Mechanically and Thermally Guided, Honeycomb-like Nanocomposites with Strain-Insensitive High Thermal Conductivity for Stretchable Electronics.

Thermal management materials have become increasingly crucial for stretchable electronic devices and systems. Drastically different from conventional thermally conductive materials, which are applied at static conditions, thermal management materials for stretchable electronics additionally require strain-insensitive thermal conductivity, as they generally undergo cyclic deformation. However, realizing such a property remains challenging mainly because conventional thermally conductive polymer composites generally lack a mechanically guided design. Here, we report a honeycomb-like nanocomposite with a three-dimensional (3D) thermally conductive network fabricated by an arrayed ice-templating technique followed by elastomer infiltration. The hexagonal honeycomb-like structure with thin, compact walls (≈ 40 µm) endows our composite with a high through-plane thermal conductivity (≈ 1.54 W m-1 K-1) at an ultralow boron nitride nanosheet (BNNS) loading (≈ 0.85 vol %), with an enhancement factor of thermal conductivity up to 820% and thermal-insensitive strain up to 200%, which are 2.7 and 2 times higher than those reported in the literature. We report an intelligent strategy for the development of advanced thermal management materials for high-performance stretchable electronics.

Preferential ice growth on grooved surface for crisscross-aligned graphene aerogel with large negative Poisson's ratio.

Ice formation on solid surfaces is a ubiquitous process in our daily life, and ice orientation plays a critical role in anti-icing/deicing, organ cryo-preservation, and material fabrication. Although previous studies have shown that surface grooves can regulate the orientation of ice crystals, whether the parallel or perpendicular alignment to the grooves is still under debate. Here, we systematically investigate ice formation and its oriented growth on grooved surfaces through both in situ observation and theoretical simulation, and discover a remarkable size effect of the grooves. With the designability of surface groove patterns, the preferential growth of ice crystals is programmed for the fabrication of a crisscross-aligned graphene aerogel with large negative Poisson's ratio. In addition, the size effect provides guidance for the design and fabrication of solid surfaces where the effective control of ice orientation is highly desired, such as efficient deicing, long time organ cryo-preservation, and ice-templated materials.

Biomimetic, knittable aerogel fiber for thermal insulation textile.

Aerogels have been considered as an ideal material for thermal insulation. Unfortunately, their application in textiles is greatly limited by their fragility and poor processability. We overcame these issues by encapsulating the aerogel fiber with a stretchable layer, mimicking the core-shell structure of polar bear hair. Despite its high internal porosity over 90%, our fiber is stretchable up to 1000% strain, which is greatly improved compared with that of traditional aerogel fibers (~2% strain). In addition to its washability and dyeability, our fiber is mechanically robust, retaining its stable thermal insulation property after 10,000 stretching cycles (100% strain). A sweater knitted with our fiber was only one-fifth as thick as down, with similar performance. Our strategy for this fiber provides rich possibilities for developing multifunctional aerogel fibers and textiles.

Scalable Fabrication of High-Performance Bulk Nacre-Mimetic Materials on a Nanogrooved Surface.

The extraordinary structural and mechanical features of nacre have been widely explored and translated into synthetic layered materials through various methods. However, it still remains challenging to achieve scale-up fabrication of these biomimetic layered materials, which is the main hurdle for their real applications. Herein, we report a facile, universal, and scalable strategy to produce bulk materials with nacre-mimetic architecture and performance. This was realized by the ordered nucleation of ice crystals on a nanogrooved surface. After the infiltration of a polymer, both the specific strength and toughness of our artificial nacre outperform those of natural nacre and other nacre-mimetic materials. Due to the scalability and availability of a nanogrooved surface, large-sized, bulk artificial nacre (30 × 20 × 5 cm) was also obtained through the directional freezing process. In addition, this efficient approach can also be extended to assemble various building blocks like functional nanomaterials such as graphene oxide and MXene nanosheets into bulk porous materials with highly ordered three-dimensional architecture, holding great potential for multifunctional applications.

Isotropically Ultrahigh Thermal Conductive Polymer Composites by Assembling Anisotropic Boron Nitride Nanosheets into a Biaxially Oriented Network.

The demand for thermally conductive but electrically insulating materials has increased greatly in advanced electronic packaging. To this end, polymer-based composites filled with boron nitride (BN) nanosheets have been intensively studied as thermal interface material (TIM). However, it remains a great challenge to achieve isotropically ultrahigh thermal conductivity in BN/polymer composites due to the inherent thermal property anisotropy of BN nanosheets and/or the insufficient construction of the 3D thermal conductive network. Herein, we present a high-performance BN/polymer composite with a biaxially oriented thermal conductive network by a dendritic ice template. The composite exhibits both ultrahigh in-plane (∼39.0 W m-1 K-1) and through-plane thermal conductivity (∼11.5 W m-1 K-1) at 80 vol % BN loading, largely exceeding those of reported BN/polymer composites. In addition, our composite as a TIM shows higher cooling efficiency than that of commercial TIM with up to 15 °C reduction of the chip temperature and retains good thermal stability even after 1000 heating/cooling cycles. Our strategy represents an effective approach for developing advanced thermal interface materials, which are greatly demanded for advanced electronics and emerging areas like wearable electronics.

Anisotropic porous ceramic material with hierarchical architecture for thermal insulation.

Porous ceramic materials are attractive candidates for thermal insulation. However, effective ways to develop porous ceramics with high mechanical and thermal insulation performances are still lacking. Herein, an anisotropic porous silica ceramic with hierarchical architecture, i.e. long-range aligned lamellar layers composed of hollow silica spheres, was fabricated applying a facile bidirectional freezing method. Due to such anisotropic structure, the as-prepared porous silica ceramic displays low thermal conductivity across the layers and high compressive strength along the layers. Additionally, the anisotropic porous silica ceramic is fire-resistant. As a proof of concept, a mini-house was roofed with the anisotropic porous silica ceramic, showing that the indoor temperature could be stabilized against environmental temperature change, making this porous ceramic a promising candidate for energy efficient buildings and other industrial applications. Our study highlights the possibility of combining intrinsically exclusive properties in engineering materials through constructing biomimetic porous structures.

Mechanically Efficient Cellular Materials Inspired by Cuttlebone.

Cellular materials with excellent mechanical efficiency are essential for aerospace structures, lightweight vehicles, and energy absorption. However, current synthetic cellular materials, such as lattice materials with a unit cell arranged in an ordered hierarchy, are still far behind many biological cellular materials in terms of both structural complexity and mechanical performance. Here, the complex porous structure and the mechanics of the cuttlebone are studied, which acts as a rigid buoyancy tank for cuttlefish to resist large hydrostatic pressure in the deep-sea environment. The cuttlebone structure, constructed like lamellar septa, separated by asymmetric, distorted S-shaped walls, exhibits superior strength and energy-absorption capability to the octet-truss lattice and conventional polymer and metal foams. Inspired by these findings, mechanically efficient cellular materials are designed and fabricated by 3D printing, which are greatly demanded for many applications including aerospace structures and tissue-engineering-scaffold. This study represents an effective approach for the design and engineering of high-performance cellular materials through bioinspired 3D printing.

Controlling ice formation on gradient wettability surface for high-performance bioinspired materials.

Ice-templating holds promise to become a powerful technique to construct high-performance bioinspired materials. Both ice nucleation and growth during the freezing process are crucial for the final architecture of the ice-templated material. However, effective ways to control these two very important factors are still lacking. Here, we demonstrate that successive ice nucleation and preferential growth can be realized by introducing a wettability gradient on a cold finger. A bulk porous material with a long-range lamellar pattern was obtained using a linear gradient, yielding a high-performance, bulk nacre-mimetic composite with excellent strength and toughness after infiltration. In addition, cross-aligned and circular lamellar structures can be obtained by freeze-casting on surfaces modified with bilayer linear gradient and radial gradient, respectively, which are impossible to realize with conventional freeze-casting techniques. Our study highlights the potential of harnessing the rich designability of surface wettability patterns to build high-performance bulk materials with bioinspired complex architectures.

Nacre-mimetic composite with intrinsic self-healing and shape-programming capability.

Replicating nacre's multiscale architecture represents a promising approach to design artificial materials with outstanding rigidity and toughness. It is highly desirable yet challenging to incorporate self-healing and shape-programming capabilities into nacre-mimetic composites due to their rigidity and high filler content. Here, we report such a composite obtained by infiltrating a thermally switchable Diels-Alder network polymer into a lamellar scaffold of alumina. The chemical bond switchability and the physical confinement by the filler endows the composite with sufficient molecular mobility without compromising its thermal dimension stability. Consequently, our composite is capable of self-healing internal damages. Additionally, in contrast to the intractable planar shape of other artificial nacres, precise control of the polymer chain dynamics allows the shape of our composite to be programmed permanently via plasticity and temporarily via shape memory effect. Our approach paves a new way for designing durable multifunctional bioinspired structural materials.

Superstretchable Nacre-Mimetic Graphene/Poly(vinyl alcohol) Composite Film Based on Interfacial Architectural Engineering.

Through designing hierarchical structures, particularly optimizing the chemical and architectural interactions at its inorganic/organic interface, nacre has achieved an excellent combination of contradictory mechanical properties such as strength and toughness, which is highly demanded yet difficult to achieve by most synthetic materials. Most techniques applied to develop nacre-mimetic composites have been focused on mimicking the "brick-and-mortar" structure, but the interfacial architectural features, especially the asperities and mineral bridges of "bricks", have been rarely concerned, which are of equal importance for enhancing mechanical properties of nacre. Here, we used a modified bidirectional freezing method followed by uniaxial pressing and chemical reduction to assemble a nacre-mimetic graphene/poly(vinyl alcohol) composite film, with both asperities and bridges introduced in addition to the lamellar layers to mimic the interfacial architectural interactions found in nacre. As such, we have developed a composite film that is not only strong (up to ∼150.9 MPa), but also tough (up to ∼8.50 MJ/m3), and highly stretchable (up to ∼10.44%), difficult to obtain by other methods. This was all achieved by only interfacial architectural engineering within the traditional "brick-and-mortar" structure, without introducing a third component or employing chemical cross-linker as in some other nacre-mimetic systems. More importantly, we believe that the design principles and processing strategies reported here can also be applied to other material systems to develop strong and stretchable materials.

Biomimetic Architectured Graphene Aerogel with Exceptional Strength and Resilience.

Materials combining lightweight, robust mechanical performances, and multifunctionality are highly desirable for engineering applications. Graphene aerogels have emerged as attractive candidates. Despite recent progresses, the bottleneck remains how to simultaneously achieve both strength and resilience. While multiscale architecture designs may offer a possible route, the difficulty lies in the lack of design guidelines and how to experimentally achieve the necessary structure control over multiple length scales. The latter is even more challenging when manufacturing scalability is taken into account. The Thalia dealbata stem is a naturally porous material that is lightweight, strong, and resilient, owing to its architecture with three-dimensional (3D) interconnected lamellar layers. Inspired by such, we assemble graphene oxide (GO) sheets into a similar architecture using a bidirectional freezing technique. Subsequent freeze-drying and thermal reduction results in graphene aerogels with highly tunable 3D architectures, consequently an unusual combination of strength and resilience. With their additional electrical conductivity, these graphene aerogels are potentially useful for mechanically switchable electronics. Beyond such, our study establishes bidirectional freezing as a general method to achieve multiscale architectural control in a scalable manner that can be extended to many other material systems.