Bottling Liquid‐Like Minerals for Advanced Materials Synthesis

Abstract

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, CO 2 -neutral cements.

Exploring the Potential of Nonclassical Crystallization Pathways to Advance Cementitious Materials

“…Recently, the Gebauer group has developed an easily scalable method that facilitates the synthesis and use of the CaCO 3 liquid precursor on a large scale. 178 This method will enable the application of CaCO 3 PILP phases on larger scales, including uses in construction materials, such as cultural heritage restoration, 179 production of molded CaCO 3 mineral, 180 and mineral coatings. 181 Although the PNC pathway is still highly debated 137,182−184 and a unification of classical and nonclassical mechanisms was suggested, 185 the experimental evidence for the PNC pathway is steadily rising, with an increasing number of systems exhibiting its involvement in nucleation, including calcium phosphate, 186 CoFe 2 O 4 , 187 iron oxides, 188 InAs 189 but also organic molecules like amino acids.…”

“…Therefore, achieving industrial applicability would require several modifications toward upscaling. Recently, the Gebauer group has developed an easily scalable method that facilitates the synthesis and use of the CaCO 3 liquid precursor on a large scale . This method will enable the application of CaCO 3 PILP phases on larger scales, including uses in construction materials, such as cultural heritage restoration, production of molded CaCO 3 mineral, and mineral coatings …”

Time evolution of moduli of a polymer-induced liquid precursor (PILP) of calcium carbonate

“…The intrinsic nature of PILP may be positioned between two limited cases, i.e. , a deformable solid with a minor elastic modulus (gel-like amorphous precursor 23 ) or a true liquid (liquid-like precursor 24 ) with a high interfacial energy. Since both the elastic modulus and the interfacial tension estimated from the data are proportional to the measured force (see eqn (1) and (13) in the supported text, ESI†), their values for any intermediate case would then be determined by a linear interpolation between the two limiting values, as shown in Fig.…”

Molecular Weight-Dependent Physiochemical Behaviors of Calcium Carbonate Chains

“…With the development of calcium carbonate oligomers, , the chain-like topologies of inorganic ionic compounds have become accessible, and their molecular weights have become adjustable. This adjustability implies a potential pathway − for investigating the molecular weights of inorganic ionic compounds and their correlations with the topologies and physicochemical behaviors of calcium carbonate. Taking advantage of molecular weights to regulate the physicochemical behaviors of inorganic ionic compounds would enable the application of mature theories and methods from polymer physics to guide future research on inorganic ionic compounds, making it easier to elucidate the correlations between structures and properties in complex inorganic materials …”