Mechanisms of Silica Fracture in Aqueous Electrolyte Solutions

Glassy silicates are substantially weaker when in contact with aqueous electrolyte solutions than in vacuum due to chemical interactions with preexisting cracks. To investigate this silicate weakening phenomenon, classical molecular dynamics (MD) simulations of silica fracture were performed using the bond-order based, reactive force field ReaxFF. Four different environmental conditions were investigated: vacuum, water, and two salt solutions (1M NaCl, 1M NaOH) that form relatively acidic and basic solutions, respectively. Any aqueous environment weakens the silica, with NaOH additions resulting in the largest decreases in the effective fracture toughness (eKIC) of silica or the loading rate at which the fracture begins to propagate. The basic solution leads to higher surface deprotonation, narrower radius of curvature of the crack tip, and greater weakening of the silica, compared with the more acidic environment. The results from the two different electrolyte solutions correspond to phenomena observed in experiments and provide a unique atomistic insight into how anions alter the chemical-mechanical fracture response of silica

Surface complexation model for strontium sorption to amorphous silica and goethite

Strontium sorption to amorphous silica and goethite was measured as a function of pH and dissolved strontium and carbonate concentrations at 25°C. Strontium sorption gradually increases from 0 to 100% from pH 6 to 10 for both phases and requires multiple outer-sphere surface complexes to fit the data. All data are modeled using the triple layer model and the site-occupancy standard state; unless stated otherwise all strontium complexes are mononuclear. Strontium sorption to amorphous silica in the presence and absence of dissolved carbonate can be fit with tetradentate Sr2+ and SrOH+ complexes on the β-plane and a monodentate Sr2+complex on the diffuse plane to account for strontium sorption at low ionic strength. Strontium sorption to goethite in the absence of dissolved carbonate can be fit with monodentate and tetradentate SrOH+ complexes and a tetradentate binuclear Sr2+ species on the β-plane. The binuclear complex is needed to account for enhanced sorption at hgh strontium surface loadings. In the presence of dissolved carbonate additional monodentate Sr2+ and SrOH+ carbonate surface complexes on the β-plane are needed to fit strontium sorption to goethite. Modeling strontium sorption as outer-sphere complexes is consistent with quantitative analysis of extended X-ray absorption fine structure (EXAFS) on selected sorption samples that show a single first shell of oxygen atoms around strontium indicating hydrated surface complexes at the amorphous silica and goethite surfaces

Capturing CO2 via reactions in nanopores.

This one-year exploratory LDRD aims to provide fundamental understanding of the mechanism of CO2 scrubbing platforms that will reduce green house gas emission and mitigate the effect of climate change. The project builds on the team member's expertise developed in previous LDRD projects to study the capture or preferential retention of CO2 in nanoporous membranes and on metal oxide surfaces. We apply Density Functional Theory and ab initio molecular dynamics techniques to model the binding of CO2 on MgO and CaO (100) surfaces and inside water-filled, amine group functionalized silica nanopores. The results elucidate the mechanisms of CO2 trapping and clarify some confusion in the literature. Our work identifies key future calculations that will have the greatest impact on CO2 capture technologies, and provides guidance to science-based design of platforms that can separate the green house gas CO2 from power plant exhaust or even from the atmosphere. Experimentally, we modify commercial MFI zeolite membranes and find that they preferentially transmit H2 over CO2 by a factor of 34. Since zeolite has potential catalytic capability to crack hydrocarbons into CO2 and H2, this finding paves the way for zeolite membranes that can convert biofuel into H2 and separate the products all in one step