Preparation of Geopolymers with Nanosilica and Water-in-Air Pickering Emulsion: Mechanisms Underlying Its Rheology, Polymerization, and Strength.

Geopolymers are alkaline-activated aluminosilicate binders recognized as a promising alternative to traditional Portland cement due to their significantly lower greenhouse emissions, energy consumption, and carbon footprint. However, the challenge is meeting or exceeding the strength of Portland cement concrete while being prepared within a desired setting time and possessing workable rheology. A "water-in-air" Pickering emulsion, also called dry water, was prepared by stabilizing water droplets with hydrophobic nano silica and using them to control the geopolymer's strength, setting time, and workability. The mechanisms that underlie the effects of dry water on the rheology, setting, and strength were studied in detail through a combination of rheological, thermal, morphological, chemical, and microstructural assessments. A reduction in the viscosity and yield shear stress manifests in a higher flow diameter, principally due to the particle size coarsening in the precursor and the flowability of hydrophobic nano silica. There was a rapid rise in temperature during the setting process as the dry water temporarily increased the local alkalinity in the mixture, which boosted the dissolution of the precursor and, hence, the reaction. Outcomes from X-ray diffraction, thermogravimetric analysis, and Fourier-transform infrared confirm the highest degree of polycondensation for the principal N-A-S-H framework in mixtures containing dry water. These eventually correspond to a denser microstructure under scanning electron microscopy and, in turn, a superior mechanical strength. Depending on the unique combination of characteristics, including size coarsening, temporary water encapsulation, microfilling effect, and supplementary silica source, dry water resolves the "trade-off" between geopolymer's fresh and hardened properties when introducing nanoparticles.

Experimental Characterization and Multi-Factor Modelling to Achieve Desired Flow, Set and Strength of N-A-S-H Geopolymers.

The interaction between compositional ratios, namely, SiO2/Al2O3, Na2O/Al2O3, H2O/Na2O and the liquid-to-solid ratio, triggers mutual sacrifice between workability, setting time and strength for N-A-S-H geopolymers. The present study characterizes the mechanism underlying the effect of these compositional ratios and, in turn, develops guidelines for mixture design that requires a simultaneous and satisfactory delivery of these engineering properties. The experimental results show that an increase in either the SiO2/Al2O3, Na2O/Al2O3 or H2O/Na2O ratio raises the liquid-to-solid ratio, which in turn improves the workability of fresh mixtures. A continuous increase beyond 2.8 for the SiO2/Al2O3 ratio boosts its strength, but also significantly extends its final set. Lowering the Na2O/Al2O3 ratio from 1.3 to 0.75 raises the compressive strength significantly, while the shortest final set was seen at the median value, 1.0. A H2O/Na2O ratio of 9~10 yields the highest strength and the fastest final set simultaneously, due to the maximized degree of geopolymerization. Moreover, the accompanying sensitivity analysis indicates that the workability depends chiefly upon the H2O/Na2O ratio, the final setting time on the SiO2/Al2O3 ratio and, that the compressive strength relies on both of them. Also, this study proposes an optimal range of 2.8~3.6 for SiO2/Al2O3, 0.75~1.0 for Na2O/Al2O3 and 9~10 for H2O/Na2O to guarantee high strength, together with high flow and within the allowable final setting time. Furthermore, multi-factor predictive models are established with acceptable accuracy for practitioners to regulate oxide compositions in N-A-S-H geopolymers, which will guide future mixture design.

Facile Synthesis of Calcium Hydroxide Nanoparticles onto TEMPO-Oxidized Cellulose Nanofibers for Heritage Conservation.

Calcium hydroxide is used in diverse applications including heritage conservation where supplying it in the form of nanoparticles allows easy carbonation with atmospheric air contacts. The effects of cellulose nanofibers on the precipitation of calcium hydroxide nanoparticles were investigated by varying the reaction time, concentration, and carboxylation content of cellulose nanofibers. Cellulose nanofibers were very effective in producing calcium hydroxide nanoparticles with less than 50 nm sizes out of calcium nitrate-sodium hydroxide precipitation reactions. The formation of smaller-size calcium hydroxide nanoparticles is believed to be the result of heterogeneous nucleation and growth of calcium hydroxide particles on cellulose nanofibers. The liquid-phase nucleated and grown calcium hydroxide nanoparticles were also deposited onto cellulose nanofibers. The resulting calcium hydroxide nanoparticles were carbonized and generated calcite under atmospheric carbon dioxide in an efficient way.

Preparation of cellulose nanofibers by TEMPO-oxidation of bleached chemi-thermomechanical pulp for cement applications.

Hardwood bleached chemi-thermomechanical pulp (BCTMP) was converted to cellulose nanofibers by 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) catalyzed oxidization along with mechanical defibrillation process. The TEMPO reaction was evaluated based on the delignification, carboxylate content of cellulose and the yield of the insoluble component. Cellulose nanofibers were characterized by conductometry, Fourier transform infrared spectroscopy (FT-IR), scanning electronic microscopy (SEM), thermogravimetric analysis (TGA) as well as X-ray diffraction (XRD) techniques. Minimum 10 mmol/g NaClO addition was needed to obtain meaningful carboxylate content and easy defibrillation by using high shear mixing. TEMPO-catalyzed oxidization process removed 74% of pentosans and 80% of lignin from bleached chemi-thermomechanical hardwood pulp while 13% of cellulose was also lost. CNF with 1.44 mmol/g carboxylate content resulted high level of water retention (13.4 g/g fiber) Cellulose nanofibers were used in cementitious mixtures. CNF with carboxyl groups resulted in better flow control in wet cement paste and reduced the crack growth in concrete.