Volumetric Additive Manufacturing of SiOC by Xolography.

Additive manufacturing (AM) of ceramics has significantly contributed to advancements in ceramic fabrication, solving some of the difficulties of conventional ceramic processing and providing additional possibilities for the structure and function of components. However, defects induced by the layer-by-layer approach on which traditional AM techniques are based still constitute a challenge to address. This study presents the volumetric AM of a SiOC ceramic from a preceramic polymer using xolography, a linear volumetric AM process that allows to avoid the staircase effect typical of other vat photopolymerization techniques. Besides optimizing the trade-off between preceramic polymer content and transmittance, a pore generator is introduced to create transient channels for gas release before decomposition of the organic constituents and moieties, resulting in crack-free solid ceramic structures even at low ceramic yield. Formulation optimization alleviated sinking of printed parts during printing and prevented shape distortion. Complex solid and porous ceramic structures with a smooth surface and sharp features are fabricated under the optimized parameters. This work provides a new method for the AM of ceramics at µm/mm scale with high surface quality and large geometry variety in an efficient way, opening the possibility for applications in fields such as micromechanical systems and microelectronic components.

3D-printed zeolite 13X-Strontium chloride units as ammonia carriers.

The selective catalytic reduction (SCR) system in automobiles using urea solution as a source of NH3 suffers from solid deposit problems in pipelines and poor efficiency during engine startup. Although direct use of high pressure NH3 is restricted due to safety concerns, which can be overcome by using solid sorbents as NH3 carrier. Strontium chloride (SrCl2) is considered the best sorbent due to its high sorption capacity; however, challenges are associated with the processing of stable engineering structures due to extraordinary volume expansion during the NH3 sorption. This study reports the fabrication of a novel structure consisting of a zeolite cage enclosing the SrCl2 pellet (SPZC) through extrusion-based 3D printing (Direct Ink Writing). The printed SPZC structure demonstrated steady sorption of NH3 for 10 consecutive cycles without significant uptake capacity and structural integrity loss. Furthermore, the structure exhibited improved sorption and desorption kinetics than pure SrCl2. The synergistic effect of zeolite as physisorbent and SrCl2 as chemisorbent in the novel composite structure enabled the low-pressure (<0.4 bar) and high-pressure (>0.4 bar) NH3 sorption, compared to pure SrCl2, which absorbed NH3 at pressures above 0.4 bar. Regeneration of SPZC composite sorbent under evacuation showed that 87.5% percent of NH3 was desorbed at 20 °C. Thus, the results demonstrate that the rationally designed novel SPZC structure offers safe and efficient storage of NH3 in the SCR system and other applications.

Improving glass nanostructure fabrication.

A new method offers high-resolution three-dimensional printing and low-temperature firing.

Biodiesel Processing Using Sodium and Potassium Geopolymer Powders as Heterogeneous Catalysts.

This work investigates the catalytic activity of geopolymers produced using two different alkali components (sodium or potassium) and four treatment temperatures (110 to 700 °C) for the methyl transesterification of soybean oil. The geopolymers were prepared with metakaolin as an aluminosilicate source and alkaline activating solutions containing either sodium or potassium in the same molar oxide proportions. The potassium-based formulation displayed a higher specific surface area and lower average pore size (28.64-62.54 m²/g; 9 nm) than the sodium formulation (6.34-32.62 m²/g; 17 nm). The reduction in specific surface area (SSA) after the heat treatment was more severe for the sodium formulation due to the higher thermal shrinkage. The catalytic activity of the geopolymer powders was compared under the same reactional conditions (70-75 °C, 150% methanol excess, 4 h reaction) and same weight amounts (3% to oil). The differences in performance were attributed to the influences of sodium and potassium on the geopolymerization process and to the accessibility of the reactants to the catalytic sites. The Na-based geopolymers performed better, with FAME contents in the biodiesel phase of 85.1% and 89.9% for samples treated at 500 and 300 °C, respectively. These results are competitive in comparison with most heterogeneous base catalysts reported in the literature, considering the very mild conditions of temperature, excess methanol and catalyst amount and the short time spent in reactions.

Ag- or Cu-modified geopolymer filters for water treatment manufactured by 3D printing, direct foaming, or granulation.

In this work, we compared the main characteristics of highly porous geopolymer components for water treatment applications manufactured by 3D printing, direct foaming, or granulation. Furthermore, different approaches to impregnate the materials with Ag or Cu were evaluated to obtain filters with disinfecting or catalytic properties. The results revealed that all of the investigated manufacturing methods enabled the fabrication of components that possessed mesoporosity, suitable mechanical strength, and water permeability, even though their morphologies were completely different. Total porosity and compressive strength values were 28 vol% and 16 MPa for 3D-printed, 70-79 vol% and 1 MPa for direct-foamed, and 27 vol% and 10 MPa for granule samples. Both the filter preparation and the metal impregnation method affected the amount, oxidation state, and stability of Ag and Cu in the filters. However, it was possible to prepare filters with low metal leaching between a pH of 3-7, so that the released Ag and Cu concentrations were within drinking water standards.

Optimization and Characterization of Preceramic Inks for Direct Ink Writing of Ceramic Matrix Composite Structures.

In a previous work, an ink based on a preceramic polymer, SiC fillers, and chopped carbon fibers was proposed for the production of Ceramic Matrix Composite (CMC) structures by Direct Ink Writing (DIW) and subsequent pyrolysis. Thanks to the shear stresses generated at the nozzle tip during extrusion, carbon fibers can be aligned along the printing direction. Fumed silica was added to the ink in order to enhance its rheological properties; however, the printed structures still showed some deformation in the Z direction. In this work, a second ink was successfully developed to limit deformation and at the same time avoid the addition of fumed silica, which limited the potential temperature of application of the composites. Instead, the positive role of the preceramic polymer on the ink rheology was exploited by increasing its concentration in the ink. Rheological characterization carried out on both inks confirmed that they possessed Bingham shear thinning behavior and fast viscosity recovery. Single filaments with different diameters (~310 µm and ~460 µm) were produced with the latter ink by DIW and subsequent pyrolysis. Tested under a four-point flexural test, the filaments showed a mean flexural strength above 30 MPa, graceful failure, and fiber pull-out. The results of this work suggest that CMC components can effectively be fabricated via DIW of a preceramic ink with embedded short fibers; the preceramic polymer is able to provide the desired rheology for the process and to develop a dense matrix capable of incorporating both fibers and ceramic particles, whereas the fibers addition contributes to an increase of the fracture toughness of the material and to the development of a graceful failure mode.

The molten glass sewing machine.

We present a fluid-instability-based approach for digitally fabricating geometrically complex uniformly sized structures in molten glass. Formed by mathematically defined and physically characterized instability patterns, such structures are produced via the additive manufacturing of optically transparent glass, and result from the coiling of an extruded glass thread. We propose a minimal geometrical model-and a methodology-to reliably control the morphology of patterns, so that these building blocks can be assembled into larger structures with tailored functionally and optically tunable properties.This article is part of the themed issue 'Patterning through instabilities in complex media: theory and applications'.

Stereolithography of SiOC Ceramic Microcomponents.

The first example of the fabrication of complex 3D polymer-derived-ceramic structures is presented with micrometer-scale features by a 3D additive manufacturing (AM) technology, starting with a photosensitive preceramic precursor. Dense and crack-free silicon-oxycarbide-based microparts with features down to 200 µm are obtained after pyrolysis at 1000 °C in a nitrogen atmosphere.