Mécanismes de consolidation et de densification de poudres de cuivre lors d'un frittage SPS

Spark plasma sintering is a manufacturing process that leads to dense materials with fine microstructures. SPS combines heating and uniaxial load as well as the Hot Pressing (HP) process but the material is heated using a pulsed current. The phenomena occurring during SPS are not fully understood and are still an open point: -Which densification and consolidation mechanisms are involved during SPS? -Why is sintering by SPS more efficient than sintering by traditional ways such as HP? –Does electrical current modify the sintering mechanisms? The aim of this work is to answer these questions in the case of spherical copper powder (from 10 to 50 µm). Comparisons between SPS and HP were performed using the same process conditions. The densification rate was studied macroscopically and microscopically. The evolution of the necks between particles was followed by cross sections and fractography. The densification is realized by plastic deformation due to the applied load and the temperature increase. No difference between SPS and HP was observed although sintering conditions favorable to the occurrence of specific phenomena were applied: oxide layer coating the particles, current forced through the sample, high intensity using a pulsed current. In the studied conditions, no specific effect was observed due to the current presence.La technologie Spark Plasma Sintering (SPS) permet la conception de matériaux denses avec des microstructures fines. Il s’agit d’une variante du pressage à chaud (HP) qui utilise un courant pulsé pour chauffer la matrice et le matériau. Les phénomènes mis en jeu restent mal compris et sujets à controverse, laissant plusieurs interrogations : - Pourquoi le frittage par SPS apparaît-il plus efficace que les méthodes de frittage sous charge classiques ? Quels sont les mécanismes de densification et de consolidation activés qui déterminent l’élaboration par SPS ? Le passage du courant joue-t-il un rôle dans ces mécanismes et si oui lequel ? Ce travail vise à répondre à ces questions dans le cas de poudres de cuivre sphériques de 10 à 50 µm. Des comparaisons systématiques ont été réalisées avec le pressage à chaud classique, dans des conditions identiques. La cinétique de densification a été étudiée à l’échelle macroscopique et à l’échelle de la microstructure. L’observation de la formation des cous de frittage a été réalisée à partir de fractographies et de sections polies. La densification est assurée par la déformation des particules due à la charge appliquée et à l’augmentation de la température. Aucune différence, ni macroscopique, ni microscopique, n’a été mise en évidence entre l’élaboration par HP et celle par SPS, même lorsque des conditions favorables à la mise en évidence ont été utilisées : couches d’oxyde développée sur les particules, passage du courant forcé dans l’échantillon, fortes intensités appliquées par des « pulses » de courant. Dans les conditions étudiées, il n’apparaît aucun effet spécifique lié au courant

Consolidation and densification mechanisms of copper powder during Spark plasma sintering (SPS)

La technologie Spark Plasma Sintering (SPS) permet la conception de matériaux denses avec des microstructures fines. Il s’agit d’une variante du pressage à chaud (HP) qui utilise un courant pulsé pour chauffer la matrice et le matériau. Les phénomènes mis en jeu restent mal compris et sujets à controverse, laissant plusieurs interrogations : - Pourquoi le frittage par SPS apparaît-il plus efficace que les méthodes de frittage sous charge classiques ? Quels sont les mécanismes de densification et de consolidation activés qui déterminent l’élaboration par SPS ? Le passage du courant joue-t-il un rôle dans ces mécanismes et si oui lequel ? Ce travail vise à répondre à ces questions dans le cas de poudres de cuivre sphériques de 10 à 50 µm. Des comparaisons systématiques ont été réalisées avec le pressage à chaud classique, dans des conditions identiques. La cinétique de densification a été étudiée à l’échelle macroscopique et à l’échelle de la microstructure. L’observation de la formation des cous de frittage a été réalisée à partir de fractographies et de sections polies. La densification est assurée par la déformation des particules due à la charge appliquée et à l’augmentation de la température. Aucune différence, ni macroscopique, ni microscopique, n’a été mise en évidence entre l’élaboration par HP et celle par SPS, même lorsque des conditions favorables à la mise en évidence ont été utilisées : couches d’oxyde développée sur les particules, passage du courant forcé dans l’échantillon, fortes intensités appliquées par des « pulses » de courant. Dans les conditions étudiées, il n’apparaît aucun effet spécifique lié au courant.Spark plasma sintering is a manufacturing process that leads to dense materials with fine microstructures. SPS combines heating and uniaxial load as well as the Hot Pressing (HP) process but the material is heated using a pulsed current. The phenomena occurring during SPS are not fully understood and are still an open point: -Which densification and consolidation mechanisms are involved during SPS? -Why is sintering by SPS more efficient than sintering by traditional ways such as HP? –Does electrical current modify the sintering mechanisms? The aim of this work is to answer these questions in the case of spherical copper powder (from 10 to 50 µm). Comparisons between SPS and HP were performed using the same process conditions. The densification rate was studied macroscopically and microscopically. The evolution of the necks between particles was followed by cross sections and fractography. The densification is realized by plastic deformation due to the applied load and the temperature increase. No difference between SPS and HP was observed although sintering conditions favorable to the occurrence of specific phenomena were applied: oxide layer coating the particles, current forced through the sample, high intensity using a pulsed current. In the studied conditions, no specific effect was observed due to the current presence

Redox properties of the carbonate molten salt Li2_2CO3_3Na2_2CO3_3-K2_2CO3_3

International audienceThe objective of this work is to study the Li2CO3Na2CO3-K2CO3 (29.5–31.1–39.4 mol%) molten salt and the behaviour of several metals (Au, Pt, C, Ni and W) by electrochemical measurements in the salt under three atmospheres (Ar, CO2 and O2/N2). Thermodynamic calculations show that the molten salt anodic and cathodic limits correspond to the carbonate ions oxidation and reduction to dioxygen and carbon respectively. An internal reference electrode has been defined based on the redox system Na+/Au2Na, which is independent of the lithium oxide activity. The widths of the electroactivity domain have been measured on gold working electrode by cyclic voltammetry: 2.21 V under Ar and O2/N2 and 2.41 V under CO2, which are larger than the values obtained by thermodynamic calculations (1.280 V and 1.025 V respectively). Gas chromatographic (GC) analysis during electrolysis at potentials ranging in the anodic limit allowed to conclude that the electrochemical domain of the carbonate molten salt is limited anodically by the oxidation of carbonate ions to dioxygen, possibly peroxide ions, and carbon dioxide. The characterisation by XRD of a platinum electrode after electrolysis at the cathodic limit has shown that the electroactivity domain of the molten salt is defined by the carbonate ions reduction into carbon, indicating that CO32−/C is an irreversible system. A carbonate ions decomposition rate of 1 × 10-3 mmol.h-1.cm−2 has been determined by GC and thermogravimetric analysis (TGA) under inert gas. A stabilization of the CO2 pressure is observed after the melting of the salt

Effect of Electric Current on SPS Densification of Spherical Copper Powder

International audienceWhen a current is involved, as in spark plasma sintering, metallic powders are heated by the Joule effect through both tool and specimen. Other mechanisms might occur, but it is difficult to separate the role of the temperature from the role of the current inside the sample as, in most cases, the two parameters are not controlled independently. In this paper, the consolidation and the densification of a pure copper powder were studied in three configurations for obtaining different electric current paths: (i) current flowing through both the powder and the die, (ii) current forced into the powder and (iii) no current allowed in the powder. Electrical conductivity measurements showed that even low-density samples displayed higher conductivities than graphite by several orders of magnitude. FEM simulations confirmed that these copper specimens were mainly heated by the graphite punches. No modification of the microstructure by the flow of current could be observed. However, the absence of current in the specimen led to a decrease in densification. No significant temperature difference was modeled between the configurations, suggesting that differences are not linked to a thermal cause but rather to a current effect

Effect of current on the sintering of pre-oxidized copper powders by SPS

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