Synthesis, densification, and cation inversion in high entropy (Co,Cu,Mg,Ni,Zn)Al2O4 spinel

The synthesis, densification behavior, and crystallographic site occupancy were investigated for four different spinel-based ceramics, including a high-entropy spinel (Co0.2Cu0.2Mg0.2Ni0.2 Zn0.2)Al2O4. Each composition was reacted to form a single phase, but analysis of X-ray diffraction patterns revealed differences in cation site occupancy with the high-entropy spinel being nearly fully normal. Densification behavior was investigated and showed that fully dense ceramics could be produced by hot pressing at temperatures as low as 1375°C for all compositions. Vickers’ hardness values were at least 10 GPa for all compositions. The cations present in the high-entropy spinel appear to have a stabilizing effect that led to nearly normal site occupancy compared to full cation inversion behavior of nickel aluminate spinel. This is the first report that compares cation site occupancy of a high-entropy spinel to conventional spinel ceramics

Carbothermal reaction of mechanically activated ZrC powders followed by DSC-TGA

Mixtures of ZrO2 and C were prepared by high-energy ball milling. Powders were milled for times from 0 to 120 minutes in air atmosphere. As milling time increased, surface area of powders increased, indicating significant particle size reduction. The thermal treatment cycle included heating at 10 °C/min to 1600 °C followed by an isothermal hold for 2 hours under the vacuum (~20 Pa) in a resistance-heated graphite element furnace. This first step of the process promoted carbothermal reaction of the starting materials. DSC-TGA was used to follow the carbothermal reaction. The onset temperature does not seem to change for non-activated and activated powders. The change in peak area may be related to the amount of the powder that reacts at this temperature. The catbothermal reaction was split into two parts for powders activated 60 and 120 minutes. Only part of the powder reacts at the initial reaction, and then higher temperatures are required for full reaction

Disordered enthalpy–entropy descriptor for high-entropy ceramics discovery

The need for improved functionalities in extreme environments is fuelling interest in high-entropy ceramics1,2,3. Except for the computational discovery of high-entropy carbides, performed with the entropy-forming-ability descriptor4, most innovation has been slowly driven by experimental means1,2,3. Hence, advancement in the field needs more theoretical contributions. Here we introduce disordered enthalpy–entropy descriptor (DEED), a descriptor that captures the balance between entropy gains and enthalpy costs, allowing the correct classification of functional synthesizability of multicomponent ceramics, regardless of chemistry and structure. To make our calculations possible, we have developed a convolutional algorithm that drastically reduces computational resources. Moreover, DEED guides the experimental discovery of new single-phase high-entropy carbonitrides and borides. This work, integrated into the AFLOW computational ecosystem, provides an array of potential new candidates, ripe for experimental discoveries

Reaction mechanisms and microstructures of ceramic-metal composites made by reactive metal penetration

Ceramic-metal composites can be made by reactive penetration of molten metals into dense ceramic performs. The metal penetration is driven by a large negative Gibbs energy for reaction, which is different from the more common physical infiltration of porous media. Reactions involving Al can be written generally as (x+2)Al + (3/y)MO{sub y} {yields} Al{sub 2}O{sub 3} + M{sub 3/y}Al{sub x}, where MO{sub y} is an oxide that is wet by molten Al. In low Po{sub 2} atmospheres and at temperature above about 900{degrees}c, molten Al reduces mullite to produce Al{sub 2}O{sub 3} + M{sub 3/y}Al{sub x}, where MO is an oxide that is wet by molten Al. In low Po{sub 2} atmospheres and at temperatures above about 900{degrees}C, molten al reduces mullite to produce Al{sub 2}O{sub 3} and Si. The Al/mullite reaction has a {Delta}G{sub r}{degrees} (1200K) of -1014 kJ/mol and, if the mullite is fully dense, the theoretical volume change on reaction is less than 1%. A microstructure of mutually-interpenetrating metal and ceramic phases generally is obtained. Penetration rate increases with increasing reaction temperature from 900 to 1150{degrees}C, and the reaction layer thickness increases linearly with time. Reaction rate is a maximum at 1150{degrees}C; above that temperature the reaction slows and stops after a relatively short period of linear growth. At 1300{degrees}C and above, no reaction layer is detected by optical microscopy. Observations of the reaction front by TEM show only al and Al{sub 2}O{sub 3} after reaction at 900{degrees}C, but Si is present in increasing amounts as the reaction temperature increases to 1100{degrees}C and above. The kinetic and microstructural data suggest that the deviation from linear growth kinetics at higher reaction temperatures and longer times is due to Si build-up and saturation at the reaction front. The activation energy for short reaction times at 900 to 1150{degrees}C varies from {approximately}90 to {approximately}200 kJ/mole

Synthesis and processing of composites by reactive metal penetration

Ceramic-metal composites are being developed as engineering materials because of their high stiffness-to-weight ratios, good fracture toughness, and because their electrical and thermal properties can be varied through control of their compositions and microstructures. Wider use of ceramic-metal composites requires improvements in synthesis and processing so that high-performance parts can be produced more economically. Over the past three years reactive metal penetration has been shown to be a promising technique for making ceramic and metal-matrix composites to near-net-shape with control of both composition and microstructure. It appears that reactive metal penetration could be an economical process for manufacturing many of the advanced ceramic composites that are needed for light-weight structural and wear applications for transportation and energy conversion devices. Near-net-shape fabrication of parts has the additional advantage that costly and energy intensive grinding and machining operations are significantly reduced, and the waste generated from such finishing operations is minimized. The goals of this research and development program are: (1) to identify compositions favorable for making composites by reactive metal penetration; (2) to understand the mechanism(s) by which these composites are formed; and (3) to control and optimize the process so that composites and composite coatings can be made economically

High temperature oxidation behaviour of Nb and HfO2 coatings on ZrB2

ZrB2 has a unique combination of properties such as high melting point (>3000°C) and low theoretical density, high strength and elastic modulus which makes itself a very attractive candidate for ultra-high temperature applications. However, its’ oxidation resistance is poor above 800°C which limits its application for aero-propulsion and hypersonic flight applications. Few studies have shown that the addition of transition metals into the ZrB2 material could improve the oxidation behaviour at high temperatures. In this study, two different materials were applied as oxidation protective coatings by means of magnetron sputtering technique on top of ZrB2 : the transition metal Nb and HfO2. The oxidation studies were performed at 1500 and 1600°C in a box furnace under synthetic air atmosphere for different times. Both coatings have shown promising results and the ZrO2 scale growth was drastically reduced. Formation of mixed oxides comprising of Nb and ZrO2 at the surface has reduced the oxygen transport at the ZrB2 reaction front. Similarly, HfO2 has acted as a barrier to the oxygen transport and a lower oxidation rate was achieved