Esther García-Tuñón

Mesoscale assembly of chemically modified graphene into complex cellular networks

The widespread technological introduction of graphene beyond electronics rests on our ability to assemble this two-dimensional building block into three-dimensional structures for practical devices. To achieve this goal we need fabrication approaches that are able to provide an accurate control of chemistry and architecture from nano to macroscopic levels. Here, we describe a versatile technique to build ultralight (density ≥1 mg cm−3) cellular networks based on the use of soft templates and the controlled segregation of chemically modified graphene to liquid interfaces. These novel structures can be tuned for excellent conductivity; versatile mechanical response (elastic-brittle to elastomeric, reversible deformation, high energy absorption) and organic absorption capabilities (above 600 g per gram of material). The approach can be used to uncover the basic principles that will guide the design of practical devices that by combining unique mechanical and functional performance will generate new technological opportunities.

Understanding Mechanical Response of Elastomeric Graphene Networks

Ultra-light porous networks based on nano-carbon materials (such as graphene or carbon nanotubes) have attracted increasing interest owing to their applications in wide fields from bioengineering to electrochemical devices. However, it is often difficult to translate the properties of nanomaterials to bulk three-dimensional networks with a control of their mechanical properties. In this work, we constructed elastomeric graphene porous networks with well-defined structures by freeze casting and thermal reduction, and investigated systematically the effect of key microstructural features. The porous networks made of large reduced graphene oxide flakes (>20 μm) are superelastic and exhibit high energy absorption, showing much enhanced mechanical properties than those with small flakes (<2 μm). A better restoration of the graphitic nature also has a considerable effect. In comparison, microstructural differences, such as the foam architecture or the cell size have smaller or negligible effect on the mechanical response. The recoverability and energy adsorption depend on density with the latter exhibiting a minimum due to the interplay between wall fracture and friction during deformation. These findings suggest that an improvement in the mechanical properties of porous graphene networks significantly depend on the engineering of the graphene flake that controls the property of the cell walls.

Designing Smart Particles for the Assembly of Complex Macroscopic Structures

Particle get-together: Surface functionalization with a branched copolymer surfactant is used to create responsive inorganic particles that can self-assemble in complex structures. The assembly process is triggered by a pH switch that reversibly activates multiple hydrogen bonds between ceramic particles (see picture; yellow) and soft templates (n-decane; green).

Ultralight, Strong, Three-Dimensional SiC Structures

Ultralight and strong three-dimensional (3D) silicon carbide (SiC) structures have been generated by the carbothermal reduction of SiO with a graphene foam (GF). The resulting SiC foams have an average height of 2 mm and density ranging between 9 and 17 mg cm(-3). They are the lightest reported SiC structures. They consist of hollow struts made from ultrathin SiC flakes and long 1D SiC nanowires growing from the trusses, edges, and defect sites between layers. AFM results revealed an average flake thickness of 2-3 nm and lateral size of 2 μm. In-situ compression tests in the scanning electron microscope (SEM) show that, compared with most of the existing lightweight foams, the present 3D SiC exhibited superior compression strengths and significant recovery after compression strains of about 70%.

An Investigation of the Mineral in Ductile and Brittle Cortical Mouse Bone

Bone is a strong and tough material composed of apatite mineral, organic matter, and water. Changes in composition and organization of these building blocks affect bones mechanical integrity. Skeletal disorders often affect bones mineral phase, either by variations in the collagen or directly altering mineralization. The aim of the current study was to explore the differences in the mineral of brittle and ductile cortical bone at the mineral (nm) and tissue (µm) levels using two mouse phenotypes. Osteogenesis imperfecta model, oim‐/‐, mice have a defect in the collagen, which leads to brittle bone; PHOSPHO1 mutants, Phospho1‐/‐, have ductile bone resulting from altered mineralization. Oim‐/‐ and Phospho1‐/‐ were compared with their respective wild‐type controls. Femora were defatted and ground to powder to measure average mineral crystal size using X‐ray diffraction (XRD) and to monitor the bulk mineral to matrix ratio via thermogravimetric analysis (TGA). XRD scans were run after TGA for phase identification to assess the fractions of hydroxyapatite and β‐tricalcium phosphate. Tibiae were embedded to measure elastic properties with nanoindentation and the extent of mineralization with backscattered electron microscopy (BSE SEM). Results revealed that although both pathology models had extremely different whole‐bone mechanics, they both had smaller apatite crystals, lower bulk mineral to matrix ratio, and showed more thermal conversion to β‐tricalcium phosphate than their wild types, indicating deviations from stoichiometric hydroxyapatite in the original mineral. In contrast, the degree of mineralization of bone matrix was different for each strain: brittle oim‐/‐ were hypermineralized, whereas ductile Phospho1‐/‐ were hypomineralized. Despite differences in the mineralization, nanoscale alterations in the mineral were associated with reduced tissue elastic moduli in both pathologies. Results indicated that alterations from normal crystal size, composition, and structure are correlated with reduced mechanical integrity of bone.

Cl–OH ion‐exchanging process in chlorapatite (Ca5(PO4)3Clx(OH)1 − x) – a deep insight

We have synthesized large chlorapatite [ClAp, Ca(5)(PO(4))(3)Cl(x)(OH)(1-x), where x = 1] single crystals using the molten salt method. We have corroborated that the hexagonal symmetry P6(3)/m describes the crystal structure best, even though the crystals are synthetic and stoichiometric. Moreover, we have performed several thermal treatments on these ClAp crystals, generating new single crystals in the apatite system [Ca(5)(PO(4))(3)Cl(x)(OH)(1-x), where x ≤ 1], where the chloride anions (Cl(-)) were systematically substituted by hydroxyl anions (OH(-)). These new single crystals were methodically characterized by powder and single-crystal X-ray diffraction (SXRD), scanning electron microscopy (SEM), Fourier transform-IR spectroscopy (FT-IR), and energy-dispersive X-ray spectroscopy (EDS). We have discovered a previously unreported OH(-) inclusion site substituting the Cl(-) anion during the ion-exchanging process. Finally, we evaluated the atomic rearrangements of the other species involved in the structure. These movements are associated with ionic exchange, which can be justified from an energetic point of view. We also found a novel phase transformation at high temperature. When the crystals are heated over 1753 K the apatite system evolves to a less ordered monoclinic structure, in which the complete loss of the species in the anionic channel (Cl(-), OH(-)) has been confirmed.

Chlorapatite Conversion to Hydroxyapatite under High Temperature Hydrothermal Conditions

The need for biomaterials in dental and orthopedic applications has increased as the world population ages. Synthetic calcium phosphate bioceramics and calcium phosphate cements are proved potential substitutes for bone and teeth due to their structural and crystallographic similarities with the biological apatites, and their biocompatibility but they show poor mechanical properties. Chlorapatite and hydroxyapatite whiskers with high aspect ratio can be used to improve this drawback. This work describes a method to transform chlorapatite single crystals into hydroxyapatite whiskers, suitable for the reinforcement of calcium phosphate bioceramics and calcium phosphate cements. Hydroxyapatite whiskers were obtained by treating chlorapatite single crystals in high-temperature hydrothermal conditions. The variable studied was furnace temperature with and without moisture conditions. The characterization of the chlorapatite and hydroxyapatite whiskers was carried out by SEM, XRD, EDS and FTIR. SXRD data were analyzed for the description of the chlorapatite structure.

Multimaterial 3D Printing of Graphene-Based Electrodes for Electrochemical Energy Storage Using Thermoresponsive Inks.

The current lifestyles, increasing population, and limited resources result in energy research being at the forefront of worldwide grand challenges, increasing the demand for sustainable and more efficient energy devices. In this context, additive manufacturing brings the possibility of making electrodes and electrical energy storage devices in any desired three-dimensional (3D) shape and dimensions, while preserving the multifunctional properties of the active materials in terms of surface area and conductivity. This paves the way to optimized and more efficient designs for energy devices. Here, we describe how three-dimensional (3D) printing will allow the fabrication of bespoke devices, with complex geometries, tailored to fit specific requirements and applications, by designing water-based thermoresponsive inks to 3D-print different materials in one step, for example, printing the active material precursor (reduced chemically modified graphene (rCMG)) and the current collector (copper) for supercapacitors or anodes for lithium-ion batteries. The formulation of thermoresponsive inks using Pluronic F127 provides an aqueous-based, robust, flexible, and easily upscalable approach. The devices are designed to provide low resistance interface, enhanced electrical properties, mechanical performance, packing of rCMG, and low active material density while facilitating the postprocessing of the multicomponent 3D-printed structures. The electrode materials are selected to match postprocessing conditions. The reduction of the active material (rCMG) and sintering of the current collector (Cu) take place simultaneously. The electrochemical performance of the rCMG-based self-standing binder-free electrode and the two materials coupled rCMG/Cu printed electrode prove the potential of multimaterial printing in energy applications.

3D Printing Bioinspired Ceramic Composites.

Natural structural materials like bone and shell have complex, hierarchical architectures designed to control crack propagation and fracture. In modern composites there is a critical trade-off between strength and toughness. Natural structures provide blueprints to overcome this, however this approach introduces another trade-off between fine structural manipulation and manufacturing complex shapes in practical sizes and times. Here we show that robocasting can be used to build ceramic-based composite parts with a range of geometries, possessing microstructures unattainable by other production technologies. This is achieved by manipulating the rheology of ceramic pastes and the shear forces they experience during printing. To demonstrate the versatility of the approach we have fabricated highly mineralized composites with microscopic Bouligand structures that guide crack propagation and twisting in three dimensions, which we have followed using an original in-situ crack opening technique. In this way we can retain strength while enhancing toughness by using strategies taken from crustacean shells.

Graphene Oxide: An All-in-One Processing Additive for 3D Printing

Many 3D printing technologies are based on the development of inks and pastes to build objects through droplet or filament deposition (the latter also known as continuous extrusion, robocasting, or direct ink writing). Controlling and tuning rheological behavior is key for successful manufacturing using these techniques. Different formulations have been proposed, but the search continues for approaches that are clean, flexible, robust and that can be adapted to a wide range of materials. Here, we show how graphene oxide (GO) enables the formulation of water-based pastes to print a wide variety of materials (polymers, ceramics, and steel) using robocasting. This work combines flow and oscillatory rheology to provide further insights into the rheological behavior of suspensions combining GO with other materials. Graphene oxide can be used to manipulate the viscoelastic response, enabling the formulation of pastes with excellent printing behavior that combine shear thinning flow and a fast recovery of their elastic properties. These inks do not contain other additives, only GO and the material of interest. As a proof of concept, we demonstrate the 3D printing of additive-free graphene oxide structures as well as polymers, ceramics, and steel. Due to its amphiphilic nature and 2D structure, graphene oxide plays multiple roles, behaving as a dispersant, viscosifier, and binder. It stabilizes suspensions of different powders, modifies the flow and viscoelasticity of materials with different chemistries, particle sizes and shapes, and binds the particles together, providing green strength for manual handling. This approach enables printing complex 3D ceramic structures using robocasting with similar properties to alternative formulations, thus demonstrating the potential of using 2D colloids in materials manufacturing.