DC conductivity and AC impedance of Mn doped magnesia alumina spinel (MgAl2-2xMn2xO4) over a large temperature range

MgAl_2-2xMn_2xO₄ (MAMO) with x = 0-0.12 was synthesized in a single-phase form by solid-state reaction. XRD analysis showed that the samples had the cubic center structure of the Fd-3 m space group. Electrical properties of the samples were studied over the temperature range of 300 K∼1073 K. The results showed that the DC conductivity (σ_DC) increased from 10⁻¹¹S/cm at 300 K (MAMO, x = 0) to 10^-3S/cm at 1073 K (MAMO, x = 0.12). The equivalent circuit of the complex impedance spectra suggested that the relaxation of charge carriers was of non-Debye type. The conduction was mainly caused by grain boundaries and the capacitance was mainly attributed to polarization. The complex permittivity values (ε’ and ε’’) were increased by two orders of magnitude with the increase in Mn content and temperature over the measured frequency range (1 Hz-1 MHz). Therefore, doping with Mn could be applied to modify the electrical properties of MAMO at high temperature.     

Rare-earth free sensitizer in NaLuCrF4:Er upconversion material

Upconversion phosphors are known as a material system that can convert near-infrared light into visible/ultraviolet emissions by sequentially absorbing multiple photons. The studies on upconversion materials often use two rare earth (RE) ions as a sensitizer-activator pair. We investigated the influences on luminescence intensity depending on Cr-doping content (x) of hexagonal NaLu_0.98–xCr_xF₄Er_0.02 (x = 0–0.9) upconversion material by substituting Lu³⁺ ions with Cr³⁺in the absence of Gd³⁺. The change in upconversion luminescence intensity appears with saddle-like shape. We suggest that Cr³⁺ ions play the dual role as a constituent in host lattice and a sensitizer in the upconversion process. Optimal conditions for gaining the strongest upconversion emission correspond to x = 0.3–0.5, where there are effective energy transfers between Cr³⁺ and Er³⁺ ions and CrEr dimers. Apart from these values, the emission intensity decreases rapidly which can be ascribed to the absence of multiple-photon absorption for the case of low Cr³⁺ contents, and to the coupling between Cr³⁺ and/or Er³⁺ ions for the case of high Cr³⁺ contents. Magnetization and electron-spin-resonant measurements were performed to understand the correlation between the optical and magnetic properties.     

Damage tolerance in additively manufactured ceramic architected materials

Technical ceramics exhibit exceptional high-temperature properties, but unfortunately their extreme crack sensitivity and high melting point make it challenging to manufacture geometrically complex structures with sufficient strength and toughness. Emerging additive manufacturing technologies enable the fabrication of large-scale complex-shape artifacts with architected internal topology; when such topology can be arranged at the microscale, the defect population can be controlled, thus improving the strength of the material. Here, ceramic micro-architected materials are fabricated using direct ink writing (DIW) of an alumina nanoparticle-loaded ink, followed by sintering. After characterizing the rheology of the ink and extracting optimal processing parameters, the microstructure of the sintered structures is investigated to assess composition, density, grain size and defect population. Mechanical experiments reveal that woodpile architected materials with relative densities of 0.38–0.73 exhibit higher strength and damage tolerance than fully dense ceramics printed under identical conditions, an intriguing feature that can be attributed to topological toughening.     

Effect of Ni/tubular g-C3N4 on hydrogen storage properties of MgH2

Additive doping is one of the effective methods to overcome the shortcomings of MgH₂ on the aspect of relatively high operating temperatures and slow desorption kinetics. In this paper, hollow g-C₃N₄ (TCN) tubes with a diameter of 2 μm are synthesized through the hydrothermal and high-temperature pyrolysis methods, and then nickel is chemically reduced onto TCN to form Ni/TCN composite at 278 K. Ni/TCN is then introduced into the MgH₂/Mg system by means of hydriding combustion and ball milling. The MgH₂–Ni/TCN composite starts to release hydrogen at 535 K, which is 116 K lower than the as-milled MgH₂ (651 K). The MgH₂–Ni/TCN composite absorbs 5.24 wt% H₂ within 3500 s at 423 K, and takes up 3.56 wt% H₂ within 3500 s, even at a temperature as low as 373 K. The apparent activation energy (E_a) of the MgH₂ decreases from 161.1 to 82.6 kJ/mol by the addition of Ni/TCN. Moreover, the MgH₂–Ni/TCN sample shows excellent cycle stability, with a dehydrogenation capacity retention rate of 98.0% after 10 cycles. The carbon material enhances sorption kinetics by dispersing and stabilizating MgH₂. Otherwise, the phase transformation between Mg₂NiH₄ and Mg₂NiH_0.3 accelerates the re/dehydrogenation reaction of the composite.     

Characterization of anisotropic gas permeability and thermomechanical properties of highly textured porous alumina

Porous alumina with a highly textured microstructure was fabricated by pulse electric current sintering (PECS) using alumina platelets. Highly oriented porous alumina with a porosity of 3%–50% was obtained by a pressure-controlled method of PECS. The properties of the highly textured porous alumina were measured in two directions. The nitrogen gas permeance and thermal conductivity at room temperature were higher in the direction along the platelet length due to the higher continuity of pores and the connectivity of alumina platelets, respectively. The anisotropy of the thermal conductivity at room temperature was investigated and explained by the effect of grain size of platelets as well as morphology and orientation of pores. The bending strength was higher with the loading direction along the platelet thickness. The thermal shock strength was clearly different in the two directions. The difference in the thermal shock strength was investigated by the measurement of properties and thermal stress analysis.     

Ceramics composites from iron ore tailings and blast furnace slag

The search for materials and methods capable of reducing human impacts on the environment is of utmost importance nowadays. This study's primary purpose was to analyze the technical feasibility of ceramic composites production utilizing Fundão Dam's Iron Ore Tailings (IOT), Blast Furnace Slag (BFS) from charcoal, and Foundry Sand (FS) as partial substitutes for the traditional raw materials – sand and clay – for application in building industry materials. The composites were molded in rectangular specimens and fired at temperatures of 900, 950, 1000, 1050, and 1200 °C. The developed materials were analyzed and characterized by X-Ray Diffraction (XRD), Scanning Electron Microscopy (SEM), Energy Dispersive Spectroscopy (EDS), Thermogravimetry (TGA), and Differential Thermal Analysis (DTA). The obtained materials had flexural strength modulus of up to 12.19 MPa, water absorption ranging from 2 to 22%, linear shrinkage ranging from 0.02 to 6.50%, and apparent density ranging from 2.03 to 1.63 g/cm³. The study of the internal structure formation process revealed the formation of amorphous structures in the composites. The results demonstrated that these waste materials may be jointly used in construction materials, contributing to the reduction of natural resource extraction, besides enabling their correct disposal, minimizing environmental impacts, and improving the life quality of the surrounding communities.     

Hydrogen from wet air and sunlight in a tandem photoelectrochemical cell

A solid-state photoelectrochemical (SSPEC) cell is an attractive approach for solar water splitting, especially when it comes to monolithic device design. In a SSPEC cell the electrodes distance is minimized, while the use of polymer-based membranes alleviates the need for liquid electrolytes, and at the same time they can separate the anode from the cathode. In this work, we have made and tested, firstly, a SSPEC cell with a Pt/C electrocatalyst as the cathode electrode, under purely gaseous conditions. The anode was supplied with air of 80% relative humidity (RH) and the cathode with argon. Secondly, we replaced the Pt/C cathode with a photocathode consisting of 2D photocatalytic g-C₃N₄, which was placed in tandem with the photoanode (tandem-SSPEC). The tandem configuration showed a three-fold enhancement in the obtained photovoltage and a steady-state photocurrent density. The mechanism of operation is discussed in view of recent advances in surface proton conduction in absorbed water layers. The presented SSPEC cell is based on earth-abundant materials and provides a way towards systems of artificial photosynthesis, especially for areas where water sources are scarce and electrical grid infrastructure is limited or nonexistent. The only requirements to make hydrogen are humidity and sunlight.     

Lignin from Annual Plants as Raw Material Source for Flavors and Basic Chemicals

The enzymatic conversion of lignins, possibly in combination with electrochemical oxidation, makes aromatics such as syringol, guaiacol, vanillin and catechol available in the qualities required by the fragrance industry. The lignins were obtained by soda digestion from wheat straw and Miscanthus, characterized and then converted with laccases. The overall yield amounted up to 9 wt % with a product spectrum confined to four substances. Catechol was the major product, with a fraction of ≈75 %. It can easily be isolated by extraction with acetone.     

Material design and development: From classical thermodynamics to CALPHAD and ICME approaches

This paper presents an overview and examples of material design and development using (1) classical thermodynamics; (2) CALPHAD (calculation of phase diagrams) modeling; and (3) Integrated Computational Materials Engineering (ICME) approaches. Although the examples are given in lightweight aluminum and magnesium alloys for structural applications, the fundamental methodology and modeling principles are applicable to all materials and engineering applications. The examples in this paper have demonstrated the effectiveness and limitations of classical thermodynamics in solving specific problems (such as nucleation during solidification and solid-state precipitation in aluminum alloys). Computational thermodynamics and CALPHAD modeling, when combined with critical experimental validation, have been used to guide the selection and design of new magnesium alloys for elevated-temperature applications. The future of material design and development will be based on a holistic ICME approach. However, key challenges exist in many aspects of ICME framework, such as the lack of diffusion/mobility databases for many materials systems, limitation of current microstructural modeling capability and integration tools for simulation codes of different length scales.