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Abstract Four commercial glass compositions were investigated to understand their mechanisms of alteration in light of the current and future regulations on food contact materials. Lead crystal (fine glassware), soda-lime (food and cosmetic containers), borosilicate (cookware) and barium glass (tableware) powders and slabs were altered for 3 years, in acetic acid (4% vol) at pH = 2.4 and 70 °C. The leaching solution was analyzed by ICP-AES while glass slabs were investigated by ToF-SIMS and Spectroscopic Ellipsometry. As a result, in acidic medium, the polymerization of the silicate network as well as the glass composition impacted the alteration rates and depleted depths of alkalis and earth-alkalis elements. Yet the rate of hydrolysis measured from the release of Si, remained similar under identical alteration conditions, whatever the glass structure and composition. For lead crystal glass, repolymerization of the silicate network was observed in the course of alteration.

Abstract Mechanical stress can directly activate chemical reactions by reducing the reaction energy barrier. A possible mechanism of such mechanochemical activation is structural deformation of the reactant species. However, the effect of deformation on the reaction energetics is unclear, especially, for shear stress-driven reactions. Here, we investigated shear stress-driven oligomerization reactions of cyclohexene on silica using a combination of reactive molecular dynamics simulations and ball-on-flat tribometer experiments. Both simulations and experiments captured an exponential increase in reaction yield with shear stress. Elemental analysis of ball-on-flat reaction products revealed the presence of oxygen in the polymers, a trend corroborated by the simulations, highlighting the critical role of surface oxygen atoms in oligomerization reactions. Structural analysis of the reacting molecules in simulations indicated the reactants were deformed just before a reaction occurred. Quantitative evidence of shear-induced deformation was established by comparing bond lengths in cyclohexene molecules in equilibrium and prior to reactions. Nudged elastic band calculations showed that the deformation had a small effect on the transition state energy but notably increased the reactant state energy, ultimately leading to a reduction in the energy barrier. Finally, a quantitative relationship was developed between molecular deformation and energy barrier reduction by mechanical stress.

Abstract In plant cells, cellulose synthase complexes (CSCs) are nanoscale machines that synthesize and extrude crystalline cellulose microfibrils (CMFs) into the apoplast where CMFs are assembled with other matrix polymers into specific structures. We report the tissue-specific directionality of CSC movements of the xylem and interfascicular fiber walls of Arabidopsis stems, inferred from the polarity of CMFs determined using vibrational sum frequency generation spectroscopy. CMFs in xylems are deposited in an unidirectionally biased pattern with their alignment axes tilted about 25° off the stem axis, while interfascicular fibers are bidirectional and highly aligned along the longitudinal axis of the stem. These structures are compatible with the design of fiber-reinforced composites for tubular conduit and support pillar, respectively, suggesting that during cell development, CSC movement is regulated to produce wall structures optimized for cell-specific functions.

In this study, we developed a multi-walled carbon nanotube (MWCNT)-based field-effect transistor (MWCNT-FET) sensor with high sensitivity and selectivity for microcystin-LR (MC-LR). Carboxylated MWCNTs were activated with an MC-LR-targeting aptamer (MCTA). Subsequently the bioactivated MWCNTs were immobilized between interdigitated drain (D) and source (S) electrodes through self-assembly. The top-gated MWCNT-FET sensor was configured by dropping the sample solution onto the D and S electrodes and immersing a Ag/AgCl electrode in the sample solution as a gate (G) electrode. We believe that the FET sensor’s conduction path arises from the interplay between the MCTAs, with the applied gate potential modulating this path. Using standard instruments and a personal computer, the sensor’s response was detected in real-time within a 10 min time frame. This label-free FET sensor demonstrated an impressive detection capability for MC-LR in the concentration range of 0.1–0.5 ng/mL, exhibiting a lower detection limit of 0.11 ng/mL. Additionally, the MWCNT-FET sensor displayed consistent reproducibility, a robust selectivity for MC-LR over its congeners, and minimal matrix interferences. Given these attributes, this easily mass-producible FET sensor is a promising tool for rapid, straightforward, and sensitive MC-LR detection in freshwater environments.

Abstract The interactive corrosion between stainless steel 316 (SS) and International Simple Glass (ISG) has been studied for 12 months. The samples were placed in intimate contact to create crevice corrosion conditions on SS in a 0.6 M NaCl solution with and without 142 ppm dissolved silica species enriched in 29Si. Corrosion on SS was observed with large pits located close to the crevice mouth at the end of 1 year in 0.6 M NaCl solution. The SS corrosion was also associated with the dissolution of nearby glass in a highly localized manner. When the leaching solution was saturated with silica species, the corrosion rate of SS was suppressed. However, the presence of SS enhances ISG dissolution in both conditions. The implications of the observed phenomena on the long-term storage of nuclear waste are discussed.

Abstract Borosilicate glasses are widely used to confine high-level radioactive wastes. The lifetime of these materials could reach hundreds of thousands of years if leaching of the glass into groundwater enables the formation of a passivating gel layer. Even in this regime, the glass will never stop corroding as thermodynamic equilibrium between glass and solution cannot be achieved. Therefore, accurate predictions of glass durability including passivation, require a deep understanding of the mechanisms controlling the so-called residual rate. However, despite tremendous efforts, these mechanisms remain poorly understood. Here, focusing on the behavior of the soluble elements of the International Simple Glass (B, Na, and Ca), we show that the residual rate is controlled by the behavior of B, a glass former supposed to dissolve instantaneously when in contact with water and thus widely considered as an ideal tracer. We then demonstrate that B release is controlled by multiple processes highly dependent on the pH. At the beginning of the passivating layer formation, the hydrolysis of B-O-Si linkages is rate-limiting and has an activation energy of ∼60 kJ mol−1, a value slightly lower than that for breaking Si-O-Si linkages. Once the fraction of closed pores resulting from gel restructuring is high enough, then diffusion of both reactants (water molecules) and some products (mainly Baq, Caaq) through the growing gel layer becomes rate-limiting. Consequently, B and Ca accumulate in an inner layer referred to as the active zone, with potential feedback on the B-O-Si hydrolysis. A new paradigm, including B as a key element of the system, is proposed to develop a comprehensive model for the corrosion of borosilicate glass.

Abstract Although graphene is well known for super-lubricity on its basal plane, friction at its step edge is not well understood and contradictory friction behaviors have been reported. In this study, friction of mono-layer thick graphene step edges was studied using atomic force microscopy (AFM) with a Si tip in dry nitrogen atmosphere. It is found that, when the tip slides over a ‘buried’ graphene step edge, there is a resistive force during the step-up motion and an assistive force during the step-down motion due to the topographic height change. The magnitude of these two forces is small and the same in both step-up and step-down motions. As for the ‘exposed’ graphene step edge, friction increases in magnitude and exhibits more complicated behaviors. During the step-down motion of the tip over the exposed step edge, both resistive and assistive components can be detected in the lateral force signal of AFM if the scan resolution is sufficiently high. The resistive component is attributed to chemical interactions between the functional groups at the tip and step-edge surfaces, and the assistive component is due to the topographic effect, same as the case of buried step edge. If a blunt tip is used, the distinct effects of these two components become more prominent. In the step-up scan direction, the blunt tip appears to have two separate topographic effects elastic deformation of the contact region at the bottom of the tip due to the substrate height change at the step edge and tilting of the tip while the vertical position of the cantilever (the end of the tip) ascends from the lower terrace to the upper terrace. The high-resolution measurement of friction behaviors at graphene step edges will further enrich understanding of interfacial friction behaviors on graphene-covered surfaces.

Abstract Understanding protein structure and function relationships in cellulose synthase (CesA), including divergent isomers, is an important goal. Here, we report results from mutant complementation assays that tested the ability of sequence variants of AtCesA7, a secondary wall CesA of Arabidopsis thaliana, to rescue the collapsed vessels, short stems, and low cellulose content of the irx3‐1 AtCesA7 null mutant. We tested a catalytic null mutation and seven missense or small domain changes in and near the AtCesA7 FTVTSK motif, which lies near the catalytic domain and may, analogously to bacterial CesA, exist within a substrate “gating loop.” A low‐to‐high gradient of rescue occurred, and even inactive AtCesA7 had a small positive effect on stem cellulose content but not stem elongation. Overall, secondary wall cellulose content and stem length were moderately correlated, but the results were consistent with threshold amounts of cellulose supporting particular developmental processes. Vibrational sum frequency generation microscopy allowed tissue‐specific analysis of cellulose content in stem xylem and interfascicular fibers, revealing subtle differences between selected genotypes that correlated with the extent of rescue of the collapsing xylem phenotype. Similar tests on PpCesA5 from the moss Physcomitrium (formerly Physcomitrella) patens helped us to synergize the AtCesA7 results with prior results on AtCesA1 and PpCesA5. The cumulative results show that the FTVTxK region is important for the function of an angiosperm secondary wall CesA as well as widely divergent primary wall CesAs, while differences in complementation results between isomers may reflect functional differences that can be explored in further work.

Relaxor ferroelectric polymers exhibit both high dielectric constants and low remnant polarization and thus deliver much higher energy densities and greater charge–discharge efficiencies than normal ferroelectrics for capacitive energy storage applications. Herein, dielectric energy storage behavior of several newly discovered relaxor ferroelectric polymers is studied from a molecular perspective. It is observed that the homopolymers exhibit very slim polarization–electric field loops and the highest charge–discharge efficiencies among ferroelectric polymers, which are attributed to the highly disordered chain conformation as evidenced from the scanning probe microscopy results. Based on the findings on the relaxor homopolymers, the benchmark relaxor ferroelectric terpolymers is revisited and insights into their outstanding capacitive performance are provided. Moreover, it is found that the disordered chain conformation in relaxor ferroelectric polymers remains as the ground state at varied temperatures and applied electric fields, which is in stark contrast to relaxor perovskites whose ground state is strongly dependent on temperatures and external electric fields. The discovery of the absence of thermal‐ and field‐induced phase transition in relaxor ferroelectric polymers makes this class of ferroelectric materials more attractive for advanced electronic and energy applications.

Abstract Background Mechanical refining is a low-capital and well-established technology used in pulp and paper industry to improve fiber bonding for product strength. Refining can also be applied in a biorefinery context to overcome the recalcitrance of pretreated biomass by opening up the biomass structure and modifying substrate properties (e.g., morphology, particle size, porosity, crystallinity), which increases enzyme accessibility to substrate and improves carbohydrate conversion. Although several characterization methods have been used to identify the changes in substrate properties, there is no systematic approach to evaluate the extent of fiber cell wall disruption and what physical properties can explain the improvement in enzymatic digestibility when pretreated lignocellulosic biomass is mechanically refined. This is because the fiber cell wall is complex across multiple scales, including the molecular scale, nano- and meso-scale (microfibril), and microscale (tissue level). A combination of advanced characterization tools is used in this study to better understand the effect of mechanical refining on the meso-scale microfibril assembly and the relationship between those meso-scale modifications and enzymatic hydrolysis. Results Enzymatic conversion of autohydrolysis sugarcane bagasse was improved from 69.6 to 77.2% (11% relative increase) after applying mechanical refining and an increase in enzymatic digestibility is observed with an increase in refining intensity. Based on a combination of advanced characterizations employed in this study, it was found that the refining action caused fiber size reduction, internal delamination, and increase in pores and swellability. Conclusions A higher level of delamination and higher increase in porosity, analyzed by TEM and DSC, were clearly demonstrated, which explain the faster digestibility rate during the first 72 h of enzymatic hydrolysis for disc-refined samples when compared to the PFI-refined samples. In addition, an increased inter-fibrillar distance between cellulose microfibrils at the nano–meso-scale was also revealed by SFG analysis, while no evidence was found for a change in crystalline structure by XRD and solid-state NMR analysis.

Abstract All materials can suffer from environmental degradation; the rate and extent of degradation depend on the details of the material composition and structure as well as the environment. The corrosion of silicate glasses, crystalline ceramics, and metals, particularly as related to nuclear waste forms, has received a lot of attention. The corrosion phenomena and mechanisms of these materials are different, but also have many similarities. This review compares and contrasts the mechanisms of environmental degradation of glass, crystalline ceramics, and metals, with the goal of identifying commonalities that can seed synergistic activities and advance the current knowledge in each area.

The continued scaling of silicon based electronic devices requires the development of increasingly innovative approaches for high-precision material removal. Here, the authors demonstrate subnanometre depth removal of silicon using scanning probe, shear-induced mechanochemical reactions.

The practical application of lithium metal anodes suffers from the poor Coulombic efficiency and growth of lithium dendrites. Here, the authors report an approach to enable the self-formation of stable and flexible solid-electrolyte interphase layers which serve to address both issues.

A modern lubricant contains various additives with different functionalities and the interactions or reactions between these additives could induce synergistic or antagonistic effects in tribological performance. In this study, sum frequency generation (SFG) spectroscopy was used to investigate competitive adsorption of lubricant additives at a solid/base oil interface. A silica substrate was used as a model solid surface. The lubricant additives studied here included two oil-soluble ionic liquids (ILs, [N888H][DEHP] and [P8888][DEHP]), an antiwear additive (secondary ZDDP), an organic friction modifier (OFM), and a dispersant (PIBSI). Our results showed that for mixtures of ZDDP and IL in a base oil (PAO4), the silica surface is dominated by the IL molecules. In the cases of base oils containing OFM and IL, the silica/lubricant interface is dominated by OFM over [N888H][DEHP], while it is preferentially occupied by [P8888][DEHP] over OFM. The presence of PIBSI in the mixture of PAO4 and IL leads to the formation of a mixed surface layer at the silica surface with PIBSI as a major component. The SFG results in this investigation provide fundamental insights that are helpful to design the formulation of new lubricant additives of desired properties.

Objectives: This study investigated injuries of the ascending reticular activating system (ARAS) following whiplash injury, in patients with excessive daytime sleepiness (EDS).Methods: Twenty-three patients with whiplash injury and 26 healthy control subjects were recruited for this study. Epworth Sleepiness Scale (ESS) was used for evaluating sleepiness. According to the ESS score, the patients were classified into two groups: subgroup A – ESS score 0.05). Conversely, the values of FA and TV in the lower ventral ARAS of the patient group were significantly lower than those of the control group (p < 0.05). Comparing the values of subgroups A and B, the TV value of subgroup B was significantly lower than subgroup A (p < 0.05). However, no significant differences were observed in the values of the FA and TV in the lower dorsal and upper ARAS, and the FA value in the lower ventral ARAS (p > 0.05).Conclusions: We found significant injury of the lower ventral ARAS in EDS patients with whiplash injury. These results suggest that diffusion tensor tractography (DTT) could provide useful information for detecting injuries of the ARAS following whiplash injury, in patients with EDS.

A double dielectric barrier discharge reactor operated at a low power frequency of 400 Hz and atmospheric pressure was utilized for regulating the wettability of glass surface. The hydrophobic treatment was performed by plasma polymerization of tetramethylsilane (TMS, in argon gas). The obtained results showed that the TMS coatings formed on the glass substrates without oxygen addition were smooth, uniform films with the maximum water contact angle (WCA) of about 106°, which were similar to those obtained by low pressure, high power frequency plasmas reported in the literature. The addition of oxygen into TMS/Ar plasma gas decreased the WCA and induced the formation of SiOSi and/or SiOC linkages, which dominated the existence of Si(CH2)nSi network formed in TMS/Ar (without oxygen) plasma.

Most inorganic material surfaces exposed to ambient air can adsorb water, and hydrogen bonding interactions among adsorbed water molecules vary depending on, not only intrinsic properties of material surfaces, but also extrinsic working conditions. When dimensions of solid objects shrink to micro- and nano-scales, the ratio of surface area to volume increases greatly and the contribution of water condensation on interfacial forces, such as adhesion (Fa) and friction (Ft), becomes significant. This paper reviews the structural evolution of the adsorbed water layer on solid surfaces and its effect on Fa and Ft at nanoasperity contact for sphere-on-flat geometry. The details of the underlying mechanisms governing water adsorption behaviors vary depending on the atomic structure of the substrate, surface hydrophilicity and atmospheric conditions. The solid surfaces reviewed in this paper include metal/metallic oxides, silicon/silicon oxides, fluorides, and two-dimensional materials. The mechanism by which water condensation influences Fa is discussed based on the competition among capillary force, van der Waals force and the rupture force of solid-like water bridge. The condensed meniscus and the molecular configuration of the water bridge are influenced by surface roughness, surface hydrophilicity, temperature, sliding velocity, which in turn affect the kinetics of water condensation and interfacial Ft. Taking the effects of the thickness and structure of adsorbed water into account is important to obtain a full understanding of the interfacial forces at nanoasperity contact under ambient conditions.

Doping and substitution methods are predominantly employed in the synthesis of ceramics to achieve their desired functional properties. We studied the behavior of excessive dopants in addition to an existing stoichiometric composition using a high-throughput continuous compositional spread sputtering method. We paid attention to the possible formation of thermodynamically unstable phases by the addition of an excessive amount of dopants. We showed that even when dopants were added as an additive, they dissolved into the existing lattice due to the benefit of the entropy of mixing. Regardless of excessiveness, all added elements incorporated into the lattice, stabilized by the tolerance factor. We also demonstrated our findings exemplarily with lead iron niobate to induce magnetic properties alongside inherent ferroelectricity (MS = 10 emu/cm3, PS = 16 μC/cm2). We compare the results from CCS with those from the non-additive solid-state method, leading to a conclusion that the benefit from the entropy of mixing allows foreign elements to substitute for the elements initially residing in the lattice to a degree in compliance with the Goldschmidt tolerance factor. This observation was confirmed by a density functional theory calculation. We anticipate that our study could necessitate intensive research on achieving desired composition through industry-friendly processing.

The friction and wear behavior of materials are not intrinsic properties, but extrinsic properties; in other words, they can drastically vary depending on test and environmental conditions. In ambient air, humidity is one such extrinsic parameter. This paper reviews the effects of humidity on macro- and nano-scale friction and wear of various types of materials. The materials included in this review are graphite and graphene, diamond-like carbon (DLC) films, ultrananocrystalline diamond (UNCD), transition metal dichalcogenides (TMDs), hexagonal boron nitride (h-BN), boric acid, silicon, silicon oxide, silicates, advanced ceramics, and metals. Details of underlying mechanisms governing friction and wear behaviors vary depending on materials and humidity; nonetheless, a comparison of various material cases revealed an overarching trend. Tribochemical reactions between the tribo-materials and the adsorbed water molecules play significant roles; such reactions can occur at defect sites in the case of two-dimensionally layered materials and carbon-based materials, or even on low energy surfaces in the case of metals and oxide materials. It is extremely important to consider the effects of adsorbed water layer thickness and structure for a full understanding of tribological properties of materials in ambient air.