Distinct Hydration Research Articles

Preparation and carbon emission analysis of high-performance pavement concrete using waste gypsums

This study explores the potential of waste gypsum, specifically phosphogypsum (PG) and desulfurization gypsum (DG), as alternative materials in supersulfated cement-based concrete (SSCC) for low-carbon road construction. The research comprehensively investigates the effects of PG and DG on the mechanical properties, corrosion resistance, and water resistance of SSCC. Additionally, the hydration kinetics and microstructure of SSC are analyzed through isothermal calorimetry, X-ray diffraction, and scanning electron microscopy. The findings show that PG-modified SSCC outperforms DG-modified SSCC, with 26.9% and 28% improvements in compressive and flexural strengths, respectively. Both PG and DG contribute to enhanced corrosion resistance, particularly in acidic environments, due to the formation of distinct hydration products compared to traditional concrete. Microstructural analysis reveals denser structures with Ettringite (AFt) and calcium silicate hydrate. Moreover, the hydration process of SSC exhibits low heat release, mitigating cracking risks in outdoor applications. A comprehensive evaluation indicates that PG-modified SSCC not only offers superior mechanical properties but also demonstrates significantly reduced carbon emissions and energy consumption, highlighting its potential as a sustainable material for road concrete.

Experimental Evaluation of Concrete Blended with Eco-Friendly Bio-Sulfur as a Cement Replacement Material.

Bio-sulfur (BS), extracted from landfill bio-gas via microbial methods, was examined herein as a potential cement replacement material. The study developed five modified BS variants through limestone incorporation processes (sulfur-to-limestone ratios of 1:0.5, 1:1, 1:1.5, 1:3, and 1:5). The study revealed that modified BS with higher limestone ratios demonstrates significant workability and strength reductions of over 50% with increased content, leading to the adoption of a sulfur-to-limestone ratio of 1:1. The concrete specimens exhibited compressive strength improvements of up to 12% with increased BS content, while the UPV showed proportional increases with increased BS content that remained independent of the water/binder (W/B) ratio. Statistical analysis confirmed significance with p-values below 0.05. XRD analysis identified initial cement hydrate peaks at 3 d that evolved into distinct Mg-S hydrate and Ca-Al-S hydrate formations in the BS-containing specimens by 28 d.

A Comparative Study on Acoustic Characteristics of Methane and Tetrahydrofuran Hydrate-Bearing Sediments

Laboratory acoustic measurements of hydrate-bearing sediments serve as an important reference for the geological interpretation of seismic exploration data. Tetrahydrofuran (THF) hydrates are relatively easy to form with precise control of hydrate saturation, and they overcome the long time it takes for methane in sediments to form hydrate. However, when THF hydrates are used as a substitute for methane hydrate, their acoustic properties yield different results. This study reports the results of a series of laboratory experiments on the formation of methane and THF hydrate in quartz sand and the evaluation of their acoustic properties. It compares the experimental results with the results of calculations from micro-distribution models of the four hydrates using effective medium theory (EMT). Methane hydrate formed by the excess gas method has higher acoustic velocities than THF hydrate at 0–80% saturation, but at 80–100% saturation, the situation reverses, with THF hydrate having a higher wave velocity. The methane hydrate synthesis process follows a mixed micro-distribution, with grain coating predominating at low saturations, the pore-filling mixing mode dominating at medium saturations, and grain coating dominating at high saturations. In addition, THF hydrate has a slow-velocity growth at low saturation and is dominated by a pore-filling model and a load-bearing model at high saturation. We compared our experimental data with a compilation of similar published results to confirm their reliability and support our conclusions. Both hydrate types exhibit distinct micro-distributions across different saturations. Therefore, when testing the elastic characteristics of hydrate sediments, the distinct hydrate synthesis methods and micro-distribution should be considered, especially when using THF hydrate as an alternative to methane hydrate.

Distinctive source and hydration state of gold-ore−forming arc magmas

Distinctive source and hydration state of gold-ore−forming arc magmas

Unraveling the adsorption dynamics of asphaltene molecules on silica surfaces

Understanding the adsorption behavior of heavy oil components on reservoir solids is crucial for improving oil recovery, yet the molecular mechanism remains unclear. This study used molecular dynamics simulations to explore the adsorption kinetics and thermodynamics of asphaltene molecules on silica surfaces. The adsorption process was divided into three stages: free, adsorption, and equilibrium. In the adsorption stage, asphaltenes must pass through two dense hydration layers and adhere to the silica surface in a flat configuration. Carboxyl groups increase asphaltene hydrophilicity, raising interaction energy with water molecules and hindering adsorption. In addition, two distinct hydration layers of water molecules on the silica surface. The first hydration layer, with a peak density of 2000 kg m−3, was located around 0.6 nm from the surface, driven by hydrogen bonding between Si-OH groups and water molecules. The second layer, found at 1.44–1.80 nm, had a lower density of 1200 kg m−3, formed through hydrogen bonding between water molecules. This study aims to enhance the understanding of the physicochemical mechanisms governing oil droplet adsorption on silica surfaces, potentially informing the design of improved oil recovery strategies.

Unveiling the Performance of SCAN Functional for Studying the Hydrated Ion in Solution: A Hybrid Forces Molecular Dynamics Study of La3+ Hydration

ABSTRACTSCAN/molecular mechanics molecular dynamics (SCAN/MM MD) simulations have been employed to investigate the structural and dynamical properties of La3+ in aqueous solution. These simulations revealed the presence of two distinct hydration shells, with the first shell exhibiting a La‐O bond distance of 2.56 Å. The water molecules in this initial hydration shell displayed a mean residence time (MRT) of 208 ps, suggesting a less rigid structure. Five successful ligand exchange events occurred within a simulation duration of 100 ps. The stretching frequency of La‐O was found to be 331 cm−1, with a force constant of 92 N/m. Notably, the data obtained from the SCAN/MM MD simulation demonstrated good agreement with experimental findings.

Early-age hydration of tricalcium aluminate in chloride solutions

Understanding the kinetics and mechanisms involved in early-age hydration of tricalcium aluminate (C3A) in chloride solutions holds promise for implementing seawater-mixed concrete in the marine environment, as C3A remains the most reactive component of Portland cement (PC), affecting both PC and concrete's early-age hardening and long-term durability. Herein, we conducted a series of meticulously designed ex-situ and in-situ experiments to elucidate the intricate hydration behaviors of C3A in various chloride solutions. The results reveal that C3A exhibits distinct hydration kinetics and structural evolution processes in different solutions. The rapid precipitation of alumino-ferrite-mono (AFm) and C3AH6 phases contributes to the swift development of hydration heat and storage modulus in water and NaCl solutions, with a slight acceleration observed in the later one. Conversely, the formation of C3AH6 is delayed in CaCl2 and MgCl2 solutions before 20 min, with the subsequent precipitation of Cl-AFm enhancing its later production, particularly in CaCl2 solutions. Ab-initio calculations further elucidate that the acceleration effect of Cl ions originates from the ionization and structurization of hydrated surface Ca ions. However, this positive effect is significantly offset by Cl pairing with counterions, resulting in a dramatic adverse effect of solution Ca ions originated from the negative entropy effect of structuralized water molecules and electrostatic repulsion with like-charged surface Ca ions and solvent dipoles. Our findings provide valuable insights for sustainable and durable designs on cement-based materials mixed with seawater.

Impact of basic oxygen furnace slag on the hydration microstructure, mechanical properties, and carbon emissions of supersulfated cement

Supersulfated cement (SSC) is recognized as a cementitious material with low CO2 emissions, consisting predominantly of ground granulated blast-furnace slag (GGBS) and a minor activator content. The production of GGBS production constitutes the primary source of CO2 emissions in SSC. In contrast, carbon emissions from the production of basic oxygen furnace slag (BOFS) are lower, and BOFS inherently exhibits substantial carbonization potential. Therefore, in this study, BOFS is employed as a replacement for GGBS in formulating an innovative low-emissions binder denoted as BOFS-modified supersulfated cement (BMSC). This study investigates the influence patterns of BOFS substitution for GGBS on the strength properties of BMSC. Furthermore, a series of experiments involving QXRD, TGA, SEM, and MIP were conducted to systematically investigate the mechanistic impact of BOFS on the hydration microstructure of BMSC. The findings reveal that substituting 10 % of GGBS with BOFS contributes to an enhancement in both flexural and compressive strength of specimens at 7 and 28 days. BOFS exerts a positive influence on the formation of ettringite in BMSC. The C2S and C4AF within BOFS also demonstrate distinct hydration activity. Additionally, BOFS can reduce large pores in the early hydration paste and contribute to narrowing the average pore size. Moreover, the evaluation of the Global Warming Potential (GWP) demonstrates that the replacement of slag with BOFS can lead to a further reduction of up to 30 % in the carbon emissions of SSC.

Unraveling the Hydration Shell Structure and Dynamics of Group 10 Aqua Ions.

We present ab initio simulations based on subsystem DFT of group 10 aqua ions accurately compared against experimental data on hydration structure. Our simulations provide insights into the molecular structures and dynamics of hydration shells, offering recalibrated interpretations of experimental results. We observe a soft, but distinct second hydration shell in Palladium (Pd) due to a balance between thermal fluctuations, metal-water interactions, and hydrogen bonding. Nickel (Ni) and platinum (Pt) exhibit more rigid hydration shells. Notably, our simulations align with experimental findings for Pd, showing axial hydration marked by a broad peak at about 3 Å in the Pd-O radial distribution function, revising the previously sharp "mesoshell" prediction. We introduce the "hydrogen bond dome" concept to describe a resilient network of hydrogen-bonded water molecules around the metal, which plays a critical role in the axial hydration dynamics.

Molecular Origin of Distinct Hydration Dynamics in Double Helical DNA and RNA Sequences.

Water molecules are essential to determine the structure of nucleic acids and mediate their interactions with other biomolecules. Here, we characterize the hydration dynamics of analogous DNA and RNA double helices with unprecedented resolution and elucidate the molecular origin of their differences: first, the localization of the slowest hydration water molecules─in the minor groove in DNA, next to phosphates in RNA─and second, the markedly distinct hydration dynamics of the two phosphate oxygen atoms OR and OS in RNA. Using our Extended Jump Model for water reorientation, we assess the relative importance of previously proposed factors, including the local topography, water bridges, and the presence of ions. We show that the slow hydration dynamics at RNA OR sites is not due to bridging water molecules but is caused by both the larger excluded volume and the stronger initial H-bond next to OR, due to the different phosphate orientations in A-form double helical RNA.

Pore-scale visualization of hydrate dissociation and mass transfer during depressurization using microfluidic experiments

Natural gas hydrate is a potential low-carbon energy resource. Extracting this resource efficiently remains a challenge, due to the intricacies involved in multiphase reactive transport during hydrate dissociation. This study employs microfluidic experimental techniques to observe pore-scale interactions during depressurization-induced hydrate dissociation, utilizing high-resolution spatial and temporal imagery. Supervised machine learning algorithms segmented these microscopic images, enabling the analysis of phase saturation changes and hydrate dissociation rates. The study identifies two distinct hydrate forms in microfluidic chips: hydrate films and crystals, each exhibiting unique dissociation characteristics. Hydrate films decomposed rapidly in response to pressure reductions below equilibrium with the dissociation rate of O(10−1 %/s) under stationary gas–water conditions. When considering gas–water migration, the gas encapsulated in the hydrate film will be displaced by water, leading to a reduced dissociation rate. The hydrate crystal dissociation is much slower with the dissociation rate of O(10−3 %/s) under stationary gas–water conditions compared to the hydrate film, hindered by mass transfer limitations. Gas-water migration can enhance crystal dissociation. The formation and expansion of gas microbubbles under depressurization accelerated hydrate dissociation within a confined temporal and spatial range, which was known as the self-promotion mechanisms. Significantly, depressurization-induced gas slug flow increases the dissociation rate by more than one order of magnitude, compared to that in stationary gas–water conditions. The depressurization process played a significant role, not only by facilitating thermodynamic feasibility for hydrate dissociation but also by inducing the critical gas slug flow. These results of the present study provide theoretical guidance for improving natural gas hydrate production efficiency.

Hydration Programmable, Shape Memorable Artificial Muscles for Antagonistic Movements

AbstractShape memory polymers (SMPs) capable of generating various deformations from anisotropic temporary shapes to permanent shapes have been emerging as soft robots. However, traditional SMPs cannot imitate the antagonistic movement of human skeletal muscles due to their modulus limitations in shape programming and recovery process. Herein, hydration programmable shape memory polymer (HP‐SMP)‐based fibers that can undergo reversible actuation by assembling antagonistic pairs are reported, where the shape programming of the antagonist muscle relies on the contraction of agonist muscle. HP‐SMP fibers are composed of tunicate cellulose nanocrystals (TCNCs) reinforced semi‐interpenetrating polymer networks. Leveraging their distinctive structure and hydration programmability, the HP‐SMP fibers exhibit large actuation strain (−60%) and high work capacity (751 J kg−1), allowing for reversible actuation under constant stress. Most significantly, the continuous antagonistic movements of HP‐SMP fibers assembled into artificial limbs are demonstrated to realize humanoid motion. This work provides new possibilities for replicating a series of lifelike human movements through the biomimetic design of antagonistic pairs of artificial muscles, utilizing renewable and sustainable biosourced materials.

Assessment of CO2 Capture in FA/GGBS-Blended Cement Systems: From Cement Paste to Commercial Products

The cement industry’s intricate production process, including kiln heating and fossil fuel use, contributes 5–8% of global CO2 emissions, marking it as a significant carbon emitter in construction. This study focuses on quantifying CO2 capture potential in blended cement systems through the utilisation of phenolphthalein and thermalgravimetric methodologies. Its primary objective is to assess the CO2 absorption capacity of these blended systems’ pastes. Initial evaluation involves calculating the carbon capture capacity within the paste, subsequently extended to estimate CO2 content in the resultant concrete products. The findings indicate that incorporating ground granulated blast-furnace slag (GGBS) or an ettringite-based expansive agent did not notably elevate carbonation depth, irrespective of their fineness. Conversely, the introduction of fly ash (FA) notably augmented the carbonation depth, leading to a substantial 36.4% rise in captured CO2 content. The observed distinctions in carbonation behaviour primarily stem from variances in pore structure, attributable to distinct hydration characteristics between GGBS and FA. Thermal analysis confirms the increased stabilisation of CO2 in FA blends, highlighting the crucial influence of material composition on carbonation and emission reduction. Incorporating both GGBS and FA notably diminishes binder emissions, constituting almost half of PC-concrete emissions. Initially, 60% GGBS shows lower emissions than 50% FA, but when considering CO2 capture, this emission dynamic significantly changes, emphasising the intricate influence of additives on emission patterns. This underscores the complexity of evaluating carbonation-induced emissions in cementitious systems.

Influence of ion and hydration atmospheres on RNA structure and dynamics: insights from advanced theoretical and computational methods.

RNA, a highly charged biopolymer composed of negatively charged phosphate groups, defies electrostatic repulsion to adopt well-defined, compact structures. Hence, the presence of positively charged metal ions is crucial not only for RNA's charge neutralization, but they also coherently decorate the ion atmosphere of RNA to stabilize its compact fold. This feature article elucidates various modes of close RNA-ion interactions, with a special emphasis on Mg2+ as an outer-sphere and inner-sphere ion. Through examples, we highlight how inner-sphere chelated Mg2+ stabilizes RNA pseudoknots, while outer-sphere ions can also exert long-range electrostatic interactions, inducing groove narrowing, coaxial helical stacking, and RNA ring formation. In addition to investigating the RNA's ion environment, we note that the RNA's hydration environment is relatively underexplored. Our study delves into its profound interplay with the structural dynamics of RNA, employing state-of-the-art atomistic simulation techniques. Through examples, we illustrate how specific ions and water molecules are associated with RNA functions, leveraging atomistic simulations to identify preferential ion binding and hydration sites. However, understanding their impact(s) on the RNA structure remains challenging due to the involvement of large length and long time scales associated with RNA's dynamic nature. Nevertheless, our contributions and recent advances in coarse-grained simulation techniques offer insights into large-scale structural changes dynamically linked to the RNA ion atmosphere. In this connection, we also review how different cutting-edge computational simulation methods provide a microscopic lens into the influence of ions and hydration on RNA structure and dynamics, elucidating distinct ion atmospheric components and specific hydration layers and their individual and collective impacts.

One-part eco-friendly alkali-activated concrete – An innovative sustainable alternative

The primary objective of this study is to develop an eco-friendly one-part alkali-activated concrete (OPAAC) by incorporating a combination of fly ash (FA), ground granulated blast furnace slag (GGBS), and micro silica (MS). In this investigation, the proportion of MS is maintained at 20% of FA, while the maximum replacement of FA with GGBS is set to 60%, varying in 20% intervals (i.e., 0%, 20%, 40%, and 60%). Further, the natural aggregates (NA) are substituted with recycled coarse aggregates (RCAs), ferrochrome slag aggregates (FCSAs), or a combination of both. The influence of GGBS and alternative aggregates (RCAs, FCSAs) on the mechanical properties of OPAAC is thoroughly examined. To provide a comprehensive assessment, the properties of OPAAC are compared against Ordinary Portland Cement (OPC) concrete (CC) of equivalent grades. Additionally, microstructural and mineralogical investigations are conducted to determine the formation of distinct hydration products, utilizing scanning electron microscopy (SEM) and X-ray diffractometry (XRD) techniques. In OPAAC containing FA, the primary hydration products identified are alkaline alumino silicate hydrates (CASH and NASH). As the GGBS content increases, calcium silicate hydrate (CSH) becomes the predominant hydration product. Furthermore, in order to assess the sustainability of OPAAC, an analysis of embodied CO2 emissions is performed, and the results are compared with CC and alkali-activated concrete. Notably, OPAAC comprising 40% FA replaced with GGBS, 50% RCAs, and 50% FCSAs demonstrates the most favourable mechanical properties and exhibits lower CO2 emissions.

“On‐Water” Synthesis of Sterically Congested γ‐Ketophosphine Oxides Featuring a CF3‐ and P(O)‐Tetrasubstituted Carbon Center

AbstractThe distinctive hydrophobic hydration effect in the aqueous solution contributes to the success of the phospha‐Michael reaction between β‐CF3‐β,β‐disubstituted enones and diarylphosphine oxides, providing an access to biologically relevant γ‐ketophosphine oxides bearing a sterically highly congested CF3‐ and P(O)‐tetrasubstituted carbon center. More importantly, the resulting products could be further transformed into densely functionalized γ‐ketophosphine oxides containing a CF3‐ and P(O)‐tetrasubstituted carbon center.

Microscopic Mechanism of Proton Transfer in Pure Water under Ambient Conditions.

Water molecules and the associated proton transfer (PT) are prevalent in chemical and biological systems and have been a hot research topic. Spectroscopic characterization and ab initio molecular dynamics (AIMD) simulations have previously revealed insights into acidic and basic liquids. Presumably, the situation in the acidic/basic solution is not necessarily the same as in pure water; in addition, the autoionization constant for water is only 10-14 under ambient conditions, making the study of PT in pure water challenging. To overcome this issue, we modeled periodic water box systems containing 1000 molecules for tens of nanoseconds based on a neural network potential (NNP) with quantum mechanical accuracy. The NNP was generated by training a dataset containing the energies and atomic forces of 17 075 configurations of periodic water box systems, and these data points were calculated at the MP2 level that considers electron correlation effects. We found that the size of the system and the duration of the simulation have a significant impact on the convergence of the results. With these factors considered, our simulations showed that hydronium (H3O+) and hydroxide (OH-) ions in water have distinct hydration structures, thermodynamic and kinetic properties, e.g., the longer-lasting and more stable hydrated structure of OH- ions than that of H3O+, as well as a significantly higher free energy barrier for the OH--associated PT than that of H3O+, leading the two to exhibit completely different PT behaviors. Given these characteristics, we further found that PT via OH- ions tends not to occur multiple times or between many molecules. In contrast, PT via H3O+ can synergistically occur among multiple molecules and prefers to adopt a cyclic pattern among three water molecules, while it occurs mostly in a chain pattern when more water molecules are involved. Therefore, our studies provide a detailed and solid microscopic explanation for the PT process in pure water.

Development of sulfate-based smart water for improving the oil recovery from the calcite formation: New insights from molecular simulation

Wettability plays a huge role in the process of oil displacements, particularly in highly complex oil-wet carbonate reservoirs. Recently, sulfate ions were witnessed to have a great potency to alter the wetting state of calcite. Though the role of sulfate ion studied extensively, still the mechanism of their wettability modification is yet to be fully understood. It is expected due to the complex surface chemistry of rock in the presence of monovalent and divalent ions. In this study, we constructed a rock-oil-brine model at a molecular level and run the simulation on the wettability dynamics with various ions. The most abundant surface structure of calcite {1014}, was considered for this atomistic simulations. The model oil consisted of n-heptane and 10% octanoate ion as a polar component and sulfate-based salts were used as smart water. Two distinct hydration layers were found on the calcite surface. The contact angle measurements were made to find the effectiveness of smart water solutions in altering the wettability of the surface. Monovalent cations were observed to form a strong electric-double-layer while the divalent cations were preferred to get distributed in the bulk; most of them were attached to polar oil ions removing them from the calcite surface thus changing the wettability.

Sequence patterns and signatures: Computational and experimental discovery of amyloid-forming peptides.

Screening amino acid sequence space via experiments to discover peptides that self-assemble into amyloid fibrils is challenging. We have developed a computational peptide assembly design (PepAD) algorithm that enables the discovery of amyloid-forming peptides. Discontinuous molecular dynamics (DMD) simulation with the PRIME20 force field combined with the FoldAmyloid tool is used to examine the fibrilization kinetics of PepAD-generated peptides. PepAD screening of ∼10,000 7-mer peptides resulted in twelve top-scoring peptides with two distinct hydration properties. Our studies revealed that eight of the twelve in silico discovered peptides spontaneously form amyloid fibrils in the DMD simulations and that all eight have at least five residues that the FoldAmyloid tool classifies as being aggregation-prone. Based on these observations, we re-examined the PepAD-generated peptides in the sequence pool returned by PepAD and extracted five sequence patterns as well as associated sequence signatures for the 7-mer amyloid-forming peptides. Experimental results from Fourier transform infrared spectroscopy (FTIR), thioflavin T (ThT) fluorescence, circular dichroism (CD), and transmission electron microscopy (TEM) indicate that all the peptides predicted to assemble in silico assemble into antiparallel β-sheet nanofibers in a concentration-dependent manner. This is the first attempt to use a computational approach to search for amyloid-forming peptides based on customized settings. Our efforts facilitate the identification of β-sheet-based self-assembling peptides, and contribute insights towards answering a fundamental scientific question: "What does it take, sequence-wise, for a peptide to self-assemble?".

Surface area and size distribution of cement particles in hydrating paste as indicators for the conceptualization of a cement paste representative volume element

The conceptualization of a representative volume element (RVE) of hardened cement paste for numerical homogenization of mechanical problems rests on identifying the largest discernible microstructural feature, i.e. unreacted cement grains. While the particle size distribution (PSD) of anhydrous cement is a well-controlled production parameter, the size evolution of a representative cement grain throughout hydration remained unresolved. This study analyzes digitized 3D cement paste microstructures obtained from X-ray micro-computed tomography, coupled with CEMHYD3D hydration model, and segmented by image-processing tools, to obtain the full PSD and specific surface area evolutions of unreacted grains throughout hydration. Results provided indicate a representative grain size in the range of 30−40μm regardless of hydration elapsed, implying a cement paste RVE should amount to 150−200μm to realistically represent cement grains. The PSD shape remained self-similar and two distinctive hydration regimes were identified, differing in dissolution rate and specific surface area decrease, correlating with calcium sulfate reactivity peak. Both measures provide easily accessible microstructural features that may be used for constructing artificial RVEs of hardened cement paste in micromechanical models and related simulations, resting on experimental data.