-conjubated polymeric materials offer large electro-optic figures of merit, ease of processing into films and fibers, ruggedness, low cost, and a plethora of design options. Several new broad classes of second-order nonlinear optical polymers were developed at the Navy's Michelson Laboratory at China Lake, California. Polar alignment in thin film waveguides was achieved by electric-field poling and Langmuir-Blodgett processing. Our polymers have high softening temperatures and good aging properties. While most of the films can be photobleached with ultraviolet (UV) light, some have excellent stability in the 500-1600 nm range, and UV stability in the 290-310 nm range. The optical nonlinear response of these polymers is subpicosecond. Electro-optic switches, frequency doublers, light modulators, and optical data storage media are some of the device applications anticipated for these polymers.

Lindsay, Geoffrey A.↗

Thermally Stable, Piezoelectric and Pyroelectric Polymeric Substrates and Method Relating Thereto

Production of an electric voltage in response to mechanical excitation (piezoelectricity) or thermal excitation (pyroelectricity) requires a material to have a preferred dipole orientation in its structure. This preferred orientation or polarization occurs naturally in some crystals such as quartz and can be induced into some ceramic and polymeric materials by application of strong electric or mechanical fields. For some materials, a combination of mechanical and electrical orientation is necessary to completely polarize the material. The only commercially available piezoelectric polymer is poly(vinylidene fluoride) (PVF2). However, this polymer has material and process limitations which prohibit its use in numerous device applications where thermal stability is a requirement. By the present invention, thermally stable, piezoelectric and pyroelectric polymeric substrates were prepared from polymers having a softening temperature greater than 1000C. A metal electrode material is deposited onto the polymer substrate and several electrical leads are attached to it. The polymer substrate is heated in a low dielectric medium to enhance molecular mobility of the polymer chains. A voltage is then applied to the polymer substrate inducing polarization. The voltage is then maintained while the polymer substrate is cooled 'freezing in' the molecular orientation. The novelty of the invention resides in the process of preparing the piezoelectric and pyroelectric polymeric substrate. The nonobviousness of the invention is found in heating the polymeric substrate in a low dielectric medium while applying a voltage.

Simpson, Joycelyn O.↗

Experimental Characterization of the Dimensional Stability of Deployable Composite Booms During Stowage

Thin-ply carbon fiber reinforced polymer materials offer the opportunity to create long thin-shell booms with high strength to weight ratios. These booms can be rolled up and stowed in small volumes to be later deployed. These features make them ideal for use in gossamer solar sails as well as other deployable space structures. It has been observed that stowing the booms in rolled-up configurations can cause time-dependent deformations. A comprehensive understanding of the detrimental effects of stowing the coiled booms is necessary to implement these structures in spaceflight missions. During stowage inside the spacecraft, the boom is subjected to a constant deformation/strain that causes it to relax over time, measurable by a decrease in stress. Using large deformation bending tests, the complete fold-stow-unfold-recover cycle of thin-laminate candidates for the rollable booms is characterized. Further bending and stowage testing is done at the boom level. The results from this test campaign will be used to evaluate the dimensional stability of deployable booms made from thin-ply composites that exhibit visco-elasto-plastic behavior and calibrate and validate numerical finite element models that include visco-elasto-plastic material models.

Experimental Characterization↗

Ceramic fibers from Si-B-C polymer precursors

Non-oxide ceramics such as silicon carbide (SiC), silicon nitride (Si3N4), and silicon borides (SiB4, SiB6) have thermal stability, oxidation resistance, hardness, and varied electrical properties. All these materials can be prepared in a fiber form from a suitable polymer precursor. The above mentioned fibers, when tested over a temperature range from 25 to 1400 C, experience degradation at elevated temperatures. Past work in ceramic materials has shown that the strength of ceramics containing both carbides and borides is sustained at elevated temperatures, with minimum oxidation. The work presented here describes the formation of ceramic fibers containing both elements, boron and silicon, prepared via the polymer precursor route previously reported by the authors, and discusses the fiber mechanical properties that are retained over the temperature range studied.

Riccitiello, S. R.↗

Physical and Electrical Characterization of Aluminum Polymer Capacitors

Conductive polymer aluminum capacitor (PA capacitor) is an evolution of traditional wet electrolyte aluminum capacitors by replacing liquid electrolyte with a solid, highly conductive polymer. On the other hand, the cathode construction in polymer aluminum capacitors with coating of carbon and silver epoxy for terminal connection is more like a combination of the technique that solid tantalum capacitor utilizes. This evolution and combination result in the development of several competing capacitor construction technologies in manufacturing polymer aluminum capacitors. The driving force of this research on characterization of polymer aluminum capacitors is the rapid progress in IC technology. With the microprocessor speeds exceeding a gigahertz and CPU current demands of 80 amps and more, the demand for capacitors with higher peak current and faster repetition rates bring conducting polymer capacitors to the center o( focus. This is because this type of capacitors has been known for its ultra-low ESR and high capacitance. Polymer aluminum capacitors from several manufacturers with various combinations of capacitance, rated voltage, and ESR values were obtained and tested. The construction analysis of the capacitors revealed three different constructions: conventional rolled foil, the multilayer stacking V-shape, and a dual-layer sandwich structure. The capacitor structure and its impact on the electrical characteristics has been revealed and evaluated. A destructive test with massive current over stress to fail the polymer aluminum capacitors reveals that all polymer aluminum capacitors failed in a benign mode without ignition, combustion, or any other catastrophic failures. The extraordinary low ESR (as low as 3 mOMEGA), superior frequency independence reported for polymer aluminum capacitors have been confirmed. For the applications of polymer aluminum capacitors in space programs, a thermal vacuum cycle test was performed. The results, as expected, show no impact on the electrical characteristics of the capacitors. The breakdown voltage of polymer capacitors has been evaluated using a steady step surge test. Initial results show the uniform distribution in the breakdown voltage for polymer aluminum capacitors. Polymer aluminum capacitors with a combination of very high capacitance, extraordinary low ESR, excellent frequency stability, and non-ignite benign failure mode make it a niche fit in space applications for both today and future. Polymer capacitors are apparently also the best substitutes of the currently used MnO2-based tantalum capacitors in the low voltage range. However, some critical aspects are still to be addressed in the next phase of the investigation for PA capacitors. These include the long term reliability test of 125 C dry life and 85 C/85%RH humidity, the failure mechanism and de-rating, the radiation tolerance, and the high temperature performance. All of the above requires the continuous NEPP funding and support.

Liu, David (Donghang)↗

Syntheses and thermal stabilities of polyamides from 2,2'-bithiophene-5,5'-dicarbonyl dichloride and diamines

The properties of 12 polymers derived from 2,2'-bithiophene-5,5'-dicarbonyl dichloride are analyzed. The solution and interfacial polymerizations of 2,2'-bithiophene-5,5'-dicarbonyl dichloride are described. It is observed that due to high glass transition temperatures and the lack of flexibility of the polyamide of 2,2'-bithiophene-5,5'-dicarbonyl dichloride most of the polymers failed to fabricate into fibers or films. The data reveal that the polyamides formed from terphenyl ether form a tough, heat-pressed film; the polyamides made from aromatic diamides show great thermal stability; and the polyamides derived from aliphatic or benzylic diamides display no thermal stability.

Barber, Patrick G.↗

Projections on structures and material strength in the computational context

The ideas associated with the subsequent viewgraphs are summarized. The primary motivation behind this presentation is to observe that certain macroscopic, microscopic, and submicroscopic phenomena are being understood that have basic influence on understanding the durability and high temperature sensitivity of polymers and polymer-based composites. This understanding covers important issues of long term stability with respect to residual stresses and deformations which can have very deleterious effects on structures used for long periods of time as a result of the heat-involving manufacturing process. Beyond this, important progress is being made in understanding the nonlinear material response of polymers in the fracture context, because the nonlinear mechanics of the material at the tip of a crack, either propagating or ready to do so, is being understood with increasing precision.

Knauss, Wolfgang G.↗

Morphological control of inter-penetrating polymer networks

Synthetic organic polymer chemistry has been successful in producing composition of matter with thermal oxidation stability and progressively higher glass transition temperatures. In part, this was done by increasing the steric-hindrance of moieties in the chain of a macromolecule. The resulting polymers are usually quite insoluble and produce molten polymers of very high viscosities. These types of polymers are not easily processed into graphite fiber prepregs by melt or solution impregnation methods. Hence, a technological need exists to produce new knowledge of how to produce polymer-fiber composites from this class of polymers. The concept of freeze drying amic-acid prepolymers with reactive thermoplastic was proposed as a research topic for the ASEE/NASA Summer Faculty Program of 1989 as a means of producing polymer-fiber composites. This process scheme has the thermodynamic attribute that the magnitude of phase separation due to differences in solubility of two organic constituents in solution will be greatly reduced by removing a solvent not by evaporation but by sublimation. Progress to date on evaluating this polymer processing concept is briefly outlined.

Hansen, Marion↗

Carboranylcyclotriphosphazenes and their polymers

Carboranyl-substituted polyphosphazenes are prepared by heat polymerizing a carboranyl halocyclophosphazene at 250 C for about 120 hours in the absence of oxygen and moisture. The cyclophosphazene is obtained by allowing a lithium carborane, e.g., the reaction product of methyl-o-carborane with n-butyllithium in ethyl ether, to react with e.g., hexachlorocyclotriphosphazene at ambient temperatures and in anhydrous conditions. For greater stability in the presence of moisture, the chlorine substituents of the polymer are then replaced by aryloxy or alkoxy groups, such as CF3CH2O. The new substantially inorganic polymers are thermally stable materials which produce a high char yield when exposed to extreme temperatures, and can thus serve to insulate less heat and fire resistant substances.

Allcock, H. R.↗

New monomers for high performance polymers

This laboratory has been concerned with the development of new polymeric materials with high thermo-oxidative stability for use in the aerospace and electronics industries. Currently, there is special emphasis on developing matrix resins and composites for the high speed civil transport (HSCT) program. This application requires polymers that have service lifetimes of 60,000 hr at 350 F (177 C) and that are readily processible into void-free composites, preferably by melt-flow or powder techniques that avoid the use of high boiling solvents. Recent work has focused on copolymers which have thermally stable imide groups separated by flexible arylene ether linkages, some with trifluoromethyl groups attached to the aromatic rings. The presence of trifluoromethyl groups in monomers and polymers often improves their solubility and processibility. The goal of this research was to synthesize several new monomers containing pendant trifluoromethyl groups and to incorporate these monomers into new imide/arylene ether copolymers. Initially, work was begun on the synthesis of three target compounds. The first two, 3,5-dihydroxybenzo trifluoride and 3-amino 5-hydroxybenzo trifluoride, are intermediates in the synthesis of more complex monomers. The third, 3,5-bis (3-amino-phenoxy) benzotrifluoride, is an interesting diamine that could be incorporated into a polyimide directly.

Gratz, Roy F.↗