A 3D-printed molecular ferroelectric metamaterial.

Molecular ferroelectrics combine electromechanical coupling and electric polarizabilities, offering immense promise in stimuli-dependent metamaterials. Despite such promise, current physical realizations of mechanical metamaterials remain hindered by the lack of rapid-prototyping ferroelectric metamaterial structures. Here, we present a continuous rapid printing strategy for the volumetric deposition of water-soluble molecular ferroelectric metamaterials with precise spatial control in virtually any three-dimensional (3D) geometry by means of an electric-field-assisted additive manufacturing. We demonstrate a scaffold-supported ferroelectric crystalline lattice that enables self-healing and a reprogrammable stiffness for dynamic tuning of mechanical metamaterials with a long lifetime and sustainability. A molecular ferroelectric architecture with resonant inclusions then exhibits adaptive mitigation of incident vibroacoustic dynamic loads via an electrically tunable subwavelength-frequency band gap. The findings shown here pave the way for the versatile additive manufacturing of molecular ferroelectric metamaterials.

Printing Air-Stable High-Tc Molecular Magnet with Tunable Magnetic Interaction.

High-Tc molecular magnets have amassed much promise; however, the long-standing obstacle for its practical applications is the inaccessibility of high-temperature molecular magnets showing dynamic and nonvolatile magnetization control. In addition, its functional durability is prone to degradation in oxygen and heat. Here, we introduce a rapid prototyping and stabilizing strategy for high Tc (360 K) molecular magnets with precise spatial control in geometry. The printed molecular magnets are thermally stable up to 400 K and air-stable for over 300 days, a significant improvement in its lifetime and durability. X-ray magnetic circular dichroism and computational modeling reveal the water ligands controlling magnetic exchange interaction of molecular magnets. The molecular magnets also show dynamical and reversible tunability of magnetic exchange interactions, enabling a colossal working temperature window of 86 K (from 258 to 344 K). This study provides a pathway to flexible, lightweight, and durable molecular magnetic devices through additive manufacturing.

Magnetically hard ferrite nanoparticles synthesized through aerogel nanoreactor.

Magnetic ferrite materials have been extensively studied for a range of technological applications, such as magnetic motors, recording media, and millimetre-wave devices. In this context, the nanosized epsilon phase of Fe2O3 (ϵ-Fe2O3) attracts significant attention due to its high coercive field at room temperature. Here, we report the in-situ aerogel nanoreactor growth of magnetic ϵ-Fe2O3 nanoparticles, exhibiting a coercive field (Hc) of 4000 Oe. We show that the control of nanoreactor plays an important role in the growth of ϵ-Fe2O3 nanoparticles. The findings provide a versatile reaction pathway for the growth of magnetically hard ferrite nanoparticles.

Additive manufacturing of eco-friendly building insulation materials by recycling pulp and paper.

Thermal insulation materials by recycling pulp and paper wastes play an important role in environmental sustainability of green buildings. As society is pursuing the goal of zero carbon emissions, it is highly desirable to use eco-friendly materials and manufacturing technologies for building insulation envelopes. Here we report additive manufacturing of flexible and hydrophobic insulation composites from recycled cellulose-based fibers and silica aerogel. The resultant cellulose-aerogel composites exhibit thermal conductivity of 34.68 mW m-1 K-1, mechanical flexibility with a flexural modulus of 429.21 MPa, and superhydrophobicity with water contact angle of 158.72°. Moreover, we present the additive manufacturing process of recycled cellulose aerogel composites, providing enormous potential for high energy efficiency and carbon-sequestration building applications.

Molecular magneto-ionic proton sensor in solid-state proton battery.

High proton conductivity originated from its small size and the diffusion-free Grotthuss mechanism offers immense promise for proton-based magneto-ionic control of magnetic materials. Despite such promise, the realization of proton magneto-ionics is hampered by the lack of proton-responsive magnets as well as the solid-state sensing method. Here, we report the proton-based magneto-ionics in molecule-based magnet which serves as both solid-state proton battery electrode and radiofrequency sensing medium. The three-dimensional hydrogen-bonding network in such a molecule-based magnet yields a high proton conductivity of 1.6 × 10-3 S cm-1. The three-dimensional printed vascular hydrogel provides the on-demand proton stimulus to enable magneto-ionics, where the Raman spectroscopy shows the redox behavior responsible for the magnetism control. The radiofrequency proton sensor shows high sensitivity in a wide proton concentration range from 10-6 to 1 molar under a low working radiofrequency and magnetic field of 1 GHz and 405 Oe, respectively. The findings shown here demonstrate the promising sensing application of proton-based magneto-ionics.

Manufacturing silica aerogel and cryogel through ambient pressure and freeze drying.

Achieving a mesoporous structure in superinsulation materials is pivotal for guaranteeing a harmonious relationship between low thermal conductivity, high porosity, and low density. Herein, we report silica-based cryogel and aerogel materials by implementing freeze-drying and ambient-pressure-drying processes respectively. The obtained freeze-dried cryogels yield thermal conductivity of 23 mW m-1 K-1, with specific surface area of 369.4 m2 g-1, and porosity of 96.7%, whereas ambient-pressure-dried aerogels exhibit thermal conductivity of 23.6 mW m-1 K-1, specific surface area of 473.8 m2 g-1, and porosity of 97.4%. In addition, the fiber-reinforced nanocomposites obtained via freeze-drying feature a low thermal conductivity (28.0 mW m-1 K-1) and high mechanical properties (∼620 kPa maximum compressive stress and Young's modulus of 715 kPa), coupled with advanced flame-retardant capabilities, while the composite materials from the ambient pressure drying process have thermal conductivity of 28.8 mW m-1 K-1, ∼200 kPa maximum compressive stress and Young's modulus of 612 kPa respectively. The aforementioned results highlight the capabilities of both drying processes for the development of thermal insulation materials for energy-efficient applications.

Tailoring thermal insulation architectures from additive manufacturing.

Tailoring thermal transport by structural parameters could result in mechanically fragile and brittle networks. An indispensable goal is to design hierarchical architecture materials that combine thermal and mechanical properties in a continuous and cohesive network. A promising strategy to create such a hierarchical network targets additive manufacturing of hybrid porous voxels at nanoscale. Here we describe the convergence of agile additive manufacturing of porous hybrid voxels to tailor hierarchically and mechanically tunable objects. In one strategy, the uniformly distributed porous silica voxels, which form the basis for the control of thermal transport, are non-covalently interfaced with polymeric networks, yielding hierarchic super-elastic architectures with thermal insulation properties. Another additive strategy for achieving mechanical strength involves the versatile orthogonal surface hybridization of porous silica voxels retains its low thermal conductivity of 19.1 mW m-1 K-1, flexible compressive recovery strain (85%), and tailored mechanical strength from 71.6 kPa to 1.5 MPa. The printed lightweight high-fidelity objects promise thermal aging mitigation for lithium-ion batteries, providing a thermal management pathway using 3D printed silica objects.

Transparent thermal insulation ceramic aerogel materials for solar thermal conversion.

Thermal management in energy-efficient solar thermal energy conversion and transparent windows requires advanced materials with low thermal conductivity and high transparency, such as transparent silica aerogel materials. However, the large scatter domains in porous silica materials would deteriorate their optical transparency. Herein, we report transparent silica aerogels by controlling hydrolyzation and meanwhile silylation modification to enhance the integrity of the microstructure under ambient pressure drying. The transparent silica aerogel materials show a broad-spectrum transparency of 70% from 400 nm and 800 nm, showing promising applications in transparent windows and solar thermal energy conversion systems. The scalability for transparent windows could be achieved with a composite material by incorporating transparent polymeric materials. The solar receiver coupled with a transparent silica aerogel could reach 122 °C within 12 min at a solar irradiance of 1 Sun, ∼200% higher than that in the ambient atmosphere. The engineered structure of the transparent porous silica backbone provides a pathway for solar thermal systems and transparent window applications.

Releasing chemical energy in spatiallyprogrammed ferroelectrics.

Chemical energy ferroelectrics are generally solid macromolecules showing spontaneous polarization and chemical bonding energy. These materials still suffer drawbacks, including the limited control of energy release rate, and thermal decomposition energy well below total chemical energy. To overcome these drawbacks, we report the integrated molecular ferroelectric and energetic material from machine learning-directed additive manufacturing coupled with the ice-templating assembly. The resultant aligned porous architecture shows a low density of 0.35 g cm-3, polarization-controlled energy release, and an anisotropic thermal conductivity ratio of 15. Thermal analysis suggests that the chlorine radicals react with macromolecules enabling a large exothermic enthalpy of reaction (6180 kJ kg-1). In addition, the estimated detonation velocity of molecular ferroelectrics can be tuned from 6.69 ± 0.21 to 7.79 ± 0.25 km s-1 by switching the polarization state. These results provide a pathway toward spatially programmed energetic ferroelectrics for controlled energy release rates.

Proton switching molecular magnetoelectricity.

The convergence of proton conduction and multiferroics is generating a compelling opportunity to achieve strong magnetoelectric coupling and magneto-ionics, offering a versatile platform to realize molecular magnetoelectrics. Here we describe machine learning coupled with additive manufacturing to accelerate the design strategy for hydrogen-bonded multiferroic macromolecules accompanied by strong proton dependence of magnetic properties. The proton switching magnetoelectricity occurs in three-dimensional molecular heterogeneous solids. It consists of a molecular magnet network as proton reservoir to modulate ferroelectric polarization, while molecular ferroelectrics charging proton transfer to reversibly manipulate magnetism. The magnetoelectric coupling induces a reversible 29% magnetization control at ferroelectric phase transition with a broad thermal hysteresis width of 160 K (192 K to 352 K), while a room-temperature reversible magnetic modulation is realized at a low electric field stimulus of 1 kV cm-1. The findings of electrostatic proton transfer provide a pathway of proton mediated magnetization control in hierarchical molecular multiferroics.

Fast Stereolithography Printing of Large-Scale Biocompatible Hydrogel Models.

Large size cell-laden hydrogel models hold great promise for tissue repair and organ transplantation, but their fabrication using 3D bioprinting is limited by the slow printing speed that can affect the part quality and the biological activity of the encapsulated cells. Here a fast hydrogel stereolithography printing (FLOAT) method is presented that allows the creation of a centimeter-sized, multiscale solid hydrogel model within minutes. Through precisely controlling the photopolymerization condition, low suction force-driven, high-velocity flow of the hydrogel prepolymer is established that supports the continuous replenishment of the prepolymer solution below the curing part and the nonstop part growth. The rapid printing of centimeter-sized hydrogel models using FLOAT is shown to significantly reduce the part deformation and cellular injury caused by the prolonged exposure to the environmental stresses in conventional 3D printing methods. Embedded vessel networks fabricated through multiscale printing allows media perfusion needed to maintain the high cellular viability and metabolic functions in the deep core of the large-sized models. The endothelialization of this vessel network allows the establishment of barrier functions. Together, these studies demonstrate a rapid 3D hydrogel printing method and represent a first step toward the fabrication of large-sized engineered tissue models.

Ductile cooling phase change material.

Cooling represents a considerable fraction of energy consumption. However, it is indispensable to develop eco-friendly, biocompatible, and ductile cooling materials for personal applications. In this study, we demonstrate the ductile cooling ability with phase change of thermally passivated hydrogel composite materials with additive manufacturing ability. Thermal evaluation of such water-based composites indicates a superior cold retention capacity with a cooling comfort over 6 hours, while the composite displays a full recovery when strained up to 80% in uniaxial compression tests as a result of the intertwining between covalent and ionic bonds. A three-layered rectangular model was utilized to simulate the problem in a steady-state thermal analysis to study the cooling effect. Our findings indicate the potential of hydrogel as a cooling phase-change medium and its contribution towards ductile cooling applications.

Flexible and printable dielectric polymer composite with tunable permittivity and thermal stability.

Lightweight and printable polymer dielectrics are ubiquitous in flexible hybrid electronics, exhibiting high breakdown strength and mechanical reliability. However, their advanced electronic applications are limited due to their relatively low permittivity, compared to their ceramic counterparts. Here, we report flexible all organic percolative nanocomposites that contain in situ grown conductive polymer networks and dielectric polymer matrix, in which their dielectric properties can be designed and guided from the percolation theory. High dielectric constant of all organic percolative nanocomposites is shown over a broad frequency range under intensive bending cycles, while their thermal stability is attributed to thermally conductive 2D montmorillonite nanosheets. The printable polymer composites with high dielectric performance and thermal stability will find broader interest in flexible hybrid electronics and radio frequency devices.