Hydrate Composition Research Articles

Insights on the Bonding Mechanism, Electronic and Optical Properties of Diamond Nanothread-Polymer and Cement-Boron Nitride Nanotube Composites.

The success of composite materials is attributed to the nature of bonding at the nanoscale and the resulting structure-related properties. This study reports on the interaction, electronic, and optical properties of diamond nanothread/polymers (cellulose and epoxy) and boron nitride nanotube/calcium silicate hydrate composites using density functional theory modeling. Our findings indicate that the interaction between the nanothread and polymer is due to van der Waals-type bonding. Minor modifications in the electronic structures and absorption spectra are noticed. Conversely, the boron nitride nanotube-calcium silicate hydrate composite displays an electron-shared type of interaction. The electronic structure and optical absorption spectra of the diamond nanothread and boron nitride nanotube in all configurations studied in the aforementioned composite systems are well maintained. Our findings offer an electronic-level perspective into the bonding characteristics and electronic-optical properties of diamond nanothread/polymer and boron nitride nanotube/calcium silicate hydrate composites for developing next-generation materials.

Influence of polypropylene fibers on the tensile mechanical properties of calcium silicate hydrate: molecular simulation.

This research assesses the influence of polypropylene (PP) fibers, both homopolymer and hydroxylated (PPOH), on the tensile properties of calcium silicate hydrate (C-S-H) composites through molecular dynamics (MD) simulations. Our models explore C-S-H matrices integrated with PP and PPOH fibers at varying polymerization degrees. The results demonstrate that both PP and PPOH fibers significantly influence the tensile strength and Young's modulus of the composites. Notably, PPOH fibers contribute to more substantial mechanical enhancements than PP, attributed to the increased polarity and enhanced intermolecular interactions from the hydroxyl groups. The study reveals a nonlinear relationship between polymer additive content and mechanical performance, with optimal properties at a polymerization degree of 20. Additionally, stress-strain analysis indicates that PPOH composites exhibit superior ductility and fracture energy, particularly at polymerization degrees of 20, showing enhanced ultimate strain and fracture energy by up to 9.6% and 13.9%, respectively, compared to PP counterparts. These results highlight the crucial role of tailored polymer additive composition and chemical modifications in maximizing the mechanical efficacy of C-S-H-based materials, enhancing their durability and structural performance. All MD simulations were conducted using LAMMPS. The models employed a combination of Clayff and Cvff force fields. During the entire tensile simulation, the system was configured under the NPT ensemble at 300K.

Molecular dynamics study of Gr(GO)/C-A-S-H composites at different temperatures: optimization of structural, dynamic and mechanical properties of civil engineering materials

In recent years, composites have been widely used in engineering fields, where nanomaterials such as graphene (Gr) and graphene oxide (GO) have potential advantages as interfacial modifiers in enhancing the properties of composites. However, the relationship between the interfacial structure and the mechanical properties of the nanocomposites is not clear, and the behavior of the composites may differ significantly at different temperatures. This study aims to investigate in depth the interfacial structure, dynamics, and mechanical properties of Gr, epoxy group-containing (-O) and hydroxyl group-containing (-OH) graphene oxide and calcium aluminosilicate hydrate (C-A-S-H) composites at different temperatures using molecular dynamics. The effect of nanomaterial composition on the interfacial chemical bonding network is revealed. The local chemical structures of bridging aluminum [Al(Q2b)] and interlayer aluminum (Alw) show different changes at different temperatures. Elevated temperature promotes the hydrolysis of interlayer water molecules to form hydroxyl groups, which affects the formation of chemical bonding networks.Al(Q2b) favors Gr and C-A-S-H linkages, whereas Alw favors GO and C-A-S-H bonding. Temperature changes lead to different chemical bonding connections and altered atomic motions. At the interface, Al atoms form a more stable chemical bonding network, which improves the interaction strength at the interface. Different composite models exhibited different mechanical properties at high temperatures and introducing epoxy and hydroxyl groups enhanced the plastic deformation of the composites. Structural analyses showed that temperature changes affected the molecular structure and interfacial bonding effects of the composites, which in turn affected the mechanical properties of the materials. At different temperatures, GO-O/C-A-S-H has higher tensile strength and Young's modulus, which can resist the degradation of performance caused by thermal expansion to a certain extent, and ensure the stability and safety of the structure, so it is more practical. These findings provide important insights to deepen the understanding of composite properties and have positive implications for future composite design and applications.

The Influence of Retreated Lithium Slag with a High Content of Alkali, Sulfate and Fluoride on the Composition and the Microstructure of Autoclaved Aerated Concrete.

In this paper, the possibility of retreated lithium slag (RTLS) with a high content of alkali, sulfate and fluoride as a partial replacement for fly ash (FA) to produce autoclaved aerated concrete (AAC) was investigated. The influence of the RTLS dosage on the AAC performance were examined. The composition and microstructure of hydrates as well as the microstructure of the RTLS-FA-based AAC compositions were determined by XRD, FTIR, TG-DSC and SEM. The results illustrated that the incorporation of RTLS changed the crystal structure and the microstructure of the tobermorite. With increased RTLS contents, the morphology of tobermorite was changed, and the grass-like tobermorite gradually transformed into network-like tobermorite. The newly formed tobermorite improved the mechanical performance of the AAC. Compared with the RTLS10, the content of tobermorite in the RTLS30 increased by 8.6%.

Temperature-Dependent Structural Properties of Nickel and Cobalt Selenite Hydrates as Solar Water Evaporators.

Solar water evaporation offers a promising solution to address global water scarcity, utilizing renewable energy for purification and desalination. Transition-metal selenite hydrates (specifically nickel and cobalt) have shown potential as solar absorbers with high evaporation rates of 1.83 and 2.34 kg∙m-2∙h-1, but the reported discrepancy in evaporation rate deserves further investigation. This investigation aims to clarify their thermal stability for applications and determine the underlying mechanisms responsible for the differences. Nickel and cobalt selenite hydrate compositions were synthesized and investigated via thermogravimetric analysis, X-ray diffraction, and Raman spectroscopy to assess their temperature-induced structural and compositional variations. The results reveal distinct phase transitions and structural alterations under various temperature conditions for these two photothermal materials, providing valuable insights into the factors influencing water transportation and evaporation rates.

Effect of microscale C–S–H on the properties of Portland cement and hydration kinetics analysis at different curing temperatures

Microscale calcium–silicate–hydrate (C–S–H) is easily accessible and readily storable, enabling a cleaner production process of cement-waste grinding and simple chemical synthesis technology. However, the temperature effects of microscale C–S–H require further exploration. In this study, we evaluated the impact of microscale C–S–H admixture on the properties of Portland cement at different curing temperatures. Microscale C–S–H can not only increase the early strength of cement pastes, but also achieve high strength in the long term. Adding microscale C–S–H to cement can effectively reduce the apparent activation energy Ea of hydration products and accelerate the reaction of C3S and C2S with water and form more hydration products. At a curing temperature of 10 °C, the microscale C–S–H increased the 1 d compressive strength by 70.0% and shortened the hydration induction period by 1.2 h. Microscale C–S–H also increased the 12 h hydration degree by 38.1%. Microscale C–S–H promoted the formation of CH and xonotlite-like C–S–H and changed the composition of hydrates, although the effects diminished with increasing curing temperature. This paper offers theoretical and fundamental data on the usage of microscale C–S–H as an admixture in cement-based materials.

Performance of the one-part geopolymer stabilized soft clay under acids attack

The evolution of globalization and rapid industrialization, coupled with intensive human activities, leads to a significant release of acidic gases and particles (e.g., NOX and SO2) is unavoidable. These emissions eventually result in dry and wet acid depositions due to atmospheric circulation. This infiltration of acidic elements alters the chemical properties of water systems, thereby deteriorating ground stability. The economically developed soft clay areas face considerable threats from these acid environmental attacks. This study focused on employing a ''one-part'' geopolymer (OPG) comprising ground granulated blast furnace slag (GGBFS), fly ash (FA), and solid sodium hydroxide (NH) to stabilize the soft clay. Simultaneously, the deterioration behavior of OPG stabilized soft clay under two different acids (HNO3 and H2SO4) with various pH values (pH of 2, 4, and 6) and varied immersion periods up to 240 days was evaluated including the mass loss, neutralization depth (ND), pH value, and unconfined compressive strength (UCS). Additionally, scanning electron microscopy (SEM) and X-ray energy spectrometry (EDS) characterized the evolution of microstructure and hydrate composition of OPG-stabilized soft clay post varied acid immersion. The results highlighted the superior acid resistance of the stabilized soft clay with an 80:20 GGBFS/FA ratio compared to other ratios. The presence of significant hydration products, such as calcium silicate hydrates (C–S–H), calcium aluminate (aluminosilicate) hydrates (C-A-(S)–H), and sodium aluminosilicate hydrates (N-A-S-H), was observed in the OPG stabilized soft clay. In addition, the contents of Si in the OPG played a significant role in enhancing the acid resistance of the OPG stabilized soft clay. Based on these experimental results, two proposed mechanisms detailed the deterioration and acid resistance of the OPG stabilized soft clay under HNO3 and H2SO4 attack. The findings of this study contribute to advancing scientific comprehension concerning the acid resistance of the OPG stabilized soft clay in ground improvement practices.

Study of the kinetics of methane-carbon dioxide exchange in gas hydrates below the ice melting point. Experimental data and computational model

Currently, gas hydrates are considered to be a potential resource of natural gas in the future. Vast quantities of gas hydrates deposits are located in the deep sea or in the permafrost zone. Among the other potential methods for extracting natural gas from these deposits is the injection of CO2 into a hydrate-bearing reservoir. This method assumes that carbon dioxide will replace methane molecules in the clathrate framework, so this method may be able to provide long-term burial for greenhouse gas CO2 along with the getting of burning gas. Understanding the kinetics of this process might be crucial for assessing the feasibility of implementation of this technology, but there is currently no clear understanding about the applicability of standard equations for heterogeneous reactions to describe the kinetics of this process. In this paper, we present some recent kinetic data on CH4/CO2 exchange at temperature below the ice melting point, focusing on the composition of hydrates. We also propose theoretical explanations for the obtained data.

Simultaneous impregnation and microencapsulation of CaCl2 using silica gel and methyl cellulose for thermal energy storage applications

Thermal energy storage utilizing the adsorption of moisture from air is a promising energy storage technology due to its high energy density and minimum heat losses. Salt hydrates and salt hydrate composites, such as calcium chloride (CaCl2) and CaCl2-based composites, have shown favourable energy storage properties in this area of research. However, these materials have shown issues with stability due to swelling and deliquescence. In this work, CaCl2 was stabilized using three methods: impregnation into silica gel, encapsulation in methyl cellulose, and both impregnation and encapsulation stabilization techniques used simultaneously. Therefore, three CaCl2-based composites were synthesized. For the first composite, silica gel was impregnated with CaCl2. For the second composite, CaCl2 was encapsulated by methyl cellulose. For the third composite, silica gel was impregnated with CaCl2 and the CaCl2 was encapsulated with methyl cellulose. These samples were structurally characterized using scanning electron microscopy as well as Brunauer-Emmett-Teller (BET) to determine surface area, pore size distribution and nitrogen adsorption isotherms at 77 K. Water vapour adsorption isotherms were also determined at 25 °C for different relative humidities by dynamic vapor sorption (DVS). Similarly, LiCl-based composites were also synthesized and examined in this work, but issues of deliquescence, swelling, and agglomeration made the materials impractical to work with. To determine the prepared materials’ thermal energy storage performance, 2–6 g of each sample was tested in a lab-scale apparatus. This process uses the exothermic adsorption of moisture from ambient air in an open thermal energy storage system. The CaCl2 impregnated silica gel that was encapsulated in methyl cellulose showed reasonably high stability and energy storage performance after 3 hydration and dehydration cycles with minimum agglomeration. An energy storage density of 241 kWh/m3 (0.87 GJ/m3) and specific energy of 630 Wh/kg (2268 kJ/kg) was achieved with this material for 90% inlet relative humidity after a regeneration at 90 °C.

Failure mechanism of steel fiber pullout in UHPC affected by alternating cryogenic and elevated variation

This paper investigates the pullout response of straight and hooked-end steel fiber embedded in Ultra-high Performance Concrete (UHPC) subjected to alternating cryogenic (−170 °C) and elevated (200 °C) temperature variation. The temporal evolution of Acoustic Emission (AE) parameters and failure behavior during the pullout process were monitored in situ using the AE test. Additionally, changes in the UHPC microstructure were also evaluated. Results showed that in addition to the UHPC matrices exposed to elevated temperature, the compressive and flexural strength of UHPC matrices subjected to single or multiple cycles were generally higher than those at ambient temperature. Whereas the bond strength/pullout energy of straight fiber increased with a single cycling exposure of UHPC specimens to either cryogenic or elevated temperature, the improvement in the pullout performance of the hooked-end fiber was obtained only after the post-cryogenic thawing of specimens. Moreover, the exposure to an increased number of temperature-variation cycles caused the pullout strength and energy of both fiber groups to gradually decrease. Nonetheless, the pullout performance of the hooked-end fiber was significantly and consistently superior to that of the straight fiber, regardless of the exposure temperature or cycles. The AE test confirmed that the pullout process of both fibers was mainly characterized by tensile failure, with a marginal occurrence of shear failure for the hooked-end fiber. When the UHPC was exposed to various temperatures, the fiber pullout behavior was predominantly influenced by the physical structure of the fibers, thermal deformation proclivity of the matrix, and the competition between mechanisms such as pore moisture phase change, secondary hydration, and the composition of hydrates.

Molecular Dynamics Simulation and Experimental Study of Mechanical Properties of Graphene-Cement Composites.

To investigate the mechanical properties of graphene (G) and calcium silicate hydrate (C-S-H) composites in different directions, molecular dynamics (MD) simulations and experiments were used, and the effects of temperature, loading rate, and graphene defects were also investigated. The experimental results show that the addition of graphene can improve the flexural, compressive, and tensile strength of the composite. The results of molecular dynamics simulation show that the addition of graphene in x and z directions can enhance the tensile strength of G/C-S-H in three directions, while the addition of graphene in y direction can reduce the tensile strength of G/C-S-H. At the same time, the tensile strength of G/C-S-H decreases with the increase in temperature and increases with the increase in loading rate. Meanwhile, the mechanical properties of G/C-S-H can be improved using a certain concentration of monatomic vacancy defects, diatomic vacancy defects, and S-W defects.

ВЛИЯНИЕ ИЗВЕСТНЯКА В ЦЕМЕНТЕ НА СТРУКТУРУ И МОДУЛЬ УПРУГОСТИ ТЯЖЁЛОГО БЕТОНА

The beginning of the 21st century in Russia was marked by the intensification of activities aimed at adapting Russian construction standards to European ones. In this connection, they cancelled the decision taken in the Soviet Union not to introduce limestone additives into binders in the new GOST 31108 “Cements for general construction. Technical conditions”. Moreover, in 2003 the Russian GOST allowed the production of CEM II/A-I with limestone content from 6 to 20%, and in 2016 – introduced also CEM II/B-I with limestone content from 21 to 35%. However, earlier, the studies of V.V. Timashev’s school proved that the use of limestone additive in the dosage up to 5% positively affects the phase composition of cement stone and makes only a stabilizing effect when it is increased to 10%.The introduction of limestone admixture in cement above 10% starts to significantly affect the phase composition of hydrates, elastic modulus and Poisson's ratio of concrete, therefore it should be used in cement composition above 5% only after additional tests of concrete composition intended for operation in strictly specified conditions.

CoCl2·6H2O crystal growth and its spectral characteristics

For the first time, a crystal of cobalt (II) chloride hexahydrate has been obtained, the size and quality of which have made it possible to study its faceting and spectral characteristics. The temperature dependence of the cobalt chloride solubility has been determined in the temperature range 29–44 °C. The temperature range of the transition area of change in the composition of equilibrium crystalline hydrates of cobalt chloride from CoCl2·6H2O to CoCl2·2H2O has been established. A CoCl2·6H2O crystal has been grown from a water solution, and its main transmission bands in the wavelength range of λ = 200–1400 nm and thermal stability have been estimated.

On the use of one-part geopolymer activated by solid sodium silicate in soft clay stabilization

The application of geopolymers in ground improvement has garnered significant attention in recent years. However, most geopolymer preparations have focused on the two-part method, which not only has negative environmental impacts but also falls short of meeting practical requirements. This study aimed to address these limitations by employing solid sodium silicate (Na2O·nSiO2, n is the molar ratio, NS) to activate binary precursors (fly ash [FA] and ground granulated blast furnace slag [GGBFS]), along with water, to synthesize a one-part geopolymer (OPG) for soft clay stabilization. The primary factors on the properties of the OPG binder were firstly identified through macro- and micro-tests. Subsequently, the optimization of the OPG mixing proportion was achieved by reducing the molar concentration of NS, and was further used for soft clay stabilization. The effects of the FA/GGBFS ratio (0, 0.1, and 0.2), curing period (7, 14, and 28 days), and binder content (0.15, 0.20, and 0.25) on the mechanical properties of the OPG-stabilized soft clay were then evaluated using unconfined compressive strength (UCS) tests. Furthermore, mercury intrusion porosimetry (MIP), scanning electron microscopy with energy dispersive X-ray spectrometry (SEM-EDS), and X-ray diffraction (XRD) techniques were employed to examine the evolution of microstructure, hydrate composition, and mineral/phase of the OPG-stabilized soft clay samples. The experimental results indicated that an appropriate OPG stabilizer proportion was achieved with an FA/GGBFS ratio of 0.1, water/precursor ratio of 0.8, molar ratio of NS of 1.0, and molar concentration of 3 mol/L. The high-early-strength feature of OPG binder contributed to the rapid strength development of the stabilized soft clay at an early age. A noticeable pozzolanic reaction was observed in the OPG-stabilized soft clay sample with an FA/GGBFS ratio of 0.1. Additionally, a binder content of 0.20 was recommended for the stabilization of soft clay due to its optimal balance between economic benefits and meeting the required UCS criteria in soil stabilization. Finally, a reliable nonlinear relationship between UCS and porosity of OPG-stabilized soft clay was established to assess the mechanical properties and stabilization effects of the OPG-stabilized soft clay for practical applications. This study greatly enhances the scientific understanding of geopolymerization in the OPG system by using a combination of the binary precursor of FA and GGBFS and the solid NS activator. It sheds light on the stabilization mechanism of OPG-stabilized soft clay. The outcomes of this study make a valuable contribution to the advancement of environmentally friendly soil stabilizers, promoting green and low-carbon practices in the field of ground improvement.

The hydraulic interface towards the anti-fatigue performance of fiber-calcium silicate hydrate composites under cyclic loading

The hydraulic interface towards the anti-fatigue performance of fiber-calcium silicate hydrate composites under cyclic loading

Dissociation of gas hydrates in different heating schemes

We present experimental and theoretical research into the dissociation and combustion behavior of methane hydrate tablets and powders of double gas hydrates methane-ethane, methane-isopropanol, and methane-propane using different heat supply schemes. Powder pressing allows significantly changing the porosity, the resistance of gas filtration through the pores, as well as the hydrate dissociation rate. To improve the combustion efficiency, it is necessary to conduct comprehensive studies on use of different schemes of heat supply. In the experiments with pressed tablets of methane hydrate, we observed stable combustion. The double gas hydrate powders showed stable combustion in a muffle furnace. The maximum dissociation rate was observed in the case of a thin (2–3 mm) methane-isopropanol hydrate burned in a muffle furnace. The data obtained for the hydrate dissociation and combustion can help predict the impact of the component composition of gas hydrates and thermal conditions around the samples.

Gas Hydrates: Applications and Advantages

Gas hydrates are promising components for a wide range of industries and the national economy. This paper outlines the gas hydrate application areas with the greatest potential. Gas hydrates of methane, ethane, propane, carbon dioxide and freon were investigated. Double gas hydrates were found to be coming into use. Natural and artificial hydrates are now being exploited. The main properties and component composition of hydrates, as well as their extraction methods are described. The key aspects of using hydrates in the energy industry, gas chemistry and petrochemistry, heat exchange systems and fire safety management are highlighted. These specific aspects were identified by analyzing the known experimental findings, results of mathematical modeling, bench and field tests, as well as trial runs of industrial systems. The recent advances in science and technology in this field were analyzed. The range of tasks that need to be tackled to improve the efficiency of using gas hydrates are defined.

Physicochemical and Mechanical Behavior of the One-Part Geopolymer Paste Exposed to Hydrochloric and Sulfuric Acids

This paper aims to assess the durability of one-part geopolymer (OPG) pastes exposed to acidic environments. Two different acids (HCl and H2SO4) with different pH values (pH of 2, 4, and 6) were used to simulate the acidic environment in the current study. Acid resistance of the OPG paste activated by sodium hydroxide [NaOH (NH)] and sodium metasilicate [Na2SiO3 (NS)], respectively, was assessed in terms of pH variation, mass change, visual appearance, deterioration depth, and compressive strength loss for varied immersion periods (∼120 days). The scanning electron microscopy with energy dispersive X-ray spectrometry (SEM-EDS) and mercury intrusion porosimetry (MIP) tests were employed to investigate the evolution of porosity, morphological change, and hydrate composition for the varied immersion times. The experimental results revealed that due to the formation of a dense structure, the NS-activated OPG paste had better resistance to the acid attack compared with the NH-activated paste. It was also found that the gypsum crystals formed in the sample immersed in H2SO4 solution could fill the open pores and adhere to the surface of the sample, which reduced the further acid attack to some extent. However, the expansion properties of gypsums would lead to a loss of mechanical performance at the later immersion period. Furthermore, higher porosity of the OPG paste developed as the pH value of the acid solution decreased, thereby inducing the loss of mass and compressive strength and the increase of deterioration depth. Finally, as the immersion age and acid concentration increased, decalcification in the sample tended to occur, which caused a greater loss of compressive strength and a higher porosity. The outcome of this study could provide guidance for the application of the novel material in acid soil layer improvements or acid-resistant geotechnical structures.

Experimental and Simulation Study for the Dissociation Behavior of Gas Hydrates─Part II: sII Mixed Gas Hydrates

This study is an extension of our research on the dissociation behavior of sI CH4 hydrates (Part I). In this study, investigations of the dissociation of binary and multicomponent structure II hydrates were carried out. A novel approach involving in situ and ex situ Raman spectroscopic measurements together with molecular dynamics simulations were applied for a systematic assessment of the hydrate dissociation and gas release behavior due to the destabilization of hydrate cavities. The hydrate decomposition was induced by thermal stimulation to mimic the warming of oceans and atmosphere brought by climate changes. The interactions between the released gas, aqueous phase, and hydrates were described. The results demonstrated that in the vicinity of the hydrate surface, the liquid phase was oversaturated with the gas molecules and some unstable partial hydrate cavities were also formed. Consequently, the release of gas was temporarily stopped or very slow. Throughout the process, the hydrate underwent decomposition–reformation–continuing decomposition until the crystal disappeared. A faster breakdown of small cavities (512) was recorded, leading to an increase in the large-to-small cavity ratio during dissociation. Moreover, the results indicated a faster release of CH4 molecules compared to C3H8 over the dissociation process of the sII CH4–C3H8 hydrate. This could be due to the higher diffusivity of CH4 molecules from the hydrate surface to the gas phase as well as its lower potential to stabilize the cavities compared to C3H8. The release of CH4 molecules was also faster compared to CO2 and C2H6 molecules in the sII mixed hydrate, leading to changes in the hydrate composition throughout the process.

Synergic effect of defects on carbon nanoparticles under interaction with calcium silicate hydrate composites

One- and two- dimensional carbon nanoparticles, i.e. graphene and CNT, are amongst the most potent additives in cementitious matrices. Their potential lies within the higher hydration degree, nano-filler effect and cracking-bridging effect that are only realized with a strong connection between the cementitious matrix and graphene. Here, Density functional theory (DFT) and molecular dynamics (MD) used to determine the nature of the interactions between the Tubermorite 14 Å and graphene. We observed that the carbon atoms on the periphery of various types of defects on the surface of a graphene nanosheet and carbon nanotube can form electrophile regions that adsorb silicate chains within the cementitious matrix, forming SiOC covalent bonds between the two species. Single vacancies are highly likely to bond with the silicate chains, with a bond energy of −90 kcal/mol at 1.5 Å length, which is also the case for the silicate – carbon nanotube (CNT) interactions. This is accompanied by the adsorption of Ca ions in Calcium Silicate Hydrates (CSH) on O atoms of functional groups in graphene interactions at the intralayer space, increasing the bond energy between the two nanostructures to 120 kcal/mol. Molecular dynamics (MD) simulations confirm the consolidation of the CSH – graphene around the two interactions, which causes a significant reduction in the mobility of the nanoparticle within the cementitious matrix. These findings provide essential information from the interactions within the interlayer and intralayer regions of CSH with carbon nanoparticles at the molecular level.