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At least 379 records · Page 21

Rhizosphere bacteria containing ACC deaminase decrease root ethylene emission and improve maize root growth with localized nutrient supply

Abstract Localized nutrient supply can enhance maize root proliferation, but also increase root ethylene production. Whether engineering ethylene signalling in the rhizosphere can further enhance root growth and nutrient uptake remains unknown. Here, field and column experiments for maize ( Zea mays . L) were designed as different nutrient treatments (broadcast or localized nutrient supply containing ammonium and phosphorus) with or without inoculation with rhizobacterium Variovorax paradoxus 5C‐2 containing the 1‐aminocyclopropane‐1‐carboxylate (ACC) deaminase. Rhizobacterial inoculation increased shoot biomass by 12% and root length density by 50% with localized nutrient supply. Meanwhile, localized nutrient supply increased root ethylene production by 54% compared with broadcast, and rhizobacterial inoculation prevented the increase in root ethylene. Reduced root ethylene production following V. paradoxus 5C‐2 inoculation was highly associated with a greater proportion of fine root proliferation under localized nutrient supply, which may account for the increased nitrogen and phosphorus uptake. Our work sheds light on the understanding of the interactions between root and microbe through taking hormone into consideration to dissect the relationship between below ground and above ground. It is useful to explore the strategy of soil–crop management by introducing rhizosphere microorganisms to regulate plant ethylene signal and then benefit sustainable agriculture.

Jin, Kemo↗

Protein3D: Enabling analysis and extraction of metal‐containing sites from the Protein Data Bank with molSimplify

Abstract Metalloenzymes catalyze a wide range of chemical transformations, with the active site residues playing a key role in modulating chemical reactivity and selectivity. Unlike smaller synthetic catalysts, a metalloenzyme active site is embedded in a larger protein, which makes interrogation of electronic properties and geometric features with quantum mechanical calculations challenging. Here we implement the ability to fetch crystallographic structures from the Protein Data Bank and analyze the metal binding sites in the program molSimplify. We show the usefulness of the newly created protein3D class to extract the local environment around non‐heme iron enzymes containing a two histidine motif and prepare 372 structures for quantum mechanical calculations. Our implementation of protein3D serves to expand the range of systems molSimplify can be used to analyze and will enable high‐throughput study of metal‐containing active sites in proteins.

Edholm, Freya↗

Impacts of Disulfide‐Containing Monomers in Alternating Diene Metathesis Polymerization

ABSTRACT Among the classes of synthetic polymers, disulfide‐containing structures offer unique opportunities due to their accessibility to redox chemistry that allows for degradation or reversible disulfide formation and exchange under mild conditions. Here, we examine the role of disulfides in olefin metathesis polymerization, specifically alternating diene metathesis (ALTMET) polymerization, for synthesizing unsaturated polyolefins with embedded disulfides. Our synthetic strategy hinged on the use of α,ω‐diacrylate monomers, including those connected by a disulfide unit, via copolymerization by the ALTMET mechanism to yield copolymers containing a range of disulfide content. In addition, the potential impacts of sulfur‐ruthenium interactions on the ALTMET process were investigated spectroscopically, while the degradation of the resultant polymers was affected by mild reducing agents. Overall, this study contributes to the development of degradable synthetic polymers using olefin metathesis methods, with an increased understanding of the potential for further use of disulfide groups in such metathesis reactions.

Lee, Kyoungwon↗

Evaluating the Lightning Strike Damage Tolerance for CFRP Composite Laminates Containing Conductive Nanofillers

Conductive nanofillers, such as carbon nanotube, graphene nanoplatelets, and carbon black particles (with diameters in nanometers) have been shown to enhance the electrical conductivity of fiber reinforced polymer matrix composites in many existing studies. The motivation is primarily for lightning strike protection, electromagnetic interference shielding, de-icing, and the manufacturing of lightweight electronic components. Here, we evaluate the lightning strike damage tolerance of carbon fiber reinforced polymer (CFRP) matrix composite laminates containing conductive nanofillers with varying weight fractions, including carbon black (CB), carbon nanotubes (CNT), and a mix of CB and CNT, through simulated lightning strike tests, followed by both non-destructive ultrasonic inspection and destructive sectioning to characterize the damage inflicted by the simulated lightning strike. Three-point flexural tests are performed to evaluate the residual strength retained by all CFRP specimens. Results show that lightning strike damage experienced varying levels of reduction for CFRP composite specimens containing conductive fillers in comparison to the baseline specimen without fillers. Notably, the delamination only penetrated to the interface between the 1st and 2nd layer for the specimen with 0.25 wt.% CNT in comparison to the baseline CFRP specimen for which the delamination penetrated to the interface between the 5th and 6th layer. Moreover, the retention of the flexural modulus increased from 26.5% to a maximum of 95.0% for the specimen with 0.25 wt.% hybrid CB and CNT. Yet, we show that using our chosen conductive fillers cannot fully eliminate lightning strike damage. Additionally, adding conductive fillers could compromise the flexural properties. We provide discussions on future recommendations on using conductive fillers for the lightning strike protection of CFRP composites.

36 MATERIALS SCIENCE↗

Total Mercury Analysis of Radioactive Waste Containing Multiple Mercury Species

In this work, a direct mercury analyzer (DMA) was used to analyze total mercury in radioactive waste samples containing methylmercury and other forms of mercury including Hg o (elemental) together with inorganic ionic mercury species and complexes. These samples were also analyzed using Cold Vapor Atomic Absorption Spectroscopy (CVAAS) and/or Inductively Coupled Plasma Mass Spectroscopy (ICMS). Comparative statistical evaluation of the results from spike solutions/simulants, liquid radioactive waste samples, and interlaboratory performance test samples demonstrated that the various methods generated accurate and/or equivalent total mercury data and equivalent precision (2σ ± < 20%). Triplicate total mercury analysis of an exemplar radioactive waste resulted in an average value of 54.1 mg/L (as Hg) using CVAAS, 55.1 mg/L using ICPMS and 56.0 mg/L using DMA. A primary advantage of the DMA in a radioactive environment is avoiding multi-step, labor-intensive, time-consuming and waste-producing sample preparation protocols needed for CVAAS and ICPMS. DMA was determined to be the preferred method for measuring total mercury in the Savannah River National Laboratory (SRNL) radioanalytical laboratory based on analytical performance combined with ease of use in a radiological containment unit.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

High-Temperature Corrosion of Chromia-Forming Ni-Based Alloys in CO 2 Containing Impurities

Future technologies require structural materials resistant to environmental degradation in high-temperature CO 2 -rich environments. In this work, we exposed several commercially available Ni-based alloys (230, 263, 282, 617, 625, and 740H) to atmospheric pressure gases intended to simulate the compositions expected in future direct-fired supercritical CO 2 power cycles. The alloys were exposed to 95% CO 2 + 4% H 2 O + 1% O 2 and the same gas containing 0.1% SO 2 at temperatures of 600, 650, 700, 750, and 800 °C for 2500 h. With minor exceptions, chromia scales formed on all alloys at all temperatures in the SO 2 -free gas, yielding parabolic growth rates that followed an Arrhenius temperature dependence. Behavior in the SO 2 -containing gas was more complex. Generally, the alloys performed well at temperatures of 650, 750, and 800 °C. While some alloys further performed relatively well across the whole temperature range, several of the alloys experienced chromia failure resulting in non-protective duplex oxide scales and high oxidation rates, at temperatures of 600 and 700 °C. Deviation from protective behavior was associated with internal sulfide formation and, additionally for the case of 600 °C, external sulfate formation. Extensive carburization accompanied growth of the non-protective duplex oxide scales, which made it more difficult for the alloy to recover after initiation of the sulfur-induced accelerated corrosion process. The thermodynamic and kinetic factors influencing the accelerated corrosion in the presence of sulfur are discussed. The results suggest that caution is required when assessing compatibility of Ni-based alloys for CO 2 -based systems when sulfur-based impurities are expected.

36 MATERIALS SCIENCE↗

Structural elucidation and immuno-stimulatory activity of a novel polysaccharide containing glucuronic acid from the fungus Echinodontium tinctorium

An immuno-stimulatory polysaccharide (EtISPFa) was purified from water extract of the fungus Echinodontium tinctorium. EtISPFa has an estimated weight average molecular weight (M w ) of 1354 kDa and is composed of glucose (66.2 %), glucuronic acid (10.1 %), mannose (6.7 %), galactose (6.4 %), xylose (5.6 %), rhamnose (3.1 %), fucose (1.8 %), and arabinose (0.2 %). It has multiple glycosidic linkages, with 3-Glcp (19.8 %), 4-GlcpA (10.8 %), 6-Glcp (10.7 %), and 3,6-Glcp (8.7 %) being the most prominent. NMR analysis showed that EtISPFa has a backbone containing mostly of 3-substituted β-glucopyranose with 4-substituted glucopyranosyluronic acid. Short side chains consisting of an average of two β-glycopyranose residues, connected through 1→6 linkages, are attached to the 6-position of about every 4th or 5th backbone glucose residue. EtISPFa is a novel glucuronic acid-containing β-glucan capable of significantly inducing the production of cytokines IL-17, IL-16, MIP-2, G-CSF,GM-CSF, LIF, MIP-1α, MIP-1β, and RANTES in vitro. EtISPFa should be further explored for its immuno-stimulatory activity in vivo.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Simultaneously improved J sc and V oc achieving 19.15% efficiency in ternary blend polymer solar cell containing a Y-type acceptor with thiophene based end groups

Simultaneously enhancing the short-circuit current density (J sc ) and open-circuit voltage (V oc ) of current state-of-the-art polymer solar cells (PSCs) containing wide bandgap polymers as donors and Y6 derivatives as acceptors is of great challenge but essential for further improvement of the photovoltaic performances. Here, in this work, two Y-type non-fullerene acceptors of BTP-T and BTP-TCl were designed and successfully synthesized with relatively weak electron-accepting thiophene based end groups, where blue-shifted absorption and upshifted LUMO energy levels were achieved to fill the well-known absorption gap at 700 nm of typical binary devices based Y-type molecules and rise the output voltage, respectively. Simultaneously increased J sc and V oc were achieved in ternary blend devices containing D18:BTP-eC9:BTP-TCl with a significantly improved PCE up to 19.15 %, which is over 7 % increase compared to the binary device. Our results illustrated the great potential of rational design of Y6 derivatives for constructing ternary PSCs to improve their performances.

36 MATERIALS SCIENCE↗

Rheology of fresh cement pastes containing polymer nanoparticles

Influences of polymer nanoparticles (PNPs) with varied charge densities on the rheological behaviors of fresh cement pastes (fcps) without and with polycarboxylate superplasticizer (PCE) were studied. In the blank fcp, the addition of PCE and highly anionically charged PNPs greatly decreases the yield stress and the plastic viscosity due to their large adsorption on cement that produces electrostatic repulsion and steric hindrance between cement grains. However, the non-adsorbing nonionic PNPs show a slightly opposite effect. In the PCE-containing fcp, both the anionic and nonionic PNPs become non-adsorbing on cement due to the stronger affinity of PCE to cement surface. In this way, the addition of the PNPs in the PCE-containing fcp slightly increases the yield stress and the plastic viscosity, but significantly decreases the pseudoplastic index, which is believed to result from the generation of the so-called depletion attractive force between cement grains induced by the non-adsorbing polymers.

36 MATERIALS SCIENCE↗

Autogenous shrinkage and hydration property of alkali activated slag pastes containing superabsorbent polymer

In this paper, the superabsorbent polymer (SAP) was applied as internal curing agent to study its effect on the autogenous shrinkage and hydration property of alkali activated slag (AAS) pastes. Liquid absorption and release processes of SAP in AAS pastes were characterized by {sup 1}H nuclear magnetic resonance ({sup 1}H NMR). Moreover, the microstructure and mechanical strength of AAS pastes containing SAP were also revealed. The results showed that the autogenous shrinkage of AAS pastes containing SAP was reduced by about 80.6%, 72.1% and 72.6%, respectively as the silicate modulus (Ms) increased from 0.8 to 1.4. The addition of SAP delayed the second exothermic peak, but increased the cumulative heat of AAS pastes. In addition, internal curing by SAP could promote the generation of C-A-S-H gels and hydrotalcite-like phases and increase the reaction degree of slag, particularly for AAS pastes with higher Ms, being attributed to the continuous release of entrained water and alkali activator solutions in SAP with the increase of hydration time. Furthermore, the addition of SAP would increase capillary pore size and pore volume of AAS pastes, and thus lead to the decrease of compressive strength.

36 MATERIALS SCIENCE↗

Polymeric ionic liquids containing copper(I) and copper(II) ions as gas chromatographic stationary phases for olefin separations

Copper(I) ions (Cu + ) are used in olefin separations due to their olefin complexing ability and low cost, but their instability in the presence of water and gases limits their widespread use. Ionic liquids (ILs) have emerged as stabilizers of Cu + ions and prevent their degradation, providing high olefin separation efficiency. There is limited understanding into the role that polymeric ionic liquids (PILs), which possess similar structural characteristics to ILs, have on Cu + ion-olefin interactions. Moreover, copper ions with diverse oxidation states, including Cu + and Cu 2+ ions, have been rarely employed for olefin separations. In this study, gas chromatography (GC) is used to investigate the interaction strength of olefins to stationary phases composed of the 1-hexyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide ([C 6 MIM + ][NTf 2 – ]) IL and the poly(1-hexyl-3-vinylimidazolium [NTf 2 – ]) (poly([C 6 VIM + ][NTf 2 – ])) PIL containing monovalent and divalent copper salts (i.e., [Cu + ][NTf 2 – ] and [Cu 2+ ]2[NTf 2 – ]). The chromatographic retention of alkenes, alkynes, dienes, and aromatic compounds was examined. Incorporation of the [Cu 2+ ]2[NTf 2 – ] salt into a stationary phase comprised of poly(dimethylsiloxane) resulted in strong retention of olefins, while its addition to the [C 6 MIM + ][NTf 2 – ] IL and poly([C 6 VIM + ][NTf 2 – ]) PIL allowed for the interaction strength to be modulated. Olefins exhibited greater affinities toward IL and PIL stationary phases containing the [Cu 2+ ]2[NTf 2 – ] salt compared to those with the [Cu + ][NTf 2 – ] salt. Elimination of water from both copper salts was observed to be an important factor in promoting olefin interactions, as evidenced by increased olefin retention upon exposure of the stationary phases to high temperatures. Furthermore, to evaluate the long-term thermal stability of the stationary phase, chromatographic retention of probes was measured on the [Cu 2+ ]2[NTf 2 – ]/[C 6 MIM + ][NTf 2 – ] IL stationary phase after its exposure to helium at a temperature of 110°C.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Enhanced crevice corrosion of stainless steel 316 by degradation of Cr-containing hollandite crevice former

This study explores the corrosion interactions between stainless steel 316 (SS316), a candidate nuclear waste canister material, and Cr-containing hollandite (Ba 1.15 Cr 2.3 Ti 5.7 O 16 ), a model ceramic nuclear waste form. The two materials were corroded in close proximity in 0.6 M NaCl solution at 90 °C for 28 days. Severe crevice corrosion was observed on the stainless steel surface after the corrosion experiment, which is likely associated with the rapid accumulation of Cr 3+ cations originating from both SS316 and the Cr-containing hollandite. Furthermore, the enhanced corrosion of SS316 by the corrosion products of hollandite is quantitatively explained using a classical crevice corrosion model.

36 MATERIALS SCIENCE↗

Anaerobic fungi contain abundant, diverse, and transcriptionally active Long Terminal Repeat retrotransposons

Long Terminal Repeat (LTR) retrotransposons are a class of repetitive elements that are widespread in the genomes of plants and many fungi. LTR retrotransposons have been associated with rapidly evolving gene clusters in plants and virulence factor transfer in fungal-plant parasite-host interactions. We report here the abundance and transcriptional activity of LTR retrotransposons across several species of the early-branching Neocallimastigomycota, otherwise known as the anaerobic gut fungi (AGF). The ubiquity of LTR retrotransposons in these genomes suggests key evolutionary roles in these rumen-dwelling biomass degraders, whose genomes also contain many enzymes that are horizontally transferred from other rumen-dwelling prokaryotes. Up to 10% of anaerobic fungal genomes consist of LTR retrotransposons, and the mapping of sequences from LTR retrotransposons to transcriptomes shows that the majority of clusters are transcribed, with some exhibiting expression greater than 104 reads per kilobase million mapped reads (rpkm). Many LTR retrotransposons are strongly differentially expressed upon heat stress during fungal cultivation, with several exhibiting a nearly three-log10 fold increase in expression, whereas growth substrate variation modulated transcription to a lesser extent. We show that some LTR retrotransposons contain carbohydrate-active enzymes (CAZymes), and the expansion of CAZymes within genomes and among anaerobic fungal species may be linked to retrotransposon activity. We further discuss how these widespread sequences may be a source of promoters and other parts towards the bioengineering of anaerobic fungi.

Genetics & Heredity↗

Quantification of active sites in yttrium containing dealuminated Beta zeolites during conversion of ethanol and acetaldehyde to butadiene

Here, in this work, yttrium containing dealuminated Beta zeolites (Y/deAlBeta) were synthesized and characterized by various spectroscopic techniques to improve understanding of ethanol upgrading over these materials. Characterization results indicate yttrium atoms partially condense with framework silanol nests formed during dealumination of parent Al-Beta supports. Active sites for conversion of ethanol and acetaldehyde to butadiene were quantified on a series of Y/deAlBeta catalysts (0.1–10 wt% yttrium) via ex situ chemisorption and transmission Fourier transformed infrared (FTIR) spectroscopy measurements by first measuring the integrated molar extinction coefficient (IMEC) for pyridine bound to Lewis acidic yttrium sites. In situ titrations with pyridine demonstrate that the number of sites quantified by ex situ chemisorption IR is quantitatively similar to the number of sites that catalyze butadiene formation, which varies (from 0.05 to 0.35) across the series of catalysts. In situ pyridine titrations impact butadiene site time yields (STY), but not crotonaldehyde STY, indicating that a distribution of yttrium sites is present, and that discrete yttrium site types participate in distinct steps in the pathway from ethanol to butadiene. Apparent kinetic parameters including activation energies and reaction orders were measured, these suggest differences in reactant (or reactant-derived intermediate) surface coverages result in higher STYs (per mol Y or per Lewis acidic Y site) for samples with low Y loadings relative to those with higher Y loadings. Isotopic labeling experiments evince the existence of other kinetically relevant steps in addition to the crotonaldehyde transformation to crotyl alcohol. Together, these findings provide further guidance into the heterogeneities in site structures in yttrium-containing zeolites and their relevance for the various steps in the pathway from ethanol to C 4 products useful for production of sustainable aviation fuel and renewable butadiene.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Synergic grain boundary segregation and precipitation in W- and W-Mo-containing high-entropy borides

The structures of W- and W-Mo-containing high-entropy borides (HEBs) are systematically studied by combining atomic-resolution transmission electron microscopy imaging, electron diffraction, and chemical analysis. Here, we reveal that W or W-Mo addition in HEBs leads to segregation of these elements to the grain boundaries (GBs). In the meantime, W- or W-Mo-rich precipitates also form along the GBs. Crystallographic analysis and atomic-scale imaging show that the GB precipitates in both W- and W-Mo-containing HEBs have a cube-on-cube orientation relationship with the matrix. With further strain analysis, the coherency of the precipitate/matrix interface is validated. Nanoindentation tests show that the simultaneous GB segregation and coherent precipitation, as a supplement to the grain hardening, provide additional hardening of the HEBs. Our work provides an in-depth understanding of the GB segregation and precipitation behaviors of HEBs. It suggests that GB engineering could be potentially used for optimizing the performance of high-entropy ceramics.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Fuel property evaluation of unique fatty acid methyl esters containing β-hydroxy esters from engineered microorganisms

Unique fatty acid methyl esters (FAME) containing ..beta..-hydroxy esters were produced using an engineered microorganism by glucose fermentation. This study investigated the properties of the unique FAME mixture both neat and in blends with conventional diesel, as well as properties of ..beta..-hydroxy esters. The unique FAME blend contained relatively shorter-chain FAME (average fatty acid chain carbon number 14.6) with 58 % monounsaturated fatty acids and 9 % saturated and monounsaturated ..beta..-hydroxy acid chains. The unique FAME had significantly lower distillation T90 (321 °C versus 352 °C) and higher cetane number (56.7 versus 52) compared to soy biodiesel. Cloud points were within method repeatability. Unexpectedly (because of the lack of methylene-interrupted double bonds), the unique FAME had low oxidation stability (1.5 h) as determined by Rancimat induction period. Stability could be improved through addition of commonly used antioxidants. We speculate that monounsaturated ..beta..-hydroxy FAME may be the source of this instability. Blends with conventional diesel up to 50 vol% showed similar kinematic viscosity (within method repeatability) as blends of conventional FAME. The unique FAME had no effect on distillation T90 even at the 80% blend level. A 30 vol% blend into conventional diesel had a Rancimat induction period of only 2 h, very nearly the same as the neat unique FAME sample. The addition of antioxidants produced blends of acceptable stability. Based on an assessment of the properties of individual ..beta..-hydroxy FAME molecules, they have higher boiling point, higher cloud point, lower cetane number, and potentially lower storage stability than analogous FAME not having the ..beta..-hydroxy group. Removing them from the fuel product in the production process may result in a biodiesel product with superior properties to what is on the market today.

09 BIOMASS FUELS↗

Electrochemical sulfate production from sulfide-containing wastewaters and integration with electrochemical nitrogen recovery

Electrochemical methods can help manage sulfide in wastewater, which poses environmental and health concerns due to its toxicity, malodor, and corrosiveness. In addition, sulfur could be recovered as fertilizer and commodity chemicals from sulfide-containing wastewaters. Wastewater characteristics vary widely among wastewaters; however, it remains unclear how these characteristics affect electrochemical sulfate production. Here, in this study, we evaluated how four characteristics of influent wastewaters (electrolyte pH, composition, sulfide concentration, and buffer strength) affect sulfide removal (sulfide removal rate, sulfide removal efficiency) and sulfate production metrics (sulfate production rate, sulfate production selectivity). We identified that electrolyte pH (3 × difference, i.e., 25.1 to 84.9 μM h –1 in average removal rate within the studied pH range) and sulfide concentration (16 × difference, i.e., 82.1 to 1347.2 μM h –1 in average removal rate) were the most influential factors for electrochemical sulfide removal. Sulfate production was most sensitive to buffer strength (6 × difference, i.e., 4.4 to 27.4 μM h –1 in average production rate) and insensitive to electrolyte composition. Together, these results provide recommendations for the design of wastewater treatment trains and the feasibility of applying electrochemical methods to varying sulfide-containing wastewaters. In addition, we investigated a simultaneous multi-nutrient (sulfur and nitrogen) process that leverages electrochemical stripping to further enhance the versatility and compatibility of electrochemical nutrient recovery.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Thermal cycling-driven microstructural changes of eutectic Al–Si phase change materials in SS304 containers revealed by multi-modal imaging

Aluminum-based Al–Si alloys are widely used as phase change materials (PCMs) in thermal energy storage (TES) systems owing to their high volumetric latent heat and superior thermal conductivity. However, their long-term reliability is limited by degradation processes that remain insufficiently understood. In this work, we employ a multimodal, correlative characterization framework to systematically resolve the degradation behavior of eutectic Al–Si PCMs in contact with SS304 containers under repeated thermal cycling. By integrating high-resolution electron microscopy, three-dimensional X-ray fluorescence (3D XRF) imaging, and differential scanning calorimetry (DSC), we directly link spatially resolved compositional and microstructural evolution to changes in thermophysical properties. The correlative analysis reveals that elemental leaching of Fe, Cr, and Ni from the stainless-steel container into the PCM drives the formation of intermetallic compounds (IMCs) both at the interface and within the bulk PCM, leading to pronounced compositional heterogeneity. These interfacial reactions and diffusion-induced transformations progressively destabilize the Al–Si eutectic, reducing the effective phase-transforming fraction. Consistent with these observations, DSC measurements show a decrease in melting temperature and latent heat of fusion with thermal cycling. These results underscore the critical influence of interfacial reactions and material compatibility on the stability, durability, and overall performance of Al–Si-based TES systems.

25 ENERGY STORAGE↗