Organic-inorganic covalent-ionic molecules for elastic ceramic plastic.

Although organic-inorganic hybrid materials have played indispensable roles as mechanical1-4, optical5,6, electronic7,8 and biomedical materials9-11, isolated organic-inorganic hybrid molecules (at present limited to covalent compounds12,13) are seldom used to prepare hybrid materials, owing to the distinct behaviours of organic covalent bonds14 and inorganic ionic bonds15 in molecular construction. Here we integrate typical covalent and ionic bonds within one molecule to create an organic-inorganic hybrid molecule, which can be used for bottom-up syntheses of hybrid materials. A combination of the organic covalent thioctic acid (TA) and the inorganic ionic calcium carbonate oligomer (CCO) through an acid-base reaction provides a TA-CCO hybrid molecule with the representative molecular formula TA2Ca(CaCO3)2. Its dual reactivity involving copolymerization of the organic TA segment and inorganic CCO segment generates the respective covalent and ionic networks. The two networks are interconnected through TA-CCO complexes to form a covalent-ionic bicontinuous structure within the resulting hybrid material, poly(TA-CCO), which unifies paradoxical mechanical properties. The reversible binding of Ca2+-CO32- bonds in the ionic network and S-S bonds in the covalent network ensures material reprocessability with plastic-like mouldability while preserving thermal stability. The coexistence of ceramic-like, rubber-like and plastic-like behaviours within poly(TA-CCO) goes beyond current classifications of materials to generate an 'elastic ceramic plastic'. The bottom-up creation of organic-inorganic hybrid molecules provides a feasible pathway for the molecular engineering of hybrid materials, thereby supplementing the classical methodology used for the manufacture of organic-inorganic hybrid materials.

Molecular Weight-Dependent Physiochemical Behaviors of Calcium Carbonate Chains.

The regulation of physiochemical behaviors by changing molecular weights is an important cornerstone of polymer physics. However, similar correlations between molecular weights and properties have not been discovered in inorganic ionic compounds. In this work, we prepared a calcium carbonate specimen with a semiflexible chain topology analogous to those of polymers. The molecular weights of the calcium carbonate chains, which ranged from 3400 to 54 100 Da, were directly correlated to their physiochemical behaviors, including gel point, zero shear viscosity, and plateau modulus. The calcium carbonate chains showed similar polymeric characteristics, including shear thinning, thixotropy, entropic elasticity, and viscoelasticity. These features agreed with recent theories and formulas in polymer physics textbooks. On the basis of this understanding, the mechanical properties of calcium carbonate-based gels could be altered by changing their molecular weights. This study could represent a fusion of inorganic chemistry and polymer physics with similar molecular weight-dependent behaviors and material properties, establishing an alternative pathway for designing future inorganic materials.

Linear Calcium Carbonate Chains by Directional Control of Ionic Bonding.

As a result of the non-directionality of ionic bonds, oppositely charged ions always assemble into closely packed clusters or crystals rather than linear structured ionic species. Here, we generated a series of linear calcium carbonate chains, (Ca2+CO32-)n, with an orientated directionality of the ionic interactions. The formation of these ionic chains with long-range ordered ionic interactions was originally induced by the dipole orientation of the ions and subsequently preserved by capping agents. According to the appropriately established folding-capping model, rational control of the capping effect can regulate the length of the (Ca2+CO32-)n chain within 100 nm, corresponding to n ≤ 250. Our discovery overturns the current understanding of ionic bonding in chemistry and opens a way to control the assembly of inorganic ions at molecular scale, pushing forward a fusion of molecular compounds and ionic compounds that share similar topological control.

High Mechanical Strength Alloy-like Minerals Prepared by Inorganic Ionic Co-cross-linking.

Alloys often combine different metals to generate superior mechanical properties. However, it is challenging to prepare high mechanical strength minerals with similar strategies. Using calcium carbonate (CaC) and calcium phosphate (CaP) as examples, this work synthesizes a group of compounds with the chemical formulas Ca(CO3 )x (PO4 )2(1- x )/3 (0 < x < 1, CaCPs) by cross-linking ionic oligomers. Unlike mixtures, these CaCPs exhibit a single temperature for the phase transition from amorphous to crystallized CaC (calcite) and CaP (hydroxyapatite). By heat-induced synchronous crystallization, dual-phase CaC/CaP with continuous crystallized boundaries are resembled to alloy-like minerals (ALMs). The mechanical properties of the ALMs are adjusted by tailoring their chemical compositions to reach a hardness of 5.6 GPa, which exceed those of control calcite and hydroxyapatite samples by 430% and 260%, respectively. This strategy expands the chemical scope of inorganic materials and holds promise for preparing high-performance minerals.

A Bioinspired Ultratough Composite Produced by Integration of Inorganic Ionic Oligomers within Polymer Networks.

The nacre-inspired laminates are promising materials for their excellent mechanics. However, the interfacial defects between organic-inorganic phases commonly lead to the crack propagation and fracture failure of these materials under stress. A natural biomineral, bone, has much higher bending toughness than the nacre. The small size of inorganic building units in bone improves the organic-inorganic interaction, which optimizes the material toughness. Inspired by these biological structures, here, an ultratough nanocomposite laminate is prepared by the integration of ultrasmall calcium phosphate oligomers (CPO, 1 nm in diameter) within poly(vinyl alcohol) (PVA) and sodium alginate (Alg) networks through a simple three-step strategy. Owing to the small size of inorganic building units, strong multiple molecular interactions within integrated organic-inorganic hierarchical structure are built. The resulting laminates exhibit ultrahigh bending strain (>50% without fracture) and toughness (21.5-31.0 MJ m-3), which surpass natural nacre and almost all of the synthetic laminate materials that have been reported so far. Moreover, the mechanics of this laminate is tunable by changing the water content within the bulk structure. This work provides a way for the development of organic-inorganic nanocomposites with ultrahigh bending toughness by using inorganic ionic oligomers, which can be useful in the fields of tough protective materials and energy absorbing materials.

A Flexible and Degradable Hybrid Mineral as a Plastic Substitute.

The development of environmentally friendly plastics is critical to ensure sustainable development. In contrast to polymer plastics derived from petrochemicals, inorganic minerals, which are the most abundant matter in Earth's crust, are environmentally friendly. However, the brittleness of these minerals limits their applications as plastics. Here, because of the advantages of both biomineralization and inorganic ionic polymerization, the calcium phosphate (CaP, a typical geological and biological mineral) oligomers are used for biomimetic mineralization under the regulation of polyvinyl alcohol and sodium alginate, resulting in flexible CaP nanofibers with periodic structural defects. The assembly of CaP nanofibers produces a hierarchically structured bulk hybrid mineral (HM), which overcomes the intrinsic brittleness of minerals and exhibits plasticity characteristics. HM exhibits better hardness and thermostability than classical polymer plastics due to its dominant mineral composition. Notably, HM is environmentally friendly and degradable in nature, as it can potentially participate in geological cycles, indicating that this material is an optimal plastic substitute. The construction of periodic structural defects within flexible minerals expands the current understanding of materials science.

Chameleon-Inspired Stress-Responsive Multicolored Ultratough Films.

Chameleons have a distinguished talent to rapidly shift their colors by active tuning of a lattice of guanine nanocrystals within a superficial thick layer of dermal iridophores. This reversible structural color variation is derived from the birefringence, which is triggered by the special anisotropic structure interacting with natural light. Inspired by the inorganic oligomers and their superiorities for constructing ultratough materials with a special structure, we demonstrated here a chameleon's skin-like film constructed by ultrasmall calcium phosphate oligomers (∼1.75 nm in diameter) as the precursor of crystalline hydroxyapatite nanoline (HNL) arrays and polyvinyl alcohol as the elastic matrix. The resulting films exhibit excellent toughness (48.3 ± 5.2 MJ m-3). Under the applied cyclic stress, the HNLs embedded in the polymer network can reversibly arrange into a highly ordered crystal arrays owing to the driving action of polymer chains. The intense birefringence of the stretched films is easily observed with the naked eye under crossed polarizers, allowing for rapid and simple measurement of the applied stress. This work provides a pathway for the development of functional composites with super toughness by ultrasmall inorganic oligomers for their potential applications in smart devices for stress detection.

Muscle-like Ultratough Hybrid Hydrogel Constructed by Heterogeneous Inorganic Polymerization on an Organic Network.

Inspired by inorganic oligomers and their polymerization, we herein develop a heterogeneous inorganic polymerization tactic that can be used to prepare a muscle-like hybrid hydrogel by inducing the polymerization of calcium phosphate oligomers (CPO) onto a polyvinyl alcohol (PVA) molecular chain network. In this heterogeneous process, the CPO units bond with PVA molecules via assistance from sodium alginate (SA), and then gradually polymerize along the organic chains to form ultrafine hydroxyapatite nanolines with a diameter of ∼1 nm. Because of the well integration of organic and inorganic phases from the heterogeneous polymerization, the hierarchical structured hydrogel can exhibit ultratough mechanical properties of ∼17.84 MPa in strength and ∼8.97 kJ m-2 in fracture energy, which exceed natural muscles and almost synthetic hydrogels. Moreover, the damaged hydrogel can be repaired readily by adding the precursors of CPO, PVA, and SA, which can induce in situ re-polymerization. The hydrogel also exhibits muscle-like rotational motion under aqueous conditions, which can be developed into a water-driven biomimetic motor. This study indicates that inorganic polymerization can achieve a novel organic-inorganic integration rather than conventional organic-inorganic composition, and it provides a novel tactic for design and manufacture of advanced materials.