Molecular Simulations of the Polymerization of Silicic Acid Molecules and Network Formation

Garofalini, Stephen H.; Martin, Glen E.

doi:10.1021/j100055a044

Cited by 121 publications

(142 citation statements)

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“…They analyzed the structure and hydroxylation of silica surfaces 62 as well as silica polymerization. 63 With advances in potential development the role of the original defective surface in forming silanol concentrations were identified. 54,56,64 Classical MD simulations have also been able to reproduce both of the silica-water reaction mechanisms found in ab initio simulations 65,66 due to the inclusion of DFT reaction pathways and energies.…”

Section: First-principles-based Simulations Of Glass-water Interactionsmentioning

confidence: 99%

Atomistic computer simulations of water interactions and dissolution of inorganic glasses

Rimsza

2017

npj Mater Degrad

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Computer simulations at the atomistic scale play an increasing important role in understanding the structure features, and the structure-property relationships of glass and amorphous materials. In this paper, we reviewed atomistic simulation methods ranging from first principles calculations and ab initio molecular dynamics (AIMD) simulations, to classical molecular dynamics (MD), and meso-scale kinetic Monte Carlo (KMC) simulations and their applications to study the reactions and interactions of inorganic glasses with water and the dissolution behaviors of inorganic glasses. Particularly, the use of these simulation methods in understanding the reaction mechanisms of water with oxide glasses, water-glass interfaces, hydrated porous silica gels formation, the structure and properties of multicomponent glasses, and microstructure evolution are reviewed. The advantages and disadvantageous of these simulation methods are discussed and the current challenges and future direction of atomistic simulations in glass dissolution presented.npj Materials Degradation (2017) 1:16 ; doi:10.1038/s41529-017-0017-yThe corrosion or degradation of glasses in aqueous solutions are critical in a number of engineering and technological processes ranging from microelectronic packaging, glass reaction chambers, and the immobilization of nuclear waste materials, as well as in healthcare and biomedical fields such as dissolution of inhaled glass fibers and bioactive glasses for biomedical applications. In particular, immobilizing radioactive waste in borosilicate glasses is widely accepted as a preferred method to treat nuclear waste materials generated from civilian and military sources. This process, also known as vitrification, is a critical component of the cycle of nuclear energy to combat global environmental and energy challenges. Researchers from around the world have extensively invested in understanding glass corrosion in an effort to predict the long-term stability and release rate radionuclides to the environment during nuclear waste storage. 1,2Various mechanisms for glass corrosion have been proposed and despite intensive experimental investigations with advanced characterization techniques results are unclear. It is generally accepted that the corrosion of glass consists of a set of complex processes including hydration, hydrolysis, and ion-exchange that are coupled during glass dissolution. The initial stage is interdiffusion of proton or hydronium ions from the solution with sodium or other alkali ions in the glass.3 This is followed by the hydrophilic attack of water on the Si-O-Si or Si-O-Al linkages that lead to hydroxylation of the silicate glass network. The remaining hydrolyzed glass skeleton then undergoes condensation and repolymerization to form the hydrated nanoporous silica rich gel layer which can be protective, decreasing dissolution to a residual rate. [4][5][6] The morphology of the gel layer, such as thickness, pore structure, and chemical composition, depends on the original glass composition and the pH...

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Section: First-principles-based Simulations Of Glass-water Interactionsmentioning

confidence: 99%

Atomistic computer simulations of water interactions and dissolution of inorganic glasses

Rimsza

2017

npj Mater Degrad

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show abstract

“…The general characteristics of Figure 4 (i.e. the progressive evolution of higher-bridged silicon atoms with increasingly longer timescales of condensation to form these species) are observed in simulation 14,24,32,50,51 and NMR 10,16 studies. The siloxane cluster size distribution is illustrated in Figure 5.…”

Section: Iiia Modeling Polycondensation In Methanolic Tetramethoxysimentioning

confidence: 74%

“…The average size of siloxane rings increases over time as additional monomers are available to form rings. Five-membered rings have been reported as the most frequent from hydroxysilanes simulations 14,24,32 . It has also been shown that the average number of silicon atoms per siloxane ring increases 32 over the course of polycondensation.…”

Section: Iiic Effects Of Alkoxysilane Water and Alcohol Compositiomentioning

confidence: 99%

“…Five-membered rings have been reported as the most frequent from hydroxysilanes simulations 14,24,32 . It has also been shown that the average number of silicon atoms per siloxane ring increases 32 over the course of polycondensation. Although the simulations are not equilibrated after 5 ns, it is clear the average ring size at all H2O:TetraMS ratios have more than four silicons.…”

Section: Iiic Effects Of Alkoxysilane Water and Alcohol Compositiomentioning

confidence: 99%

“…To date reactive molecular dynamics studies 14,24,[31][32][33][34] have modeled the polycondensation of pure hydroxysilanes, or in solutions in pure water. However, in practice precursor solutions contain a mixture of alkoxysilane, solvent 1,15,27 and water.…”

Section: Scheme 1: Reaction Equations For Hydrolysis Condensation Amentioning

confidence: 99%

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Reactive modeling of the initial stages of alkoxysilane polycondensation: effects of precursor molecule structure and solution composition

Deetz

Faller

2015

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Thermochemistry of aqueous silicate solution precursors to ceramics

Šefčı́k

McCormick

1997

AIChE J.

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A quantitative understanding of the thermochemistry of silicate solution systems is necessary for the design, optimization and control of sol-gel, colloid and zeolite preparations. This review is intended to be a compendium of ready information for the growing number of chemical engineers active in solution-based materials synthesis. Experimental measurements of Silica solubility, silicate speciation and silanol deprotonation in aqueous solutions are summarized and critiqued. The thermochemical properties of monomeric and dimeric silicate anions are also assessed. The trends that are then evident are compared with expectations fr om simplistic gas-phase molecular orbital calculations to illustrate the importance of solvation. Finally, the equilibrium behavior of simple silicate oligomers is rationalized, and the future direction to quantitative modeling of the behavior of more complex oligomers is suggested

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Molecular Simulations of the Polymerization of Silicic Acid Molecules and Network Formation

Cited by 121 publications

References 6 publications

Atomistic computer simulations of water interactions and dissolution of inorganic glasses

Atomistic computer simulations of water interactions and dissolution of inorganic glasses

Reactive modeling of the initial stages of alkoxysilane polycondensation: effects of precursor molecule structure and solution composition

Thermochemistry of aqueous silicate solution precursors to ceramics

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