High Energy Absorption Nacre‐Like Calcium Silicate Hydrate (C‐S‐H) Composite Toward Elastic Cementitious Materials
2023-10-30, Liu, Xin, Feng, Pan, Ruiz Agudo, Cristina, Sun, Huiwen, Yu, Xiaohan, Avaro, Jonathan Thomas, Huang, Jiale, Hou, Dongshuai, Ran, Qianping, Cölfen, Helmut
The low toughness under the tension of cement and concrete materials has been a long‐standing issue for decades and it has become increasingly urgent to address in modern society due to the growing demand for the development of high‐performance and sustainable constructions. Manipulating calcium silicate hydrate (C‐S‐H), the main hydration product of Portland cement, which determines the mechanical properties of cementitious materials, is an attractive method for improving their toughness following a bottom‐up approach. Inspired by the microstructure of nacre, a high energy absorption C‐S‐H‐based composite with a highly ordered structure is fabricated by a designed ternary building block, in which exfoliated montmorillonite provides a template for the nucleation and growth of C‐S‐H generating the “brick”, and polyvinyl alcohol acts as a “mortar” binding all the building blocks together. With the hierarchical toughening strategy explored here, the obtained C‐S‐H composite achieves a remarkable energy absorption of 16.2 ± 2.6 MJ m −3 , which surprisingly outperforms the ultra‐high toughness cementitious materials by a factor of 20–60 and is even higher than that of natural nacre and other nacre‐like composites. These findings not only provide valuable insights into enhancing the toughness of cementitious materials but also open possibilities for broadening potential applications of C‐S‐H.
Biodegradable Mineral Plastics
2023-07-19, Avasthi, Ilesha, Lerner, Harry, Grings, Jonas, Gräber, Carla, Schleheck, David, Cölfen, Helmut
Mineral plastics are a promising class of bio-inspired materials that offer exceptional properties, like self-heal ability, stretchability in the hydrogel state, and high hardness, toughness, transparency, and non-flammability in the dry state along with reversible transformation into the hydrogel by addition of water. This enables easy reshape-ability and recycling like the solubility in mild acids to subsequently form mineral plastics again by base addition. However, current mineral plastics rely on petrochemistry, are hardly biodegradable, and thus persistent in nature. This work presents the next generation of mineral plastics, which are bio-based and biodegradable, making them a promising, new class of polymers for the development of environmentally friendly materials. Physically cross-linked (poly)glutamic-acid (PGlu)-based mineral plastics are synthesized using various alcohol-water mixtures, metal ion ratios and molecular weights. The rheological properties are easily adjusted using these parameters. The general procedure involves addition of equimolar solution of CaCl2 to PGlu in equal volumes followed by addition of iPrOH (iPrOH:H2O = 1:1) under vigorous stirring conditions. The ready biodegradability of PGlu/CaFe mineral plastic is confirmed in this study where the elements N, Ca, and Fe present in it tend to act as additional nutrients, supporting the growth of microorganisms and consequently, promoting the biodegradation process.
Toward Understanding the Formation Mechanism and OER Catalytic Mechanism of Hydroxides by In Situ and Operando Techniques
2023, Chen, Zongkun, Fan, Qiqi, Zhou, Jian, Wang, Xingkun, Huang, Minghua, Jiang, Heqing, Cölfen, Helmut
Developing efficient and affordable electrocatalysts for the sluggish oxygen evolution reaction (OER) remains a significant barrier that needs to be overcome for the practical applications of hydrogen production via water electrolysis, transforming CO2 to value‐added chemicals, and metal‐air batteries. Recently, hydroxides have shown promise as electrocatalysts for OER. In situ or operando techniques are particularly indispensable for monitoring the key intermediates together with understanding the reaction process, which is extremely important for revealing the formation/OER catalytic mechanism of hydroxides and preparing cost‐effective electrocatalysts for OER. However, there is a lack of comprehensive discussion on the current status and challenges of studying these mechanisms using in situ or operando techniques, which hinders our ability to identify and address the obstacles present in this field. This review offers an overview of in situ or operando techniques, outlining their capabilities, advantages, and disadvantages. Recent findings related to the formation mechanism and OER catalytic mechanism of hydroxides revealed by in situ or operando techniques are also discussed in detail. Additionally, some current challenges in this field are concluded and appropriate solution strategies are provided.
Organized mineralized cellulose nanostructures for biomedical applications
2023, Feng, Yanhuizhi, Cölfen, Helmut, Xiong, Rui
Cellulose is the most abundant naturally-occurring polymer, and possesses a one-dimensional (1D) anisotropic crystalline nanostructure with outstanding mechanical robustness, biocompatibility, renewability and rich surface chemistry in the form of nanocellulose in nature. Such features make cellulose an ideal bio-template for directing the bio-inspired mineralization of inorganic components into hierarchical nanostructures that are promising in biomedical applications. In this review, we will summarize the chemistry and nanostructure characteristics of cellulose and discuss how these favorable characteristics regulate the bio-inspired mineralization process for manufacturing the desired nanostructured bio-composites. We will focus on uncovering the design and manipulation principles of local chemical compositions/constituents and structural arrangement, distribution, dimensions, nanoconfinement and alignment of bio-inspired mineralization over multiple length-scales. In the end, we will underline how these cellulose biomineralized composites benefit biomedical applications. It is expected that this deep understanding of design and fabrication principles will enable construction of outstanding structural and functional cellulose/inorganic composites for more challenging biomedical applications.
Localized Crystallization of Calcium Phosphates by Light‐Induced Processes
2023-10-19, Besirske, Patricia, Menichetti, Arianna, Montalti, Marco, García‐Ruiz, Juan Manuel, Winterhalder, Martin, Boneberg, Johannes, Cölfen, Helmut
Medical treatment options for bones and teeth can be significantly enhanced by taking control over the crystallization of biomaterials like hydroxyapatite in the healing process. Light‐induced techniques are particularly interesting for this approach as they offer tremendous accuracy in spatial resolution. However, in the field of calcium phosphates, light‐induced crystallization has not been investigated so far. Here, proof of principle is established to successfully induce carbonate‐hydroxyapatite precipitation by light irradiation. Phosphoric acid is released by a photolabile molecule exclusively after irradiation, combining with calcium ions to form a calcium phosphate in the crystallization medium. 4‐Nitrophenylphosphate (4NPP) is established as the photolabile molecule and the system is optimized and fully characterized. A calcium phosphate is crystallized exclusively by irradiation in aqueous solution and identified as carbonate apatite. Control over the localization and stabilization of the carbonate apatite is achieved by a pulsed laser, triggering precipitation in calcium and 4NPP‐containing gel matrices. The results of this communication open up a wide range of new opportunities, both in the field of chemistry for more sophisticated reaction control in localized crystallization processes and in the field of medicine for enhanced treatment of calcium phosphate containing biomaterials.
Growth strategy for solution-phase growth of two-dimensional nanomaterials via a unified model
2023-03-30, Chen, Zongkun, Schmid, Ralf, Wang, Xingkun, Fu, Mengqi, Han, Zhongkang, Fan, Qiqi, Scheer, Elke, Huang, Minghua, Nielaba, Peter, Cölfen, Helmut
Two-dimensional (2D) materials prepared by a solution-phase growth route exhibit many unique properties and are promising for use in various fields. However, simple, rational and green fabrication of target materials remains challenging due to the lack of guiding principles. Here we propose a universal qualitative model for 2D materials grown for layered and non-layered crystal structures by a solution-phase growth route; both theoretical simulation and experimental results confirm the model’s validity. This model demonstrates that 2D growth can be controlled by only tuning the reaction concentration and temperature, and has been applied to fabricate more than 30 different 2D nanomaterials in water at room temperature and in the absence of additives. Furthermore, the model shows promise for optimizing the experimental design of numerous other 2D nanomaterials.
Cationic Coacervates : Novel Phosphate Ionic Reservoir for the Mineralization of Calcium Phosphates
2023, Gruber, Dominik, Ruiz Agudo, Cristina, Cölfen, Helmut
Cationic complex coacervates are contemplated for various medical applications controlling carrier or release processes. Here, lower Mw poly(allylamine hydrochloride) (15 kg/mol) and (hydrogen)phosphate as cross-linking units were chosen to facilitate a sufficient coacervation and subsequently a controllable phosphate release, essential for consecutive mineralization reactions. In addition, the rheological characteristics of the obtained coacervates were assessed, exhibiting a pronounced liquid character, which enables beneficial properties toward remineralization applications such as high wettability and moldability. In light of our results, macroscopic hydrogels are considered for the first time as an ion source for the mineralization of crystalline calcium phosphate phases, representing an entirely new class of preceding mineralization species for potential applications in dentistry and osteology.
Tuning the growth morphology of gypsum crystals by polymers
2023-02, Madeja, Benjamin, Avaro, Jonathan Thomas, Van Driessche, Alexander E.S., Rückel, Markus, Wagner, Elisabeth, Cölfen, Helmut, Kellermeier, Matthias
True control over the morphology of gypsum crystals formed via homogeneous precipitation from solution has rarely been reported in the literature. In this work, we have tested a large number of dissolved additives (polymers as well as small molecules) with respect to their ability to alter the typical microscopic appearance of precipitated gypsum powders, which is usually characterized by a mixture of single-crystalline needles and twinned plates. Among the many additives studied, a copolymer of vinylpyrrolidone and acrylic acid (PVP-co-PAA) was identified as powerful growth modifier for gypsum already at low concentrations. In both slow titration and rapid mixing experiments, unconventional blocky crystals with tilted stacking edges as well as pseudo-hexagonal plates could be synthesized reproducibly with the help of the copolymer. Systematic characterization revealed the dynamic mode of action of the newly identified growth modifier, which seems to stabilize a highly reactive face of gypsum and promote the formation of macrosteps. The degree of morphological control achieved in this way is unprecedented in the case of calcium sulfate and may devise entirely new concepts for additive design in the areas of plasters and cementitious materials, gypsum wallboard production and/or scale prevention.
Cross-Linking of Apatite–Gelatin Nanocomposites as the Basis for Dentine Replacement Materials
2023, Konsek, Julian, Knaus, Jennifer, Avaro, Jonathan Thomas, Sturm, Elena V., Cölfen, Helmut
A novel approach for the production of a bioinspired dentine replacement material is introduced. An apatite–gelatin nanocomposite material was cross-linked with various cross-linkers. These nanocomposites have a high resemblance to mammalian dentine regarding its composition and properties. A precipitation reaction was used to produce apatite–gelatin nanocomposites as starting materials. Cross-linking of the gelatin has to be performed to produce dentine-like and thus tough and robust apatite–gelatin nanocomposites. Therefore, the efficacy of various protein cross-linkers was tested, and the resulting materials were characterized by scanning electron microscopy, transmission electron microscopy, powder X-ray diffraction, and EXAFS as well as CHNS analysis and tested for their mechanical performance using Vickers hardness measurements as well as for their dissolution stability in EDTA. Especially glutaraldehyde, proanthocyanidins, and transglutaminase gave promising results with hardness values of up to 63 HV0.2. To further improve the material properties, we combined the effective cross-linker transglutaminase with casein, which led to an improved interconnection between the single nanocomposite platelets. By doing so, a cross-linked composite was obtained, which shows even higher hardness values than does human dentine, at 76 HV0.2. The combination of apatite–gelatin nanocomposites with an effective cross-linker resulted in a bioinspired material with composition and properties close to those of human dentine.