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At least 991 records · Page 55

Effect of Molecular Weight and Layer Thickness on Dielectric Breakdown Strength of Neat and Homopolymer Swollen Lamellar Block Copolymer Films

Designing next-generation lightweight pulsed power devices hinges on understanding the factors influencing the energy storage performance of dielectric materials. Polymer dielectric films have a quadratic dependence of energy storage on the voltage breakdown strength and strategies to enhance the breakdown strength are expected to yield a path toward high energy storage densities. Highly stratified lamellar block copolymer (L-BCP) films of model polystyrene-b-polymethylmethacrylate (PS-b-PMMA) exhibited as much as ~50% enhancement in breakdown voltage (E BD ), (225 % increase in stored energy density, U~ E BD 2 ), compared to unordered as-cast L-BCP films. Such an energy density using amorphous polymer is on par with industry-standard semi-crystalline biaxially oriented polypropylene (BOPP), and as such a notable development in the field. This work develops a deeper understanding of the molecular mechanisms of E BD enhancement in L-BCP films, due to combination of interface formation and spatial isolation of the chain ends into segregated zones. We further confirm the role of chain ends in the breakdown process blending a low M n L-BCP with matched M n homopolymers to attain same layer spacing as neat L-BCP of higher M n . E BD shows a significant decrease at low homopolymer fractions due to increased net chain end density within swollen ordered L-BCP domains in wet-brush regime, followed by increased E BD due to layer thickness increase via segregated “interphase layer” formation by excess homopolymers. Notably, E BD of homopolymer swollen L-BCPs is always lower than neat L-BCP of the same domain spacing, due to overall adverse chain ends contribution from homopolymers. These findings provide important selection rules for L-BCPs for designing next-generation flexible electronics with high energy density solid-state BCP film capacitors.

36 MATERIALS SCIENCE↗

Structural Effects on Solubility and Crystallinity in Polyamide Ionomers

Although polyamides have been an industrial staple for decades, their solubility and processability remain limited due to the strong hydrogen bonding between amide groups. Here, we report a family of polyamides in which aryl rings, alkyl spacers, sulfonate groups, and amide linkages are regularly spaced along the polymer backbone, allowing us to probe the structural elements that affect processability. We accessed these polymers through a synthetic route based on an expanded diamine monomer and characterized them through a range of physical and spectroscopic techniques. Our results show that the combination of sulfonate groups with increased amide content results in highly soluble polymers, which can dissolve in polar solvents such as water, methanol, and N,N-dimethylformamide. Infrared spectroscopy on the solid polymers shows that the aliphatic amides engage in hydrogen bonding with the sulfonate groups, thus inhibiting ion aggregation, crystallization, and microphase separation. These findings expand the avenue to sulfonate-containing polyamide chemistry and provide design rules for the synthesis of more processable ionic polyamides.

amides↗

Reactive Modified Epoxy Resin and Its Miscible Blends Based on Recycled Oligomers from Solvolysis

Chemical depolymerization of fully cured epoxy resin with 20% reactive modifier was successfully performed via a solvent-assisted solvolysis process into low molecular weight recyclable oligomers (RO) at 240 °C in a pressure vessel at 650 psi for 4 h. The thermoset epoxy resin was depolymerized into transparent brown viscous fluid with a higher viscosity than the uncured epoxy resin with approximately 93% yield. Different concentrations of the RO were homogeneously mixed with the pure epoxy resin, and their curing kinetics, viscosity, FTIR, mechanical properties, DMA, and cross-link density were investigated. The curing kinetics of the pure reactive modified epoxy resin (baseline) and its mixtures with RO of different concentrations were investigated under both isothermal and nonisothermal conditions using small amplitude oscillatory shear flow. The elastic and viscous moduli (G′ and G″), complex viscosity (η*), and tan δ values were evaluated at different curing times and temperatures. The G′, G″, and η* increased dramatically, while tan δ decreased strongly by several orders of magnitude at the gel point. The zero-shear viscosity (η 0 ) was determined from the angular frequency dependent on η* based on the Cross model for different blend compositions in the liquid state before curing. The composition dependence of η 0 showed a positive deviation from the linear mixing rule and was well described by the Lecyar model. Here, the apparent activation energy of curing (E a ) was also evaluated according to the Arrhenius equation and was found to be 46 ± 2 kJ/mol regardless of the different contents of RO. For all blends up to 40 wt % RO, only one tan δ peak systematically shifting to lower temperatures with increasing content of RO was observed in the DMA measurements, indicating that the epoxy resin and the RO are miscible with up to 40 wt % RO.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Mechanisms of Ethylene Epoxidation over Silver from Machine Learning-Accelerated First-Principles Modeling and Microkinetic Simulations

In this work we employed machine learning-augmented density functional theory (DFT) thermodynamic calculations to assess the stability of different AgO x structures under catalytic ethylene epoxidation reaction conditions. We found that there are multiple AgO x surface motifs that could co-exist under the relevant conditions. These included Ag surface oxides (e.g., AgO_p(4 × 4) and Ag 1.83 O) and atomic oxygen-covered Ag(111) surfaces. Furthermore, we employed DFT calculations to evaluate the energetics of different reaction mechanisms by which ethylene and oxygen can react on these surfaces. These studies revealed several energetically viable reaction pathways for ethylene epoxidation. Microkinetic modeling analyses, based on the DFT-calculated reaction pathways, showed that ethylene epoxidation can proceed on all surfaces and that multiple pathways, including those involving Langmuir–Hinshelwood and Eley–Rideal mechanisms, could be involved in selective and unselective reactions. The diversity of mechanisms that we discovered in the context of the relatively simple ethylene epoxidation reaction on Ag suggests that the richness and complexity of surface chemistry are most likely a rule rather than an exception in heterogeneous catalytic chemical transformations on metal surfaces and that the concept of a single or even a dominant mechanism and reaction intermediates might need to be revisited for many reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Methanol Synthesis from CO 2 Hydrogenation over a Potassium-Promoted Cu x O/Cu(111) ( x ≤ 2) Model Surface: Rationalizing the Potential of Potassium in Catalysis

Alkalis have been reported as a promotor in the heterogeneous catalysis, being able to enhance the activity and selectivity of catalysts. The effective utilization of alkalis in catalyst optimization requires the fundamental understanding of the underlying mechanism. In this work, we take a potassium (K)-modified Cu x O/Cu(111) (x ≤ 2) model surface as a case study to rationalize the nature of K during the carbon dioxide hydrogenation using combined density functional theory (DFT) calculation and the kinetic Monte Carlo (KMC) simulation. Our result demonstrates the significant tuning of selectivity from carbon monoxide to methanol on going from Cu(111) to K-modified Cu x O/Cu(111). The deposited K + stabilizes the Cu x O thin film under the reducing condition of carbon dioxide hydrogenation. More importantly, our study reveals that K + acts as an active center for selective tuning in the binding, an accelerator for charge transfer, and a mediator for the electron tunneling. As a result, the K-modified Cu x O/Cu(111) opens a methanediol [H 2 C(OH) 2 ]-mediated formate pathway to facilitate the selective conversion of carbon dioxide to methanol. Our study develops the intrinsic rules of design to tune the catalytic performance using alkali metals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Long-Term 13 C Uptake by 12 C-Enriched Calcite

Knowledge of the exchange of carbon isotopes between dissolved inorganic carbon and calcite minerals is of long-standing importance for the interpretation of sedimentary paleoclimate records and 14 C transport in the geosphere. To assess the mechanism and rates of carbon isotope exchange, we equilibrated 12 C-pure synthetic calcite particles in water, first in a glovebox and then in contact with atmospheric P CO 2 and 13 C/ 12 C ratio, at two different temperatures. Cavity ring-down infrared spectroscopy δ 13 C measurements of the solid revealed sustained 13C incorporation for over a period of 500 days (21 °C) and 125 days (50 °C). We developed a quantitative model for recrystallization and isotope exchange, assuming that the interfacial free energy provides a thermodynamic driving force for the growth of larger particles at the expense of smaller ones. Furthermore, this Ostwald ripening model did not reproduce the kinetics of 13C uptake and required greater coarsening than observed. Rather, the data were best explained by a mechanism involving surface exchange and solid-phase diffusion of 13C into the particles with an inferred effective diffusion constant at 21 °C of about 10 –25 m 2 /s. Although this work cannot rule out the possibility that structural or chemical aspects of the synthetic particles enabled faster 13 C uptake than could be observed in natural systems, this study adds to the body of the recent work, suggesting that fast exchange processes are possible, likely through grain boundaries and other defects.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Enhanced Detection of Primary Biological Aerosol Particles Using Machine Learning and Single-Particle Measurement

Accurately identifying primary biological aerosol particles (PBAPs) using analytical techniques poses inherent challenges due to their resemblance to other atmospheric carbonaceous particles. Here, we present a study of an enhanced method for detecting PBAPs by combining single-particle measurement with advanced supervised machine learning (SML) techniques. We analyzed ambient particles from a variety of environments and lab-generated standards, focusing on chemical composition for traditional rule-based and clustering approaches and incorporating morphological features into the SML approaches, neural networks and XGBoost, for improved accuracy. This study demonstrates that SML methods outperform traditional methods in quantifying PBAPs, achieving significant improvements in precision, recall, F1-score, and accuracy, leading to an increased number of detected PBAPs by at least 19%. The adaptability of the proposed XGBoost-based SML model is showcased in comparison to traditional methods in categorizing PBAPs for blind data sets from different geographical locations. Two field case studies were investigated, over agricultural land and Amazonia rain forest, representing relatively low and high concentrations of PBAPs, respectively, where XGBoost consistently detected up to 3.5 times more PBAPs than traditional methods. Precise detection of PBAPs in the atmosphere could significantly improve the prediction of climatic impacts by them.

42 ENGINEERING↗

Current Density Regulated Atomic to Nanoscale Process on Li Deposition and Solid Electrolyte Interphase Revealed by Cryogenic Transmission Electron Microscopy

Current density has been perceived to play a critical rule for controlling Li deposition morphology and solid electrolyte interphase (SEI). However, the atomic level mechanism of current density on Li deposition and the SEI remains unclear. In this work, based on cryogenic transmission electron microscopy imaging combined with energy dispersive X-ray spectroscopy and electron energy loss spectroscopy electronic structure analyses, we reveal the atomic level correlation of Li deposition morphology and SEI with current density. We discover that increasing current density leads to increased overpotential for Li nucleation and growth, leading to the transition from growth-limited to nucleation-limited mode for Li dendrite. Independence of current density, the electrochemically deposited Li metal (EDLi) exhibits crystalline whisker-like morphology. The SEI formed at low current density (0.1 mA cm -2 ) is monolithic amorphous; while, a current density of above 2 mA cm -2 leads to a mosaic structured SEI, featuring an amorphous matrix with Li 2 O and LiF dispersoids, and the thickness of the SEI increases with the increase of current density. Uniquely, the Li 2 O particles is spatially located at the top surface of the SEI, while LiF is spatially adjacent to the Li-SEI interface. These results highlight the possible tuning of crucial structural and chemical features of EDLi and SEI through altering deposit conditions and consequently direct correlation with electrochemical performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Tracking Optical Phonon Dynamics in InP Nanocrystals via Transient Absorption and Femtosecond Stimulated Raman Spectroscopy

Semiconductor nanocrystals (NCs) offer actualized and prospective utility in optoelectronic technologies, yet key aspects of their thermal and vibrational behaviors remain unresolved. Compared with bulk crystals, heat dissipation involving NCs can differ substantially owing to pervasiveness of interfacial scattering, phonon confinement, and relaxed phonon momentum selection rules, as well as influences of ligands. Here, in addition to transient absorption, we use femtosecond stimulated Raman spectroscopy to track nonequilibrium optical-phonon dynamics in InP NCs capped with myristic acid ligands and compare the same particles coated with a ZnS shell. We identify distinct phonon decay pathways in ligand-capped versus ZnS-shelled NCs. Increasing the excitation density and introducing the ZnS shell measurably modify optical-phonon lifetimes, whereas phonon formation times remain largely unchanged. In addition, we observe phonon mode softening in ligand-capped nanocrystals, consistent with lattice expansion. Together, these results demonstrate that core–shell structures can strongly govern nanocrystal thermal dissipation pathways and should be considered a key design parameter for optoelectronic operation.

dissipation↗

Magnetism in Mixed Valence, Defect, Cubic Perovskites: BaIn 1– x Fe x O 2.5+δ , x = 0.25, 0.50, and 0.75. Local and Average Structures

The series BaIn 1–x Fe x O 2.5+δ , x = 0.25, 0.50, and 0.75, has been prepared under air-fired and argon-fired conditions and studied using X-ray diffraction, d.c. and a.c. susceptibility, Mössbauer spectroscopy, neutron diffraction, X-ray near edge absorption spectroscopy (XANES), and X-ray pair distribution (PDF) methods. While Ba 2 In 2 O 5 (BaInO 2.5 ) crystallizes in an ordered brownmillerite structure, Ibm2, and Ba 2 Fe 2 O 5 (BaFeO 2.5 ) crystallizes in a complex monoclinic structure, P2 1 /c, showing seven Fe 3+ sites with tetrahedral, square planar, and octahedral environments, all phases studied here crystallize in the cubic perovskite structure, Pm$\bar{}3}$m, with long-range disorder on the small cation and oxygen sites. 57 Fe Mössbauer studies indicate a mixed valency, Fe 4+ /Fe 3+ , for both the air-fired and argon-fired samples. The increased Fe 3+ content for the argon-fired samples is reflected in increased cubic cell constants and in the increased Mössbauer fraction. It appears that the Pm$\bar{}3}$m phases are only metastable when fired in argon. From a slightly modified percolation theory for a primitive cubic lattice (taking into account the presence of random O atom vacancies), long-range spin order is permitted for the x = 0.50 and 0.75 phases. Instead, the d.c. susceptibility shows only zero-field-cooled (ZFC) and field-cooled (FC) divergences at ~6 K [5 K] for x = 0.50 and at ~22 K [21 K] for x = 0.75, with values for the argon-fired samples in [ ]. Neutron diffraction data for the air-fired samples confirm the absence of long-range magnetic order at any studied temperature. For the air-fired x = 0.50, a.c. susceptibility data show a frequency-dependent χ'(max) and spin glass behavior, while for x = 0.75, χ'(max) is invariant with frequency, ruling out either a spin glass or a superparamagnetic ground state. These behaviors are discussed in terms of competing Fe 3+ –Fe 3+ antiferromagnetic exchange and ferromagnetic Fe 3+ –Fe 4+ exchange. The PDF and 57 Fe Mössbauer data indicate a local structure at short interatomic distances, which deviates strongly from the average Pm$\bar{}3}$m model. Fe Mössbauer, PDF, and XANES data show a systematic dependence on x and indicate that the Fe 3+ sites are largely fourfold-coordinated and Fe 4+ sites are fivefold- or sixfold-coordinated.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Chemical Compensation Challenges in Processing Antiferroelectric PbZrO 3 Thin Films

The electric field-induced antipolar-to-polar phase transition in antiferroelectric materials is accompanied by large changes in the structural and functional response, making them attractive for many applications ranging from pulsed energy capacitors to high-strain-high (blocking-)force actuators, solid-state heating and cooling systems, and optoelectronic devices. PbZrO 3 , as an end member of the PZT, (x)PbZr 1–x Ti x O 3 , solid solution, has been the subject of many studies. However, processing of perovskite PbZrO 3 is extremely challenging due to phase instabilities induced by Pb loss at the temperatures necessary for perovskite crystallization. Here, we discuss the challenges associated with Pb loss, as well as its compensation through bulk Pb overstoichiometry and interfacial PbO additions, in chemical solution processed, highly oriented PbZrO 3 thin films. For both 042 o - and 001 o -oriented (o-orthorhombic distortion) PbZrO 3 thin films, the crystallization interfaces are the most important contributors to Pb loss and off-stoichiometric outcomes, and no single approach was sufficient to address these challenges. Pb-rich and Pb-deficient nonperovskite phases including ZrO x were only observable through microscopic characterization, and X-ray diffraction alone could not rule out the presence of such secondary phases. “Ideal” macroscopic antiferroelectric polarization-electric field double hysteresis curves were observed despite (at times) the large presence of secondary phases. However, reduced saturation polarization and increased phase transition electric fields were observed concomitantly with the presence of secondary phase(s) and tentatively assigned to the voltage drop across the ZrO x nanocrystals. Based on these results, it is imperative that the presence of secondary phases always be addressed (beyond X-ray diffraction spectra) in order to correctly evaluate the properties of antiferroelectric films.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Assessing the Effect of Explicit Polarizability on Models of Carbon Dioxide Solvation in Ionic Liquids

Ionic liquids are an important possible carbon capture material because of their anomalously high sorption selectivity for carbon dioxide over other gases common in air. Many research groups have investigated the molecular origins of this property and provided important insights, including using 1D and 2D-IR spectroscopy. Molecular dynamics simulations have been indispensable to the interpretation of these experiments. In prior molecular dynamics simulation work, charge-scaled force fields have typically been used to provide a mean-field treatment of effects vital to ionic liquid systems such as charge transfer and polarization. Here, we compare models of carbon dioxide solvated in ionic liquids with explicit polarization to models of the same with implicit polarizability through charge-scaling. We calculate structural, dynamical, and spectroscopic properties, and make comparisons to the same items measured in experiment. In this study, we focus on two ionic liquids: 1-butyl-3- methylimidazolium (BMIM + ) paired with bis(trifluoromethane sulfonyl imide) (Tf 2 N − ) and 1-butyl-3-methylimidazolium (BMIM+) paired with hexafluorophosphate (PF 6 − ). We find that many structural, dynamical, and spectroscopic properties are changed when polarization is modeled explicitly. We also find that explicit polarizability softens local ion cages around the carbon dioxide and that the long-time diffusion of the carbon dioxide is gated by the reorganization of the ionic liquid molecules. Comparisons to experiment show modest improvement of many observables compared with experiment for the explicitly polarizable model over the charge-scaled model. Overall, our results show that charge-scaled force fields are likely sufficient to compute spectroscopic properties of carbon dioxide in ionic liquids and suggest some interpretive rules for understanding their structural and dynamical properties. Those using charge-scaled force fields should generally assume that the ion cages around solutes such as carbon dioxide are too stiff and cation-rich in their models and adjust their interpretations and predictions accordingly.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Paramagnetic Properties of Rare Earth Hydroxides, Oxalates, and Dibutyl Phosphates

Magnetic separations present a promising approach for the recovery of rare earth (RE) elements from mixtures, particularly when coupled with precipitation techniques that enhance process efficiency and selectivity. However, the magnetic properties of RE materials typically encountered in the separations industry are not well characterized. Here, we synthesized a series of RE materials, combining four REs – praseodymium (Pr), neodymium (Nd), terbium (Tb), and dysprosium (Dy) – with three precipitating agents – hydroxide, oxalate, and dibutyl phosphate. All materials showed typical paramagnetic behavior consistent with the Curie-Weiss law. At low temperatures, we observed weak antiferromagnetic correlations, which were more pronounced for the lighter RE ions (Pr, Nd). Particle morphology and crystallography analyses showed that the dibutyl phosphates were well-ordered metal-organic frameworks, the oxalates were crystals with mixed hydration states, and the hydroxides were mostly amorphous. Regardless of the degree of crystallinity, the effective magnetic moments aligned well with theoretical estimates based on Hund's rules and 4f electron configurations of the corresponding RE ions. For a given RE ion, the magnetophoretic response was thus determined by the size of the particles rather than specific metal-ligand coupling, with dibutyl phosphate promoting the formation of larger crystals that were the most strongly attracted to magnets.

Wang, Qingpu (ORCID:0000000156041571)↗

Cascaded Optical Nonlinearities in Dielectric Metasurfaces

Since the discovery of the laser, optical nonlinearities have been at the core of efficient light conversion sources. Typically, thick transparent crystals or quasi-phase matched waveguides are utilized in conjunction with phase-matching techniques to select a single parametric process. In recent years, due to the rapid developments in artificially structured materials, optical frequency mixing has been achieved at the nanoscale in subwavelength resonators arrayed as metasurfaces. Phase matching becomes relaxed for these wavelength-scale structures, and all allowed nonlinear processes can, in principle, occur on an equal footing. This could promote harmonic generation via a cascaded (consisting of several frequency mixing steps) process. However, so far, all reported work on dielectric metasurfaces have assumed frequency mixing from a direct (single step) nonlinear process. In this work, we prove the existence of cascaded second-order optical nonlinearities by analyzing the second- and third-wave mixing from a highly nonlinear metasurface in conjunction with polarization selection rules and crystal symmetries. We find that the third-wave mixing signal from a cascaded process can be of comparable strength to that from conventional third-harmonic generation and that surface nonlinearities are the dominant mechanism that contributes to cascaded second-order nonlinearities in our metasurface.

36 MATERIALS SCIENCE↗

Hydrogen Stabilized RhPdH 2D Bimetallene Nanosheets for Efficient Alkaline Hydrogen Evolution

The design of catalysts with high activity and robust stability for alkaline hydrogen evolution reaction (HER) remains a great challenge. Here, we report an efficient catalyst of two-dimensional bimetallene hydrides, in which H atoms stabilize the rhodium palladium bimetallene. The system exists because of the introduction of H that is in-situ chemically released from the formaldehyde solution during the synthesis. This provides a highly stable catalyst based on an unstable combination of metal elements. Density functional theory calculations show the H is confined by electronic interactions and the Miedema rule of reverse stability of the RhPd alloy.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Scaling Laws of Exciton Recombination Kinetics in Low Dimensional Halide Perovskite Nanostructures

Carrier recombination is a crucial process governing the optical properties of a semiconductor. Although various theoretical approaches have been utilized to describe carrier behaviors, a quantitative understanding of the impact of defects and interfaces in low dimensional semiconductor systems is still elusive. Here, we develop a model system consisting of chemically tunable, highly luminescent halide perovskite nanocrystals to illustrate the role of carrier diffusion and material dimensionality on the carrier recombination kinetics and luminescence efficiency. Our advanced synthetic methods provide a well-controlled colloidal system consisting of nanocrystals with different aspect ratios, halide compositions, and surface conditions. Using this system, we reveal the scaling laws of photoluminescence quantum yield and radiative lifetime with respect to the aspect ratio of nanocrystals. The scaling laws derived herein are not only a phenomenological observation but proved a powerful tool disentangling the carrier dynamics of microscopic systems in a quantitative and interpretable manner. The investigation of our model system and theoretical formulation bring to light the dimensionality, as a hidden constraint on carrier dynamics, and identify the diffusion length as an important parameter that distinguishes nanoscale and macroscale carrier behaviors. Furthermore, the conceptual distinction in carrier dynamics in different dimensionality regimes informs new design rules for optical devices where complex microstructures are involved.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Dynamically Stable Active Sites from Surface Evolution of Perovskite Materials during the Oxygen Evolution Reaction

Perovskite oxides are an important class of oxygen evolution reaction (OER) catalysts in alkaline media, despite the elusive nature of their active sites. In this work, we demonstrate that the origin of the OER activity in a La 1-x SrxCoO 3 model perovskite arises from a thin surface layer of Co hydr(oxy)oxide (CoO x H y ) that interacts with trace-level Fe species present in the electrolyte, creating dynamically stable active sites. Generation of the hydr(oxy)oxide layer is a consequence of a surface evolution process driven by the A-site dissolution and O-vacancy creation. In turn, this imparts a 10-fold improvement in stability against Co dissolution and a 3-fold increase in the activity-stability factor for CoO x H y / LSCO when compared to nanoscale Co-hydr(oxy)oxides clusters. Our results suggest new design rules for active and stable perovskite oxide-based OER materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗