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Magnesium and its alloys are the most investigated materials for solid-state hydrogen storage in the form of metal hydrides, but there are still unresolved problems with the kinetics and thermodynamics of hydrogenation and dehydrogenation of this group of materials. Severe plastic deformation (SPD) methods, such as equal-channel angular pressing (ECAP), high-pressure torsion (HPT), intensive rolling and fast forging, have been widely used to enhance the activation, air resistance, and hydrogenation/dehydrogenation kinetics of Mg-based hydrogen storage materials by introducing ultrafine/nanoscale grains and crystal lattice defects. These severely deformed materials, particularly in the presence of alloying additives or second-phase nanoparticles, can show not only fast hydrogen absorption/desorption kinetics but also good cycling stability. It was shown that some materials that are apparently inert to hydrogen can absorb hydrogen after SPD processing. Moreover, the SPD methods were effectively used for hydrogen binding-energy engineering and synthesizing new magnesium alloys with low thermodynamic stability for reversible low/room-temperature hydrogen storage, such as nanoglasses, high-entropy alloys, and metastable phases including the high-pressure {\gamma}-MgH2 polymorph. This article reviews recent advances in the development of Mg-based hydrogen storage materials by SPD processing and discusses their potential in future applications.

To have an insight into the occurrence of inverse Hall-Petch relationship in ultrafine-grained (UFG) aluminum alloys produced by severe plastic deformation (SPD), ultra-SPD (i.e. inducing several ten thousand shear strains via high-pressure torsion, HPT) followed by aging is applied to an Al-La-Ce alloy. Average nanograin sizes of 40 and 80 nm are successfully achieved together with strain-induced Lomer-Cottrell dislocation lock formation and aging-induced semi-coherent Al11(La,Ce)3 precipitation. Analysis of hardening mechanisms in this alloy compared to SPD-processed pure aluminum with micrometer grain sizes, SPD-processed Al-based alloys with submicrometer grain sizes and ultra-SPD-processed Al-Ca alloy with nanograin sizes reveals the presence of two breaks in the Hall-Petch relationship. First, a positive up-break appears when the grain sizes decrease from micrometer to submicrometer which is due to extra hardening by solute-dislocation interactions. Second, a negative down-break and softening occur by decreasing the grain sizes from submicrometer to nanometer which is caused by weakening the dislocation hardening mechanism with minor contribution of the inverse Hall-Petch mechanism. Detailed analyses confirm that nanograin formation is not necessarily a solution for extra hardening of Al-based alloys and other accompanying strategies such as grain-boundary segregation and precipitation are required to overcome such a down-break and softening.

CO$_2$ photoreduction on photocatalysts is a nature-friendly solution to decrease the CO$_2$ amount, but the method still has low efficiency because of difficult separation and easy recombination of charge carriers in available catalysts. In this study, a high-entropy oxynitride was introduced as an active photocatalyst for photoreduction. The material had a chemical composition of TiZrNbHfTaO$_6$N$_3$ and was produced by a high-pressure torsion method followed by oxidation and nitriding. It showed higher photocatalytic CO$_2$ to CO conversion compared to corresponding high-entropy oxide, benchmark photocatalyst P25 TiO$_2$, and almost all catalysts introduced in the literature. The high activity of this oxynitride, which also showed good chemical stability, was attributed to the large absorbance of light and easy separation of electrons and holes, the low recombination of charge carriers, and the high CO$_2$ adsorption on the surface. These findings introduce high-entropy oxynitrides as promising photocatalysts for CO$_2$ photoreduction.

In this work, a melt-spun amorphous Fe73.5Si13.5B9Cu1Nb3 alloy is subjected to high-pressure torsion (HPT) treatment under 6 GPa in order to enhance the alkaline hydrogen evolution reaction (HER) performance. Different HPT turns, including 1, 2, 5 and 10, are selected and the samples are marked as HPT-1N, HPT-2N, HPT-5N and HPT-10 N, respectively. The HPT treatment can lead to a significant structural change such as partial crystallization and defect generation on the Fe-based amorphous alloy with a considerable increase in the HER electrocatalytic activity. The HPT-5N sample shows the best catalytic performance, with an overpotential of only 174 mV at 10 mA cm−2 current density in 1 M KOH, which is 244 mV lower than that of the melt-spun alloy at the same condition. Moreover, it was established that the HPT-treated amorphous alloy shows good stability during the HER cycling process.

Transition metal-based amorphous alloys have attracted increasing attention as precious-metal-free electrocatalysts for oxygen evolution reaction (OER) of water splitting due to their high macro-conductivity and abundant surface active sites. However, the catalysis of bulk amorphous alloy only originates from a few atomic layers of the surface, and the catalytic activity usually rapidly decreases due to the coverage of corrosion products during the OER process. Here, we report a Fe78Si9B13 nanoglass covered by in situ formed FeOOH (FeOOH@NG) that can perfectly combine self-activation and synergistic catalysis between volume and surface, leading to high activity, fast reaction kinetics, and stability of activity for OER. The Fe78Si9B13 nanoglass with abundant ordered boundaries introduced in the amorphous matrix is prepared via melt-spinning followed by high-pressure torsion (HPT). Afterwards, a FeOOH layer is introduced on the surface of the nanoglass by a cathodic corrosion activation method. The FeOOH layer not only exposes more active sites, but also generates hydroxyl radicals (OH) in oxygen vacancies to activate the Fe-based nanoglass matrix. The FeOOH@NG generates an overpotential of only 240 mV at 10 mA cm−1 in 1 M KOH, and the Tafel slope is as low as 42 mV dec−1.

Metal oxynitrides are promising photocatalysts due to their narrow bandgap, but their lower stability compared to metal oxides is a drawback. The introduction of high-entropy alloys with entropy-stabilization features has shown high potential for various functional applications in recent years. By considering these two types of materials, we developed a high-entropy oxynitride for photocatalytic water splitting. The material, with a general composition of TiZrHfNbTaO6N3 and a d0 electronic configuration, showed a narrow bandgap of 1.6 eV, which is much lower than the bandgaps of relevant binary and high-entropy oxides. The material exhibited photocurrent generation and photocatalytic hydrogen production with high chemical stability, suggesting the high potential of high-entropy oxynitrides as advanced low-bandgap and stable photocatalysts.

This paper presents a current research trend for micro- and nano-structure controls using severe plastic deformation (SPD). The survey is carried out based on the special issue published in July and August, 2019, in Materials Transactions (Vol. 60, Nos. 7 and 8). The SPD-related research is rapidly growing particularly after the year 2000. The research ranges over processing, modeling, simulation, synthesis, characterization and evaluation. Among the various topics, a brief introduction is given for innovative approaches which will further promote the development of the SPD-related research.

A Fe78Si9B13 nanoglass with improved alkaline hydrogen evolution performances is prepared by melt spinning followed by high-pressure torsion (HPT). HPT treatment induces slight unique crystallization meanwhile generates abundant interfaces/regions both inside the amorphous matrix and between the amorphous matrix and nanocrystallites. In 1.0 M KOH, the nanoglass requires an overpotential of only 112 mV to achieve the current density of 10 mA cm–2, which is much smaller than those of the corresponding amorphous alloy (385 mV) and crystalline alloy (465 mV). Furthermore, catalytic performance of the nanoglass remains almost unchanged after 50 h continuous reaction.

The hydrogen storage properties of the novel equiatomic TiZrNbFeNi and non-equiatomic Ti20Zr20Nb5Fe40Ni15 high entropy alloys (HEAs) were studied. These alloys were designed with the aid of thermodynamic calculations using the CALPHAD method due to their tendency to form single C14 Laves phase, a phase desirable for room-temperature hydrogen storage. The alloys, which were synthesized by arc melting, showed a dominant presence of C14 Laves phases with the (Zr, Ti)1(Fe, Ni, Nb, Ti)2 constitution and small amounts of cubic phases (

Bismuth oxide (Bi2O3), a yellow semiconductor ceramic, is considered as an advanced photoactive energy material, but its activity still needs further improvement for practical applications. In this study, black Bi2O3 with nanocrystalline structure and large fraction of oxygen vacancies is synthesized by mechanical straining via the high-pressure torsion (HPT) method. The black oxide exhibits enhanced light absorbance under both UV and visible lights. It shows a bipolar photocurrent behavior with up to six times higher photocurrent density compared with the unprocessed yellow Bi2O3. This study shows the high potential of severely-strained black Bi2O3 for photovoltaic, photoconductivity and photocatalytic applications.

Titanium oxide (TiO2), with the anatase and rutile structures, has been widely studied for photovoltaic and solar cell applications, but its main drawback is large bandgap, which limits its activit...

Despite potential of hydride-forming alloys for hydrogen storage, there have been few alloys which can reversibly store hydrogen without heating or activation treatment. In this study, a high-entropy alloy is designed for room temperature hydrogen storage based on three criteria: total valence electron concentration (VEC) of 6.4, single-phase thermodynamic stability (examined by CALPHAD calculations) and AB2H3 hydride formation (A: hydride-forming elements, B: elements without affinity to hydrogen, H: hydrogen). The designated alloy, TiZrCrMnFeNi containing 95 wt% C14 Laves phase, absorbs and desorbs 1.7 wt% of hydrogen (hydrogen-to-metal ratio: 1) at room temperature with a fast kinetics and without activation treatment.

Oxynitrides are considered as new potential candidates for photocatalysis due to their lower bandgap compared with traditional oxide photocatalysts. However, the formation of native nitrogen monovacancies during the synthesis of oxynitrides reduces their photocatalytic activity due to the vacancy-induced electron/hole recombination. This study shows that a transition from the native nitrogen monovacancies to the nitrogen-based vacancy complexes in a GaN–ZnO oxynitride not only diminishes the recombination but also enhances the photocatalytic hydrogen production. Here, the vacancy complexes are introduced by mechanical straining via the high-pressure torsion (HPT) method and it is shown that the vacancy complexes reduce the bandgap and increase the over-potential for hydrogen production on the conduction band. The current results introduce a simple but effective approach to turn the nitrogen vacancies to favorable defects for photocatalysis.

Superfunctional materials are defined as materials with specific properties being superior to the functions of engineering materials. Numerous studies introduced severe plastic deformation (SPD) as an effective process to improve the functional and mechanical properties of various metallic and non-metallic materials. Moreover, the concept of ultra-SPD—introducing shear strains over 1000 to reduce the thickness of sheared phases to levels comparable to atomic distances—was recently utilized to synthesize novel superfunctional materials. In this article, the application of ultra-SPD for controlling atomic diffusion and phase transformation and synthesizing new materials with superfunctional properties is discussed. The main properties achieved by ultra-SPD include: (i) high-temperature thermal stability in new immiscible age-hardenable aluminum alloys; (ii) room-temperature superplasticity for the first time in magnesium and aluminum alloys; (iii) high strength and high plasticity in nanograined intermetallics; (iv) low elastic modulus and high hardness in biocompatible binary and high-entropy alloys; (v) superconductivity and high strength in the Nb-Ti alloys; (vi) room-temperature hydrogen storage for the first time in magnesium alloys; and (vii) superior photocatalytic hydrogen production, oxygen production, and carbon dioxide conversion on high-entropy oxides and oxynitrides as a new family of photocatalysts.

Excessive CO2 emission from fossil fuel usage has resulted in global warming and environmental crises. To solve this problem, the photocatalytic conversion of CO2 to CO or useful components is a new strategy that has received significant attention. The main challenge in this regard is exploring photocatalysts with high efficiency for CO2 photoreduction. Severe plastic deformation (SPD) through the high-pressure torsion (HPT) process has been effectively used in recent years to develop novel active catalysts for CO2 conversion. These active photocatalysts have been designed based on four main strategies: (i) oxygen vacancy and strain engineering, (ii) stabilization of high-pressure phases, (iii) synthesis of defective high-entropy oxides, and (iv) synthesis of low-bandgap high-entropy oxynitrides. These strategies can enhance the photocatalytic efficiency compared with conventional and benchmark photocatalysts by improving CO2 adsorption, increasing light absorbance, aligning the band structure, narrowing the bandgap, accelerating the charge carrier migration, suppressing the recombination rate of electrons and holes, and providing active sites for photocatalytic reactions. This article reviews recent progress in the application of SPD to develop functional ceramics for photocatalytic CO2 conversion.

High-entropy oxides (HEOs), as multi-component ceramics with high configurational entropy, have been of recent interest due to their attractive properties including photocatalytic activity for H2 production and CO2 conversion. However, the photocatalytic activity of HEOs is still limited to ultraviolet light. In this study, to achieve visible-light-driven photocatalysis, 10 different heterojunctions were simultaneously introduced in the Ti-Zr-Nb-Ta-W-O system. The oxide, which was synthesized by a high-pressure torsion method and oxidation, successfully produced oxygen from water under visible light without co-catalyst addition. The photocatalytic performance was attributed to high visible-light absorption, narrow bandgap, appropriate band structure, presence of multiple heterojunctions and accordingly easy electron-hole separation and slow recombination. These results not only show the potential of high-entropy oxides as new visible-light-active photocatalysts, but also introduce the multiple-heterojunction introduction as a strategy to achieve photocatalysis under visible light.

High-pressure torsion (HPT) is widely used not only as a severe plastic deformation (SPD) method to produce ultrafine-grained metals but also as a mechanical alloying technique to synthesize different alloys. In recent years, there have been several attempts to synthesize functional high-entropy alloys using the HPT method. In this paper, the application of HPT to synthesize high-entropy materials including metallic alloys, hydrides, oxides and oxynitrides for enhanced mechanical and hydrogen storage properties, photocatalytic hydrogen production and high light absorbance is reviewed.

TiO2 and ZnO, two semiconductors with promising optical properties, are considered as potential candidates for solar and photocatalytic applications. Although chemical methods have been primarily used to enhance the optical properties of these oxides, the current authors recently reported enhanced photocatalytic performance of pure TiO2 and ZnO by plastic straining due to the generation of high-pressure phases and oxygen vacancies. In this study, to improve the optical properties further, large fractions of ZnO/TiO2 interphase boundaries are also introduced by application of high-pressure torsion (HPT) straining to a mixture of anatase-TiO2 and wurtzite-ZnO powders. It was found that the amounts of oxygen vacancies and nanograined high-pressure TiO2-II and rocksalt-ZnO phases increase with increasing plastic strain. Moreover, due to the plastic strain effect, the rutile-TiO2 phase is formed at room temperature, which is at least 600 K below the reported anatase-to-rutile transition temperature. These structural features, together with the formation of large fraction of interphase boundaries, lead to electron spin resonance, optical bandgap narrowing, diminishing of the band-to-band photoluminescence and thus, improvement of photocatalytic hydrogen generation. Despite improvements in the photocatalytic activity of TiO2-ZnO composites after large straining, photocatalytic activity becomes poor by processing at ultra-large strains due to the significant reduction in crystallinity.

Photocatalysis on semiconductors using solar energy sources provides a clean technology to produce hydrogen from water splitting. Although zirconia (ZrO2) is a semiconductor oxide, it is not generally considered as a photocatalyst owing to its poor light absorbance and wide bandgap (over 5 eV). In this study, black ZrO2 with a large concentration of lattice defects such as oxygen vacancies, dislocations and nanograin boundaries is stabilized by high-pressure torsion (HPT) straining. The black ZrO2, which experiences monoclinic–tetragonal phase transformations during the HPT process, shows large light absorption, a small bandgap, reduced conduction band energy and high photocatalytic activity for hydrogen evolution due the presence of oxygen vacancies. These results confirm that the introduction of strain-induced oxygen vacancies is a potential method to produce low-bandgap photocatalysts.

The introduction of high-entropy oxides (HEOs), i.e. compounds containing oxygen and five or more cations in their crystal structure, has led to interesting functional properties in recent years. In this study, the first high-entropy photocatalyst is synthesized by mechanical alloying via the high-pressure torsion (HPT) method followed by high-temperature oxidation. The synthesized oxide contains 60 mol% of AB2O7 monoclinic perovskite and 40 mol% of A6B2O17 orthorhombic perovskite, where A represents Ti, Zr and Hf and B represents Nb and Ta. This two-phase oxide with an overall composition of TiHfZrNbTaO11 and a d0 electronic configuration shows an appreciable light absorbance in the visible-light region with a bandgap of 2.9 eV and appropriate valence and conduction bands for water splitting. The material successfully produces hydrogen by photocatalytic water splitting, suggesting the potential of HEOs as new low-bandgap photocatalysts.

In fifth-group element superconductors V, Nb, and Ta, the increase in superconducting transition temperature (Tc) was attempted by using both high-pressure torsion (HPT) and additional hydrostatic pressure (HP) compression. The former brings about the grain refinement and strain accumulation in the unit-cell level. The additional compression for severely strained superconductors triggers strengthening intergrain-contact and/or structural deformation in the unit-cell level. The manner of the appearance of the above two effects depends on the kind of elements: First, in V, there is no prominent effect of HPT, comparing to the hydrostatic compression effects on its non-strained material. Next, in Ta, the effect of strengthening intergrain-contact appears at small hydrostatic compression, resulting in temporal increase in Tc. Finally, Nb exhibits prominent increase in Tc by both effects and, in particular, the structural deformation in the unit-cell level promotes the increase in Tc. Thus, the accumulation of residual strain in the level of starting material can be a promising work to manipulate Tc under HP compression.

Recently, authors have proposed a unique "non-firing sintering" method for solidifying various ceramics without applying an external pressure and/or temperature.Surface activation of powders by ball milling plays an important role in this method, however many aspects of this method regarding its mechanism is not well understood. Since there are many similarities between ball milling and high-pressure torsion (HPT) method in terms of inducing strain to the surface of powder, in this review some well-known metal oxides like titania (TiO₂), zirconia (ZnO), and yttria (Y₂O₃) have been subjected to the severe plastic deformation, and effect of plastic strain on the phase transformations of them is investigated. In addition, the optical/photocatalyic properties of HPT processed samples is also investigated.

This overview describes the progressive results of the superconducting critical temperature in bulk nanostructured metals (niobium, vanadium and tantalum) processed by high-pressure torsion (HPT). Bulk nanostructured superconductors provide a new route to control superconducting property, because ultrafine-grain structures with a high density of grain boundaries, dislocations, and other crystalline defects modify the superconducting order parameter. The critical temperature Tc in Nb increases with the evolution of grain refinement owing to the quantum confinement of electrons in ultrafine grains. In V and Ta, however, Tc decreases at a certain HPT revolution number (i.e. at certain strain levels). The different behaviour of Tc in the three materials is explained by the competition effect between the quantum size effect and disorder effect; these effects are characterized by the parameters of grain size, electron mean free path, and superconducting coherence length.