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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 91 records · Page 5

Sensitivity Studies for In-Situ Automated Tape Placement of Thermoplastic Composites

This modeling effort seeks to improve the interlaminate bond strength of thermoplastic carbon composites produced by the in-situ automated tape placement (ATP) process. An existing high productivity model is extended to lower values of the Peclet number that correspond to the present operating conditions of the Langley ATP robot. (The Peclet number is the dimensionless ratio of inertial to diffusive heat transfer.) In sensitivity studies, all of the process and material parameters are individually varied. The model yields the corresponding variations in the effective bonding time (EBT) referred to the glass transition temperature. According to reptation theory, the interlaminate bond strength after wetting occurs is proportional to the one-fourth power of EBT. The model also computes the corresponding variations in the thermal input power (TIP) and the mass and volumetric process rates. Process studies show that a 10 percent increase in the consolidation length results in a 20 percent increase in EBT and a 5 percent increase in TIP. A surprising result is that a 10 K decrease in the tooling temperature results in a 25 percent increase in EBT and an 8 percent increase in TIP. Material studies show that a 10 K decrease in glass transition temperature results in an 8 percent increase in EBT and a 8 percent decrease in TIP. A 20 K increase in polymer degradation temperature results in a 23 percent increase in EBT with no change in TIP.

Costen, Robert C.↗

Polymer-gas reactions (air pollutants: NO2 and SO2) as function of pressure, UV light, temperature, and morphology: A survey

Reactions of various polymers, such as polystyrene and its stereo-specific isomers, butylrubber, nylon, etc., with nitrogen dioxide and sulfur-dioxide were studied over the past few years. More recently, work has been initiated on the influence of polymer morphology on degradation of polymers in presence of these gases, near UV radiation and oxygen. Unexpected effects have been observed during chain scission near room temperature. Thus, for instance, isotactic polystyrene of various crystallinities, as far as extent and type are concerned, show marked differences in their degradation characteristics. Thus, for instance, crystalline polymers show faster degradation than amorphous ones, which seems to be contrary to expectations. However, this phenomenon can be explained in quite a consistent manner. The importance of all these reactions in connection with air pollution is briefly discussed.

Jellinek, H. H. G.↗

A Multicontinuum-Theory-Based Approach to the Analysis of Fiber-Reinforced Polymer Composites with Degraded Stiffness and Strength Properties Due to Moisture Absorption

Marine energy generation technologies such as wave and tidal power have great potential in meeting the need for renewable energy in the years ahead. Yet, many challenges remain associated with marine-based systems because of the corrosive environment. Conventional materials like metals are subject to rapid corrosive breakdown, crippling the lifespan of structures in such environments. Fiber-reinforced polymer composites offer an appealing alternative in their strength and corrosion resistance, but can experience degradation of mechanical properties as a result of moisture absorption. An investigation is conducted to test the application of a technique for micromechanical analysis of composites, known as multicontinuum theory and demonstrated in past works, as a mechanism for predicting the effects of prolonged moisture absorption on the performance of fiber-reinforced composites. Experimental tensile tests are performed on composite coupons with and without prolonged exposure to a salt water solution to obtain stiffness and strength properties. Multicontinuum theory is applied in conjunction with micromechanical modeling to deduce the effects of moisture absorption on the behavior of constituent materials within the composites. The results are consistent with experimental observations when guided by known mechanisms and trends from previous studies, indicating multicontinuum theory as a potentially effective tool in predicting the long-term performance of composites in marine environments.

36 MATERIALS SCIENCE↗

High Temperature Degradation Mechanisms in Polymer Matrix Composites

Polymer matrix composites are increasingly used in demanding structural applications in which they may be exposed to harsh environments. The durability of such materials is a major concern, potentially limiting both the integrity of the structures and their useful lifetimes. The goal of the current investigation is to develop a mechanism-based model of the chemical degradation which occurs, such that given the external chemical environment and temperatures throughout the laminate, laminate geometry, and ply and/or constituent material properties, we can calculate the concentration of diffusing substances and extent of chemical degradation as functions of time and position throughout the laminate. This objective is met through the development and use of analytical models, coupled to an analysis-driven experimental program which offers both quantitative and qualitative information on the degradation mechanism. Preliminary analyses using a coupled diffusion/reaction model are used to gain insight into the physics of the degradation mechanisms and to identify crucial material parameters. An experimental program is defined based on the results of the preliminary analysis which allows the determination of the necessary material coefficients. Thermogravimetric analyses are carried out in nitrogen, air, and oxygen to provide quantitative information on thermal and oxidative reactions. Powdered samples are used to eliminate diffusion effects. Tests in both inert and oxidative environments allow the separation of thermal and oxidative contributions to specimen mass loss. The concentration dependency of the oxidative reactions is determined from the tests in pure oxygen. Short term isothermal tests at different temperatures are carried out on neat resin and unidirectional macroscopic specimens to identify diffusion effects. Mass loss, specimen shrinkage, the formation of degraded surface layers and surface cracking are recorded as functions of exposure time. Geometry effects in the neat resin, and anisotropic diffusion effects in the composites, are identified through the use of specimens with different aspect ratios. The data is used with the model to determine reaction coefficients and effective diffusion coefficients. The empirical and analytical correlations confirm the preliminary model results which suggest that mass loss at lower temperatures is dominated by oxidative reactions and that these reaction are limited by diffusion of oxygen from the surface. The mechanism-based model is able to successfully capture the basic physics of the degradation phenomena under a wide range of test conditions. The analysis-based test design is successful in separating out oxidative, thermal, and diffusion effects to allow the determination of material coefficients. This success confirms the basic picture of the process; however, a more complete understanding of some aspects of the physics are required before truly predictive capability can be achieved.

Cunningham, Ronan A.↗

High Temperature Degradation Mechanisms in Polymer Matrix Composites

Polymer matrix composites are increasingly used in demanding structural applications in which they may be exposed to harsh environments. The durability of such materials is a major concern, potentially limiting both the integrity of the structures and their useful lifetimes. The goal of the current investigation is to develop a mechanism-based model of the chemical degradation which occurs, such that given the external chemical environment and temperatures throughout the laminate, laminate geometry, and ply and/or constituent material properties, we can calculate the concentration of diffusing substances and extent of chemical degradation as functions of time and position throughout the laminate. This objective is met through the development and use of analytical models, coupled to an analysis-driven experimental program which offers both quantitative and qualitative information on the degradation mechanism. Preliminary analyses using coupled diffusion/reaction model are used to gain insight into the physics of the degradation mechanisms and to identify crucial material parameters. An experimental program is defined based on the results of the preliminary analysis which allows the determination of the necessary material coefficients. Thermogravimetric analyses are carried out in nitrogen, air, and oxygen to provide quantitative information on thermal and oxidative reactions. Powdered samples are used to eliminate diffusion effects. Tests in both inert and oxidative environments allow the separation of thermal and oxidative contributions to specimen mass loss. The concentration dependency of the oxidative reactions is determined from the tests in pure oxygen. Short term isothermal tests at different temperatures are carried out on neat resin and unidirectional macroscopic specimens to identify diffusion effects. Mass loss, specimen shrinkage, the formation of degraded surface layers and surface cracking are recorded as functions of exposure time. Geometry effects in the neat resin, and anisotropic diffusion effects in the composites, are identified through the use of specimens with different aspect ratios. The data is used with the model to determine reaction coefficients and effective diffusion coefficients. The empirical and analytical correlations confirm the preliminary model results which suggest that mass loss at lower temperatures is dominated by oxidative reactions and that these reaction are limited by diffusion of oxygen from the surface. The mechanism-based model is able to successfully capture the basic physics of the degradation phenomena under a wide range of test conditions. The analysis-based test design is successful in separating out oxidative, thermal, and diffusion effects to allow the determination of material coefficients. This success confirms the basic picture of the process; however, a more complete understanding of some aspects of the physics are required before truly predictive capability can be achieved.

Cunningham, Ronan A.↗

Impact of Molecular Design on Degradation Lifetimes of Degradable Imine-Based Semiconducting Polymers

Transient electronics are a rapidly emerging field due to their potential applications in the environment and human health. Recently, a few studies have incorporated acid-labile imine bonds into polymer semiconductors to impart transience; however, understanding of the structure–degradation property relationships of these polymers is limited. In this work, we systematically design and characterize a series of fully degradable diketopyrrolopyrrole-based polymers with engineered sidechains to investigate the impact of several molecular design parameters on the degradation lifetimes of these polymers. By monitoring degradation kinetics via ultraviolet–visible spectroscopy, we reveal that polymer degradation in solution is aggregation-dependent based on the branching point and M n , with accelerated degradation rates facilitated by decreasing aggregation. Additionally, increasing the hydrophilicity of the polymers promotes water diffusion and therefore acid hydrolysis of the imine bonds along the polymer backbone. The aggregation properties and degradation lifetimes of these polymers rely heavily on solvent, with polymers in chlorobenzene taking six times as long to degrade as in chloroform. We develop a new method for quantifying the degradation of polymers in the thin film and observe that similar factors and considerations (e.g., interchain order, crystallite size, and hydrophilicity) used for designing high-performance semiconductors impact the degradation of imine-based polymer semiconductors. We found that terpolymerization serves as an attractive approach for achieving degradable semiconductors with both good charge transport and tuned degradation properties. This study provides crucial principles for the molecular design of degradable semiconducting polymers, and we anticipate that these findings will expedite progress toward transient electronics with controlled lifetimes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Degradation of ESR in Polymer Tantalum Capacitors During High Temperature Storage

Replacement of MnO2 cathodes with conductive polymers in chip tantalum capacitors allows for a substantial reduction of the equivalent series resistance (ESR), improvement of frequency characteristics, and elimination of the possibility of ignition during failures. One of the drawbacks of chip polymer tantalum capacitors (CPTCs) is a relatively poor long-term stability at high temperatures. Due to degradation processes in conductive polymer materials, the existing quality assurance testing that has been developed for MnO2 capacitors is not sufficient to guarantee long-term stability of CPTCs. Insertion of CPTCs in hi-rel systems requires development of models that can predict degradation of the parts at operating conditions. In this work, variations of AC characteristics (capacitance, DF and ESR) in different types of capacitors from three manufacturers have been monitored during storage at temperatures from 100ºC to 175ºC for periods of up to 15,000 hours. Results show that the most sensitive to degradation parameter is ESR. Distributions of times to parametric failure during storage have been simulated using a Weibull-Arrhenius model that allowed for assessments of activation energies of degradation and prediction of times to failure at use temperatures. Mechanisms of degradation and the effect of packaging are discussed.

equivalent series resistance (ESR)↗

Steady-State Vacuum Ultraviolet Exposure Facility With Automated Lamp Calibration and Sample Positioning Fabricated

The Next Generation Space Telescope (NGST) will be placed in an orbit that will subject it to constant solar radiation during its planned 10-year mission. A sunshield will be necessary to passively cool the telescope, protecting it from the Sun s energy and assuring proper operating temperatures for the telescope s instruments. This sunshield will be composed of metalized polymer multilayer insulation with an outer polymer membrane (12 to 25 mm in thickness) that will be metalized on the back to assure maximum reflectance of sunlight. The sunshield must maintain mechanical integrity and optical properties for the full 10 years. This durability requirement is most challenging for the outermost, constantly solar-facing polymer membrane of the sunshield. One of the potential threats to the membrane material s durability is from vacuum ultraviolet (VUV) radiation in wavelengths below 200 nm. Such radiation can be absorbed in the bulk of these thin polymer membrane materials and degrade the polymer s optical and mechanical properties. So that a suitable membrane material can be selected that demonstrates durability to solar VUV radiation, ground-based testing of candidate materials must be conducted to simulate the total 10- year VUV exposure expected during the Next Generation Space Telescope mission. The Steady State Vacuum Ultraviolet exposure facility was designed and fabricated at the NASA Glenn Research Center at Lewis Field to provide unattended 24-hr exposure of candidate materials to VUV radiation of 3 to 5 times the Sun s intensity in the wavelength range of 115 to 200 nm. The facility s chamber, which maintains a pressure of approximately 5 10(exp -6) torr, is divided into three individual exposure cells, each with a separate VUV source and sample-positioning mechanism. The three test cells are separated by a water-cooled copper shield plate assembly to minimize thermal effects from adjacent test cells. Part of the interior sample positioning mechanism of one test cell is shown in the illustration. Of primary concern in VUV exposure is the maintenance of constant measured radiation intensity so that the sample s total exposure can be determined in equivalent Sun hours. This is complicated by the fact that a VUV lamp s intensity degrades over time, necessitating a decrease in the distance between the test samples and the lamp. The facility overcomes this challenge by periodically measuring the lamp s intensity with a cesium-iodide phototube and adjusting the sample distance as required to maintain constant exposure intensity. Sample positioning and periodic phototube location under the lamp are both achieved by a single lead-screw assembly. The lamps can be isolated from the main vacuum chamber for cleaning or replacement so that samples are not exposed to the atmosphere during a test.

Sechkar, Edward A.↗

NASA Glenn Research Center's Materials International Space Station Experiments (MISSE 1-7)

NASA Glenn Research Center (Glenn) has 39 individual materials flight experiments (>540 samples) flown as part of the Materials International Space Station Experiment (MISSE) to address long duration environmental durability of spacecraft materials in low Earth orbit (LEO). MISSE is a series of materials flight experiments consisting of trays, called Passive Experiment Carriers (PECs) that are exposed to the space environment on the exterior of the International Space Station (ISS). MISSE 1-5 have been successfully flown and retrieved and were exposed to the space environment from one to four years. MISSE 6A & 6B were deployed during the STS-123 shuttle mission in March 2008, and MISSE 7A & 7B are being prepared for launch in 2009. The Glenn MISSE experiments address atomic oxygen (AO) effects such as erosion and undercutting of polymers, AO scattering, stress effects on AO erosion, and in-situ AO fluence monitoring. Experiments also address solar radiation effects such as radiation induced polymer shrinkage, stress effects on radiation degradation of polymers, and radiation degradation of indium tin oxide (ITO) coatings and spacesuit fabrics. Additional experiments address combined AO and solar radiation effects on thermal control films, paints and cermet coatings. Experiments with Orion Crew Exploration Vehicle (CEV) seals and UltraFlex solar array materials are also being flown. Several experiments were designed to provide ground-facility to in-space calibration data thus enabling more accurate in-space performance predictions based on ground-laboratory testing. This paper provides an overview of Glenn s MISSE 1-7 flight experiments along with a summary of results from Glenn s MISSE 1 & 2 experiments.

deGroh, Kim K.↗

Toward a Circular Bioeconomy: Designing Microbes and Polymers for Biodegradation

Polymer production is rapidly increasing, but there are no large-scale technologies available to effectively mitigate the massive accumulation of these recalcitrant materials. One potential solution is the development of a carbon-neutral polymer life cycle, where microorganisms convert plant biomass to chemicals, which are used to synthesize biodegradable materials that ultimately contribute to the growth of new plants. Realizing a circular carbon life cycle requires the integration of knowledge across microbiology, bioengineering, materials science, and organic chemistry, which itself has hindered large-scale industrial advances. This review addresses the biodegradation status of common synthetic polymers, identifying novel microbes and enzymes capable of metabolizing these recalcitrant materials and engineering approaches to enhance their biodegradation pathways. Design considerations for the next generation of biodegradable polymers are also reviewed, and finally, opportunities to apply findings from lignocellulosic biodegradation to the design and biodegradation of similarly recalcitrant synthetic polymers are discussed.

59 BASIC BIOLOGICAL SCIENCES↗

HyBlend Collaborative Research Partnership (CRADA Final Report)

This agreement assembles a multi-lab, multi-industry team to address high-priority research topics related to the blending of hydrogen (H2) into the U.S. natural gas (NG) pipeline network. There are four main research objectives: 1. Compatibility of metals (SNL) – Develop general principles for operation of HyBlend™ delivery systems in the context of structural integrity and assess the role of gas impurities on degradation of metal pipelines. 2. Compatibility of polymers (PNNL) – Assess gas impurities in HyBlend for polymer pipeline degradation and lifetime predictions. 3. Life cycle analysis (LCA) (ANL) – Analyze the life cycle of technology pathways for hydrogen and NG blends, as well as alternative pathways. 4.Techno-economic analysis (TEA) (NREL) – Quantify the costs and opportunities for hydrogen production and blending with the NG network, as well as alternative pathways.

08 HYDROGEN↗

Characterization and degradation studies on synthetic polymers for aerospace application

The anti-misting additive for jet fuels known as FM-9 (proprietary polymer) was characterized by elemental analysis, solubility studies and molecular weight determination. Physical properties of surface tension, viscosity, specific gravity and other physical parameters were determined. These results are compared with properties of polyisobutylene and fuels modified with the same; the misting characteristics of polyisobutylene and FM-9 in Jet A fuel are included. Characterization and degradation of phthalocyanine and its derivatives were accomplished by use of a mass spectrometer and a pyroprobe solid pyrolyzer. Metal phthalocyanine tetracarboxylic acids and phthalocyanine-tetraamine cured epoxies were studied. Epoxy/graphite composite panels were exposed to a NASA-Ames radiant panel fire simulator in the flaming and non-flaming modes; toxic gases of HCN and HZS were measured along with oxygen, Co2, Co, and organic gases.

Hsu, M. T. S.↗

On the Mechanism of the Steady-State Gamma Radiolysis-Induced Scissions of the Phenyl-Vinyl Polyester-Based Resins

The major societal problem of polymeric waste necessitates new approaches to break down especially challenging discarded waste streams. Gamma radiation was utilized in conjunction with varying solvent environments in an attempt to discern the efficacy of radiolysis as a tool for the deliberate degradation of model network polyesters. Our EPR results demonstrated that gamma radiolysis of neat resin and in the presence of four widely used solvents induces glycosidic scissions on the backbone of the polyester chains. EPR results clearly show the formation of alkoxy radicals and C-centered radicals as primary intermediate radiolytic products. Despite the protective role of the phenyl groups on the backbone of the radiation-induced polyester chains, the radiolytic-glycosidic scissions predominate. Among the following three solvents used in this study (water, isopropyl alcohol, and dichloromethane), the highest radiolytic yield of glycosidic scission was achieved using water. The •OH radicals produced in the radiolysis of phenyl unsaturated polyester aqueous suspensions very rapidly abstract H atoms from the methylene group, which is followed by a very rapid glycosidic scission. The lowest glycosidic yield was found in the dichloromethane solutions of these polyester resins due to scavenging by the fast electron capture reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Review of oxidative degradations of certain heterocyclic polymers

The curing and decompositions of polyphenylenes and several nitrogen-containing condensation polymers, particularly polybenzimidazoles and pyrones, are reviewed critically. It is concluded that the condensations are usually imperfect and incomplete and that in most of the published work the late stages of the condensation are complicated by the beginnings of the charring and carbonization processes. Most discussions of mechanisms in this range are highly speculative and of little value. The most promising fields for further research are at lower temperatures, where slow oxidation processes deserve study, and at higher temperatures, where it may be possible to influence carbonization processes to obtain better products.

Mayo, F. R.↗