Silicate Chains Research Articles

Unveiling the dissolution mechanism of calcium ions from CSH substrates in Na2SO4 solution: Effects of Ca/Si ratio

The decalcification behavior of calcium silicate hydrate (CSH) under sulfate attack poses a critical challenge to the long-term durability of cement-based infrastructure, yet understanding its underlying microscopic mechanisms remains elusive. This study employs molecular dynamics to compare the differences in calcium ion dissolution capability of CSH substrates with varying Ca/Si ratios under sulfate solution exposure. The results show that the dissolution amount and dissolution efficiency of Ca are positively correlated with Ca/Si, and the root cause depends on the basic structure of CSH. With the increase of Ca/Si, the electronegativity of CSH decreases, and the adsorption capacity and stability of cations weaken. Meanwhile, Ca ions are less limited by the silicate chain coordination, water molecules are more likely to invade the substrate interior and replace the Ca ions. This research aims to provide a molecular basis for cement production and durability applications in marine engineering.

Polysomatic intergrowths between amphiboles and non-classical pyriboles in magnetite: Smallest-scale features recording a protracted geological history

Abstract Non-classical pyriboles (NCPs) have tetrahedral silicate chains (Ibeam) of multiplicity higher than single (pyroxene) or double (amphibole) Ibeams and are known from amphiboles in altered mafic-ultramafic complexes. NCPs, their polysomatic sequences, and inherent chain-width disorder are petrogenetic tools for interpreting igneous and metamorphic processes. Magnetite, a refractory mineral that can trap and preserve NCPs is a major constituent of iron oxide-copper-gold (IOCG) deposits. We undertook a nanoscale study to show that NCPs and amphiboles are hosted within magnetite cores from the Jatobá Ni-bearing IOCG deposit, Carajás Mineral Province, Brazil. Monoclinic amphiboles and NCPs form polysomatic intergrowths or occur as sparse inclusions along {111}magnetite. There are two chemical populations of amphiboles: Mg-Fe- and Ca-(Al)-amphiboles, the latter including Ce-bearing Mg-hornblende and (ferro)tschermakite. The occurrence contains one of the widest ranges of chain silicates ever recorded, from simple intergrowths of single to triple Ibeam zippers, including pyroxene slabs, to longer NCP polysomes up to 15-Ibeam chains. Clinojimthompsonite (Cjim) is observed for the first time within magnetite. Although no discrete polysomes could be defined, the NCP-amphibole intergrowths have compositions between Mg-Fe amphiboles and Cjim based on Ibeam averages of 2.5–2.7. Relationships between increase in the number of C and A cations from amphibole (2-Ibeam) to n chain silicates (nIbeam) are formulated as nIbeam = T(2 + n) = C(5 + 3n) = A(1 + n), n = integer. Empirical models of crystal structures, validated by STEM simulation, are shown for 4- and 5-Ibeam chain silicates. Co-crystallization of double- and triple-chain silicate structures with rhythmic intergrowths as larger blocks along b is often accompanied by rhythmic Ca-Fe zonation along a, supporting primary NCP crystallization via self-patterning during amphibole growth within magnetite in a close-to-equilibrium system. Chain-width disorder is documented from defects including planar faults, derailments, jogs, and swells. Violations of zipper termination rules indicate primary growth rather than replacement. Amphibole-NCPs inclusions support a multi-stage evolution for Jatobá magnetite. They formed during the first cycle of magnetite overprinting within a mafic/ultramafic lithology that records syn-shearing events. Subsequent formation of calcicamphiboles, including Ce-bearing species, indicate IOCG-related fluids at the onset of mineralization. (Ferro) tschermakite formed at ~7.5 kbar during high-pressure shearing is preserved during main ore deposition. The multi-stage amphibole-NCPs generations in magnetite revealed by our nanoscale study emphasize the interpretive value of magnetite for overprinting events in terranes with protracted geological histories. Analogous NCPs are likely to be abundant in magnetite from magmatic-hydrothermal deposits hosted by greenstone belts and altered mafic/ultramafic complexes. Likewise, discovery of Ce-rich hornblende provides new avenues to understand the early, alkali-calcic alteration stages of IOCG systems and models for REE incorporation into, and subsequent release from chain silicates.

Effect of alumina on formation mechanism and structure characteristic of sodium calcium silicate compounds with different stoichiometric coefficients

In order to illustrate the effects of Al2O3 on silicate structure for synthesizing sodium calcium silicate compounds, the formation characteristics, lattice parameters, molecular structure and element chemical state of sodium calcium silicates with different Al2O3 proportions through solid-state reaction were investigated using XRD, SEM-EDS, Raman spectroscopy and XPS analyses. Increasing the Al2O3 content facilitates the formation of Na2CaSiO4 and converts the polymorph of Na2Ca6Si4O15 from γ-type into β-type. The product particles aggregate to form clumps by increasing the Al2O3 content when the molar ratios of Na2O and CaO to SiO2 are 0.5 and 1.5, and the network orderliness of silicates deteriorates to form glassy phase at the low CaO and Na2O contents. Al2O3 can engage in the bonding process with silicate crystals to produce a finite solid solution. Increasing the Al2O3 porportion is advantageous for facilitating the participation of [AlO6] in the Si-O-Al bonding reaction, which leads to the depolymerization of [Si2O7]6-, [Si3O10]8- and [Si6O18]12− and promotes the formation of silicate chains of [SiO4]4- and [Si2O7]6-. Moreover, increasing the contents of Na2O and CaO promote the formation of [AlO4] and the depolymerization within silicate chains, which increases the bonding number of Si-Oter and Al-Oter and then reduces the binding energies of Si2p and Al2p orbits.

Using waste to improve the weak: Recycled seashell as an ideal way to regulate the interfacial transition zone in biochar-cement composites

The strategy of partially substituting cement with carbon-negative biochar to fabricate biochar-cement composites can represent a promising approach to reducing the carbon emissions of the construction industry. However, the detrimental impact on strength development from excessive biochar incorporation remains a significant challenge. To address this issue, this study pioneers a strategy to modify wood waste-derived biochar using seashell waste for enhancing its binding with the cement matrix. Employing a mechanochemical process, the shell-modified biochar was synthesized using oyster shell (OS) and wood waste (WW). The compressive strength of cement composites incorporating 5 wt% modified biochar improved by 3.9–17% compared to the referenced biochar. Even with high biochar incorporation (30 wt%), the compressive strength increased by 58.2% upon modifying the biochar at the OS/WW ratio of 1:9 (10SBC). The modified biochar refined the pore structures, accelerated the hydration kinetics, improved the degree of hydration, and fostered the development of the C-S-H gel network with a longer silicate chain and a higher polymerization degree. Furthermore, the strength enhancement of the biochar-cement composites was attributed to the improved micro-mechanical properties at the interfacial transition zone (ITZ), which increased the volume fraction of high-density C-S-H by 64.4–112% and decreased the low-density C-S-H fraction by 41.8–52.6%. Notably, 10SBC demonstrated a superior improvement due to its cohesive bond with the C-S-H gel and the concurrent densification of C-S-H in the ITZ, which was facilitated by the growth of Ca-/Al-rich hydration products. Overall, this study synergistically upcycled wood and seashell waste into value-added cement additives, thereby achieving strength enhancement of the cement composites.

New insights into the hardening mechanism of calcium silicate hydrates under creep deformation: A reactive molecular simulation study

Understanding the time-dependent behaviour of calcium silicate hydrates (C-S-H) under stresses is crucial for unraveling the microscopic creep behavior of concrete and its consequences on the evolution of nanostructure of C-S-H. In this study, the structural evolution of C-S-H nanostructure under stress was investigated using reactive molecular dynamics and stress perturbation technique. Under sustained stress, C-S-H nanostructure undergoes a relaxation process leading to a creep deformation and transitioning the system towards a more energetically stable state. The process was comprehensively examined under shear stress through a detailed analysis of the system's potential energy. A hardening phenomenon was observed within calcium silicate layers throughout this relaxation process, categorizing in three distinct stages. in Stage I, structural reorganization occurred in the silicate chains, progressing towards a stable state by reducing non-bonded interactions. The calcium-oxygen ionic bonds within the intralayer were strengthened in Stage II, leading to a decrease in bonding energy. Finally, the interface between calcium silicate layers and the interlayer contributed to overall structural stability in StageIII.

Multi-step nucleation of C-S-H: DFT simulation on silicate oligomerization and Si(Qn) evolution dynamics

Understanding the nucleation processes of calcium-silicate-hydrate (C-S-H) is fundamental to advancing the performance of cement. This study employs Density Functional Theory (DFT) to reveal the initial stages of C-S-H formation by focusing on silicate oligomerization. It examines the progression from monomer silicate species to the precursor formation, containing a range of silicate tetrahedra. Through DFT simulations, free energy changes and barriers of oligomerization reactions up to pentamers are obtained, unveiling an anionic condensation mechanism that establishes the kinetic and thermodynamic profile of this transformation. Observations reveal a dynamic evolution of Si species, with Si(Q3) indicating a transient presence, suggesting an intricate pathway towards the well-established silicate chain structure of C-S-H. This study provides detailed computational insight into the energy barriers, reaction pathways, and the thermodynamics of C-S-H formation, contributing substantial knowledge to the field of cement chemistry and its multi-step nucleation theory.

APTES/Calcium silica hydrate nano-hybrid composites with enhanced mechanical properties

Reducing the cement content in the concrete mix by developing cementitious materials with enhanced properties can contribute considerably to cut the CO2 emissions produced by the cement industry. In this work, we used a bottom-up approach to enhance the mechanical performance of the calcium silicate hydrate (C-S-H), by the covalent bonding of the 3-aminopropyltriethoxysilane (APTES), to create a nano-hybrid C-S-H/APTES. The intercalation of APTES within the C-S-H contributes to increase the bulk modulus by 35 % due to the stiffening along all the lattice directions. The stiffer behavior along a- and b- lattice directions is due to the formation of covalent bonds between the APTES molecules and the non-bonding oxygens of the C-S-H, blocking the silicate chain relaxation and increasing the overall stiffness of the ab-plane. In the c-direction, the stiffening is attributed to the densification of the hydrogen bond network in the interlaminar space caused by the APTES intercalation.

Elucidating the role of magnesium in alkali-silica reaction: Performance and mechanisms

Alkali-silica reaction (ASR) is a major concrete deterioration causing volume expansion, cracking, and hence degradations in the strength and permeability of concrete structures. Despite a variety of ASR mitigation approaches having been investigated, the successful use of chemical admixture is limited to lithium salts, which have negative impacts on cement hydration and shrinkage behavior of concrete. To explore alternative substances for effective and economic ASR mitigation, the role of magnesium nitrate in mortars containing reactive aggregate is investigated at varying Mg/alkali ratios from 0 to 3.0 in terms of volume expansion, cracking behavior, silica dissolution, and modifications of ASR products. The results indicate that, at a Mg/alkali ratio of 0.74, the expansion and surface cracking density of the ASR-impacted mortar were decreased by 21.1 % and 39.1 %, respectively, which is superior to the efficacy of lithium nitrate. The 51.3 % less silica dissolution from aggregate, suppressed ASR gel formation, fewer Q3 polymerization sites in the silicate chains, less packed structure, and reduced alkali/Si ratio of the reaction products elucidate the underlying mechanisms across multiple length scales.

Reinforcing cementitious composites with nitrogen-doped graphene: insights into molecular interactions and interfacial behavior

Graphene materials are useful functional fillers in cementitious materials. They are essential in creating intelligent cementitious materials, enabling the construction of internal conductive networks and the addition of thermoelectric properties. The success of this process hinges on the functional filler's compatibility with the cement matrix, which must be excellent to ensure optimal results. In this study, we delved into the interactions between nitrogen-doped graphene and calcium silicate hydrate (C-S-H), which is the principal binding phase in cementitious materials, employing Density Functional Theory (DFT) calculations. In this study, we explored diverse nitrogen doping configurations and levels, while concurrently analyzing the influence of calcium cations at the C-S-H matrix interface. The findings indicate that nitrogen atoms in doped graphene interact considerably with nucleophilic oxygen atoms on silicate chains, forming covalent N-O bonds with high bonding energies (length 1.4 A, −107.81 kcal/mol) during graphitic nitrogen doping. The presence of calcium ions further strengthens the interaction energy between C-S-H and graphene, suggesting a synergistic effect between different types of nitrogen doping. The binding and total bond energies under the synergistic effect were −479.52 kcal/mol and −183.23 kcal/mol, respectively. These values were 1.5 times higher than those of single nitrogen doping. These findings offer significant insights into the molecular-level interaction between CSH and carbon nanoparticles.

Transformation of Silicate Ions into Silica under the Influence of Acid on the Structure of Serpentinite.

The process of transformation of the silicate components of the crystal lattice structure of chrysotile during its quantitative interaction with aqueous solutions containing various stoichiometrically required amounts of sulfuric acid (SRA H2SO4) calculated with respect to the magnesium content in the composition of chrysotile is investigated. It has been shown by IR spectroscopic, X-ray phase, thermal and chemical methods of investigation and analysis that, with quantitative interactions of chrysotile and sulfuric acid, first of all, the "brucite layer" of the molecular structural structure of chrysotile is exposed to acid at SRA H2SO4 = 0.1-0.3. As a result of ion exchange processes, acidic silanol (≡Si-O-H) or disilanol (=Si=(O-H)2) bonds are formed. These acid groups form one-dimensional silicate chains with transverse bridges (≡Si-O-Si≡), where the angles (Si-O-Si = 180 °C) straighten, which are recorded in the IR spectra in the region of characteristic absorption of 1220-1250 cm-1 silica. The association of the resulting acid groups into silicate chains, dimers, and trimers with transverse bridges, leads to the appearance of colloidal silica particles in the system, which cause some inhibition of the dissolution of layered magnesium hydrosilicate in sulfuric acid solutions containing H2SO4 ˃ 0.3 SRA.

Sodium aluminate activated waste glass: Reduced efflorescence behavior by C(N)−A−S−H transformation

Waste glass has been highly used in alkali activated materials, but the efflorescence behavior remains an intractable issue. This study investigates the effect of sodium aluminate as an activator to activate waste glass with the aim to mitigate the efflorescence behavior, and blast furnace slag is used as calcium source as well as to promote the early age strength. The gel structure (reaction product) was characterized by 29Si and 27Al NMR, subsequently the efflorescence behavior was investigated. Results show that sodium aluminate provides more AlOH4−, which acts as cross-linking agents, linking silicate tetrahedra to form a three-dimensional gel network. A longer mean chain length of gels increases hydrogen sites at end-chain Q1 silicate species, which can be replaced by cations along the silicate chain. The promoted formation of C(N)−A−S−H gel captures more Na+ in the pore solution, contributing to a limited Na+ leaching and higher resistance towards efflorescence.

New insights into the immobilisation of Ce(IV) in Portland cement: Properties, hydration, microstructure and occurrence status of Ce

The immobilisation mechanism of Pu(IV) by Portland cement-based material is not well understood. This study aims to reveal the immobilisation mechanism and occurrence status of Ce(IV) (chemical analogue of Pu(IV)) in Portland cement paste. The addition of Ce(NO3)4 first slightly retarded then accelerated the early-age hydration of Portland cement, thereby resulting in an increase of compressive strength by 29 %. The main contributor to immobilisation of Ce is Portland cement rather than zeolite. The hydration products were not altered by Ce(NO3)4 addition, whereas the hydration degree and mean chain length of C-(Al/Ce)-S-H increased. Over 99.99 % of Ce was immobilised by synthesised C-S-H. A analysis of the synthesised C-S-H confirmed the formation of C-Ce-S-H, where Ce tetrahedra took the bridging site of silicate chain of C-Ce-S-H. Nano-crystalline CeO2 grains were identified, which intermixed with C-Ce-S-H. Approximately 90 % of Ce were immobilised by C-Ce-S-H, and the rest exist as nano-crystalline CeO2 grains.

A Mathematical Investigation for the Temperature Indices of $$SiO_{4}$$ in Silicate and Silicate Chain Networks

A Mathematical Investigation for the Temperature Indices of $$SiO_{4}$$ in Silicate and Silicate Chain Networks

Interchain-expanded extra-large-pore zeolites.

Stable aluminosilicate zeolites with extra-large pores that areopen through rings of more than 12 tetrahedra could be used to process molecules larger than those currently manageable in zeolite materials. However, until very recently1-3, they proved elusive. In analogy to the interlayer expansion of layered zeolite precursors4,5, we report a strategy that yields thermally and hydrothermally stable silicates by expansion of a one-dimensional silicate chain with an intercalated silylating agent that separates and connects the chains. As a result, zeolites with extra-large pores delimited by 20, 16 and 16 Si tetrahedra along the three crystallographic directions are obtained. The as-made interchain-expanded zeolite contains dangling Si-CH3 groups that, by calcination, connect to each other, resulting in a true, fully connected (except possible defects) three-dimensional zeolite framework with a very low density. Additionally, it features triple four-ring units not seen before in any type of zeolite. The silicate expansion-condensation approach we report may be amenable to further extra-large-pore zeolite formation. Ti can be introduced in this zeolite, leading to a catalyst that isactive in liquid-phase alkene oxidations involving bulky molecules, which shows promise in the industrially relevant clean production of propylene oxide using cumene hydroperoxide as an oxidant.

Impact of Atomic Defects on Ceria Surfaces on Chemical Mechanical Polishing of Silica Glass Surfaces.

This study investigates the impact of atomic defects, such as oxygen vacancies and Ce3+ ions, on cerium oxide (ceria) surfaces during chemical mechanical polishing (CMP) for silica glass finishing. Using density functional theory (DFT) and reactive molecular dynamics simulations, the interaction of orthosilicic molecules and silica glass with dry and wet ceria surfaces is explored. Defects alter the surface reactivity, leading to the dissociation of orthosilicic acid on oxygen vacancies, forming a strong Si-O-Ce bond. Hydroxylated surfaces exhibit easier oxygen vacancy formation and thermodynamically favored substitution of hydroxyl groups with orthosilicic acid. A new ReaxFF library for silica/ceria interfaces with defects is validated using DFT outcomes. Reactive MD simulations demonstrate that ceria surfaces with 30% Ce3+ ions on (111) planes exhibit higher polishing efficiency, attributed to increased Si-O-Ce bond formation. The simultaneous presence of oxygen vacancies and various acidic and basic sites on ceria surfaces enhances the polishing efficiency, involving acid-base reactions with silica. Defective surfaces show superior efficiency by removing silicate chains, contrasting with nondefective surfaces removing isolated orthosilicate units. This study provides insights into optimizing CMP processes for high-precision glass industry surface finishing.

Atomic‐level structure evolution of calcium silicate hydrate nucleation process, the amorphous‐to‐crystalline pathway

AbstractCalcium silicate hydrate (C‐S‐H) synthesis follows multistep nucleation processes ranging from amorphous globules to nanocrystals. This type of nonclassical nucleation pathway attracts extensive interest and yet related molecular processes are mostly unexplored. Herein, atomic‐level structure evolution during this process is unveiled. From inside to outside of the globule, the atomic arrangement evolves from amorphous configuration to layered stacking of calcium silicate layers with layers spaced by 1.1 nm. Numerous cations surrounding the globules provide extra calcium ions to form nano C‐S‐H foils at the edge of the globule. The polymerization to form calcium silicate chains has almost been completed before 5 min reaction, and the C‐S‐H structure formation is basically based on the self‐assembly to be calcium silicate layers and then lamellar crystal inside the globule. Silicate chain defects inhibit a‐ and c‐axes crystallization, but promote b‐axes one, leading to anisotropic growth of crystalline C‐S‐H. The defects lead to the crystallization pathways conversion from Si–O–Si bonds formation to Ca2+ electrostatic linking.

Reaction molecular dynamics study of calcium alumino-silicate hydrate gel in the hydration deposition process at the calcium silicate hydrate interface: The influence of Al/Si

Supplementary cementitious materials (SCMs) can partially replace cement in concrete production, forming calcium alumino-silicate hydrate (C-A-S-H). This enhances concrete durability while recycling waste. However, the early hydration reaction process of C-A-S-H and its deposition and aggregation behavior at the interface with the primary hydration product of cement, calcium silicate hydrate (C–S–H), remain unknown. Therefore, this study utilizes reactive molecular dynamics to model the deposition and growth behaviors of C-A-S-H precursors with different Al/Si ratios on C–S–H, and discusses the effects of the Al/Si ratio on C-A-S-H gel aggregation behavior and structural evolution at the C–S–H interface. The results show that increasing Al content significantly promotes the early hydration reaction rate of C-A-S-H gel, the degree of polymerization of silicate chains, and the amount of Qn(n ≥ 2) species. Moreover, higher Al content leads to the precursors aggregating among themselves rather than depositing on the C–S–H substrate surface. The incorporation of Al–O polyhedra can effectively bridge silicate chains on the C–S–H surface and alter the growth patterns of hydration products from linear chains to three-dimensional networks. This work provides molecular-level insights into the influences of the Al/Si ratio on the early hydration reaction process and interfacial deposition behaviors of C-A-S-H gel.

Sorption behavior of cesium ions to Mg-containing calcium silicate hydrate in a co-precipitation process

The sorption behavior of Cs to Mg-containing calcium silicate hydrate (C–S–H) was examined to consider C–S–H formation under the water-saturated conditions around a radioactive waste repository. The amount of Cs sorption was slightly lower for Mg-containing C–S–H than for C–S–H, because Mg leads to a decrease in sorption sites by facilitating the polymerization of silicate chains. However, the apparent sorption distribution coefficient Kd of Cs on C–S–H with a Ca/Si molar ratio of 0.8 and Mg contents up to 20% was estimated to be 3.4–6.1 mL/g. Furthermore, the amount of Cs sorption was not decreased by the presence of Ba. The apparent Kd obtained in this study was about 10 times higher than that conventionally estimated for host rocks in the plutonic repository, indicating that C–S–H retains the effect of Cs immobilization even when it contains Mg.Graphical abstract

The effect of curing regimes on the hydration products of lightweight ultra-high performance concrete: From experiments to MD simulations

The hydration products and microstructure of ultra-high performance concrete are influenced by the curing regime. In this study, the influence of curing regimes on the hydration products of lightweight UHPC was explored using experiments and molecular dynamics (MD) simulations. Experimental results show that the high temperature stimulates the pozzolanic activity of silica fume and fly ash promoting the hydration reaction of cement. AFt is decomposed to AFm under high temperature conditions, and the high temperature and high pressure promote C-A-S-H gel to transform into denser Tobermorite crystals. On this basis, the realistic molecular models of C-A-S-H gel corresponding to the hydration product of lightweight UHPC under different curing environments were established. The simulation results indicate that the mechanical properties of C-A-S-H were improved significantly after steam and autoclave curing compared with standard curing. The molecular models of lightweight UHPC exhibit an increased level of ductility and indentation modulus in comparison to ordinary Portland cement, which can be attributed to the inclusion of Al phase and a higher degree of silicate chain polymerization.

Dissolution-precipitation hydration mechanism of steel slag based on ion exchange of a layered alkali-activator

This paper provided a new alkali activator for steel slag cementitious material - layered sodium disilicate (LSD), and focused on its dissolution-precipitation mechanism based on ion exchange capacity of LSD. The results showed that LSD could act as an effective activator for steel slag and the higher compressive strength of pastes (S3(14.9 MPa) and S10(22.3 MPa) increased by 222% and 332% respectively) were achieved and a matrix with much denser pore structure was formed. The pore solution analysis indicated LSD could play a role as ions transporter to facilitate the dissolution of steel slag (mainly C2S and C3S). Analysis of the hydration products showed that the addition of LSD increased the formation of C-S-H gels, CaCO3 and Mg(OH)2, but reduced the content of hydrotalcite-like phase. In addition, TEM and FTIR analysis indicated that the laminar C-S-H gel generated from LSD-activated steel slag had a higher SiO2 and Al content and a higher degree of silicate chain polymerization.