Gypsum (calcium sulfate dihydrate) is one of the most used inorganic binding materials in the world. During calcination, calcium sulfate subhydrates are formed and, for technical reasons, are mixed with water to form dihydrate again. Therefore, the dehydration process of gypsum and the rehydration of hemihydrate were investigated. This dehydration process is technically performed in three different ways. Heating up, i.e., in a rotary kiln, leads to a preferred formation of β-hemihydrate, which crystallizes in comparatively small crystals. Similar results can be achieved by recrystallization from gypsum slurry around 100 °C in an autoclave or under a water steam atmosphere. However, in contrast, the recrystallization process here leads to the formation of a larger, needle-like morphology and sometimes branched α-hemihydrate crystals. The synthesis of β-hemihydrate was investigated in detail with a special thermal stage for optical microscopy on natural single gypsum crystals. It was observed that the crystal loses transparency because of the breaking surface of the crystals due to water evaporation. Furthermore, within a deeper layer of the crystal, new crystals become visible but disappear during dehydration of the upper layers. These are expected to be α-hemihydrate. This theory of the formation of α-hemihydrate inside of a gypsum crystal is experimentally proven in the present work. This work firstly shows that the observed crystallization inside of gypsum during dehydration is the formation of alpha-hemihydrate.

One of the most significant global challenges for humans is environmental pollution. The technology to control this problem is the utilization of semiconductors as photocatalysts. In the current study, iron-doped titania nanotubes (Fe/TiNTs) with increased photocatalytic effect were synthesized via a modified hydrothermal method. The products were characterized by X-ray powder diffraction, scanning electron microscopy, transmission electron microscopy (TEM), gas adsorption, electron spin resonance (ESR) and UV–Vis diffuse reflectance spectroscopy (DRS). TEM results indicated that Fe/TiNTs have a tubular and uniform structure with an average outer diameter of 23–48 nm and length of 10–15 µm. ESR and DRS revealed that Fe³⁺ ions were successfully introduced into the TiNT structure by replacing Ti⁴⁺ ions. An enhanced light absorption in the range of 400–600 nm additionally indicated successful doping. The band gap was narrowed as iron wt% was increased. The photocatalytic activity was evaluated by the degradation of methyl orange (MO) in the presence of Fe/TiNTs and TiTNs by monitoring the degradation of MO under UV light irradiation. An acceleration on the hydration of Portland cement was observed in the presence of 2.0 wt% Fe/TiNTs. Fe/TiNTs can be used as a nanomaterial in cement-based building materials to provide self-cleaning properties to the surface of concrete even in indoor environments.

Environmental pollution is one of the most serious and global problems for humans. Photocatalysis is a promising technology to control environmental pollution via the utilization of semiconductor materials as a photocatalyst. In this study, iron-doped TiO₂ nanotubes (Fe/TiNTs) with an increased photocatalytic effect at longer wavelengths compared to undoped TiNTs were used, and the effect on the early hydration and mechanical properties of the main clinker phase tricalcium silicate (C₃S) was investigated for the first time. Prior to the incorporation of nanotubes into C₃S, it was treated with a supersaturated Ca(OH)₂ solution. The addition of 1 and 2 wt.% of Fe/TiNTs into the C₃S system significantly accelerated the course of hydration. The degree of hydration for the hydration products after 8 h, 1 d and 7 d have improved. The enhancement of compressive strength after 7 d, 14 d and 28 d were observed compared to normal TiO₂ nanotubes (TiNTs). Treating Fe/TiNTs with a supersaturated Ca(OH)₂ solution revealed a stronger interaction between Ca²⁺-ions and nanotubes. Fe/TNTs were synthesized via a modified hydrothermal process. The study shows that Fe/TiNTs can be used as a nanomaterial in cement-based building materials due to their enhanced interaction with the system.