TiO2 is an important material widely used in optoelectronic devices due to its semiconducting and photocatalytic properties, nontoxicity, and chemically inert nature. Some indicative applications include water purification systems and energy harvesting. The use of solution, water-based inks for the direct writing of TiO2 on flexible substrates is of paramount importance since it enables low-cost and low-energy intensive large-area manufacturing, compatible with roll-to-roll processing. In this work we study the effect of crystalline TiO2 and polymer addition on the rheological and direct writing properties of Ti-organic/TiO2 inks. We also report on the bridging crystallite formation from the Ti-organic precursor into the TiO2 crystalline phase, under ultraviolet (UV) exposure or mild heat treatments up to 150 °C. Such crystallite formation is found to be enhanced by polymers with strong polarity and pKα such as polyacrylic acid (PAA). X-ray diffraction (XRD) coupled with Raman and X-ray photoelectron (XPS) spectroscopy are used to investigate the crystalline-phase transformation dependence based on the initial TiO2 crystalline-phase concentration and polymer addition. Transmission electron microscopy imaging and selected area electron diffraction patterns confirm the crystalline nature of such bridging printed structures. The obtained inks are patterned on flexible substrates using nozzle-based robotic deposition, a lithography-free, additive manufacturing technique that allows the direct writing of material in specific, digitally predefined, substrate locations. Photocatalytic degradation of methylene blue solutions highlights the potential of the studied films for chemical degradation applications, from low-cost environmentally friendly materials systems.

Three-dimensional (3D) printing of hierarchically ordered cellular materials with tunable microstructures is a major challenge from both synthesis and scalable manufacturing perspectives. A simple, environmentally friendly, and scalable concept to realize morphologically and microstructurally engineered cellular ceramics is herein demonstrated by combining direct foam writing with colloidal processing. These cellular structures are widely applicable across multiple technological fields including energy harvesting, waste management/water purification, and biomedicine. Our concept marries sacrificial templating with direct foaming to synthesize multiscale porous TiO2 foams that can be 3D printed into planar, free-standing, and spanning hierarchical structures. The latter being reported for the first time. We show how by varying the foam-inks’ composition and frothing conditions, the rheological properties and foam configurations (i.e., open- or closed-cell) are tuned. Furthermore, our printing studies indicate a synergy between intermediate extrusion pressures and low speeds for realizing spanning features. Additionally, the dimensional changes associated with the postprocessing of the different foam configurations are discussed. We investigate the effects of the foams’ composition on their microstructure and surface area properties. Additionally, the foams’ photocatalytic performance is correlated with their microstructure, improving for open-cell architectures. The proposed synthesis and scalable manufacturing method can be extended to fabricate similar structures from alternative ceramic foam systems, where control of the porosity and surface properties is crucial, demonstrating the great potential of our synthesis approach.

ZnO-based materials are commonly used in electronic device fabrication due to the interesting piezoelectric, pyroelectric, and optical properties of this tunable band-gap semiconductor. In this research, Al-doped ZnO structures have been fabricated through continuous-flow direct writing of sol-gel inks on glass substrates. We focus on understanding the transformations occurring in the materials synthesis from solution to crystalline structures as an essential step for their use in electronic devices. We investigate the relationships between the inks' rheological properties and direct writing parameters with respect to the printed pattern dimensions, and obtained microstructures, after annealing at 500 °C. We demonstrate how, by varying the printing conditions and composition of the ink formulations, the crystallographic-growth and materials' microstructure can be controlled. Finally, we illustrate an example of the optoelectronic functionality of the directly written AZO patterns using their photosensitivity properties upon different illumination conditions as well as their flexibility. Our work aims to establish relationships between materials processing and properties in emerging additive printing methods, which is of paramount importance towards innovation and new paradigms in advanced manufacturing.

3D printing of amorphous and crystalline ceramics is of paramount importance for the fabrication of a wide range of devices with applications across different technology fields. Printed ceramics are remarkably enabled by the sol–gel synthesis method in conjunction with continuous filament direct ink writing. During printing, multiple processes contribute to the evolution of inks including shape retention, chemical conversion, solidification, and microstructure formation. Traditionally, depending on the ink composition and printing environment, several mechanisms have been associated with the shape retention and solidification of 3D printed structures: gelation, rapid solvent evaporation, energy-driven phase transformation, and chemical-driven phase transformation. Understanding the fundamental differences between these mechanisms becomes key since they strongly influence the spatiotemporal evolution of the materials, as the out-of-equilibrium processes inherent to the extrusion, relaxation, and solidification of printed materials have significant effects on the materials properties. In this work, we investigate the shape retention mechanism and the hydrolysis-induced material conversion and microstructure formation during the 3D printing of a water reactive sol–gel ink that transforms into titanium dioxide-based ceramic. This study aims at identifying characteristic mechanisms associated with the material transformation, establishing connections between the microstructure development and the timescales associated with solidification under operando 3D-printing conditions. The investigation of this material’s out-of-equilibrium pathways under processing conditions is enabled by time-resolved coherent X-ray scattering, providing simultaneous access to temporospatially resolved microstructural and dynamics information. Furthermore, we explore X-ray speckle tracking as a tool to resolve deformations of the microstructure in a printed filament associated with the deposition of consecutive filaments. Through this work, we aim at providing a fundamental understanding of the relationships behind these transformative processes in 3D printing and their timescales as the basis for achieving unprecedented control over printed materials microstructure.

There is currently a great interest in developing flexible electrodes. Such components are used in most electronic devices from displays to solar cells to flexible sensors. To date most of them are fabricated using expensive vacuum techniques, and are based on transparent conducting oxides. These oxides are not entirely compatible with flexible substrates under the application of mechanical stresses, due to their brittle nature. Therefore, there is a need to explore novel low-cost, large-area fabrication methods to deposit alternative conducting materials with enhanced electro-mechanical performance. This work focuses on Ag patterns fabricated at low temperatures (below 150°C) on flexible polyethylene naphthalate utilizing a robotic printing approach. Such lithography-free method minimizes material waste by printing exact amounts of inks on digitally predefined locations. Additionally, it allows a broad feature size range, from a few μm to a few mm, and a variety of ink viscosities for better pattern control. We investigate the synthesis and direct writing of Ag particle-based inks, patterned-on-flex as lines and grids in the μm scale. We report on a high-yield ink synthesis method (~61.6%) with controlled particle size. It is found that the electrical resistivity (1.75 * 10 −4 Ω cm) of the patterns is in the same range with similar particlebased conductive components. The correlation between annealing temperature, microstructural evolution, and electrical performance is established. Also, the optical transmittance of the patterns can be controlled to meet specific application requirements by regulating the substrate surface area covered. Finally, the mechanical behavior under both monotonic and cyclic conditions shows a superior performance compared to brittle counterparts and underlines the potential of such metallic micro-patterns to be utilized in a wide range of flexible electronic applications. It is believed that direct writing of Ag patterns on compliant substrates may hold the key in developing the next generation of truly flexible devices.