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At least 631 records · Page 35

A new hypothesis for air loss in cement systems containing fly ash

Although there are many benefits gained from incorporating fly ash into concrete, carbon contamination in the fly ash has been shown to interfere with the efficacy of organic additives in an unpredictable manner. This work uses surface tension measurements to quantify the adsorption of air-entraining agents (AEA) onto cement and fly ash. Both the adsorption capacity of the adsorbents and the adsorption isotherms indicate that the fly ash particles, rather than the carbon itself, dominate adsorption in a carbon-contaminated ash in cement pore solution. We propose that adsorption onto fly ash particles and cement actually improve air entrainment via Pickering stabilization. While the carbon is still expected to contribute to air loss via hydrophobic adsorption of the surfactants, we suggest that the primary way in which the carbon interferes is by shielding surfactant-coated fly ash particles from participating in air development and Pickering stabilization during mixing.

36 MATERIALS SCIENCE↗

Measurement-induced purification in large- N hybrid Brownian circuits

Competition between unitary dynamics that scrambles quantum information nonlocally and local measurements that probe and collapse the quantum state can result in a measurement-induced entanglement phase transition. Here we study this phenomenon in an analytically tractable all-to-all Brownian hybrid circuit model composed of qubits. The system is initially entangled with an equal sized reference, and the subsequent hybrid system dynamics either partially preserves or totally destroys this entanglement depending on the measurement rate. Our approach can access a variety of entropic observables which are distinguished by the averaging procedure, and for concreteness we focus on a particular purity quantity for which the averaging is particularly simple. We represent the purity as a path integral coupling four replicas with twisted boundary conditions. Saddle-point analysis reveals a second-order phase transition corresponding to replica permutation symmetry breaking below a critical measurement rate. The transition is mean-field-like and we characterize the critical properties near the transition in terms of a simple Ising field theory in 0 + 1 dimensions. In addition to studying the purity of the entire system, we study subsystem purities and relate these results to manifestations of quantum error correction in the model. Here, we also comment on the experimental feasibility for simulating this averaged purity, and corroborate our results with exact diagonalization for modest system sizes.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Design Principles for Efficient and Stable Water Splitting Photoelectrocatalysts

Photoelectrochemical water splitting is a promising avenue for sustainable production of hydrogen used in the chemical industry and hydrogen fuel cells. The basic components of most photoelectrochemical water splitting systems are semiconductor light absorbers coupled to electrocatalysts, which perform the desired chemical reactions. A critical challenge for the design of these systems is the lack of stability for the majority of desired semiconductors under operating water splitting conditions. One strategy to address this issue is to protect the semiconductor by covering it with a stabilizing insulator layer, creating a metal–insulator–semiconductor (MIS) architecture, which has demonstrated improved stability. In addition to enhanced stability, the insulator layer may significantly affect the electron and hole transfer, which governs the recombination rates. Furthermore, the insertion of an insulator layer leads to the introduction of additional insulator/electrocatalyst and insulator/semiconductor interfaces. These interfaces can impact the system’s performance significantly, and they need to be carefully engineered to optimize the efficiencies of MIS systems. In this Account, we describe our recent progress in shedding light on the critical role of the insulator and the interfaces on the performance of MIS systems. We discuss our findings by focusing on the concrete example of planar n-type Si protected by a HfO 2 insulator layer and coupled to a Ni or Ir electrocatalyst that performs the oxygen evolution reaction, one of the water splitting half-reactions. To improve our fundamental understanding of the insulator layer, we precisely control the HfO 2 insulator thickness using atomic layer deposition (ALD), and we perform a series of rigorous electrochemical experiments coupled with theory and modeling. We demonstrate that by tuning the insulator thickness, we can control the flux and recombination of photogenerated electrons and holes to optimize the generated photovoltage. Despite optimizing the thickness, we find that the maximum generated photovoltage in MIS systems is often significantly lower than the upper performance limit, i.e., there are additional losses in the system that could not be addressed by optimizing the insulator thickness. We identify the sources of these losses and describe strategies to minimize them by a combination of improving the semiconductor light absorption, removing nonidealities associated with interfacial defects, and finding alternative insulators with improved charge carrier selectivity. Finally, we quantify the improvements that can be obtained by implementing these specific strategies. Our collective work outlines strategies to analyze MIS systems, identify the sources of efficiency losses, and optimize the design to approach the fundamental performance limits. Furthermore, these general approaches are broadly applicable to photoelectrochemical materials that utilize sunlight to produce value-added chemicals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Graduating Sustainable Industrial Decarbonization Solutions from the Laboratory to Real-World Deployments

Accelerating innovation and integration of industrial decarbonization technology solutions is crucial for achieving industry-wide net-zero greenhouse gas emissions targets. This can be accomplished in various ways through increased utilization of low-embodied carbon materials and the adoption of advanced manufacturing techniques in construction practices. At the National Renewable Energy Laboratory (NREL), we facilitate dialogue and action across all sectors to uncover industry needs to inform innovation, and explore ways we can help with implementation of emerging solutions in the real world. As an applied laboratory, NREL sits between academia and industry to fully bridge the gap from foundational science research to examining the feasibility of market applications. Integration of innovative technologies and solutions that are efficient, resilient, and grid-interactive will play a pivotal role in supporting a clean energy future. However, it is imperative that these solutions prioritize equitable outcomes, addressing the challenges faced by all communities. By embracing decarbonization, the construction industry can revolutionize itself, promoting sustainability, reducing carbon emissions, conserving resources, while enhancing performance and durability - all major steps toward a greener and more sustainable future.

cement↗

Test for BCS-BEC crossover in the cuprate superconductors

Abstract In this paper we address the question of whether high-temperature superconductors have anything in common with BCS-BEC crossover theory. Towards this goal, we present a proposal and related predictions which provide a concrete test for the applicability of this theoretical framework. These predictions characterize the behavior of the Ginzburg-Landau coherence length, $${\xi }_{0}^{{{{\rm{coh}}}}}$$ ξ 0 coh , near the transition temperature T c , and across the entire superconducting T c dome in the phase diagram. That we are lacking a systematic characterization of $${\xi }_{0}^{{{{\rm{coh}}}}}$$ ξ 0 coh in the entire class of cuprate superconductors is perhaps surprising, as it is one of the most fundamental properties of any superconductor. This paper is written to motivate further experiments and, thus, address this shortcoming. Here we show how measurements of $${\xi }_{0}^{{{{\rm{coh}}}}}$$ ξ 0 coh contain direct indications for whether or not the cuprates are associated with BCS-BEC crossover and, if so, where within the crossover spectrum a particular superconductor lies.

Materials Science↗

Cs retention and diffusion in C-S-H at different Ca/Si ratio

Cement and concrete are commonly used in the construction of repository sites for radioactive wastes. The correct isolation of those contaminants requires good adsorption and low diffusion rates. Both parameters are highly affected by many factors, such as pH, temperature or composition. The large variability of experimental conditions and formulations makes it extraordinarily difficult to tackle the influence of each of them independently in experimental samples. To this effect, molecular dynamics simulations have been employed in this study to investigate the role of the composition in the capacity to retain Cs and diffusivity of these ions in calcium silicate hydrate (C-S-H) gel pores. The results indicate that the adsorption of Cs ions is worsened at high Ca/Si ratios due to a lower interaction of the cations with the C-S-H surface, while hydrophilicity of the C-S-H nanopore rises, resulting in higher long-range ordering and lower diffusion coefficients of Cs ions.

36 MATERIALS SCIENCE↗

Silicon ion radiation as a viable surrogate for emulating neutron radiation damage in silicates

Abstract Nuclear power plants are aging around the world, and a precise assessment of irradiation damage in their components is needed. One key component, concrete, and specifically the silicates in its aggregates, can undergo significant expansion upon neutron radiation, which can lead to cracking and, ultimately, structural failure. However, assessing and predicting the extent of damage via neutron radiation is challenging due to reasons such as residual radioactivity and, most importantly, the high time involved. Here, we evaluate whether ion radiation can be a viable surrogate. Specifically, by employing Si 2+ ion radiations and a comprehensive multi-modal imaging protocol, we report mineral-specific responses for key silicates such as quartz, albite, anorthite, and microcline. We find that 10 MeV Si 2+ ions result in mineral expansions that are remarkably comparable to neutron radiation equivalent expansions (R 2 = 0.86, RMSE = 1.29%), opening up pathways towards rapid assessment of silicates subject to irradiation.

36 MATERIALS SCIENCE↗

Development and Validation of Quantitative Model-Based Image Reconstruction for NDE of Reinforced Steel-Lined Concrete Structures: Kal-El FY 2020

This project studied the capabilities of Model-Based Image Reconstruction (MBIR) and Machine Learning (ML) algorithms in the imaging and estimation of rebar corrosion from ultrasound signals. The application was challenging due to the introduction of a steel liner between the sensor and the concrete containing the rebar. The study focused in a synthetic specimen with a 6.35 mm thick steel liner, and a 19.05 mm diameter rebar at a depth of 44.5 mm and with four levels of corrosion; 0%, 20%, 50%, and 100% corrosion level. The corrosion was applied uniformly around the rebar, generating a ring in the perimeter of the rebar with different acoustic density. In order to generate a realistic synthetic dataset, we added random texture to the concrete of the synthetic specimens. This texture will mimic the variations encountered in real concrete specimens.We adapted our MBIR algorithm for the application and enhanced the algorithm to integrate in the physical model known specimen features, such as the steel liner thickness. The new MBIR method was able to cancel out reverberation from the steel liner and properly image the rebar. In particular, corrosion for the 50% and 100% cases were easily visible and quantitative metrics showed a slight separation for the 0% and 20% levels. The quantitative results were in agreement with the qualitative assessment. We also developed a ML XGBoost model to estimate corrosion level from the ultrasound signals. By combining the ML method with MBIR, we can pinpoint in the ultrasound signals the section that corresponds to the echoes from the rebar. The extract signals are processed by the XGBoost model for prediction. From each system scan, we obtain 15 predictions. The median prediction value is used as the final prediction. The True Acceptance Rate for the method is over 99%.

36 MATERIALS SCIENCE↗

A cost and community perspective on the barriers to microbiome data reuse

Microbiome research is becoming a mature field with a wealth of data amassed from diverse ecosystems, yet the ability to fully leverage multi-omics data for reuse remains challenging. To provide a view into researchers’ behavior and attitudes towards data reuse, we surveyed over 700 microbiome researchers to evaluate data sharing and reuse challenges. We found that many researchers are impeded by difficulties with metadata records, challenges with processing and bioinformatics, and problems with data repository submissions. We also explored the cost constraints of data reuse at each step of the data reuse process to better understand “pain points” and to provide a more quantitative perspective from sixteen active researchers. The bioinformatics and data processing step was estimated to be the most time consuming, which aligns with some of the most frequently reported challenges from the community survey. From these two approaches, we present evidence-based recommendations for how to address data sharing and reuse challenges with concrete actions for future work.

59 BASIC BIOLOGICAL SCIENCES↗

Uniaxial stress increases layer stacking disorder in calcium silicate hydrates with low calcium content

The long-term stress response of concrete is controlled by the intergrain and intragrain interactions of calcium-silicate-hydrates (C-S-H), nanocrystalline forms of tobermorites. To investigate both types of interactions, we examined the deviatoric stress response of 11 Å tobermorite powder with X-ray diffraction, finding that its layer stacking (i.e., sliding) disorder significantly increases. A similar experiment was performed on nanocrystalline C-S-H powders before and after applying a 360 MPa uniaxial stress. Layer stacking disorder (in the form of intragrain deformation) increases when there is low water content and when the basal spacing is large. We also find that grains with a smaller thickness-to-diameter aspect ratio are first to develop preferred orientation (in the form of intergrain sliding), facilitated by gel water. Furthermore, these findings show that intragrain deformations in C-S-H can occur at relatively low stresses and provide insights into the creep mechanism of C-S-H.

36 MATERIALS SCIENCE↗

Production of α' H -belite-CSA cement at low firing temperatures

A global increase in population creates a need for infrastructure development to stimulate economic growth and improve quality of life. Concrete plays a significant role in this development due to its availability and mechanical strength. Ordinary Portland cement (OPC) has been the most utilized binder in the construction industry since its formulation. However, OPC production has an enormous energy demand and generates large quantities of CO 2 . This research investigates the production of a clinker, containing mainly the hydraulically activated alpha'H-belite polymorph and calcium sulfoaluminate (ye'elimite or C4A3$\acute{S}$), at a lower firing temperature, using a combination of fluoride and boron oxide. This novel clinker addresses the problem of creating high strength cements at extremely low firing temperatures of 1000–1050 °C (a decrease of 450–500 °C as compared to OPC, and a decrease of 200–250 °C as compared to calcium sulfoaluminate (CSA) cement). This clinker reduces CO 2 emissions from energy consumption and by producing phases with lower limestone requirements. The combination of lower firing temperatures and clinker phases that require lower limestone requirements provide a means to reduce CO 2 emissions.

36 MATERIALS SCIENCE↗

Microstructural Simulation of Ion-Irradiated Natural Rocks and Minerals

This report details the contribution of Oak Ridge National Laboratory to the Nuclear Energy University Program (NEUP) project, "Rapid Characterization of Concrete Mineralogy using Multi-Scale Tools" led by the University of Illinois at Urbana-Champaign. To support the subsequent license renewal (SLR) of the US nuclear power plants (NPPs) fleet, the performance of concrete-forming aggregates against neutron irradiation needs to be assessed. Ion irradiation is proposed as a rapid, cost-effective surrogate method to full neutron irradiation testing. To complement the characterization of ion-irradiated rock specimens, ORNL has run finite-elements and fast-Fourier transform (FFT-based) simulations using the codes MARS and Microstructure-Oriented Scientific Analysis of Irradiated Concrete (MOSAIC). The main conclusion of this analysis is that the apparent post–ion-irradiation step-height underestimates the accumulated free radiation-induced volumetric expansion (RIVE) in the ion-implanted depth by about 15% at full amorphization and about 25% toward the beginning of the ion irradiation experiment. The discrepancy is explained by the fact that the step height is proportional to the sum of the RIVE (i.e., one third of the RIVE) and the irradiation-assisted plastic strains in the vertical direction (lower than two thirds of the RIVE). Because of the large lateral compressive stresses caused by the restraining effect of the unirradiated substrate, the stress field in the mineral grains and at the grain boundary (GB) in the ion-implanted layer is much different than the comparable stress field occurring during neutron irradiation. Hence, the mismatch RIVE causing cracks in the rock-forming minerals leads to different cracking patterns. Ion irradiation continues to be used as a rapid technique to assess the RIVE potential of rocks.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Mineralogical and microstructural alterations in a portland cement paste after an accelerated decalcification process

Cement paste leaching and concomitant decalcification is a common cause of concrete structure deterioration. Such alterations entail microstructural changes that condition concrete durability. This study analysed those changes in cement pastes exposed to accelerated decalcification, layer-by-layer, from the surface in contact with the leaching agent, 6 M NH{sub 4}NO{sub 3,} to the unaltered area. The microstructural changes were analysed with BSEM, MIP and BET whilst the mineralogical and nanostructural alterations in each layer were assessed with XRD, FTIR, {sup 29}Si and {sup 27}Al MAS NMR and BSD. Decalcification affected not only portlandite and CSH gel, but also the anhydrous clinker and ettringite, inducing major micro- and nano-structural changes, particularly in the two layers closest to the leaching agent. CSH gel decalcification was more intense in the outer layers where long chain gels co-existed with silicon rich gels. BDS, in turn, revealed differences between the amount of bound water in the surface interfacing with the leaching agent and in the leaching front. More specifically, larger numbers of water molecules were tightly bound to silanol groups in the outer, whereas hydroxyl group distribution was more orderly in the inner layers.

36 MATERIALS SCIENCE↗

Ultra-high gamma irradiation of calcium silicate hydrates: Impact on mechanical properties, nanostructure, and atomic environments

The concrete biological shield in a nuclear power plant receives ~100–200 MGy gamma dosage during an 80-year design life. However, precise changes in the mechanical properties and atomic environments of C-S-H at ultrahigh irradiation dosages have not been systematically documented. Here, we report that irradiation decreases C-S-H basal spacing (~ 0.6 ± 0.1 Å for 189 MGy) and increases its Young's modulus, which is attributed to the lower basal spacing as the nano porosity potentially increased and microporosity remained unchanged. Irradiation also decreased the molecular water content and increased hydroxyl groups in C-S-H, showing that interlayer water removal reduces the basal spacing. Finally, 1 H and 29 Si NMR results indicate some disorder in the local proton CaO-H species and slight depolymerization of the silicate structure. Together, these results indicate that the C-S-H gel stiffens upon ultrahigh gamma irradiation dosage, a finding which concerns long-term nuclear power plants operations worldwide.

1H NMR↗

Radiation-induced Alteration of Meta-chert

Concrete aggregate identified as “meta-chert” was irradiated with gamma-rays and neutrons. To identify the volume expansion of the aggregate under neutron irradiation, herein the following analyses were performed for pristine and irradiated α-quartz and meta-chert: X-ray diffraction (XRD)/Rietveld analysis, dimension change, water pycnometry, He-pycnometry, light optical microscopy (LOM), and scanning electron microscopy (SEM). From the difference of volume expansion observed from dimension change and water / helium pycnometry, the crack opening inside the aggregate subjected to irradiation was elucidated, and this was confirmed by LOM and SEM analysis. The crack contribution to the expansion of the aggregate was significant for neutron fluence > 6.99 × 1019 n/cm 2 , for E ≥ 0.01 MeV. Based on the XRD analysis, changes in lattice parameters were identified and the cell volume expansion was compared with the data by helium pycnometry. Based on the density change calculation and phase calculation data, the density of X-ray amorphous phase was consistent with that of expanded crystal α-quartz.

36 MATERIALS SCIENCE↗

Effect of chloride ingress on self-healing recovery of smart cementitious composite incorporating crystalline admixture and MgO expansive agent

Highlights: • Crack closure under wet/dry cycles in chloride solution is higher than the one in distilled water. • Element analysis shows that calcium is vital for crack healing either in water or chloride solution. • AFm is consumed by chloride ion to form Fs, and Fs were decomposed to AH{sub 3} by carbonation. • Soluble reactive silica reacts with calcium hydrate to form C-S-H gel to heal concrete cracks. • Expansion of magnesium hydroxide facilitates crack self-healing by interconnected network. In this study, the effect of chloride environment containing various concentrations of chloride ion (Cl{sup −}) on self-healing performance of pre-cracked cementitious composite containing crystalline admixture (CA) and MgO expansive agent (MEA) was investigated under wet-dry cycles in chloride solutions. The results revealed that the Cl{sup −} changed the mineralogy of self-healing products, and consequently, affected the crack closure ratio and mechanical strength recovery. When self-healing occurred in distilled water, a large amount of ettringite (AFt) were detected, whereas in Cl{sup −} solution, monosulfate (AFm) was consumed by Cl{sup −} to form Friedel's salt (Fs), and then the Fs was decomposed to Al(OH){sub 3}(AH{sub 3}) due to carbonation. During the multiphase conversion process, hydroxide (OH{sup −}) was released into crack solution, therefore the dissolved carbon dioxide (CO{sub 2}) concentration was increased. The carbonation of the crystals formed in cracks was accelerated with the volume expansion, which achieved rapid crack sealing but contributed little to the mechanical performance recovery.

36 MATERIALS SCIENCE↗

Characterization and effects of impurities on carbonate quantification in heterogenous matrices

Mineral carbonation simulates a natural weathering phenomena by breaking down silicates and oxides to form Ca & Mg carbonates. Various mineralization methods have been demonstrated as a potential technique to improve the quality of slags and tailings through neutralization and stabilization of problematic species to yield a product better suited for use in concrete. This study aims to characterize, quantify and analyze carbonates in various carbonated products such as mineralized CaCO 3 , CO 2 mineralized Steel Slags and Mine Tailings. More than 10 samples were analyzed for carbonate measurement and verification from industrial and academic partners that pioneer commercial CO 2 mineralization technologies. The samples were characterized primarily by using X-ray diffraction (XRD), Thermogravimetric Analyses (TGA), and Scanning Electron Microscopy (SEM) to gain insights into CaCO 3 content. A baseline characterization of lab-grade CaCO 3 and MgCO 3 also revealed important considerations for CaCO 3 measurement using TGA alone. The experiments using synthetic lab-grade samples also revealed that the presence of MgCO 3 /MgO can accelerate the decomposition of CaCO 3 and thus can affect measurement parameters. Lab-grade CaCO 3 samples dosed into steel slag and mine tailing also showed significant deviation in their decomposition behavior. These insights are used to inform the development of a standardized protocol for the measurement and verification of carbonate-bearing products.

97 MATHEMATICS AND COMPUTING↗

New Laboratory and Astrophysical Probes of Physics Beyond the Standard Model (Final Technical Report)

The first of these directions centers on new ideas in dark matter detection. As experimental scrutiny narrows the window for new physics at the weak scale, it has become apparent that the solution to the dark matter mystery may not reside there. Theoretical developments such as the hidden sector/valley paradigm have, at the same time, shown that compelling theories of dark matter reside below the weak scale. Searching for dark matter at lower mass scales requires looking beyond the current paradigm of dark matter direct detection based on nuclear recoils. It is the goal of this project to provide new ideas to guide the experimental program looking for light dark matter. I am actively proposing ideas for detecting dark matter as light as a meV, well beyond the current focus of GeV-TeV scale dark matter. Some of the ideas I have proposed, such as superconducting, superfluid, and polar material targets, are actively being developed into experiments. My group will provide the relevant calculations to determine dark matter reach, providing crucial input to experiment on which targets should be developed. We will also provide an effective field theory framework to understand which types of experiments are most sensitive to each interaction type. The second of these directions is on probes of dark matter substructure as a mean to constrain, or observe, models of dark matter. The standard ΛCDM paradigm assumes that the dark matter density perturbations are adiabatic, scale invariant, and produced during inflation. However, many standard models of dark matter will produce modifications of this prediction, such as axion models with symmetry broken below the inflationary scale. Remarkably, we have limited direct measurements of the dark matter clumpiness at mass scales below dwarf galaxies. This allows for the possibility of observing modifications from vanilla ΛCDM due to particle dynamics. In many cases, simulations of dark matter structure in the presence of non-scale invariant fluctu- ations are understudied or completely lacking. I plan to develop both theoretical predictions for small scale structure in models with additional matter power on small scales, as well as observa- tional probes of small scale halos or clumps. One idea I have been recently focused on is pulsar timing, though my group will pursue a variety of lensing and astrometric probes. Lastly, the most risky direction involves spacetime fluctuations from quantum gravity. I showed that if one assumes that metric fluctuations in the Minkowski vacuum, at a surface separating a region in and out of causal contact (which we call a “horizon”), are determined by standard thermodynamic considerations at horizon, these metric fluctuations are large enough to observe in an interferometer with similar sensitivity to LIGO. In a follow-up paper we showed that these assumption holds for the vacuum in AdS/CFT. In future work, I plan to connect this work to recent soft graviton results, to frame this work in a concrete Randall-Sundrum model, and to work out concrete phenomenological predictions from the model. This work unquestionably takes a less trodden path, and works well as part of a well-rounded portfolio of less and more risky ideas. Particle physics is currently at a juncture which requires bold exploration of qualitatively new directions. This proposal outlines some of my plans over the coming years in these directions, leaving room also for surprises.

79 ASTRONOMY AND ASTROPHYSICS↗