This review article aims to provide an updated and comprehensive description of the development of the Electric Current Activated/assisted Sintering technique (ECAS) for the obtainment of dense materials including nanostructured ones. The use of ECAS for pure sintering purposes, when starting from already synthesized powders promoters, and to obtain the desired material by simultaneously performing synthesis and consolidation in one-step is reviewed. Specifically, more than a thousand papers published on this subject during the past decades are taken into account. The experimental procedures, formation mechanisms, characteristics, and functionality of a wide spectrum of dense materials fabricated by ECAS are presented. The influence of the most important operating parameters (i.e. current intensity, temperature, processing time, etc.) on product characteristics and process dynamics is reviewed for a large family of materials including ceramics, intermetallics, metal–ceramic and ceramic–ceramic composites. In this review, systems where synthesis and densification stages occur simultaneously, i.e. a fully dense product is formed immediately after reaction completion, as well as those ones for which a satisfactory densification degree is reached only by maintaining the application of the electric current once the full reaction conversion is obtained, are identified. In addition, emphasis is given to the obtainment of nanostructured dense materials due to their rapid progress and wide applications. Specifically, the effect of mechanical activation by ball milling of starting powders on ECAS process dynamics and product characteristics (i.e. density and microstructure) is analysed. The emerging theme from the large majority of the reviewed investigations is the comparison of ECAS over conventional methods including pressureless sintering, hot pressing, and others. Theoretical analysis pertaining to such technique is also proposed following the last results obtained on this topic.

Consolidation/synthesis of materials by electric current activated/assisted sintering

Processes of severe plastic deformation (SPD) are defined as metal forming processes in which a very large plastic strain is imposed on a bulk process in order to make an ultra-fine grained metal The objective of the SPD processes for creating ultra-fine grained metal is to produce lightweight parts by using high strength metal for the safety and reliability of micro-parts and for environmental harmony In this keynote paper, the fabrication process of equal channel angular pressing (ECAP), accumulative roll-bonding (ARB), high pressure torsion (HPT), and others are introduced, and the properties of metals processed by the SPD processes are shown Moreover, the combined processes developed recently are also explained Finally, the applications of the ultra-fine grained (UFG) metals are discussed

Severe Plastic Deformation (SPD) Processes for Metals

In this paper we report a strategy to simultaneously increase the ductility and strength of bulk nanostructured materials. By engineering very small second-phase particles into a nanostructured Al alloy matrix, we were able to more than double its uniform elongation, while further gaining rather than sacrificing its yield strength. The simultaneous enhancement of ductility and strength is due to the increased dislocation accumulation and resistance to dislocation-slip by second-phase particles, respectively. Our strategy is applicable to many nanostructured alloys and composites, and paves a way for their large-scale industrial applications. The material used in this model study is 7075 Al alloy. The alloy was solution-treated to obtain a coarse-grained (CG) solid solution. The CG sample was immediately cryogenically rolled to produce nanostructures with an average grain size of ca. 100 nm (designated as NS sample). The NS sample was then aged at low temperature to introduce very small secondphase particles (designated as NS+P sample). The engineering stress–strain curves of these samples are compared in Figure 1a. The 0.2 % yield strengths (marked by circles) of the CG, NS, and NS+P samples are 145 MPa, 550 MPa, and 615 MPa, respectively. Therefore, the low-temperature aging enhanced the yield strength of the NS sample by 12 %. The uniform elongation (marked by the symbol on the curves in Fig. 1a) was determined by the Considere criterion (Eq. 1) governing the onset of localized deformation [8]

Simultaneously Increasing the Ductility and Strength of Nanostructured Alloys

Fe3Al-based iron aluminides have been of interest for many years because of their excellent oxidation and sulfidation resistance. However, limited room temperature ductility (<5%) and a sharp drop in strength above 600 °C have limited their consideration for use as structural materials. Recent improvements in tensile properties, especially improvements in ductility produced through control of composition and microstructure, and advances in the understanding of environmental embrittlement in intermetallics, including iron aluminides, have resulted in renewed interest in this system for structural applications. The purpose of this paper is to summarize recent developments concerning Fe3Al-based aluminides, including alloy development efforts and environmental embrittlement studies. This report will concentrate on literature published since about 1980, and will review studies of fabrication, mechanical properties, and corrosion resistance that have been conducted since that time.

A review of recent developments in Fe3Al-based alloys

Review on superior strength and enhanced ductility of metallic nanomaterials

Large enhancement in mechanical properties of the 6061 Al alloys after a single pressing by ECAP

AlN/CrN nanoscale multilayered superlattice coatings have been deposited on M2 HSS by reactive D.C. magnetron sputtering with Al and Cr targets under Ar and N2 atmosphere. The bilayer period of the coatings was controlled from 2.0 nm to 11.7 nm by changing rotation speed of the substrate holder. The crystalline structures of the AlN and CrN single layer were wurtzite and B1, respectively, whereas the AlN/CrN nanoscale multilayered superlattice coatings were stabilized to B1 structure, irrespective of bilayer period within the experimental parameter range. The maximum hardness, 40 GPa, could be obtained for the AlN/CrN nanoscale multilayered superlattice coating with the bilayer period of 3.8 nm, which is much higher than those of AlN and CrN single layer coatings. After heat-treatment at high temperatures in air, the AlN/CrN nanoscale multilayered superlattice coatings have shown excellent oxidation resistance compared with AlN and CrN single layers.

The crystalline structure, hardness and thermal stability of AlN/CrN superlattice coating prepared by D.C. magnetron sputtering

Effect of post equal-channel-angular-pressing aging on the modified 7075 Al alloy containing Sc

Monolayer MoS2 (1L-MoS2) has photoluminescence (PL) properties that can greatly vary via transition between neutral and charged exciton PLs depending on carrier density. Here, for the first time, we present a chemical doping method for reversible transition between neutral and charged excitons of 1L-MoS2 using chlorine-hydrogen-based plasma functionalization. The PL of 1L-MoS2 is drastically increased by p-type chlorine plasma doping in which its intensity is easily tuned by controlling the plasma treatment duration. We find that despite their strong adhesion, a post hydrogen plasma treatment can very effectively dedope chlorine adatoms in a controllable way while maintaining robust structural integrity, which enables well-defined reversible PL control of 1L-MoS2. After exhaustive chlorine dedoping, the hydrogen plasma process induces n-type doping of 1L-MoS2, degrading the PL further, which can also be recovered by subsequent chlorine plasma treatment, extending the range of tunable PL into a bidirectional regime. This cyclically-tunable carrier doping method can be usefully employed in fabricating highly-tunable n- and p-type domains in monolayer transition-metal dichalcogenides suitable for two-dimensional electro-optic modulators, on-chip lasers, and spin- and valley-polarized light-emitting diodes.

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Plasma functionalization for cyclic transition between neutral and charged excitons in monolayer MoS2.

The electrosynthesis of formate from CO2 can mitigate environmental issues while providing an economically valuable product. Although stannic oxide is a good catalytic material for formate production, a metallic phase is formed under high reduction overpotentials, reducing its activity. Here, using a fluorine-doped tin oxide catalyst, a high Faradaic efficiency for formate (95% at 100 mA cm-2) and a maximum partial current density of 330 mA cm-2 (at 400 mA cm-2) is achieved for the electroreduction of CO2. Furthermore, the formate selectivity (≈90%) is nearly constant over 7 days of operation at a current density of 100 mA cm-2. In-situ/operando spectroscopies reveal that the fluorine dopant plays a critical role in maintaining the high oxidation state of Sn, leading to enhanced durability at high current densities. First-principle calculation also suggests that the fluorine-doped tin oxide surface could provide a thermodynamically stable environment to form HCOO* intermediate than tin oxide surface. These findings suggest a simple and efficient approach for designing active and durable electrocatalysts for the electrosynthesis of formate from CO2. 

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Jong-Keuk Park

Papers

Large enhancement in mechanical properties of the 6061 Al alloys after a single pressing by ECAP

The crystalline structure, hardness and thermal stability of AlN/CrN superlattice coating prepared by D.C. magnetron sputtering

Effect of post equal-channel-angular-pressing aging on the modified 7075 Al alloy containing Sc

Plasma functionalization for cyclic transition between neutral and charged excitons in monolayer MoS2.

Exploring dopant effects in stannic oxide nanoparticles for CO2 electro-reduction to formate