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Pure calcium carbonate (calcite and aragonite) solid materials of different particle size (100-200 microm fragments and millimeter-sized single crystals) were interacted with Pb in aqueous solutions at room temperature under atmospheric PCO2. In the case of the micrometer-sized samples, the macroscopic investigation using a batch-type treatment procedure (solutions between 10 and 1000 mg/L Pb) and ICP-AES, SEM-EDS, and powder-XRD showed that the metal is readily removed from the aqueous media by both materials and indicated the sorption processes (mainly surface precipitation leading to overgrowth of cerussite and hydrocerussite crystals) taking place in parallel with surface dissolution processes. The various processes occurring at the calcium carbonate solid-water interface were clearly distinguished and defined in the case of the millimeter-sized samples interacted with 1000 mg/L Pb using a combination of wet-chemical, in-situ (AFM) and ex-situ (AFM, SEM) microscopic, and surface spectroscopic (XPS, 12C-RBS) techniques. The in-situ AFM data revealed the dissolution processes on the surface of the calcium carbonates and the simultaneous heterogeneous nucleation of lead carbonate phases and confirmed the secondary dissolution of lead carbonate crystals grown epitaxially from the initial nuclei. The XPS spectra confirmed that adsorption of Pb occurs simultaneously to dissolution at short interaction times (less than approximately 10 min, prior to precipitation-nucleation/crystal growth) in the case of both CaCO3 polymorphs and that the calcite surface with adsorbed Pb may have an aragonite-type character. The 12C-RBS spectra indicated that absorption (incorporation of Pb2+ ions) also takes place in parallel at the surface layers of the calcium carbonates, resulting in formation of solid solutions.
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PMID:Interaction of calcium carbonates with lead in aqueous solutions. 1296 81

In this paper, we show the electrochemical deposition of a subnanometer film of nickel (Ni) on top of titanium nitride (TiN). We exploit the concept of cluster growth inhibition to enhance the nucleation of new nuclei on the TiN substrate. By deliberately using an unbuffered electrolyte solution, the degree of nucleation is enhanced as growth is inhibited more strongly. This results in a very high particle density and therefore an ultralow coalescence thickness. To prevent the termination of Ni deposition that typically occurs in unbuffered solutions, the concentration of Ni(2+) in solution was increased. We have verified with RBS and ICP-MS that the deposition of Ni on the surface in this case did not terminate. Furthermore, annealing experiments were used to visualize the closed nature of the Ni film. The closure of the deposited film was also confirmed by TOF-SIMS measurements and occurs when the film thickness is still in the subnanometer regime. The ultrathin Ni film was found to be an excellent catalyst for carbon nanotube growth on conductive substrates and can also be applied as a seed layer for bulk deposition of a smooth Ni film on TiN.
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PMID:Electrochemical deposition of subnanometer Ni films on TiN. 2452 Aug 57