Hippolyte DORY
defended his PhD thesis on 20 December 2024
“3D ceramics: synthesis, characterization and applications (catalysis and water purification)”
Front of the jury composed of :
– Miryana HEMADI, Professor, Université Paris Cité – Examinatrice
– Emanuel IONESCU, Lecturer, Technische Universität Darmstadt, Fraunhofer IWKS – Rapporteur
– Nicholas. M. BEDFORD, Associate Professor, Colorado School of Mines – Rapporteur
– Philippe MIELE, Professor, Ecole Nationale Supérieure de Chimie de Montpellier – Co-directeur de thèse
– Chrystelle SALAMEH, Associate Professor, Ecole Nationale Supérieure de Chimie de Montpellier- Directrice de thèse
– Damien VOIRY, Research Director, CNRS – Invité
Abstract:
Advances in additive manufacturing have opened new frontiers in the development of high-performance ceramic materials for critical applications, including catalysis and water purification. This study presents a detailed investigation into the synthesis, 3D printing, and functionalization of advanced ceramic systems—namely silicon oxycarbide (SiOC), silicon carbonitride (SiCN), and mullite ceramics—through photopolymerization-based additive manufacturing techniques. In Chapter 2, we introduce a versatile approach to 3D printing ceramics by formulating photocurable preceramic polymers via two methods: (i) blending the preceramic polymer with photoactive monomers and (ii) grafting photopolymerizable groups onto precursor polymers. These systems are processed using UV-LCD 3D printing and subsequently converted into dense or porous ceramic structures through controlled pyrolysis. The resulting SiOC and SiCN ceramics exhibit high resolution, tunable surface roughness, and excellent structural integrity, laying the foundation for their use in demanding applications.
Building upon this, Chapter 3 explores the catalytic potential of the 3D-printed SiOC and SiCN ceramics. By leveraging the tailored surface properties and porous architectures achieved through additive manufacturing, these ceramics are functionalized via atomic layer deposition (ALD) to introduce active catalytic species, palladium nanoparticles. This thesis is the first study, to our knowledge, to combine SiOC ceramics and ALD. The materials demonstrate great catalytic activity and stability in a model Suzuki-Miyaura reaction, with potential applications in industrial chemical processes. This chapter also highlights the robustness and reusability of the catalysts, underscoring their practical significance in sustainable and energy-efficient catalytic systems. Additionally, in the second part, new metal-containing preceramic polymeric precursors were synthesized using a coordination chemistry approach by grafting ligands on the preceramic polymer backbone. These precursors lead to the fabrication of Cu- and Co- containing ceramics in both oxide and non-oxide forms. These ceramics have been intensively characterized using high energy X-Ray diffraction and total scattering using synchrotron radiations.
In Chapter 4, the scope of application extends to environmental remediation, specifically water purification. Mullite-based ceramic membranes are fabricated via 3D printing using a photocurable ceramic slurry, followed by surface modification using a Vapor-Liquid-Solid (VLS) process to enhance their filtration properties. The modified membranes demonstrate remarkable efficiency in oil-water separation across various organic solvents, achieving high flow rates and selectivity.
Overall, this work highlights the significant potential of 3D-printed ceramics in advanced functional applications, from catalysis to environmental protection. The findings underscore the versatility of additive manufacturing in creating complex ceramic architectures and open new avenues for developing high-performance materials that address industrial and environmental challenges.
Key words
Ceramic, 3D printing, Preceramic polymer, catalysis, water treatment
