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At least 397 records · Page 22

Mechanistic origins of corrosion protection of aluminum alloys by graphene/polyetherimide nanocomposite coatings

Light-weighting vehicular components through adoption of light-metal structural alloys holds promise for reducing the fuel consumption of internal combustion engine vehicles and increasing the range of battery electric vehicles. However, the alloyed microstructure and surface precipitates of aluminum alloys render these materials susceptible to corrosion under modest excursions from neutral pH. Traditional chromium-based anodic passivation layers are subject to increasingly stringent environmental regulations, whereas options for sacrificial cathodic films are sparse for electropositive metals. While hybrid nanocomposite coatings have shown initial promise, mechanistic underpinnings remain poorly understood. Here, a fully imidized polyetherimide (PEI) resin is utilized as the continuous phase with inclusion of unfunctionalized exfoliated graphite (UFG). A comprehensive investigation of the mechanisms of corrosion protection reveals key fundamental design principles underpinning corrosion inhibition. First, strong interfacial adhesion, which for PEI is facilitated by binding of imide carbonyl moieties to Lewis acidic sites on Al surfaces. Second, the miscibility of ion-impervious nanoscopic UFG fillers and stabilization of a substantial interphase region at UFG/PEI boundaries that result in minimizing the free volume at the filler/polymer interface. Finally, extended tortuosity of ion diffusion pathways imbued by the below-percolation-threshold 2D fillers. These three design principles help govern and modulate ion transport from electrolyte/coating interfaces to the coating/metal interface and are crucial for the extended preservation of barrier properties. The results suggest an approach to systematically activate multiple modes of corrosion inhibition through rational design of hybrid nanocomposite coatings across hard-to-abate sectors where light metal alloys are likely to play an increasingly prominent role.

36 MATERIALS SCIENCE↗

Impact of nitrogen on lithium-induced corrosion and cracking of RAFM steel

The emergence of private fusion enterprises, combined with advancements in U.S. and EU ITER-TBM as well as EU DEMO liquid breeder blanket concepts, has renewed focus on the materials challenges. This study examines the compatibility of reduced activation ferritic/martensitic (RAFM) steel in liquid Lithium (Li) containing various Nitrogen (N) concentrations, tested at 600 and 700 °C for 500 and 1000 h under static conditions. Microstructural characterization revealed the corrosion-induced dissolution and precipitation in Li containing 0.082 and 0.17 wt.% N at 600 °C, while limited dissolution and precipitation were observed in N-gettered Li using zirconium (Zr) and titanium (Ti) foils at 600 °C. Tensile testing at room temperature after Li exposure revealed a decrease in strength and ductility of the RAFM steel as a function of N content in Li. Severe embrittlement was observed after 500 h in Li containing 0.17 wt.% N at 600 °C and after 500 h in hot-gettered Li at 700 °C. Chromium (Cr) depletion from the steel matrix was observed, leading to the formation of M6C-type carbides on the surface identified by electron microscopy (SEM), X-ray diffraction (XRD), in agreement with thermodynamic calculations. These findings highlight the critical materials challenges posed by liquid Li breeder blanket concepts, emphasizing the need for improved strategies to address Li-induced dissolution, precipitation, and steel embrittlement due to N contamination of the coolant.

Romedenne, Marie [ORNL] (ORCID:0000000317936561)↗

Spin and lattice dynamics of the two-dimensional van der Waals ferromagnet CrI3

Chromium tri-iodide (CrI 3 ) is a prototypical ferromagnetic van der Waals insulator with its genuinely two-dimensional (2D) long-range magnetic order below 45 K demonstrated recently. The underlying magnetic anisotropy has not been completely understood while both the Dzyaloshinskii-Moriya (DM) interaction and the Kitaev—Γ type interaction have been considered as the relevant magnetic Hamiltonian. In addition, the relation between the crystal structure and the magnetic order needs to be further elucidated concerning their possible coupling in few-layer samples and in the topmost surface layers of bulk samples. Here, we investigate these issues via temperature- and magnetic field-dependent terahertz spectroscopy on bulk CrI 3 single crystals, focusing on the dynamics of ferromagnetic resonances (FMRs) and optical phonons in the terahertz (THz) region from 4 to 120 cm -1 (from 0.5 to 15 meV). We narrow down the possible ranges of the interaction parameters such as the off-diagonal symmetric terms and the single-ion anisotropy. The accurate values of these parameters significantly constrain the magnitude of possible Kitaev—Γ exchange interaction and the topological magnon gap. Moreover, the structure-magnetism relationship was critically analyzed based on the temperature- and field-dependences of two E u in-plane optical phonon modes, which shows that the commonly believed structural phase diagram of CrI 3 , derived from surface-preferential data, has to be seriously modified.

36 MATERIALS SCIENCE↗

Magnetic ordering through itinerant ferromagnetism in a metal-organic framework

In this report, the materials that combine magnetic order with other desirable physical attributes could find transformative applications in spintronics, quantum sensing, low-density magnets and gas separations. Among potential multifunctional magnetic materials, metal-organic frameworks, in particular, bear structures that offer intrinsic porosity, vast chemical and structural programmability, and the tunability of electronic properties. Nevertheless, magnetic order within metal-organic frameworks has generally been limited to low temperatures, owing largely to challenges in creating a strong magnetic exchange. Here we employ the phenomenon of itinerant ferromagnetism to realize magnetic ordering at T C = 225 K in a mixed-valence chromium(II/III) triazolate compound, which represents the highest ferromagnetic ordering temperature yet observed in a metal-organic framework. The itinerant ferromagnetism proceeds through a double-exchange mechanism, which results in a barrierless charge transport below the Curie temperature and a large negative magnetoresistance of 23% at 5 K. These observations suggest applications for double-exchange-based coordination solids in the emergent fields of magnetoelectrics and spintronics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Inhibiting collective cation migration in Li-rich cathode materials as a strategy to mitigate voltage hysteresis

Lithium-rich cathodes are promising energy storage materials due to their high energy densities. However, voltage hysteresis, which is generally associated with transition metal migration, limits their energy efficiency and implementation in practical devices. Here we reveal that voltage hysteresis is related to the collective migration of metal ions, and that isolating the migration events from each other by creating partial disorder can create high-capacity reversible cathode materials, even when migrating transition metal ions are present. In this study, we demonstrate this on a layered Li-rich chromium manganese oxide that in its fully ordered state displays a substantial voltage hysteresis (>2.5 V) associated with collective transition metal migration into Li layers, but can be made to achieve high capacity (>360 mAh g –1 ) and energy density (>1,100 Wh kg –1 ) when the collective migration is perturbed by partial disorder. This study demonstrates that partially cation-disordered cathode materials can accommodate a high level of transition metal migration, which broadens our options for redox couples to those of mobile cations.

36 MATERIALS SCIENCE↗

Super-moiré spin textures in twisted two-dimensional antiferromagnets

Stacking two-dimensional layered materials offers a platform to engineer electronic and magnetic states. In general, the resulting states—such as moiré magnetism—have a periodicity at the length scale of the moiré unit cell. Here we study magnetic order in twisted double-bilayer chromium triiodide by means of scanning nitrogen-vacancy microscopy. We observe long-range magnetic textures extending beyond the single moiré unit cell, which we dub a super-moiré magnetic state. At small twist angles, the size of the spontaneous magnetic texture increases with twist angle, opposite to the underlying moiré wavelength. The spin-texture size reaches a maximum of about 300 nm in 1.1° twisted devices, an order of magnitude larger than the underlying moiré wavelength, and vanishes at twist angles above 2°. The obtained magnetic field maps suggest the formation of antiferromagnetic Néel-type skyrmions spanning multiple moiré cells. The twist-angle-dependent study, combined with large-scale atomistic Monte Carlo simulations, suggests that the magnetic competition between the Dzyaloshinskii–Moriya interaction, magnetic anisotropy and exchange interactions—which all depend on the relative rotation of the layers—produces the topological textures that emerge in the super-moiré spin order.

Wong, King Cho [Univ. of Stuttgart (Germany)] (ORC↗

Discovery and characterization of an acridine radical photoreductant

Not provided.Photoinduced electron transfer (PET) is a phenomenon whereby the absorption of light by a chemical species provides an energetic driving force for an electron-transfer reaction. This mechanism is relevant in many areas of chemistry, including the study of natural and artificial photosynthesis, photovoltaics and photosensitive materials. In recent years, research in the area of photoredox catalysis has enabled the use of PET for the catalytic generation of both neutral and charged organic free-radical species. These technologies have enabled previously inaccessible chemical transformations and have been widely used in both academic and industrial settings. Such reactions are often catalysed by visible-light-absorbing organic molecules or transition-metal complexes of ruthenium, iridium, chromium or copper. Although various closed-shell organic molecules have been shown to behave as competent electron-transfer catalysts in photoredox reactions, there are only limited reports of PET reactions involving neutral organic radicals as excited-state donors or acceptors. This is unsurprising because the lifetimes of doublet excited states of neutral organic radicals are typically several orders of magnitude shorter than the singlet lifetimes of known transition-metal photoredox catalysts. Here we document the discovery, characterization and reactivity of a neutral acridine radical with a maximum excited-state oxidation potential of -3.36 volts versus a saturated calomel electrode, which is similarly reducing to elemental lithium, making this radical one of the most potent chemical reductants reported. Spectroscopic, computational and chemical studies indicate that the formation of a twisted intramolecular charge-transfer species enables the population of higher-energy doublet excited states, leading to the observed potent photoreducing behaviour. Finally, we demonstrate that this catalytically generated PET catalyst facilitates several chemical reactions that typically require alkali metal reductants and can be used in other organic transformations that require dissolving metal reductants.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Heavy-ion production of 77 Br and 76 Br

Many radioisotopes with potential medical applications are difficult to produce routinely, especially those on the proton-rich side of the valley of stability. Current production methods typically use light-ion (protons or deuteron) reactions on materials of similar mass to the target radioisotope, which limits the elemental target material available and may require the use of targets with poor thermal properties (as is the case for the production of radiobromine). These reactions may also create significant amounts of proton-rich decay products which require chemical separation from the desired product in a highly radioactive environment. A promising alternative method using heavy-ion fusion-evaporation reactions for the production of the medically relevant bromine radioisotopes 76 Br (t 1/2 = 16.2 h) and 77 Br (t 1/2 = 57.0 h) is presented. Heavy-ion beams of 28 Si and 16 O were used to bombard natural chromium and copper targets just above the Coulomb barrier at the University of Notre Dame's Nuclear Science Laboratory to produce these bromine and precursor radioisotopes by fusion-evaporation reactions. Production yields for these reactions were measured and compared to PACE4 calculations. In addition to using more robust targets for irradiation, a simple physical–chemical separation method is proposed that will lead to very high radiopurity yields. A summary of accelerator facility requirements needed for routine production of these radioisotopes is also presented.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Imaging and speciation of intracellular metallic implant debris using synchrotron-based X-ray fluorescence micro-spectroscopy: a study of two cases

Debris generated from total hip arthroplasty (THA) components made from metal alloys can cause, in some cases, inflammatory cell (e.g., macrophages) responses that lead to adverse local tissue reactions (ALTR) and implant failure. The lack of information on intracellular chemical alterations of metal debris has hindered the understanding of the pathogenesis of ALTR. The goal of this study was to characterize intracellular debris within macrophages using Synchrotron imaging and spectroscopy. We studied periprosthetic tissues of two retrieved THAs with (1) a metal-on-metal (MoM) articulation and (2) a metal-on-polyethylene (MoP) articulation exhibiting corrosion of the metal femoral head. The MoM-THA exhibited different valence states of chromium- and cobalt-containing debris, suggesting three different moieties: Cr 2 O 3 , CrPO 4 , and an alloy-oxide mixture. The findings further suggest that Cr 2 O 3 formed in the tribological interfaces of the implant, while CrPO 4 is a by-product of the phagocytosis process of cobalt alloy-containing debris. Titanium debris appeared to occur in a mixed crystalline/amorphous oxide state. It remains unclear if this chemical state results from the tribochemical processes at the implant surface or intracellular alterations. The MoP-THA specimen exhibited no intracellular particulate debris associated with macrohpages, indicating that the ALTR may be entirely triggered by metal ionic species in this case. A better understanding of in vivo chemical alteration of implant debris will aid in assessing the risk for ALTR during implant design and material choice. However, various techniques are needed to accurately determine the interaction between metal particles and the inta- and extra-cellular environment.

60 APPLIED LIFE SCIENCES↗

Polyester functional graphenic materials as a mechanically enhanced scaffold for tissue regeneration

Traditional metal implants such as titanium, cobalt, and chromium have found wide utility in medicine; however, these come with a risk of toxicity. To overcome metal-related toxicity and enable degradability, polyesters including polycaprolactone (PCL), polylactic acid (PLA), and polyglycolic acid (PGA) show promise for the replacement of various biomedical applications of metals due to their accepted biocompatibility and FDA approval. However, polyesters are less stiff than their metallic counterparts, limiting their application to non-load bearing injury sites, such as fixation hardware for fingers. To improve mechanical properties, graphene oxide (GO)-polyester composites are a promising class of biodegradable scaffolds. Initial reports of these composites are encouraging, but mechanical properties still fall short. Traditional composites rely on non-covalent association between GO and the polyesters, which often leads to failure at the interface and weakens the overall strength of the material. Herein, we present a strategy for attachment of these FDA-approved polyesters onto a derivative of GO using a robust covalent bond. By covalently functionalizing the graphenic backbone with polyesters and without metal catalysts, we create functional graphenic materials (FGMs) to not only simultaneously retain biodegradability and compatibility, but also mechanically strengthen PCL, PLA, and PGA; we observed an average increase in the Young's modulus of over 140% compared to the graphenic backbone. These polyester-functionalized FGMs are a promising platform technology for tissue implants.

60 APPLIED LIFE SCIENCES↗

Fast microflow kinetics and acid catalyst deactivation in glucose conversion to 5-hydroxymethylfurfural

5-Hydroxymethyl furfural (HMF) is an important platform chemical because it can be upgraded to various drop-in and performance-advantaged products. The cascade reaction of HMF production from glucose over a Lewis acid (CrCl 3 ) and a Brønsted acid (HCl) catalyst in aqueous media is investigated in a microreactor at short residence times and high temperatures. We study the formation of various chromium species using UV-visible spectrophotometry and elucidate the Cr(III) speciation. The catalyst reactivity increases sharply at short residence times, and then drops at long times. This indicates that the catalyst treatment plays a vital role in getting optimal reactivity, and recording the catalyst history is necessary. We develop a kinetic model to describe the catalyst speciation as well as the Lewis and Brønsted acid-catalyzed reaction kinetics using a hierarchical approach. Here, the model is in good agreement with experiments. We demonstrate the benefits of tandem Lewis-external added Brønsted acid catalysis in processing time, productivity, and catalyst stability. We apply this model to optimize the HMF yield and obtain ~36% yield at 200 °C in 7 min and report the highest productivity of ~15% yield per min, demonstrating the opportunity of reaching high productivity at short residence times.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ethylene polymerization with a crystallographically well-defined metal–organic framework supported catalyst

The inherent crystallinity of metal–organic framework (MOF) catalysts offers the possibility to understand the structure of the active site at the molecular level. This property is often lacking in traditional amorphous supports. Cr-SIM-NU-1000, a MOF-supported Cr 3+ heterogeneous catalyst, is shown to be competent for ethylene polymerization after activation with AlEt 2 Cl (DEAC), producing crystalline linear polyethylene (PE). The polymer produced has a low polydispersity (D = 2.0), in marked contrast to the Phillips supported chromium catalyst, Cr@SiO 2 (D ~ 8–65). Cr-SIM-NU-1000 achieves a turnover frequency of 2.6 × 10 3 h –1 under 40 bar ethylene pressure at room temperature, with corresponding PE productivity of 1.3 × 10 5 g PE mol –1 Cr per h. Single crystal X-ray diffraction (SC-XRD) of the pre-catalyst was conducted by collecting a structure of alkyl aluminum (DEAC) co-catalyst treated Cr-SIM-NU-1000. This crystal structure provides insight into the interactions between DEAC co-catalyst and Cr active site, revealing a Cr–C bond after treatment with DEAC. Furthermore, DEAC is crystallographically resolved at the terminal oxy-ligands of the node and likely also exists within the window pores of the framework between nodes, based on electron density mapping. Cr-SIM-NU-1000 offers the opportunity to study a structurally well-defined olefin polymerization system, with atomically precise characterization of the pre-catalyst structure. Furthermore, this allows the proposal of a mechanism and feeds into future development of next-generation heterogeneous catalyst systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Prussian blue as a co-catalyst for enhanced Cr (VI) photocatalytic reduction promoted by titania-based nanoparticles and aerogels

Hexavalent chromium (Cr(VI)) is an noxious and highly toxic heavy metal that presents a serious threat to human health if present even in low concentrations in drinking water. Photocatalytic reduction of Cr(VI) to its less toxic Cr(III) state is a potential strategy to combat Cr(VI) pollution, but the efficiency of the process is low, especially in the absence of hole scavenger organic reagents. To address this issue and prepare efficient photocatalysts for Cr(VI) removal from water, in this study, we explored Prussian blue (PB) as a co-catalyst for improving the photoreduction performance of different high surface area TiO 2 -based materials (titania or silica–titania nanoparticles and aerogels). Here, the photocatalyst nanomaterials were surface-modified with nanocrystalline PB using the photodeposition route. The PB layer acts as an effective electron acceptor/mediator between the semiconductor photocatalyst and Cr(VI) species. All the PB-modified photocatalysts exhibit higher photocatalytic activity (up to 9 times faster) as compared to the unmodified photocatalysts towards reduction of Cr(VI). Importantly, the PB-modified photocatalysts exhibited high photocatalytic performance (98–99% reduction in 40 min for pH = 5.6 and in 10 min for pH = 3) without addition of organic reagents. The simple approach reported herein can be followed to prepare new PB-photocatalyst systems with improved photocatalytic performance towards Cr(VI) reduction and other target applications.

36 MATERIALS SCIENCE↗

Percolative phase transition in few-layered MoSe 2 field-effect transistors using Co and Cr contacts

The metal-to-insulator phase transition (MIT) in two-dimensional (2D) materials under the influence of a gating electric field has revealed interesting electronic behavior and the need for a deeper fundamental understanding of electron transport processes, while attracting much interest in the development of next-generation electronic and optoelectronic devices. Although the mechanism of the MIT in 2D semiconductors is a topic under debate in condensed matter physics, our work demonstrates the tunable percolative phase transition in few-layered MoSe 2 field-effect transistors (FETs) using different metallic contact materials. Here, we attempted to understand the MIT through temperature-dependent electronic transport measurements by tuning the carrier density in a MoSe 2 channel under the influence of an applied gate voltage. In particular, we have examined this phenomenon using the conventional chromium (Cr) and ferromagnetic cobalt (Co) as two metal contacts. For both Cr and Co, our devices demonstrated n-type behavior with a room-temperature field-effect mobility of 16 cm 2 V −1 s −1 for the device with Cr-contacts and 92 cm 2 V −1 s −1 for the device with Co-contacts, respectively. Further, with low temperature measurements at 50 K, the mobilities increased significantly to 65 cm 2 V −1 s −1 for the device with Cr and 394 cm 2 V −1 s −1 for the device with Co-contacts. By fitting our experimental data to the percolative phase transition theory, the temperature-dependent conductivity data show a transition from an insulating-to-metallic behavior at a bias of ∼28 V for Cr-contacts and ∼20 V for Co-contacts. This cross-over of the conductivity can be attributed to an increase in carrier density as a function of the gate bias in temperature-dependent transfer characteristics. By extracting the critical exponents, we find that the transport behavior in the device with Co-contacts aligns closely with the 2D percolation theory. In contrast, the devices with Cr-contacts deviate significantly from the 2D limit at low temperatures.

36 MATERIALS SCIENCE↗

Designing molecular qubits: computational insights into first-row and group 6 transition metal complexes

In the realm of optically addressable qubits, a previously synthesized and characterized Cr( IV ) pseudo-tetrahedral complex, featuring four strongly donating ligands surrounding the chromium center, has demonstrated potential as a qubit candidate. This study proposes analogs of this complex through a metal substitution strategy, extending the investigation to different complexes based on metal centers selected from first-row and Group 6 transition metals. Computational modeling based on multiconfigurational methods CASPT2 and MC-PDFT was utilized to calculate energy gaps between ground and excited electronic spin states, and zero-field splitting parameters. Simulations were applied to each equilibrium geometry and related deformations based on vibrational modes. All results align with previous experimental findings, but also show that qubits based on V and Ti centers could be more electronically stable than the Cr one, suggesting a lower electronic features dependency from their related geometry. In some cases geometrical deformations provide changes in relative energy gaps between triplet and singlet excited state, that could potentially swap, offering a different initialization process, and some inspiration for ligand design based on such deformations. Additionally, this study identifies an unsynthesized Ti( II ) compound as a promising candidate for molecular qubits. This finding highlights the role of computational multireference methods in the rational design of qubit systems.

Sauza-de la Vega, Arturo [Univ. of Chicago, IL (Un↗

Cobalt ferrite nanoparticle intercalated carbon nanotubes for a nanomagnetic ultrasensitive sensor of Cr-VI in water

Nanocomposites of cobalt ferrite (CFO) magnetic nanoparticles intercalated on carbon nanotubes (CNTs) are evaluated as a nanomagnetic ultrasensitive sensor for the environmental toxin, hexavalent chromium (Cr-VI). Specifically, the structural and magnetic changes that accompany the infiltration of the CFO/CNTs by Cr-VI are presented. Extended x-ray absorption fine structure (EXAFS) shows that the atomic spacing within the CFO structure changes in the presence of Cr, suggesting that the Cr is incorporated into the nanoparticles. Vibrating sample magnetometry (VSM) reveals that CFO/CNTs composite infiltrated with Cr-VI have a 71% enhancement in saturation magnetization compared with the uninfiltrated CFO/CNTs, while small-angle neutron scattering (SANS) suggests that this magnetic enhancement is not associated with the nanoparticle lengthscales, but may arise from longer-ranged clusters. Both VSM and SANS clearly demonstrate that the Cr-doped CFO/CNTs are hysteretic with a net magnetization at remanence that is about 1/3 that of saturation, while this hysteresis is absent in the undoped CFO/CNTs. These magnetic differences at either remanence or saturation are promising for the magnetic detection of Cr-VI using CFO/CNTs sensors.

36 MATERIALS SCIENCE↗

A combined first principles study of the structural, magnetic, and phonon properties of monolayer CrI3

The first magnetic 2D material discovered, monolayer (ML) CrI3, is particularly fascinating due to its ground state ferromagnetism. However, because ML materials are difficult to probe experimentally, much remains unresolved about ML CrI3’s structural, electronic, and magnetic properties. Here, we leverage Density Functional Theory (DFT) and high-accuracy Diffusion Monte Carlo (DMC) simulations to predict lattice parameters, magnetic moments, and spin–phonon and spin–lattice coupling of ML CrI3. We exploit a recently developed surrogate Hessian DMC line search technique to determine CrI3’s ML geometry with DMC accuracy, yielding lattice parameters in good agreement with recently published STM measurements—an accomplishment given the ~10% variability in previous DFT-derived estimates depending upon the functional. Strikingly, we find that previous DFT predictions of ML CrI3’s magnetic spin moments are correct on average across a unit cell but miss critical local spatial fluctuations in the spin density revealed by more accurate DMC. DMC predicts that magnetic moments in ML CrI3 are 3.62 μB per chromium and -0.145 μB per iodine, both larger than previous DFT predictions. The large disparate moments together with the large spin–orbit coupling of CrI3’s I-p orbital suggest a ligand superexchange-dominated magnetic anisotropy in ML CrI3, corroborating recent observations of magnons in its 2D limit. We also find that ML CrI3 exhibits a substantial spin–phonon coupling of ~3.32 cm-1. Our work, thus, establishes many of ML CrI3’s key properties, while also continuing to demonstrate the pivotal role that DMC can assume in the study of magnetic and other 2D materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗