The Influence of Thermal Dilution on the Microstructure Evolution of Some Combustion-Synthesized Refractory Ceramic Composites

Modeling the self-sustained high-temperature synthesis (SHS) reaction via thermal dilution and transformation of the reaction heterogeneous media into a moderate exothermic one has unlimited potential for designing inorganic powders of a certain morphology beneficial for advanced consolidation. Thermal/inert dilution of the high-exothermic mixtures leads to the fluent decrease of both the combustion temperature and velocity, thus allowing to tailor the thermal regime of the combustion process, therewith contributing to high yield of reaction and governing the microstructural features of the combustion products. In the current review, we shed on light on the possibilities of this effective strategy to control the thermal behavior of the SHS process for the preparation of applicable powder precursors for the subsequent successful sintering. Since the SHS process of some refractory ceramics (MoSi2, TiB2, TiC, etc.) involves a relatively violent reaction rate and high combustion temperature, achieving a high level of microstructure control in these systems is often challenging. The challenge was tackled with a thermal dilution approach, attaining considerable enhancement in the homogeneity among phases with an increase of diluent content along with microstructure refinement

The Influence of Thermal Dilution on the Microstructure Evolution of Some Combustion-Synthesized Refractory Ceramic Composites

Modeling the self-sustained high-temperature synthesis (SHS) reaction via thermal dilution and transformation of the reaction heterogeneous media into a moderate exothermic one has unlimited potential for designing inorganic powders of a certain morphology beneficial for advanced consolidation. Thermal/inert dilution of the high-exothermic mixtures leads to the fluent decrease of both the combustion temperature and velocity, thus allowing to tailor the thermal regime of the combustion process, therewith contributing to high yield of reaction and governing the microstructural features of the combustion products. In the current review, we shed on light on the possibilities of this effective strategy to control the thermal behavior of the SHS process for the preparation of applicable powder precursors for the subsequent successful sintering. Since the SHS process of some refractory ceramics (MoSi2, TiB2, TiC, etc.) involves a relatively violent reaction rate and high combustion temperature, achieving a high level of microstructure control in these systems is often challenging. The challenge was tackled with a thermal dilution approach, attaining considerable enhancement in the homogeneity among phases with an increase of diluent content along with microstructure refinement

SHS-Derived Powders by Reactions’ Coupling as Primary Products for Subsequent Consolidation

The capability of self-propagating high-temperature synthesis (SHS) to produce powders that are characterized by a high sintering ability, owing to high heating and cooling rates inherent to the exothermic reaction, is of a special interest for the industry. In particular, SHS-derived powders comprise a significant defect concentration in order to effectively enhance the mass transfer processes during the sintering, which allows for the successful consolidation of difficult-to-sinter materials at relatively low sintering temperatures. From this perspective, the design of precursors suitable for sintering, synthesis in a controlled temperature regime and the optimization of geometrical and structural parameters of SHS powders as a potential feedstock for the consolidation is of key importance. Here, we report on the comparative studies concerning the SHS processing of composites for advanced powder metallurgy techniques. The synthesis and sintering peculiarities of the SHS through coupled reactions in the Me’O3(WO3,MoO3)-Me’’O(CuO,NiO)-Mg-C, Ti-B-Al12Mg17 systems are comparatively reviewed. The SHS coupling approach was used for the preparation of powders with a tuned degree of fineness (a high specific surface area of particles), a high-homogeneity and a controllable distribution of elements via both the regulation of the thermal regime of combustion in a wide range and the matching of the thermal and kinetic requirements of two interconnected reactions. Microstructural features of the powder feedstock greatly contributed to the subsequent consolidation process

The Mechanism of Joint Reduction of MoO₃ and CuO by Combined Mg/C Reducer at High Heating Rates

Understanding of the decisive role of non-isothermal treatment on the interaction mechanism and kinetics of the MoO3-CuO-Mg-C system is highly relevant for the elaboration of optimal conditions at obtaining Mo-Cu composite powder in the combustion processes. The reduction pathway of copper and molybdenum oxides with combined Mg + C reducing agents at high heating rates from 100 to 5200 K min−1 was delivered. In particular the sequence of the reactions in all the studied binary, ternary and quaternary systems contemporaneously demonstrating the effect of the heating rate on products’ phase composition and microstructure was elucidated. The combination of two highly exothermic and speedy reactions (MoO3 + 3Mg and CuO + Mg vs. MoO3 + CuO + 4Mg) led to a slow interaction with weak self-heating (dysynergistic effect) due to a change in the reaction mechanism. Furthermore, it has been shown that upon the simultaneous utilization of the Mg and C reducing agents, the process initiates exclusively with carbothermic reduction, and at relatively high temperatures it continues with magnesiothermic reaction. The effective activation energy values of the magnesiothermic stages of the studied reactions were determined by Kissinger isoconversional method

Kinetic Highlights of the Reduction of Silver Tungstate by Mg + C Combined Reducer

The programmed reduction of tungstates and molybdates may yield the production of an intimate mixture of metals, pseudo-alloys or composite powders. As an extension of the study of obtaining powders of tungsten-copper, molybdenum-copper and tungsten-nickel from their respective salts, in the present study the reduction of silver tungstate was performed. Considering the extreme conditions for the synthesis of W-Ag alloys in the combustion wave and the limited toolkit for the study of the associated reduction mechanism, the interaction in the Ag2WO4-Mg-C system was modeled at high heating rates closer to the heating rates of reagents in the combustion wave, namely by the high-speed temperature scanner (HSTS). For the effective study of the interaction mechanism and calculation of the kinetic parameters of the individual stages, the heating rate of the reagents was changed in a wide range (from 100 to 1200 °C min−1). The interaction scheme and the sequence of the reactions along with their starting temperatures were deduced; the nature of intermediates formed during the reduction process and the microstructure evolution were monitored

Joint Reduction of NiO/WO3 Pair and NiWO4 by Mg + C Combined Reducer at High Heating Rates

Functional features of Ni-W composite materials combined with successful performance enabled a breakthrough in their broad application. To disclose the formation pathway of Ni-W composite materials at extreme conditions of combustion synthesis in the NiO-WO3-Mg-C and NiWO4-Mg-C systems for the optimization of the synthesis procedure, the process was modeled under programmed linear heating conditions by thermal analysis methods. The reduction kinetics of tungsten and nickel oxides mixture and nickel tungstate by Mg + C combined reducer at non-isothermal conditions was studied at high heating rates (100–1200 °C min−1) by high-speed temperature scanner techniques. It was shown that when moving from low heating to high heating rates, the mechanism of both the magnesiothermic and magnesio-carbothermic reductions of the initial mixtures changes; that is, the transition from a solid-solid scheme to a solid-liquid scheme is observed. The strong influence of the heating rate on the reduction degree and kinetic parameters of the systems under study was affirmed. The simultaneous utilization of magnesium and carbon as reducers allowed the lowering of the starting and maximum temperatures of reduction processes, as evidenced by the synergetic effect at the utilization of a combined reducer. The effective values of activation energy (Ea) for the reactions proceeding in the mixtures NiO + WO3 + 4Mg, NiO + WO3 + 2.5Mg + 1.5C, NiWO4 + 4Mg and NiWO4 + 2Mg + 2C were estimated by Kissinger isoconversional method and were 146 ± 10, 141 ± 10, 216 ± 15 and 148 ± 15 kJ mol−1, respectively

High-Temperature Wear Performance of hBN-Added Ni-W Composites Produced from Combustion-Synthesized Powders

This work reports on the spark plasma sintering (SPS) of self-propagating high-temperature-synthesis (SHS)-derived Ni-W and Ni-W-2wt%hBN (4:1 molar ratio of metals) powders. The synthesis was carried out from a mixture of NiO and WO3 using Mg + C combined reducers through a thermo-kinetic coupling approach. Experiments performed in the thermodynamically optimal area demonstrated the high sensitivity of combustion parameters and product phase composition to the amount of reducers and hBN powder. The powder precursors with and without the addition of hBN were consolidated using SPS at a temperature and pressure of 1300 °C and 50 MPa, respectively, followed by a thorough phase and microstructural characterization of the obtained specimens. SHS-derived powders comprised the nano-sized agglomerates and were characterized by a high sinterability. The specimens of >95% density were subjected to ball-on-plate dry sliding wear tests at a sliding speed of 0.1 ms−1 and a distance of 1000 m utilizing an alumina ball of 10 mm in diameter under a 15 N normal load. The tests were performed at a temperature of 800 °C. A significant improvement in wear behavior was demonstrated for SHS-processed composites in comparison with their counterparts produced via conventional high-energy ball milling technique owing to the phenomena of ‘micro-polishing’, cyclic ‘self-healing’ and fatigue. However, the decisive effect of hBN addition in imparting lubrication during an HT wear test was not confirmed