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At least 91 records · Page 5

Viscoelastic characterization of thin-film polymers exposed to low Earth orbit

The materials made available through the Long Duration Exposure Facility (LDEF) satellite provide a set of specimens that can be well characterized and have a known exposure history with reference to atomic oxygen and ultraviolet radiation exposure. Mechanical characteristics measured from control samples and exposed samples provide a data base for predicting the behavior of polymers in low earth orbit. Samples of 1.0 mil thick low density polyethylene were exposed to the low earth orbit environment for a period of six years. These materials were not directly exposed to ram atomic oxygen and offer a unique opportunity for measuring the effect of atomic oxygen and UV radiation on mechanical properties with little concern to the effect of erosion. The viscoelastic characteristics of these materials were measured and compared to the viscoelastic characteristics of control samples. To aid in differentiating the effects of changes in crystallinity resulting from thermal cycling, from the effects of changes in chemical structure resulting from atomic oxygen/UV attack to the polymer, a second set of control specimens, annealed to increase crystallinity, were measured as well. The resulting characterization of these materials will offer insight into the impact of atomic oxygen/UV on the mechanical properties of polymeric materials. The viscoelastic properties measured for the control, annealed, and exposed specimens were the storage and loss modulus as a function of frequency and temperature. From these datum is calculated the viscoelastic master curve derived using the principle of time/temperature superposition. Using the master curve, the relaxation modulus is calculated using the method of Ninomiya and Ferry. The viscoelastic master curve and the stress relaxation modulus provide a direct measure of the changes in the chemical or morphological structure. In addition, the effect of these changes on long-term and short-term mechanical properties is known directly. It should be noted that the dependence on directionality for the polymer films was considered since these films were manufactured by a blown-film process.

Letton, Alan

Polyimide characterization studies - Effect of pendant alkyl groups

The effect on selected polyimide properties when pendant alkyl groups were attached to the polymer backbone was investigated. A series of polymers were prepared using benzophenone tetracarboxylic acid dianhydride (BTDA) and seven different p-alkyl-m,p'-diaminobenzophenone monomers. The alkyl groups varied in length from C(1) (methyl) to C(9) (nonyl). The polyimide prepared from BTDA and m,p'-diaminobenzophenone was included as a control. All polymers were characterized by various chromatographic, spectroscopic, thermal, and mechanical techniques. Increasing the length of the pendant alkyl group resulted in a systematic decrease in glass transition temperature (Tg) for vacuum cured films. A 70 C decrease in Tg to 193 C was observed for the nonyl polymer compared to the Tg for the control. A corresponding systematic increase in Tg indicative of crosslinking, was observed for air cured films. Thermogravimetric analysis revealed a slight sacrifice in thermal stability with increasing alkyl length. No improvement in film toughness was observed.

Jensen, B. J.

Techniques for Measuring Low Earth Orbital Atomic Oxygen Erosion of Polymers

Polymers such as polyimide Kapton and Teflon FEP (fluorinated ethylene propylene) are commonly used spacecraft materials due to their desirable properties such as flexibility, low density, and in the case of FEP, a low solar absorptance and high thermal emittance. Polymers on the exterior of spacecraft in the low Earth orbit (LEO) environment are exposed to energetic atomic oxygen. Atomic oxygen reaction with polymers causes erosion, which is a threat to spacecraft durability. It is therefore important to understand the atomic oxygen erosion yield (E, the volume loss per incident oxygen atom) of polymers being considered in spacecraft design. The most common technique for determining E is through mass loss measurements. For limited duration exposure experiments, such as shuttle experiments, where the atomic oxygen fluence is often so low that mass loss measurements can not produce acceptable uncertainties, recession measurements based on atomic force microscopy analyses can be used. Equally necessary to knowing the mass loss or recession depth for determining the erosion yield of polymers is the knowledge of the atomic oxygen fluence that the polymers were exposed to in space. This paper discusses the procedures and relevant issues for mass loss and recession depth measurements for passive atomic oxygen erosion yield characterization of polymers, along with techniques for active atomic oxygen fluence and erosion characterization. One active atomic oxygen erosion technique discussed is a new technique based on optical measurements. Details including the use of both semi-transparent and opaque polymers for active erosion measurement are reviewed.

deGroh, Kim K.

High Performance Polymers and Composites (HiPPAC) Center

NASA University Research Centers funding has allowed Clark Atlanta University (CAU) to establish a High Performance Polymers and Composites (HiPPAC) Research Center. Clark Atlanta University, through the HiPPAC Center has consolidated and expanded its polymer and composite research capabilities through the development of research efforts in: (1) Synthesis and characterization of polymeric NLO, photorefractive, and piezoelectric materials; (2) Characterization and engineering applications of induced strain smart materials; (3) Processable polyimides and additives to enhance polyimide processing for composite applications; (4) Fabrication and mechanical characterization of polymer based composites.

Mintz, Eric A.

Thermally stable, low dielectric polyquinolines for aerospace and electronics applications

Four new high molecular weight, linear chain polyquinolines have been synthesized and fabricated into high quality free standing films. These polymers are characterized by moderate to high glass transition temperatures, excellent thermal and thermooxidative stability, extremely low dielectric constants and good planarizing characteristics. The polymers absorb very low quantities of moisture. As a consequence, the dielectric constant of one new polyquinoline has been shown to be quite insensitive to exposure to warm/wet conditions. Isothermal aging of one new derivative in air has been carried out at elevated temperatures (250 C to 345 C). The results demonstrate truly outstanding thermooxidative stability. Additional characterizations include molecular weight determinations, solubilities and film-forming characteristics, density measurements, and UV-Vis spectroscopy. The data acquired to date suggest that the polymers may find use as refractive films and coatings and as interlevel planarizers in microelectronics applications.

Hendricks, Neil H.

Correlative molecular-to-mesoscale evolution in conjugated polymers for intrinsically stretchable organic photovoltaics

Conjugated polymer thin films offer a unique combination of tunable optoelectronic properties and mechanical flexibility, making them as promising materials for intrinsically stretchable optoelectronic devices. However, achieving both mechanical robustness and high device performance remains a key challenge. Addressing this requires a fundamental understanding of how molecular and mesoscale structures evolve under mechanical strain. Here, we employ a comprehensive suite of X-ray spectroscopy and scattering techniques to investigate the multiscale structural evolution of conjugated polymer thin films during uniaxial deformation. We uncover a two-stage morphological response: an initial stage characterized by polymer chain alignment and rapid crystallite disruption, followed by continued chain orientation accompanied by intrachain torsion at higher strains. These correlative structural adaptations govern key material properties, including stress dissipation, optical absorption, and photovoltaic performance. Our findings establish a mechanistic framework for understanding deformation in semiconducting polymers and provide design principles for developing mechanically robust, high-performance stretchable electronics.

36 MATERIALS SCIENCE

All-Atom Modeling and Simulation of Biopolymer Interface: Dual Role of Antifouling Polymer Brushes

Antifouling polymer brushes are well-known for their exceptional resistance to unwanted protein adsorption. While experimental studies have extensively characterized protein–polymer brush interactions, computational investigations remain limited, largely due to the challenges in accurately modeling and integrating these complex, multicomponent systems without resorting to oversimplification. To address this challenge, this study presents one of the most comprehensive and realistic model systems to date, comprising the substrate, grafted polymers, and proteins. Our work interprets the interactions between polymer brush and protein based on realistic modeling without simplification. In particular, this study utilizes molecular modeling and simulation of polycationic and polyzwitterionic brushes─poly(dimethylaminoethyl methacrylate) (PDMAEMA), poly(2-(N-oxide-N,N-dimethylamino)ethyl methacrylate) (PNOMA), and poly(2-(N-3-sulfopropyl-N,N-dimethylammonium)ethyl methacrylate) (PSBMA)─grafted onto α-quartz substrates via polymerization initiator linkers. The brush models were developed to closely replicate experimentally synthesized samples and to provide detailed insights into structural and dynamical changes at the molecular level during protein adsorption. Using steered molecular dynamics simulations, we show that the PSBMA brush, due to its high local density, exhibits the greatest resistance to protein insertion. Cα root-mean-square deviation and interaction pattern analyses further reveal that the PSBMA brush also induces the most significant destabilization of lysozyme, while the PDMAEMA brush enhances protein stability through ion-mediated interactions. The PNOMA brush, while requiring the lowest force for protein adsorption, induces greater protein destabilization than the PDMAEMA brush, primarily due to electrostatic repulsion caused by a short carbon spacer length. Hydration analysis reveals that both the PSBMA brush and the lysozyme interacting with it exhibit the most rapid dehydration, attributed to the brush’s high local chain density, which results in the greatest lysozyme destabilization and the highest adsorption force. These findings highlight the dual role of antifouling polymer brushes: resisting protein adsorption and modulating protein structural dynamics. In conclusion, this study provides valuable insights for the rational design of next-generation antifouling materials and offers a framework for realistic model development in complex multicomponent systems.

Adsorption

The Synthesis and Ring-Opening Metathesis Polymerization of Energetic Norbornene Materials

Energetic norbornenes are promising candidates toward the development of new energetic polymers due to the synthetic versatility of norbornene ring-opening metathesis polymerizations used in commercial applications. We report the synthesis of two energetic norbornene materials that can be made in two steps with modest yields, containing either trinitroethanol or fluorodinitroethanol substituents. The norbornene monomers were then polymerized, and the polymers were characterized by Fourier transform infrared spectroscopy (FT-IR), differential scanning calorimetry (DSC), contact angle measurements, and proton and carbon nuclear magnetic resonance spectroscopies ( 1 H and 13 C{ 1 H} NMR). Additionally, small-scale safety data consisting of electrostatic discharge (ESD), friction (FS), and impact (IS) sensitivities were measured for the norbornene monomers and their resulting polymers. These analyses revealed that energetic norbornene materials are relatively insensitive and have densities comparable to that of TNT (1.47–1.81 g·cm –3 ).

36 MATERIALS SCIENCE

Development of polyphenylquinoxaline graphite composites

Six polyphenylquinoxalines (PPQ) containing pendant cyano (CN) groups were synthesized. The polymers were characterized in terms of inherent viscosity, glass transition temperature, softening temperature and weight loss due to aging in air at 316 C (600 F). The potential for crosslinking PPQs by trimerization of pendant CN groups was investigated. A polymer derived from 1 mole 3,3,4,4 -tetraaminobenzophenone, .2 mole p-bis(p -cyanophenoxyphenylglyoxalyl)benzene and .8 mole p-bis(phenylglyoxalyl)benzene was selected for more extensive characterization in HM-S graphite fiber-reinforced composites. Mechanical properties were determined using composites made from HM-S fiber and polymer and composites made from HM-S fiber, polymer and a potential CN group trimerization catalyst. Composite mechanical properties, inter-laminar shear strength and flexure properties, were determined over the temperature range of +21 C to 316 C.

Shdo, J. D.

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.

Emerging polyheterocyclic films, coatings and resins - Thermoplastic polyquinolines

The processing and performance characteristics of a soluble, thermoplastic polyquinoline suggest its utility in a variety of high performance applications. The polymer is characterized by excellent thermal and oxidative stability, very low moisture absorption, good mechanical properties, very low dielectric constant, and an unusually low thermal expansion coefficient. This polymer, designated PQ-100 (TM), can be cast into strong, transparent, free standing films from common solvents. Coatings of variable thickness can be spin-coated on to silicon and other surfaces. After processing into films, PQ-100 (TM) can be rendered insoluble in a wide range of solvents using a proprietary process. The low CTE contributes to very low residual stress when the polymer is spin-coated onto silicon wafers. PQ-100 (TM) is currently under evaluation for use as an interlayer dielectric substrate in high-density interconnect applications, including multichip modules. Many of the characteristics of the polymer also suggest its utility as a high-performance film and as a matrix resin for specialty composite applications.

Hendricks, Neil H.

Novel Ordered Crown Ether-Containing Polyimides for Ion Conduction

We report the synthesis and characterization of thermally-stable polyimides for use as battery and fuel cell electrolyte membranes. Dianhydrides used were 1,4,5,8- naphthalenetetracarboxylic dianhydride and/or 4,4'-(hexafluoroisopropylidene)diphthalic anhydride. Diamines used were anti-4,4-diaminodibenzo-l8-crown-6, 4,4'- diaminodibenzo-24-crown-8, 2,2-bis(4-aminophenyl)hexafluoropropane, and/or 2,5- diaminobenzenesulfonic acid. The polymers were characterized using electrochemical impedance spectroscopy (EIS), thermal analysis and X-ray diffraction. Polymers containing the hexafluoroisopropylidene (HFIP) group were soluble in common organic solvents, while polymers without the HFIP group were very poorly soluble. Sulfonation yields polymers that are sparingly soluble in aqueous base and/or methanol. Degree of sulfonation, determined by titration, was between one and three sulfonate groups per repeat unit. Proton conductivity was determined as a function of water content, with a maximum conductivity of l x 10(exp -2) per centimeter when fully hydrated. Crown ether-containing polymers exhibit a high degree of order that may be indicative of crown ether channel formation, which may facilitate Li(+) transport for use in battery membranes.

Irvin, Jennifer A.

Initial Results of the MISSE-Flight Facility Polymers and Composites Experiment 1-4 (PCE 1-4)

Spacecraft in low Earth orbit (LEO) are subjected to harsh environmental conditions, including radiation (cosmic rays, ultraviolet (UV), x-ray and charged particle radiation), micrometeoroids and orbital debris, temperature extremes, thermal cycling, and atomic oxygen (AO). These environmental exposures can result in erosion, embrittlement and optical property degradation of susceptible materials threatening spacecraft performance and durability. To increase our understanding of effects such as AO erosion and radiation induced embrittlement of spacecraft materials, NASA Glenn Research Center has developed a series of experiments that are flown as part of the Materials International Space Station Experiment (MISSE) missions on the exterior of the International Space Station (ISS). These experiments have provided critical space environmental durability data such as AO erosion data of polymers and composites, and radiation induced mechanical property degradation of spacecraft insulation materials, after long term space exposure. In continuing these studies, four Glenn experiments with 365 flight samples have been flown on ISS’s external MISSE-Flight Facility (MISSE-FF). These experiments are the Polymers and Composites Experiment-1 (PCE-1) flown as part of the inaugural MISSE-9 mission, the PCE-2 flown as part of the MISSE-10 mission, the PCE-3 flown as part of the MISSE-12 and MISSE-15 missions, and the PCE-4 flown as part of the MISSE-13 mission. The primary objective of the PCE 1-4 experiments is to determine the AO and radiation durability of spacecraft polymers and composites. In addition, each experiment has a wide variety of spacecraft materials and hence they each have numerous additional sample objectives. Each of the PCE 1-4 is designed to examine the consequences of AO interactions including AO erosion yield (Ey) and optical and thermal property characterization. Several polymers were flown in both ram and zenith flight orientations to determine the effect of varying solar to AO ratios on Ey. Common spacecraft materials including Teflon FEP, white Tedlar and Upilex-S were included on multiple MISSE missions so erosion dependence on environment exposure can be determined. The PCE-1 includes epoxy composite samples with varying ZnO levels to determine the effect of inorganic filler level on AO durability. And, a variety of samples were flown to characterize AO scattering and AO undercutting processes. All four PCE experiments include samples to provide better insight into radiation durability of polymers and composites. The MISSE-9 PCE-1 includes Teflon FEP tensile samples flown in the wake and zenith direction so variations in radiation exposure from the different flight directions can provide insight into radiation induced embrittlement of Teflon FEP. Teflon FEP tensile samples were also flown in the wake direction as part of the MISSE-13 PCE-4. In addition, shape memory alloys, shape memory composites, melanin based composites, stressed and unstressed gossamer sun shield materials, coated and uncoated docking seal samples, and new solar cell cover slides were flown for space radiation durability and/or shielding assessment. This paper provides an overview of Glenn’s PCE 1-4 MISSE-FF experiments and provides initial post-flight observations and results.

atomic oxygen

Rational sub-nanometer manipulation of polymer morphology for efficient chemical separations

The ability to control polymer morphology on the sub-nanometer length scale has broad implications for chemical separations. To achieve such control on easily processable systems, this proposal focuses on the synthesis and characterization of polymers containing appended labile moieties that are easily detached by thermolysis or UV irradiation deep within the glassy state. Once liberated, these moieties can diffuse from the polymer matrix as gaseous products, leaving behind templated pathways for selective diffusion and sorption of small molecules. With a specific target of creating polymeric membrane materials with unprecedented diffusion and (ad)sorption characteristics for chemical separations, synthesis of new materials will be complemented with advanced metrologies, simulations, and evaluation of thermodynamic and transport theory.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Fire- and heat-resistant laminating resins based on maleimido-substituted aromatic cyclotriphosphazenes

A novel class of flame- and heat-resistant polymers has been synthesized by the thermal polymerization of maleimido-substituted aromatic cyclotriphosphazenes. The polymer obtained from tris-(aminophenoxy)tris(maleimidophenoxy)cyclotriphosphazene has good thermal stability and is noteworthy for its high char yield, viz., 82 percent at 800 C in nitrogen and 81 percent at 700 C in air. Graphite-fabric laminates prepared with this polymer did not burn in pure oxygen, even at 300 C, and were tested for mechanical properties. Hexakis(4-maleimidophenoxy)cyclotriphosphazene and some fluorine-containing monomers have also been synthesized. The structures of these cyclic phosphazene precursors and polymers were characterized by FT IR spectrophotometry, H-1 NMR, F-19 NMR, and P-31 solid-state magic angle spinning NMR spectroscopy, and mass spectrometry. The curing behavior of the polymer precursors and the thermal stabilities of the polymers were evaluated by differential scanning calorimetry (DSC) and thermogravimetric analyses (TGA).

Kumar, D.

Semiconducting polymers for gas detection

Conjugated polyenes, and polyesters containing phthalocyanine in their backbone, were synthesized. These polymers were characterized by chemical analysis, thermogravimetric analysis, spectral analysis, and X-ray diffraction studies for crystallinity, as well as for their film-forming capability and gas/polymer interactions. Most of the polymers were relatively insensitive to water vapor up to 50 percent relative humidity, but the polyester/phthalocyanine (iron) polymer was relatively insensitive up to 100 percent RH. On the other hand, poly(p-dimethylaminophenylacetylene) was too conductive at 100 percent RH. Of the gases tested, the only ones that gave any evidence of interacting with the polymers were SO2, NOx, HCN and NH3. Poly(imidazole)/thiophene responded to each of these gases at all relative humidities, while the other polymers gave varying response, depending upon the RH. Thus, since most of these gases were electron-accepting, the electron-donating character of poly(imidazole)/thiophene substantiates the concept of electronegativity being the operating principle for interaction effects. Of the six polymers prepared, poly(imidazole)/thiophene first showed a very good response to smoldering cotton, but it later became nonresponsive; presumably due to oxidation effects.

Byrd, N. R.

Polyimides with pendant alkyl groups

The effect on selected polyimide properties when pendant alkyl groups were attached to the polymer backbone was investigated. A series of polymers were prepared using benzophenone tetracarboxylic acid dianhydride (BTDA) and seven different p-alkyl-m,p'-diaminobenzophenone monomers. The alkyl groups varied in length from C(1) (methyl) to C(9) (nonyl). The polyimide prepared from BTDA and m,p'-diaminobenzophenone was included as a control. All polymers were characterized by various chromatographic, spectroscopic, thermal, and mechanical techniques. Increasing the length of the pendant alkyl group resulted in a systematic decrease in glass transition temperature (Tg) for vacuum cured films. A 70 C decrease in Tg to 193 C was observed for the nonyl polymer compared to the Tg for the control. A corresponding systematic increase in Tg indicative of crosslinking, was observed for air cured films. Thermogravimetric analysis revealed a slight sacrifice in thermal stability with increasing alkyl length. No improvement in film toughness was observed.

Jensen, B. J.