In the present study we employ electronic structure calculations (based on Density Functional Theory -DFT approach) and Fully Atomistic Reactive Molecular Dynamics (FARMD) simulations (based on ReaxFF reactive force field) to evaluate the reactivity of branched polyfuran (PF) derivatives and identify promising systems for chemical sensing. Condensed-to-atoms Fukui indexes (CAFI) were employed to identify the most reactive sites on the oligomers structure. The chemical sensing abilities of the most promising systems were evaluated via FARMD simulations in the presence of distinct gaseous compounds. The results indicate the derivatives PF-CCH and PF-NO₂ (i.e. CCH and NO2 as side groups) as the most promising systems for chemical sensor applications, presenting higher reactivity on the most accessible sites. An interesting correspondence between DFT and MD results was also identified, suggesting the plausibility of using CAFI parameters for the identification of improved materials for chemical sensors.

Herein, we report a methodology that leads to the formation of Ru metallic sites, followed by the development and anchorage of Pt-Ru alloyed nanoparticles on the surface of Ordered Mesoporous Hollow Carbon Spheres (OMHCS). Along with the Ru sites, it is demonstrated that the functionalization promotes the formation of functional groups on the surface of the OMHCS. In a first stage, OMHCS are functionalized with the [(η6-C6H5OCH2CH2OH)RuCl2]2 (Ru-dim) and [(η6-C6H4CH(CH3)2CH3)RuCl2]2 (Ru-cym) organometallic compounds. Afterwards, Pt nanoparticles are dispersed by the microwave-assisted polyol method over the functionalized supports obtaining the low-metal content 5 wt. % Pt/OMHCSRu-dim and Pt/OMHCSRu-cym nanocatalysts. The degree of Ru alloyed is found to be around 35%. The low-Pt content Pt/OMHCSRu-cym and Pt/OMHCSRu-dim exhibit a higher catalytic activity for the Oxygen (OER) and the Hydrogen (HER) Evolution Reactions than the Pt/C benchmark and the Pt/OMHCS nanocatalysts. The overpotential for the OER at 10 mA cm-2 (ηOER) is 300 mV and 210 mV smaller at Pt/OMHCSRu-cym and Pt/OMHCSRu-dim compared to Pt/C, respectively. The corresponding values of the HER at -10 mA cm-2 (ηHER) are 14 and 18 mV smaller, respectively. The high catalytic activity of Pt/OMHCSRu-cym and Pt/OMHCSRu-dim has been attributed in part to the presence of Ru0 and RuO2 species from organometallic functionalization, and the modification of the d-valence band of Pt. Their high performance for the OER and the HER opens new lines of research for the design of nanocatalysts for alkaline electrochemical water splitting.

Design of composite semiconductor nanostructures with proper band alignment for efficient charge separation and carrier transport has been at the center of research for photoelectrochemical water splitting. This work demonstrates the deposition of a NiFe2O4 @Fe2O3 core-shell nanostructured film sensitized with CdS to form a ternary heterojunction for cascade type electron transfer. The hematite nanostructures were grown by hydrothermal approach through dipping into a solution of Nickel Nitrate yielded anchoring of Ni2+ ions on the outer surface. The films were then annealed at 650 0C for the diffusion of Ni2+ ions into the hematite lattice which forms core-shell NiFe2O4 @Fe2O3 heterojunction. The films were further sensitized with CdS nanoparticles deposited by a hydrothermal approach to form the final ternary heterojunction photoanode. Several different nanostructures were grown and the effect of crystal facet tailoring was observed on Ni loading and photoelectrochemical performance. The photoelectrochemical measurements were carried out using a potentiostat under 100 mW/cm2 light source (150W Xenon Lamp) with Pt counter electrode and 0.5 M Na2S and 0.5 M Na2SO3 electrolyte. A current density of 3.47 mA/cm2 was observed at 1.23 V (vs Ag/AgCl). An Applied Bias to Photocurrent Efficiency (ABPE) of 1.8 % photoconversion efficiency was observed using the fabricated electrodes at 0.288V (vs Ag/AgCl).

Recently, an experimental study developed an efficient way to obtain sulfur-doped γ-graphdiyne. This study has shown that this new material could have promising applications in lithium-ion batteries, but the complete understanding of how the sulfur atoms are incorporated into the graphdiyne network is still missing. In this work, we have investigated the sulfur doping process through molecular dynamics and density functional theory simulations. Our results suggest that the doped induced distortions of the γ-graphdiyne pores prevent the incorporation of more than two sulfur atoms. The most common configuration is the incorporation of just one sulfur atom per the graphdiyne pore.

Bendable p-type NiO and n-type In2O3 thin films were epitaxially grown on synthetic mica using mist chemical vapor deposition. It was found that at a growth temperature of 400 °C, epitaxially grown cubic (111) NiO thin films developed twin rotational domains, and the epitaxial relationship between each domain and the substrate was (111) NiO [1-10] or [10-1] || (001) synthetic mica [100]. In the visible light region, the epitaxial NiO thin films showed high transparencies, and their cut-offs appeared in the UV region. Additionally, at a growth temperature of 500 °C, cubic (111) In2O3 thin films with and without Sn doping were epitaxially grown on synthetic mica. As a result of the plasma oscillation of free carriers, Sn-doped In2O3 thin films exhibited reflection characteristics in the infrared region, while maintaining their visible light transmission characteristics. Furthermore, compared with non-doped In2O3, Sn doping decreased the sheet resistance by two digits.

The application of intense pulsed light (IPL) to printed copper nanoparticle (CuNP) films enables rapid curing on low temperature substrates in ambient conditions. In this work, we printed CuNP ink on liquid crystal polymer (LCP; Vectra A resin) and then cured the films using a high energy density light pulse. High-resolution SEM images of the cured films revealed that the CuNPs on LCP were fused together. Optimal curing parameters were a 5 ms pulse, 75% duty cycle, and an energy density range of 4.2–5.2 J⋅cm-2. Sheet resistance, Rs, values as low as ~0.1 Ω⋅sq-1were obtained. The LCP substrate took on a yellowed appearance after the application of five pulses and exhibited a surface free energy increase. A filter that blocked wavelengths <450 nm was placed over the printed copper film on LCP. As expected, the presence of the filter decreased the total energy density and produced a cured film with high Rs; however, when the energy density was increased in the presence of the filter, the Rs remained high (0.95 Ω⋅sq-1). This preliminary work indicates that additional studies are required not only to understand low thermal budget curing on LCP, but also to elucidate the properties of substrates that enable low Rs.

Recognizing materials development was advancing slower than technological needs, the 2011 the Materials Genome Initiative (MGI) advocated interdisciplinary approaches employing an informatics framework in materials discovery and development. In response, an interdisciplinary graduate program, funded by the National Science Foundation, was designed at the intersection of materials science, materials informatics, and engineering design, aiming to equip the next generation of scientists and engineers with Material Data Science. Based on the 4- year implementation experience, this report demonstrates how intellectual communities bridge students interdisciplinary learning processes and support a transition from disciplinary grounding to interdisciplinary learning and research. We hope this training model can benefit other interdisciplinary graduate programs, and produce a more productive and interdisciplinary materials workforce.

Recently, two-dimensional layered structures, especially MoS2 has come out as the most investigated electrode material for batteries and supercapacitors, possessing well preserved in-plane covalent bonding, leading to extraordinary mechanical elasticity within the layers as well as outstanding firmness along the c-axis. The present work is aimed to fabricate vertically aligned edge exposed molybdenum disulfide nanoflakes on the surface of the self-standing hydrophilic carbon nanotubes, using a two-step process involving a chemical route and magnetron sputtering techniques for flexible supercapacitor application. These hybrid heterostructures have been characterized using XRD, FESEM, and cyclic voltammetry. In the aqueous electrolyte of 1M Li2SO4, the symmetric device revealed very high areal capacitance of 182.5 mF/cm2 and 155 mF/cm2, at scan rates of 2 and 5 mV/s, respectively. The device shows high energy density of 365 mWh/cm2.

A perfluorinated ionic liquid, 1-(perfluorohexyl)-3-methylimidazolium iodide, was synthesized via microwave reaction and compared to a non-fluorinated analog. Typically, the synthesis of fluorinated ionic liquids involves long reaction times and multiple steps. We have demonstrated a shortened synthesis and a more straightforward procedure, by using a microwave reactor for the microwave-assisted synthesis of 1-(perfluorohexyl)-3-methylimidazolium iodide. The addition of fluorinated alkyl chains on imidazolium ionic liquid cations increases the molecular free volume of the ionic liquid which is beneficial for increasing CO2 physisorption. Computational and experimental data shows an increased CO2 solubility and capacity for fluorinated ionic liquids. The perfluoroalkyl functionalized ionic liquid is characterized using 1H and 19F NMR spectroscopy, FTIR spectroscopy, and DSC. By DSC, a crystallization onset is near -31 °C and while the onset of the melting point between -30 and -17 °C.

Crack initiation in zirconium alloys is an important issue for the safety of water-cooled fission reactors. Zirconium hydrides that precipitate in service are potential crack nucleation sites. In this work, the deformation and cracking of zirconium hydrides was studied during room temperature deformation of a Zircaloy-4 tensile sample up to fracture. The sample contained a hydrogen concentration of 100 ± 20 ppm. The main aims of this study were to better understand the mechanisms behind the hydride fracture in a polycrystalline matrix, and to identify at which point in the deformation of the Zr matrix the first hydrides break. Cracks thus nucleated may coalesce and propagate through the hydrided Zr-alloy. Scanning electron microscopy (SEM) images of a number of hydrides, both intergranular and intragranular, were taken at discrete increments of deformation during an interrupted tensile test. The results show that cracks in hydrides tend to always occur normal to the applied load, signalling the importance of the external stress. However, evidence is also provided to support the hypothesis that internal stresses generated by microstructural constraints may lead to the fracture of some intergranular hydrides.

The REE (rare-earth-elements) cerium (Ce) is the most abundant earth-crust element and their oxides have great attention in the form of nanocrystalline nature with superior physical and chemical properties. Pure and Co (1%, 3% and 5%) doped CeO2 nanoparticles (NPs) synthesized by co-precipitation technique were characterized through X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), UV-visible spectroscopy. XRD shows face-centred-cubic (FCC) crystal symmetry with average crystallite size 6–12 nm. HRTEM exhibits almost identical cubical shaped particles with average size 4–10 nm. Tuned band-gap may be observed from UV-visible spectrum of CeO2-NPs upon Co (1%, 3% & 5%) incorporation. Enhancement of the photocatalytic activity observed for Co-doped (1%, 3% & 5%) to the degradation of methylene-blue (MB) dye under visible-light absorption.

We divide the corrosion products on ancient bronzes into two categories, i.e., "inward growth" and “outward growth” corrosions. Several selected Chinese ancient bronzes with the "inward growth” corrosion are studied; and their chemical compositions, microstructures and morphologies are characterized systematically. According to the results, it is found that the “inward growth” corrosion can be further divided into three types, i.e., "noble patina", "noble-like patina" and "lamellar peeling patina". We propose that the growth mechanism of the “inward growth” corrosion is that the corrosion initiates at and develops along α-Cu phase. Furthermore, the effect of alloy Sn content on the “inward growth” corrosion is also studied.

The majority of highly efficient perovskite light-emitting diodes (PeLED) contain PEDOT:PSS (poly(3,4-ethylenedioxythiophene):polystyrenesulfonate) as hole transport layer (HTL). However, the hygroscopic and acidic nature of PEDOT:PSS may lead to deterioration of PeLED performance. Moreover, due to its inferior electron-blocking properties, an additional electron-blocking layer (EBL) is required to establish charge balance and consequently obtain superior emission characteristics in typically electron-rich PeLED structures. In this work, PTAA (poly(bis(4-phenyl)(2,4,6-trimethylphenyl)amine)) serving both as HTL and EBL is employed to substitute PEDOT:PSS in PeLED. The perovskite CsPbBr3 is chosen as emissive layer (EML) material due to its high color purity and photoluminescence (PL) quantum yield. Dense CsPbBr3 films are fabricated on PTAA-coated ITO substrates by employing a one-step spin-coating approach based on nonstoichiometric perovskite precursor solutions. To suppress non-radiative recombination, a small amount of methylammonium bromide (MABr) is incorporated in the CsPbBr3 lattice. The resulting films exhibit excellent coverage and PL intensity. PeLED containing pure CsPbBr3 films as EML show a green emission with a peak at 520 nm, maximum luminance of 11,000 cd/m2, an external quantum efficiency (EQE) of 3.3 % and a current efficiency (CE) of 10.3 cd/A. Further enhancement to 21,000 cd/m2, 7.5 % and 27.0 cd/A is demonstrated by PeLED with MABr-doped CsPbBr3 layers.

Thermosetting resins are one of the most widely used functional materials in industrial applications. Although some of the physical properties of thermosetting resins are controlled by changing the functional groups of the raw materials or adjusting their mixing ratios, it was conventionally challenging to construct machine learning (ML) models, which include both mixing ratio and chemical information such as functional groups. To overcome this problem, we propose a machine learning approach based on extended circular fingerprint (ECFP) in this study. First, we predicted the classification of raw materials by the random forest, where ECFP was used as the explanatory variable. Then, we aggregated ECFP for each classification predicted by the random forest. After that, we constructed the prediction model by using the aggregated ECFP, feature quantities of reaction intermediates, and curing conditions of resin as explanatory variables. As a result, the model was able to predict in high accuracy (R^2 = 0.8), for example, the elastic modulus of thermosetting resins. Furthermore, we also show the result of verification of prediction accuracy in first step, such as using the one-hot-encording. Therefore, we confirmed that the properties of thermosetting resins could be predicted using mixed raw materials by the proposed method.

Recent efforts have been made toward the integration of the back-end of the nuclear fuel cycle in the United States. The back-end integration seeks to address several management challenges: 1) current storage practices are not optimized for transport and disposal; 2) the impact of interim storage on the disposal strategy needs to be evaluated; and 3) the back-end is affected by—and affects—nuclear fuel cycle and energy policy choices. The back-end integration accounts for the various processes of nuclear waste management—onsite storage, consolidated storage, transport and geological disposal. Ideally, these processes should be fully coupled so that benefits and impacts can be assessed at the level of the full fuel cycle. The paper summarizes the causes and consequences of the absence of integration at the back-end of the nuclear fuel cycle in the U.S., critically reviews ongoing integration efforts, and suggests a framework that would support the back-end integration.

This paper presents the residual tensile strength test results of corroded high yield steel bars. Single steel bars were embedded at a cover depth of 20 mm in 150 × 150 × 625 mm long cracked concrete beam specimens made with 70/30 PC/FA and 50/50 PC/SL binders with a constant w/b ratio of 0.40. The steel bars were placed in the cross-section centre and near the orthogonal edge of the beams, and selected beam faces epoxy-coated in order to simulate, respectively, 1D and 2D chloride ingress. The beams were subjected to 2-week wetting (with 5% NaCl) and 2-week air-drying cycles in the laboratory for 110 weeks after which the corroded steel bars were extracted, assessed for corrosion morphology, and tested in tension for ultimate strength, fracture strength and ductility performance. The steel bars in concretes exposed to 1D chloride ingress had isolated corrosion pits while both general and isolated corrosion pits were observed in specimens exposed to 2D chloride ingress. The residual ultimate and fracture tensile strengths, and ductility of corroded steel reinforcing bars in concretes exposed to 2D chloride ingress are lower than those for steel bars in concretes exposed to 1D chloride ingress.

We report 3D colloidal self-assembly (crystallization) of poly(ionic liquid) latexes to produce crystals that exhibit reversible melting and recrystallization in water, due to “classical” interparticle interactions, typical of multifunctional polymers. These new materials are derived from an ionic liquid monomer that is polymerized at room temperature by redox-initiated polymerization. Particle synthesis, self-assembly, thermal properties, and introductory light diffraction effects are reported with a focus on melting. These crystals are distinguishable from classical colloidal crystalline arrays, and are the first such crystals to exhibit thermal melting. This new hydrogel offers promise for engineering large volume production of photonic crystals active in the visible and proximal spectral regions, by crystallization from suspension (solution), characteristic of most useful chemical compounds.