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Potentiometric titrations have been routinely used to measure the proton-related surface charge density (SCD) of particles in solution. Here, we quantify the SCD of silica nanoparticles (NPs) that are commercially available as charge-stabilized colloids (by the addition of NaOH) in the presence of known amounts of added NaCl. The experimental results are simulated by surface complexation models (SCMs) of the electrical double layer (EDL). The modeling results suggest that involving only the added NaCl electrolyte yields poor agreement between the experiment and the best achievable fit. An increase in the Na concentration accounting for the colloid inherent salt (CIS) associated with these charge-stabilized colloids results in much better simulations. In the available literature, this CIS has often been disregarded. However, in the modeling, the total concentration of Na must be known for a consistent mole balance and derivation of reliable ion-pair binding constants. If the CIS is not accounted for or the original suspensions are not dialyzed, the presence of CIS renders the study of those colloids difficult, particularly when investigating specific ion effects, since the CIS always interferes. In the present work, we show that the SCM-estimated amount of CIS from varying the total salt and solid concentration agrees surprisingly well with the manufacturer specification.

In this work, the adsorption behavior of Sr onto a synthetic iron(III) oxide (hematite with traces of goethite) has been studied. This solid, which might be considered a representative of Fe3+ solid phases (iron corrosion products), was characterized by X-Ray Diffraction (XRD) and X-Ray Photoelectron Spectroscopy (XPS), and its specific surface area was determined. Both XRD and XPS data are consistent with a mixed solid containing more than 90% hematite and 10% goethite. The solid was further characterized by fast acid-base titrations at different NaCl concentrations (from 0.1 to 5 M). Subsequently, for each background NaCl concentration used for the acid-base titrations, Sr-uptake experiments were carried out involving two different levels of Sr concentration (1 × 10−5 and 5 × 10−5 M, respectively) at constant solid concentration (7.3 g/L) as a function of −log([H+]/M). A Surface Complexation Model (SCM) was fitted to the experimental data, following a coupled Pitzer/surface complexation approach. The Pitzer model was applied to aqueous species. A Basic Stern Model was used for interfacial electrostatics of the system, which includes ion-specific effects via ion-specific pair-formation constants, whereas the Pitzer-approach involves ion-interaction parameters that enter the model through activity coefficients for aqueous species. A simple 1-pK model was applied (generic surface species, denoted as >XOH−1/2). Parameter fitting was carried out using the general parameter estimation software UCODE, coupled to a modified version of FITEQL2. The combined approach describes the full set of data reasonably well and involves two Sr-surface complexes, one of them including chloride. Monodentate and bidentate models were tested and were found to perform equally well. The SCM is particularly able to account for the incomplete uptake of Sr at higher salt levels, supporting the idea that adsorption models conventionally used in salt concentrations below 1 M are applicable to high salt concentrations if the correct activity corrections for the aqueous species are applied. This generates a self-consistent model framework involving a practical approach for semi-mechanistic SCMs. The model framework of coupling conventional electrostatic double layer models for the surface with a Pitzer approach for the bulk solution earlier tested with strongly adsorbing solutes is here shown to be successful for more weakly adsorbing solutes.

The Data in Brief contains data on the electrokinetic mobility of PTFE and silica particles in aqueous suspensions as a function of pH and temperature. Furthermore, the concomitant conductivities and pH values are reported both for systems in the absence and presence of PTFE particles as a function of temperature and are compatible with the associated research paper “The influence of temperature on the charging of Polytetrafluoroethylene surfaces in electrolyte solutions” (Barisic et al.). The trend of the electrokinetic charging with temperature can be inferred from this for both kinds of particles. The data on the evolution of the pH and the measured conductivities are valuable input for future models that simulate the charge of inert surfaces at variable temperature. Keywords: Surface charge, Inert surface, Silica, Temperature dependence, Point of zero charge

We studied the charging of inert surfaces (polytetrafluoroethylene, i.e., PTFE; graphite; graphene; and hydrophobic silica) using classical colloid chemistry approaches. Potentiometric titrations showed that these surfaces acquired less charge from proton-related reactions than oxide minerals. The data from batch-type titrations for PTFE powder did not show an effect of ionic strength, which was also in contrast with results for classical colloids. In agreement with classical colloids, the electrokinetic results for inert surfaces showed the typical salt level dependence. In some cases, the point of zero net proton charge as determined from mass and tentatively from acid–base titration differed from isoelectric points, which has also been previously observed, for example by Chibowski and co-workers for ice electrolyte interfaces. Finally, we found no evidence for surface contaminations of our PTFE particles before and after immersion in aqueous solutions. Only in the presence of NaCl-containing solutions did cryo-XPS detect oxygen from water. We believe that our low isoelectric points for PTFE were not due to impurities. Moreover, the measured buffering at pH 3 could not be explained by sub-micromolar concentrations of contaminants. The most comprehensive explanation for the various sets of data is that hydroxide ion accumulation occurred at the interfaces between inert surfaces and aqueous solutions.

Streaming current measurements were used to study the interaction of polyoxometalates (POMs) and nanoparticles (NPs) with flat surfaces as an alternative, innovative approach to infer POM and NP properties of potential sparse material in terms of charge and magnitude. With respect to POMs, the approach was able to reveal subtle details of charging properties of +7 vs. +8 charge at very low POM concentrations. For NPs, the sign of charge and even the zeta-potential curve was retrieved. Concerning NPs, mutual interaction between TiO2 and SiO2 surfaces was studied in some detail via macroscopic measurements. Post-mortem analysis of samples from electrokinetic studies and separate investigations via AFM and HRTEM verified the interactions between TiO2 NPs and SiO2 collector surfaces. The interactions in the SiO2/TiO2 system depend to some extent on NP morphology, but in all our systems, irreversible interactions were observed, which would make the studied types of NPs immobile in natural environments. Overall, we conclude that the measurement of streaming currents at flat surfaces is valuable (i) to study NP and POM collector surface interactions and (ii) to simultaneously collect NPs or POM (or other small mobile clusters) for further (structural, morphological or release) investigations.

The rheological properties of fresh cement paste are highly influenced by a large number of parameters, among which the most important factors are the applied shear stress, and the shear history, the age of the sample and the temperature. The effects of these parameters on the yield stress (designated as structural limit stress in this work), the viscosity and the structural recovery rate (i.e., the change in dynamic viscosity with time at rest) were studied. In parallel, the changes in ion composition of the carrier liquid, mineral phase content and granulometry were investigated. The results reveal that all investigated rheological parameters exhibit an approximated bi-linear trend with respect to the degree of hydration, with a period of quasi-constant properties until a degree of hydration of approximately 0.07, followed by a non-linear increase. This increase could be attributed to the formation of calcium hydroxide (CH) and calcium-silicate-hydrate (C-S-H) via calorimetry results. With regard to the effect of the shear history of the sample on the rheological properties, the structural limit stress showed a minor dependency on the shear history immediately after the end of shearing, which, however, vanished within the first minute at rest. The same is true for the structural recovery rate. The presented results give detailed insights into the influences of hydration and shear on the rheological properties—especially the thixotropy—of fresh cement pastes.

Studies of the interaction of uranyl species with the surface of quartz are reported. Two approaches were applied. These were (i) the classical static batch adsorption approach in which only the forward adsorption uptake reaction is usually studied and (ii) a dynamic column approach in which the retention of a solute during its migration through a porous medium is investigated and where adsorption and desorption are both relevant for the final breakthrough curve. In this paper, we present the results of a column study at pH 4. Under these conditions, the interference of the carbonate ion (via the formation of dissolved or adsorbed uranyl-carbonato species), the effects of quartz surface charge (quartz/silica is virtually uncharged under these conditions) and the potential effects of quartz dissolution on uranyl speciation (via the formation of dissolved or adsorbed uranyl-silicato species) are minimised. The reported batch adsorption results are reasonably predicted by a model which under similar conditions successfully described batch and column data on a quartz sample with grains smaller than the quartz particles used in the present study by a factor of ca. 25. However, this model was incapable of describing the breakthrough behaviour of uranyl species. This failure was attributed to the heterogeneity of the quartz particles used, which may be more important for column breakthrough than for batch adsorption data.