Nacre-like block lattice metamaterials with targeted phononic band gap and mechanical properties.

The extraordinary quasi-static mechanical properties of nacre-like composite metamaterials, such as high specific strength, stiffness, and toughness, are due to the periodic arrangement of two distinct phases in a "brick and mortar" structure. It is also theorized that the hierarchical periodic structure of nacre structures can provide wider band gaps at different frequency scales. However, the function of hierarchy in the dynamic behavior of metamaterials is largely unknown, and most current investigations are focused on a single objective and specialized applications. Nature, on the other hand, appears to develop systems that represent a trade-off between multiple objectives, such as stiffness, fatigue resistance, and wave attenuation. Given the wide range of design options available to these systems, a multidisciplinary strategy combining diverse objectives may be a useful opportunity provided by bioinspired artificial systems. This paper describes a class of hierarchically-architected block lattice metamaterials with simultaneous wave filtering and enhanced mechanical properties, using deep learning based on artificial neural networks (ANN), to overcome the shortcomings of traditional design methods for forward prediction, parameter design, and topology design of block lattice metamaterial. Our approach uses ANN to efficiently describe the complicated interactions between nacre geometry and its attributes, and then use the Bayesian optimization technique to determine the optimal geometry constants that match the given fitness requirements. We numerically demonstrate that complete band gaps, that is attributed to the coupling effects of local resonances and Bragg scattering, exist. The coupling effects are naturally influenced by the topological arrangements of the continuous structures and the mechanical characteristics of the component phases. We also demonstrate how we can tune the frequency of the complete band gap by modifying the geometrical configurations and volume fraction distribution of the metamaterials. This research contributes to the development of mechanically robust block lattice metamaterials and lenses capable of controlling acoustic and elastic waves in hostile settings.

3D printing nacre powder/sodium alginate scaffold loaded with PRF promotes bone tissue repair and regeneration.

Bone defects are a common complication of bone diseases, which often affect the quality of life and mental health of patients. The use of biomimetic bone scaffolds loaded with bioactive substances has become a focal point in the research on bone defect repair. In this study, composite scaffolds resembling bone tissue were created using nacre powder (NP) and sodium alginate (SA) through 3D printing. These scaffolds exhibit several physiological structural and mechanical characteristics of bone tissue, such as suitable porosity, an appropriate pore size, applicable degradation performance and satisfying the mechanical requirements of cancellous bone, etc. Then, platelet-rich fibrin (PRF), containing a mass of growth factors, was loaded on the NP/SA scaffolds. This was aimed to fully maximize the synergistic effect with NP, thereby accelerating bone tissue regeneration. Overall, this study marks the first instance of preparing a bionic bone structure scaffold containing NP by 3D printing technology, which is combined with PRF to further accelerate bone regeneration. These findings offer a new treatment strategy for bone tissue regeneration in clinical applications.

Physical Phenomena Governing Mineral Morphogenesis in Molluscan Nacre.

Mollusks, as well as many other living organisms, have the ability to shape mineral crystals into unconventional morphologies and to assemble them into complex functional mineral-organic structures, an observation that inspired tremendous research efforts in scientific and technological domains. Despite these, a biochemical toolkit that accounts for the formation of the vast variety of the observed mineral morphologies cannot be identified yet. Herein, phase-field modeling of molluscan nacre formation, an intensively studied biomineralization process, is used to identify key physical parameters that govern mineral morphogenesis. Manipulating such parameters, various nacre properties ranging from the morphology of a single mineral building block to that of the entire nacreous assembly are reproduced. The results support the hypothesis that the control over mineral morphogenesis in mineralized tissues happens via regulating the physico-chemical environment, in which biomineralization occurs: the organic content manipulates the geometric and thermodynamic boundary conditions, which in turn, determine the process of growth and the form of the biomineral phase. The approach developed here has the potential of providing explicit guidelines for the morphogenetic control of synthetically formed composite materials.

Calcitic Prisms of The Giant Seashell Pinna Nobilis Form Light Guide Arrays.

The shells of the Pinnidae family are based on a double layer of single-crystal-like calcitic prisms and inner aragonitic nacre, a structure known for its outstanding mechanical performance. However, on the posterior side, shells are missing the nacreous layer, which raises the question of whether there can be any functional role in giving up this mechanical performance. Here, it is demonstrated that the prismatic part of the Pinna nobilis shell exhibits unusual optical properties, whereby each prism acts as an individual optical fiber guiding the ambient light to the inner shell cavity by total internal reflection. This pixelated light channeling enhances both spatial resolution and contrast while reducing angular blurring, an apt combination for acute tracking of a moving object. These findings offer insights into the evolutionary aspects of light-sensing and imaging and demonstrate how an architectured optical system for efficient light-tracking can be based on birefringent ceramics.

A Molecular-Scale Understanding of Misorientation Toughening in Corals and Seashells.

Biominerals are organic-mineral composites formed by living organisms. They are the hardest and toughest tissues in those organisms, are often polycrystalline, and their mesostructure (which includes nano- and microscale crystallite size, shape, arrangement, and orientation) can vary dramatically. Marine biominerals may be aragonite, vaterite, or calcite, all calcium carbonate (CaCO3 ) polymorphs, differing in crystal structure. Unexpectedly, diverse CaCO3 biominerals such as coral skeletons and nacre share a similar characteristic: Adjacent crystals are slightly misoriented. This observation is documented quantitatively at the micro- and nanoscales, using polarization-dependent imaging contrast mapping (PIC mapping), and the slight misorientations are consistently between 1° and 40°. Nanoindentation shows that both polycrystalline biominerals and abiotic synthetic spherulites are tougher than single-crystalline geologic aragonite. Molecular dynamics (MD) simulations of bicrystals at the molecular scale reveal that aragonite, vaterite, and calcite exhibit toughness maxima when the bicrystals are misoriented by 10°, 20°, and 30°, respectively, demonstrating that slight misorientation alone can increase fracture toughness. Slight-misorientation-toughening can be harnessed for synthesis of bioinspired materials that only require one material, are not limited to specific top-down architecture, and are easily achieved by self-assembly of organic molecules (e.g., aspirin, chocolate), polymers, metals, and ceramics well beyond biominerals.

Biomimetic mineralization of nacre-inspired multiple crosslinked PVA/CaAlg/SiO2 membrane with simultaneously enhanced mechanical and separation properties.

Inspired by the natural nacre structure, we propose a new strategy to fabricate mineralized, multiple crosslinked hydrogel membranes with the "rigid silica in soft polymer" nacre-like structure. In-situ SiO2 nanoparticles (NPs) and polyvinyl alcohol/sodium alginate (PVA/NaAlg) are used to simulate the rigid "bricks" and soft "mortar" compositions of nacre, respectively. The nacre-like mineralized (PVA/CaAlg/SiO2) membrane showed a higher tensile strength of 4.1 ± 0.08 MPa, excellent pure water flux of 170 ± 3 L/m2h, and an oil/water rejection rate of 99 %. The interwoven hierarchal structure, similar to nacre, was determined by SEM analysis. In addition, incorporating SiO2 NPs increases the anti-swelling, roughness, and hydrophilicity of the membranes. PVA/CaAlg/SiO2 membrane exhibited excellent superhydrophilicity (WCA value was 0°) and superoleophobicity underwater (OCA value was 162°). PVA/CaAlg/SiO2 membrane also showed excellent separation performance for water-soluble organic pollutants and can be used for dye separation with rejection efficiencies of 99.5 %, 99.1 %, and 98.3 % for Congo red (CR), Alizarin red (AR), and Sunset yellow (SY), respectively. Moreover, PVA/CaAlg/SiO2 membrane had outstanding long-term filtration and antifouling performance. The biomineralization-inspired structure provides a promising technique that can be used to prepare high-performance organic-inorganic membranes with great promise for wastewater separation application.

Failure progression and toughening mechanism of 3D-printed nacre-like structures under in-plane compression.

Nacre (also called mother-of-pearl) is known to have a delicate balance of stiffness, strength, and toughness, which originates from its 'brick-and-mortar' structure. In this study, nacre-like structures are fabricated using a high-resolution, multi-material 3D printer, where two different polyurethane acrylates (one that is hard and another that is soft) are used to represent the tablets and matrix. Six nacre-like structures are designed and fabricated to explore the influence of geometric parameters on the mechanical behaviors. Quasi-static in-plane compression tests and simulations are carried out to explore the failure mechanism of the nacre-like structures. The results show that the quasi-static compression responses of nacre-like structures have four stages: elastic, plateau, fragmentation, and densification. It is found that tuning the nacre architecture can optimize the mechanical performance of the specimen, including the peak load, ductility and stress reduction behavior et al. As the results of the numerical model show good agreement with the stress-strain response observed in the experiments, the model is applied to further investigate the strain distributions of the nacre-like structures. The patterns of the strain distribution suggest that synergistic deformation is the key toughening mechanism for the nacre-like structures.

Interfacial Mechanical Behavior in Nacre of Red Abalone and Other Shells: A Review.

Interfaces between nacreous tablets are crucial to the outstanding mechanical properties of nacre in natural shells. Excellent research has been conducted to probe the effect of interfaces on strength and toughness of nacre, providing critical guidelines for the design of human-made laminated composites. This article reviews recent studies on interfacial mechanical behavior of nacre in red abalone and other shells, including experimental methods, analytical and numerical modeling. The discussions focus on the mechanical properties of dry and hydrated nacreous microstructures. The review concludes with discussions on representative studies of nacre-like composites with interfaces tuned using multiple approaches, and provides an outlook on improving the performance of composites with better interfacial controls.

Anomalous inapplicability of nacre-like architectures as impact-resistant templates in a wide range of impact velocities.

Nacre is generally regarded as tough body armor, but it was often smashed by predators with a certain striking speed. Nacre-like architectures have been demonstrated to dissipate abundant energy by tablets sliding at static or specific low-speed loads, but whether they're still impact-resistant templates in a wide range of impact velocities remains unclear. Here, we find an anomalous phenomenon that nacre-like structures show superior energy-dissipation ability only in a narrow range of low impact velocities, while they exhibit lower impact resistance than laminated structures when impact velocity exceeds a critical value. This is because the tablets sliding in nacre-like structure occurs earlier and wider at low impact velocities, while it becomes localized at excessive impact velocities. Such anomalous phenomenon remains under different structural sizes and boundary conditions. It further inspires us to propose a hybrid architecture design strategy that achieves optimal impact resistance in a wide range of impact velocities.

A novel bifunctional protein PNU7 in CaCO3 polymorph formation: Vaterite stabilization and surface energy minimization.

CaCO3, which occurs in three crystalline anhydrous polymorphs named calcite, aragonite, and vaterite, is always found in mineralized skeletons or growing shells of many marine organisms. However, understanding how these organisms achieve this control has been a significant challenge in biomineralization. In this work, we proposed a novel vaterite stabilizer acidic matrix protein PNU7 that existed in both prism and nacre of Pinctada fucata, and identified its functional domain DDDDDDHDDVEETED. Our experiments reveal that PNU7 triggers a stable large vaterite formation with Mg2+ deficiency even under low Ca2+. Increasing PNU7 in the calcium carbonate crystallization system with Mg2+ leads to a significant shrinking in crystal size and rising in nucleation quantity. Moreover, it converts an atomically rough dome-like shape to a smooth sphere on unsiliconized glass. These effects rescind after removing the asp-rich region at the C-terminus. We also find that decreasing pnu7 mRNA in vivo leads to nacreous inner surface growth substantially lessened. Thus, PNU7 may not only supply vaterite in shell formation but also involve the nacreous regulation via surface energy minimization.

Ultrahigh Mechanical Strength and Robust Room-Temperature Self-Healing Properties of a Polyurethane-Graphene Oxide Network Resulting from Multiple Dynamic Bonds.

Addressing the conflict between achieving high mechanical properties and room-temperature self-healing ability is extremely significant to achieving a breakthrough in the application of self-healing materials. Therefore, inspired by natural spider silk and nacre, a room-temperature self-healing supramolecular material with ultrahigh strength and toughness is developed by synergistically incorporating flexible disulfide bonds and dynamic sextuple hydrogen bonds (H-bonds) into polyurethanes (PUs). Simultaneously, abundant H-bonds are introduced at the interface between graphene oxide nanosheets with dynamic multiple H-bonds and the PU matrix to afford strong interfacial interactions. The resulting urea-containing PU material with an inverse artificial nacre structure has a record mechanical strength (78.3 MPa) and toughness (505.7 MJ m-3), superior tensile properties (1273.2% elongation at break), and rapid room-temperature self-healing abilities (88.6% at 25 °C for 24 h), forming the strongest room-temperature self-healing elastomer reported to date and thus upending the previous understanding of traditional self-healing materials. In addition, this bionic PU-graphene oxide network endows the fabricated flexible intelligent robot with functional repair and shape memory capabilities, thus providing prospects for the fabrication of flexible functional devices.

Nacre-Mimetic Hierarchical Architecture in Polyborosiloxane Composites for Synergistically Enhanced Impact Resistance and Ultra-Efficient Electromagnetic Interference Shielding.

Pervasive mechanical impact is growing requirement for advanced high-performance protective materials, while the electromagnetic interference (EMI) confers severe risk to human health and equipment operation. Bioinspired structural composites achieving outstanding safeguards against a single threat have been developed, whereas the synergistic implementation of impact/EMI coupling protection remains a challenge. This work proposes the concept of nacre-mimetic hierarchical composite duplicating the "brick-and-mortar" arrangement, which consists of freeze-drying constructed chitosan/MXene lamellar architecture skeleton embedded in a shear stiffening polyborosiloxane matrix. The resulting composite effectively attenuates the impact force of 85.9%-92.8% with extraordinary energy dissipation capacity, in the coordinative manner of strain-rate enhancement, structural densification, lamella dislocation and crack propagation. Attributed to the alternate laminated structure promoting the reflection loss of electromagnetic waves, it demonstrates an ultraefficient EMI shielding effectiveness of 47.2-71.8 dB within extremely low MXene loadings of 1.1-1.3 wt %. Furthermore, it serves favorably in impact monitoring and wireless alarm systems and accomplishes performance optimization through the combination of multiple biomimetic strategies. In conclusion, this function-integrated structural composite is shown to be a competitive candidate for sophisticated environments by resisting impact damage and EMI hazards.

A biomimetic laminated strategy enabled strain-interference free and durable flexible thermistor electronics.

The development of flexible thermistor epidermal electronics (FTEE) to satisfy high temperature resolution without strain induced signal distortion is of great significance but still challenging. Inspired by the nacre microstructure capable of restraining the stress concentration, we exemplify a versatile MXene-based thermistor elastomer sensor (TES) platform that significantly alleviates the strain interference by the biomimetic laminated strategy combining with the in-plane stress dissipation and nacre-mimetic hierarchical architecture, delivering competitive advantages of superior thermosensitivity (-1.32% °C-1), outstanding temperature resolution (~0.3 °C), and unparalleled mechanical durability (20000 folding fatigue cycles), together with considerable improvement in strain-tolerant thermosensation over commercial thermocouple in exercise scenario. By a combination of theoretical model simulation, microstructure observation, and superposed signal detection, the authors further reveal the underlying temperature and strain signal decoupling mechanism that substantiate the generality and customizability of the nacre-mimetic strategy, possessing insightful significance of fabricating FTEE for static and dynamic temperature detection.

Ultralight and Superelastic Gd2O3/Bi2O3 Nanofibrous Aerogels with Nacre-Mimetic Brick-Mortar Structure for Superior X-ray Shielding.

The widespread use of X-rays has prompted a surge in demand for effective and wearable shielding materials. However, the Pb-containing materials currently used to shield X-rays are commonly bulky, hard, and biotoxic, severely limiting their applications in wearable scenarios. Inspired by the nacre, we report on ultralight, superelastic, and nontoxic X-ray shielding nanofibrous aerogels with microarch-engineered brick/mortar structure by combining polyurethane/Bi2O3 nanofibers (brick) and Gd2O3 nanosheets (mortar). The synergistic attenuation effect toward X-rays from the reflection of microarches and absorption of Bi/Gd elements significantly enhances the shielding efficiency of aerogels, and microarches/robust nanofibrous networks endow the materials with superelasticity. The resultant materials exhibit integrated properties of superior X-ray shielding efficiency (91-100%), ultralow density (52 mg cm-3), large stretchability of 800% reversible elongation, and high water vapor permeability (8.8 kg m-2 day-1). The fabrication of such novel aerogels paves the way for developing next-generation effective and wearable X-ray shielding materials.

Evolution of nacre- and prisms-related shell matrix proteins in the pen shell, Atrina pectinata.

The molluscan shell is a good model for understanding the mechanisms underlying biomineralization. It is composed of calcium carbonate crystals and many types of organic molecules, such as the matrix proteins, polysaccharides, and lipids. The pen shell Atrina pectinata (Pterioida, Pinnidae) has two shell microstructures: an outer prismatic layer and an inner nacreous layer. Similar microstructures are well known in pearl oysters (Pteriidae), such as Pinctada fucata, and many kinds of shell matrix proteins (SMPs) have been identified from their shells. However, the members of SMPs that consist of the nacreous and prismatic layers of Pinnidae bivalves remain unclear. In this study, we identified 114 SMPs in the nacreous and prismatic layers of A. pectinata, of which only seven were found in both microstructures. 54 of them were found to bind calcium carbonate. Comparative analysis of nine molluscan shell proteomes showed that 69 of 114 SMPs of A. pectinata were found to have sequential similarity with at least one or more SMPs of other molluscan species. For instance, nacrein, tyrosinase, Pif/BMSP-like, chitinase (CN), chitin-binding proteins, CD109, and Kunitz-type serine proteinase inhibitors are widely shared among bivalves and gastropods. Our results provide new insights for understanding the complex evolution of SMPs related to nacreous and prismatic layer formation in the pteriomorph bivalves.

Bioinspired stretchable molecular composites of 2D-layered materials and tandem repeat proteins.

Protein based composites, such as nacre and bone, show astounding evolutionary capabilities, including tunable physical properties. Inspired by natural composites, we studied assembly of atomistically thin inorganic sheets with genetically engineered polymeric proteins to achieve mechanically compliant and ultra-tough materials. Although bare inorganic nanosheets are brittle, we designed flexible composites with proteins, which are insensitive to flaws due to critical structural length scale (∼2 nm). These proteins, inspired by squid ring teeth, adhere to inorganic sheets via secondary structures (i.e., ß-sheets and α-helices), which is essential for producing high stretchability (59 ± 1% fracture strain) and toughness (54.8 ± 2 MJ/m3). We find that the mechanical properties can be optimized by adjusting the protein molecular weight and tandem repetition. These exceptional mechanical responses greatly exceed the current state-of-the-art stretchability for layered composites by over a factor of three, demonstrating the promise of engineering materials with reconfigurable physical properties.

Optical properties of novel luminescent nacre-like epoxy/graphene nanocomposite coating integrated with lanthanide-activated aluminate nanoparticles.

Nacre structure has aragonite polygonal tablets, tessellated to generate separate layers, and exhibits adjacent layers and tablets within a layer bonded by a biopolymer. Here, we report the development of a nacre-like organic/inorganic hybrid nanocomposite coating consisting of epoxy tablets as well as rare-earth-activated aluminate and graphene oxide tablet/tablet interfaces. The lanthanide-activated aluminate was prepared using a high temperature solid-state approach followed by top-down technology to provide the phosphor nanoparticles (PNPs). Graphene oxide nanosheets were prepared from graphite. The prepared epoxy/graphene/phosphor nanocomposites were applied onto mild steel. Covalent bonds were formed between epoxy polymer chains resin and the graphene oxide nanosheets. These interface interactions resulted in a tough surface, high tensile strength, and excellent durability. The use of phosphor in the nanoparticle form guaranteed that no agglomerations were produced throughout the hardening procedure by allowing better distribution of PNPs in the nacre-like matrix. The generated nacre-like substrates displayed reversible fluorescence. The excitation of the white coloured nacre-like coats at 367 nm resulted in a green emission band at 518 nm as designated by the Commission Internationale de l'éclairage (CIE) Laboratory and photoluminescence spectra. Various analysis methods were utilized to inspect the surface structure and elemental composition of the nacre-like coats. An improved hydrophobicity and mechanical characteristics were detected when increasing the phosphor concentration. Due to the astonishing characteristics of the prepared nacre-like composite paint, both ceramics and metals can benefit from the current simple strategy.

Chitin based multi-layered coatings with flame retardancy an approach to mimic nacre: Synthesis, characterization and mechanical properties.

Nacre mimetic coatings are attractive candidates for food packaging, electronics, textiles, protective insulation, and flame retardant materials. Inspired by the hierarchical structure of nacre, we present an environmentally friendly strategy to construct robust and flame retardant films using chitin, which is an abundantly available biopolymer. Chitin was phosphorylated to make it water-soluble. Multilayered films were constructed by assembling poly (vinyl alcohol) (PVA), graphene oxide (GO) nanosheets, phosphorylated chitin (p. chitin), and laponite (LAP) via Layer-by-Layer (LbL) and vacuum-assisted filtration (VAF) assemblies. SEM micrographs revealed the nacre-like layered structure while photographic images showed a similar sheen to that of the mother of pearl. The fabricated coatings possess good mechanical properties with a reduced modulus of 25.53 GPa and hardness of 1.45 GPa. In addition, multilayered films exhibited iridescence and attractive flame retardancy. We believe that our strategy of embedding chitin offers cost-effective and environmentally friendly coatings for textiles, food packaging, barrier, and electronic materials.

Development of photoluminescent artificial nacre-like nanocomposite from polyester resin and graphene oxide.

Long-lasting phosphorescent nacre-like material was simply prepared from a nanocomposite of inorganic and organic materials. Low molecular weight unsaturated polyester (PET), graphene oxide (GO), and nanoparticles of rare-earth activated aluminate pigment were used in the preparation process of an organic/inorganic hybrid nanocomposite. Using methylethylketone peroxide (MEKP) as a hardener, we were able to develop a fluid solution that hardens within minutes at room temperature. Covalent and hydrogen bonds were introduced between the polyester resin and graphene oxide nanosheets. The interface interactions of those bonds resulted in toughness, excellent tensile strength, and high durability. The produced nacre substrates demonstrated long-persistent and reversible luminescence. The excitation of the produced nacre substrates at 365 nm resulted in a 524 nm emission. After being exposed to UV light, the photoluminescent nacre substrates became green. The increased superhydrophobic activity of the produced nacre substrates was achieved without affecting their physico-mechanical properties. HIGHLIGHTS: Colorless photoluminescent smart nacre-like nanocomposites were prepared. Graphene oxide and polyester were mixed with phosphor nanoparticles at 25°C. Photostable long-persistent phosphorescence lighting was observed in the dark. Photochromic change to green emission was detected under ultraviolet light. The nacre-like composites exhibit improved hardness and hydrophobicity.

Orientation-dependent micromechanical behavior of nacre: In situ TEM experiments and finite element simulations.

Nacre's superior mechanical properties and failure behavior are strongly orientation-dependent due to its brick-and-mortar microstructure. In this work, the anisotropic microscopic deformation and the resulting macroscopic mechanical properties are evaluated under different loading conditions. Our in situ transmission electron microscopy deformation experiments and finite element simulations reveal that nacre possesses enhanced indentation resistance along the direction normal to the tablets through delocalization of indentation-induced deformation by taking advantage of its layered structure. In addition, nacre's ability to recover from large deformations is observed. We study the strong loading direction dependence of nacre's macroscopic mechanical properties and elucidate the underlying microscopic deformation patterns in the tablets and the soft matrix. Particularly, its performance along the transverse direction is optimized to withstand the loading conditions in nature. We show the importance of the vertical matrix for the initial stiffness and fracture toughness of the composite. These findings provide guidelines for designing nacre-inspired artificial composites with enhanced mechanical properties. STATEMENT OF SIGNIFICANCE: Nacre is widely recognized as an excellent structural model for designing bio-inspired tough and strong artificial composites. Due to its brick-and-mortar microstructure, it exhibits loading direction-dependent mechanical behavior. In this contribution, we investigate the macroscopic mechanical properties and microscopic deformation behavior of nacre under different loading conditions by means of in situ TEM deformation tests and FE simulations. It is found that effective elastic moduli and microscopic deformation strongly depend on the loading direction. The organic matrix is highly deformable. The indentation resistance along the direction normal to tablets is enhanced via deformation delocalization. Our quantitative and qualitative results provide guidelines on optimizing the mechanical properties of nacre-inspired novel composites.