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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 271 records · Page 15
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Rheology of fresh cement pastes containing polymer nanoparticles

Influences of polymer nanoparticles (PNPs) with varied charge densities on the rheological behaviors of fresh cement pastes (fcps) without and with polycarboxylate superplasticizer (PCE) were studied. In the blank fcp, the addition of PCE and highly anionically charged PNPs greatly decreases the yield stress and the plastic viscosity due to their large adsorption on cement that produces electrostatic repulsion and steric hindrance between cement grains. However, the non-adsorbing nonionic PNPs show a slightly opposite effect. In the PCE-containing fcp, both the anionic and nonionic PNPs become non-adsorbing on cement due to the stronger affinity of PCE to cement surface. In this way, the addition of the PNPs in the PCE-containing fcp slightly increases the yield stress and the plastic viscosity, but significantly decreases the pseudoplastic index, which is believed to result from the generation of the so-called depletion attractive force between cement grains induced by the non-adsorbing polymers.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Phosphonium-Based Polyzwitterions: Influence of Ionic Structure and Association on Mechanical Properties

This manuscript describes a synthetic strategy and structure–property investigation of unprecedented phosphonium-based zwitterionic homopolymers (polyzwitterions) and random copolymers (zwitterionomers). Free radical polymerization of 4-(diphenylphosphino)styrene (DPPS) provided neutral polymers containing reactive triarylphosphines. Quantitative postpolymerization alkylation of these pendant functionalities generated a library of polymers containing various concentrations of neutral phosphines, phosphonium ions, and phosphonium sulfobetaine zwitterions. The zwitterionic homo- and copolymers exhibited significantly higher glass transition temperatures (T g ) and enhanced mechanical reinforcement in comparison to neutral and phosphonium analogues. These changes in T g and mechanical properties were attributed to nanoscale morphological domains, which formed due to electrostatic interactions between zwitterionic groups, as revealed by X-ray scattering and broadband dielectric spectroscopy (BDS). BDS revealed increased static dielectric constants (>25) for the phosphonium zwitterionomers compared to ionomeric or neutral analogues. These high static dielectric constants for the solvent-free polyzwitterions supported their stronger polarization response in comparison with polymers containing neutral phosphines and phosphonium ions, and these interactions accounted for morphological differences and enhanced mechanical behavior. This work describes a versatile strategy for modulating electrostatic interactions with tunable mechanical properties for an unprecedented family of zwitterionic polymers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Crystallization kinetics and nanoparticle ordering in semicrystalline polymer nanocomposites

There has been considerable interest in the nucleation and crystallization of polymers in the presence of nanoparticles (NPs, or nanofillers in general, NFs). Most of the extensive work in this area has focused on anisotropic, non-Brownian NFs (e.g., clay sheets, carbon nanotubes) whose spatial dispersion state in these nanocomposites is controlled by the process by which they are formed. Hence, NF spatial dispersion is generally limited and often remains poorly characterized. Thermodynamic handles that can be used to control NF dispersion state in the polymer melt include (a) favorable interactions between the polymer chains and the bare NP surfaces, or (b) the density and length of the chains, with the same chemistry as the matrix, grafted to the NP surface. These relatively large NFs merely act as stationary objects that affect the kinetics of nucleation by providing heterogeneous sites, and the crystallization rate by confining the polymer in the melt state. The dispersion state of the NFs can dramatically affect the nucleation and crystallization of the matrix, but in most cases reported, the NFs increase nucleation efficiency relative to the neat polymer. At higher NF loadings, the effect of polymer confinement by the NFs dominates, leading to a decrease in crystal growth rates. This review describes the most important lessons learned from these commonly studied systems and then extends to polymer composite systems containing small, mobile spherical NPs (typically smaller than 100 nm in size). The role of NP mobility, which provides for dynamic confinement of the polymer melt, on the kinetics of polymer crystallization (nucleation, growth, and overall crystallization) and how this behavior is mostly consistent with the case of immobile NF is a second important focus of this review. In addition to the role of NFs on crystallization kinetics, recently reported nanoparticle ordering phenomena such as the effect of matrix crystallization on the organization of small spherical NPs within the amorphous regions of the semicrystalline morphology are discussed. In conclusion, such phenomena are clearly not observed for large NFs and hence provide a point of departure from past works in this area.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Polymer Retention “Tailing” Phenomenon Associated with the Milne Point Polymer Flood

Summary Associated with the Milne Point polymer flood (on Alaska’s North Slope), this paper explores the unusual shape of hydrolyzed polyacrylamides (HPAM) breakout/propagation during dynamic polymer retention measurements in Milne Point core material. In contrast to conventional expectations, polymer retention does not delay the initial polymer arrival at the end of a Milne Point core. However, after effluent polymer concentrations rapidly rise to at least 50% of the injected value, the concentration gradually “tails” up over many pore volumes (PVs) before it finally achieves the injected value. To understand the origin and significance of this behavior, a wide range of core experiments were performed, including substantial variations in polymer concentration and molecular weight, core length, preservation state, sand grain size, and mineral composition. Illite was identified as primarily responsible for the tailing phenomenon. This phenomenon has important consequences that must be considered when projecting the performance of the field project. This work suggests that mineralogy analysis (especially for illite and kaolinite) may reveal whether tailing should be accounted for during simulations of polymer propagation/retention in a given field application.

Engineering↗
DOE OSTI2023

A Physics-Based Data-Driven Approach for Modeling of Environmental Degradation in Elastomers

Abstract Elastomers are now commonly used in a number of industries, including aerospace, structure, transportation, shipbuilding, and automotive, due to their excellent workability, formability, and flexibility. During their activity, elastomers are subjected to harsh environmental conditions, which decreases their resilience. False predictions made early in their lives can have major financial and environmental implications. Elastomers’ performance and properties, such as strength, durability, and density, are influenced by chemical changes in these materials, known as degradation, which occurs over time. This process can alter the morphology of a polymer matrix as well as cause chain scission and cross-linking, resulting in different behaviors than that of the unaged material. To demonstrate the effect of thermaloxidative aging on the mechanical behavior of elastomers, several experimental and theoretical models have been proposed. In view of the large volume of experimental data available on micro-structural evolution in the course of aging, we propose a physics-based data-driven approach to overcome the shortcomings of both phenomenological and micro-mechanical models. This work presents a novel thermodynamically consistent, multiagent machine-learned model for predicting the constitutive behavior of cross-linked elastomers during environmental aging, such as thermo-oxidative and hydrolytic aging for various states of deformation. Single mechanism degradation changes the polymer matrix over time where it is causing chain scission, reduction of cross-links, and morphology change. To capture the idealized Mullins effect and permanent set due to the effect of single aging mechanisms on nonlinear mechanical responses of elastomers, we propose a data-driven model for simulating inelastic elements in a polymer matrix. By using a sequential order reduction, we were able to reduce the 3D stress-strain tensor mapping problem to a small number of super-constrained 1D mapping problems. To systematically classify such mapping problems into a few categories, an assembly of multiple replicated conditional neural network learning agents (L-agents) is used based on our recent work. Each category is represented by a different type of agent. The effect of deformation history, aging time, and aging temperature is captured by this model. The model is validated using a broad collection of data, ranging from our experimental results to data from the literature. In addition, thermodynamic consistency and frame independence are investigated. The most significant achievements of this model are its precision, simplicity, and prediction of inelasticity under various states of deformation. The model’s accuracy and simplicity make it a good option for commercial and industrial applications. Conveniently, due to the model modular nature, it can be expanded in the future to include viscoelasticity and non-isotropic formation for better precision.

Ghaderi, Aref↗
DOE OSTI2025

Impact of Irradiation on Corrosion Performance of Hybrid Organic/Inorganic Coatings on Austenitic Stainless Steel

The effects of gamma radiation on the performance of two corrosion-resistant coatings applied to stainless-steel 304L (SS304L) surfaces are presented. Specifically, the ability of the coatings to mitigate corrosion of SS304L surfaces as a function of the dose received (0–1300 Mrad) and dose rate (176 compared to 1054 rad/s) is evaluated using electrochemical methods, spectroscopy, and microscopy. Coating A, an organic/inorganic hybrid coating consisting of a two-part silica ceramic component and a polymer linker was evaluated in comparison to Coating B, which utilized Coating A as a topcoat for a commercial, off-the-shelf, Zn-rich primer. Post irradiation, Coating A demonstrated some corrosion protection following exposure to low levels of gamma radiation, but coating degradation occurred with an increased exposure dose and resulted in isolated regions of corrosion initiation. For Coating B, greater corrosion resistance was observed compared to Coating A due to the sacrificial nature of the Zn at elevated doses of gamma radiation. No effect of the dose rate (for the single dose examined) was observed for either coating. It is proposed for Coating B that as the polymer coating thermally degrades above 250 °C (bond scission of the polymer occurs), the remaining Zinc layer adhered to the SS304L post-irradiation enables enhanced corrosion resistance as compared to Coating A, which displays solely polymer degradation. The results presented herein establish an understanding of coating behavior with radiation exposure, specifically the relationship between corrosion coating performance and radiation dose, and can inform ageing and lifetime management for various applications.

degradation↗
DOE OSTI2019

Brush-Modified Materials: Control of Molecular Architecture, Assembly Behavior, Properties and Applications

Recent progress in surface-initiated polymerization enables the deliberate polymer modification of nanoscopic surfaces with high levels of precision. This has given rise to the development of brush particle-based materials (sometimes referred to as ‘hairy nanoparticles’) that are formed by tethering of polymer chains to the surface of nanoparticle-like objects. Brush particles have attracted interest as model systems to understand the effect of surface modification on the structure and interactions in polymer modified colloidal systems (which play a role across fields as diverse as functional coatings, cosmetics, foods or pharmaceuticals) but also as building blocks for the assembly of ‘one-component hybrid materials’ that exhibit unprecedented property combinations, not realizable in classical composite materials. This review presents a summary and analysis of the developments in the field of ‘particle brush materials’. The evolution of synthetic methodologies from the original pioneering work to emerging trends and opportunities in the field of brush synthesis is presented first. Subsequently, the effect of brush architecture on the structure, interaction and assembly of brush particles both with and without a matrix is discussed. Lastly, recent advances in the development of functional hybrid materials with applications in energy, catalysis, sensing and other areas is presented.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Closing the loop between microstructure and charge transport in conjugated polymers by combining microscopy and simulation

A grand challenge in materials science is to identify the impact of molecular composition and structure across a range of length scales on macroscopic properties. We demonstrate a unified experimental–theoretical framework that coordinates experimental measurements of mesoscale structure with molecular-level physical modeling to bridge multiple scales of physical behavior. Here we apply this framework to understand charge transport in a semiconducting polymer. Spatially-resolved nanodiffraction in a transmission electron microscope is combined with a self-consistent framework of the polymer chain statistics to yield a detailed picture of the polymer microstructure ranging from the molecular to device relevant scale. Using these data as inputs for charge transport calculations, the combined multiscale approach highlights the underrepresented role of defects in existing transport models. Short-range transport is shown to be more chaotic than is often pictured, with the drift velocity accounting for a small portion of overall charge motion. Local transport is sensitive to the alignment and geometry of polymer chains. At longer length scales, large domains and gradual grain boundaries funnel charges preferentially to certain regions, creating inhomogeneous charge distributions. While alignment generally improves mobility, these funneling effects negatively impact mobility. The microstructure is modified in silico to explore possible design rules, showing chain stiffness and alignment to be beneficial while local homogeneity has no positive effect. This combined approach creates a flexible and extensible pipeline for analyzing multiscale functional properties and a general strategy for extending the accesible length scales of experimental and theoretical probes by harnessing their combined strengths.

42 ENGINEERING↗
DOE OSTI2021

Intramolecular structure and dynamics in computationally designed peptide-based polymers displaying tunable chain stiffness

Here, polymers assembled using computationally designed coiled coil bundlemers display tunable stiffness via control of interbundlemer covalent connectivity as confirmed using small-angle neutron scattering. Neutron spin echo spectroscopy reveals that rigid rod polymers show a decay rate Γ~Q 2 (Q is the scattering vector) expected of straight cylinders. Semirigid polymers assembled using bundlemers linked via 4-armed organic linker show flexible segmental dynamics at mid-Q and Γ~Q 2 behavior at high Q. The results give insight into linker flexibility-dependent interbundlemer dynamics in the hybrid polymers.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Measuring Topological Constraint Relaxation in Ring-Linear Polymer Blends

Polymers are an effective test bed for studying topological constraints in condensed matter due to a wide array of synthetically available chain topologies. When linear and ring polymers are blended together, emergent rheological properties are observed as the blend can be more viscous than either of the individual components. This emergent behavior arises since ring-linear blends can form long-lived topological constraints as the linear polymers thread the ring polymers. Here, in this work, we demonstrate how the Gauss linking integral can be used to efficiently evaluate the relaxation of topological constraints in ring-linear polymer blends. For majority-linear blends, the relaxation rate of topological constraints depends primarily on reptation of the linear polymers, resulting in the diffusive time τ d,R for rings of length N R blended with linear chains of length N l to scale as τ d,R ~ N$^2_R$N$^{3.4}_L$.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Conformational Entropy as a Means to Control the Behavior of Poly(diketoenamine) Vitrimers In and Out of Equilibrium

Abstract Control of equilibrium and non‐equilibrium thermomechanical behavior of poly(diketoenamine) vitrimers is shown by incorporating linear polymer segments varying in molecular weight (MW) and conformational degrees of freedom into the dynamic covalent network. While increasing MW of linear segments yields a lower storage modulus at the rubbery plateau after softening above the glass transition (T g ), both T g and the characteristic time of stress relaxation are independently governed by the conformational entropy of the embodied linear segments. Activation energies for bond exchange in the solid state are lower for networks incorporating flexible chains; the network topology freezing temperature decreases with increasing MW of flexible linear segments but increases with increasing MW of stiff segments. Vitrimer reconfigurability is therefore influenced not only by the energetics of bond exchange for a given network density, but also the entropy of polymer chains within the network.

He, Changfei↗
DOE OSTI2024

Autonomous phototaxis of hydrogel swimmers

The design of synthetic soft matter capable of emulating the complex behaviors of living organisms, such as sensing and adapting to their environment, remains an important challenge in developing biomimetic materials. Functionalized hydrogels are ideal candidates for such materials since they are highly responsive to their environment and can be operated in water. In this work, we investigate a hybrid bonding hydrogel composed of peptide amphiphile supramolecular nanofibers covalently attached to a photoresponsive network, in which high-aspect-ratio ferromagnetic nanowires are aligned along the length of the sample, designed to swim under oscillating magnetic fields. This hybrid hydrogel swimmer can autonomously swim toward a light source by utilizing photoinduced interactions between supramolecular and covalent networks reminiscent of phototactic swimming in living systems. Using a combination of experimental techniques and a continuum model incorporating photochemistry, magnetoelasticity, and hydrodynamics, we explain the swimming mechanism and predict phototactic behavior. Our work highlights the potential role of hybrid bonding polymers, which leverage the interplay between supramolecular assemblies and covalent networks. We demonstrate how these polymers can be tailored to react dynamically to their environment, paving the way for developing intelligent and autonomous robotic systems.

Science & Technology - Other Topics↗
DOE OSTI2019

Effect of surface treatment of microfiberlated cellulose fibers on biocomposite properties and additive manufacturing process

Polymer additive manufacturing (AM) is a rapidly growing technology and it is transitioning to become an advanced manufacturing technique with the introduction of fiberlar reinforcing materials such as carbon and glass fibers into polymer feedstock. As a result of increasing environmental and long-term sustainability concerns, there is an increasing interest in using bio-derived cellulose fibers to reinforce composites instead of carbon and glass fibers. Melt extrusion/fused filament fabrication method is the most commonly used polymer AM technique which enables direct digital manufacturing of parts with complex geometry with a controlled anisotropic distribution of reinforcing phase. However, there are multiple factors that affect the mechanical performance of the final part such as the dispersion and orientation of the reinforcing fibers, the adhesion between the fibers and the polymer matrix, and the porosity/defects present in the part. Chemical modification of the surface of the reinforcing fibers is an effective way of improving the fiber-polymer interaction. Furthermore, the improved adhesion between the fibers and the polymer can also enhance the fiber dispersion, improve the rheological behavior of the molten feedstock and minimize the formation of porosity during the printing process, which is one of the major issues in AM. In this study, we are investigating the effect of silane surface treatment of micro-cellulose fibers on the thermal, rheological and mechanical properties of cellulose-PLA biocomposites and on the 3D-printing process. X-ray photoelectron spectroscopy results confirmed the increase in amine and silane groups on the surface of modified fibers, indicating successful functionalization. Thermal and mechanical characterization of modified fiber-PLA composites showed significant increases in storage modulus, glass transition temperature, and complex viscosity compared to neat PLA.

Tekinalp, Halil↗
DOE OSTI2020

Heterogeneous Polymer Dynamics Explored Using Static 1H NMR Spectra

NMR spectroscopy continues to provide important molecular level details of dynamics in different polymer materials, ranging from rubbers to highly crosslinked composites. It has been argued that thermoset polymers containing dynamic and chemical heterogeneities can be fully cured at temperatures well below the final glass transition temperature (Tg). In this paper, we described the use of static solid-state 1H NMR spectroscopy to measure the activation of different chain dynamics as a function of temperature. Near Tg, increasing polymer segmental chain fluctuations lead to dynamic averaging of the local homonuclear proton-proton (1H-1H) dipolar couplings, as reflected in the reduction of the NMR line shape second moment (M2) when motions are faster than the magnitude of the dipolar coupling. In general, for polymer systems, distributions in the dynamic correlation times are commonly expected. To help identify the limitations and pitfalls of M2 analyses, the impact of activation energy or, equivalently, correlation time distributions, on the analysis of 1H NMR M2 temperature variations is explored. It is shown by using normalized reference curves that the distributions in dynamic activation energies can be measured from the M2 temperature behavior. An example of the M2 analysis for a series of thermosetting polymers with systematically varied dynamic heterogeneity is presented and discussed.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Cross-Linker Selection Controls Glass Transition Elevation or Reduction in Dynamic Covalently Bonded Polymer Networks

Introducing cross-links is a powerful approach to improve polymeric material performance relevant to controlling viscoelasticity, thermal and creep resistance, degradability, and efficient membrane separations. The chemically specific glass transition temperature T g is of fundamental importance in determining the time scales of key dynamical processes and physical state of the material in such applications. Here, we study experimentally how the introduction of relatively large cross-linking molecules in slowly exchanging dynamic bond-forming polymers (vitrimers) impacts vitrification for diverse polymer chemistries and a wide range of cross-link fractions. We find T g can increase, decrease, or even remain essentially unchanged, in qualitative contrast to the generic elevation of T g in traditional permanent polymer networks. We formulate an effective terpolymer network model to understand this rich behavior, which emerges as a consequence of a competition between pure cross-linking and generalized plasticization effects. The latter is associated with the tunable cross-linker size and intrinsic dynamic mobility that can offset slowing down due to traditional permanent cross-linking constraints. Here, a new strategy for functional polymer network design is suggested based on adjusting the relative importance of the two competing physical effects, which potentially can significantly enhance energy savings in applications while retaining other intrinsic properties germane to advanced materials performance.

Copolymers↗
DOE OSTI2021

How Do Ionic Liquids “Fold” Ionenes? Computational and Experimental Analysis of Imidazolium Polymers Based on Ether and Alkyl Chain Variations Dissolved in an Ionic Liquid

Molecular dynamics (MD) simulations and complementary experiments are used here to understand the inter- and intramolecular structure and conformational properties of ionenes (i.e., cationic polymers formed from condensation reactions) dissolved in an ionic liquid (IL), 1-ethyl-3-methylimidazolium bistriflimide [C 2 mim + ][Tf 2 N - ]. The simulated structural properties are benchmarked against experimental analyses of these same polymers, mainly using dynamic light scattering (DLS) experiments. Four different imidazolium ionenes are considered, corresponding to variations in the chemistry and structure of the repeat units including: (1) poly (decylimidazolium) (PD 10 ); (2) poly (tetraethyleneglycolimidazolium) (PE 10 ); (3) alternating copolymer (P(ED) 5 ); and (4) a block copolymer (PE 5 D 5 ). Detailed computational analyses of the polymer structure and conformational properties were performed, including the radius of gyration, end-to-end distance, torsional distributions, and site-site and spatial distribution functions. Overall, there is a competition between intramolecular associations between the imidazolium groups and the ether sites in the polymers versus the intermolecular interactions of the polymer imidazolium groups with the surrounding anion molecules. The polymer with only ether linkages (PE 10 ) results in the most intramolecular interactions, leading to significant coiling behavior and chain contraction. These strong interactions reduce chain flexibility, but they also result in much more linear chain configurations and alignment of the imidazolium groups. The polymer structure is strongly affected as the concentration of alkyl groups is increased, and we find that the polymer architecture (alternating versus block copolymer) also has an important influence. Furthermore, these detailed observations are important for understanding the connection between the molecular design of imidazolium polymers and their emergent structural properties, which could lead to unique opportunities for creating polymer composites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Bioderived Radical Polymers for Sustainable Energy Storage Materials

Organic mixed ionic and electronic conductors have emerged as promising materials for next-generation energy applications, and a variety of molecular designs have been implemented to push performance to higher levels. Importantly, nonconjugated redox-active radical polymers capable of charge transport offer benefits such as ready synthesis in large quantities and the capability to separate thermomechanical and electrochemical behaviors. This affords more freedom with respect to macromolecular backbone design; thus, the resultant materials properties make this class of polymers appealing alternatives for energy storage. However, these radical polymers often still rely on petrochemically derived polymer backbones. Here, we demonstrate the polymerization of the bioderived terpene β-myrcene and its functionalization by attaching stable radical pendant groups capable of mixed electronic and ionic conduction. The electrochemical enhancement of these materials was substantial as the addition of carbon black and doping of lithium salts electronic conductivities of ~60 S cm -1 were achieved for the composite systems. The addition of the lithium salts proved fruitful as the electric and ionic conductivities of the radical polymers surpassed 10 -4 S cm -1 at elevated temperatures when both lithium hexafluorophosphate and lithium chloride, a more bio and environmentally friendly material, where introduced to the system. Finally, these findings demonstrate a bioderived alternative for an organic mixed conductor serving as both potential cathode and polymer electrolyte for a more sustainable alternative for energy storage applications.

25 ENERGY STORAGE↗
DOE OSTI2025

Hydration and Restructuring of Polar Polymer Interfaces: Implications in Antifouling and Responsive Materials

Manipulating polymer interfaces is crucial for understanding how structure influences function in applications spanning biofouling prevention to energy storage. Moreover, observing how polymers adapt their microscopic structure to changes in their local environment can reveal essential properties that govern their performance in such applications, providing key insights into how to design more effective interfaces. Here, in this study, a series of “grafting-from” polymer brushes with side chains varying in charge, are probed by sum frequency generation (SFG) and modeled using all-atom molecular dynamics (MD) simulations to elucidate how chemical makeup and charge mediate interfacial restructuring in dry versus hydrated states. Results show that charge, in progressing from nonpolar to cationic to zwitterionic, results in dramatic changes in interfacial structure and overall hydration. While net neutral systems, regardless of bulk phase polarity, show minimal interfacial water structuring, the cationic species exhibits strong bulk water signals from the surface potential. Meanwhile, the polymer brushes themselves restructure in water differently independent of charge, impacting the functional groups that are presented to the aqueous phase. Nonpolar and cationic species for instance undergo a change in alkyl group orientations to accommodate hydrating water molecules, whereas the zwitterionic polymer becomes completely disordered in water. Overall, the structure-based behavior trends presented herein have implications in antifouling applications and responsive material interfaces.

biointerface↗