Search NASA⌕ Search

SEARCH · Search NASA

Results for “Grafting density”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 91 records · Page 5
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Strategy for Nonenzymatic Harvesting of Cells via Decoupling of Adhesive and Disjoining Domains of Nanostructured Stimulus-Responsive Polymer Films

The nanostructured polymer film introduces a novel mechanism of nonenzymatic cell harvesting by decoupling solid cell-adhesive and soft stimulus-responsive cell-disjoining areas on the surface. The key characteristics of this architecture are the decoupling of adhesion from detachment and the impermeability to the integrin protein complex of the adhesive domains. This surface design eliminates inherent limitations of thermoresponsive coatings, namely, the necessity for the precise thickness of the coating, grafting or cross-linking density, and material of the basal substrate. The concept is demonstrated with nanostructured thermoresponsive films made of cell-adhesive epoxy photoresist domains and cell-disjoining poly(N-isopropylacrylamide) brush domains.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Thermoosmotic Transport in Nanochannels Grafted with pH-responsive Polyelectrolyte Brushes Modelled Using Augmented Strong Stretching Theory

In this paper, we develop a theory to establish that the thermoosmotic (TOS) effects, induced by the application of an axial temperature gradient, leads to a massive enhancement in liquid transport in nanochannels grafted with charged polyelectrolyte (PE) brushes. Here, we quantify the TOS transport by quantifying the induced electric field and the induced TOS flow field. The different components of the electric field, namely the ionic component, the thermal component, and the osmotic component, as well as the contributions of different ions to these components, are quantified. Furthermore, we express the TOS velocity as a combination of chemiosmotic (COS), thermal, and electroosmotic (EOS) components. The COS and the thermal components augment each other and the overall strength and direction of the TOS flow are dictated by the direction and the relative strength of the EOS component. Most importantly, we compare the cases of brush-grafted nanochannels with those of the brush-free nanochannels of identical surface charge densities: the TOS transport is massively augmented in the brush-grafted nanochannels attributed to the combination of the localization of the EDL (and hence any body force that depends on the EDL charge density) away from the nanochannel wall (i.e., the location of the maximum drag force) and the presence of a possible molecular slip (experienced by the liquid) along the brush surface.

42 ENGINEERING↗
DOE OSTI2025

Theoretical and Experimental Insights into CO 2 Capture and Methanation over Amine-Grafted Ru-Based Catalysts

Carbon capture and storage (CCS) technologies, along with CO 2 capture and conversion methods, have emerged as crucial research areas to address rising CO 2 emissions. In this study, we seek to understand the mechanistic role of amines in enabling lower-energy pathways for CO 2 conversion. Our research focuses on the development and analysis of dual-functional materials (DFMs) engineered for the reactive capture and conversion (RCC) of CO 2 into methane, utilizing Ru catalysts grafted with amine groups. We employ Density Functional Theory (DFT) calculations using methylamine as a model amine to investigate the impact of amine groups on CO 2 methanation on a Ru(0001) surface, both in the presence and absence of amine groups. The amine ligand alters the carbon coordination environment, promoting direct C–O dissociation and potentially destabilizing the CO* adsorbate, thereby reducing the risk of CO poisoning. Additionally, we observe a preference for hydrogenation, although it becomes more energetically uphill in the amine-bound scenario. Our experiments, however, report similar CO 2 conversion and CH 4 production rates over the synthesized catalysts “Ru/TiO 2 ” and the amine (N-(2-aminoethyl)-3-aminoproplytrimethoxysilane (“diaminosilane”)) deposited catalyst “Diamine−Ru/TiO 2 ”. By constructing comparative reaction-free energy diagrams and performing microkinetic modeling (MKM) simulations, we link our theoretical findings with experimentally observed CO 2 uptake, conversion, and methane production rates. A microkinetic model was employed to investigate the anomaly, showing reduced amine–carbon complex coverage and increased CO 2 coverage at all temperatures. The MKM simulations consistently confirmed these trends. In conclusion, this comprehensive approach offers key insights into the role of the amine-CO 2 bond in methanation, highlighting a pathway toward lower-energy, more efficient CO 2 capture and conversion processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Polarized X-ray scattering measures molecular orientation in polymer-grafted nanoparticles

Polymer chains are attached to nanoparticle surfaces for many purposes, including altering solubility, influencing aggregation, dispersion, and even tailoring immune responses in drug delivery. The most unique structural motif of polymer-grafted nanoparticles (PGNs) is the high-density region in the corona where polymer chains are stretched under significant confinement, but orientation of these chains has never been measured because conventional nanoscale-resolved measurements lack sensitivity to polymer orientation in amorphous regions. Here, we directly measure local chain orientation in polystyrene grafted gold nanoparticles using polarized resonant soft X-ray scattering (P-RSoXS). Using a computational scattering pattern simulation approach, we measure the thickness of the anisotropic region of the corona and extent of chain orientation within it. These results demonstrate the power of P-RSoXS to discover and quantify orientational aspects of structure in amorphous soft materials and provide a framework for applying this emerging technique to more complex, chemically heterogeneous systems in the future.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2024

Understanding the effect of density functional choice and van der Waals treatment on predicting the binding configuration, loading, and stability of amine-grafted metal organic frameworks

Metal organic frameworks (MOFs) are crystalline, three-dimensional structures with high surface areas and tunable porosities. Made from metal nodes connected by organic linkers, the exact properties of a given MOF are determined by node and linker choice. MOFs hold promise for numerous applications, including gas capture and storage. M2(4,4′-dioxidobiphenyl-3,3′-dicarboxylate)—henceforth simply M2(dobpdc), with M = Mg, Mn, Fe, Co, Ni, Cu, or Zn—is regarded as one of the most promising structures for CO2 capture applications. Further modification of the MOF with diamines or tetramines can significantly boost gas species selectivity, a necessity for the ultra-dilute CO2 concentrations in the direct-air capture of CO2. There are countless potential diamines and tetramines, paving the way for a vast number of potential sorbents to be probed for CO2 adsorption properties. The number of amines and their configuration in the MOF pore are key drivers of CO2 adsorption capacity and kinetics, and so a validation of computational prediction of these quantities is required to suitably use computational methods in the discovery and screening of amine-functionalized sorbents. In this work, we study the predictive accuracy of density functional theory and related calculations on amine loading and configuration for one diamine and two tetramines. In particular, we explore the Perdew–Burke–Ernzerhof (PBE) functional and its formulation for solids (PBEsol) with and without the Grimme-D2 and Grimme-D3 pairwise corrections (PBE+D2/3 and PBEsol+D2/3), two revised PBE functionals with the Grimme-D2 and Grimme-D3 pairwise corrections (RPBE+D2/3 and revPBE+D2/3), and the nonlocal van der Waals correlation (vdW-DF2) functional. We also investigate a universal graph deep learning interatomic potential’s (M3GNet) predictive accuracy for loading and configuration. These results allow us to identify a useful screening procedure for configuration prediction that has a coarse component for quick evaluation and a higher accuracy component for detailed analysis. Our general observation is that the neural network-based potential can be used as a high-level and rapid screening tool, whereas PBEsol+D3 gives a completely qualitatively predictive picture across all systems studied, and can thus be used for high accuracy motif predictions. We close by briefly exploring the predictions of relative thermal stability for the different functionals and dispersion corrections.

Chemistry↗
DOE OSTI2025

Comparison of Mechanical Properties of Lignin/High-Density Polyethylene (HDPE) Composites and Wood/HDPE Composites

Lignin is a plant-derived, the second most abundant natural polymer, and a waste byproduct of the pulp industry. Incorporation of lignin into plastic composites using scalable approaches is commercially favored and low carbon-cost. Potential end applications for lignin plastic composites (LPCs) could be found in buildings and furniture where wood plastic composites (WPCs) are used in various components. This study compares the mechanical properties of LPCs and WPCs, aiming at the examination of the viability of the use of LPCs as alternative materials to WPCs in the building industry. Sodium ligninsulfonate (SLS)-based LPC blended with high-density polyethylene (HDPE) (45 wt.%) and maleic anhydride grafted polyethylene (MAPE) as a compatibilizer (5 wt.%) reached flexural strength (35.17 and 30.92 MPa respectively) and moduli (2.87 and 1.79 GPa respectively) comparable to benchmarking WPCs. Lignin dealkaline (LD)-based LPC exhibited higher ultimate strain but lower strength than SLS-based LPC, probably due to fragmentation during the post-sulfite treatment steps.

cellulose and other wood products↗
DOE OSTI2025

One-Step Radical-Induced Synthesis of Graft Copolymers for Effective Compatibilization of Polyethylene and Polypropylene

The synthesis of copolymers from high-density polyethylene (HDPE) and isotactic polypropylene (iPP) has gained increasing attention due to their ability to improve the recycling of incompatible mixed polyolefin waste feed streams. Herein, we report a new radical grafting process that yields HDPE-g-iPP copolymers from HDPE and iPP by using a commercially available peroxide. Tensile testing of brittle 70/30 HDPE/iPP mixtures with these graft copolymers added showed promising compatibilization, improving the elongation at break of the blends from 20% up to 1080%. Detailed kinetic studies coupled with thermal and rheological characterization revealed optimized conditions for HDPE and iPP macroradical coupling and a deeper understanding of the grafting reaction. This optimization yielded HDPE-g-iPP copolymers that compatibilize HDPE and iPP blends at loadings as low as 2.5 wt %. In conclusion, the versatility of this macroradical grafting reaction was demonstrated by preparing an effective compatibilizer from untreated postconsumer waste plastics.

compatibilization↗
DOE OSTI2026

Neutron Reflectometry Reveals Diffusion in Contrast-Matched Brush Particle Bilayers

A material system for performing layer-spread experiments on brush particle bilayers is presented and used to determine the diffusion constant of brush particles in the melt state. Selective deuteration of the core and shell of organo-silica nanoparticles grafted with poly(methyl methacrylate) was used to match the scattering length density of the core and the polymer canopy layer. This subdued the scattering of particle cores (i.e., formfactor scattering) and enabled the analysis of the interdiffusion kinetics using neutron reflectivity. For low molecular grafts, i.e., grafts with a molecular weight below the entanglement limit, the interdiffusion kinetics revealed both a sub- and Fickian diffusion regime. The former was attributed to the local dynamics that was constrained by the slow-moving cores of neighboring brush particles that acted as long-lived physical cross-links. No transition to Fickian diffusion was observed for entangled systems, even at prolonged annealing times. This suggested a higher level of kinetic restraint in entangled brush particle melts as compared to, for example, star polymers with a comparable chain length for which Fickian diffusion has been reported under similar conditions.

Diffusion, Polymer Grafted Nanoparticles, Neutron ↗
NASA NTRSDate not supplied

Electrostrictive Graft-Elastomers (G-Elastomers) - Materials, Devices and Applications - A Review

Electroactive polymers, especially electromechanically active polymers, have drawn extensive attention worldwide since the piezoelectricity and ferroelectricity of poly (vinylidene fluoride) (PVDF) was discovered in 1969. In the past three decades, several new classes of electroactive polymers that demonstrate promising electromechanical properties have been developed. Electrostrictive Graft Elastomers (G-elastomer) developed at NASA Langley Research Center have been recognized as one of the more promising electroactive polymers due to their large electric field-induced strain (~4%) and high mechanical modulus (~700 MPa). Electromechanical performance of the G-elastomer is a promising class of electroactive polymer materials because it exhibits a novel molecular mechanism that allows enhancement in the field induced strain and in the mechanical modulus synergistically. The combination of large induced strain and high mechanical modulus allows the electrostrictive graft elastomer to offer very promising electromechanical properties, in terms of output mechanical energy density, making it plausible as a candidate for use in high performance and low mass actuation devices in various aerospace applications. In this presentation, the molecular structures, properties, processing and mechanisms of the electromechanical performance, as well as its applications in actuation devices for advanced aerospace technologies, will be comprehensively reviewed and discussed.

Polymer↗
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 OSTI2025

Ultra-Confined Environments May Restrict the Possible Configurations of Supported Metal Complexes

Here, the rotation frequencies of amido ligands are highly sensitive to the electronic structure of d 0 transition metal complexes and have been used to study ligand donor properties. While attempting to study the donor properties of silanolate ligands in a silica-supported Cr complex, we observed highly restricted motions due to the added steric hindrance from the support, with only approximately half of the amides rotating on a 50 ms time scale. Surprisingly, when the same species is grafted into narrow 2.2 nm pores, all amido ligands are able to rotate. Density functional theory calculations suggest that confinement may limit the possible coordination sites and the configuration of the formed surface species, potentially enabling the formation of conformationally homogeneous surface site populations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRSDate not supplied

TPSAS-NF1676L-30019-DND

Electroactive polymers, especially electromechanically active polymers, have drawn extensive attention worldwide since the piezoelectricity and ferroelectricity of poly (vinylidene fluoride) (PVDF) was discovered in 1969. In the past three decades, several new classes of electroactive polymers that demonstrated promising electromechanical properties have been developed. Electrostrictive Graft Elastomers (G-elastomer) developed at NASA Langley Research Center have been recognized as one of the newly developed promising eletroactive polymers due to their large electric field-induced strain (~4%) and high mechanical modulus (~700 MPa). The combination of large induced strain and high mechanical modulus makes the electrostrictive graft elastomer offer very promising electromechanical properties, in terms of output mechanical energy density, and plausible as a candidate for use in high performance and low mass actuation devices in various aerospace applications. In this presentation, the molecular structures, properties, processing and mechanisms of the electromechanical performance, as well as its applications in actuation devices for advanced aerospace technologies will be comprehensively reviewed and discussed.

Ji Su↗
DOE OSTI2020

Charge regulation mechanism in end-tethered weak polyampholytes

Weak polyampholytes, containing oppositely charged dissociable groups, are expected to be responsive to changes in ionic conditions. Here, we determine structural and thermodynamic properties, including the charged groups’ degrees of dissociation, of end-tethered weak polyampholyte layers as a function of salt concentration, pH, and the solvent quality. For diblock weak polyampholytes grafted by their acidic blocks, we find that the acidic monomers increase their charge while the basic monomers decrease their charge with decreasing salt concentration for pH values less than the pK a value of both monomers and vice versa when the pH > pK a . This complex charge regulation occurs because the electrostatic attraction between oppositely charged blocks is stronger than the repulsion between monomers with the same charge in both good and poor solvents when the screening by salt ions is weak. This is shown by the retraction of the top block into the bottom layer. In the case of poor solvent conditions to the basic block (the top block), we find lateral segregation of basic monomers into micelles, forming a two-dimensional hexagonal pattern on the surface at intermediate and high pH values for monovalent salt concentrations from 0.01 to 0.1 M. When the solvent is poor to both blocks, we find lateral segregation of the grafted acidic block into lamellae with longitudinal undulations of low and high acidic monomer density. By exploiting weak block polyampholytes, our work expands the parameter space for creating responsive surfaces stable over a wide range of pH and salt concentration.

36 MATERIALS SCIENCE↗
NASA NTRSDate not supplied

TPSAS-NF1676L-31622-DND

Electroactive polymers, especially electromechanically active polymers, have drawn extensive attention worldwide since the piezoelectricity and ferroelectricity of poly (vinylidene fluoride) (PVDF) was discovered in 1969. In the past three decades, several new classes of electroactive polymers that demonstrate promising electromechanical properties have been developed. Electrostrictive Graft Elastomers (G-elastomer) developed at NASA Langley Research Center have been recognized as one of the promising newly developed eletroactive polymers due to their large electric field-induced strain (~4%) and high mechanical modulus (~700 MPa). The combination of large induced strain and high mechanical modulus allows the electrostrictive graft elastomer to offer very promising electromechanical properties, in terms of output mechanical energy density, and plausible as a candidate for use in high performance and low mass actuation devices in various aerospace applications. In this presentation, the molecular structures, properties, processing and mechanisms of the electromechanical performance, as well as its applications in actuation devices for advanced aerospace technologies will be comprehensively reviewed and discussed.

Ji Su↗
NASA NTRSDate not supplied

TPSAS-NF1676L-31666-DND

Electroactive polymers, especially electromechanically active polymers, have drawn extensive attention worldwide since the piezoelectricity and ferroelectricity of poly (vinylidene fluoride) (PVDF) was discovered in 1969. In the past three decades, several new classes of electroactive polymers that demonstrate promising electromechanical properties have been developed. Electrostrictive Graft Elastomers (G-elastomer) developed at NASA Langley Research Center have been recognized as one of the promising newly developed eletroactive polymers due to their large electric field-induced strain (~4%) and high mechanical modulus (~700 MPa). The combination of large induced strain and high mechanical modulus allows the electrostrictive graft elastomer to offer very promising electromechanical properties, in terms of output mechanical energy density, and plausible as a candidate for use in high performance and low mass actuation devices in various aerospace applications. In this presentation, the molecular structures, properties, processing and mechanisms of the electromechanical performance, as well as its applications in actuation devices for advanced aerospace technologies will be comprehensively reviewed and discussed.

Ji Su↗
NASA NTRS1999

Electrostrictive Graft Elastomers and Applications

Efficient actuators that are lightweight, high performance and compact are needed to support telerobotic requirements for future NASA missions. In this work, we present a new class of electromechanically active polymers that can potentially be used as actuators to meet many NASA needs. The materials are graft elastomers that offer high strain under an applied electric field. Due to its higher mechanical modulus, this elastomer also has a higher strain energy density as compared to previously reported electrostrictive polyurethane elastomers. The dielectric, mechanical and electromechanical properties of this new electrostrictive elastomer have been studied as a function of temperature and frequency. Combined with structural analysis using x-ray diffraction and differential scanning calorimetry on the new elastomer, structure-property interrelationship and mechanisms of the electric field induced strain in the graft elastomer have also been investigated. This electroactive polymer (EAP) has demonstrated high actuation strain and high mechanical energy density. The combination of these properties with its tailorable molecular composition and excellent processability makes it attractive for a variety of actuation tasks. The experimental results and applications will be presented.

Su, J.↗
DOE OSTI2021

Ethane Dehydrogenation on Single and Dual Centers of Ga-modified γ-Al 2 O 3

Density-functional theory calculations and microkinetic analysis are used to investigate the efficacy of Ga-modified γ-Al 2 O 3 (110) surfaces for the catalytic dehydrogenation of ethane and elucidate the synergy between Ga and Al sites. The model surfaces are modified by either Ga grafting or doping. We consider and analyze numerous active sites and rank them using microkinetic analysis. The kinetic parameters obtained from microkinetic modelling are compared with experimental values for ethane dehydrogenation over Ga 2 O 3 -Al 2 O 3 mixed oxides prepared by co-precipitation. The dominant reaction pathway proceeds via heterolytic C-H bond dissociation to a surface proton and a metal-carbanion intermediate that undergoes β-hydride elimination. We find that grafted Ga sites are catalytically inactive. In contrast, Ga-doped sites exhibit fivefold enhancement in catalytic activity when compared to the sites on pristine Al 2 O 3 , owed to the synergy between neighboring AlIII and GaIV sites. Furthermore, we model and investigate the effect of surface hydroxylation, demonstrate how surface water interferes with the aforementioned synergy between AlIII and GaIV sites and discuss the implications for the catalytic activity of the modified surfaces. Here, an increase in the partial pressure of H 2 O significantly increases the apparent activation energies of dehydrogenation and interestingly changes the most active site.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗