Generality of liquid precursor phases in gas diffusion-based calcium carbonate synthesis

The ammonia diffusion method (ADM) is one of the most widely used strategies for the bioinspired synthesis of minerals. Herein, we present investigations of the mineralization mechanism using an advanced ADM to solve the limitations of the conventional ADM. This allows us to confirm the presence of liquid calcium carbonate precursor species in additive-free and polymer-stabilized gas diffusion systems, indicating that liquid-liquid phase separated species exhibit sufficient kinetic stability to be detected. Time-dependent experiments reveal the role of these precursor phases during the early stages of the crystallization process, demonstrating that liquid calcium carbonate mineral precursors play an important role in the precipitation pathway and must be generally considered for the interpretation of gas diffusion experiments, with and without additives. This discovery poses an important step in the understanding of how minerals are formed, highlighting that nonclassical mineralization processes must be considered for material synthesis. Last but not least, the advanced ADM may be useful for the exploration of the formation mechanism of other minerals than calcium carbonate, which are also of broad interest in the materials chemistry community

Bottling Liquid-Like Minerals for Advanced Materials Synthesis

Materials synthesis via liquid-like mineral precursors has been studied since their discovery almost 25 years ago, because their properties offer several advantages, for example, the ability to infiltrate small pores, the production of non-equilibrium crystal morphologies or mimicking textures from biominerals, resulting in a vast range of possible applications. However, the potential of liquid-like precursors has never been fully tapped, and they have received limited attention in the materials chemistry community, largely due to the lack of efficient and scalable synthesis protocols. Herein, the “scalable controlled synthesis and utilization of liquid-like precursors for technological applications” (SCULPT) method is presented, allowing the isolation of the precursor phase on a gram scale, and its advantage in the synthesis of crystalline calcium carbonate materials and respective applications is demonstrated. The effects of different organic and inorganic additives, such as magnesium ions and concrete superplasticizers, on the stability of the precursor are investigated and allow optimizing the process for specific demands. The presented method is easily scalable and therefore allows synthesizing and utilizing the precursor on large scales. Thus, it can be employed for mineral formation during restoration and conservation applications but can also open up pathways toward calcium carbonate-based, CO2-neutral cements

Revision of the calibration experiment in asymmetrical flow field-flow fractionation

Asymmetrical flow field-flow fractionation is a versatile chromatographic fractionation method. In combination with at least one detection technique it is used for size-based separation of colloids, biomolecules and polymers. Although often used as pure separation method, a well-elaborated theory is available that allows precise quantification of the translational diffusion coefficient D. Still, current literature suggests different ways to transform this theory into applicable experimental procedures and no “gold standard” for correct data processing exists. While some sources report a direct way to extract diffusion information from the fractogram, others suggest the necessity of an external calibration measurement to obtain the channel width w. In this work, we compare the different approaches and calibration algorithms based on original and literature data using our own open-source AF4 evaluation software. Based on the results, we conclude that available AF4 setups do not fulfill the requirements for absolute measurements of D. We show that the best way to conduct is to consider the area of the channel and D of the calibrant while neglecting the small peak which occurs in the void peak region.publishe