Alicia Weibel

From core–shell BaTiO3@MgO to nanostructured low dielectric loss ceramics by spark plasma sintering

We report a quite general way to design materials with tailored properties by combining thermolysis and fast sintering approaches. Submicrometric-sized BaTiO3 particles have been directly coated in a continuous nanocrystalline MgO shell through a thermal decomposition process. The electron microscopy study has evidenced a shell composed of randomly oriented MgO nanocrystallites. The final nanostructured composite, made of sub-micrometric MgO and BaTiO3 grains uniformly distributed, is obtained in situ during the SPS process. Such a rearrangement can be explained by the initial core–shell architecture, the weak cohesion of the MgO nanocrystallites and their soft plastic behavior under SPS conditions. The composite effect leads to significant modifications in both the dielectric properties and Curie–Weiss parameters compared to uncoated BaTiO3, especially a decrease and thermal stabilization of both the permittivity and the dielectric losses. We ascribe such changes to the stress generated during SPS through the extended interfaces between the two components.

Dog-bone copper specimens prepared by one-step spark plasma sintering

Copper dog-bone specimens are prepared by one-step spark plasma sintering (SPS). For the same SPS cycle, the influence of the nature of the die (graphite or WC–Co) on the microstructure, microhardness, and tensile strength is investigated. All samples exhibit a high Vickers microhardness and high ultimate tensile strength. A numerical electro-thermal model is developed, based on experimental data inputs such as simultaneous temperature and electrical measurements at several key locations in the SPS stack, to evaluate the temperature and current distributions for both dies. Microstructural characterizations show that samples prepared using the WC–Co die exhibit a larger grain size, pointing out that it reached a higher temperature during the SPS cycle. This is confirmed by numerical simulations demonstrating that with the WC–Co die, the experimental sample temperature at the beginning of the dwell is higher than the experimental control temperature measured at the outer surface of the die. This difference is mostly ascribed to a high vertical thermal contact resistance and a higher current density flowing through the WC–Co punch/die interface. Indeed, simulations show that current density is maximal just outside the copper sample when using the WC–Co die, whereas by contrast, with the graphite die, current density tends to flow through the copper sample. These results are guidelines for the direct, one-step, preparation of complex-shaped samples by SPS which avoids waste and minimizes machining.

Flash sintering of dielectric nanoparticles as a percolation phenomenon through a softened film

Recent work [Biesuz et al., J. Appl. Phys. 120, 145107 (2016)] showed analogies between the flash sintering and dielectric breakdown in α-aluminas pre-sintered to different densities. Here, we show that flash sintering of dielectric nanoparticles can be described as a universal behavior by the percolation model. The electrical system is composed of particles and their contact point resistances, the latter softened first due to preferred local Joule heating and thermal runaway during the flash. Local softening has a hierarchical and invasive nature and propagates between the electrodes. The flash event signals the percolation threshold by invasive nature of the softened layer at the particle surfaces. Rapid densification is associated with local particle rearrangements due to attractive capillary forces induced by the softened film at the particle contacts. Flash sintering is a critical phenomenon with a self-organizing character. The experimental electric conductivity results from flash sintering are in full agreement with those calculated from the percolation model.

Grain growth during spark plasma and flash sintering of ceramic nanoparticles: a review

AbstractSpark plasma and flash sintering process characteristics together with their corresponding sintering and densification mechanisms and field effects were briefly reviewed. The enhanced and inhibited grain growth obtained using these field-assisted densification techniques were reported for different ceramic nanoparticle systems and related to their respective densification mechanisms. When the densification is aided by plastic deformation, the kinetics of grain growth depends on the particles’ rotation/sliding rate and is controlled by lattice and pipe diffusion. When the densification is aided by spark, plasma, and the particles’ surface softening, grain growth kinetics is controlled by viscous diffusion and interface reactions. Grain growth in both cases is hierarchical by grain rotation, grain cluster formation and sliding, as long as the plastic deformation proceeds or as long as plasma exists. Densification by diffusion in a solid state via defects leads to normal grain growth, which takes over at the final stage of sintering. Various field effects, as well as the effect of external pressure on the grain growth behaviour were also addressed.n

Innovative architectures in ferroelectric multi-materials: Chemistry, interfaces and strain

Breakthroughs can be expected in multi-component ceramics by adjusting the phase assembly and the micro–nanostructure. Controlling the architecture of multi-materials at different scales is still challenging and provides a great opportunity to broaden the range of functionalities in the field of ferroelectric-based ceramics. We used the potentialities of Spark Plasma Sintering (SPS) to control a number of key parameters regarding the properties: anisotropy, interfaces, grain size and strain effects. The flexibility of the wet and supercritical chemistry routes associated with the versatility of SPS allowed designing newferroelectric composite ceramics at different scales. These approaches are illustrated through various examples based on our work on ferroelectric/dielectric composites.

Synthesis of γ-(Al1-xFex)2O3 solid solutions from oxinate precursors and formation of carbon nanotubes from the solid solutions using methane or ethylene as carbon source

This work reports for the first time the synthesis of ?-(Al1-xFex)2O3 solid solutions with a high specific surface area (200-230 m2/g) by the decomposition of metal oxinate [(Al1-xFex)(C9H6ON)3] and investigated the potential of these materials as catalysts for the synthesis of carbon nanotubes by catalytic chemical vapor deposition using methane or ethylene as carbon the source. The nanocomposite powders prepared by reduction in H2-CH4 contain carbon nanotubes (CNTs), which are mostly double-walled but also contain a fair amount of undesirable carbon nanofibers, hollow carbon particles, and metal particles covered by carbon layers. Moreover, abundant metallic particles are observed to cover the surfaces of the matrix grains. By contrast, the nanocomposite powders prepared by reduction in N2-C2H4 are not fully reduced, and the CNTs are much more abundant and homogeneous. However, they are multiwalled CNTs with a significant proportion of defects. The powders were studied by several techniques including Mossbauer spectroscopy and electron microscopy.

Shaping of Nanostructured Materials or Coatings through Spark Plasma Sintering

In the field of advanced ceramics, Spark Plasma Sintering (SPS) is known to be very efficient for superfast and full densification of ceramic nanopowders. This property is attributed to the simultaneous application of high density dc pulsed current and load, even though the sintering mechanisms involved remain unclear. In the first part of the paper, the mechanisms involved during SPS of two insulating oxide nanopowders (Al2O3 and Y2O3) are discussed while in the second part illustrations of the potential of SPS will be given for (i) Consolidation of mesoporous or unstable nanomaterials like SBA-15 or biomimetic apatite, respectively; (ii) Densification of core (BT or BST)/shell (SiO2 or Al2O3) nanoparticles with limited or controlled reaction at the interface. (iii) In-situ preparation of surface-tailored Fe–FeAl2O4–Al2O3 nanocomposites, and finally (iv) One-step preparation of multilayer materials like a complete thermal barrier system on single crystal Ni-based superalloy.

Mesoporous binder-free monoliths of few-walled carbon nanotubes by spark plasma sintering

Carbon nanotubes with few walls (FWCNTs) are prepared by catalytic chemical vapor deposition. Transmission electron microscopy investigations for each sample show the average number of walls (3, 4 and 8) as well as the internal and external diameter distributions. Binder-free FWCNT monoliths are prepared by spark plasma sintering (SPS) at temperatures in the range 1000–1600xa0°C. A combination of techniques including Raman spectroscopy, scanning- and transmission electron microscopy, electron microdiffraction is used to characterize the samples. Compared to the FWCNT powders, the high temperatures used for SPS favor the elimination of surface defects in CNT walls but also some limited amorphization, without dramatic damage to the CNTs. Increasing the SPS temperatures produces an increase in densification. N2 adsorption–desorption cycles revealed that the powders and monoliths show microporosity and, mostly, mesoporosity. Some monoliths show a specific surface area equal to about 500xa0m2/g. The 4WCNTs when consolidated into monoliths by SPS at 1000 or 1100xa0°C are able to retain a high amount of mesoporosity that contributes to a high porous volume of the order of 0.8xa0cm3/g.