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Low-gravity electrodeposition and growth of polymer thin films with large third-order optical nonlinearities by electrochemical processes for devices: Thiophene-based polymers

It has been proposed that NLO thin film properties may be improved by low-gravity processing. Strong candidates for NLO thin film applications are the polythiophenes. Polymeric thiophenes are attractive materials due to their ease of preparation, stability, and high X(exp 3). A simple and convenient method for preparation of polythiophenes is electrochemical oxidation. We will apply some of our experience and lessons learned in low-gravity metal, metal/cermet electrode position to improve the quality of polythiophene(s) thin films. In low gravity electrode position of Ni at a high rate on an Au substrate often results in the production of an x-ray non diffracting surface. Cobalt metal deposition does not give this result nor does Ni when deposited similarly on a glassy carbon substrate. Co/Ni alloy composition produced during electrode position is strongly dependent upon the amount of convection. Code position of neutral inert cermets with metals is influenced significantly by the presence of gravity and the size of the cermets. Tracks left in the 1-g surfaces by unsuccessful particle occlusion indicate suspension of the large particles is not the only reason for poor volume percentages of the larger particles in the deposits. All size particles are more homogeneously distributed in the deposits in low-gravity electrocodeposition than in 1-g. Low gravity gives larger volume percentages for the larger particles in the deposits, while 1-g gives larger volume percentages for the smaller particles. Intermediate size particles give mixed results. The experimental cells were constructed with flat electrode end plates such that 1-g bench reference electrode positions could be carried out at various orientations with respect to gravity. A series of bench studies using similar designed cells are suggested so that convection modification can be applied to electrochemical thin film preparation. Convection effects can then be coupled with other parameter variations in current, temperature, concentration, solvent, electrolyte, and anode substrates to optimize the properties of NLO thin films before resorting to low-gravity processing.

Penn, Benjamin G.↗

The 3F condensation polyimides: Review and update

Nine new condensation polyimides containing the phenyltrifluoroethylidene (3F) linkage were synthesized by the amic-acid route. Several other polyimides, including some with hexafluoroisopropylidene (6F) linkage, were also prepared as controls. Amic-acid solutions were characterized by determining their inherent viscosities prior to thermal conversion into polyimide films. Glass transition temperatures (T sub g), thermogravimetric analysis (TGA), and isothermal weight loss data (at 316, 371, and 371 C under 0.5 MPa air pressure) were obtained for the films. The films were pulverized into molding powders which, in turn, were thermally processed under pressure into neat resin disks. The disks were also characterized by T sub g's and 316 and 371 C isothermal weight losses. The film study identified two new polyimides with T sub g's greater than 371 C and two new polyimides with low rates of weight loss. The resin disks exhibited the same overall trends in T sub g and weight loss as the respective films, however the weight loss per unit surface area was always greater, presumably due to molecular degradation induced during preparation of the molding powders. The overall results indicate that polyimides containing the 3F linkage have T sub g's and thermo-oxidative stability comparable to polyimides containing the 6F group. Alternate technology was also shown by the synthesis of two new polyalkyl substituted 3F diamines and five more new 3F polymers. Their potential as photoresists was demonstrated by T sub g advancement after ultraviolet exposure. Last, four U.S. patents on 3F monomers and polymers were issued and up to eight more are pending.

Alston, William B.↗

Adjusting Measured Weight Loss of Aged Graphite Fabric/PMR-15 Composites

The purposes of this study were to evaluate the growth of the surface damage layer in polymer matrix composites (PMC's) fabricated with graphite fabric reinforcement and to determine the effects of the cut-surface degradation on the overall thermo-oxidative (TOS) stability of these materials. Four important conclusions were made about the TOS behavior of T650-35/PNIR- 15 fabric-reinforced composites: (1) Three stages of composite weight loss were seen on the plot of weight loss versus aging time; (2) the depth of the cut-edge damage is related to the composite thickness; (3) the actual weight loss realized by a mechanical test specimen that has had all the aging-induced cut-edge damage removed during the preparation process is significantly less than the weight loss measured using specimens with a high percentage of cut edges exposed to the damaging environment; and (4) an extrapolation of a section of the weight loss curve can be used to obtain a more correct estimate of the actual weight loss after extended periods of aging at elevated temperatures.

Bowles, Kenneth J.↗

Imidazolium-Based Polymeric Materials as Alkaline Anion-Exchange Fuel Cell Membranes

Polymer electrolyte membranes that conduct hydroxide ions have potential use in fuel cells. A variety of polystyrene-based quaternary ammonium hydroxides have been reported as anion exchange fuel cell membranes. However, the hydrolytic stability and conductivity of the commercially available membranes are not adequate to meet the requirements of fuel cell applications. When compared with commercially available membranes, polystyrene-imidazolium alkaline membrane electrolytes are more stable and more highly conducting. At the time of this reporting, this has been the first such usage for imidazolium-based polymeric materials for fuel cells. Imidazolium salts are known to be electrochemically stable over wide potential ranges. By controlling the relative ratio of imidazolium groups in polystyrene-imidazolium salts, their physiochemical properties could be modulated. Alkaline anion exchange membranes based on polystyrene-imidazolium hydroxide materials have been developed. The first step was to synthesize the poly(styrene-co-(1-((4-vinyl)methyl)-3- methylimidazolium) chloride through a free-radical polymerization. Casting of this material followed by in situ treatment of the membranes with sodium hydroxide solutions provided the corresponding hydroxide salts. Various ratios of the monomers 4-chloromoethylvinylbenzine (CMVB) and vinylbenzine (VB) provided various compositions of the polymer. The preferred material, due to the relative ease of casting the film, and its relatively low hygroscopic nature, was a 2:1 ratio of CMVB to VB. Testing confirmed that at room temperature, the new membranes outperformed commercially available membranes by a large margin. With fuel cells now in use at NASA and in transportation, and with defense potential, any improvement to fuel cell efficiency is a significant development.

Narayan, Sri R.↗

A Limited Comparison of the Thermal Durability of Polyimide Candidate Matrix Polymers with PMR-15

Studies were conducted with six different candidate high-temperature neat matrix resin specimens of varied geometric shapes to investigate the mechanisms involved in the thermal degradation of polyimides like PMR-15. The metrics for assessing the quality of these candidates were chosen to be glass transition temperature (T(sub g)), thermo-oxidative stability, dynamic mechanical properties, microstructural changes, and dimensional stability. The processing and mechanical properties were not investigated in the study reported herein. The dimensional changes and surface layer growth were measured and recorded. The data were in agreement with earlier published data. An initial weight increase reaction was observed to be dominating at the lower temperatures. However, at the more elevated temperatures, the weight loss reactions were prevalent and probably masked the weight gain reaction. These data confirmed the findings of the existence of an initial weight gain reaction previously reported. Surface- and core-dependent weight losses were shown to control the polymer degradation at the higher temperatures.

Bowles, Kenneth J.↗

High temperature solid lubricants: When and where to use them

The state of the art of solid lubrication for moderate to extremely high temperature lubrication (to 1600 F) is reviewed. Lubricating characteristics, stability in various environments, and relevant machine design considerations are discussed. Lubricating materials discussed include the layer lattice compounds: MoS2, WS2, graphite and graphite fluoride, the high temperature polyimide polymer, and calcium fluoride based coating and composites. The scope of the information includes results from wear testers, ball bearing, and journal bearings.

Sliney, H. E.↗

Anion permselective membrane

The efforts on the synthesis of polymer anion redox membranes were mainly concentrated in two areas, membrane development and membrane fabrication. Membrane development covered the preparation and evaluation of experimental membranes systems with improved resistance stability and/or lower permeability. Membrane fabrication covered the laboratory scale production of prime candidate membranes in quantities of up to two hundred and sizes up to 18 inches x 18 inches (46 cm x 46 cm). These small (10 in x 11 in) and medium sized membranes were mainly for assembly into multicell units. Improvements in processing procedures and techniques for preparing such membrane sets lifted yields to over 90 percent.

Hodgdon, R. B.↗

Symposium on Rechargeable Lithium Batteries, Hollywood, FL, Oct. 19-24, 1989, Proceedings

Recent advances in the technology and applications of rechargeable Li cells are discussed in reviews and reports. A general overview of the field is provided, and sections are devoted to organic electrolyte systems, polymeric electrolyte systems, inorganic electrolytes systems, and molten-salt electrolytes. Particular attention is given to electrolyte stabilization, the effects of organic additives on electrolyte performance, a cycle-life sensor, consumer-product applications, in situ measurements of gas evolution in Li secondary cells, ultrathin polymer cathodes, electrochemical growth of conducting polymers, and sealing Li/FeS(x) cells for a bipolar battery.

Subbarao, S.↗

Polyimides Made From 3,5-Diaminobenzotrifluoride

Polyimides synthesized from 3,5-diaminobenzotrifluoride (DABTF). One monomer of major importance in preparing these high-temperature polymers is 1,3-phenylenediamine (mPDA). Fluorinated polyimides exhibit characteristics potentially attractive for aerospace and electronic applications. Includes optical transparency, solubility in common polar solvents, enhanced thermo-oxidative stability, low dielectric constants, and high glass-transition temperatures. Polyimides also used to form free-standing films, coatings, and moldings.

St. Clair, Terry L.↗

Microcracking of Materials for Space

The effect of thermal-cycling-induced microcracking in fiber-reinforced polymer matrix composites is studied. Specific attention is focused on microcrack density as a function of the number of thermal cycles, and the effect of microcracking on the dimensional stability of composite materials. Changes in laminate coefficient of thermal expansion (CTE) and laminate stiffness are of primary concern. Included in the study are materials containing four different Thornel fiber types: a PAN-based T50 fiber and three pitch-based fibers, P55, P75, and P120. The fiber stiffnesses range from 55 Msi to 120 Msi. The fiber CTE's range from -0.50 x 1O(exp -6)/degrees F to -0.80 x 10(exp -6)/degrees F. Also included are three matrix types: Fiberite's 934 epoxy, Amoco's ERL1962 toughened epoxy, and YLA's RS3 cyanate ester. The lamination sequences of the materials considered include a cross-ply configuration, [0/90](sub 2s), and two quasi-isotropic configurations, [0/+45/-45/90](sub s), and [0/+45/90/-45](sub s). The layer thickness of the materials range from a nominal 0.001 in. to 0.005 in. In addition to the variety of materials considered, three different thermal cycling temperature ranges are considered. These temperature ranges are +/-250 degrees F, +/-l5O degrees F, and +/-50 degrees F. The combination of these material and geometric parameters and temperature ranges, combined with thermal cycling to thousands of cycles, makes this one of the most comprehensive studies of thermal-cycling-induced microcracking to date. Experimental comparisons are presented by examining the effect of layer thickness, fiber type, matrix type, and thermal cycling temperature range on microcracking and its influence on the laminates. Results regarding layer thickness effects indicate that thin-layer laminates microcrack more severely than identical laminates with thick layers. For some specimens in this study, the number of microcracks in thin-layer specimens exceeds that in thick-layer specimens by more than a factor of two. Despite the higher number of microcracks in the thin-layer specimens, small changes in CTE after thousands of cycles indicate that the thin-layer specimens are relatively unaffected by the presence of these cracks compared to the thick-layer specimens. Results regarding fiber type indicate that the number of microcracks and the change in CTE after thousands of cycles in the specimens containing PAN-based fibers are less than in the specimens containing comparable stiffness pitch-based fibers. Results for specimens containing the different pitch-based fibers indicate that after thousands of cycles, the number of microcracks in the specimens does not depend on the modulus or CTE of the fiber. The change in laminate CTE does, however, depend highly on the stiffness and CTE of the fiber. Fibers with higher stiffness and more negative CTE exhibit the lowest change in laminate CTE as a result of thermal cycling. The overall CTE of these specimens is, however, more negative as a result of the more negative CTE of the fiber. Results regarding matrix type based on the +/-250 degree F temperature range indicate that the RS3 cyanate ester resin system exhibits the greatest resistance to microcracking and the least change in CTE, particularly for cycles numbering 3000 and less. Extrapolations to higher numbers of cycles indicate, however, that the margin of increased performance is expected to decrease with additional thermal cycling. Results regarding thermal cycling temperature range depend on the matrix type considered and the layer thickness of the specimens. For the ERL1962 resin system, microcrack saturation is expected to occur in all specimens, regardless of the temperature range to which the specimens are exposed. By contrast, the RS3 resin system demonstrates a threshold effect such that cycled to less severe temperature ranges, microcracking does not occur. For the RS3 specimens with 0.005 in. layer thickness, no microcracking or changes in CTE are observed in specimens cycled between +/-150 degree F or +/- 50 degree F. For the RS3 specimens with 0.002 in. layer thickness, no microcracking or changes in CTE are observed in specimens cycled between +/-50 degree F. Results regarding laminate stiffness indicate negligible change in laminate stiffness due to thermal cycling for the materials and geometries considered in this investigation. The study includes X-ray examination of the specimens, showing that cracks observed at the edge of the specimens penetrate the entire width of the specimen. Glass transition temperatures of the specimens are measured, showing that resin chemistry is not altered as a result of thermal cycling. Results are also presented based on a one-dimensional shear lag analysis developed in the literature. The analysis requires material property information that is difficult to obtain experimentally. Using limited data from the present investigation, material properties associated with the analysis are modified to obtain reasonable agreement with measured microcrack densities. Based on these derived material properties, the analysis generally overpredicts the change in laminate CTE. Predicted changes in laminate stiffness show reasonable correlation with experimentally measured values.

Brown, Timothy L.↗

Ceramic Adhesive and Methods for On-Orbit Repair of Re-Entry Vehicles

This adhesive is capable of repairing damaged leading edge components of reentry vehicles while in space, and is novel with regard to its ability to be applied in the vacuum of space, and in a microgravity environment. Once applied, the adhesive provides thermal and oxidation protection to the substrate (in this case, reinforced carbon/carbon composites, RCCs) during re-entry of a space vehicle. Although there may be many formulations for repair adhesives, at the time of this reporting, this is the first known adhesive capable of an on-orbit repair. The adhesive is an engineered ceramic material composed of a pre-ceramic polymer and refractory powders in the form of a paste or putty that can be applied to a scratched, cracked, or fractured composite surface, covering and protecting the damaged area. The adhesive is then "cured" with a heat cycle, thereby cross-linking the polymer into a hardened material and bonding it to the substrate. During the heat of reentry, the material is converted to a ceramic coating that provides thermal and oxidative stability to the repaired area, thus allowing the vehicle to pass safely from space into the upper atmosphere. Ceramic powders such as SiC, ZrB2 and Y2O3 are combined with allylhydridopolycarbosilane (AHPCS) resin, and are mixed to form a paste adhesive. The material is then applied to the damaged area by brush, spatula, trowel, or other means to fill cracks, gaps, and holes, or used to bond patches onto the damaged area. The material is then cured, in a vacuum, preferably at 250F (approximately equal to 121C) for two hours. The re-entry heating of the vehicle at temperatures in excess of 3,000F (approximately equal to 1,650C) then converts this material into a ceramic coating. This invention has demonstrated advantages in resistance to high temperatures, as was demonstrated in more than 100 arc-jet tests in representative environments at NASA. Extensive testing verified oxidation protection for the repaired substrate (RCC), and confirmed that the microstructure of the resulting repair leads to durability and resistance to melting or flow. Its processability and working life in a vacuum was demonstrated by NASA astronauts in glovebox processing studies, as well as on-orbit in the open space shuttle bay. All of these advantages increase the working life of NASA vehicles, as well as improve safety for any crew on a manned vehicle. The adhesive, trademarked NOAX(TM). or Non-Oxide Adhesive Experimental, flew on all space shuttle missions from Return To Flight (STS-114) until the final flight (STS- 135) as a crack repair material for the leading edges and nose cap of the vehicle. NOAX(TM) was patented under U.S. Patents 7,628,878 and 7,888,277.

Riedell, James A.↗

Soluble aromatic polyimides for film and coating applications

Linear all-aromatic polyimides have been synthesized and characterized which show much potential as films and coatings for electronic applications. Structure-property relations with regard to methods for obtaining solubility of fully imidized polymers will be discussed. Methods used to obtain solubility include variation of polymer molecular structure, variation of isomerism of the diamine monomer, modification of cure time/temperature and atmosphere. Other properties of soluble polyimides will be presented which include glass transition temperatures, thermooxidative stabilities, UV-visible spectra, and refractive indices.

St.clair, Anne K.↗

Soluble aromatic polyimides for film and coating applications

Linear all-aromatic polyimides have been synthesized and characterized which show much potential as films and coatings for electronic applications. Structure-property relations with regard to methods for obtaining solubility of fully imidized polymers will be discussed. Methods used to obtain solubility include variation of polymer molecular structure, variation of isomerism of the diamine monomer, modification of cure time/temperature and atmosphere. Other properties of soluble polyimides will be presented which include glass transition temperatures, thermooxidative stabilities, UV-visible spectra, and refractive indices.

St.clair, Anne K.↗

Dynamics and control of coherent structures in the turbulent wall layer: An overview

We expand the velocity field in the vicinity of the wall in empirical eigenfunctions obtained from experiment. Truncating our system and using Galerkin projection, we obtain a closed set of non-linear ordinary differential equations with ten degrees of freedom. We find a rich dynamical behavior, including in particular a heteroclinic attracting orbit giving rise to intermittency. The intermittent jump from one attracting point to the other resembles in many respects the bursts observed in experiments. Specifically, the time between jumps and the duration of the jumps, is approximately that observed in a burst; the jump begins with the formation of a narrowed and intensified updraft, like the ejection phase of a burst, and is followed by a gentle, diffuse downdraft like the sweep phase of a burst. The magnitude of the Reynolds stress spike produced during a burst is limited by our truncation. The behavior is quite robust, much of it being due to the symmetries present (Aubry's group has examined dimensions up to 128 with persistence of the global behavior). We have examined eigenvalues and coefficients obtained from experiment, and from exact simulation, which differ in magnitude. Similar behavior is obtained in both cases; in the latter case, the heteroclinic orbits connect limit cycles instead of fixed points, corresponding to cross-stream waving of the streamwise rolls. The bifurcation diagram remains structurally similar, but somewhat distorted. The role of the pressure term is made clear - it triggers the intermittent jumps, which otherwise would occur at longer and longer intervals, as the system trajectory is attracted closer and closer to the heteroclinic cycle. The pressure term results in the jumps occurring at essentially random times, and the magnitude of the signal determines the average timing. Stretching of the wall region shows that the model is consistent with observations of polymer drag reduction. Change of the third order coefficients, corresponding to acceleration or deceleration of the mean flow, changes the heteroclinic cycles from attracting to repelling, increasing or decreasing the stability, in agreement with observations. The existence of fixed points is an artifact introduced by the projection; however, a decoupled model still displays the rich dynamics. Numerous assumptions made in Aubry et al. (1988) can now be proved exactly. Feeding back eigenfuncitons with the proper phase can delay the bursting, (the heteroclinic jump to the other fixed point), decreasing the drag. It is also possible to speed up the bursting, increasing mixing to control separation. Our approach is optimal for short time tracking in control.

Berkooz, Gal↗

Numerical simulation of the non-Newtonian mixing layer

This work is a continuing effort to advance our understanding of the effects of polymer additives on the structures of the mixing layer. In anticipation of full nonlinear simulations of the non-Newtonian mixing layer, we examined in a first stage the linear stability of the non-Newtonian mixing layer. The results of this study show that, for a fluid described by the Oldroyd-B model, viscoelasticity reduces the instability of the inviscid mixing layer in a special limit where the ratio (We/Re) is of order 1 where We is the Weissenberg number, a measure of the elasticity of the flow, and Re is the Reynolds number. In the present study, we pursue this project with numerical simulations of the non-Newtonian mixing layer. Our primary objective is to determine the effects of viscoelasticity on the roll-up structure. We also examine the origin of the numerical instabilities usually encountered in the simulations of non-Newtonian fluids.

Azaiez, Jalel↗

Wholly aromatic liquid crystalline polyetherimide (LC-PEI) resins

The benefits of liquid crystal polymers and polyetherimides are combined in an all-aromatic thermoplastic liquid crystalline polyetherimide. Because of the unique molecular structure, all-aromatic thermotropic liquid crystal polymers exhibit outstanding processing properties, excellent barrier properties, low solubilities and low coefficients of thermal expansion in the processing direction. These characteristics are combined with the strength, thermal, and radiation stability of polyetherimides.

Weiser, Erik S.↗

Material Response Analysis of PICA-NuSil at the Hypersonic Materials Environmental Test System

Phenolic impregnated carbon ablator (PICA) is a thermal protection system (TPS) that gained heritage during the Stardust mission and is the baseline TPS material for expeditions to Mars (e.g., Mars Science Laboratory and Mars 2020).1 PICA is friable; therefore, a polysiloxane resin (NuSil CV-1144-0) is deposited onto the surface of flight hardware before assembly, test, and launch operations (ATLO) to mitigate particle shedding. Furthermore, the Mars Science Laboratory (MSL) and Mars 2020 heatshields were instrumented with an array of thermocouple plugs (MEDLI Integrated Sensor Plugs or MISP) designed to measure the in-depth thermal response of PICA during flight. Post-flight analysis of MISP data suggests that recession was lower than predicted, and NuSil is suspected as a reasonable cause. NuSil primarily consists of a copolymer blend of dimethyl and diphenyl-substituted polysiloxane resin. Four decades of research in the field of polymer-derived ceramics demonstrate that polysiloxane resins form oxidation-resistant silicon oxycarbide materials at pyrolysis temperatures as low as 800 °C. -2 Furthermore, silicon oxycarbide materials exhibit excellent thermal stability at relatively high-temperatures (< 1200 °C) but eventually decompose via carbothermal reduction. -3 Therefore, it is reasonable to suggest that NuSil forms an oxidation-resistant thermal barrier coating on the TPS surface and influences the material response during atmospheric entry. Evidence for this notion was observed during prior arc-jet testing at both the Aerodynamic Heating Facility (AHF) and the Panel Test Facility (PTF) at the NASA Ames Research Center. Articles of PICA were subjected to testing in airflow, and a temperature discontinuity was recorded at the surface of coupons coated with NuSil. A glassy coating was observed to form at the surface in shear flow configurations (wedge and panel) under moderate heat fluxes. Furthermore, state-of-the-art material response models have yet to account for the underlying physics and chemistry of the temperature discontinuity. To this end, a pathfinder test campaign was executed at the Hypersonic Materials Environmental Test System (HyMETS) to enhance the fundamental understanding of PICA-NuSil ablation phenomena and provide a preliminary data set to aid in the development of material response models.

PICA↗

Radiation Stability Evaluation of Protein-Based Nanopores for Mars and Europa Missions

Exploration of our Solar System has revealed a number of locations that are now habitable or could have supported life in the past. One approach to finding life involves detection of informational polymers like deoxyribonucleic acid (DNA) and ribonucleic acid (RNA) that are definitive biosignatures for life as we know it. Alternatively, structural variants of DNA and RNA, collectively termed xenonucleic acids (XNAs) have been shown in the laboratory to behave similarly. Nanopore-based sequencers differ from traditional sequencing technologies in that they do not explicitly require synthesis of DNA before or during analysis. Because of this, nanopore sequencers have been used for the direct sequencing of RNA, and could be used for the detection and analysis of other charged polymers. Here we describe results of exposing the MinION hardware, flow cells, and key reagents to ionizing radiation at doses relevant to Mars and Europa missions (10 to 3000 silicon-equivalent gray).

Burton, Aaron S.↗