D. Vrel

Mechanical activation effect on the self-sustaining combustion reaction in the Mo-Si system

Abstract Nanostructured molybdenum disilicide (MoSi2) was synthesized using an alternative route called MASHS (mechanically activated self-propagating high-temperature synthesis). This original process combines a short duration ball milling (MA) with a self-sustaining combustion (SHS). These two steps were investigated. The microstructure evolution of the powder mixture during mechanical activation was monitored using XRD profile analysis and TEM investigations. Short duration ball milling of (Mo+2Si) powder produces Mo and Si nanocrystallites into micrometric particles. It was demonstrated that pure α-MoSi2 with nanometric structure (DMoSi2=88 nm) could be produced via a very fast combustion front in contrast to the classical SHS process.

Investigations of the formation mechanism of nanostructured NbAl3 via MASHS reaction

Abstract The nanostructured NbAl3 intermetallic compound was synthesized using the mechanically-activated self-propagating high-temperature synthesis (MASHS) technique. This process results from the combination of two steps: a short duration ball-milling of a pure elemental Nb+3Al powder mixture followed by a self-propagating high-temperature synthesis (SHS) reaction induced by the Nb+3Al reaction exothermicity. Synchrotron time-resolved XRD coupled with a 2D infrared camera were used to investigate the structural and thermal evolutions during the SHS reaction, and to study in situ the mechanism of NbAl3 formation. The influence of the incoming heat flux and the mechanical activation effect on the phase transformation kinetics induced by the SHS process were studied. Owing to the temporal resolution of 100 and 200 ms between two consecutive diffraction patterns and IR images, respectively, it was shown that solid niobium reacts with liquid aluminium via a heterogeneous nucleation reaction, to form the NbAl3 compound by successive combustion fronts.

A new experimental setup for the time resolved x-ray diffraction study of self-propagating high-temperature synthesis

A new experimental setup for time resolved x-ray diffraction is described. Designed for the LURE H10 beamline and its 4 (+2) circles goniometer, it allows simultaneous recordings of x-ray patterns with a rate of 30 patterns per second, a maximum 2θ range of 120°, infrared thermography at the same rate, and thermocouples readings at a frequency of up to 3×104 Hz. Preliminary results obtained using this setup are presented, showing how it is possible to analyze a solid–solid or solid-liquid reaction. As an example, an in situ study of phase transformation and temperature evolution during the self-sustaining synthesis of an FeAl intermetallic compound starting from a mechanically activated mixture is investigated. The versatility of the setup was proved and could even be enhanced by the design of new sample holders, thus expanding its area of use at low cost.

Time-resolved X-ray diffraction study of SHS-produced NiAl and NiAl-ZrO2 composites

NiAl and NiAl-ZrO2 intermetallic composites were prepared from pressed elemental powders by SHS in a dynamic vacuum. The effect of diluent properties (such as conductivity and grain size) on the parameters of the SHS reaction has been investigated by time-resolved X-ray diffraction (TRXRD). By decreasing the reactivity of the green mixture, these nonreactive additives not only slow down the velocity of combustion front propagation but can also give rise to local melting of the product. Synchrotron radiation was also used to elucidate the reaction mechanism. It has been found that the combustion synthesis of NiAl is triggered by aluminum melting and proceeds via the formation of two transient intermetallic phases, NiAl3 and Ni2Al3. In the final product, only the NiAl phase has been detected.

Self-propagating high-temperature synthesis of boron subphosphide B12P2

Two new methods to produce nanopowders of B12P2 boron subphosphide by self-propagating high-temperature synthesis have been proposed. Bulk polycrystalline B12P2 with microhardness of HV = 35(3) GPa and stability in air up to 1300 K has been prepared by sintering these powders at 5.2 GPa and 2500 K.

Main recent contributions to SHS from France

Both in situ TRXRD and IR thermography, on the one hand, and different levels of modeling, on the other, have generated a strong progress in the knowledge and control of numerous SHS reactions. The SHS of simple binary materials, such as intermetallics (FeAl, MoSi2, NbAl3, etc.), oxides (e.g. ZrO2), carbides (e.g. SiC) or nitrides, more complex materials, such as mullite, SiAlONs, MAX phases, composites (SiO2-Al2O3, NiAl-ZrO2), powders in their more complicated states, such as well controlled microstructures, fully densified intermetallics, smart composites, and hard coatings carried out by GFA researchers greatly contributed to the worldwide competition to harness the potential of SHS. On the occasion of the 40th anniversary of SHS, this paper is giving an overview of the main results obtained by GFA over the last ten years.

One-step synthesis and densification of Ti-Al-C-based cermets by ETEPC

The Electro-Thermal Explosion under Pressure with Confinement (ETEPC) mode of SHS has been studied for producing possibly low-porosity Ti2AlC and Ti3AlC2 from elemental powders in a very short processing time. The effect of maintaining the electric current after the ignition of exothermic reaction has also been studied. A better achievement of the desired reaction, with a total yield of MAX phases up to 73%, was obtained with maintaining the electric current for 4 s after ignition of the exothermic reaction in the Ti: Al: C = 2:1:1 composition. XRD studies revealed also composition gradients.

SHS reactions in the NiO-Al system: Influence of stoichiometry

Thermite reactions in the NiO-Al system have been studied. In addition to the case when the stoichiometry is set up to produce metallic nickel and alumina, we studied the case when Al is added in excess in order to react with the Ni produced through the reduction of nickel monoxide with Al to produce various nickel aluminides. As thermite reactions are highly exothermic, in order to provide a better understanding of the reactions, alumina has been added to the green mixture to reduce the reaction rate and overall exothermicity, in amounts corresponding up to 50% of the overall heat capacity of the sample.

Combustion synthesis in the Ni-Al-W system: Some structural features

Explored was combustion synthesis in the Ni-Al-W system with special emphasis on structural features of the process. Using SHS in the 1500–1700°C temperature range, we observed the diffusion-induced processes at the interface between synthesized NiAl and W particles resulting in the formation of W2Ni and W-Ni intermetallics.

A novel method for synthesis of low-cost Ti-Al-C-based cermets

Ti2AlC-Ti3AlC2/Al2O3 samples have been successfully synthesized by aluminothermic reduction of TiO2 in the presence of C. Phase composition of resultant products obtained at different Al excess was characterized by XRD. Microstructures of the samples were observed by SEM. XRD analysis proved that it is possible to improve the yield of MAX phases using Al excess. With increasing Al excess, a major MAX phase was found to change from Ti2AlC to Ti3AlC2.