Tuning, Impedance Matching, and Temperature Regulation during High-Temperature Microwave Sintering of Ceramics

International audienceOver the years, microwave radiation has emerged as an efficient source of energy for material processing. This technology provides a rapid and a volumetric heating of material. However, the main issues that prevent microwave technology from being widespread in material processing are temperature control regulation and heating distribution within the sample. Most of the experimental works are usually manually monitored, and their reproducibility is rarely evaluated and discussed. In this work, an originally designed 915MHz microwave single-mode applicator for high-temperature processing is presented. The overall microwave system is described in terms of an equivalent electrical circuit. This circuit has allowed to point out the different parameters which need to be adjusted to get a fully controlled heating process. The basic principle of regulation is then depicted in terms of a block function diagram. From it, the process has been developed and tested to sinter zirconia-and spinel-based ceramics. It is clearly shown that the process can be successfully used to program multistep temperature cycles up to similar to 1550 degrees C, improving significantly the reproducibility and the ease of use of this emerging high-temperature process technology

Microwave sintering of spinel MgAl2O4 : towards transparent ceramics

Les conditions nécessaires pour obtenir des céramiques transparentes (absence de porosité, absence de seconde phase) requièrent une totale maitrise de chacune des étapes (synthèse, mise en forme, frittage) intervenant dans le processus, ce qui rend encore difficile l'industrialisation d'un procédé d'élaboration reproductible. Dans ce contexte, ce travail de thèse s’est focalisé à développer et évaluer la capacité du procédé de frittage micro-ondes à améliorer la robustesse du processus d'élaboration de spinelle transparent. La mise en place d'un dispositif de dilatométrie optique et une nouvelle technique de calibration originale, basée sur la fusion d'oxyde, ont permis de caractériser le frittage micro-ondes du spinelle pur avec une plus grande confiance. Même si aucun effet lié au procédé micro-onde n’a pu être mis en évidence pour le frittage du spinelle pur (trajectoire de frittage, mécanisme de densification et évolution de la porosité identiques), ces travaux ont démontré que l’impact de dopants pouvait être amplifié en présence du rayonnement micro-ondes. Ainsi, un décalage des courbes de retrait vers les basses températures a été observé lors du frittage micro-ondes du spinelle dopé avec TiO2 et MgO. L'existence d'un couplage particulier entre les défauts ponctuels chargés (lacunes, cations interstitiels) et le champ électrique pourrait être à l'origine de ce phénomène. Ces travaux de thèse ont également démontré la faisabilité de fritter des pièces de spinelle carrées de grandes dimensions (< 65 mm) compatibles avec un post-traitement HIP, en vue d'obtenir des pièces transparentes. Pour cela, un four micro-ondes monomode 915 MHz a été automatisé et une cellule de frittage adaptée a été développée. A l'issue du traitement HIP, les pièces ont présenté une transparence et des propriétés mécaniques (dureté; ténacité) comparables à celles des pièces pré frittées par voie conventionnelle.The elaboration of transparent ceramics (no porosity, no second phase) requires a strict control of all steps of the process (synthesis, shaping, sintering). As a result, the industrialization of a reproducible process is still difficult to achieve. In this context, this thesis has focused on developing and evaluating the ability of the microwave sintering process to improve the robustness of the transparent spinel elaboration process.The set-up of an optical dilatometer and a new original calibration method, based of melting of different oxides, allowed to characterize the microwave sintering with a greater confidence. Even if no microwave effect has been observed on the sintering of pure spinel (identical sintering trajectory, densification mechanism and porosity evolution), this work has shown an amplification of the impact of dopants during microwave sintering. A shift of the shrinkage curves towards the low temperatures was observed during the microwave sintering of the spinel doped with TiO2 and MgO. The existence of a particular interaction between charged point defects (vacancies, interstitial cations) and the electric field could explain this phenomenon.This work thesis has shown also the feasibility of sintering of large square spinel pieces (< 65 mm) compatible with post treatment HIP in order to produce transparent ceramics. For this purpose, the microwave system working at 915 MHz was automatized and a new sintering configuration was developed. After a post-treatment, the transparency and mechanical properties (hardness; tenacity) of microwave pre-sintered samples were comparable with those of samples sintered by conventional heating

Frittage micro-ondes du matériau spinelle MgAl2O4 : vers des céramiques transparentes

The elaboration of transparent ceramics (no porosity, no second phase) requires a strict control of all steps of the process (synthesis, shaping, sintering). As a result, the industrialization of a reproducible process is still difficult to achieve. In this context, this thesis has focused on developing and evaluating the ability of the microwave sintering process to improve the robustness of the transparent spinel elaboration process.The set-up of an optical dilatometer and a new original calibration method, based of melting of different oxides, allowed to characterize the microwave sintering with a greater confidence. Even if no microwave effect has been observed on the sintering of pure spinel (identical sintering trajectory, densification mechanism and porosity evolution), this work has shown an amplification of the impact of dopants during microwave sintering. A shift of the shrinkage curves towards the low temperatures was observed during the microwave sintering of the spinel doped with TiO2 and MgO. The existence of a particular interaction between charged point defects (vacancies, interstitial cations) and the electric field could explain this phenomenon.This work thesis has shown also the feasibility of sintering of large square spinel pieces (< 65 mm) compatible with post treatment HIP in order to produce transparent ceramics. For this purpose, the microwave system working at 915 MHz was automatized and a new sintering configuration was developed. After a post-treatment, the transparency and mechanical properties (hardness; tenacity) of microwave pre-sintered samples were comparable with those of samples sintered by conventional heating.Les conditions nécessaires pour obtenir des céramiques transparentes (absence de porosité, absence de seconde phase) requièrent une totale maitrise de chacune des étapes (synthèse, mise en forme, frittage) intervenant dans le processus, ce qui rend encore difficile l'industrialisation d'un procédé d'élaboration reproductible. Dans ce contexte, ce travail de thèse s’est focalisé à développer et évaluer la capacité du procédé de frittage micro-ondes à améliorer la robustesse du processus d'élaboration de spinelle transparent. La mise en place d'un dispositif de dilatométrie optique et une nouvelle technique de calibration originale, basée sur la fusion d'oxyde, ont permis de caractériser le frittage micro-ondes du spinelle pur avec une plus grande confiance. Même si aucun effet lié au procédé micro-onde n’a pu être mis en évidence pour le frittage du spinelle pur (trajectoire de frittage, mécanisme de densification et évolution de la porosité identiques), ces travaux ont démontré que l’impact de dopants pouvait être amplifié en présence du rayonnement micro-ondes. Ainsi, un décalage des courbes de retrait vers les basses températures a été observé lors du frittage micro-ondes du spinelle dopé avec TiO2 et MgO. L'existence d'un couplage particulier entre les défauts ponctuels chargés (lacunes, cations interstitiels) et le champ électrique pourrait être à l'origine de ce phénomène. Ces travaux de thèse ont également démontré la faisabilité de fritter des pièces de spinelle carrées de grandes dimensions (< 65 mm) compatibles avec un post-traitement HIP, en vue d'obtenir des pièces transparentes. Pour cela, un four micro-ondes monomode 915 MHz a été automatisé et une cellule de frittage adaptée a été développée. A l'issue du traitement HIP, les pièces ont présenté une transparence et des propriétés mécaniques (dureté; ténacité) comparables à celles des pièces pré frittées par voie conventionnelle

Frittage micro-ondes du matériau spinelle MgAl2O4 : vers des céramiques transparentes

The elaboration of transparent ceramics (no porosity, no second phase) requires a strict control of all steps of the process (synthesis, shaping, sintering). As a result, the industrialization of a reproducible process is still difficult to achieve. In this context, this thesis has focused on developing and evaluating the ability of the microwave sintering process to improve the robustness of the transparent spinel elaboration process.The set-up of an optical dilatometer and a new original calibration method, based of melting of different oxides, allowed to characterize the microwave sintering with a greater confidence. Even if no microwave effect has been observed on the sintering of pure spinel (identical sintering trajectory, densification mechanism and porosity evolution), this work has shown an amplification of the impact of dopants during microwave sintering. A shift of the shrinkage curves towards the low temperatures was observed during the microwave sintering of the spinel doped with TiO2 and MgO. The existence of a particular interaction between charged point defects (vacancies, interstitial cations) and the electric field could explain this phenomenon.This work thesis has shown also the feasibility of sintering of large square spinel pieces (< 65 mm) compatible with post treatment HIP in order to produce transparent ceramics. For this purpose, the microwave system working at 915 MHz was automatized and a new sintering configuration was developed. After a post-treatment, the transparency and mechanical properties (hardness; tenacity) of microwave pre-sintered samples were comparable with those of samples sintered by conventional heating.Les conditions nécessaires pour obtenir des céramiques transparentes (absence de porosité, absence de seconde phase) requièrent une totale maitrise de chacune des étapes (synthèse, mise en forme, frittage) intervenant dans le processus, ce qui rend encore difficile l'industrialisation d'un procédé d'élaboration reproductible. Dans ce contexte, ce travail de thèse s’est focalisé à développer et évaluer la capacité du procédé de frittage micro-ondes à améliorer la robustesse du processus d'élaboration de spinelle transparent. La mise en place d'un dispositif de dilatométrie optique et une nouvelle technique de calibration originale, basée sur la fusion d'oxyde, ont permis de caractériser le frittage micro-ondes du spinelle pur avec une plus grande confiance. Même si aucun effet lié au procédé micro-onde n’a pu être mis en évidence pour le frittage du spinelle pur (trajectoire de frittage, mécanisme de densification et évolution de la porosité identiques), ces travaux ont démontré que l’impact de dopants pouvait être amplifié en présence du rayonnement micro-ondes. Ainsi, un décalage des courbes de retrait vers les basses températures a été observé lors du frittage micro-ondes du spinelle dopé avec TiO2 et MgO. L'existence d'un couplage particulier entre les défauts ponctuels chargés (lacunes, cations interstitiels) et le champ électrique pourrait être à l'origine de ce phénomène. Ces travaux de thèse ont également démontré la faisabilité de fritter des pièces de spinelle carrées de grandes dimensions (< 65 mm) compatibles avec un post-traitement HIP, en vue d'obtenir des pièces transparentes. Pour cela, un four micro-ondes monomode 915 MHz a été automatisé et une cellule de frittage adaptée a été développée. A l'issue du traitement HIP, les pièces ont présenté une transparence et des propriétés mécaniques (dureté; ténacité) comparables à celles des pièces pré frittées par voie conventionnelle

Sintering paths and mechanisms of pure MgAl2O4 conventionally and microwave sintered

International audienceIn this paper, a comparative study between conventional and microwave sintering of pure spinel MgAl2O4 is presented. The goal is to clarify and identify the possible microwave effects on densification and microstructure of the pure spinel. Sintering trajectories obtained for microwave and conventional sintering are similar and converge into a unique trajectory. Therefore, microwave processing does not refine the grain size of pure spinel. The dominant mechanism of initial and intermediate stages of sintering was determined from the shrinkage curves and sintering trajectory. It was shown that densification is mostly controlled by grain boundary diffusion for both processes. Porosity of microwave and conventionally sintered samples was also characterized by mercury porosimetry and BET analysis. The evolution of the open porosity and pore size distribution is the same whatsoever the process used. This work shows that microwave sintering does not differ that much from conventional sintering on pure MgAl2O4 material

Sintering paths and mechanisms of pure MgAl2O4 conventionally and microwave sintered

International audienceIn this paper, a comparative study between conventional and microwave sintering of pure spinel MgAl2O4 is presented. The goal is to clarify and identify the possible microwave effects on densification and microstructure of the pure spinel. Sintering trajectories obtained for microwave and conventional sintering are similar and converge into a unique trajectory. Therefore, microwave processing does not refine the grain size of pure spinel. The dominant mechanism of initial and intermediate stages of sintering was determined from the shrinkage curves and sintering trajectory. It was shown that densification is mostly controlled by grain boundary diffusion for both processes. Porosity of microwave and conventionally sintered samples was also characterized by mercury porosimetry and BET analysis. The evolution of the open porosity and pore size distribution is the same whatsoever the process used. This work shows that microwave sintering does not differ that much from conventional sintering on pure MgAl2O4 material

Raman Study of the Comparative Effects of Conventional and Microwave Annealing on MgTiO 3 Thin Films Sputtered on Si Substrate

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Microwave sintering of pure and TiO2 doped MgAl2O4 ceramic using calibrated, contactless in-situ dilatometry

International audienceThis work describes the development of a contactless dilatometry system for simultaneously measuring the shrinkage and the temperature during microwave sintering of materials in a 2.45 GHz single-mode cavity. An original temperature calibration method has been developed using a monochromatic Infrared pyrometer, taking into account that the apparent emissivity depends on the temperature. Different calibration oxide materials were selected according to their melting points to determine the temperature dependence of the thermal emissivity. This parameter was then used to get the most accurate temperature values over the entire processing temperature range. Afterwards, microwave sintering kinetics and microstructures of pure MgAl2O4 and TiO2-doped spinel material were studied and compared to those of conventionally sintered samples. It was shown that there was no significant difference in the densification behavior of the pure spinet material compared to the conventionally sintered material. On the contrary, the shrinkage curve of the microwave sintered TiO2-doped spinel was found to be shifted to lower temperature compared to the conventional shrinkage curve. This result occurs due to likely species diffusivity enhancement provided by a specific coupling between microwaves and point defects, such as [Ti4+-V-Mg ''] pair dipoles

Raman Study of the Comparative Effects of Conventional and Microwave Annealing on MgTiO 3 Thin Films Sputtered on Si Substrate

International audienc

Tuning, Impedance Matching, and Temperature Regulation during High-Temperature Microwave Sintering of Ceramics

International audienceOver the years, microwave radiation has emerged as an efficient source of energy for material processing. This technology provides a rapid and a volumetric heating of material. However, the main issues that prevent microwave technology from being widespread in material processing are temperature control regulation and heating distribution within the sample. Most of the experimental works are usually manually monitored, and their reproducibility is rarely evaluated and discussed. In this work, an originally designed 915MHz microwave single-mode applicator for high-temperature processing is presented. The overall microwave system is described in terms of an equivalent electrical circuit. This circuit has allowed to point out the different parameters which need to be adjusted to get a fully controlled heating process. The basic principle of regulation is then depicted in terms of a block function diagram. From it, the process has been developed and tested to sinter zirconia-and spinel-based ceramics. It is clearly shown that the process can be successfully used to program multistep temperature cycles up to similar to 1550 degrees C, improving significantly the reproducibility and the ease of use of this emerging high-temperature process technology