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At least 217 records · Page 12

Synthesis of improved moisture resistant polymers

The synthesis and characterization of novel moisture resistant aliphatic polyimides are described. Several novel aliphatic imides of diversified functionalities were synthesized, purified, and characterized, they include: (1) N-(12-aminododecyl)-5-norbornene-2,3-dicarboximide; (2) N,N'-2,2,2-trifluoro-1-(trifluoromethyl)ethylidene bis (1,3-dioxo-5,2-iosoindolinediyl)dodecamethylene di-5-norbornene-2,3-dicarboximide; (3) N,N'-dodecamethylenedi-5-nobornene-2,3-dicarbonoximide; (4) N,N'-dodecamethylenebis 5,6-epoxy-2,3-norbornanedicarboximide ; and (5) N,N'-Bis 12-(5-norbornene-2, 3-dicarboximidido)dodecyl - 1,2,3,4- butanetetracarboxylic 1,2:3,4-diimide. The structures of these compounds were established by elemental analysis, IR, NMR, and mass spectra.

Scola, D. A.↗

Performance Characterization of a Lithium-ion Gel Polymer Battery Power Supply System for an Unmanned Aerial Vehicle

Unmanned aerial vehicles (UAVs) are currently under development for NASA missions, earth sciences, aeronautics, the military, and commercial applications. The design of an all electric power and propulsion system for small UAVs was the focus of a detailed study. Currently, many of these small vehicles are powered by primary (nonrechargeable) lithium-based batteries. While this type of battery is capable of satisfying some of the mission needs, a secondary (rechargeable) battery power supply system that can provide the same functionality as the current system at the same or lower system mass and volume is desired. A study of commercially available secondary battery cell technologies that could provide the desired performance characteristics was performed. Due to the strict mass limitations and wide operating temperature requirements of small UAVs, the only viable cell chemistries were determined to be lithium-ion liquid electrolyte systems and lithium-ion gel polymer electrolyte systems. Two lithium-ion gel polymer cell designs were selected as candidates and were tested using potential load profiles for UAV applications. Because lithium primary batteries have a higher specific energy and energy density, for the same mass and volume allocation, the secondary batteries resulted in shorter flight times than the primary batteries typically provide. When the batteries were operated at lower ambient temperatures (0 to -20 C), flight times were even further reduced. Despite the reduced flight times demonstrated, for certain UAV applications, the secondary batteries operated within the acceptable range of flight times at room temperature and above. The results of this testing indicate that a secondary battery power supply system can provide some benefits over the primary battery power supply system. A UAV can be operated for hundreds of flights using a secondary battery power supply system that provides the combined benefits of rechargeability and an inherently safer chemistry.

Reid, Concha M.↗

Polymer research at NASA Langley Research Center

Polymer synthesis programs involve the development of Novel thermoplastics, pseudothermoplastics, and thermosets. These systems are prepared to elucidate structure-property relationships involving thermal capabilities, toughness, processability and environmental stability. Easily processable polyimides, solvent-resistant polysulfones and polyphenylquinoxalines, and tougher high and intermediate temperature polymers were developed. Characterization efforts included high pressure liquid chromatography methodology, the development of toughness tests for fiber reinforced composites, a study of electrical properties of metal ion filled polyimides, and a study of the mutagenicity of aromatic diamines. Also the mechanism of cure/degradation of experimental polymers was studied by rheology, mechanical behavior, separation techniques and spectroscopy. The degradative crosslinking of alkyl-containing polyimides, the separation and identification of crosslinked phenylquinoxalines, the rheological behavior of hot-melt polyimides, and the elucidation of the cure of norbornene endcapped imides were also studied.

Terry L. St. Clair↗

Synthesis of Polymers Containing Covalently Bonded NLO Chromophores

Polymers containing covalently bonded nonlinear optical (NLO) chromophores are expected to possess special properties such as greater stability, better mechanical processing, and easier film formation than their non-polymeric equivalent. For the present work, polymethylmethacrylate (PMMA) was selected as the basic polymer unit on which to incorporate different NLO chromophores. The NLO components were variations of DIVA {[2-methoxyphenyl methylidene]-propanedinitrile} which we prepared from vanillin derivatives and malononitrile. These were esterified with methacrylic acid and polymerized either directly or with methyl methacrylate to form homopolymers or copolymers respectively. Characterization of the polymers and NLO property studies are underway.

Denga, Xiao-Hua↗

Orientational Ordering within Semiconducting Polymer Fibrils

Abstract Due to a general paucity of suitable characterization methods, the internal orientational ordering of polymer fibrils has rarely been measured despite its importance particularly for semi‐conducting polymers. An emerging tool with sensitivity to bond orientation is polarized resonant soft X‐ray scattering (P‐RSoXS). Here, P‐RSoXS reveals the molecular arrangement within fibrils (if type I or type II fibrils), the extent of orientation in the fibril crystal, and an explicit crystal‐amorphous interphase. Neat films as well as binary blends with a fullerene derivative are characterized for three different polymers, that are prototypical materials widely used in organic electronics applications. Anisotropic P‐RSoXS patterns reveal two different fibril types. Analysis of the q ‐dependence of the anisotropy from simulated and experimental scattering patterns reveal that neat polymer fibrillar systems likely comprise more than two phases, with the third phase in addition to crystal and amorphous likely being an interphase with distinct density and orientation. Intriguingly, the fibril type correlates to the H‐ or J‐aggregation signature in ultraviolet‐visible (UV–vis) spectroscopy, revealing insight into the fibril formation. Together, the results will open the door to develop more sophisticated structure‐function relationships between chemical design, fibril type, formation pathways and kinetics, interfacial ordering, and eventually device functions.

Mukherjee, Subhrangsu↗

Characterization of Encapsulated Corrosion Inhibitors for Environmentally Friendly Smart Coatings

Research efforts are under way to replace current corrosion inhibitors with more environmentally friendly alternatives. However, problems with corrosion inhibition efficiency, coating compatibility and solubility have hindered the use of many of these materials as simple pigment additives.This paper will present technical details on how the Corrosion Technology Lab at NASAs Kennedy Space Center (KSC) has addressed these issues by encapsulating environmentally friendly inhibitors into organic and inorganic microparticles and microcapsules. The synthetic process for polymer particles was characterized and post-synthesis analysis was performed to determine the interactions between the inhibitors and the encapsulation material. The pH-controlled release of inhibitors from various particle formulations in aqueous base was monitored and compared to both electrochemical and salt immersion accelerated corrosion experiment. Furthermore, synergistic corrosion inhibition effects observed during the corrosion testing of several inhibitor combinations will be presented.

Environmentally Friendly↗

Solution Structure and Scaling Laws of Cylindrical and Tapered Bottlebrush Polymers

Bottlebrush polymers are a unique class of macromolecular architectures with a plethora of potential industrial and pharmaceutical applications that critically depend on the bottlebrush shape and dimensions. Here, a systematic series of 12 cylindrical and 12 cone-shaped (tapered) bottlebrush polymers with poly(tert-butyl acrylate) (PtBA) or polystyrene (PS) side chains were synthesized using the sequential addition of macromonomers ring-opening metathesis polymerization (SAM-ROMP) grafting-through method. Small-angle neutron scattering (SANS) studies on dilute solutions of the two types of bottlebrush polymers provided noninvasive characterization of their structural dimensions and chain conformations. Simulated SANS traces, generated using coarse-grained molecular dynamics simulations, reproduced the distinctive features observed in the experimental SANS signals and provided necessary validation for data modeling. The combined analysis of experimental and simulated SANS signals yielded key structural and conformational parameters, including the bottlebrush radius, length, and Kuhn length as well as the excluded volume parameter and the correlation length of the polymer side chains. Importantly, the obtained structural parameters followed well-defined scaling laws as a function of the backbone and side chain degrees of polymerization, as predicted by mean field theories. In conclusion, these findings provide clear experimental and computational evidence of the interdependence of structural and conformational properties in an important class of polymer architectures.

36 MATERIALS SCIENCE↗

Characterization of the electromechanical properties of ionomeric polymer-metal composite (IPMC)

IPMC is an electroactive polymer (EAP) that has been the subject of research and development since 1992. Its required low activation voltage and the large bending strain led to its consideration for various potential applications. However, before the benefits of IPMC can be effectively exploited for practical use, the electromechanical behavior of this group of EAP materials must be properly understood and quantified.

EAP↗

Characterization of wear debris generated in accelerated rolling-element fatigue tests

A ferrographic analysis was used to determine the types and quantities of wear debris generated during accelerated rolling contact fatigue tests. The five-ball rolling contact fatigue tester was used. Ball specimens were made of a corrosion resistant, high-temperature bearing steel. The lubricant was a superrefined naphthenic mineral oil. Conditions included a maximum Hertz stress of 5.52 10 to the 9th power Pa and a shaft speed of 10,000 rpm. Four types of wear debris were observed: (1) normal rubbing wear particles, (2) fatigue microspall particles, (3) spheres, and (4) friction polymer deposits. The characterization of wear debris as a function of time was of limited use in predicting fatigue failures in these accelerated tests.

Jones, W. R., Jr.↗

High Temperature Polymers for use in Fuel Cells

NASA Glenn Research Center (GRC) is currently working on polymers for fuel cell and lithium battery applications. The desire for more efficient, higher power density, and a lower environmental impact power sources has led to interest in proton exchanges membrane fuels cells (PEMFC) and lithium batteries. A PEMFC has many advantages as a power source. The fuel cell uses oxygen and hydrogen as reactants. The resulting products are electricity, heat, and water. The PEMFC consists of electrodes with a catalyst, and an electrolyte. The electrolyte is an ion-conducting polymer that transports protons from the anode to the cathode. Typically, a PEMFC is operated at a temperature of about 80 C. There is intense interest in developing a fuel cell membrane that can operate at higher temperatures in the range of 80 C- 120 C. Operating the he1 cell at higher temperatures increases the kinetics of the fuel cell reaction as well as decreasing the susceptibility of the catalyst to be poisoned by impurities. Currently, Nafion made by Dupont is the most widely used polymer membrane in PEMFC. Nafion does not function well above 80 C due to a significant decrease in the conductivity of the membrane from a loss of hydration. In addition to the loss of conductivity at high temperatures, the long term stability and relatively high cost of Nafion have stimulated many researches to find a substitute for Nafion. Lithium ion batteries are popular for use in portable electronic devices, such as laptop computers and mobile phones. The high power density of lithium batteries makes them ideal for the high power demand of today s advanced electronics. NASA is developing a solid polymer electrolyte that can be used for lithium batteries. Solid polymer electrolytes have many advantages over the current gel or liquid based systems that are used currently. Among these advantages are the potential for increased power density and design flexibility. Automobiles, computers, and cell phones require highly efficient power density for lowering emissions and meeting increasing consumer demands. Many of the solutions can be provided by proton exchange membrane fuel cells and lithium batteries. NASA Glenn Research Center has recognized this need, and is presently engaged in a solution. The goals for the summer include mastering synthesis techniques, understanding the reactions occurring during the synthesis, and characterizing the resulting polymer membranes using NMR, DSC, and TGA for the PEMFC and lithium batteries.

Peplowski, Katherine M.↗

Strain Rate Dependent Deformation and Strength Modeling of a Polymer Matrix Composite Utilizing a Micromechanics Approach

Potential gas turbine applications will expose polymer matrix composites to very high strain rate loading conditions, requiring an ability to understand and predict the material behavior under extreme conditions. Specifically, analytical methods designed for these applications must have the capability of properly capturing the strain rate sensitivities and nonlinearities that are present in the material response. The Ramaswamy-Stouffer constitutive equations, originally developed to analyze the viscoplastic deformation of metals, have been modified to simulate the nonlinear deformation response of ductile, crystalline polymers. The constitutive model is characterized and correlated for two representative ductile polymers. Fiberite 977-2 and PEEK, and the computed results correlate well with experimental values. The polymer constitutive equations are implemented in a mechanics of materials based composite micromechanics model to predict the nonlinear, rate dependent deformation response of a composite ply. Uniform stress and uniform strain assumptions are applied to compute the effective stresses of a composite unit cell from the applied strains. The micromechanics equations are successfully verified for two polymer matrix composites. IM7/977-2 and AS4/PEEK. The ultimate strength of a composite ply is predicted with the Hashin failure criteria that were implemented in the composite micromechanics model. The failure stresses of the two composite material systems are accurately predicted for a variety of fiber orientations and strain rates. The composite deformation model is implemented in LS-DYNA, a commercially available transient dynamic explicit finite element code. The matrix constitutive equations are converted into an incremental form, and the model is implemented into LS-DYNA through the use of a user defined material subroutine. The deformation response of a bulk polymer and a polymer matrix composite are predicted by finite element analyses. The results compare reasonably well to experimental values, with some discrepancies. The discrepancies are at least partially caused by the method used to integrate the rate equations in the polymer constitutive model.

Goldberg, Robert K.↗

Effects of Intercalating Molecules on the Polymer Properties of DNA

Atomic force microscopy (AFM) enables determination of physical properties from single DNA molecules. Insertion of aromatic molecules into the structure of DNA results in morphological changes. However, the accompanying changes to elastic properties due to this insertion are not fully understood. AFM was used to examine the morphological effects of intercalator binding and report changes in the elastic properties of intrinsically straight DNA molecules. The persistence length and polymer extension were characterized in the presence of three intercalating molecules: ethidium bromide and the less well studied chloroquine and acridine. It was found that all three intercalators significantly increased the bending persistence length. In addition, an analysis of the normal bending modes of the static molecules corroborated these results. Furthermore, this approach of measuring binding effects of intercalators on DNA physical properties using a model system of intrinsically straight DNA is applicable to other DNA binding ligands and other modes of DNA interaction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Trace Compound Analysis in TATB by Liquid Chromatography coupled with Spectroscopic and Spectrometric Detection

Accurate quantitation of 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) is important because of its strategic use as an energetic material. A purity determination is also needed for the proper assessment of performance. A fast and sensitive method has been developed to measure the purity of TATB in polymer-bonded materials. The target material is extracted with DMSO, and the extract is separated on a reversed-phase chromatography column. The column effluent is monitored by diode array detection (DAD) at 354 nm. The characteristic UV-Vis response and retention time identify the individual components when compared to pure compound standards. The chemical structures of compounds with no pure standards available have been determined by high-resolution mass spectrometry (MS) and MS/MS. The major component, TATB, along with 1-chloro-3,5-dinitro-2,4,6-triaminobenzene (T4A) and mono-benzofuroxan (FX1) were quantitated directly from pure compound standards. Several trace concentration components, mono-benzofurazan (F1), 1-bromo-3,5-dinitro-2,4,6-triaminobenzene (Br-T4A), 2,4,6-triamino-1-nitroso-3,5-dinitrobenzene (MN-TATB), 2,4,6-triamino-1-hydroxyl-3,5-dinitrobenzene (HO-TATB), and 2,4,6-triamino-1-nitrile-3,5-dinitrobenzene (Nitrile-TATB) were also detected and structures verified via MS/MS. Approximate concentrations were determined using calibrations from standards of similar structures. Additional trace components were also detected by MS. Contained herein are the results of analyses of TATB-based materials characterized for polymer-bonded formulations compared to different preparations of TATB. The accuracy, details, and process of developing this method are reported here.

36 MATERIALS SCIENCE↗

Solution-processable and functionalizable ultra-high molecular weight polymers via topochemical synthesis

Abstract Topochemical polymerization reactions hold the promise of producing ultra-high molecular weight crystalline polymers. However, the totality of topochemical polymerization reactions has failed to produce ultra-high molecular weight polymers that are both soluble and display variable functionality, which are restrained by the crystal-packing and reactivity requirements on their respective monomers in the solid state. Herein, we demonstrate the topochemical polymerization reaction of a family of para -azaquinodimethane compounds that undergo facile visible light and thermally initiated polymerization in the solid state, allowing for the first determination of a topochemical polymer crystal structure resolved via the cryoelectron microscopy technique of microcrystal electron diffraction. The topochemical polymerization reaction also displays excellent functional group tolerance, accommodating both solubilizing side chains and reactive groups that allow for post-polymerization functionalization. The thus-produced soluble ultra-high molecular weight polymers display superior capacitive energy storage properties. This study overcomes several synthetic and characterization challenges amongst topochemical polymerization reactions, representing a critical step toward their broader application.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗