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This paper presents viewgraphs of NASA's strategic and fundamental research program at the Office of Biological and Physical Research (OBPR). The topics include: 1) Colloid-Polymer Samples; 2) Pool Boiling Experiment; 3) The Dynamics of Miscible Interfaces: A Space Flight Experiment (MIDAS); and 4) ISS and Ground-based Facilities.
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The effect of force field type on the predicted elastic properties of a polyimide is examined using a multiscale modeling technique. Molecular Dynamics simulations are used to predict the atomic structure and elastic properties of the polymer by subjecting a representative volume element of the material to bulk and shear finite deformations. The elastic properties of the polyimide are determined using three force fields: AMBER, OPLS-AA, and MM3. The predicted values of Young s modulus and shear modulus of the polyimide are compared with experimental values. The results indicate that the mechanical properties of the polyimide predicted with the OPLS-AA force field most closely matched those from experiment. The results also indicate that while the complexity of the force field does not have a significant effect on the accuracy of predicted properties, small differences in the force constants and the functional form of individual terms in the force fields determine the accuracy of the force field in predicting the elastic properties of the polyimide.
In this study, we demonstrate that a multiblock lithium-ion-conducting polymer can be swollen with ethylene carbonate solvent to increase the conductivity relative to the dry polymer material by nearly 4 orders of magnitude. This increase is due to the partial solvation of lithium ions by ethylene carbonate, which leads to Li + diffusion along the solvent–polymer interface. This differs from the vehicular transport mechanism for lithium ions in pure solvent. We use a combination of broadband dielectric spectroscopy, X-ray scattering, and all-atom molecular dynamics simulations to probe the effect of the solvent on the polymer morphology and to elucidate the mechanism of lithium ion transport.
The interactions between polymers and metal oxide surfaces affect the physical properties of polymer composites and the selectivity of catalysts used for plastic conversion. Gauging the strengths of these interactions and how they depend on adsorption conformations and polymer structure is nevertheless quite challenging. Herein, we evaluate whether a recently introduced dynamic nuclear polarization-based surface-to-atom distance measurement method can be used to gauge the specific interactions between five vinyl polymers and an oxide support (alumina). The adsorption conformations of polymer monolayers were studied using site-specific 13 C{ 27 Al} rotational-echo saturation-pulse double-resonance (RESPDOR) experiments. The method is effective in revealing the average distance between the adsorbed polymer and the surface, as well as the fraction of the monomers that are adsorbed. Polymers that possess larger side chains are more weakly adsorbed, as evidenced by their formation of more numerous loop and tail structures. In conclusion, the measured RESPDOR dephasing data further reveals that polymer adsorption conformations are largely disordered and involve few hydrogen bonding interactions.
Abstract Polymers are a unique class of materials from the perspective of normal mode analysis. Polymers consist of individual chains with repeating units and strong intra-chain covalent bonds, and amorphous arrangements among chains with weak inter-chain van der Waals and for some polymers also electrostatic interactions. Intuitively, this strong heterogeneity in bond strength can give rise to special features in the constituent phonons, but such effects have not been studied deeply before. Here, we use lattice dynamics and molecular dynamics to perform modal analysis of the thermal conductivity in amorphous polymers. We find an abnormally large population of localized modes in amorphous polymers, which is fundamentally different from amorphous inorganic materials. Contrary to the common picture of thermal transport, localized modes in amorphous polymers are found to be the dominant contributors to thermal conductivity. We find that a significant portion of the localization happens within individual chains, but heat is dominantly conducted when localized modes involve two chains. These results suggest localized modes generally play a key role in thermal transport for different polymers. The results provide an alternative perspective on why polymer thermal conductivity is generally quite low and gives insight into how to potentially change it.
Solvent-free, solid polymer electrolytes (SPEs) are promising candidates for next-generation, electrochemical energy storage systems due to their potential to enhance safety and performance, enable flexible device architectures, and streamline manufacturing processes. Conventional SPEs suffer from limited ionic conductivity due to the strong coupling between ion transport and (generally slow) polymer segmental relaxation. The realization of superionic conduction in SPEs, in which ions move faster than the structural relaxation of the polymers, requires a shift in design principles to promote this type of decoupled ion motion. In this perspective, we discuss how polymer architecture, ion–ion correlations, and ion–polymer interactions can unlock superionic behavior. We highlight several key design features, such as crystallinity, bulky side groups, high molecular weight, and percolating ionic aggregation, with a focus on creating low-barrier transport pathways in various polymer systems. We also demonstrate opportunities to combine polymer chemistry and data science through high-throughput and automated screening approaches to reveal how phase behavior, ion dynamics, and ionic interactions govern transport, thereby potentially enabling data-driven discovery of superionic polymer electrolyte materials.
Measuring the catalytic activity of specific sizes of polymers with active catalysts in solution is typically challenging, due to limited instrument detection sensitivity and/or dynamic range. Here, a fluorescence correlation spectroscopy (FCS) method is developed to determine the catalytic activity of living polymers of a specific apparent size in solution. Deviation from a single-component FCS data fitting, as assessed by χ2, is also introduced and developed as a “speciation index”—a method to evaluate and track changes in the relative amount of distinct polymer sizes with reaction progress. These methods are enabled by incorporating a selectively reactive fluorescent monomer into growing polydicyclopentadiene or polynorbornene during ring-opening metathesis polymerization (ROMP). Compared to polynorbornene, data showed that catalysts in aggregates of polyDCPD retained higher activity for longer—outcomes not directly inferable from simple diffusional-access predictions. Here, the ability to assign catalytic activity to polymers of specific sizes, and then to determine how this activity evolves with reaction progress, support long-term goals in the development and measurement of nano-objects that possess size-dependent catalytic activity.
The purpose of this paper is to analyze the migration process of long polymer molecules in a melt or in concentrated solutions as it may be observed from the dynamics of the transverse magnetization of nuclear spins linked to these chains. The low frequency viscoelastic relaxation of polymer systems is known to be mainly controlled by the mechanism of dissociation of topological constraints excited on chains and which are called entanglements. This mechanism exhibits a strong dependence upon the chain molecular weight. These topological constraints also govern the diffusion process of polymer chains. So, the accurate description of the diffusion motion of a chain may be a convenient way to characterize disentanglement processes necessarily involved in any model proposed to explain viscoelastic effects.
Abstract Living cells regulate the dynamics of developmental events through interconnected signaling systems that activate and deactivate inert precursors. This suggests that similarly, synthetic biomaterials could be designed to develop over time by using chemical reaction networks to regulate the availability of assembling components. Here we demonstrate how the sequential activation or deactivation of distinct DNA building blocks can be modularly coordinated to form distinct populations of self-assembling polymers using a transcriptional signaling cascade of synthetic genes. Our building blocks are DNA tiles that polymerize into nanotubes, and whose assembly can be controlled by RNA molecules produced by synthetic genes that target the tile interaction domains. To achieve different RNA production rates, we use a strategy based on promoter “nicking” and strand displacement. By changing the way the genes are cascaded and the RNA levels, we demonstrate that we can obtain spatially and temporally different outcomes in nanotube assembly, including random DNA polymers, block polymers, and as well as distinct autonomous formation and dissolution of distinct polymer populations. Our work demonstrates a way to construct autonomous supramolecular materials whose properties depend on the timing of molecular instructions for self-assembly, and can be immediately extended to a variety of other nucleic acid circuits and assemblies.
Research at NASA Langley Research Center (NASA LaRC) has identified several commercially available thermoplastic polymers that self-heal after ballistic impact and through-penetration. One of these resins, polybutadiene graft copolymer (PB(sub g)), was processed with unsized IM7 carbon fibers to fabricate reinforced composite material for further evaluation. Temperature dependent characteristics, such as the degradation point, glass transition (T(sub g)), and viscosity of the PBg polymer were characterized by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and dynamic parallel plate rheology. The PBg resin was processed into approximately equal to 22.0 cm wide unidirectional prepreg tape in the NASA LaRC Advanced Composites Processing Research Laboratory. Data from polymer thermal characterization guided the determination of a processing cycle used to fabricate quasi-isotropic 32-ply laminate panels in various dimensions up to 30.5cm x 30.5cm in a vacuum press. The consolidation quality of these panels was analyzed by optical microscopy and acid digestion. The process cycle was further optimized based on these results and quasi-isotropic, [45/0/-45/90]4S, 15.24cm x 15.24cm laminate panels were fabricated for mechanical property characterization. The compression strength after impact (CAI) of the IM7/pBG composites was measured both before and after an elevated temperature and pressure healing cycle. The results of the processing development effort of this composite material as well as the results of the mechanical property characterization are presented in this paper.
In the development of advanced aircraft-engine fan cases and containment systems, composite materials are beginning to be used due to their low weight and high strength. The design of these structures must include the capability of withstanding impact loads from a released fan blade. Relatively complex triaxially braided fiber architectures have been found to yield the best performance for the fan cases. To properly work with and design these structures, robust analytical tools are required that can be used in the design process. A new analytical approach models triaxially braided carbon fiber composite materials within the environment of a transient dynamic finite-element code, specifically the commercially available transient dynamic finite-element code LS-DYNA. The geometry of the braided composites is approximated by a series of parallel laminated composites. The composite is modeled by using shell finite elements. The material property data are computed by examining test data from static tests on braided composites, where optical strain measurement techniques are used to examine the local strain variations within the material. These local strain data from the braided composite tests are used along with a judicious application of composite micromechanics- based methods to compute the stiffness properties of an equivalent unidirectional laminated composite required for the shell elements. The local strain data from the braided composite tests are also applied to back out strength and failure properties of the equivalent unidirectional composite. The properties utilized are geared towards the application of a continuum damage mechanics-based composite constitutive model available within LS-DYNA. The developed model can be applied to conduct impact simulations of structures composed of triaxially braided composites. The advantage of this technology is that it facilitates the analysis of the deformation and damage response of a triaxially braided polymer matrix composite within the environment of a transient dynamic finite-element code such as LS-DYNA in a manner which accounts for the local physical mechanisms but is still computationally efficient. This methodology is tightly coupled to experimental tests on the braided composite, which ensures that the material properties have physical significance. Aerospace or automotive companies interested in using triaxially braided composites in their structures, particularly for impact or crash applications, would find the technology useful. By the development of improved design tools, the amount of very expensive impact testing that will need to be performed can be significantly reduced.
Abstract Materials are more easily damaged during accidents that involve rapid deformation. Here, a design strategy is described for electronic materials comprised of conducting polymers that defies this orthodox property, making their extensibility and toughness dynamically adaptive to deformation rates. This counterintuitive property is achieved through a morphology of interconnected nanoscopic core–shell micelles, where the chemical interactions are stronger within the shells than the cores. As a result, the interlinked shells retain material integrity under strain, while the rate of dissociation of the cores controls the extent of micelle elongation, which is a process that adapts to deformation rates. A prototype based on polyaniline shows a 7.5‐fold increase in ultimate elongation and a 163‐fold increase in toughness when deformed at increasing rates from 2.5 to 10 000% min −1 . This concept can be generalized to other conducting polymers and highly conductive composites to create “self‐protective” soft electronic materials with enhanced durability under dynamic movement or deformation.
The room-temperature dynamic fracture response of reaction-bonded silicon nitride is investigated using a hybrid experimental-numerical procedure. In this procedure, experimentally determined crack velocities are utilized to drive a dynamic finite-element code or dynamic finite-difference code in its generation mode in order to extract numerically the dynamic stress intensity factor of the fracturing specimen. Results show that the dynamic fracture toughness vs crack velocity relations of the two reaction-bonded silicon nitrides do not follow the general trend in those relations of brittle polymers and steel. A definite slow crack velocity during the initial phase of dynamic crack propagation is observed in reaction-bonded silicon nitride, which results in a nonunique dynamic fracture toughness vs crack velocity relation. In addition, it is found that a propagating crack will continue to propagate under a static stress intensity factor substantially lower than K(IC).
Polymers such as PTFE (polytetrafluorethylene or Teflon), EPDM (ethylene propylene diene monomer) rubber, FKM fluoroelastomer (Viton), Nylon 11, Nitrile butadiene (NBR) rubber, hydrogenated nitrile rubber (HNBR) and perfluoroelastomers (FF_202) are commonly employed in super critical CO 2 (sCO2) energy conversion systems. O-rings and gaskets made from these polymers face stringent performance conditions such as elevated temperatures, high pressures, pollutants, and corrosive humid environments. In FY 2019, we conducted experiments at high temperatures (100°C and 120°C) under isobaric conditions (20 MPa). Findings showed that elevated temperatures accelerated degradation of polymers in sCO2, and that certain polymer microstructures are more susceptible to degradation over others. In FY 2020, the focus was to understand the effect of sCO2 on polymers at low (10 MPa) and high pressures (40 MPa) under isothermal conditions (100°C). It was clear that the same selectivity was observed in these experiments wherein certain polymeric functionalities showed more propensity to failure over others. Fast diffusion, supported by higher pressures and long exposure times (1000 hours) at the test temperature, caused increased damage in sCO2 environments to even the most robust polymers. We also looked at polymers under compression in sCO2 at 100°C and 20 MPa pressure to imitate actual sealing performance required of these materials in sCO2 systems. Compression worsened the physical damage that resulted from chemical attack of the polymers under these test conditions. In FY 2021, the effect of cycling temperature (from 50°C to 150°C to 50°C) for polymers under a steady sCO2 pressure of 20 MPa was studied. The aim was to understand the influence of cycling temperatures of sCO2 for typical polymers under isobaric (20 MPa) conditions. Thermoplastic polymers (Nylon, and PTFE) and elastomers (EPDM, Viton, Buna N, Neoprene, FF202, and HNBR) were subjected to 20 MPa sCO2 pressure for 50 cycles and 100 cycles in separate experiments. Samples were extracted for ex-situ characterization at 50 cycles and upon the completion of 100 cycles. Each cycle constituted of 175 minutes of cycling from 50°C to 150°C. The polymer samples were examined for physical and chemical changes by Dynamic Mechanical and Thermal Analysis (DMTA), Fourier Transform Infrared (FTIR) spectroscopy, and compression set. Density and mass changes immediately after removal from test were measured for degree of swell comparisons. Optical microscopy techniques and micro computer tomography (micro CT) images were collected on select specimens. Evaluations conducted showed that exposures to super-critical CO2 environments resulted in combinations of physical and/or chemical changes. For each polymer, the dominance of cycling temperatures under sCO2 pressures, were evaluated. Attempts were made to qualitatively link the permanent sCO2 effects to polymer micro- structure, free volume, backbone substitutions, presence of polar groups, and degree of crystallinity differences. This study has established that soft polymeric materials are conducive to failure in sCO2 through mechanisms of failure that are dependent on polymer microstructure and chemistry. Polar pendant groups, large atom substitutions on the backbone are some of the factors that are influential structural factors.
Solid-state batteries with lithium metal anodes present the highest energy density batteries for applications in electric vehicles, leading to massive R&D investments over the past decade. Although most research focuses on preventing lithium metal dendrites that eventually short the battery, the nature of these shorts remains elusive. Soft-shorts, in particular, receive little attention or are not recognized, even in published data. Here, in this study, we present a comprehensive outline of the detection and analysis of soft -shorts in solid-state lithium metal cells with composite polymer electrolytes as well as a fundamental understanding of the dynamics of soft -shorts. Transient un-shorting of soft -shorts that occurs on the micro-to-millisecond timescale-driven by joule heating, chemical reactivity, and other processes-limits one's ability to determine whether the cell was or is still shorted. We provide numerous experimental methods to detect and analyze soft-shorts in any battery type as a resource to all battery researchers.
This research program focused on the characterization of both molecular structure and dynamics of aqueous solutions in various metal-organic frameworks (MOFs) and organic polymers that have recently been proposed for applications in water treatment technologies. This was accomplished by integrating ultrafast vibrational spectroscopy and microscopy, which are sensitive to local environments, molecular orientation, and dynamical couplings, with many-body molecular dynamics (MB-MD) simulations, which enable realistic modeling of aqueous systems and porous materials under different thermodynamic conditions. Our studies allowed for identifying the physical mechanisms and characterizing the underlying molecular interactions between water and host materials that determine the adsorption and transport processes of water in various MOFs and β-cyclodextrin polymers – prototypical examples of porous materials and polymers, that have recently been proposed for technological applications in water purification. By combining bulk- and surface-sensitive, spatially resolved ultrafast vibrational spectroscopy with MB-MD simulations, it was possible to gain broad insight into the structure and mobility of water under heterogeneous confinement at various length scales. In particular, measurements of surface- and bulk-sensitive vibrational spectra at single crystal level, integrated with MB-MD simulations were used to characterize domain-specific, structure–binding affinity relationships. Besides providing specific information about the behavior of aqueous solutions in prototypical MOFs and organic polymers for potential applications in water treatment technologies, our studies also provided fundamental insights into the properties of aqueous solutions in confined heterogeneous environments, which have broad implications in many areas, ranging from heterogeneous catalysis to oil recovery, ion transport processes, and reaction-diffusion processes in crowded systems.
Stable hydration in perfluorinated polyelectrolyte membranes such as Nafion is essential to maintain good ion conductivity and manage permeation, especially in vapor-fed devices where water content depends on relative humidity in a gas stream. Extensive studies in the literature have shown that Nafion hydration in water vapor is controlled by its interfacial transport resistance. Nafion forms a fluorine-rich layer at the polymer-gas interface, and it has been proposed that this layer blocks water transport due to its hydrophobicity. To develop a molecular-level description of the physics underlying transport resistance in this system, we have performed a computational reaction-diffusion kinetics study of water evaporation from Nafion. Two distinct models are examined, one mimicking the blocking function proposed in the literature and the other assuming that there is no blocking, treating instead water evaporation as a dynamic balance between uptake from the gas and desorption from the polymer surface. Simulation results are compared to time-dependent infrared data over a range of 100-0% relative humidity from the literature. Only the dynamic model successfully reproduces experimental observations. This indicates that the physical nature of interfacial transport resistance is not slow diffusion across an interfacial layer; rather, it is due to the competition between dehydration and rehydration. The simulation data provide details on the accompanying water distributions throughout the membrane and on interfacial kinetics, showing that they are characterized by strong fluctuations.