Bulk Value Research Articles

Dielectric properties of nanoconfined water.

The dielectric function of a dipolar liquid exhibits a strong wavenumber dependence in the bulk homogeneous state. Such a behavior seems to suggest the possibility of a strong system size dependence of the dielectric constant (DC) of a nanoconfined liquid, although details have been revealed only recently. The dielectric properties of nanoconfined water, indeed, show a marked sensitivity not only to the size and shape (dielectric boundaries) of confinement but also to the nature of surface-water interactions. For geometries widely studied, namely, water confined in a narrow slit, nanocylinder, and nanospherical cavity, the asymptotic approach to the bulk value of the DC with the increase in confinement size is found to be surprisingly slow. This seems to imply the appearance of a dipolar cross correlation length, much larger than the molecular length-scale of water. In narrow slits and narrow cylinders, the dielectric function becomes both inhomogeneous and anisotropic, and the longitudinal and transverse components display markedly different system size dependencies. This sensitivity can be traced back to the dependence of the DC on the ratio of the mean square dipole moment fluctuation to the volume of the system. The observed sensitivity of collective dipole moment fluctuations to the length scale of confinement points to the possibility of using DC to estimate the orientational correlation length scale, which has been an elusive quantity. Furthermore, the determination of volume also requires special consideration when the system size is in nanoscale. We discuss these and several other interesting issues along with several applications that have emerged in recent years.

Optical Second‐ and Third‐Order Nonlinearities in Plasma‐Enhanced Chemical Vapor Deposition‐Grown Silicon Oxides and Silicon Nitrides

Optical second‐ and third‐order nonlinearities ( and ) in nonstoichiometric silicon oxides and silicon nitrides grown by plasma‐enhanced chemical vapor deposition are investigated by second‐harmonic generation (SHG) and electric field‐induced second‐harmonic (EFISH) measurements. The free‐space SHG measurements with a fundamental wavelength of 1030 nm allow us to determine the bulk values of both material platforms for various material compositions. It is demonstrated that the bulk values can be strongly enhanced by increasing the silicon content, reaching maximum values of the main tensor component of for silicon‐rich nitrides and for silicon‐rich oxides. EFISH measurements demonstrate that the values can be pushed even further by adding a static electric field to the materials. Similar to the values, the values are strongly enhanced by increasing the silicon content, leading to a maximum value of m2 V−2 for the silicon‐rich nitrides and m2 V−2 for the silicon‐rich oxides.

Colossal Strain Tuning of Ferroelectric Transitions in KNbO3 Thin Films.

Strong coupling between polarization (P) and strain (ɛ) in ferroelectric complex oxides offers unique opportunities to dramatically tune their properties. Here colossal strain tuning of ferroelectricity in epitaxial KNbO3 thin films grown by sub-oxide molecular beam epitaxy is demonstrated. While bulk KNbO3 exhibits three ferroelectric transitions and a Curie temperature (Tc) of ≈676K, phase-field modeling predicts that a biaxial strain of as little as -0.6% pushes its Tc >975K, its decomposition temperature in air, and for -1.4% strain, to Tc >1325K, its melting point. Furthermore, a strain of -1.5% can stabilize a single phase throughout the entire temperature range of its stability. A combination of temperature-dependent second harmonic generation measurements, synchrotron-based X-ray reciprocal space mapping, ferroelectric measurements, and transmission electron microscopy reveal a single tetragonal phase from 10 K to 975K, an enhancement of ≈46% in the tetragonal phase remanent polarization (Pr),and a ≈200% enhancementin its optical second harmonic generation coefficients over bulk values. These properties in a lead-free system, but with properties comparable or superior to lead-based systems, make it an attractive candidate for applications ranging from high-temperature ferroelectric memory to cryogenic temperature quantum computing.

Coherent Acoustic Phonons in Plasmonic Nanoparticles: Elastic Properties and Dissipation at Low Temperatures.

We studied the frequency and quality factor of mechanical plasmonic nanoresonators as a function of temperature, ranging from ambient to 4 K. Our investigation focused on individual gold nanorods and nanodisks of various sizes. We observed that oscillation frequencies increase linearly as temperature decreases until saturation is reached at cryogenic temperatures. This behavior is explained by the temperature dependence of the elastic modulus, with a Debye temperature compatible with reported bulk values for gold. To describe the behavior of the quality factor, we developed a model considering the nanostructures as anelastic solids, identifying a dissipation peak around 150 K due to a thermally activated process, likely of the Niblett-Wilks mechanism type. Importantly, our findings suggest that external dissipation factors are more critical to improving quality factors than internal friction, which can be increased by modifying the nanoresonator's environment. Our results enable the future design of structures with high vibration frequencies and quality factors by effectively controlling external losses.

Anomalously High Apparent Young's Modulus of Ultrathin Freestanding PZT Films Revealed by Machine Learning Empowered Nanoindentation.

The mechanical properties at small length scales are not only significant for understanding the intriguing size-dependent behaviors but also critical for device applications. Nanoindentation via atomic force microscopy is widely used for small-scale mechanical testing, yet determining the Young's modulus of quasi-2D films from freestanding force-displacement curve of nanoindentation remains challenging, complicated by both bending and stretching that are highly nonlinear. To overcome these difficulties, a machine learning model is developed based on the back propagation (BP) neural network and finite element training to accurately determine the Young's modulus, pretension, and thickness of freestanding films from nanoindentation force-displacement curves simultaneously, improving the computational efficiency by two orders of magnitude over conventional brute force curve fitting. Using this technique, anomalously high apparent Young's modulus is discovered of 2.8nm thick PbZr0.2Ti0.8O3 (PZT) film as large as 229.4±12.1GPa, much higher than the bulk value. The enhancement can be attributed to the strain gradient-induced flexoelectric effect, and the corresponding flexoelectric coefficient is estimated to be ≈200nCm-1. The method is developed to enable an artificial intelligence (AI) system to study the mechanical properties of a wide range of low-dimensional materials.

Conventional epitaxy of NiO thin films on muscovite mica and c-Al2O3 substrates

Fiber-textured and epitaxial NiO thin films were deposited on Si(100), c-Al2O3, and muscovite mica(001) substrates using reactive magnetron sputtering at substrate temperatures of 300°C and 400°C, to investigate the effect of film thickness and substrate temperature on epitaxial growth of NiO films. The as-deposited films exhibited a face-centered cubic structure with a larger lattice constant, attributed to strain induced during the sputtering process. With an increase in substrate temperature to 400°C, the d-spacing decreased due to strain release, approaching the NiO bulk value for the thickest film. The NiO film grown on Si(100) displayed fiber texture. On c-plane sapphire, NiO thin films exhibited twin domains and three-fold symmetry, consistent with expected crystallographic orientation relationship for NaCl-structured materials on sapphire:(111)NiO∥(0001)Al2O3and[01¯1]NiO∥[1¯010]Al2O3, [011¯]NiO∥[101¯0]Al2O3. On muscovite mica(001) substrates, the observed epitaxial shows that the mechanism is conventional epitaxy, rather than van der Waals epitaxy, consistent with the epitaxial growth of the non-layered non-van-der-Waals compound NiO. The epitaxial relationship was identified as of (111)NiO∥(001)Mica and [01¯1]NiO∥[010]Mica, [011¯]NiO∥[01¯0]Mica.

Diverse prehistoric cattle husbandry strategies in the forests of Central Europe.

During the sixth millennium BCE, the first farmers of Central Europe rapidly expanded across a varied mosaic of forested environments. Such environments would have offered important sources of mineral-rich animal feed and shelter, prompting the question: to what extent did early farmers exploit forests to raise their herds? Here, to resolve this, we have assembled multi-regional datasets, comprising bulk and compound-specific stable isotope values from zooarchaeological remains and pottery, and conducted cross-correlation analyses within a palaeo-environmental framework. Our findings reveal a diversity of pasturing strategies for cattle employed by early farmers, with a notable emphasis on intensive utilization of forests for grazing and seasonal foddering in some regions. This experimentation with forest-based animal feeds by early farmers would have enhanced animal fertility and milk yields for human consumption, concurrently contributing to the expansion of prehistoric farming settlements and the transformation of forest ecosystems. Our study emphasizes the intricate relationship that existed between early farmers and forested landscapes, shedding light on the adaptive dynamics that shaped humans, animals and environments in the past.

Success and failure of the spreading law for large drops of dense granular suspensions

The spreading of large viscous drops of density-matched suspensions of non-Brownian spheres on a smooth solid surface is investigated experimentally at the global drop scale. The focus is on dense suspensions with a solid volume fraction equal to or greater than $40\,\%$ , and for drops larger than the capillary length, i.e. for which the spreading is governed by the balance of gravitational and viscous forces. Our findings indicate that all liquids exhibit a power-law behaviour typical of gravity-driven dynamics, albeit with an effective suspension viscosity that is smaller than the bulk value. When the height of the drop is of the order of the particle size, the power law breaks down as the particles freeze while the contact line continues to advance.

Elucidating the Fate of the Organochlorine Pesticide Chlordecone under Abiotic Reductive and Oxidative Processes: Kinetics, Transformation Products, and C vs Cl Isotope Fractionation.

Pollution of French West Indies (FWI) soils by the organochlorine pesticide chlordecone poses environmental and societal concerns due to its long-term persistence. Assessing chlordecone degradation remains challenging due to analytical constraints to identify transformation products. Here, multielement compound-specific isotope analysis (ME-CSIA) was used to identify changes in stable isotope signatures of chlordecone produced during abiotic transformation reactions under reducing and oxidative conditions. Effective chlordecone transformation was shown in reactions with zerovalent iron (ZVI), vitamin B12 and sodium sulfide (VSS), alkaline ascorbic acid (AA), and sodium persulfate activated by microwave irradiation (MWPS). Significant enrichment of 13C and 37Cl was observed in all abiotic reactions, with εC,bulk and εCl,bulk values ranging from -4.3 ± 0.4‰ to -2.3 ± 0.2‰ and from -2.6 ± 0.4‰ to -1.3 ± 0.3‰, respectively. Distinct mechanisms were evidenced in dual isotope plots, resulting in Λ values of 1.17 ± 0.28 for ZVI, 1.26 ± 0.50 for VSS, 2.06 ± 0.30 for AA, and 2.90 ± 0.50 for MWPS. Two major products were formed, 10-monohydrochlordecone and 8-monohydrochlordecone. Cl-CSIA data suggested that the first Cl substitution at the C10-position likely produced secondary Cl isotope effects (via nucleophilic substitution). Overall, results suggest that ME-CSIA can help quantify in situ chlordecone degradation, distinguishing between different ongoing degradation mechanisms and fingerprinting pollutant sources from chlordecone formulations (Curlone).

Thermal, mechanical, and electrical properties of Si-stacked nanosheet transistors using machine learning interatomic potentials

Thermal and mechanical properties play a key role in optimizing the performance of nanoelectronic devices. In this study, the lattice thermal conductivity (κL) and elastic constants of Si nanosheets at different sheet thicknesses were determined using recently developed machine learning interatomic potentials (MLIPs). A Si nanosheet with a minimum thickness of 10 atomic layers was used for model training to predict the properties of sheets with greater thicknesses. The training dataset was efficiently constructed using stochastic sampling of the potential energy surface (PES). Density functional theory (DFT) calculations were used to extract
the MLIP, which served as the basis for further analysis. The Moment Tensor Potential (MTP) method was used to obtain the MLIP in this study. The results showed that, at sub-6 nm sheet thickness, the thermal conductivity dropped to ∼ 7 % of its bulk value, whereas some stiffness tensor components dropped to ∼ 3 % of the bulk values. These findings contribute to the understanding of heat transport and mechanical behavior of ultrathin Si nanosheets, which is crucial for designing and optimizing nanoelectronic devices. The technological implications of the extracted parameters on nanosheet field-effect transistor (NS-FET) performance at advanced technology nodes were evaluated using TCAD device simulations.

Mathematical lipid correction of δ13C and effect of lipid extraction on δ15N of European eel (Anguilla anguilla) muscle: Lipid correction of δ13C in European eels.

Carbon (δ13C) and nitrogen (δ15N) stable isotope analysis is a powerful tool to investigate diverse questions in fish ecology, such as their trophic position or migration strategies. These questions appear particularly important to protect endangered European eel. However, elevated lipid content in eel muscle can bias δ13C values, as lipids are 13C-depleted compared to proteins and carbohydrates. We measured δ13C and δ15N values of bulk and lipid-free samples of eel muscle. Lipid-free samples were obtained after the extraction of lipids with cyclohexane. Lipid-corrected δ13C values, using five different mathematical equations based on bulk δ13C values, were compared to lipid-free δ13C values. We also evaluated the effect of lipid extraction on δ15N values. The analyses were based on linear regression performed on 333 individuals captured in nine lagoons and four rivers. Independently to the capture site or habitat (river or lagoon), the predicted lipid-corrected δ13C values were highly consistent with the measured lipid-free δ13C values (R2 > 0.90). The application of specific equations for each habitat or capture site only slightly increases these R2 (1.5% or less). The lipid extraction treatment significantly decreased by 0.2‰ the δ15N values compared to bulk samples. Given the excellent prediction of mathematical equations and the small decrease of δ15N values after lipids extraction, we propose to use mathematical correction to estimate δ13C values of eel muscle. As the habitats or sites did not strongly influence the results, the coefficients from our study can be applied to other studies on European eel.

Relationship between Capillary Wettability, Mass, and Momentum Transfer in Nanoconfined Water: The Case of Water in Nanoslits of Graphite and Hexagonal Boron Nitride.

The flow of water confined in nanosize capillaries is subject of intense research due to its relevance in the fabrication of nanofluidic devices and in the development of theories for fluid transport in porous media. Here, using molecular dynamics simulations carried out on 2D capillaries made up of graphite, hexagonal boron nitride (hBN) and a mix of the two, and of sizes from subnanometer to few nanometers, we investigate the relationship between the wettability of the wall capillary, the water diffusion, and its flow rate. We find that the water diffusion is decoupled from its flow properties as the former is not affected either by the height or chemistry of the capillary (except for the subnanometer slits), while the latter is dependent on both. The capillaries containing hBN show a reduced flow rate compared to those that are purely graphitic, likely due to the high friction coefficient between water and hBN. Such resistance to the flow is, however, at its maximum in the smallest capillary and lower for larger ones. Finally, we show that the flow rate values obtained from the Hagen-Poiseuille theory are almost always smaller than those obtained from simulations, indicating that either the slip length or the viscosity of nanoconfined water could be substantially different from the bulk values.

From unbound to bound states: Ab initio molecular dynamics of ammonia clusters with an excess electron.

Ab initio molecular dynamics simulations of negatively charged clusters of 2-48 ammonia molecules were performed to elucidate the electronic stability of the excess electron as a function of cluster size. We show that while the electronic stability of finite temperature clusters increases with cluster size, as few as 5-7 ammonia molecules can bind an excess electron, reaching a vertical binding energy slightly less than half of the bulk value for the largest system studied. These results, which are in agreement with previous studies wherever available, allowed us to analyze the excess electron binding patterns in terms of its radius of gyration and shape anisotropy and provide a qualitative interpretation based on a particle-in-a-spherical-well model.

Computational study of some seismic observations through compounds (Mgx,Ca(1-x))O at PREM model pressures up to 135.75 GPa

This computational study aims to track the change of some seismic observations by (Mgx,Ca(1-x))O compounds, this was at the PREM model pressures representing of Earth’s material. Based on the link between seismology and metallurgy in addition the Hashin & Shtrikman relationships, with taking into the results of our previous study, especially magnesium and calcium oxides. We were able to study the change in the values of density, bulk and shear modulus, longitudinal, transversal and bulk sound waves velocity of these compounds, with the change of x from a percentage to a hundred thousand. We were able to identify the compounds that he evaluated for those parameters very close to that of the Earth’s material at the pressures of the PREM model, especially at the most important spacing between the Earth’s internal layers until to the limits of the Earth's outer core. But not a single compound has been found to match all values once, meaning that no compound can be found in Earth's deep layers.

Bridging the gap between high-entropy alloys and metallic glasses: Control over disorder and mechanical properties of coatings

High-entropy alloys (HEAs) and high-entropy metallic glasses (HEMGs) represent two intensively researched classes of materials with high technological interest for applications as functional coatings with high strength, hardness, toughness, and corrosion resistance. The distinctive structural difference between single-phase crystalline solid solutions for HEAs and liquid-like disorder for HEMGs generates a seemingly insuperable contrast. In this work, we demonstrate that we can deliberately choose between crystalline or glassy properties by introducing structural disorder in HfMoNbTiZr thin films of identical composition. Using pulsed laser deposition (PLD) at different growth conditions, we reproducibly tune the structure of HfMoNbTiZr coatings from crystalline to fully amorphous. We show that the level of disorder has a profound impact on the mechanical properties of the coatings using the hardness derived from nanoindentation measurements as an example. While the hardness of polycrystalline HfMoNbTiZr layers already exceeds the single-phase bulk value, the amorphous HfMoNbTiZr is even clearly harder, demonstrating a distinctive improvement with introducing disorder. Our findings bridge the two seemingly different concepts of HEAs and HEMGs and demonstrate that structural disorder is not a given material property. Instead, disorder can serve as a useful design parameter for customizing the properties of functional coatings.

Synthesis and characterization of hydroxyapatite nanowires on tricalcium phosphate bone discs using a hydrothermal reaction

This study reports a hydrothermal process for synthesizing hydroxyapatite (HA) nanowires (NWs). Unlike the conventional hydrothermal process, only β-phase tricalcium phosphate (β-TCP) bone discs and deionized (DI) water, without any additional chemicals or precursor solutions, were used as raw materials. The concept behind this is that β‐TCP can be dissolved in DI water in an autoclave at high temperature and pressure, and the Ca2⁺ and PO43⁻ precursors in the newly formed aqueous solution spontaneously initiate self-assembled nucleation of HA NWs through hydrothermal reaction with the OH⁻ ions. The dissolution of β-TCP in DI water produces all the chemical species involved in the hydrothermal process, including the precursors and ions. The structural and morphological evolution of bone discs were investigated as a function of reaction time. It was found that HA nanoprisms were initially formed, and as the reaction proceeded the HA NWs dominated and formed HA NWs/β‐TCP bone discs with a shell/core structure. The HA NWs had an aspect ratio of approximately 270 with ∼150 μm in length, and a width of ∼0.55 μm. A slightly lower Ca/P molar ratio of ∼1.625, compared to the bulk value of approximately 1.67, indicates that the HA NWs were defective or Ca-deficient. Our findings indicate that the hydrothermal process of β-TCP bone discs is suitable for producing biphasic calcium phosphate bone scaffolds composed of HA NWs/β-TCP crystals with a shell/core structure.

Revealing chemistry-structure-function relationships in shark vertebrae across length scales

Shark cartilage presents a complex material composed of collagen, proteoglycans, and bioapatite. In the present study, we explored the link between microstructure, chemical composition, and biomechanical function of shark vertebral cartilage using Polarized Light Microscopy (PLM), Atomic Force Microscopy (AFM), Confocal Raman Microspectroscopy, and Nanoindentation. Our investigation focused on vertebrae from Blacktip and Shortfin Mako sharks. As typical representatives of the orders Carcharhiniformes and Lamniformes, these species differ in preferred habitat, ecological role, and swimming style. We observed structural variations in mineral organization and collagen fiber arrangement using PLM and AFM. In both sharks, the highly calcified corpus calcarea shows a ridged morphology, while a chain-like network is present in the less mineralized intermedialia. Raman spectromicroscopy demonstrates a relative increase of glucosaminocycans (GAGs) with respect to collagen and a decrease in mineral-rich zones, underlining the role of GAGs in modulating bioapatite mineralization. Region-specific testing confirmed that intravertebral variations in mineral content and arrangement result in distinct nanomechanical properties. Local Young's moduli from mineralized regions exceeded bulk values by a factor of 10. Overall, this work provides profound insights into a flexible yet strong biocomposite, which is crucial for the extraordinary speed of cartilaginous fish in the worlds’ oceans. Statement of significanceShark cartilage is a morphologically complex material composed of collagen, sulfated proteoglycans, and calcium phosphate minerals. This study explores the link between microstructure, chemical composition, and biological mechanical function of shark vertebral cartilage at the micro- and nanometer scale in typical Carcharhiniform and Lamniform shark species, which represent different vertebral mineralization morphologies, swimming styles and speeds. By studying the intricacies of shark vertebrae, we hope to lay the foundation for biomimetic composite materials that harness lamellar reinforcement and tailored stiffness gradients, capable of dynamic and localized adjustments during movement.

Unveiling Strong Thin Film Confinement Effects on Semirigid Conjugated Polymers.

Nanoconfinement has been recognized to induce significant changes in the physical properties of polymeric films when their thickness is less than 100 nm. Despite extensive research on the effect of nanoconfinement on nonconjugated polymers, studies focusing on the confinement effects on dynamics and associated electronic and mechanical properties for semiconductive and semirigid conjugated polymers remain limited. In this study, we conducted a comprehensive investigation into the nanoconfinement effects on both p- and n-type conjugated polymers having varying chain rigidity under different degrees of confinement. Using the flash differential scanning calorimetry technique, it was found that the increased molecular mobility with decreasing film thickness, as indicated by the depression of glass transition temperature (T g) from its bulk values, was directly proportional to chain rigidity. This relationship between chain rigidity and enhanced segmental mobility was further corroborated through molecular dynamics simulations. Thinner films exhibited a higher degree of crystallinity for all conjugated polymers, and a significant reduction of more than 50% in elastic modulus was observed for films with approximately 20 nm thickness compared to those of 105 nm thickness, particularly for highly rigid conjugated polymers. Interestingly, we found that the charge mobility remained independent of film thickness, with all samples demonstrating good charge mobility regardless of the different film thicknesses for devices measured here. Nanoconfined conjugated polymer thin films exhibited a combination of mechanical compliance and good charge carrier mobility properties, making them promising candidates for the next generation of flexible and portable organic electronics. From an engineering standpoint, confinement could be an effective strategy to tailor the dynamics and mechanical properties without significant loss of electronic property.

Diblock Rings as Topological Adhesives at Immiscible Polymer Interfaces.

Disparate polymers often do not mix well, and the resulting immiscible interfaces are mechanically weaker than the bulk, which is undesirable for many technological applications. Large-scale molecular simulations are performed to demonstrate the effectiveness of diblock ring polymers as a new type of adhesive for immiscible polymer interfaces. The peak stress σp and the failure strain γp upon shear deformation approach the bulk values with increasing diblock ring length and coverage. Breaking the diblock rings into pairs of diblock linear chains creates a reference system for comparison. The diblock rings increase both σp and γp compared to the diblock linear chains at the same coverage. Further topological analysis based on the Gauss Linking Number reveals that the threading of diblock rings by linear chains from the two opposite sides is the key mechanism for stronger adhesion, which is analogous to the hook-and-loop process in Velcro tape.

Water Thermal Conductivity in Nanoscale and Its Effect on Dropwise Condensation Heat Transfer

The present study employs equilibrium molecular dynamics simulation based on the Green-Kubo approach to investigate the thermal conductivity of liquid water at the nanoscale. Specifically, the discussion centers around the influence of the size and surface wettability of two-dimensional nanochannels on the confined water thermal conductivity. The simulation results reveal a significant impact of nanochannel size on the thermal conductivity of confined water, with a decrease in channel spacing leading to a reduction in thermal conductivity below its bulk value. However, the thermal conductivity of water confined within a surface is not influenced by the water surface wettability. Additionally, the study investigates the influence of water thermal conductivity on droplet formation. The results indicate that incorporating changes in droplet thermal conductivity during the nucleation process can partially address the issue of overestimating the heat transfer coefficient for dropwise condensation.