Disordered enthalpy-entropy descriptor for high-entropy ceramics discovery.

The need for improved functionalities in extreme environments is fuelling interest in high-entropy ceramics1-3. Except for the computational discovery of high-entropy carbides, performed with the entropy-forming-ability descriptor4, most innovation has been slowly driven by experimental means1-3. 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.

Cf/SiC Ceramic Matrix Composites with Extraordinary Thermomechanical Properties up to 2000 °C.

The thermomechanical properties of carbon fiber reinforced silicon carbide ceramic matrix composites (Cf/SiC CMCs) were studied up to 2000 °C using high-temperature in situ flexural testing in argon. The CMC specimens were fabricated using an ultrahigh concentration (66 vol%) aqueous slurry containing nano-sized silicon carbide powder. The SiC powder compacts were obtained by drying the slurry and were densified using the precursor impregnation and pyrolysis (PIP) method with field assisted sintering technology/spark plasma sintering (FAST/SPS). The high relative density of the SiC green body (77.6%) enabled densification within 2.5 days using four PIP cycles. In contrast, conventional PIP processes take over 7 days. The in situ flexural strength of the Cf/SiC CMC was 434 MPa at 1750 °C, which was 84% higher than the room temperature value. The value further increased to 542 MPa at 2000 °C. Possible mechanisms to explain the excellent strength of the CMC at elevated temperatures are discussed.

Mechanical Activation and Cation Site Disorder in MgAl2O4.

The synthesis and crystallographic site occupancy were investigated for MgAl2O4 with and without mechanical activation of the precursor powders. Heating to 1200 °C or higher resulted in the formation of a single spinel phase regardless of whether the powders were mechanically activated or not. Neutron diffraction analysis was used to determine cation site occupancy and revealed that mechanical activation resulted in a lower degree of cation site inversion compared to the nonactivated materials, which indicated that the powders were closer to thermodynamic equilibrium. This is the first study to characterize the effects of mechanical activation on crystallographic site occupancy in magnesium aluminate spinel using neutron diffraction.

Microstructural and Optical Properties of MgAl2O4 Spinel: Effects of Mechanical Activation, Y2O3 and Graphene Additions.

Magnesium aluminate and other alumina-based spinels attract attention due to their high hardness, high mechanical strength, and low dielectric constant. MgAl2O4 was produced by a solid-state reaction between MgO and α-Al2O3 powders. Mechanical activation for 30 min in a planetary ball mill was used to increase the reactivity of powders. Yttrium oxide and graphene were added to prevent abnormal grain growth during sintering. Samples were sintered by hot pressing under vacuum at 1450 °C. Phase composition and microstructure of sintered specimens were characterized by X-ray powder diffraction and scanning electron microscopy. Rietveld analysis revealed 100% pure spinel phase in all sintered specimens, and a decrease in crystallite size with the addition of yttria or graphene. Density measurements indicated that the mechanically activated specimen reached 99.6% relative density. Furthermore, the highest solar absorbance and highest spectral selectivity as a function of temperature were detected for the mechanically activated specimen with graphene addition. Mechanical activation is an efficient method to improve densification of MgAl2O4 prepared from mixed oxide powders, while additives improve microstructure and optical properties.

Entropy Landscaping of High-Entropy Carbides.

The entropy landscape of high-entropy carbides can be used to understand and predict their structure, properties, and stability. Using first principles calculations, the individual and temperature-dependent contributions of vibrational, electronic, and configurational entropies are analyzed, and compare them qualitatively to the enthalpies of mixing. As an experimental complement, high-entropy carbide thin films are synthesized with high power impulse magnetron sputtering to assess structure and properties. All compositions can be stabilized in the single-phase state despite finite positive, and in some cases substantial, enthalpies of mixing. Density functional theory calculations reveal that configurational entropy dominates the free energy landscape and compensates for the enthalpic penalty, whereas the vibrational and electronic entropies offer negligible contributions. The calculations predict that in many compositions, the single-phase state becomes stable at extremely high temperatures (>3000 K). Consequently, rapid quenching rates are needed to preserve solubility at room temperature and facilitate physical characterization. Physical vapor deposition provides this experimental validation opportunity. The computation/experimental data set generated in this work identifies "valence electron concentration" as an effective descriptor to predict structural and thermodynamic properties of multicomponent carbides and educate new formulation selections.

Characterization of Cobalt-Containing and Cobalt-free Trivalent Chromium Passivation Layers on γ-ZnNi-Coated Al6061-T6 Substrates.

The corrosion performance and electrical contact resistance were investigated for a trivalent chromium passivation layer and a cobalt-free version of that same passivation layer on γ-ZnNi-coated Al 6061-T6. Both passivation layers had a similar surface morphology, were amorphous, had similar thicknesses, and contained pores within the passivation layer. The cobalt-containing passivation layer initially had an exchange current density of 9.5 × 10-4 A/cm2 and a polarization resistance of 290 Ω/cm2. The cobalt-free passivation layer initially had an exchange current density of 10.6 × 10-4 A/cm2 and a polarization resistance of 116 Ω/cm2. After 500 h of exposure to neutral salt spray, the cobalt-containing passivation layer showed no visible corrosion and had an exchange current density of 2.9 × 10-4 A/cm2 and a polarization resistance of 136 Ω/cm2. The cobalt-free passivation layer showed uniform corrosion and had an exchange current density of 5.2 × 10-4 A/cm2 and a polarization resistance of 80 Ω/cm2. After 500 h of exposure to neutral salt spray on specimens which were scribes down to the Al substrate, the cobalt-free passivation layers were uniformly corroded, but scribed specimens with the cobalt-containing passivation layers were only partially corroded. Both the cobalt-containing and cobalt-free passivation layers were found to be viable alternatives to hexavalent chromium as per the requirements of cobalt-containing MIL-DTL-81706 offering protection comparable to hexavalent chromium and cobalt-free offering less. The presence of cobalt in the TCP layer was found to improve corrosion performance and suggested that an intermediate species such as cobalt is beneficial to the oxidation of Cr(III) to Cr(VI).

Super-strong materials for temperatures exceeding 2000 °C.

Ceramics based on group IV-V transition metal borides and carbides possess melting points above 3000 °C, are ablation resistant and are, therefore, candidates for the design of components of next generation space vehicles, rocket nozzle inserts, and nose cones or leading edges for hypersonic aerospace vehicles. As such, they will have to bear high thermo-mechanical loads, which makes strength at high temperature of great importance. While testing of these materials above 2000 °C is necessary to prove their capabilities at anticipated operating temperatures, literature reports are quite limited. Reported strength values for zirconium diboride (ZrB2) ceramics can exceed 1 GPa at room temperature, but these values rapidly decrease, with all previously reported strengths being less than 340 MPa at 1500 °C or above. Here, we show how the strength of ZrB2 ceramics can be increased to more than 800 MPa at temperatures in the range of 1500-2100 °C. These exceptional strengths are due to a core-shell microstructure, which leads to in-situ toughening and sub-grain refinement at elevated temperatures. Our findings promise to open a new avenue to designing materials that are super-strong at ultra-high temperatures.