Detecting Early-Stage Cohesion Due to Calcium Silicate Hydration with Rheology and Surface Force Apparatus.

Extremely robust cohesion triggered by calcium silicate hydrate (C-S-H) precipitation during cement hardening makes concrete one of the most commonly used man-made materials. Here, in this proof-of-concept study, we seek an additional nanoscale understanding of early-stage cohesive forces acting between hydrating model tricalcium silicate (C3S) surfaces by combining rheological and surface force measurements. We first used time-resolved small oscillatory rheology measurements (SAOSs) to characterize the early-stage evolution of the cohesive properties of a C3S paste and a C-S-H gel. SAOS revealed the reactive and viscoelastic nature of C3S pastes, in contrast with the nonreactive but still viscoelastic nature of the C-S-H gel, which proves a temporal variation in the cohesion during microstructural physicochemical rearrangements in the C3S paste. We further prepared thin films of C3S by plasma laser deposition (PLD) and demonstrated that these films are suitable for force measurements in the surface force apparatus (SFA). We measured surface forces acting between two thin C3S films exposed to water and subsequent in situ calcium silicate hydrate precipitation. With the SFA and SFA-coupled interferometric measurements, we resolved that C3S surface reprecipitation in water was associated with both increasing film thickness and progressively stronger adhesion (pull-off force). The lasting adhesion developing between the growing surfaces depended on the applied load, pull-off rate, and time in contact. These properties indicated the viscoelastic character of the soft, gel-like reprecipitated layer, pointing to the formation of C-S-H. Our findings confirm the strong cohesive properties of hydrated calcium silicate surfaces that, based on our preliminary SFA measurements, are attributed to sharp changes in the surface microstructure. In contact with water, the brittle and rough C3S surfaces with little contact area weather into soft, gel-like C-S-H nanoparticles with a much larger surface area available for forming direct contacts between interacting surfaces.

Visualization of Ion|Surface Binding and In Situ Evaluation of Surface Interaction Free Energies via Competitive Adsorption Isotherms.

Function and properties at biologic as well as technological interfaces are controlled by a complex and concerted competition of specific and unspecific binding with ions and water in the electrolyte. It is not possible to date to directly estimate by experiment the interfacial binding energies of involved species in a consistent approach, thus limiting our understanding of how interactions in complex (physiologic) media are moderated. Here, we employ a model system utilizing polymers with end grafted amines interacting with a negatively charged mica surface. We measure interaction forces as a function of the molecule density and ion concentration in NaCl solutions. The measured adhesion decreases by about 90%, from 0.01 to 1 M electrolyte concentration. We further demonstrate by molecular resolution imaging how ions increasingly populate the binding surface at elevated concentrations, and are effectively competing with the functional group for a binding site. We demonstrate that a competing Langmuir isotherm model can describe this concentration-dependent competition. Further, based on this model we can quantitatively estimate ion binding energies, as well as binding energy relationships at a complex solid|liquid interface. Our approach enables the extraction of thermodynamic interaction energies and kinetic parameters of ionic species during monolayer level interactions at a solid|liquid interface, which to-date is impossible with other techniques.

Photocorrosion of ZnO Single Crystals during Electrochemical Water Splitting.

Degradation and dissolution of transparent semiconducting oxides is central to various areas, including design of catalysts and catalysis conditions, as well as passivation of metal surfaces. In particular, photocorrosion can be significant and plays a central role during photoelectrochemical activity of transparent semiconducting oxides. Here, we utilize an electrochemical flow cell combined with an inductively coupled plasma mass spectrometer (ICP-MS) to enable the in situ study of the time-resolved release of zinc into solution under simultaneous radiation of UV-light. With this system we study the dissolution of zinc oxide single crystals with (0001) and (101̅0) orientations. At acidic and alkaline pH, we characterized potential dependent dissolution rates into both the oxygen and the hydrogen evolving conditions. A significant influence of the UV radiation and the pH of the electrolyte was observed. The observed dissolution behavior agrees well with the surface chemistry and stabilization mechanism of ZnO surfaces. In particular, polar ZnO(0001) shows ideal stability at low potentials and under hydrogen evolution conditions. Whereas ZnO(101̅0) sustains higher dissolution rates, while it is inactive for water splitting. Our data demonstrates that surface design and fundamental understanding of surface chemistry provides an effective path to rendering electroactive surfaces stable under operating conditions.

Adsorption and Diffusion Moderated by Polycationic Polymers during Electrodeposition of Zinc.

Electrodeposition of metals is relevant to much of materials research including catalysis, batteries, antifouling, and anticorrosion coatings. The sacrificial characteristics of zinc used as a protection for ferrous substrates is a central corrosion protection strategy used in automotive, aviation, and DIY industries. Zinc layers are often used for protection by application to a base metal in a hot dip galvanizing step; however, there is a significant interest in less energy and material intense electroplating strategies for zinc. At present, large-scale electroplating is mostly done from acidic zinc solutions, which contain potentially toxic and harmful additives. Alkaline electroplating of zinc offers a route to using environment-friendly green additives. Within the scope of this study an electrolyte containing soluble zinc hydroxide compound and a polyquarternium polymer as additive were studied during zinc deposition on gold model surfaces. Cyclic voltammetry experiments and in-situ electrochemical quartz crystal microbalance with dissipation (QCM-D) measurements were combined to provide a detailed understanding of fundamental steps that occur during polymer-mediated alkaline zinc electroplating. Data indicate that a zincate-loaded polymer can adsorb within the inner sphere of the electric double layer, which lowers the electrostatic penalty of the zincate approach to a negatively charged surface. X-ray photoelectron spectroscopy also supports the assertion that the zincate-loaded polymer is brought tightly to the surface. We also find an initial polymer depletion followed by an active deposition moderation via control of the zincate diffusion through the adsorbed polymer.