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Influence of vanadium incorporation on the microstructure, mechanical and tribological properties of Nb–V–Si–N films deposited by reactive magnetron sputtering
Composite Nb–V–Si–N films with various V contents (3.7–13.2 at.%) were deposited by reactive magnetron sputtering and the effects of V content on the microstructure, mechanical and tribological properties of Nb–V–Si–N films were investigated. The results revealed that a three-phase structure, consisting of face-centered cubic (fcc) Nb–V–Si–N, hexagonal close-packed (hcp) Nb–V–Si–N and amorphous Si{sub 3}N{sub 4}, co-exists in the Nb–V–Si–N films and the cubic phase is dominant. The hardness and critical load (L{sub c}) of Nb–V–Si–N films initially increased gradually and reached a summit, then decreased with the increasing V content in the films and the maximum values were 35 GPa and 9.8 N, respectively, at 6.4 at.% V. The combination of V into Nb–Si–N film led to the fracture toughness linearly increasing from 1.11 MPa·m{sup 1/2} at 3.7 at.% V to 1.67 MPa·m{sup 1/2} at 13.2 at.% V. At room temperature (RT), the average friction coefficient decreased from 0.80 at 3.7 at.% V to 0.55 at 13.2 at.% V for the Nb–V–Si–N films. The wear rate of Nb–V–Si–N films initially decreased and then increased after reaching a minimum value of about 6.35 × 10{sup −} {sup 7} mm{sup 3}/N·mm at 6.4 at.% V. As the rise of testing temperature from 200 °C to 600 °C, the average friction coefficient of Nb–V–Si–N films decreased with the increase of the testing temperature regardless of V content. However, the wear rate gradually increased for all films. The average friction coefficient and wear rate at RT and elevated temperatures were mainly influenced by the vanadium oxides with weakly bonded lattice planes. - Highlight: • Fcc-Nb–V–Si–N, hcp-Nb–V–Si–N and amorphous Si{sub 3}N{sub 4} co-existed in the films. • The amount of Si{sub 3}N{sub 4} decreased with increasing V content in the films. • Hardness of Nb–V–Si–N film (6.4 at.%) reached a maximum value of 35 GPa. • Addition of V led to the increase of fracture toughness. • Tribological properties were influenced by lubricant wear debris.
Investigation of the Self-Assembly Behavior of Statistical Bottlebrush Copolymers via Self-Consistent Field Theory Simulations
Bottlebrush copolymers, a class of high-density side-chain-grafted copolymers with high molecular weights, have recently attracted extensive research attention due to the dramatic reduction of chain entanglement in these copolymers, unique self-assembly behaviors, and distinctive physical properties. In this study, we employ self-consistent field theory simulations to systemically investigate the phase behavior of statistical bottlebrush copolymers A-stat-B, an intriguing subclass of bottlebrush copolymers with random or alternating sequences of A and B side chains. We find that a broader variety of ordered mesophases can be stabilized in the melts of these copolymers relative to the more extensively studied bottlebrush block copolymers. In particular, we observe that these statistical copolymers can stabilize sphere phases over a larger range of species volume fractions than their diblock and tetrablock counterparts but require much higher segregation strength to achieve this. The sphere and hexagonally packed cylinder phases formed by conformationally symmetric statistical bottlebrush copolymers possess interesting discrete core–shell structures with the backbone and lower volume fraction side-chain species forming shells and cores, respectively. Moreover, we uncover a new strategy of stabilizing the Frank–Kasper phase A15 by introducing conformational asymmetry through different side-chain lengths and also observe deflection of order–order phase boundaries and significant mixing between the backbones and short side chains as conformational asymmetry is introduced.
Nonadditive Interactions Unlock Small-Particle Mobility in Binary Colloidal Monolayers
We examine the organization and dynamics of binary colloidal monolayers composed of micron-scale silica particles interspersed with smaller-diameter silica particles that serve as minority component impurities. These binary monolayers are prepared at the surface of ionic liquid droplets over a range of size ratios (σ = 0.16–0.66) and are studied with low-dose minimally perturbative scanning electron microscopy (SEM). The high resolution of SEM imaging provides direct tracking of all particle coordinates over time, enabling a complete description of the microscopic state. In these bidisperse size mixtures, particle interactions are nonadditive because interfacial pinning to the droplet surface causes the equators of differently sized particles to lie in separate planes. By varying the size ratio, we control the extent of nonadditivity in order to achieve phase behavior inaccessible to additive 2D systems. Across the range of size ratios, we tune the system from a mobile small-particle phase (σ < 0.24) to an interstitial solid (0.24 < σ < 0.33) and furthermore to a disordered glass (σ > 0.33). These distinct phase regimes are classified through measurements of hexagonal ordering of the large-particle host lattice and the lattice’s capacity for small-particle transport. Altogether, we explain these structural and dynamic trends by considering the combined influence of interparticle interactions and the colloidal packing geometry. Our measurements are reproduced in molecular dynamics simulations of 2D nonadditive disks, suggesting an efficient method for describing confined systems with reduced dimensionality representations.
Automated Transformation of Lignin Topologies into Atomic Structures with LigninBuilder
Lignin is an abundant aromatic heteropolymer found in secondary plant cell walls and is a potential feedstock for conversion into bioderived fuels and chemicals. Lignin chemical diversity complicates traditional structural studies, and so, relatively little experimental evidence exists for how lignin structure exists in aqueous solution or how lignin polymers respond to changes in their chemical environment. Molecular modeling can address these concerns; however, prior computational structural lignin models typically did not capture lignin heterogeneity, as only a few polymers were considered. LigninBuilder creates a framework for building structural libraries for lignin from existing topological libraries, permitting significantly greater diversity of lignin structures to be sampled at atomic detail. As a demonstration of its capabilities, LigninBuilder was applied to three libraries of lignin from hardwood, softwood, and grass, and the resulting polymer structures were simulated in an aqueous environment. The lignins adopted compact globular structures, as would be expected for polymers in poor solvents. The differences between the libraries were largest when quantifying the packing of nonadjacent aromatic residues, with greater branching within the polymer resulting in poorer aromatic packing. Individual lignin polymers were also found to undergo rapid conformational changes, with the dwell time within a state growing as the square of the molecular weight. This first application of LigninBuilder demonstrates the potential for atomic-level insight into lignin interactions. LigninBuilder is distributed as a plugin to the visualization software VMD, lowering the barrier for modeling lignin structure in diverse environments.
Direct CO 2 Capture from Air using Poly(ethylenimine)-Loaded Polymer/Silica Fiber Sorbents
Direct CO2 capture from atmospheric air is gaining increased attention as one of the most scalable negative carbon approaches available to tackle climate change if coupled with the sequestration of CO2 geologically. Furthermore, it can also provide CO2 for further utilization from a globally uniform source, which is especially advantageous for economies without natural sources of carbon-based feedstocks. Solid-supported amine-based materials are effective for direct air capture (DAC) due to their high CO2 uptakes and acceptable sorption kinetics at ambient temperature. In this work, we describe the application of polymer/silica fiber sorbents functionalized with a primary amine-rich polymer, poly(ethylenimine) (PEI), for DAC. Monolithic fiber sorbents composed of cellulose acetate and SiO2 are synthesized via the dry-jet, wet quench spinning technique. These fibers are then functionalized with PEI (Mw 800 Da) in a simple and scalable postspinning infusion step and tested for CO2 capture under pseudoequilibrium conditions as well as under breakthrough conditions. An investigation to study the effect of feed flow rate, adsorption temperature, and presence of moisture in the feed on the CO2 breakthrough performance of a densely packed fiber sorbent module is conducted to highlight the potential application of this class of structured contactors in direct air capture. The pressure drop of these contactors at high gas velocities is also evaluated. Finally, a vacuum-assisted desorption step is demonstrated for production of high-purity CO2 from both dry and humid ambient air mixtures.
Adsorbate-Induced Adatom Formation on Lithium, Iron, Cobalt, Ruthenium, and Rhenium Surfaces
Recent experimental and theoretical studies have demonstrated the reaction-driven metal–metal bond breaking in metal catalytic surfaces even under relatively mild conditions. Here, we construct a density functional theory (DFT) database for the adsorbate-induced adatom formation energy on the close-packed facets of three hexagonal close-packed metals (Co, Ru, and Re) and two body-centered cubic metals (Li and Fe), where the source of the ejected metal atom is either a step edge or a close-packed surface. For Co and Ru, we also considered their metastable face-centered cubic structures. We studied 18 different adsorbates relevant to catalytic processes and predicted noticeably easier adatom formation on Li and Fe compared to the other three metals. The NH 3 - and CO-induced adatom formation on Fe(110) is possible at room temperature, a result relevant to NH 3 synthesis and Fischer-Tropsch synthesis, respectively. There also exist other systems with favorable adsorbate effects for adatom formation relevant to catalytic processes at elevated temperatures (500–700 K). Our results offer insight into the reaction-driven formation of metal clusters, which could play the role of active sites in reactions catalyzed by Li, Fe, Co, Ru, and Re catalysts.
Photo-actuators via epitaxial growth of microcrystal arrays in polymer membranes
Photomechanical crystals composed of three-dimensionally ordered and densely packed photochromes hold promise for high-performance photochemical actuators. However, bulk crystals with high structural ordering are severely limited in their flexibility, resulting in poor processibility and a tendency to fragment upon light exposure, while previous nano- or microcrystalline composites have lacked global alignment. Here we demonstrate a photon-fuelled macroscopic actuator consisting of diarylethene microcrystals in a polyethylene terephthalate host matrix. These microcrystals survive large deformations and show a high degree of three-dimensional ordering dictated by the anisotropic polyethylene terephthalate, which critically also has a similar stiffness. Overall, these ordered and compliant composites exhibit rapid response times, sustain a performance of over at least hundreds of cycles and generate work densities exceeding those of single crystals. In conclusion, our composites represent the state-of-the-art for photochemical actuators and enable properties unattainable by single crystals, such as controllable, reversible and abrupt jumping (photosalient behaviour).
The Effect of Pressure on Halogen Bonding in 4-Iodobenzonitrile
The crystal structure of 4-iodobenzonitrile, which is monoclinic (space group I2/a) under ambient conditions, contains chains of molecules linked through C≡N···I halogen-bonds. The chains interact through CH···I, CH···N and π-stacking contacts. The crystal structure remains in the same phase up to 5.0 GPa, the b axis compressing by 3.3%, and the a and c axes by 12.3 and 10.9 %. Since the chains are exactly aligned with the crystallographic b axis these data characterise the compressibility of the I···N interaction relative to the inter-chain interactions, and indicate that the halogen bond is the most robust intermolecular interaction in the structure, shortening from 3.168(4) at ambient pressure to 2.840(1) Å at 5.0 GPa. The π∙∙∙π contacts are most sensitive to pressure, and in one case the perpendicular stacking distance shortens from 3.6420(8) to 3.139(4) Å. Packing energy calculations (PIXEL) indicate that the π∙∙∙π interactions have been distorted into a destabilising region of their potentials at 5.0 GPa. The structure undergoes a transition to a triclinic ( P 1 ¯ ) phase at 5.5 GPa. Over the course of the transition, the initially colourless and transparent crystal darkens on account of formation of microscopic cracks. The resistance drops by 10% and the optical transmittance drops by almost two orders of magnitude. The I···N bond increases in length to 2.928(10) Å and become less linear [
Plans for a large deployable reflector for submillimeter and infrared astronomy from space
Continuing plans for a large deployable reflector (LDR), conceived as a 10- to 30-m-diameter clear-aperture telescope, operating at wavelengths from 1000 microns to a diffraction-limited 30 microns, and to be placed in orbit for a life of 10 years by the Space Shuttle, are discussed. The primary reflector will be composed of a number of closely packed hexagonal segments of glass or lightweight composite material and attached to a truss integrating structure through position actuators providing three degrees of freedom for each segment. Technical aspects of optical design, surface measurement systems, deployment, and detectors are discussed, as are practical and fiscal limitations.
Specifications Physiological Monitoring System
The operation of a physiological monitoring system (PMS) is described. Specifications were established for performance, design, interface, and test requirements. The PMS is a compact, microprocessor-based system, which can be worn in a pack on the body or may be mounted on a Spacelab rack or other appropriate structure. It consists of two modules, the Data Control Unit (DCU) and the Remote Control/Display Unit (RCDU). Its purpose is to collect and distribute data from physiological experiments in the Spacelab and in the Orbiter.
Accurate computational design of three-dimensional protein crystals
Protein crystallization plays a central role in structural biology. Despite this, the process of crystallization remains poorly understood and highly empirical, with crystal contacts, lattice packing arrangements and space group preferences being largely unpredictable. Programming protein crystallization through precisely engineered side-chain-side-chain interactions across protein-protein interfaces is an outstanding challenge. Here, in this study, we develop a general computational approach for designing three-dimensional protein crystals with prespecified lattice architectures at atomic accuracy that hierarchically constrains the overall number of degrees of freedom of the system. We design three pairs of oligomers that can be individually purified, and upon mixing, spontaneously self-assemble into >100 µm three-dimensional crystals. The structures of these crystals are nearly identical to the computational design models, closely corresponding in both overall architecture and the specific protein-protein interactions. The dimensions of the crystal unit cell can be systematically redesigned while retaining the space group symmetry and overall architecture, and the crystals are extremely porous and highly stable. Our approach enables the computational design of protein crystals with high accuracy, and the designed protein crystals, which have both structural and assembly information encoded in their primary sequences, provide a powerful platform for biological materials engineering.
Effects of Ionic Group Distribution on the Structure and Dynamics of Amorphous Polymer Melts
Ionizable groups tethered to a polymer backbone often associate to form ionic clusters, whose features are determined by the balance of the polymer backbone and electrostatics. These assemblies impact the dynamics of the macromolecules and their ability to transport ions. Here, using fully atomistic molecular dynamics (MD) simulations, we investigate the effects of the distribution of ionizable groups along the polymer backbone on cluster characteristics and the resulting impacts on the structure and dynamics of amorphous polymers. Particularly, we probe polystyrene sulfonates (PSS) with random, precise, and block configurations of the SO 3 – sulfonate groups along the backbone with Na + as the counterion. We find that the distribution of the ionic groups affects the shape and distribution of the clusters as well as the internal packing of the ionizable groups in the cluster and the number of unique chains that participate in each cluster, affecting the structure and the dynamics of the polymers. Furthermore, the signature of ionic clusters, observed in the static structure factor S(q) for all three distributions, is significantly more pronounced for the precise and blocky polymers compared to the random one. Remarkably, we find that the local mobility of the polymer segments is not only affected by the number and size of the clusters but also by the number of polymer chains associated with clusters.
Exploring Hilbert space on a budget: Novel benchmark set and performance metric for testing electronic structure methods in the regime of strong correlation
This work explores the ability of classical electronic structure methods to efficiently represent (compress) the information content of full configuration interaction (FCI) wave functions. We introduce a benchmark set of four hydrogen model systems of different dimensionalities and distinctive electronic structures: a 1D chain, a 1D ring, a 2D triangular lattice, and a 3D close-packed pyramid. To assess the ability of a computational method to produce accurate and compact wave functions, we introduce the accuracy volume, a metric that measures the number of variational parameters necessary to achieve a target energy error. Using this metric and the hydrogen models, we examine the performance of three classical deterministic methods: (i) selected configuration interaction (sCI) realized both via an a posteriori (ap-sCI) and variational selection of the most important determinants, (ii) an a posteriori singular value decomposition (SVD) of the FCI tensor (SVD-FCI), and (iii) the matrix product state representation obtained via the density matrix renormalization group (DMRG). We find that the DMRG generally gives the most efficient wave function representation for all systems, particularly in the 1D chain with a localized basis. For the 2D and 3D systems, all methods (except DMRG) perform best with a delocalized basis, and the efficiency of sCI and SVD-FCI is closer to that of DMRG. For larger analogs of the models, the DMRG consistently requires the fewest parameters but still scales exponentially in 2D and 3D systems, and the performance of SVD-FCI is essentially equivalent to that of ap-sCI.
Structure and morphology evolution of silica-modified pseudoboehmite aerogels during heat treatment
Silica-modified pseudoboehmite aerogels (0, 10, 20 at% of Si) were prepared by sol–gel method followed by supercritical drying. The phase transformations, changes in structure and morphology upon calcination were thoroughly investigated by advanced X-Ray diffraction (XRD) techniques and high-resolution transmission electron microscopy (HRTEM). Obtained pseudoboehmite samples had specific nanostructure: ultrathin two-dimensional (2D) crystallites were loosely packed. The silica dopant drastically enhanced the crystallite anisotropy. Thus, the aerogel with Al:Si atomic ratio of 9:1 consisted of the pseudoboehmite nanosheets with thickness of one unit cell (average dimensions of 14.0×1.2×14.5 nm). The specific nanostructure caused remarkable features of experimental XRD patterns, including anisotropic peak broadening and appearance of forbidden reflection. Direct simulation of XRD patterns with using the Debye Scattering Equation allowed the size and morphology of pseudoboehmite crystallites to be determined. The silica addition strongly delayed formation of γ-alumina and further phase transformations upon calcinaton. Thermal stability of alumina was suggested to be affected by the particle morphology inherited from the pseudoboehmite precursor. - Graphical abstract: Pseudoboehmite samples had specific nanostructure: ultrathin two-dimensional (2D) crystallites were loosely packed. - Highlights: • Silica-doped boehmites were prepared by sol–gel method with supercritical drying. • Ultrathin two-dimensional crystallites of pseudoboehmite were obtained. • Changes in structure and morphology upon calcination were studied. • Simulation of XRD patterns was performed with use of the Debye Scattering Equation. • Thermal stability of alumina depended on morphology inherited from pseudoboehmite.
Probing the solidification of quasicrystals via joint experiment and simulation (Final Report)
Quasicrystals (QCs) possess long-range positional order but non-crystallographic orientational order. Their classically ‘forbidden’ symmetry has long attracted the interest of scientists worldwide. Despite their frequent observation in both metal alloys and soft matter structures in the 35 years since their discovery, little is known about how QCs evolve from a liquid, amorphous, or crystalline precursor. In this project, we sought to resolve the enigma of QC self-assembly through a combined experimental and computational program. The Shahani group employed in situ electron and synchrotron X ray imaging to peer into the growth dynamics of QCs in a liquid, covering a broad range of length scales and solidification pathways. Glotzer's team developed new simulation models incorporating phasonic defects — which are unique to quasicrystals — and used this model to investigate two grains growing together, closely mimicking the experimental conditions. While QCs remain exceptional structures, most compounds in the realm of intermetallics adopt non-trivial geometries. In fact, only around 6% of phases are comprised of the simplest sphere packings that researchers so readily associate with metals. State-of-the-art knowledge of phase transformations at the outset of this collaborative project did not encompass the remaining 94% of intermetallic compounds that possess complex and aperiodic structure types. Therefore, we expect that outcomes from this project will have immediate and profound impact on synthesis and processing science: our efforts will be used to not only explain the growth dynamics of QCs but also complex intermetallics more broadly.
Crystal structure of 2-diazoimidazole-4,5-dicarbonitrile
In the title compound, C 5 N 6 , all the atoms are approximately coplanar. In the crystal, molecules are packed with short contact distances of 2.885 (2) (between the diazo N atom connected to the ring and a cyano N atom on a neighboring molecule) and 3.012 (2) Å (between the terminal diazo N atom and an N atom of a neighboring imidazole ring).
Structure and thermodynamics of core-softened models for alcohols
The phase behavior and the fluid structure of coarse-grain models for alcohols are studied by means of reference interaction site model (RISM) theory and Monte Carlo simulations. Specifically, we model ethanol and 1-propanol as linear rigid chains constituted by three (trimers) and four (tetramers) partially fused spheres, respectively. Thermodynamic properties of these models are examined in the RISM context, by employing closed formulæ for the calculation of free energy and pressure. Gas-liquid coexistence curves for trimers and tetramers are reported and compared with already existing data for a dimer model of methanol. Critical temperatures slightly increase with the number of CH{sub 2} groups in the chain, while critical pressures and densities decrease. Such a behavior qualitatively reproduces the trend observed in experiments on methanol, ethanol, and 1-propanol and suggests that our coarse-grain models, despite their simplicity, can reproduce the essential features of the phase behavior of such alcohols. The fluid structure of these models is investigated by computing radial distribution function g{sub ij}(r) and static structure factor S{sub ij}(k); the latter shows the presence of a low−k peak at intermediate-high packing fractions and low temperatures, suggesting the presence of aggregates for both trimers and tetramers.