Carbonated wollastonite - An effective supplementary cementitious material?

Carbonated wollastonite clinker (CS) may be suitable as supplementary cementitious material (SCM) for mortar and concrete. The microstructure of unground CS clinker, carbonated CS slurry and a mortar blended with carbonated CS are investigated by scanning electron microscopy. Additionally, a reference mortar with pure Portland cement and one with a cement replacement level of 30 mass-% by carbonated CS are produced to assess its contribution to compressive strength development. The calcium silicates are decalcified during carbonation resulting in CaCO3 and amorphous SiO2 . The latter reacts when used as SCM in mortar influencing the Ca/Si ratio of calcium-silicate-hydrate and contributing to compressive strength development.

Precipitation of anionic emulsifier with ordinary Portland cement.

Cement has traditionally been used to accelerate bitumen emulsion breaking in cold mix asphalt and cold recycling asphalt. For cold emulsion mixtures, the mixing stability of bitumen emulsion is a crucial property, because it determines the distribution of bitumen and eventually affects the microstructure and the strength development of asphalt mixtures. Recent studies have proven that the interaction between cement and emulsifiers causes the destabilization of bitumen emulsions. The objective of this study is to understand the interaction between cement particles and rosin emulsifiers. For this purpose, the Ca(2+) ions and rosin emulsifier concentration after filtration were measured to identify the interaction between cement and rosin emulsifiers. The consumed emulsifier increases linearly with the amount of added cement or CaCl2 concentration in the case of diluted rosin emulsifier solutions in which the rosin emulsifier concentration is below the CMC (critical micelle concentration). In the case of concentrated rosin emulsifier solutions (above the CMC), the rosin emulsifier concentration shows a sharp decrease when a certain amount of cement or CaCl2 is added. This study indicates that cement destabilizes anionic bitumen emulsion due to the precipitation of rosin emulsifiers caused by Ca(2+) ions which are released by early cement hydration. Further studies on precipitation behavior have shown that micelles of rosin emulsifier can complex Ca(2+) ions but do not precipitate. These findings explain why slow-setting bitumen emulsions, which contain a higher concentration of emulsifier, show better mixing stability.

Lime as an Anti-Plasticizer for Self-Compacting Clay Concrete.

This paper focuses on the modification of clay properties with inorganic additives to deflocculate and flocculate inorganic soil for the development of a material that would be as easy to use as the current concrete products, but with a much lower environmental impact. Considering that the rheological behaviour of clays is controlled by their surface charge, we first introduce potential determining ions to deflocculate the clay particles and to reduce the yield stress of the earth material. Their efficiency is characterized using zeta potential measurements and rheological tests. We then achieve the flocculation of clay particles by using natural minerals that slowly dissolve in the interstitial liquid and ultimately precipitate calcium silicate hydrate (C-S-H). The precipitation products are identified by X-ray diffraction and the consequences of this delayed precipitation are followed by oscillatory rheometric measurements. Finally, it is suggested that in this process, C-S-H precipitation is not used as a binding vector but as an anti-plasticizer that removes the inorganic dispersant additives.

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.

Merging high doxorubicin loading with pronounced magnetic response and bio-repellent properties in hybrid drug nanocarriers.

Hybrid magnetic drug nanocarriers are prepared via a self-assembly process of poly(methacrylic acid)-graft-poly(ethyleneglycol methacrylate) (p(MAA-g-EGMA)) on growing iron oxide nanocrystallites. The nanocarriers successfully merge together bio-repellent properties, pronounced magnetic response, and high loading capacity for the potent anticancer drug doxorubicin (adriamicin), in a manner not observed before in such hybrid colloids. High magnetic responses are accomplished by engineering the size of the magnetic nanocrystallites (∼13.5 nm) following an aqueous single-ferrous precursor route, and through adjustment of the number of cores in each colloidal assembly. Complementing conventional magnetometry, the magnetic response of the nanocarriers is evaluated by magnetophoretic experiments providing insight into their internal organization and on their response to magnetic manipulation. The structural organization of the graft-copolymer, locked on the surface of the nanocrystallites, is further probed by small-angle neutron scattering on single-core colloids. Analysis showed that the MAA segments selectively populate the area around the magnetic nanocrystallites, while the poly(ethylene glycol)-grafted chains are arranged as protrusions, pointing towards the aqueous environment. These nanocarriers are screened at various pHs and in highly salted media by light scattering and electrokinetic measurements. According to the results, their stability is dramatically enhanced, as compared to uncoated nanocrystallites, owing to the presence of the external protective PEG canopy. The nanocarriers are also endowed with bio-repellent properties, as evidenced by stability assays using human blood plasma as the medium.

Hydration kinetics of tricalcium silicate by calorimetric methods.

The kinetics of the cement hydration reaction is a relevant issue in the cement research field, particularly in the presence of additional inorganic and organic components that consistently increase the complexity of the cement paste. In the present study, the hydration reaction of pure tricalcium silicate has been monitored by different calorimetric approaches: the conventional Isothermal Conduction Calorimetry (IC) and a novel Differential Scanning Calorimetry (DSC) protocol. The measured hydration curves have been modeled by using the Boundary Nucleation and Growth Model (BNGM) to extract thermodynamic parameters of the early stages of the hydration reaction. IC and DSC methods provide similar results in terms of rate constants, linear growth, and nucleation rates even though the IC accesses the total evolved heat while DSC discloses the fraction of unreacted water. The validation of the DSC approach as a reliable analytical method to the study of cement hydration kinetic is of particular importance because it allows following very long hydration processes, such as those of pastes containing organic retarders or superplasticizers. The thermodynamic and kinetic parameters for the tricalcium silicate setting has been also evaluated and discussed as a function of the surface area of the powder.

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.

Adsorption of polyelectrolytes and its influence on the rheology, zeta potential, and microstructure of various cement and hydrate phases.

In this study the influence of polycarboxylate-based polyelectrolytes on the particle interaction among tricalcium silicate (C(3)S, main clinker phase), calcium silicate hydrates (CSH), and calcium aluminate sulfate hydrates (ettringite) (main hydration phases) has been examined. These phases are the constituents of major concern during early hydration of cement suspensions. The results of zeta potential measurements on single mineral phase experiments show that the phases C(3)S and CSH are positively charged in synthetic pore solution (liquid phase of hydrating cement suspension), whereas the ettringite is negatively charged. Due to these opposite charges, ettringite crystals should coagulate with CSH phases and/or deposit on surfaces of the much larger C(3)S clinker particles. This behavior was proven by cryo-microscopic analysis of high-pressure frozen cement suspensions, which illustrates the consequences of colloidal mechanisms on the microstructure of early cement suspensions. Furthermore, it is shown that the polyelectrolytes have a much higher adsorption affinity to ettringite surfaces (hydrate phase) compared to silicate surfaces. However, the results from rheology experiments reveal that the presence of polyelectrolytes has a strong impact on the suspension properties of all investigated mineral phases by decreasing yield stress and plastic viscosity. From the results it can be concluded that the ettringite is the dominant mineral phase in terms of the state of dispersion which includes particle-particle and particle-polyelectrolyte interaction in the bulk cement system.

In situ nanomanipulators as a tool to separate individual tobermorite crystals for AFM studies.

Atomic force microscopy (AFM) studies of cementitious materials are limited, mainly due to the lack of appropriate sample preparation techniques. In porous autoclaved aerated concrete (AAC), calcium silicate hydrate (C-S-H) is produced in its crystalline form, tobermorite. The crystals are lath-like with a length of several micrometers. In this work, we demonstrate the application of nanomanipulators to separate an individual tobermorite crystal from the bulk AAC for subsequent AFM investigations. The nanomanipulators are operated directly in an environmental scanning electron microscope (ESEM). We studied the interaction between moisture and the tobermorite surface under controlled relative humidity (RH). The results of topography and adhesion force measurements with AFM suggest that the surface of tobermorite is hydrophobic, which contrasts the macroscopic material properties (e.g. moisture transport in capillary pores).