Christian Pritzel

Gypsum (CaSO₄·2H₂O) crystallization is highly sensitive to the supersaturation pathway, which governs the balance between nucleation and crystal growth and ultimately controls growth morphology. In this study, gypsum was synthesized via two contrasting routes—diffusion-controlled crystallization and rapid precipitation—using identical reactant systems to enable a direct comparison of distinct kinetic regimes. A polycarboxylate-based superplasticizer was incorporated to investigate pathway-dependent additive effects. Time-resolved observations reveal that rapid precipitation is characterized by high nucleation density under steep supersaturation, whereas diffusion-controlled crystallization proceeds under gradually increasing supersaturation with restricted nucleation and sustained anisotropic growth. Powder X-ray diffraction confirms the formation of phase-pure gypsum under all conditions. Scanning electron microscopy shows that the presence of the superplasticizer reduces crystal number density and modifies crystal habit in both pathways, although the extent and manifestation of these effects depend strongly on the governing kinetic regime. Under diffusion-controlled conditions, the increasing superplasticizer dosage promotes the transition from elongated to more tabular morphologies, while rapid precipitation results in dense, intergrown aggregates under high supersaturation. Overall, the results demonstrate that the effectiveness of the superplasticizer is not intrinsic but depends on the crystallization pathway. These findings provide new insight into how supersaturation profiles mediate the interplay between additive interactions and growth processes, enabling improved control over gypsum crystal morphology.

Gypsum (CaSO₄·2H₂O) crystallization underpins numerous industrial processes, yet its response to chemical admixtures remains incompletely understood. This study investigates diffusion-controlled crystal growth in a coaxial test tube system to evaluate how three Sika^® ViscoCrete^® superplasticizers—430P, 111P, and 120P—affect nucleation, growth kinetics, morphology, and thermal behavior. The superplasticizers, selected for their surface-active properties, were hypothesized to influence crystallization via interfacial interactions. Ion diffusion was maintained quasi-steadily for 12 weeks, with crystal evolution tracked weekly by macro-photography; scanning electron microscopy and thermogravimetric/differential scanning were performed at the final stage. All admixtures delayed nucleation in a concentration-dependent manner. Lower dosages (0.5–1.0 wt%) yielded platy-to-prismatic morphologies and higher dehydration enthalpies, indicating more ordered lattice formation. In contrast, higher dosages (1.5–2.0 wt%) produced denser, irregular crystals and shifted dehydration to lower temperatures, suggesting structural defects or increased hydration. Among the additives, 120P showed the strongest inhibitory effect, while 111P at 0.5 wt% resulted in the most uniform crystals. These results demonstrate that ViscoCrete^® superplasticizers can modulate gypsum crystallization and thermal properties.

The increasing demand for sustainable energy as a means to combat the impact of climate change is addressed via a novel concept in the present work. Herein presented are developed transferable encapsulated dye-sensitized solar cells, canonically “solar capsules”, for photovoltaic applications on alternative surfaces, such as facades. The solar capsule assembly houses all the components necessary for photovoltaic energy conversion, enclosed within a semiconductor nanotubular array, making them truly unique in their construction. This capsule-style unit enables an easy transfer and draft onto a wide range of materials and surfaces for photovoltaic functionalization and applications. This type of dye-sensitized solar cell typically consists of transferred solar capsules and two additional electrodes. The design and construction of solar capsules means they have a high economic viability as they can seamlessly be up-scaled using commercially established techniques such as anodization and subsequent functionalization. This work demonstrates a working model of such transferable solar capsules by fabricating TiO₂ nanotubes that are functionalized via facile dip- and spin-coating techniques in a wet lab at ambient conditions. These prototypes are characterized in bulk and are thoroughly investigated at the nanoscale for information on the chemical distribution of the constituents, as they may be influenced during the manufacturing process.

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.

The increasing demand for sustainable energy as a means to combat the impact of climate change is addressed via a novel concept in the present work. Herein, the development of encapsulated dye-sensitized solar cells, canonically “solar capsules”, for photovoltaic applications on alternative surfaces, such as facades, is presented. The solar capsule assembly houses all components necessary for photovoltaic energy conversion, enclosed within a semiconductor nanotubular array, making them truly unique in their construction. This capsule-style unit enables an easy transfer and draft onto a wide range of materials and surfaces for photovoltaic functionalization and applications. This type of dye-sensitized solar cell typically consists of transferred solar capsules and two additional electrodes. The design and construction of solar capsules have high economic viability as they can seamlessly be up-scaled using commercially established techniques such as anodization and subsequent functionalization. This work demonstrates a working model of such a capsule by fabricating TiO2 nanotubes that are functionalized via facile dip- and spin-coating techniques in a wet lab at ambient conditions. These prototype solar capsules are characterized in bulk and are thoroughly investigated at the nanoscale for information on the chemical distribution of the constituents, as they may be influenced during the manufacturing process.

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.

We report on the synthesis route for metal-oxide nanotubes via electro-chemical anodization of zirconium foil resulting in the formation of zirconia nanotubular (ZrNT) films, subsequently transferred onto pre-formed zirconia (ZrO2) implant material. The approach was based on a direct transfer of ZrNT films onto the ceramic implant via an acetone bath. The ZrNT film was detached from the metal-foil using regular adhesive-tape prior to transfer. This simple technique allows to impart a robust micro-nanoscale structure to bulk-ceramics that can potentially offer enhanced surface-reaction sites and functionality in the field of ceramic-biomaterial applications.

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.

Due to a recent change concerning the risk and hazard regulations of titanium dioxide powders, which possibly leads to restrictions in the use of those materials in photocatalytic applications, an alternative utilization of titanium dioxide is shown in this work. This is achieved by covering surfaces of cement-based materials with a regular-shaped monolayer of photocatalytically active titanium dioxide nanotube arrays which are not affected by the regulation changes due to their shape and size. This study delivers a proposal for the synthesis of TiO2 nanotubes via anodization and their post-treatment to generate detached crystalline nanotube arrays which can be easily transferred onto material surfaces. We show that the transfer of such nanostructured materials can be achieved by modifying the cement mold, showing the opportunity for applying the material to precast elements. The composite material is characterized by referencing the morphology and photocatalytic activity.

In this study, the effect of Al on the high temperature oxidation of Al-containing refractory high entropy alloys (RHEAs) Ta-Mo-Cr-Ti-xAl (x = 5; 10; 15; 20 at%) was examined. Oxidation experiments were performed in air for 24 h at 1200 °C. The oxidation kinetics of the alloy with 5 at% Al is notably affected by the formation of gaseous MoO₃ and CrO₃, while continuous mass gain was detected for alloys with the higher Al concentrations. The alloys with 15 and 20 at% Al form relatively thin oxide scales and a zone of internal corrosion due to the formation of dense CrTaO₄ scales at the interface oxide/substrate. The alloys with 5 and 10 at% Al exhibit, on the contrary, thick and porous oxide scales because of fast growing Ta₂O₅. The positive influence of Al on the formation of Cr₂O₃ followed by the growth of CrTaO₄ to yield a compact scale is explained by getter and nucleation effects.