Self-propagating high-temperature reactions: remarks and recent results

Solid-solid and gas-solid self-propagating high temperature reactions are exploited for interesting and relatively new technological applications based on the so called Self-propagating High-temperature Synthesis (SHS) technique This paper reviews the recent results obtained, also in the framework of national and international collaborations, by Cao and coworkers in the field of self-propagating high-temperature reactions with particular emphasis on SHS fundamentals and applications. In particular, the research activity conducted so far can be divided into three main topics: Macrokinetics studies on SHS using structural statics as well as dynamics approaches; Modeling studies on SHS, with the aim of developing analytical expressions of combustion front velocity and simulating experimental techniques applied for macrokinetics investigations; Technological applications related to the synthesis of centrifugal coatings and environmental protection. The activities outlined above will be described in this review paper in separate sections as discussed next

Fabrication of Fully Dense UHTC by Combining SHS and SPS

The combination of the Self-propagating High-temperature Synthesis (SHS) technique and the Spark Plasma Sintering (SPS) technology is adopted in this work for the fabrication of fully dense MB2-SiC and MB2-MC-SiC (M = Zr, Hf, Ta) Ultra High Temperature Ceramics (UHTCs). Specifically, Zr, Hf or Ta, B4C, Si, and graphite reactants are first converted to the desired composites by SHS. For the case of the lowexothermic Ta-based compositions, a preliminary 20 min ball milling treatment of the starting reactants is required to activate the corresponding synthesis reactions. When the resulting powders are then subjected to consolidation by SPS, it is found that products with relative densities greater than 96% can be obtained for all systems investigated within 30 min of total processing time, when setting the dwell temperature to 1800 °C and the mechanical pressure to 20 MPa. Hardness, fracture toughness, and oxidation resistance characteristics of the resulting dense UHTCs are comparable to, or superior than, those relative to similar products synthesized by alternative, less rapid, processing routes. Moreover, it is found that the ternary composites display relatively low resistance to oxidation as a consequence of the lower SiC content in the composite, in comparison with the binary systems, as well as to the presence of transition metal carbides. Indeed, although the latter ones are potentially able to increase mechanical and resistance to ablation properties, they tend to oxidize rapidly to form MO2 and COx, so that the resulting porosity make the material bulk more sensitive to oxidation.</p

Self-Propagating High-Temperature Synthesis Reactions for ISRU and ISFR Applications

In the framework of ISRU (In-Situ Resource Utilization) and ISFR (In-Situ Fabrication and Repair) applications, a novel recently patented process based on the occurrence of Self-propagating High temperature Synthesis (SHS) reactions potentially exploitable for the in-situ fabrication of construction materials in Lunar and Martian environments is described in this work. Specifically, the SHS process involves thermite reactions type between Lunar or Martian regolith simulants and aluminum as reducing agent. To overcome the fact that the original content of ilmenite (FeTiO3) and ferric oxide (Fe2O3) on Moon and Mars soils, respectively, is not enough to make the SHS process possible, suitable amounts of these species have to be added to the starting mixtures. The dependence of the most important processing parameters, particularly the composition of the starting mixture, evacuation level, and gravity conditions, on SHS process behaviour and product characteristics is specifically examined for the case of Lunar regolith. All the obtained findings allows us to conclude that the optimized results obtained under terrestrial conditions are valid for in-situ applications in Lunar environment. In particular, parabolic flight experiments evidenced that neither SHS process dynamics nor product characteristics are significantly influenced in both Lunar and Martian systems when passing from Earth to low gravity conditions. Finally, the complete scheme involving all stages required for the fabrication of physical assets to be used as protection against solar rays, solar wind and meteoroids, etc., is reported.</p

Mechanistic investigation of electric field-activated self-propagating reactions: experimental and modeling studies

The mechanism of electric field-activated self-propagating reactions is investigated using the combustion front quenching technique. In particular, previously published experimental results obtained through the Field Assisted Combustion Synthesis (FACS) of b-SiC, TaC, Ti3Al and B4C-TiB2 are re-examined and compared. Pre-combustion and combustion stages involved during synthesis wave propagation are postulated for all systems. Subsequently, modeling results aimed at simulating the process where an electric field-activated self-propagating reaction takes place are presented. In particular, a one-dimensional model of FACS technique is developed to simulate the rapid quenching of the reaction during its progress as the applied field is turned off. A rate expression which accounts for the influence of temperature, particle size, compaction density, reactant stoichiometry, and inert content is included in the model

Optimization of the spark plasma sintering conditions for the consolidation of hydroxyapatite powders and characterization of the obtained products

A comparative investigation regarding the consolidation behavior displayed by three commercially available hydroxyapatite powders during Spark Plasma Sintering (SPS) is performed in this work. Starting powders are different in terms of purity, particle size, morphology and thermochemical stability. A completely dense product without secondary species is produced by SPS at 900 °C, when starting from highly pure powders with relatively small sized particles and grains. The resulting consolidated material, consisting of sub-micrometer sized hydroxyapatite grains, exhibits optical transparency and good mechanical properties. On the other hand, temperature levels up to 1,200 °C are needed to sinter powders with larger particles. This holds also true when relatively finer powders are used, also containing CaHPO4, are used. In both the latter cases products with coarser microstructures and/or significant amount of β-TCP, as a result of hydroxyapatite decomposition, are obtained. Optical, chemical resistance and mechanical properties of the resulting dense materials are correspondingly deteriorated

Simultaneous spark plasma synthesis and consolidation of WC/Co composites

The single-step synthesis and densification of the WC-6Co cemented carbide starting from elemental powders was obtained by the spark plasma sintering (SPS) technique. The operating conditions that guarantee the complete conversion of the reactants to the desired full dense material have been identified. Specifically, under the application of 800 A and a mechanical pressure of 40 MPa for about 200 s, a product with relative density higher than 99%, hardness of 14.97 ± 0.35 GPa, and 12.5 ± 1.0 MPa m0.5 fracture toughness was obtained. A kinetic investigation of the SPS process was also performed. It revealed that an intermediate phase, i.e., W2C, is the first carbide formed during the carburization process. It was observed that the synthesis and sintering stages take place simultaneously. It was also found that as the applied pulsed current intensity was augmented, the synthesis/sintering time required decreased significantly

Novel processing route for the fabrication of bulk high-entropy metal diborides

A single high-entropy phase material with hexagonal structure is produced by a two-steps processing method. Elemental reactants are first remarkably converted by Self-propagating High-temperature Synthesis (SHS). The completion of the chemical transformation to the desired (Hf0.2Mo0.2Ta0.2Nb0.2Ti0.2)B2 phase and its concurrent consolidation up to 92.5% relative density is achieved by processing the SHS powders at 1950 °C via Spark Plasma Sintering. It is clearly evidenced that the use of the SHS technique is extremely beneficial to promote the formation of high-entropy ceramics, as compared to the time consuming ball milling treatment alternatively adopted

Mechanochemical Treatment of Soils Contaminated by Heavy Metals in Attritor and Impact Mills: Experiments and Modeling

An integrative approach was developed to support the scale-up from lab-into pilot-scale mechano-chemical reactors for immobilize heavy metals in contaminated mining soil

High-entropy transition metal diborides by reactive and non-reactive spark plasma sintering: A comparative investigation

The direct synthesis and consolidation by SPS (1950 °C, 20 min, 20 MPa) of high-entropy (Hf0.2Mo0.2Zr0.2Nb0.2Ti0.2)B2 from elemental powders resulted in a multiphase product. An increase of the heating rate determined a change of the mechanism governing the synthesis reaction from gradual solid-state diffusion to rapid combustion regime, while the final conversion degree was 67 wt.%. The sintered product displayed a non-uniform microstructure with the presence of 10–15 μm sized pores, due to volatilization phenomena occurring during the combustion synthesis reaction. In contrast, when the SPS process was preceded by powder synthesis via SHS, a homogeneous single-phase ceramic was obtained. Clear benefits are derived by the use of SHS, able to provide very shortly powders with elemental species very well intermixed, so that the obtainment of (Hf0.2Mo0.2Zr0.2Nb0.2Ti0.2)B2 during the subsequent SPS stage is strongly promoted. The resulting 92.5% dense product shows superior oxidation resistance with respect to individual borides prepared with the same method.ARCHIMEDES project sponsored by Regione Autonoma della Sardegna (Italy) - Fondo di Sviluppo e Coesione (FSC) 2014-2020 (Cod. RAS: RASSR88309, Cod. CUP: F76C18000980002). One of the authors (G.T.) performed her activity in the framework of the International PhD in Innovation Sciences and Technologies at the University of Cagliari, Italy. One of us (G.C.) acknowledges the results obtained in this manuscript as quite important for the “Ithermal” and “Generazione E” projects, sponsored by Sardegna Ricerche, Italy (Cod. CUP: F21I18000130006) and by the Italian Ministry of Education, University and Research, Italy (Cod. CUP: B96G18000560005), respectivel