Porosity of Calcium Silicate Hydrates Synthesized from Natural Rocks

In this work, the suitability of natural raw materials with various modifications of SiO₂—granite sawing waste (quartz) and opoka (a mixture of cristobalite, tridymite, quartz, and an amorphous part)—for the 1.13 nm tobermorite and xonotlite synthesis is examined, and their specific surface area, pore diameter and volume, and the predominant pores are determined. Hydrothermal syntheses were carried out at 200 °C for 12 and 72 h from mixtures with a molar ratio of CaO/SiO₂ = 1.0. X-ray diffraction analysis, simultaneous thermal analysis, and scanning electronic microscopy were used, which showed that in the lime–calcined opoka mixture the formation of crystalline calcium silicate hydrates takes place much faster than in the lime–granite sawing waste mixture. The high reactivity of amorphous SiO₂ results in the rapid formation of 1.13 nm tobermorite and xonotlite (12 h). According to Brunauer, Emmet and Taller (BET) analysis data, this product features a specific surface area of ~68 m²/g, a total pore volume of 245 × 10⁻³ cm³/g, and has dominating 1–2.5 nm and 5–20 nm diameter pores. This porosity of the material should provide good thermal insulation properties of the products made from it as no air convection occurs in the fine pores.     

Synthesis of High Crystallinity 1.13 nm Tobermorite and Xonotlite from Natural Rocks,Their Properties and Application for Heat-Resistant Products

The main measure to reduce energy losses is the usage of insulating materials. When the temperature exceeds 500 °C, silicate and ceramic products are most commonly used. In this work, high-crystallinity 1.13 nm tobermorite and xonotlite were hydrothermally synthesized from lime and Ca–Si sedimentary rock, opoka. By XRD, DSC, TG and dilatometry methods, it has been shown that 1.13 nm tobermorite becomes the predominant compound in stirred suspensions at 200 °C after 4 h of synthesis in the mixture with a molar ratio CaO/SiO₂ = 0.83. It is suitable for the production of insulating products with good physical–mechanical properties (average density < 200 kg·m⁻¹, compressive strength ~0.9 MPa) but has a limited operating temperature (up to 700 °C). Sufficiently pure xonotlite should be used to obtain materials with a higher operating temperature. Even small amounts of semi-amorphous C–S–H(I) significantly increase its linear shrinkage during firing. It has also been observed that an increase in the strength values of the samples correlated well with the increase in the size of xonotlite crystallites. The optimal technological parameters are as follows: molar ratio of mixture CaO/SiO₂ = 1.2; water/solid ratio W/S = 20.0; duration of hydrothermal synthesis at 220 °C—8 h, duration of autoclaving at 220 °C—4 h. The average density of the samples was ~180 kg·m⁻¹, the operating temperature was at least 1000 °C, and the compressive strengths exceeded 1.5 MPa.