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At least 721 records · Page 40

Tailoring Growth Interfaces of Virtual Substrates for Power Electronics

Power electronics materials are poised to play a critical role in fulfilling next generation energy needs, with up to 90% of future energy demand predicted to flow through power electronics at some point.[1] Among a number of candidate materials, AlxGa1-xN is the strongest, having bipolar dopability, thermal and chemical stability, an ultra-wide bandgap, and demonstrated experimental feasibility. However, AlGaN growth is limited by a lack of lattice-matched substrates, ultimately stunting material quality at higher thicknesses needed for power electronics applications. Further, high power applications increasingly call for fully vertical device structures, necessitating a conductive substrate. [1] Recently our group identified the (111) plane of TaC as a conductive surface lattice-matched to Al0.55Ga0.45N, taking inspiration from prior work of AlN and GaN binaries on carbide and boride substrates. [2,3,4] In this talk we demonstrate the growth of (111)-oriented TaC by RF sputtering. We investigate the interface of TaC with sapphire and SiC substrates and identify means to suppress competing Ta2C nucleation in order to stabilize (111)-oriented TaC. Potential stacking sequences are identified with respect to crystal structure and observed twinning in the TaC films. We next assess structural changes and film recrystallization that results from face-to-face annealing of TaC thin films at high temperatures above 1500 degrees Celsius. Changes to grain structure and domain size are assessed by x-ray diffraction and surface morphology is explored using atomic force microscopy. Figure 1 shows significant improvements to in- and out-of-plane strain following annealing along with the formation of terraced step edges at the film surface. Strain as a function of material composition and thickness is considered, as this may play a major role in future nucleation of AlGaN layers.

CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SU↗

Molecular Recognition at Mineral Interfaces: Implications for the Beneficiation of Rare Earth Ores

Ce-bastnäsite is the single largest mineral source for light rare-earth elements. In view of the growing industrial importance of rare-earth minerals, it is critical to develop more efficient methods for separating the valuable rare-earth-containing minerals from the surrounding gangue. In this work, we employ a combination of periodic density functional theory (DFT) and molecular mechanics (MM) calculations together with the de novo molecular design program HostDesigner to identify bis-phosphinate ligands that preferentially bind to the (100) Ce-bastnäsite surface rather than the (104) calcite surface. DFT calculations for a simple phosphinate ligand were employed to qualitatively understand key behaviors involved in ligand–metal, ligand–solvent, and solvent–metal interactions. These insights were then used to guide the search for flexible, rigid, and semirigid hydrocarbon linkers to identify candidate bis-phosphinate ligands with the potential to bind preferentially to Ce-bastnäsite. Among the five most promising bis-phosphinate ligands suggested by theoretical studies, three ligands were synthesized and their adsorption characteristics to bastnäsite (100) interfaces were characterized using vibrational sum-frequency (vSFG) spectroscopy, attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy, and isothermal titration calorimetry (ITC). The efficacy of the selective interfacial molecular binding was demonstrated by identifying a bis-phosphinate ligand capable of providing an overall higher surface coverage of alkyl groups relative to a monophosphinate ligand. The results highlight the interplay between adsorption binding strength and maximum surface coverage in determining ligand efficiency to render the mineral surface hydrophobic. DFT calculations further indicate that all tested ligands have higher affinity for Ce-bastnäsite than for calcite. Finally, this is consistent with the ITC data showing stronger adsorption enthalpy to bastnäsite than to calcite, making these ligands promising candidates for selective flotation of Ce-bastnäsite.

58 GEOSCIENCES↗

Measured Boundary Layer Transition and Rotor Hover Performance at Model Scale

An experiment involving a Mach-scaled, 11:08 f t: diameter rotor was performed in hover during the summer of 2016 at NASA Langley Research Center. The experiment investigated the hover performance as a function of the laminar to turbulent transition state of the boundary layer, including both natural and fixed transition cases. The boundary layer transition locations were measured on both the upper and lower aerodynamic surfaces simultaneously. The measurements were enabled by recent advances in infrared sensor sensitivity and stability. The infrared thermography measurement technique was enhanced by a paintable blade surface heater, as well as a new high-sensitivity long wave infrared camera. The measured transition locations showed extensive amounts, x=c>0:90, of laminar flow on the lower surface at moderate to high thrust (CT=s > 0:068) for the full blade radius. The upper surface showed large amounts, x=c > 0:50, of laminar flow at the blade tip for low thrust (CT=s < 0:045). The objective of this paper is to provide an experimental data set for comparisons to newly developed and implemented rotor boundary layer transition models in CFD and rotor design tools. The data is expected to be used as part of the AIAA Rotorcraft SimulationWorking Group

Overmeyer, Austin D.↗

Pt Nanoparticles on Atomic-Metal-Rich Carbon for Heavy-Duty Fuel Cell Catalysts: Durability Enhancement and Degradation Behavior in Membrane Electrode Assemblies

Proton exchange membrane fuel cells (PEMFCs) are a promising zero-emission power source for heavy-duty vehicles (HDVs). However, long-term durability of up to 25,000 h is challenging because current carbon support, catalyst, membrane, and ionomer developed for traditional light-duty vehicles cannot meet the stringent requirement. Therefore, understanding catalyst degradation mechanisms under the HDV condition is crucial for rationally designing highly active and durable platinum group metal (PGM) catalysts for high-performance membrane electrode assemblies (MEAs). Herein, we report a PGM catalyst consisting of platinum nanoparticles with a high content (40 wt %) on atomic-metal-site (e.g., MnN 4 )-rich carbon support. MEAs with the Pt (40 wt %)/Mn–N–C cathode catalyst achieved significantly enhanced performance and durability, generating 1.41 A cm –2 at 0.7 V under HDV conditions (0.25 mgPt cm –2 and 250 kPa abs pressure) and retaining 1.20 A cm –2 after an extended and accelerated stress test up to 150,000 voltage cycles. Electron microscopy studies indicate that most fine Pt nanoparticles are retained on or/and in the carbon support covered with the ionomer throughout the catalyst layer at the end of life. During the long-term stability test, the observed electrochemical active surface area reduction and performance loss primarily result from Pt depletion in the catalyst layer due to Pt dissolution and redeposition at the interface of the cathode and membrane. Importantly, the first-principle density functional theory calculations further reveal a support entrapment effect of the Mn–N–C, in which the MnN 4 site can specifically adsorb the Pt atom and further retard the Pt dissolution and migration, therefore enhancing long-term MEA durability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Development of Software to Model AXAF-I Image Quality

This draft final report describes the work performed under the delivery order number 145 from May 1995 through August 1996. The scope of work included a number of software development tasks for the performance modeling of AXAF-I. A number of new capabilities and functions have been added to the GT software, which is the command mode version of the GRAZTRACE software, originally developed by MSFC. A structural data interface has been developed for the EAL (old SPAR) finite element analysis FEA program, which is being used by MSFC Structural Analysis group for the analysis of AXAF-I. This interface utility can read the structural deformation file from the EAL and other finite element analysis programs such as NASTRAN and COSMOS/M, and convert the data to a suitable format that can be used for the deformation ray-tracing to predict the image quality for a distorted mirror. There is a provision in this utility to expand the data from finite element models assuming 180 degrees symmetry. This utility has been used to predict image characteristics for the AXAF-I HRMA, when subjected to gravity effects in the horizontal x-ray ground test configuration. The development of the metrology data processing interface software has also been completed. It can read the HDOS FITS format surface map files, manipulate and filter the metrology data, and produce a deformation file, which can be used by GT for ray tracing for the mirror surface figure errors. This utility has been used to determine the optimum alignment (axial spacing and clocking) for the four pairs of AXAF-I mirrors. Based on this optimized alignment, the geometric images and effective focal lengths for the as built mirrors were predicted to cross check the results obtained by Kodak.

Ahmad, Anees↗

QCD moat regime and its real-time properties

Dense quantum chromodynamics (QCD) matter may exhibit crystalline phases. Their existence is reflected in a moat regime, where mesonic correlations feature spatial modulations. We study the real-time properties of pions at finite temperature and density in QCD in order to elucidate the nature of this regime. We show that the moat regime arises from particle-hole-like fluctuations near the Fermi surface. This gives rise to a characteristic peak in the spectral function of the pion at nonzero spacelike momentum. This peak can be interpreted as a new quasi particle, the moaton. In addition, our framework also allows us to directly test the stability of the homogeneous chiral phase against the formation of an inhomogeneous condensate in QCD. We find that an inhomogeneous instability is highly unlikely for baryon chemical potentials μ B ≤ 630 MeV . Published by the American Physical Society 2025

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Geophysical Impacts and Spectroscopic Identification of a Hydrous Iron Sulfate on Icy Worlds

Over geologic time-scales, large volumes of exogenic sulfur ions from Io's plasma torus have been supplied to the surface of Europa and Ganymede, which, combined with recent interpretations of orbiter images, dynamical modeling, and surface-subsurface exchange, suggests further sulfur transport into the interior of the icy worlds. These observations motivate mixed-phase spectral modeling for interpreting orbiter spectroscopy data and determination of hydration states of candidate surface materials including hydrous sulfates. In this work, we present a combined experimental and theoretical study of the low temperature and high pressure vibrational spectral signature of the iron-sulfate monohydrate endmember, szomolnokite (FeSO 4 ·H 2 O). By employing synchrotron Fourier-transform infrared spectroscopy (FTIR) in the diamond anvil cell up to 23 GPa and down to 20 K, we explore the extreme range of pressure-temperature domains relevant to icy environments throughout our solar system and beyond. Combined with our density-functional theory quantum-mechanics molecular dynamics results, we demonstrate that experimentally observed infrared features in the O-H stretching region commonly associated with nH 2 O (n > 1) hydration states can be attributed to a pure monohydrate without the need for pressure-induced exsolved ice, other coexisting hydrous iron sulfates, or strong overtone and combination modes. We further discuss the possibility of lateral variations in density and shear properties on icy worlds associated with temperature variations and the high-pressure phases of kieserite group monohydrated sulfates.

Geosciences↗

Renormalization-group approach to Kohn-Luttinger superconductivity: Amplification of the pairing gap from ℓ 4 to ℓ

Here, we revisit the renormalization group (RG) analysis of the Kohn-Luttinger (KL) mechanism for superconductivity. The KL mechanism leads to superconductivity in a system with a repulsive bare interaction. The key ingredient is the screening effect that renders the induced interaction attractive in channels with nonzero angular momentum ℓ ≠ 0, thereby triggering the Bardeen-Cooper-Schrieffer (BCS) instability. According to the original argument, the resulting gap is exponentially small, with its exponent scaling as −ℓ 4 . However, the KL mechanism was originally formulated within perturbation theory, where the series is known to converge poorly in certain cases—most notably, for the 𝑝-wave paring gap induced by a repulsive 𝑠-wave contact interaction. This poor convergence may be attributed to a divergent integrand in a specific class of diagrams containing both the BCS logarithm and the Kohn anomaly, suggesting that one must resum the Kohn anomaly contributions separately from the BCS logarithm. In this work, we incorporate the Kohn anomaly contribution into the 𝛽 function of the RG equation governing the BCS instability near the Fermi surface. Our solution shows that the KL gap exponent is then proportional to −ℓ, indicating a significant enhancement of the KL mechanism beyond the previously known result. To illustrate this, we study the spin-triplet 𝑝-wave pairing gap arising from a repulsive 𝑠-wave contact interaction and compare our RG-based results with those obtained from the Bethe-Salpeter equation in perturbation theory.

nuclear matter in neutron stars↗

Sedimentary Parameters Controlling Occurrence and Preservation of Microbial Mats in Siliciclastic Depositional Systems

Shallow-marine, siliciclastic depositional systems are governed by physical sedimentary processes. Mineral precipitation or penecontemporaneous cementation play minor roles. Today, coastal siliciclastic environments may be colonized by a variety of epibenthic, mat-forming cyanobacteria. Studies on microbial mats showed that they are not randomly distributed in modern tidal environments. Distribution and abundancy is mainly function of a particular sedimentary facies. Fine-grained sands composed of "clear" (translucent) quartz particles constitute preferred substrates for cyanobacteria. Mat-builders also favor sites characterized by moderate hydrodynamic flow regimes, which permit biomass enrichment and construction of mat fabrics without lethal burial of mat populations by fine sediments. A comparable facies relationship can be observed in ancient siliciclastic shelf successions from the terminal Neoproterozoic Nama Group, Namibia. Wrinkle structures that record microbial mats are present but sparsely distributed in mid- to inner shelf sandstones of the Nudaus Formation. The sporadic distribution of these structures reflects both the narrow ecological window that governs mat development and the distinctive taphonomic conditions needed to preserve the structures. These observations caution that statements about changing mat abundance across the Proterozoic-Cambrian boundary must be firmly rooted in paleoenvironmental and taphonomic analysis. Understanding the factors that influence the formation and preservation of microbial structures in siliciclastic regimes can facilitate exploration for biological signatures in Earth's oldest rocks. Moreover, insofar as these structures can be preserved on bedding surfaces and are not easily mimicked by physical processes, they constitute a set of biological markers that can be searched for on Mars by remotely controlled rovers.

Noffke, Nora↗

Molten-Metal Droplet Deposition on a Moving Substrate in Microgravity: Aiding the Development of Novel Technologies for Microelectronic Assembly

Driven by advancements in microelectronics manufacturing, this research investigates the oblique (non-axisymmetric) impact of liquid-metal droplets on flat substrates. The problem of interest is relevant to the development of the novel technology of on-demand dispension (printing) of microscopic solder deposits for the surface mounting of microelectronic devices. The technology, known as solder jetting, features on-demand deposition of miniature solder droplets (30 to 120 microns in diameter) in very fine, very accurate patterns using techniques analogous to those developed for the ink-jet printing industry. Despite its promise, severe limitations exist currently with regards to the throughput rates of the technology; some of these limitations are largely due to the lack of the capability for reliable prediction of solder bump positioning and shapes, especially under ballistic deposition conditions where the droplet impact phenomena are inherently three-dimensional. The study consists of a theoretical and an experimental component. The theoretical work uses a finite element formulation to simulate numerically the non-axisymmetric (3-D) fluid mechanics and heat transfer phenomena of a liquid solder droplet impacting at an angle alpha on a flat substrate. The work focuses on the pre-solidification regime. The modeling of the most challenging fluid mechanics part of the process has been completed successfully. It is based upon the full laminar Navier-Stokes equations employing a Lagrangian frame of reference. Due to the large droplet deformation, the surface (skin) as well as the volumetric mesh have to be regenerated during the calculations in order to maintain the high accuracy of the numerical scheme. The pressure and velocity fields are then interpolated on the newly created mesh. The numerical predictions are being tested against experiments, for cases where wetting phenomena are not important. For the impact parameters used in the example shown (We = 2.38, Fr = 16300, Re = 157), the droplet rolls along the substrate, but its shape remains practically axisymmetric for all impact angles within the range from 0 to 60 deg. Interestingly, the substrate/droplet contact area during the recoiling phase of the impact is not a monotonically decreasing function of time. The experimental component of the research tests the numerical predictions and provides necessary input data (contact angles) for the theoretical model. The experiments are performed in microgravity (2.2s drop tower of the NASA GRC) in order to allow for the use of mm-size solder droplets, which make feasible the performance of accurate measurements, while maintaining similitude of the relevant fluid dynamic groups (Re, Fr, We, Ste). Preliminary oblique impact experiments have been performed using water droplets in normal gravity.

Megaridis, C. M.↗

Reversible Emulsions from Polyoxometalate–Polymer: A Robust Strategy to Cyclic Emulsion Catalysis and High-Internal-Phase Emulsion Materials

Reversible Pickering emulsions, achieved by switchable, interfacially active colloidal particles, that enable on-demand emulsification/demulsification or phase inversion, hold substantial promise for biphasic catalysis, emulsion polymerization, cutting fluids, and crude oil pipeline transportation. However, particles with such a responsive behavior usually require complex chemical syntheses and surface modifications, limiting their extensive use. Herein, we report a simple route to generate emulsions that can be controlled and reversibly undergo phase inversion. The emulsions are prepared and stabilized by the interfacial assembly of polyoxometalate (POM)–polymer, where their electrostatic interaction at the interface is dynamic. The wettability of the POMs that dictates the emulsion type can be readily regulated by tuning the number of polymer chains bound to POMs, which, in turn, can be controlled by varying the concentrations of both components and the water/oil ratio. In addition, the number of polymer chains anchored to the POMs can be varied by controlling the number of negative charges on the POMs through an in situ redox reaction. As such, a reversible inversion of the emulsions can be triggered by switching between exposure to ultraviolet light and the introduction of oxygen. Combining the functions of POM itself, a cyclic interfacial catalysis system was realized. Inversion of the emulsion also affords a pathway to high-internal-phase emulsions. Finally, the diversity of the POMs, the polymers, and the responsive switching groups open numerous new, simple strategies for designing a wide range of responsive soft matter for cargo loading, controlled release, and delivery in biomedical and engineering applications without time-consuming particle syntheses.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Highly functional microspheres facilitating Diels–Alder network formation

Introducing particles to dynamic covalent networks is a common approach to improve their performance. However, network formation can be impacted by their size and functionality. The influence can be predicted by common theories for small molecular precursors, but it is unclear whether they are applicable to precursors bearing numerous reactive groups and micrometer-scale dimensions. In this work, an experimental study was undertaken using dynamic covalent networks formed by the Diels–Alder reaction between furan and maleimide groups. The gelation behavior of the Diels–Alder networks was studied using rheometry to track their network formation at 40 °C with varying maleimide-functionalized microsphere loading. The highly functional microspheres can interact with the furan precursor, aiding in the formation of the Diels–Alder networks. A 5 wt% microsphere sample can reduce the gelation time by 23% and facilitate network formation in an unbalanced stoichiometry near the critical composition to form a percolating network.

36 MATERIALS SCIENCE↗

High Carrier Lifetimes in Epitaxial Germanium-Tin/Al(In)As Heterostructures with Variable Tin Compositions

Group IV-based germanium-tin (Ge1-ySny) compositional materials have recently shown great promise for infrared detection, light emission and ultra-low power transistors. High carrier lifetimes are desirable for enhancing the detection limit and efficiency of photodetectors, low threshold current density in lasers, and low tunneling barrier height by lowering defects and dislocations at the heterointerface of a source and a channel. Here, carrier lifetimes in epitaxial germanium (Ge) and variable tin (Sn) compositional Ge1-ySny materials were experimentally determined on GaAs substrates using the contactless microwave photoconductive decay (u-PCD) technique at an excitation wavelength of 1500 nm. Sharp (2 x 2) reflection high energy electron diffraction patterns and low surface roughness were observed from the surface of the Ge0.97Sn0.03 epilayer. X-ray rocking curves from Ge0.97Sn0.03 and Ge0.94Sn0.06 layers demonstrated the pseudomorphic and lattice-matched growth on AlAs and In0.12Al0.88As buffers, respectively, further substantiated by reciprocal space maps and abrupt heterointerfaces evident from the presence of Pendellosung oscillations. High effective carrier lifetimes of 150 ns to 450 ns were measured for Ge1-ySny epilayers as a function of Sn composition, surface roughness, growth temperature, and layer thickness. The observed increase in the carrier lifetime with an increasing Ge layer thickness and a reducing surface roughness, by incorporating Sn, were explained. The enhancement of the carrier lifetime with an increasing Sn concentration was achieved by controlling the defects with lattice-matched Ge0.94Sn0.06/In0.12Al0.88As heterointerfaces or the pseudomorphic growth of Ge0.94Sn0.06 on GaAs. Therefore, our monolithic integration of variable Sn alloy compositional Ge1-ySny materials with high carrier lifetimes opens avenues to realize electronic and optoelectronic devices.

carrier lifetimes↗

Rheological dynamics and structural characteristics of supramolecular assemblies of β-cyclodextrin and sulfonic surfactants

Cyclodextrins are highly functional compounds with a hydrophobic cavity capable of forming supramolecular inclusion complexes with various classes of molecules including surfactants. The resultant rich nanostructures and their dynamics are an interesting research problem in the area of soft condensed matter and related applications. In this paper, we report novel dynamical supramolecular assemblies based on the complexation of β-cyclodextrin with 3 different sulfonic surfactants, which are sodium hexadecylsulfate, sodium dodecylbenzenesulfonate, and myristyl sulfobetaine. It was observed that a β-cyclodextrin : surfactant/2 : 1 molar ratio was ideal for inducing axial growth and imparting large viscosities in the suspensions. Such complexation processes were accompanied by intriguing nanostructural phase behaviors and rheological properties that were very sensitive to the molecular architecture of sulfonic surfactants. The presence of an amino group in the head group of the surfactant allowed for large viscosities that reached 2.4 × 10 4 Pa s which exhibited gel-like behavior. In contrast, smaller viscosity values with a lower consistency index were observed when a bulky aromatic ring was present instead. DIC microscopy was used to visually probe the microstructure of the systems with respect to sulfonate molecular architecture. Additionally, surface tension measurements, and FTIR and NMR spectroscopies were used to gain insights into the nature of interactions that lead to the complexation and nanostructural characteristics. Finally, mechanics correlating the supramolecular morphologies to the rheological properties were proposed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electrochemical Characterization of Biomolecular Electron Transfer at Conductive Polymer Interfaces

Bio-electrochemical systems (BESs) are promising for renewable energy generation but remain hindered by inefficient electron transfer at electrode surfaces. As the toolbox of bio-anode materials increases, rigorous electrochemical characterization of emerging materials is needed. Here, we holistically characterize the electrochemical interaction of flavin mononucleotide (FMN), an electron shuttle in biological systems and a cofactor for oxidoreductase enzymes, with the bio-inspired mixed conducting polymer poly{3-[6'-(N-methylimidazolium)hexyl]thiophene} (P3HT-Im + ). The behavior of this polymer is compared to the equivalent polymer without the histidine-like imidazolium. We find improved conductivity and charge storage in imidazolium-containing polymers beyond what is explained by differences in the electroactive area. The P3HT-Im + further shows internal charge storage but with negligible faradaic contribution, indicating that charge storage capacity may translate to improved biocatalysis non-intuitive ways. Finally, one-electron transfer is observed between FMN and glassy carbon, while a bio-similar two-electron transfer is observed for the P3HT-Im + . To our knowledge, this is the first example of a concerted two-electron transfer between FMN and an electrode interface, which we attribute to the bio-inspired, histidine-like imidazolium functional groups in the polymer. These studies demonstrate the importance of bio-relevant materials characterization when such materials are deployed in BESs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Experiment K-7-16: Effects of Microgravity or Simulated Launch on Testicular Function in Rats

Fixed or frozen testicular tissues from five rats per group were analyzed by: subjective and quantitative evaluations of spermatogenesis; Northern-blot analysis for expression of selected genes; quantification of testosterone and receptors for LH; and morphometric analysis of Leydig cells. Based on observations of fixed tissue, it was evident that some rats in the flight and vivarium groups had testicular abnormalities unassociated with treatment, and probably existing when they were assigned randomly to the four treatment groups; the simulated-launch group contained no abnormal rat. Lesions induced in testes of caudal-elevation rats precluded discernment of any pre-existing abnormality. Considering rats without pre-existing abnormalities, diameter of seminiferous tubules and numbers of germ cells per tubule cross section were lower (E less than 0.05) in flight rats than in simulated-launch or vivarium rats. However, ratios of germ cells to each other, or to Sertoli cells, and number of homogenization-resistant spermatids did not differ from values for simulated-launch or vivarium controls. There was no effect of flight on normal expression of testis-specific hsp gene products, or evidence for production of stress-inducible transcripts of the hsp70 or hsp90 genes. Concentration of receptors for rLH in testicular tissue, and surface densities of smooth endoplasmic reticulum and peroxisomes in Leydig cells, were similar in flight and simulated-launch rats. However, concentrations of testosterone in testicular tissue or peripheral blood plasma were reduced (P less than 0.05) in flight rats to less than 20 percent of values for simulated-launch or vivarium controls. Thus, spermatogenesis was essentially normal in flight rats, but production of testosterone was severely depressed. Sequela of reduced androgen production on turnover of muscle and bone should be considered when interpreting data from mammals exposed to microgravity.

Amann, R. P.↗

Fluorophilic Sigma(σ)‐Lock Self‐Healable Copolymers

Abstract Although F‐Containing molecules and macromolecules are often used in molecular biology to increase the binding with Lewis acidic groups by introducing favorable C−F dipoles, there is virtually no experimental evidence and limited understanding of the nature of these interactions, especially their role in synthetic polymeric materials. These studies elucidate the molecular origin of inter‐ and intra‐Chain interactions responsible for self‐healing of F‐Containing copolymers composed of pentafluorostyrene and n‐butyl acrylate units (p(PFS/nBA). Guided by dynamic surface oscillating force (SOF) and spectroscopic measurements supported by molecular dynamics (MD) simulations, these studies show that the reformation of σ‐σ orbitals in −C−F of PFS and CH 3 CH 2 − of nBA units enables the recovery of entropic energy via fluorophilic‐σ‐lock van der Waals forces when PFS/nBA molar ratios are ~50/50. The strength of these interactions determined experimentally for self‐healable PFS/nBA compositions is in the order ~0.3 kcal/mol which primarily comes from fluorophilic‐σ‐lock (~70 %) contributions. These interactions are significantly diminished for non‐self‐healable counterparts. Strongly polarized −C−F σ orbitals create lateral dipolar forces enhancing the affinity towards −C−H orbitals, facilitating energetically favorable interactions. Entropic recovery driven by non‐Covalent bonding offers a valuable tool in designing materials with unique functionalities, particularly self‐healable batteries and energy storage devices.

Gaikwad, Samruddhi↗

The role of precursor decomposition in the formation of samarium doped ceria nanoparticles via solid-state microwave synthesis

The impact on the final morphology of ceria (CeO 2 ) nanoparticles made from different precursors (commercial: cerium acetate/nitrate) and in house: cerium tri(methylsilyl)amide (Ce-TMSA)) via a microwave solid state reaction has been determined. In all instances, powder X-ray diffraction indicated that the cubic fluorite CeO 2 phase (PDF# 04–004-9150, with the space group Fm-3 m) had formed. Scanning electron microscopy (SEM) images revealed spherical nanoparticles were produced from the Ce-TMSA precursor. The commercial acetate and nitrate precursors produced particles with irregular morphology. The roles of the precursor decomposition and binding energy in the synthesis of the nanocrystals with various morphologies, as well as a possible growth mechanism, were evaluated based on experimental and computational data. The formation of spherical shaped nanoparticles was determined to be due to the preferential single-step decomposition of the Ce-TMSA as well as the low activation energy to overcome decomposition. Due to the complicated decomposition of the commercial precursors and high activation energy the resulting particles adopted an irregular morphology. Highly uniform samarium doped ceria (Sm x Ce 1-x O 2-δ ) nanospheres were also synthesized from Ce-TMSA and samarium tri(methylsilyl)amide (Sm-TMSA). The effects of reaction time and temperature, on the final morphology were observed through SEM. The rapid single-step decomposition of TMSA-based precursors as observed through thermogravimetric analysis (TGA) and confirmed through the calculation of potential energy surfaces and binding energies from density functional theory (DFT) calculations, indicated that nanoparticle formation follows LaMer’s classical nucleation theory.

36 MATERIALS SCIENCE↗