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At least 19 records

Accelerated Self-Healing and Property Recovery in Brush Particle Solids Featuring Brush Dispersity

Brush particles, hybrid materials consisting of polymer chains tethered to particle surfaces, offer tunable properties that make them promising candidates for advanced functional materials. This study investigated the role of chain dispersity in the viscoelastic self-healing of poly (methyl acrylate) (PMA)-based brush particle solids. Increasing the molecular weight dispersity of grafted chains significantly enhanced both strain-to-fracture and toughness of brush particle solids, while the elastic modulus and glass transition temperature were independent of chain dispersity. Cut-and-adhere testing revealed a significant acceleration of the rate of toughness recovery in high-dispersity systems as compared to low-dispersity analogs for which toughness recovery markedly lagged the recovery of Young’s modulus. The results suggest that structure and property recovery in brush particle solids are sensitive to the dynamical heterogeneity of brush canopies and highlight the role of molecular weight dispersity as a design parameter to enable hybrid materials with advanced self-healing ability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

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 ↗

Microscopic Dynamics Controls Coupling and Cluster Formation in Brush Particle Solids

Thermodynamics-based models predict the structure of polymer-grafted nanoparticles (PGNs) as well as their assembly behavior based on geometric parameters such as particle size, degree of polymerization, and density of grafted chains. The role of microscopic polymer dynamics, such as the mobility of repeat units in the melt state, in the evolution of the structure and properties remains unknown. Brillouin light spectroscopy (BLS), due to its capability to concurrently discern the local and global elastic properties of PGN assemblies, enables the probing of microscopic processes, such as brush interdigitation, sensitive to the annealing of the assembly. For poly(methyl methacrylate) (PMMA)-grafted silica (SiO 2 ) PGNs in the dry powder state and annealed above the glass transition temperature, BLS revealed fully reversible local elasticity, indicative of limited interdigitation between adjacent PGNs. This contrasts with polystyrene (PS)−SiO 2 analogs that displayed ready (and irreversible) fusion of brush layers during annealing. The retardation of brush interdigitation in PMMA-grafted systems is surprising, given the similar thermomechanical properties of both polymers, and is rationalized as the consequence of higher friction between PMMA repeats compared to PS. Microscopic dynamics thus has a profound impact on the kinetic path of structure (and property) evolution and thus should be considered during the processing of PGNs into functional hybrid materials.

chemical structure↗

Confinement-Driven Segregation Enables Glassy Polymer Hybrid Materials Featuring Disordered Hyperuniformity and Integrated Self-Healing

The blending of glassy copolymer-brush modified colloids with a viscoelastic linear copolymer featuring intrinsic self-healing enabled disordered hyperuniform hybrid materials that combined mechanical robustness with structural color, processability, environmental stability, and the ability to recover structure and properties after incurring physical damage via ‘integrated self-healing’. Symmetric linear n-butyl acrylate/methyl methacrylate (BA/MMA) were co-assembled with asymmetric glassy BA/MMA statistical copolymer brush (silica) particles. ‘Confinement-driven segregation’ resulted in a microphase-separated morphology in which the linear copolymer resided within the interstitial regions of a rigid (∼1 GPa) copolymer brush particle template with disordered hyperuniform microstructure. Diffusion of the self-healing copolymer additive into damage regions drove the recovery after damage, along with the restoration of structural color due to the materials hyperuniform microstructure. The synergistic action of intrinsic and extrinsic healing mechanisms could provide a versatile platform for the bottom-up fabrication of multifunctional hybrid materials with increased damage resistance and functional longevity.

36 MATERIALS SCIENCE↗

Polymer-Grafted Nanoparticles as All-in-One Nanoplatforms

Polymer-grafted nanoparticles (PGNPs) represent a versatile class of hybrid nanomaterials, in which nanoparticle cores and tethered polymer coronas are integrated into structurally programmable building blocks. Rapid advances in nanoparticle surface functionalization and surface-initiated polymerization have enabled increasingly precise control over the nanoparticle core composition and brush architecture, greatly expanding the accessible structural and functional landscape of PGNPs. This review summarizes recent progress in the modular design and structural regulation of PGNPs, with an emphasis on nanoparticle platforms and associated surface functionalization strategies, polymer brush synthesis and architectural control, and the structure−property relationships that govern PGNP behavior. Emerging applications are further highlighted, including additive manufacturing, self-healing materials, membrane-based gas separations, and battery-related systems, where PGNPs provide unique opportunities to couple nanoscale interfacial design with macroscopic performance. Finally, future opportunities are discussed for extending PGNP concepts to increasingly complex, multifunctional, and application-oriented hybrid materials.

functional nanocomposites↗

Organic nanoparticles with tunable size and rigidity by hyperbranching and cross-linking using microemulsion ATRP

Unlike inorganic nanoparticles, organic nanoparticles (oNPs) offer the advantage of “interior tailorability,” thereby enabling the controlled variation of physicochemical characteristics and functionalities, for example, by incorporation of diverse functional small molecules. In this study, a unique inimer-based microemulsion approach is presented to realize oNPs with enhanced control of chemical and mechanical properties by deliberate variation of the degree of hyperbranching or cross-linking. The use of anionic cosurfactants led to oNPs with superior uniformity. Benefitting from the high initiator concentration from inimer and preserved chain-end functionality during atom transfer radical polymerization (ATRP), the capability of oNPs as a multifunctional macroinitiator for the subsequent surface-initiated ATRP was demonstrated. This facilitated the synthesis of densely tethered poly(methyl methacrylate) brush oNPs. Detailed analysis revealed that exceptionally high grafting densities (~1 nm −2 ) were attributable to multilayer surface grafting from oNPs due to the hyperbranched macromolecular architecture. The ability to control functional attributes along with elastic properties renders this “bottom-up” synthetic strategy of macroinitiator-type oNPs a unique platform for realizing functional materials with a broad spectrum of applications.

ATRP↗

Facile Strategy to Prepare Poly(ionic liquid)-Coated Solid Polymer Electrolytes through Layer-by-Layer Assembly

The inability of solid polymer electrolytes to preserve strong mechanical strength with high ionic conductivity hinders the commercialization of lithium metal batteries (LMBs). The success of fabricating layer-by-layer (LbL)-assembled electrolytes has realized the application of flexible solid polymer electrolytes in electrochemical devices. Here, we demonstrate a rational strategy to construct solid electrolytes coated with multiple ultrathin layers of polyanions (poly(sodium 4-styrenesulfonate)) and polycations (linear poly(1-butyl-3-(4-vinylbenzyl)-1H-imidazolium chloride) (BVIC)/linear poly(PEG 4 -VIC)/SiO 2 -g-poly(PEG 4 -VIC)) using an LbL assembly method. Poly(ionic liquid) backbones and PEG side groups are employed to facilitate the transport of lithium ions via the segmental motion of the macromolecular matrix. The fabricated free-standing membranes exhibited good ionic conductivities of 9.03–10 × 10 –4 S cm –1 . Furthermore, a Li/LiFePO 4 cell assembled with the LbL-membrane electrolytes exhibits an initial high discharge capacity of 143–158 mAhg –1 at 60 °C with high columbic efficiency. In conclusion, this approach, which combines polymer synthesis and LbL self-assembly, is an effective and facile route to fabricate solid polymer electrolyte membranes with superior ionic conductivity and mechanical robustness, which are useful for electrochemical devices and high-voltage battery applications.

25 ENERGY STORAGE↗

Method for Fabricating Soft Tissue Implants with Microscopic Surface Roughness

A method for fabricating soft tissue implants using a mold. The cavity surface of an initially untextured mold. made of an organic material such as epoxy. is given a thin film coating of material that has pinholes and is resistant to atomic particle bombardment. The mold cavity surface is then subjected to atomic particle bombardment, such as when placed in an isotropic atomic oxygen environment. Microscopic depressions in the mold cavity surface are created at the pinhole sites on the thin film coating. The thin film coating is removed and the mold is then used to cast the soft tissue implant. The thin film coating having pinholes may be created by chilling the mold below the dew point such that water vapor condenses upon it; distributing particles, that can partially dissolve and become attached to the mold cavity surface, onto the mold cavity surface; removing the layer of condensate, such as by evaporation; applying the thin film coating over the entire mold surface; and, finally removing the particles, such as by dissolving or brushing it off. Pinholes are created in the thin film coating at the sites previously occupied by the particles.

Banks, Bruce A.↗

The MSP 2001 Mars Environmental Compatibility Assessment (MECA)

The Mars Environmental Compatibility Assessment (MECA) will evaluate the Martian environment for soil and dust-related hazards to human exploration as part of the Mars Surveyor Program 2001 Lander. Sponsored by the Human Exploration and Development of Space (HEDS) enterprise, MECA's goal is to evaluate potential geochemical and environmental hazards that may confront future Martian explorers, and to guide HEDS scientists in the development of high fidelity Mars soil simulants. The integrated MECA payload contains a wet-chemistry laboratory, a microscopy station, an electrometer to characterize the electrostatics of the soil and its environment, and arrays of material patches to study the abrasive and adhesive properties of soil grains. The instrument will acquire soil samples with a robotic arm equipped with a camera. MECA will examine surface and subsurface soil and dust in order to characterize particle size, shape, hardness, and also physical characteristics that may provide clues to mineralogy. MECA will characterize soil/water mixtures with respect to pH, redox potential, total dissolved ions, and trace toxins. MECA will determine the nature of electrostatic charging associated with excavation of soil, and the influence of ionizing radiation on material properties. It will also observe natural dust accumulation on engineering materials. To accomplish these objectives, MECA is allocated a mass of 10 kg within an enclosure of 35 x 25 x 15 cm. The Wet Chemistry Laboratory (WCL) consists of four identical cells that will accept samples from surface and subsurface regions accessible to the Lander's robotic arm, mix them with water, and perform extensive analysis of the solution. Ion-selective electrodes and related sensors will evaluate total dissolved solids, redox potential, pH, and the concentration of many soluble ions and gases in wet Martian soil. These electrodes can detect potentially dangerous heavy-metal ions, emitted pathogenic gases, and the soil's corrosive potential. Experiments will include cyclic voltammetry and anodic stripping voltammetry. Complementary to the Viking experiments, the chemical laboratory will characterize the water-soil solution rather than emitted gases. Nonetheless, through analysis of dissolved gases it will be able to replicate many of the Viking observations related to oxidants. MECA's microscopy station combines optical and atomic-force microscopy (AFM) in an actively focused, controlled illumination environment to image particles from millimeters to nanometers in size. Careful selection of substrates allows controlled experiments in adhesion, abrasion, hardness, aggregation, magnetic and other properties. Special tools allow primitive manipulation (brushing and scraping) of samples. Soil particle properties including size, shape, color, hardness, adhesive potential (electrostatic and magnetic), will be determined using an array of sample receptacles and collection substrates. The simple, rugged atomic-force microscope will image in the submicron size range and has the capability of performing a particle-by-particle analysis of the dust and soil. On Earth, the earliest forms of life are preserved as microfossils. The atomic-force microscope will have the required resolution to image down to the scale of terrestrial microfossils and beyond. Mounted on the end of the robot arm, MECA's electrometer actually consists of four types of sensors: an electric field meter, several triboelectricity monitors, an ion gauge, and a thermometer. Tempered only by ultraviolet-light-induced ions and a low-voltage breakdown threshold, the dry, cold, dusty martian environment presents an imposing electrostatic hazard to both robots and humans. The field meter will measure the ambient field on nearby objects while the triboelectric sensors, using identical circuitry, will measure the charge accumulated on test substances as they are dragged through the soil by the arm. The ion chamber, open to the environment, will sense both charged dust and free ions in the air. Over and above the potential threat to electronics, the electrostatic environment holds one of the keys to transport of dust and, consequently, Martian meteorology. Viewed with the robot arm camera, the abrasion and adhesion plates are strategically placed to allow direct observation of the interaction between materials and soils on a macroscopic scale. Materials of graded hardness are placed directly under the robot arm scoop to sense wear and soil hardness. A second array, placed on the lander deck, is deployed after the dust plume of landing has settled. It can be manipulated in a primitive fashion by the arm, first having dirt deposited on it from the scoop and subsequently shaken clean. A third array will passively collect dust from the atmosphere. In addition to objectives related to human exploration, the MECA data set will be rich in information relevant to basic geology, paleoclimate, and exobiology issues. To understand both contemporaneous and ancient processes on Mars, the mineralogy, petrology, and reactivity of Martian surface materials should be constrained. The MECA experiment will shed light on these quantities through its combination of chemistry and microscopy. MECA will be capable of measuring the composition of ancient surface water environments, observing microscopic evidence of geological (and biological?) processes, inferring soil and dust transport, comminution and weathering mechanisms, and characterizing soil horizons that might be encountered during excavation.

Hecht, M. H.↗

Soil Analysis Micro-Mission Concepts Derived from the MSP 2001 Mars Environmental Compatibility Assessment (MECA)

The Mars Environmental Compatibility Assessment (MECA) will evaluate the Martian environment for soil and dust-related hazards to human exploration as part of the Mars Surveyor Program 2001 Lander. The integrated MECA payload contains a wet-chemistry laboratory, a microscopy station, an electrometer to characterize the electrostatic environment, and arrays of material patches to study abrasion and adhesion. Heritage will be all-important for low cost micro-missions, and adaptations of instruments developed for the Pathfinder, '98 and '01 Landers should be strong contenders for '03 flights. This talk has three objectives: (1) Familiarize the audience with MECA instrument capabilities; (2) present concepts for stand-alone and/or mobile versions of MECA instruments; and (3) broaden the context of the MECA instruments from human exploration to a comprehensive scientific survey of Mars. Due to time limitations, emphasis will be on the chemistry and microscopy experiments. Ion-selective electrodes and related sensors in MECA's wet-chemistry laboratory will evaluate total dissolved solids, redox potential, pH, and the concentration of many soluble ions and gases in wet Martian soil. These electrodes can detect potentially dangerous heavy-metal ions, emitted pathogenic gases, and the soil's corrosive potential, and experiments will include cyclic voltammetry and anodic stripping. For experiments beyond 2001, enhancements could allow multiple use of the cells (for mobile experiments) and reagent addition (for quantitative mineralogical and exobiological analysis). MECA's microscopy station combines optical and atomic-force microscopy (AFM) in an actively focused, controlled illumination environment to image particles from millimeters to nanometers in size. Careful selection of substrates allows controlled experiments in adhesion, abrasion, hardness, aggregation, magnetic and other properties. Special tools allow primitive manipulation (brushing and scraping) of samples. Soil particle properties including size, shape, color, hardness, adhesive potential (electrostatic and magnetic), will be determined using an array of sample receptacles and collection substrates. The simple, rugged atomic-force microscope will image in the submicron size range and has the capability of performing a particle-by-particle analysis of the dust and soil. Future implementations might enhance the optical microscopy with spectroscopy, or incorporate advanced AFM techniques for thermogravimetric and chemical analysis.

Hecht, M. H.↗

Contactless Rotary Electrical Couplings

Rotary electrical couplings based on induction (transformer action) rather than conduction between rotating and stationary circuitry have been invented. These couplings provide an alternative to slip rings and contact brushes. Mechanical imperfections of slip-ring and brush contact surfaces and/or dust particles trapped between these surfaces tend to cause momentary interruptions in electrical contact and thereby give rise to electrical noise. This source of noise can be eliminated in the inductive rotary couplings because no direct contact is necessary for transformer action.

Kumagai, Hiroyuki↗

Bio-inspired Surface Structures to Mitigate Interfacial Particle Adhesion and Erosion - A Review

Lunar dust known as regolith is a huge challenge for lunar exploration missions. Formed over millennia by a complex process involving impacts of meteoroids and micrometeoroids on the lunar surface, lunar dust is porous, highly abrasive with sharp jagged edges, chemically reactive, electrostatically charged and sometimes magnetic. The chemical composition and thickness of the dust layer also varies in different regions of the lunar surface. From samples obtained by previous lunar missions, the average particle size is below 100 microns. This dust has the tendency to strongly adhere to any exposed surfaces, and often degrades the material functionality to eventually cause failure. Any material on the lunar surface is also subject to harsh temperature cycles ranging from -178 ̊C to + 123 ̊C and extreme ultraviolet radiation. While on the lunar surface, different classes of materials would be required for different applications. Advanced materials have been and will be used throughout the lunar lander, habitat, and mission equipment. Examples include: polymeric materials for astronaut protective clothing; metals and ceramics for the lunar lander legs and habitats, and excavating equipment; and semiconductors for solar panels and on-board electronics. In all these applications, the surfaces of the materials are expected or understood to be exposed to the extreme lunar environment condition that includes the regolith dust. During the Apollo missions, the dust clung to and abraded the astronaut’s suits, degraded seals, optics, clogged sensors and reduced performance of thermal radiators. The lunar dust adheres to the surface by various mechanisms, which include electrostatic and Coulombic interactions, Van-der-Waals forces, magnetic forces, mechanical interlocking, chemical bonding and donor-acceptor interactions. There are three primary strategies for developing technologies to minimize the lunar dust adhesion: active, passive and a combination of active and passive. In the active approach, an external energy is needed to prevent or remove particles from collecting on the surface. Mechanically powered brushes and electrodynamic dust screens are two examples. In the passive approach, no external power is needed, and the material surface properties are able to mitigate dust adhesion. A well-known example of this strategy is the low work function coatings for non-stick surfaces. In most cases a combination of active and passive methods might be needed to optimally manage the lunar regolith. The passive method is significantly more attractive as it does not require any external power or an additional control subsystem. These approaches optimize the mission payload and reduce risk. Surface modification to minimize the dust adhesion is thus very important to lunar missions. Here, naturally evolved surface structures might provide guidance for solutions. There are several factors that have to be considered for minimizing particle adhesion to a surface. These include the substrate material properties, surface topography, chemistry, and the characteristics of the adhering particles. When engineering a surface, the substrate material chosen would be dependent on the needs of the application. Tailoring the surface microstructure or chemistry opens up more possibilities for its optimal utilization

Lunar Dust↗

Corona And Ultraviolet Equipment For Testing Materials

Two assemblies of laboratory equipment developed for use in testing abilities of polymers, paints, and other materials to withstand ultraviolet radiation and charged particles. One is vacuum ultraviolet source built around commercial deuterium lamp. Other exposes specimen in partial vacuum to both ultraviolet radiation and brush corona discharge. Either or both assemblies used separately or together to simulate approximately combination of solar radiation and charged particles encountered by materials aboard spacecraft in orbit around Earth. Also used to provide rigorous environmental tests of materials exposed to artificial ultraviolet radiation and charged particles in industrial and scientific settings or to natural ultraviolet radiation and charged particles aboard aircraft at high altitudes.

Laue, Eric G.↗

Localized and Areally Extensive Alterations in Marathon Valley, Endeavour Crater Rim, Mars

Mars Exploration Rover Opportunity is exploring the rim of 22 km diameter, Noachian-aged Endeavour crater. Marathon Valley cuts through the central region of the western rim providing a window into the local lower rim stratigraphic record. Spectra from the Compact Reconnaissance Imaging Spectrometer for Mars show evidence for the occurrence of Fe-Mg smectite in this valley, indicating areally extensive and distinct lithologic units and/or styles of aqueous alteration. The Alpha Particle X-ray Spectrometer has determined the compositions of 59 outcrop targets on untreated, brushed and abraded surfaces. Rocks in the Marathon Valley region are soft breccias composed of mm- to cm-sized darker clasts set in a lighter-toned, finegrained matrix. They are basaltic in non-volatile-element composition and compositionally similar to breccias investigated elsewhere on the rim. Alteration styles recorded in the rocks include: (1) Enrichments in Si, Al, Ti and Cr in more reddish-colored rock, consistent with leaching of more soluble cations and/or precipitation of Si +/- Al, Ti, Cr from fluids. Coprecipitation of Ge-rich phases with Si occurred in the western area only; high water:rock is indicated. Pancam multispectral observations indicate higher nanophase ferric oxide contents, but the rocks have lower Fe contents. The highly localized nature of the red zones indicate they cannot be the source of the widespread smectite signature observed from orbit. (2) Outcrops separated by approximately 65 m show common compositional changes between brushed and abraded (approximately 1 mm deep) targets: increases in S and Mg; decreases in Al, Cl and Ca. These changes are likely due to relatively recent, surface-related alteration of valley rocks and formation of surface coatings under low water:rock. (3) One target, from the center of a region of strong CRISM smectite signature, shows modest differences in composition (higher Si, K; lower Mn) compared to most Marathon Valley rocks, while another target approximately 40 cm away on the same outcrop does not; a change towards smectite bulk compositions is not observed. The smectite signature likely resulted from alteration under low water:rock such that primary minerals were partially altered to phyllosilicates, but wholesale leaching of cations by fluids did not occur.

Mittlefehldt, David W.↗

Brush-modified fluorescent organic nanoparticles by ATRP with rigidity-regulated emission

Organic nanoparticles provide exceptional intraparticle tailorability, enabling the incorporation of functional molecules for diverse applications. In this study, we present the synthesis and characterization of fluorescent organic nanoparticles (FoNPs) with encapsulated aggregation-induced emission (AIE) luminogens with emission properties regulated by particle rigidity. Atom transfer radical polymerization (ATRP) was employed in dispersed media to develop various fluorescence colors tuned by precise control over particle rigidity. Comprehensive analyses revealed that increased particle rigidity significantly enhanced photoluminescence, achieving quantum yields of up to 22% in selected solvents. The high chain-end fidelity facilitated the grafting of hydrophilic polymer brushes from surfaces of FoNPs used as macroinitiators, enabling their dispersion in aqueous media while maintaining bright fluorescence. These findings highlight the potential of rigidity-regulated FoNPs as versatile platforms for advanced material applications, particularly in fluorescent waterborne films and aqueous-phase sensing systems.

Yin, Rongguan [Carnegie Mellon Univ., Pittsburgh, ↗

Sol-gel based oxidation catalyst and coating system using same

An oxidation catalyst system is formed by particles of an oxidation catalyst dispersed in a porous sol-gel binder. The oxidation catalyst system can be applied by brush or spray painting while the sol-gel binder is in its sol state.

Watkins, Anthony N.↗