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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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71 records · Page 4

Multifunctional Tunable Polymethacrylates for Enhanced Shear Stability and Wear Prevention

This paper describes the design, synthesis, and characterization of linear, polar, and non-polar polymethacrylates designed for use as lubricant viscosity index improvers with enhanced shear and anti-wear resistance. The polymers were prepared via Reversible Addition-Fragmentation Chain Transfer (RAFT) to obtain relatively low, narrow, molecular weights, with random polar moieties. The resulting polymers were evaluated as oil solutions to determine their viscosity index, shear stability performance, and antiwear characteristics. The polymers had molecular weights (Mw) ranging from 120-170 kDa, and the resulting viscosity indexes (VIs) in general tracked the Mw. Although the VIs were modest (140-189), all polymers displayed higher values than a commercial product designed for similar applications, both at 2% (w/w) and when kinematic viscosities (KVs) were normalized to the lowest KV100 of ~5cSt. One of the imidazole-containing polymers displayed an anomalously high VI for a low apparent Mw. As hypothesized, many of the polar polymers demonstrated substantial wear reduction compared to the non-polar homopolymers or a commercial benchmark. The low-molecular-weight imidazole-containing polymer produced less than 4% of the wear displayed by the commercial standard. The higher molecular weight polymers containing imidazole, hydroxy group and amino group also produced as little as 10% of the wear shown by the benchmark. The strategy demonstrated the benefit of low, narrow, molecular weight polymers to achieve good shear stability in viscosity modifiers while minimizing wear, rendering them suitable for fluid-power applications.

friction modifiers↗

What is the effect of lipophilic polymeric ionic liquids on friction and wear?

In this work, methacrylate-type ionic liquid (IL) monomers containing a quaternary ammonium cation and two different counter-anions were synthesized and used as co-monomers to obtain functional poly(alkyl methacrylates) (PAMAs) as friction and wear reducing additives for lubricants. The effect of molecular weight, polymer topology (random or diblock), and IL counter anion on friction and wear behavior of polymer PAO (poly-alpha olefin) solutions have been investigated. The results were compared to those of PAO solutions additized with a small molecule, non-polymeric ionic liquid, or non-ionic copolymers containing 2-(dimethylamino)ethyl methacrylate (DMAEMA) as the polar comonomer. No clear correlation between polymer molecular weight and friction or wear behavior was observed. Random ionic liquid copolymers led to lower wear volumes than their block counterparts. Polymers containing dicyanamide (DCA) counter anion showed lower wear volume compared to those containing bis((trifluoromethyl)sulfonyl)imide (TFSI) anion. Surprisingly, none of the IL copolymers studied outperformed the DMAEMA containing block copolymer in terms of wear volume reduction, suggesting the IL moiety had no beneficial effect on wear.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Customized Nanostructured Ceramics via Microphase Separation 3D Printing

To date, the restricted capability to fabricate ceramics with independently tailored nano- and macroscopic features has hindered their implementation in a wide range of crucial technological areas, including aeronautics, defense, and microelectronics. In this study, a novel approach that combines self- and digital assembly to create polymer-derived ceramics with highly controlled structures spanning from the nano- to macroscale is introduced. Polymerization-induced microphase separation of a resin during digital light processing generates materials with nanoscale morphologies, with the distinct phases consisting of either a preceramic precursor or a sacrificial polymer. By precisely controlling the molecular weight of the sacrificial polymer, the domain size of the resulting material phases can be finely tuned. Pyrolysis of the printed objects yields ceramics with complex macroscale geometries and nanoscale porosity, which display excellent thermal and oxidation resistance, and morphology-dependent thermal conduction properties. This method offers a valuable technological platform for the simplified fabrication of nanostructured ceramics with complex shapes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Poly(alkyl methacrylate) Brush-Grafted Silica Nanoparticles as Oil Lubricant Additives: Effects of Alkyl Pendant Groups on Oil Dispersibility, Stability, and Lubrication Property

This paper reports on the synthesis of a series of poly(alkyl methacrylate) brush-grafted, 23 nm silica nanoparticles (hairy NPs) and the study of the effect of alkyl pendant length on their use as oil lubricant additives for friction and wear reduction. The hairy NPs were prepared by surface-initiated reversible addition–fragmentation chain transfer polymerization from trithiocarbonate chain transfer agent (CTA)-functionalized silica NPs in the presence of a free CTA. We found that hairy NPs with sufficiently long alkyl pendant groups (containing >8 carbon atoms, such as 12, 13, 16, and 18 in this study) could be readily dispersed in poly(alphaolefin) (PAO), forming clear, homogeneous dispersions, and exhibited excellent stability at low and high temperatures as revealed by visual inspection and dynamic light scattering studies. Whereas poly(n-hexyl methacrylate) hairy NPs cannot be dispersed in PAO under ambient conditions or at 80 °C, interestingly, poly(2-ethylhexyl methacrylate) hairy NPs can be dispersed in PAO at 80 °C but not at room temperature, with a reversible clear-to-cloudy transition observed upon cooling. High-contact-stress ball-on-flat reciprocating sliding tribological tests at 100 °C showed significant reductions in both the coefficient of friction (up to 38%) and wear volume (up to 90% for iron flat) for transparent, homogeneous dispersions of hairy NPs in PAO at a concentration of 1.0 wt % compared with neat PAO. Finally, the formation of a load-bearing tribofilm at the rubbing interface was confirmed using scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy.

36 MATERIALS SCIENCE↗

Miktoarm Star Polymers: Synthesis and Applications

Polymers with precisely controlled structure and function are in high demand across a diverse array of applications spanning the life sciences and nanotechnology. One prototypical example is a class of branched block copolymers known as miktoarm stars (μ-stars), which contain two or more arm compositions connected at a common junction. Miktoarm stars have attracted considerable attention since their physical properties can be different from conventional linear block copolymers. This perspective highlights the latest developments and historical context in the field of miktoarm star polymers, including design strategies, synthetic techniques, and advanced characterization tools used to avoid common preparation pitfalls and tailor properties for emerging applications. Furthermore, our contemporary perspective on μ-star polymers is a resource for inspiring future research into this exciting class of materials at the intersection of chemistry, physics, and advanced technology.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Molecular Picture of the Transient Nature of Lipid Rafts

In biological membranes, lipid rafts are now thought to be transient and nanoscopic. However, the mechanism responsible for these nanoscopic assemblies remains poorly understood, even in the case of model membranes. Therefore, it has proven extremely challenging to probe the physicochemical properties of lipid rafts at the molecular level. Here, we use all-atom molecular dynamics (MD) simulations and inelastic X-ray scattering (IXS), an intrinsically nanoscale technique, to directly probe the energy transfer and collective short-wavelength dynamics (phonons) of biologically relevant model membranes. We show that the nanoscale propagation of stress in lipid rafts takes place in the form of collective motions made up of longitudinal (compression waves) and transverse (shear waves) molecular vibrations. Importantly, we provide a molecular picture for the so-called van der Waals mediated "force from lipid" [Anishkin, A. et al. Proc. Natl. Acad. Sci. U.S.A. 2014, 111, 7898], a key parameter for the ionic channel mechano-transduction and the mechanism for the lipid transfer of molecular level stress [Aponte-Santamaría, C. et al. J. Am. Chem. Soc. 2017, 139, 13588]. Specifically, we describe how lipid rafts are formed and maintained through the propagation of molecular stress, lipid raft rattling dynamics, and a relaxation process. Eventually, the rafts dissipate through the self-diffusion of lipids making up the rafts. We also show that the molecular stress and viscoelastic properties of transient lipid rafts can be modulated through the use of hydrophobic biomolecules such as melatonin and tryptophan. Overall, the herein proposed mechanism describing the molecular interactions for the formation and dissolution of lipid rafts may offer insights as to how lipid rafts enable biological function.

36 MATERIALS SCIENCE↗

Investigating the Role of Polymer Architecture in Poly(methyl methacrylate) Depolymerization

Advanced architectures in polymers have garnered traction within the last two decades due to their distinct and tunable properties compared to linear analogs. However, the effects of architecture on nascent polymethacrylate depolymerization strategies remain underexplored. Herein, we investigate the depolymerization behavior of poly(methacrylate)-based star copolymers synthesized via a core-first approach. By incorporating either labile chain-end or pendent-group triggers, we demonstrate the first direct comparison of bulk depolymerization behaviors in star versus linear methacrylate copolymers under matched conditions. While pendent-triggered systems required higher loadings of N-(methacryloxy)phthalimide methacrylate (PhthMA) to achieve similar mass loss compared to linear copolymers, chain-end-initiated depolymerization showed enhanced efficiency of monomer liberation in the star topology. Furthermore, these findings highlight the importance of considering macromolecular architecture in designing sustainable polymers and provide actionable guidelines for installing depolymerization triggers based on polymer topology.

Copolymers↗

Anisotropic Dynamics and Mechanics of Macromolecular Crystals Containing Lattice-Patterned Polymer Networks

The mechanical and functional properties of many crystalline materials depend on cooperative changes in lattice arrangements in response to external perturbations. However, the flexibility and adaptiveness of crystalline materials are limited. Additionally, the bottom-up, molecular-level design of crystals with desired dynamic and mechanical properties at the macroscopic level remains a considerable challenge. To address these challenges, we had previously integrated mesoporous, cubic ferritin crystals with hydrogel networks, resulting in hybrid materials (polymer integrated crystals or PIX) which could undergo dramatic structural changes while maintaining crystalline periodicity and display efficient self-healing. Here, the dynamics and mechanics of these ferritin-PIX were devoid of directionality, which is an important attribute of many molecular and macroscopic materials/devices. In this study, we report that such directionality can be achieved through the use of ferritin crystals with anisotropic symmetries (rhombohedral or trigonal), which enable the templated formation of patterned hydrogel networks in crystallo. The resulting PIX expand and contract anisotropically without losing crystallinity, undergo prompt bending motions in response to stimuli, and self-heal efficiently, capturing some of the essential features of sophisticated biological devices like skeletal muscles.

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Mapping Composition Evolution through Synthesis, Purification, and Depolymerization of Random Heteropolymers

Random heteropolymers (RHPs) consisting of three or more comonomers have been routinely used to synthesize functional materials. While increasing the monomer variety diversifies the side-chain chemistry, this substantially expands the sequence space and leads to ensemble-level sequence heterogeneity. Most studies have relied on monomer composition and simulated sequences to design RHPs, but the questions remain unanswered regarding heterogeneities within each RHP ensemble and how closely these simulated sequences reflect the experimental outcomes. Here, we quantitatively mapped out the evolution of monomer compositions in four-monomer-based RHPs throughout a design-synthesis-purification-depolymerization process. By adopting a Jaacks method, we first determined 12 reactivity ratios directly from quaternary methacrylate RAFT copolymerization experiments to account for the influences of competitive monomer addition and the reversible activation/deactivation equilibria. The reliability of in silico analysis was affirmed by a quantitative agreement (<4% difference) between the simulated RHP compositions and the experimental results. Furthermore, we mapped out the conformation distribution within each ensemble in different solvents as a function of monomer chemistry, composition, and segmental characteristics via high-throughput computation based on self-consistent field theory (SCFT). These comprehensive studies confirmed monomer composition as a viable design parameter to engineer RHP-based functional materials as long as the reactivity ratios are accurately determined and the livingness of RHP synthesis is ensured.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Selective Electrochemical End‐Group Removal Enhances Polymer Thermal Stability

Here we introduce an electrochemical strategy for the selective and quantitative removal of thiocarbonylthio end groups from polymers prepared by reversible addition–fragmentation chain transfer (RAFT) or photoiniferter polymerization. Our results indicate that applying a cathodic potential in an undivided cell promotes reductive cleavage of the thiocarbonylthio moiety, generating terminal polymer radicals that are efficiently capped with hydrogen atoms in the presence of benign donors. This transformation proceeds cleanly across diverse polymer backbones and end-group chemistries, including trithiocarbonates and dithiobenzoates, without chain coupling or degradation. Moreover, the applied potential can be tuned to enable chemoselective end-group removal in mixed-polymer systems, a level of control inaccessible by thermal, photochemical, or nucleophilic strategies. Beyond delivering colorless and optically transparent materials, electrochemical end-group removal significantly enhances polymer stability. Poly(methyl methacrylate) subjected to electrochemical end-group removal exhibited a T 95 of 342 °C, exceeding the stabilities of analogous polymers with end groups removed by aminolysis (T 95 = 260 °C) or radical-based methods (T 95 = 299 °C). These findings demonstrate redox-directed post-polymerization modification as a tool for designing robust, transparent, and thermally stable macromolecules and establish electrochemistry as a platform strategy in polymer synthesis and processing.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Rational Polymer Design of Stretchable Poly(ionic liquid) Membranes for Dual Applications

Many functional polymeric materials are inherently fragile at ambient conditions. Consequently, making them elastic and flexible is a challenging task, and such achievement is especially meaningful in a wide range of applications including separation membranes and stretchable devices. Poly(ionic liquids) (PILs), such as vinyl-imidazolium-based polymers, are known to be “brittle” functional polymers due to their “glassy” nature at ambient temperature. We herein developed a viable approach to enable glassy PILs with high flexibility and good elasticity via a rational molecular design of chemical composition and polymer architectures. The reversible addition/fragmentation chain transfer agents (RAFT-CTAs) were attached to the flexible poly(dimethylsiloxane) (PDMS) backbones. The polymerization of functional ionic liquid monomers from RAFT-CTAs provided grafted copolymers with the functional side chains, which were further cross-linked by di-functional PDMS. Poly(ethylene glycol) methacrylate is copolymerized with ionic liquid monomers to reduce the glass transition temperature (Tg), providing higher chain mobility and elasticity at ambient temperature. The synthesized elastic PIL-based membranes (E-PILs) have dramatically improved stretchability, reaching 122–422%. In addition to significantly improved extensibility, the synthesized E-PILs also exhibit higher ionic conductivity, critical for potential applications in solid-state batteries. Moreover, in comparison to glassy solid PIL membranes, the E-PILs also exhibited enhanced flexibility and excellent gas-separation performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A high pressure cell for supercritical CO{sub 2} on-line chemical reactions studied with x-ray techniques

A versatile high pressure X-ray sample cell has been developed for conducting in situ time-resolved X-ray scattering experiments in the pressure and temperature regime required (pressures up to 210 bars and temperatures up to 120 °C) for chemical reactions in supercritical fluids. The large exit opening angle of the cell allows simultaneous performance of SAXS-WAXS experiments. Diamond windows are used in order to benefit from the combination of maximum strength, minimal X-ray absorption and chemical inertia. The sample cell can also be utilised for X-ray spectroscopy experiments over a wide range of photon energies. Results of the online synthesis of a block copolymer, poly(methyl methacrylate-block-poly(benzyl methacrylate), by Reversible Addition-Fragmentation Chain Transfer (RAFT) in a supercritical CO{sub 2} dispersion polymerisation will be discussed. The contribution of the density fluctuations, as function of temperature, to the X-ray scattering signal has been quantified in order to allow appropriate background subtractions.

36 MATERIALS SCIENCE↗

Amphiphilic Block Copolymers for Flocculation and Hydrophobization of Legacy Waste Suspensions in Flotation Driven Dewatering Operations - 20162

Flotation has been effectively demonstrated as a low footprint, high efficiency separation process when utilising simple anionic surface modifying agents such as sodium dodecyl sulphate (SDS). These agents increase hydrophobicity to remove suspended cationic surface charged particulates such as Mg(OH){sub 2} from waste suspensions similar to those at British nuclear fuel management sites- where corrosion processes have degraded fuel cladding. The technology is advantageous as it could effectively be retrofitted into existing waste management facilities at nuclear waste management sites such Sellafield and Hanford as the simplicity (no moving parts) and size of this technology coupled with low cost of construction could be rapidly deployed to aid in risk and hazard reduction decommissioning operations with minimum impact to secondary waste generation. Previously, sodium dodecyl sulphate has been deployed as a collector agent to increase the hydrophobicity of Mg(OH){sub 2} suspended particles, achieving a maximum particulate extraction percentage of 93%. To achieve further particulate extraction, flotation performance has been determined to be a function of the hydrodynamic limitations extracting fine material (>20 μm). Fine particulates have been shown in the minerals industry to have an inability to overcome slipstreams created from rising bubbles in flotation cells, likely due to the low mass and thus momentum of the colloidal material, preventing interaction between the hydrophobized particles and air-water interfaces (bubbles). To combat this mass transfer resistance poly(acrylic acid)-block-poly(n-butyl acrylate) amphiphilic diblock copolymers were synthesised via reversible addition-fragmentation chain-transfer (RAFT) polymerisation. The anticipated mode of action of these polymers involves the hydrophilic poly(acrylic acid) block polymer acting as a flocculation agent to increase the mass of the aggregates, and the hydrophobic poly(n-butyl acrylate) modifies the hydrophobicity of the resulting flocs. The concentration of this polymer (termed a macro-collector) was varied and the change in particle size distribution of the particulate suspension was analysed using static light scattering. The flotation performance was then characterised by several methods including percentage particulate recovery, volume reduction factor and residual bulk particulate concentration. This was then benchmarked against the traditional surfactant collector agent SDS. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗