Nanomaterials as Promising Additives for High-Performance 3D-Printed Concrete: A Critical Review.

Three-dimensional (3D) printed concrete (3DPC), as one of the subset of digital fabrication, has provided a revolution in the construction industry. Accordingly, scientists, experts, and researchers in both academic and industry communities are trying to improve the performance of 3DPC. The mix design of all kinds of concrete has always been the most crucial property to reach the best efficiency. Recently, many studies have been performed to incorporate nano- and micro-scale additives to ameliorate the properties of 3DPC. The current study aims to present the main design properties of 3DPC and completely cover both fresh and hardened state characteristics of 3DPC containing different nano- and micro-additives. Our observations illustrate that nanomaterials can be mainly utilized as a thickener to ameliorate the thixotropic behavior and the structural build-up of 3DPC, resulting in higher yield stress and better viscosity recovery. Furthermore, each nanomaterial, through its unique impact, can provide lower porosity and permeability as well as better mechanical strengths for 3DPC. Although much research investigate the fresh properties of 3DPC containing nano and micro additives, future studies are needed to provide better insight into the impact of these kinds of additives on the hardened characteristics of 3DPC. In addition, researchers may devote more research to address the effects of the additives discussed herein on the performance of other kinds of 3DPC such as lightweight, self-compacting, etc. It should be noted that the effect mechanism of nanomaterials on the inter-layer bond strength of 3DPC is another crucial issue that should be investigated in future studies. Furthermore, nano-scale fillers from source of waste and biomass can be attractive additives for future research to achieve high performance of sustainable 3D-printed concrete.

Designing Angstrom-Scale Asymmetric MOF-on-MOF Cavities for High Monovalent Ion Selectivity.

Biological ion channels feature angstrom-scale asymmetrical cavity structures, which are the key to achieving highly efficient separation and sensing of alkali metal ions from aqueous resources. The clean energy future and lithium-based energy storage systems heavily rely on highly efficient ionic separations. However, artificial recreation of such a sophisticated biostructure has been technically challenging. Here, a highly tunable design concept is introduced to fabricate monovalent ion-selective membranes with asymmetric sub-nanometer pores in which energy barriers are implanted. The energy barriers act against ionic movements, which hold the target ion while facilitating the transport of competing ions. The membrane consists of bilayer metal-organic frameworks (MOF-on-MOF), possessing a 6 to 3.4-angstrom passable cavity structure. The ionic current measurements exhibit an unprecedented ionic current rectification ratio of above 100 with exceptionally high selectivity ratios of 84 and 80 for K+ /Li+ and Na+ / Li+ , respectively (1.14 Li+ mol m-2 h-1 ). Furthermore, using quantum mechanics/molecular mechanics, it is shown that the combined effect of spatial hindrance and nucleophilic entrapment to induce energy surge baffles is responsible for the membrane's ultrahigh selectivity and ion rectification. This work demonstrates a striking advance in developing monovalent ion-selective channels and has implications in sensing, energy storage, and separation technologies.

Mechanical hydrolysis imparts self-destruction of water molecules under steric confinement.

Decoding behavioral aspects associated with the water molecules in confined spaces such as an interlayer space of two-dimensional nanosheets is key for the fundamental understanding of water-matter interactions and identifying unexpected phenomena of water molecules in chemistry and physics. Although numerous studies have been conducted on the behavior of water molecules in confined spaces, their reach stops at the properties of the planar ice-like formation, where van der Waals interactions are the predominant interactions and many questions on the confined space such as the possibility of electron exchange and excitation state remain unsettled. We used density functional theory and reactive molecular dynamics to reveal orbital overlap and induction bonding between water molecules and graphene sheets under much less pressure than graphene fractures. Our study demonstrates high amounts of charge being transferred between water and the graphene sheets, as the interlayer space becomes smaller. As a result, the inner face of the graphene nanosheets is functionalized with hydroxyl and epoxy functional groups while released hydrogen in the form of protons either stays still or traverses a short distance inside the confined space via the Grotthuss mechanism. We found signatures of a new hydrolysis mechanism in the water molecules, i.e. mechanical hydrolysis, presumably responsible for relieving water from extremely confined conditions. This phenomenon where water reacts under extreme confinement by disintegration rather than forming ice-like structures is observed for the first time, illustrating the prospect of treating ultrafine porous nanostructures as a driver for water splitting and material functionalization, potentially impacting the modern design of nanofilters, nanochannels, nano-capacitators, sensors, and so on.

Evaluation of the dispersion of metakaolin-graphene oxide hybrid in water and cement pore solution: can metakaolin really improve the dispersion of graphene oxide in the calcium-rich environment of hydrating cement matrix?

Graphene oxide (GO) is a promising candidate for reinforcing cement composites due to its prominent mechanical properties and good dispersibility in water. However, the severe agglomeration of GO nanosheets in the Ca2+ ion loaded environment of a freshly mixed cement composite is the main obstacle against the mentioned goal. Recent studies, based on the SEM images, have shown that the incorporation of pozzolans can ameliorate the GO agglomeration in cement matrix. Considering the fact that, for identifying the GO dispersion in cement matrix, SEM characterization is not preferred due to the hydrated cement matrix complexity and presence of small dosages of GO, this research has investigated the potential of Metakaolin (MK) as a highly reactive pozzolan against GO agglomeration in the non-hydrated environment of simulated cement pore solution (SCPS) for different MK/GO weight ratios. Additionally, the interaction between MK and GO in water is evaluated through different characterization methods. Visual investigation and UV-vis spectroscopy revealed that there should be a probable interaction between MK particles and GO nanosheets in water which was interpreted by Lewis acid-base interaction and further examined by FTIR spectroscopy. Moreover, the zeta potential measurements indicated that the increase in MK/GO weight ratio could lead to higher adsorption of GO on the surface of MK particles which was confirmed by the particle size analysis. Almost all of the conducted experiments on the MK-GO hybrid in simulated cement pore solution showed that different dosages of MK particles were incapable of preventing GO agglomeration; thus, despite the proposed mechanisms in previous studies, MK cannot effectively restrict the unfavorable effects of Ca2+ ions on GO dispersion in SCPS and analogously in the hydrating cement matrix.

Orbital Overlapping through Induction Bonding Overcomes the Intrinsic Delamination of 3D-Printed Cementitious Binders.

3D printing of cementitious materials holds a great promise for construction due to its rapid, consistent, modular, and geometry-controlled ability. However, its major drawback is low cohesion in the interlayer region. Herein, we report a combined experimental and computational approach to understand and control fabrication of 3D-printed cementitious materials with significantly enhanced interlayer strength using multimaterial 3D printing, in which the composition, function, and structure of the materials are programmed. Our results show that the intrinsic low interlayer cohesion is caused by excess moisture and time lag that block the majority of valuable interactions in the interlayer zone between the adjacent cement matrices. As a remedy, a thin epoxy layer is introduced as an intermediator between the adjacent extruded layers, both to improve the interlayer cohesion and to extend the possible time delay between printed adjacent layers. Our ab initio calculations demonstrate that an orbital overlap between the calcium ions, as the main electrophilic part of the cement structure, and the hydroxyl groups, as the nucleophilic part of the epoxy, create strong interfacial absorption sites. These electronic absorptions lead to several iono-covalent bonds between the cement matrix and epoxy, leading to significant improvements in tensile, shear, and compressive strengths as well as ductility of the 3D-printed composites. This is verified by our experimental data, which showed an average of 84% improvement in interlayer bonding. The upward augmentation of interlayer bonding helps 3D printing cementitious material to overcome their intrinsic limitation of weak interlayer cohesion, thereby mitigating/eliminating the key bottleneck of additive manufacturing in constructing materials.

Design principles of ion selective nanostructured membranes for the extraction of lithium ions.

It is predicted that the continuously increasing demand for the energy-critical element of lithium will soon exceed its availability, rendering it a geopolitically significant resource. The present work critically reviews recent reports on Li+ selective membranes. Particular emphasis has been placed on the basic principles of the materials' design for the development of membranes with nanochannels and nanopores with Li+ selectivity. Fundamental and practical challenges, as well as prospects for the targeted design of Li+ ion-selective membranes are also presented, with the goal of inspiring future critical research efforts in this scientifically and strategically important field.

Tunable, Multifunctional Ceramic Composites via Intercalation of Fused Graphene Boron Nitride Nanosheets.

Ternary two-dimensional (2D) materials such as fused graphene-boron nitride (GBN) nanosheets exhibit attractive physical and tunable properties far beyond their parent structures. Although these features impart several multifunctional properties in various matrices, a fundamental understanding on the nature of the interfacial interactions of these ternary 2D materials with host matrices and the role of their individual components has been elusive. Herein, we focus on intercalated GBN/ceramic composites as a model system and perform a series of density functional theory calculations to fill this knowledge gap. Propelled by more polarity and negative Gibbs free energy, our results demonstrate that GBN is more water-soluble than graphene and hexagonal boron nitride (h-BN), making it a preferred choice for slurry preparation and resultant intercalations. Further, a chief attribute of the intercalated GBN/ceramic is the formation of covalent C-O and B-O bonds between the two structures, changing the hybridization of GBN from sp2 to sp3. This change, combined with the electron release in the vicinity of the interfacial regions, leads to several nonintuitive mechanical and electrical alterations of the composite such as exhibiting higher young's modulus, strength, and ductility as well as sharp decline in the band gap. As a limiting case, though both tobermorite ceramic and h-BN are wide band gap materials, their intercalated composite becomes a p-type semiconductor, contrary to intuition. These multifunctional features, along with our fundamental electronic descriptions of the origin of property change, provide key guidelines for synthesizing next generation of multifunctional bilayer ceramics with remarkable properties on demand.

Mechanical and electromechanical properties of functionalized hexagonal boron nitride nanosheet: A density functional theory study.

Hydroxylation as a technique is mainly used to alter the chemical characteristics of hexagonal boron nitride (h-BN), affecting physical features as well as mechanical and electromechanical properties in the process, the extent of which remains unknown. In this study, effects of functionalization on the physical, mechanical, and electromechanical properties of h-BN, including the interlayer distance, Young's modulus, intrinsic strength, and bandgaps were investigated based on density functional theory. It was found that functionalized layers of h-BN have an average distance of about 5.48 Å. Analyzing mechanical properties of h-BN revealed great dependence on the degree of functionalization. For the amorphous hydroxylated hexagonal boron nitride nanosheets (OH-BNNS), the Young's modulus moves from 436 to 284 GPa as the coverage of -OH increases. The corresponding variations in the Young's modulus of the ordered OH-BNNS with analogous coverage are bigger at 460-290 GPa. The observed intrinsic strength suggested that mechanical properties are promising even after functionalization. Moreover, the resulted bandgap reduction drastically enhanced the electrical conductivity of this structure under imposed strains. The results from this work pave the way for future endeavors in h-BN nanocomposites research.