Topotactic Hydrogen in Nickelate Superconductors and Akin Infinite-Layer Oxides ABO_{2}.

Superconducting nickelates appear to be difficult to synthesize. Since the chemical reduction of ABO_{3} [rare earth (A), transition metal (B)] with CaH_{2} may result in both ABO_{2} and ABO_{2}H, we calculate the topotactic H binding energy by density functional theory (DFT). We find intercalating H to be energetically favorable for LaNiO_{2} but not for Sr-doped NdNiO_{2}. This has dramatic consequences for the electronic structure as determined by DFT+dynamical mean field theory: that of 3d^{9} LaNiO_{2} is similar to (doped) cuprates, 3d^{8} LaNiO_{2}H is a two-orbital Mott insulator. Topotactic H might hence explain why some nickelates are superconducting and others are not.

Impact of particle size on interaction forces between ettringite and dispersing comb-polymers in various electrolyte solutions.

The inter-particle forces play a fundamental role for the flow properties of a particle suspension in response to shear stresses. In concrete applications, cement admixtures based on comb-polymers like polycarboxylate-ether-based superplasticizer (PCE) are used to control the rheological behavior of the fresh mixtures, as it is negatively impacted by certain early hydration products, like the mineral ettringite. In this work, dispersion forces due to PCE were measured directly at the surface of ettringite crystals in different electrolyte solutions by the means of atomic force microscopy (AFM) applying spherical and sharp silicon dioxide tips. Results show an effective repulsion between ettringite surface and AFM tips for solutions above the IEP of ettringite (pH∼12) and significant attraction in solution at lower pH. The addition of polyelectrolytes in solution provides dispersion forces exclusively between the sharp tips (radius ≈ 10 nm) and the ettringite surface, whereas the polymer layer at the ettringite surface results to be unable to disperse large colloidal probes (radius ≈ 10 µm). A simple modeling of the inter-particle forces explains that, for large particles, the steric hindrance of the studied PCE molecules is not high enough to compensate for the Van der Waals and the attractive electrostatic contributions. Therefore, in cement suspensions the impact of ettringite on rheology is probably not only related to the particle charge, but also related to the involved particle sizes.

Interaction of cement model systems with superplasticizers investigated by atomic force microscopy, zeta potential, and adsorption measurements.

Polyelectrolyte-based dispersants are commonly used in a wide range of industrial applications to provide specific workability to colloidal suspensions. Their working mechanism is based on adsorption onto the surfaces of the suspended particles. The adsorbed polymer layer can exercise an electrostatic and/or a steric effect which is responsible for achieving dispersion. This study is focused on the dispersion forces induced by polycarboxylate ether-based superplasticizers (PCEs) commonly used in concrete. They are investigated by atomic force microscopy (AFM) applying standard silicon nitride tips exposed to solutions with different ionic compositions in a wet cell. Adsorption isotherms and zeta potential analysis were performed to characterize polymer displacement in the AFM system on nonreactive model substrates (quartz, mica, calcite, and magnesium oxide) in order to avoid the complexity of cement hydration products. The results show that PCE is strongly adsorbed by positively charged materials. This fact reveals that, being silicon nitride naturally positively charged, in most cases the superplasticizer adsorbs preferably on the silicon nitride tip than on the AFM substrate. However, the force-distance curves displayed repulsive interactions between tip and substrates even when polymer was poorly adsorbed on both. These observations allow us to conclude that the dispersion due to PCE strongly depends on the particle charge. It differs between colloids adsorbing and not adsorbing PCE, and leads to different forces acting between the particles.

Analysis of cement-bonded materials by multi-cycle mercury intrusion and nitrogen sorption.

The pore systems of cement-based materials are studied by N(2) sorption and mercury intrusion porosimetry (MIP). Pore size distributions and internal surfaces are derived. Especially in materials with a broad pore size distribution, these (and other) methods generally do not lead to coincident results. It is shown here, how the interpretation of the experimental data of the two methods may be modified in order to obtain coincident pore size distributions from both methods. The studied pore systems are described as array of chambers which are connected by smaller throats. N(2) adsorption is used to calculate the size of the pores, whereby no distinction between throat or chamber type is possible with this method. Assuming mercury entrapping in ink-bottle type pores (pores that are connected to an external surface through smaller pores only) being the dominant process for mercury snap-off during extrusion and applying multi-cycle MIP, the calculation of the size of the entrances of these ink-bottles is possible. It is shown that similar results also may be derived from mercury extrusion data by applying a contact angle correction for the retracting mercury meniscus. A good agreement of the pore size distribution of the connected, non-ink-bottle type pores derived from either N(2) sorption or mercury intrusion is obtained. Samples of cement paste and mortar are analysed. A significant difference between cement paste and mortar regarding the neck entrances of ink-bottle type pores is found and attributed to the coarse pore space around the aggregates, the interfacial transition zone.