Synthesis of Metastable Calcium Carbonate Using Long-Chain Bisphosphonate Molecules.

Cementation in construction materials primarily relies on the aqueous precipitation of minerals such as carbonates and silicates. The kinetics of nucleation and growth play a critical role in the development of strength and durability, yet our understanding of the kinetic controls governing phase formation and porosity reduction in cements remains limited. In this study, we synthesized bisphosphonate molecules with varying alkyl chain lengths and functional groups to investigate their impact on calcium carbonate precipitation. Through conductivity measurements, infrared spectroscopy, and thermogravimetric analysis, we uncovered the selective formation of polymorphs and the specific incorporation of these molecules within the carbonate matrix. Further, in situ atomic force microscopy revealed that these molecules influenced the morphology of the precipitates, indicating a possible effect on the ionic organization through sorption mechanisms. Interestingly, amorphous calcium carbonate (ACC), when formed in the presence of bisphosphonates, showed metastability for at least seven months without inhibiting further calcium carbonate precipitation. Our research sheds light on the diverse mechanisms by which organic additives can modify mineral nucleation and growth, offering valuable insights for the control and enhancement of carbonate-based cementation processes.

Electrolytic Seawater Mineralization and the Mass Balances That Demonstrate Carbon Dioxide Removal.

We present the mass balances associated with carbon dioxide (CO2) removal (CDR) using seawater as both the source of reactants and as the reaction medium via electrolysis following the "Equatic" (formerly known as "SeaChange") process. This process, extensively detailed in La Plante E.C.; ACS Sustain. Chem. Eng.2021, 9, ( (3), ), 1073-1089, involves the application of an electric overpotential that splits water to form H+ and OH- ions, producing acidity and alkalinity, i.e., in addition to gaseous coproducts, at the anode and cathode, respectively. The alkalinity that results, i.e., via the "continuous electrolytic pH pump" results in the instantaneous precipitation of calcium carbonate (CaCO3), hydrated magnesium carbonates (e.g., nesquehonite: MgCO3·3H2O, hydromagnesite: Mg5(CO3)4(OH)2·4H2O, etc.), and/or magnesium hydroxide (Mg(OH)2) depending on the CO32- ion-activity in solution. This results in the trapping and, hence, durable and permanent (at least ∼10 000-100 000 years) immobilization of CO2 that was originally dissolved in water, and that is additionally drawn down from the atmosphere within: (a) mineral carbonates, and/or (b) as solvated bicarbonate (HCO3-) and carbonate (CO32-) ions (i.e., due to the absorption of atmospheric CO2 into seawater having enhanced alkalinity). Taken together, these actions result in the net removal of ∼4.6 kg of CO2 per m3 of seawater catholyte processed. Geochemical simulations quantify the extents of net CO2 removal including the dependencies on the process configuration. It is furthermore indicated that the efficiency of realkalinization of the acidic anolyte using alkaline solids depends on their acid neutralization capacity and dissolution reactivity. We also assess changes in seawater chemistry resulting from Mg(OH)2 dissolution with emphasis on the change in seawater alkalinity and saturation state. Overall, this analysis provides direct quantifications of the ability of the Equatic process to serve as a means for technological CDR to mitigate the worst effects of accelerating climate change.

Calcination-free production of calcium hydroxide at sub-boiling temperatures.

Calcium hydroxide (Ca(OH)2), a commodity chemical, finds use in diverse industries ranging from food, to environmental remediation and construction. However, the current thermal process of Ca(OH)2 production via limestone calcination is energy- and CO2-intensive. Herein, we demonstrate a novel aqueous-phase calcination-free process to precipitate Ca(OH)2 from saturated solutions at sub-boiling temperatures in three steps. First, calcium was extracted from an archetypal alkaline industrial waste, a steel slag, to produce an alkaline leachate. Second, the leachate was concentrated using reverse osmosis (RO) processing. This elevated the Ca-abundance in the leachate to a level approaching Ca(OH)2 saturation at ambient temperature. Thereafter, Ca(OH)2 was precipitated from the concentrated leachate by forcing a temperature excursion in excess of 65 °C while exploiting the retrograde solubility of Ca(OH)2. This nature of temperature swing can be forced using low-grade waste heat (≤100 °C) as is often available at power generation, and industrial facilities, or using solar thermal heat. Based on a detailed accounting of the mass and energy balances, this new process offers at least ≈65% lower CO2 emissions than incumbent methods of Ca(OH)2, and potentially, cement production.

Atomic Dislocations and Bond Rupture Govern Dissolution Enhancement under Acoustic Stimulation.

By focusing the power of sound, acoustic stimulation (i.e., often referred to as sonication) enables numerous "green chemistry" pathways to enhance chemical reaction rates, for instance, of mineral dissolution in aqueous environments. However, a clear understanding of the atomistic mechanism(s) by which acoustic stimulation promotes mineral dissolution remains unclear. Herein, by combining nanoscale observations of dissolving surface topographies using vertical scanning interferometry, quantifications of mineral dissolution rates via analysis of solution compositions using inductively coupled plasma optical emission spectrometry, and classical molecular dynamics simulations, we reveal how acoustic stimulation induces dissolution enhancement. Across a wide range of minerals (Mohs hardness ranging from 3 to 7, surface energy ranging from 0.3 to 7.3 J/m2, and stacking fault energy ranging from 0.8 to 10.0 J/m2), we show that acoustic fields enhance mineral dissolution rates (reactivity) by inducing atomic dislocations and/or atomic bond rupture. The relative contributions of these mechanisms depend on the mineral's underlying mechanical properties. Based on this new understanding, we create a unifying model that comprehensively describes how cavitation and acoustic stimulation processes affect mineral dissolution rates.

Enhancing Polyvalent Cation Rejection Using Perfluorophenylazide-Grafted-Copolymer Membrane Coatings.

Surface modification offers a straightforward means to alter and enhance the properties and performance of materials, such as nanofiltration membranes for water softening. Herein, we demonstrate how a membrane's surface charge can be altered by grafting different electrostatically varying copolymers onto commercial membrane surfaces using perfluorophenylazide (PFPA) photochemistry for enhanced ion separation performance. The native membrane's performance-i.e., in terms of divalent cation separation-with copolymer coatings containing a positively charged quaternary ammonium (-N(Me)3+), a negatively charged sulfonate (-SO3-), and an essentially neutral zwitterion (sulfobetaine, -N(Me)2R2+, and -SO3-), respectively, indicates that: (a) the sulfonated polymer induces robust Coulombic exclusion of divalent anions as compared to the negatively charged native membrane surface on account of its higher negative charge; (b) the positively charged ammonium coating induces exclusion of cations more effectively than the native membrane; and significantly, (c) the zwitterion polymer coating, which reduces the surface roughness and improves wettability, in spite of its near-neutral charge enhances exclusion of both divalent cations and anions on account of aperture sieving by the compact zwitterion polymer that arises from its ability to limit the size of ions that transport through the polymer along with dielectric exclusion. The outcomes thereby inform new pathways to achieve size- and charge-based exclusion of ionic, molecular, and other species contained in liquid streams.

Elucidating the corrosion-related degradation mechanisms of a Ti-6Al-4V dental implant.

OBJECTIVE: The Ti-6Al-4V (TAV) alloy is commercially used as a dental implant material. This work seeks to elucidates the origins of degradation of Ti-6Al-4V (TAV) implant alloys that result in peri-implant bone loss. 
Methods: In this work, a combination of microstructure, surface, and solution analyses was utilized to study the corrosion mechanism of the TAV alloy in oral environments. The corrosion of TAV alloys in the F--enriched environment of a crevice was evaluated through nanoscale surface analysis. And, the findings were further rationalized via electrochemical means. 
 RESULTS: Our results suggest the bone loss was caused by crevice corrosion and the consequential release of by-products, and the crevice corrosion was potentially induced by the buildup of corrosive species such as fluorides, which are common additives in dental products. In turn, the corrosion properties of the TAV alloy were evaluated in fluoride enriched environments. Nanoscale analysis of corroded surfaces, carried out using vertical scanning interferometry (VSI) showed that the corrosion susceptibility of the constituent phases dictates the corrosion product species. In specific, the aluminum-rich α phase preferentially dissolves under potential-free conditions and promotes the formation of insoluble Al-Ti oxides. Notably, under conditions of applied potential, oxidative dissolution of the vanadium-rich ß phase is favored, and the vanadium release is promoted. 
 SIGNIFICANCE: These findings elucidate the origins of degradation of TAV-implants that result in the release of corrosion by-products into the local biological environment. More important, they offer guidelines for materials design and improvement to prevent this nature of degradation of dental implants.

Direct observation of pitting corrosion evolutions on carbon steel surfaces at the nano-to-micro- scales.

The Cl--induced corrosion of metals and alloys is of relevance to a wide range of engineered materials, structures, and systems. Because of the challenges in studying pitting corrosion in a quantitative and statistically significant manner, its kinetics remain poorly understood. Herein, by direct, nano- to micro-scale observations using vertical scanning interferometry (VSI), we examine the temporal evolution of pitting corrosion on AISI 1045 carbon steel over large surface areas in Cl--free, and Cl--enriched solutions. Special focus is paid to examine the nucleation and growth of pits, and the associated formation of roughened regions on steel surfaces. By statistical analysis of hundreds of individual pits, three stages of pitting corrosion, namely, induction, propagation, and saturation, are quantitatively distinguished. By quantifying the kinetics of these processes, we contextualize our current understanding of electrochemical corrosion within a framework that considers spatial dynamics and morphology evolutions. In the presence of Cl- ions, corrosion is highly accelerated due to multiple autocatalytic factors including destabilization of protective surface oxide films and preservation of aggressive microenvironments within the pits, both of which promote continued pit nucleation and growth. These findings offer new insights into predicting and modeling steel corrosion processes in mid-pH aqueous environments.

Revealing How Alkali Cations Affect the Surface Reactivity of Stainless Steel in Alkaline Aqueous Environments.

Stainless steel is a ubiquitous structural material and one that finds extensive use in core-internal components in nuclear power plants. Stainless steel features superior corrosion resistance (e.g., as compared to ordinary steel) due to the formation of passivating iron and/or chromium oxides on its surfaces. However, the breakdown of such passivating oxide films, e.g., due to localized deformation and slip line formation following exposure to radiation, or aggressive ions renders stainless steel susceptible to corrosion-related degradation. Herein, the effects of alkali cations (i.e., K+, Li+) and the interactions between the passivated steel surface and the solution are examined using 304L stainless steel. Scanning electrochemical microscopy and atomic force microscopy are used to examine the inert-to-reactive transition of the steel surface both in the native state and in the presence of applied potentials. Careful analysis of interaction forces, in solution, within ≤10 nm of the steel surface, reveals that the interaction between the hydrated alkali cations and the substrate affects the structure of the electrical double layer (EDL). As a result, a higher surface reactivity is indicated in the presence of Li+ relative to K+ due to the effects of the former species in disrupting the EDL. These findings provide new insights into the role of the water chemistry not only on affecting metallic corrosion but also in other applications, such as batteries and electrochemical devices.

Effects of Irradiation on Albite's Chemical Durability.

Albite (NaAlSi3O8), a framework silicate of the plagioclase feldspar family and a common constituent of felsic rocks, is often present in the siliceous mineral aggregates that compose concrete. When exposed to radiation (e.g., in the form of neutrons) in nuclear power plants, the crystal structure of albite can undergo significant alterations. These alterations may degrade its chemical durability. Indeed, careful examinations of Ar+-implanted albite carried out using Fourier transform infrared spectroscopy (FTIR) and molecular dynamics simulations show that albite's crystal structure, upon irradiation, undergoes progressive disordering, resulting in an expansion in its molar volume (i.e., a reduction of density) and a reduction in the connectivity of its atomic network. This loss of network connectivity (i.e., rigidity) results in an enhancement of the aqueous dissolution rate of albite-measured using vertical scanning interferometry (VSI) in alkaline environments-by a factor of 20. This enhancement in the dissolution rate (i.e., reduction in chemical durability) of albite following irradiation has significant impacts on the durability of felsic rocks and of concrete containing them upon their exposure to radiation in nuclear power plant (NPP) environments.