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At least 361 records · Page 20

Identifying Topological Defects in Lamellar Phases through Contour Analysis of Complex Wave Fields

Lamellar phases frequently contain structural imperfections that significantly affect their behaviors and properties. Our previous research successfully reconstructed real-space configurations of defective lamellar phases from diffuse scattering patterns, indicating the presence of phase vortices as a potential method for identifying topological defects disrupting the smectic ordering. Here, this report presents a mathematical framework using regularized wave fields to represent defective lamellar structures in real space. Phase singularities, resulting from the interference of random waves and indicating lamellar order disruption, are identified through a contour integral. These wave fields, derived from coherent scattering in reciprocal space, were validated via computational benchmarks analyzing small-angle neutron scattering data from AOT surfactant solutions, facilitating further statistical analysis of the defects. Our study highlights the potential to extract meaningful information about topological defects in lyotropic phases by inversely analyzing experimentally measured two-point static correlations. Our method allows for detailed structural analysis of various lyotropic phases, both particulate and nonparticulate, in their quiescent states and facilitates quantitative investigation of defects’ role in phase transitions. By integrating small-angle scattering, deep learning, and vortex tangle analysis, our comprehensive approach shows promise in addressing complex challenges in the structural analysis of soft matter systems.

36 MATERIALS SCIENCE↗

Machine learning inversion from scattering for mechanically driven polymers

A machine learning inversion method is developed for analyzing scattering functions of mechanically driven polymers and extracting the corresponding feature parameters, which include energy parameters and conformation variables. The polymer is modeled as a chain of fixed-length bonds constrained by bending energy, and it is subject to external forces such as stretching and shear. We generate a data set consisting of random combinations of energy parameters, including bending modulus, stretching and shear force, along with Monte Carlo-calculated scattering functions and conformation variables such as end-to-end distance, radius of gyration and off-diagonal component of the gyration tensor. The effects of the energy parameters on the polymer are captured by the scattering function, and principal component analysis ensures the feasibility of the machine learning inversion. Finally, we train a Gaussian process regressor using part of the data set as a training set and validate the trained regressor for inversion using the rest of the data. The regressor successfully extracts the feature parameters.

Gaussian process regressors↗

Crystal structures and rotational dynamics of a two-dimensional metal halide perovskite (OA) 2 PbI 4

The extended charge carrier lifetime in metal halide perovskites is responsible for their excellent optoelectronic properties. Recent studies indicate that the superb device performance in these materials is intimately related to the organic cation dynamics. Here, we focus on the investigation of the two-dimensional hybrid perovskite, (C 8 H 17 NH 3 ) 2 PbI 4 (henceforth, OA + = C 8 H 17 NH 3 + ). Using elastic and quasielastic neutron scattering techniques and group theoretical analysis, we studied the structural phase transitions and rotational modes of the C 8 H 17 NH 3 + cation in (OA) 2 PbI 4 . Here, our results show that, in the high-temperature orthorhombic ( T > 310 K) phase, the OA + cation exhibits a combination of a twofold rotation of the NH 3 –CH 2 head group about the crystal c -axis with a characteristic relaxation time of ~6.2 ps, threefold rotations (C 3 ) of NH 3 and CH 3 terminal groups, and slow librations of the other atoms. Contrastingly, only the C 3 rotation is present in the intermediate-temperature orthorhombic (238 K < T < 310 K) and low-temperature monoclinic ( T < 238 K) phases.

36 MATERIALS SCIENCE↗

Core Mass Estimates in Strong Lensing Galaxy Clusters Using a Single-halo Lens Model

The core mass of galaxy clusters is an important probe of structure formation. Here we evaluate the use of a single-halo model (SHM) as an efficient method to estimate the strong lensing cluster core mass, testing it with ray-traced images from the Outer Rim simulation. Unlike detailed lens models, the SHM represents the cluster mass distribution with a single halo and can be automatically generated from the measured lensing constraints. In this work we find that the projected core mass estimated with this method, $M_{\text{SHM}}$, has a scatter of 8.52% and a bias of 0.90% compared to the "true" mass within the same aperture. Our analysis shows no systematic correlation between the scatter or bias and the lens-source system properties. The bias and scatter can be reduced to 3.26% and 0.34%, respectively, by excluding models that fail a visual inspection test. We find that the SHM success depends on the lensing geometry, with single giant arc configurations accounting for most of the failed cases due to their limiting constraining power. When excluding such cases, we measure a scatter and bias of 3.88% and 0.84%, respectively. Finally, we find that when the source redshift is unknown, the model-predicted redshifts are overestimated, and the $M_{\text{SHM}}$ is underestimated by a few percent, highlighting the importance of securing spectroscopic redshifts of background sources. Our analysis provides a quantitative characterization of $M_{\text{SHM}}$, enabling its efficient use as a tool to estimate the strong lensing cluster core masses in the large samples, expected from current and future surveys.

79 ASTRONOMY AND ASTROPHYSICS↗

Extending the capillary wave model to include the effect of bending rigidity: X-ray reflectivity and diffuse scattering

The surface roughness of a thin film at a liquid interface exhibits contributions of thermally excited fluctuations. This thermal roughness depends on temperature (𝑇), surface tension (𝛾), and elastic material properties, specifically the bending modulus (𝜅) of the film. A nonzero 𝜅 suppresses the thermal roughness at small length scales compared to an interface with zero 𝜅, as expressed by the power spectral density of the thermal roughness. The description of the x-ray scattering of the standard capillary wave model (CWM), which is valid for zero 𝜅, is extended to include the effect of 𝜅. The extended CWM (eCWM) provides a single analytical form for both the specular x-ray reflectivity (XRR) and the diffuse scattering around the specular reflection, and recovers the expression of the CWM at its zero 𝜅 limit. This theoretical approach enables the use of single-shot grazing incidence x-ray off-specular scattering (GIXOS) measurements for characterizing the structure of thin films on a liquid surface. The eCWM analysis approach decouples the thermal roughness factor from the surface scattering signal, providing direct access to the intrinsic surface-normal structure of the film and its bending modulus. Moreover, the eCWM facilitates the calculation of reflectivity at any desired resolution (pseudo-XRR approach). The transformation into pseudo-XRR provides the benefit of using widely available XRR software to perform GIXOS analysis. The extended range of the vertical scattering vector (𝑄 𝑧 ) available with the GIXOS pseudo-XRR approach allows for a higher spatial resolution than with conventional XRR. Experimental results are presented for various lipid systems, showing strong agreement between conventional specular XRR and pseudo-XRR methods. This agreement validates the proposed approach and highlights its utility for analyzing soft, thin films.

36 MATERIALS SCIENCE↗

Two-dimensional assembly of gold nanoparticles grafted with charged-end-group polymers

We introduced charged terminal groups to polymers that graft nanoparticles enable Coulombic control over their assembly by tuning the pH and salinity of their aqueous suspensions. Gold nanoparticles (AuNPs) are grafted with poly (ethylene glycol) (PEG) terminated with CH 3 (charge-neutral), COOH (negatively charged) or NH 2 groups (positively charged), and characterized with dynamic light scattering, ζ-potential, and thermal gravimetric analysis. Liquid surface X-ray reflectivity (XR) and grazing incidence small-angle X-ray scattering (GISAXS) are used to determine the density profile and in-plane structure of the AuNPs assembly at the aqueous surface. Assembly of PEG-AuNPs at the liquid/vapor interface is tunable by adjusting pH or salinity for COOH but less for NH 2 terminals. The distinct assembly behaviors are attributed to the overall charge of PEG-AuNPs as well as PEG conformation. COOH-PEG corona is more compact than those of the other terminal groups, leading to a crystalline structure with a smaller superlattice. The net charge per particle depends not only on the PEG terminal groups but also on the cation sequestration of PEG and the intrinsic negative charge of the AuNP surface. The closeness to overall charge neutrality, and hydrogen bonding in play, brought by NH 2 -PEG, drive NH 2 -PEG-AuNPs to assembly and crystallinity without additives to the suspensions.

36 MATERIALS SCIENCE↗

High Thermoelectric Performance through Crystal Symmetry Enhancement in Triply Doped Diamondoid Compound Cu 2 SnSe 3

The presence of high crystallographic symmetry and nanoscale defects are favorable for thermoelectrics. With proper electronic structures, a highly symmetric crystal tends to possess multiple carrier channels and promote electrical conductivity without sacrificing Seebeck coefficient. In addition, nanoscale defects can effectively scatter acoustic phonons to suppress thermal conductivity. Here, we report that the triple doping of Cu 2 SnSe 3 leads to a high ZT value of 1.6 at 823 K for Cu 1.85 Ag 0.15 (Sn 0.88 Ga 0.1 Na 0.02 )Se 3 , and a decent average ZT (ZT ave ) value of 0.7 is also achieved for Cu 1.85 Ag 0.15 (Sn 0.93 Mg 0.06 Na 0.01 )Se 3 from 475 to 823 K. Our study reveals: (1) Ag doping on Cu sites generates numerous point defects and greatly decreases lattice thermal conductivity. (2) Doping Mg or Ga converts the monoclinic Cu 2 SnSe 3 into a cubic structure. This symmetry enhancing leads to increase in the effective mass from 0.8 m e to 2.6 m e (m e , free electron mass) and the power factor from 4.3 μW/cm –1 K –2 for Cu 2 SnSe 3 to 11.6 μW/cm –1 K –2 . (3) Na doping creates dense dislocation arrays and nanoprecipitates, which strengthens the phonon scattering. (4) Pair distribution function analysis shows localized symmetry breakdwon in the cubic Cu 1.85 Ag 0.15 (Sn 0.88 Ga 0.1 Na 0.02 )Se 3 . Furthermore, the present work provides a standpoint to design promising thermoelectric materials by synergistically manipulating crystal symmetry and nanoscale defects.

36 MATERIALS SCIENCE↗

The Central Role of Oxo Clusters in Zirconium‐Based Esterification Catalysis

Oxo clusters are a unique link between oxide nanocrystals and Metal‐Organic Frameworks (MOFs), representing the limit of downscaling each of the respective crystals. Herein, the superior catalytic activity of clusters, compared to zirconium MOF UiO‐66 and nanocrystals is shown. Focus is on esterification reactions given their general importance in consumer products and the challenge of converting large substrates. Oxo clusters have a higher surface‐to‐volume ratio than nanocrystals, rendering them more active. For large substrates, for example, oleic acid, MOF UiO‐66 has negligible catalytic activity while clusters provide almost quantitative conversion, a fact we ascribe to limited diffusion of large substrates through the MOF pores. Clusters do not suffer from limited mass transfer and we also obtain high conversion in solvent‐free reactions with sterically hindered alcohols (hexanol, 2‐ethyl hexanol, benzyl alcohol, and neopentyl alcohol). The cluster catalyst can be recovered and shows identical activity when reused. The structural integrity of the cluster is confirmed using X‐ray total scattering and pair distribution function analysis. Moreover, when homogeneous zirconium alkoxides are used as catalysts, the same oxo cluster is retrieved, showing that oxo clusters are the active catalytic species, even in previously assumed homogeneously catalyzed reactions.

Pulparayil Mathew, Jikson↗

Evidence for strong electronic correlations in the bulk state of grey arsenic

Here, we investigate the electron band structure of grey arsenic, whose (111) face hosts the topological Shockley state. Interestingly, the bulk band close to the touching point with the surface state exhibits the characteristics of inelastic scattering. Moreover, the band structure analysis reveals linearity in the imaginary part of electron self-energy. These features are analogous to those observed in high-temperature superconductors and marginal Fermi liquid systems, respectively, where strong electronic correlations exist. Our results suggest that correlated many-body states can be connected by non-interacting topological states, providing a viable playground to explore the coupling between topological and correlated states via grey arsenic surface.

ARPES↗

Graphene Oxide Nanoribbons for High Early-Strength Cement Concrete

Longitudinal oxidative unzipping of the outer walls of multiwalled carbon nanotubes (MWCNTs) yields graphene oxide nanoribbons (GONRs), which exhibit greater open surface area and functional edge content than MWCNTs. This paper presents a study of the nano-amendment of Portland cement concrete with GONRs in concentrations between 0.05% (in weight of cement, wt%) and 0.0005 wt%, thus up to two orders of magnitude lower than that reported as lower-bound in the archival literature. The dispersibility in aqueous solution as a function of GONR concentration and oxygen weight content (O%) was assessed through dynamic light scattering (DLS) and zeta potential analysis. The results indicated that less effective suspensions were obtained for 0.05 wt% of GONRs and 22.7 O%. Therefore, GONR water suspensions with 30-40% O% were used to manufacture 50 mm × 100 mm cylindrical concrete specimens. After 7 days of curing, results from uniaxial compression tests using four specimens per configuration (MWCNT concentration and O%) showed that the incorporation of GONRs resulted in an average increase in compressive strength up to 45%. Consistent with the DLS and compression test results, SEM micrographs showed well-dispersed GONRs together with accelerated and preferential formation of calcium silicate hydrates (C-S-H) for all GONR concentrations. The results indicate, for the first time, that the incorporation of very small concentrations (as low as 0.0005 wt%) of well-dispersed GONR amendments can significantly enhance the early-age concrete strength. However, such enhancement became insignificant after 28 days of curing.

cement↗

Size Dependent Optical Properties and Structure of ZnS Nanocrystals Prepared from a Library of Thioureas

Here, ZnS nanocrystals (λ max (1S e -1S 3/2h ) = 260 - 320 nm, d = 1.7 - 10.0 nm) are synthesized from Zn(O 2 CR) 2 (O 2 CR = tetra-decanoate, oleate and 2-hexyldecanoate), N,N'-disubstituted and N,N',N'-trisubstituted thioureas, and P,P,N-trisubstituted phos-phanecarbothioamides. The influence of precursor substitution, ligand sterics, and reaction temperature on the final nanocrystal size were evaluated. By using saturated hydrocarbon solvents and saturated aliphatic carboxylate ligands, polymeric byproducts could be avoided and pure ZnS nanocrystals isolated. Elevated temperatures, slower precursor conversion reactivity and branched zinc 2-hexyldecanoate yield the largest ZnS nanocrystals. Carefully purified zinc carboxylate, rapidly converting precursors, and cooling the synthesis mixture following complete precursor conversion provide quasi spherical nanocrystals with the narrowest shape dispersity. Nanocrystal sizes were measured using pair distribution function (PDF) analysis of X-ray scattering and scanning transmission electron microscopy (STEM) and plotted versus the energy of their first excitonic optical absorption. The resulting empirical relationship provides a useful method to characterize the nanocrystal size from 1.7-4.0 nm using optical absorption spectroscopy.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Oxyanion Surface Complexes Control the Kinetics and Pathway of Ferrihydrite Transformation to Goethite and Hematite

The rate and pathway of ferrihydrite (Fh) transformation at oxic conditions to more stable products is controlled largely by temperature, pH, and the presence of other ions in the system such as nitrate (NO 3 - ), sulfate (SO 4 2- ), and arsenate (AsO 4 3- ). Although the mechanism of Fh transformation and oxyanion complexation have been separately studied, the effect of surface complex type and strength on the rate and pathway remains only partly understood. We have developed a kinetic model that describes the effects of surface complex type and strength on Fh transformation to goethite (Gt) and hematite (Hm). Two sets of oxyanion-adsorbed Fh samples were prepared, nonbuffered and buffered, aged at 70 ± 1.5 °C, and then characterized using synchrotron X-ray scattering methods and wet chemical analysis. Kinetic modeling showed a significant decrease in the rate of Fh transformation for oxyanion surface complexes dominated by strong inner-sphere (SO 4 2- and AsO 4 3- ) versus weak outer-sphere (NO 3 - ) bonding and the control. The results also showed that the Fh transformation pathway is influenced by the type of surface complex such that with increasing strength of bonding, a smaller fraction of Gt forms compared with Hm. In conclusion, these findings are important for understanding and predicting the role of Fh in controlling the transport and fate of metal and metalloid oxyanions in natural and applied systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Temperature Dependent Local Atomic Structure and Vibrational Dynamics of Barium Hydride and Calcium Hydride

Solid-state ionic conductors that exhibit pure ionic transport of hydride anions are rare. Here, we investigate two alkaline earth metal hydrides, barium hydride and calcium hydride, using neutron scattering techniques to understand how the local atomic environment plays a role in the diffusion of hydride ions. At high temperatures, barium hydride exhibits exceptional transport properties with ionic conductivities that are higher than those of many of the typical proton and oxide ion conductors in use today. Total neutron scattering and pair distribution function analysis reveal how a structural phase transition converts barium hydride from a modest ionic conductor into a fast ionic conductor through the introduction of disorder, deuterium site splitting, and dynamic structural fluctuations. Furthermore, neutron vibrational spectroscopy is employed to probe changes in the temperature evolution of the lattice dynamics and local energy landscape. These results improve our fundamental knowledge of the interplay between structure and dynamics governing a rare conduction process of hydride ions in solid-state materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Inhibition of Reaction Layer Formation on MgO(100) by Doping with Trace Amounts of Iron

Despite extensive research on MgO’s reactivity in the presence of CO 2 under various conditions, little is known about whether impurities incorporated into the solid, such as iron, enhance or impede hydroxylation and carbonation reactions. The purity of the MgO required for the successful implementation of MgO looping as a direct air capture technology affects the deployment costs. With this motivation, we tested how incorporated iron impacts MgO (100) reactivity and passivation layer formation under ambient conditions by using atomic force microscopy, electron microscopy, and synchrotron-based X-ray scattering. Based on electron microprobe analysis, our MgO samples were 0.5 wt % iron, and Mössbauer spectroscopy results indicated that 70% of the iron is present as Fe(II). We find that even these low levels of iron dopants impeded both the hydroxylation at various relative humidities (10%, 33%, 75%, and >95%) and carbonation in CO 2 (33%, 75%, and >95%) on the (100) surface. Crystalline reaction products were formed. Reaction layers on the sample were easily removed by exposing the sample to deionized water for 2 min. Overall, our findings demonstrate that the presence of iron dopants slows the reaction rate of MgO, indicating that MgO without incorporated iron is preferable for mineral looping applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Hybrid-Supported Bilayers Formed with Mixed-Charge Surfactants on C 18 -Functionalized Silica Surfaces

Mixtures of cationic-anionic surfactants have been demonstrated to spontaneously form ordered monolayers at hydrophobic-hydrophilic boundaries including air-water and oil-water interfaces. Here, confocal Raman microscopy is used to investigate the structure of hybrid-supported surfactant bilayers (HSSBs) formed by deposition of a distal leaflet of mixed cationic-anionic surfactants onto a proximal leaflet of n-alkane (C 18 ) chains on the interior surfaces of chromatographic silica particles. The surface coverage of the two surfactants in a hybrid bilayer was determined from carbon analysis and the relative Raman scattering of their respective head-groups. Within the measurement uncertainty, the stoichiometric ratio of the two surfactants is one-to-one, equivalent to mixed-charge-surfactant monolayers at air-water and oil-water interfaces and consistent with the role of the head-group electrostatic interactions in their formation. When self-assembled on the hydrophobic surface, pairs of oppositely-charged n-alkyl-chain surfactants resemble a phospholipid (phosphati¬dylcholine) molecule, with its zwitterionic head group and two hydrophobic acyl-chain tails. Indeed, the structure of these hybrid-supported surfactant bilayers on C 18 -modified silica surfaces is similar to that of hybrid-supported lipid bilayers (HSLBs) on the same supports, but with denser and more-ordered n-alkyl chains. Hybrid-supported surfactant bilayers exhibit a melting phase transition (gel to liquid-crystalline phase) with structural and energetic characteristics similar to hybrid-supported bilayers prepared from a zwitterionic phospholipid of the same alkyl chain length. These mixed-charge surfactants on n-alkane modified silica are stable in water over time (months), results that suggest the potential use of these hybrid bilayers for generating supported lipid bilayer-like surfaces or for separation applications.

36 MATERIALS SCIENCE↗

Addition of Short Polymer Chains Mechanically Reinforces Glassy Poly(2-vinylpyridine)–Silica Nanoparticle Nanocomposites

The addition of hard fillers to a polymer matrix is a well-known process for achieving mechanical reinforcement. With a decrease in the size of the fillers, the contribution from polymer–particle nanometer-sized interfaces become significant, and these interfaces affect the mechanical performance of polymer nanocomposites (PNCs) beyond the limits established for conventional composites. However, the molecular mechanisms underlying the improvement in the mechanical performance of glassy PNCs remain unresolved, necessitating a deeper understanding of the structure–property relationships in these intrinsically heterogeneous systems. In this effort, by using Brillouin light scattering (BLS) and dynamic mechanical analysis (DMA), we demonstrated that adding shorter chains to a PNC prepared with high molecular weight polymers significantly improved the mechanical properties of the PNC in the glassy state. The strongest enhancement of mechanical properties occurred at an optimum concentration of short chains. This is in contrast to behavior of the glass transition temperature of PNCs which shows a monotonic decrease with an increase in the concentration of shorter chains. Using experimental data and coarse-grained molecular dynamics (MD) simulations, we have identified the molecular mechanism leading to the observed non-monotonic changes in mechanical reinforcement. Here, this mechanism includes changes in the nanoscale organization at the interface, combined with chain stretching amplified by the addition of the short chains. Overall, our approach paves a simple, cost-effective pathway to fabricating glassy PNCs with significantly improved mechanical properties that will fill various practical needs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Double-pulse speckle contrast correlations with near Fourier transform limited free-electron laser light using hard X-ray split-and-delay

Abstract The ability to deliver two coherent X-ray pulses with precise time-delays ranging from a few femtoseconds to nanoseconds enables critical capabilities of probing ultra-fast phenomena in condensed matter systems at X-ray free electron laser (FEL) sources. Recent progress made in the hard X-ray split-and-delay optics developments now brings a very promising prospect for resolving atomic-scale motions that were not accessible by previous time-resolved techniques. Here, we report on characterizing the spatial and temporal coherence properties of the hard X-ray FEL beam after propagating through split-and-delay optics. Speckle contrast analysis of small-angle scattering measurements from nanoparticles reveals well-preserved transverse coherence of the beam. Measuring intensity fluctuations from successive X-ray pulses also reveals that only single or double temporal modes remain in the transmitted beam, corresponding to nearly Fourier transform limited pulses.

42 ENGINEERING↗

Cluster defects in gibbsite nanoplates grown at acidic to neutral pH

Gibbsite [α-Al(OH) 3 ] is the solubility limiting phase for aluminum across a wide pH range, and it is a common mineral phase with many industrial applications. The growth mechanism of this layered-structure material, however, remains incompletely understood. Synthesis of gibbsite at low to circumneutral pH yields nanoplates with substantial interlayer disorder. Here we examine defects in this material in detail, and the effects of recrystallization in highly alkaline sodium hydroxide solution at 80 °C. We employed a multimodal approach, including scanning electron microscopy, magic-angle spinning nuclear magnetic resonance (MAS-NMR), Raman and infrared spectroscopies, X-ray diffraction (XRD), and X-ray total scattering pair distribution function (XPDF) analysis to characterize the ageing of the nanoplates over several days. Additionally, XRD and XPDF indicate that gibbsite nanoplates precipitated at circumneutral pH contain dense, truncated sheets imparting a local difference in interlayer distance. These interlayer defects appear well described by flat Al 13 aluminum hydroxide nanoclusters nearly isostructural with gibbsite sheets present under synthesis conditions and trapped as interlayer inclusions during growth. Ageing at elevated temperature in alkaline solutions gradually improves crystallinity, showing a gradual increase in H-bonding between interlayer OH groups. Between 7 to 8 vol% of the initial gibbsite nanoparticles exhibit this defect, with the majority of differences disappearing after 2–4 hours of recrystallization in alkaline solution. The results not only identify the source of disorder in gibbsite formed under acidic/neutral conditions but also point to a possible cluster-mediated growth mechanism evident through inclusion of relict oligomers with gibbsite-like topology trapped in the interlayer spaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗