The adsorption behavior of calcium carbonate is an important factor in many processes in nature, industry, and biological systems. We determined and compared the adsorption energies for a series of small molecules of different sizes and polarities (i.e., water, several alcohols, and acetic acid) on three synthetic CaCO3 polymorphs (calcite, aragonite, and vaterite). We measured isosteric heats of adsorption from vapor adsorption isotherms for 273 < T < 293 K, and we used XRD and SEM to confirm that samples did not change phase during the experiments. Density functional calculations and molecular dynamics simulations complemented the experimental results and aided interpretation. Alcohols with molecular mass greater than that of methanol bind more strongly to the calcium carbonate polymorphs than water and acetic acid. The adsorption energies for the alcohols are typical of chemisorption and indicate alcohol displacement of water from calcium carbonate surfaces. This explains why organisms favor biomolecules that contain alcohol functional groups (-OH) to control which polymorph they use, the crystal face and orientation, and the particle shape and size in biomineralization processes. This new insight is also very useful in understanding organic molecule adsorption mechanisms in soils, sediments, and rocks, which is important for predicting the behavior of mineral-fluid interactions when the challenge is to remediate contaminated groundwater aquifers or to produce oil and gas from reservoirs.
3-Aminopropylsilane (APS) coupling agent is widely used in industrial, biomaterial, and medical applications to improve adhesion of polymers to inorganic materials. However, during exposure to elevated humidity and temperature, the deposited APS layers can decompose, leading to reduction in coupling efficiency, thus decreasing the product quality and the mechanical strength of the polymer-inorganic material interface. Therefore, a better understanding of the chemical state and stability of APS on inorganic surfaces is needed. In this work, we investigated APS adhesion on silica wafers and compared its properties with those on complex silicate surfaces such as those used by industry (mineral fibers and fiber melt wafers). The APS was deposited from aqueous and organic (toluene) solutions and studied with surface sensitive techniques, including X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), streaming potential, contact angle, and spectroscopic ellipsometry. APS configuration on a model silica surface at a range of coverages was simulated using density functional theory (DFT). We also studied the stability of adsorbed APS during aging at high humidity and elevated temperature. Our results demonstrated that APS layer formation depends on the choice of solvent and substrate used for deposition. On silica surfaces in toluene, APS formed unstable multilayers, while from aqueous solutions, thinner and more stable APS layers were produced. The chemical composition and substrate roughness influence the amount of deposited APS. More APS was deposited and its layers were more stable on fiber melt than on silica wafers. The changes in the amount of adsorbed APS can be successfully monitored by streaming potential. These results will aid in improving industrial- and laboratory-scale APS deposition methods and increasing adhesion and stability, thus increasing the quality and effectiveness of materials where APS is used as a coupling agent.
Mineral wool products, composed of stone wool fibers and organic binder, are used in many construction applications. Among all their beneficial properties, the most important requirement is safety for human health, such as when fibers are inhaled. For determining long-term toxicity, biosolubility and biopersistence studies in vitro and in vivo are essential. In vitro fiber dissolution rate, which depends on the medium, fiber composition, and the surface available for dissolution, is a key parameter in determining biopersistence of the material in vivo. We investigated how organic binder (phenol-ureaformaldehyde), which can partially shield fiber surfaces from the solution, influences fiber dissolution kinetics in synthetic lung fluid (modified Gamble's solution) at pH 4.5 and temperature 37 °C, in vitro. Dissolution experiments were made in batch and continuous flow using stone wool fibers with typical insulation product binder amounts (0−6 wt %), applied by the standard industrial process. Dissolution rates were determined from element concentrations in the reacted solution, and changes in fiber surface composition and morphology were monitored. Stone wool fiber dissolution was close to stoichiometric and was similar, whether or not the material contained binder. The high dissolution rate (508 ng of fiber/cm 2 /h) is explained by Al and Fe complexing agents, that is, citrate and tartrate, in the synthetic lung fluid. The organic binder mainly forms micrometersized discrete droplets on the fiber surfaces rather than a homogeneous thick coating. During in vitro tests, fibers with organic binder preferentially dissolved in the areas free of binder, forming cavities, whereas the untreated fibers dissolved homogeneously. Propagation of cavities undermined the binder droplets, leading to complete fiber dissolution. Thus, presence of organic binder on stone wool fibers, produced by the standard industrial process, had no measurable effect on dissolution rate in synthetic lung fluid containing Al and Fe complexing agents.
The development of dental materials with improved properties and increased longevity can save costs and minimize discomfort for patients. Due to their good biocompatibility, glass ionomer cements are an interesting restorative option. However, these cements have limited mechanical strength to survive in the challenging oral environment. Therefore, a better understanding of the structure and hydration process of these cements can bring the necessary understanding to further developments. Neutrons and X-rays have been used to investigate the highly complex pore structure, as well as to assess the hydrogen mobility within these cements. Our findings suggest that the lower mechanical strength in glass ionomer cements results not only from the presence of pores, but also from the increased hydrogen mobility within the material. The relationship between microstructure, hydrogen mobility and strength brings insights into the material's durability, also demonstrating the need and opening the possibility for further research in these dental cements.
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