Room-temperature super-elongation in high-entropy alloy nanopillars.

Nanoscale small-volume metallic materials typically exhibit high strengths but often suffer from a lack of tensile ductility due to undesirable premature failure. Here, we report unusual room-temperature uniform elongation up to ~110% at a high flow stress of 0.6-1.0 GPa in single-crystalline <110>-oriented CoCrFeNi high-entropy alloy nanopillars with well-defined geometries. By combining high-resolution microscopy and large-scale atomistic simulations, we reveal that this ultrahigh uniform tensile ductility is attributed to spatial and synergistic coordination of deformation twinning and dislocation slip, which effectively promote deformation delocalization and delay necking failure. These joint and/or sequential activations of the underlying displacive deformation mechanisms originate from chemical compositional heterogeneities at the atomic level and resulting wide variations in generalized stacking fault energy and associated dislocation activities. Our work provides mechanistic insights into superplastic deformations of multiple-principal element alloys at the nanoscale and opens routes for designing nanodevices with high mechanical reliability.

Strong and ductile titanium-oxygen-iron alloys by additive manufacturing.

Titanium alloys are advanced lightweight materials, indispensable for many critical applications1,2. The mainstay of the titanium industry is the α-ß titanium alloys, which are formulated through alloying additions that stabilize the α and ß phases3-5. Our work focuses on harnessing two of the most powerful stabilizing elements and strengtheners for α-ß titanium alloys, oxygen and iron1-5, which are readily abundant. However, the embrittling effect of oxygen6,7, described colloquially as 'the kryptonite to titanium'8, and the microsegregation of iron9 have hindered their combination for the development of strong and ductile α-ß titanium-oxygen-iron alloys. Here we integrate alloy design with additive manufacturing (AM) process design to demonstrate a series of titanium-oxygen-iron compositions that exhibit outstanding tensile properties. We explain the atomic-scale origins of these properties using various characterization techniques. The abundance of oxygen and iron and the process simplicity for net-shape or near-net-shape manufacturing by AM make these α-ß titanium-oxygen-iron alloys attractive for a diverse range of applications. Furthermore, they offer promise for industrial-scale use of off-grade sponge titanium or sponge titanium-oxygen-iron10,11, an industrial waste product at present. The economic and environmental potential to reduce the carbon footprint of the energy-intensive sponge titanium production12 is substantial.

Electrosynthesis of chlorine from seawater-like solution through single-atom catalysts.

The chlor-alkali process plays an essential and irreplaceable role in the modern chemical industry due to the wide-ranging applications of chlorine gas. However, the large overpotential and low selectivity of current chlorine evolution reaction (CER) electrocatalysts result in significant energy consumption during chlorine production. Herein, we report a highly active oxygen-coordinated ruthenium single-atom catalyst for the electrosynthesis of chlorine in seawater-like solutions. As a result, the as-prepared single-atom catalyst with Ru-O4 moiety (Ru-O4 SAM) exhibits an overpotential of only ~30 mV to achieve a current density of 10 mA cm-2 in an acidic medium (pH = 1) containing 1 M NaCl. Impressively, the flow cell equipped with Ru-O4 SAM electrode displays excellent stability and Cl2 selectivity over 1000 h continuous electrocatalysis at a high current density of 1000 mA cm-2. Operando characterizations and computational analysis reveal that compared with the benchmark RuO2 electrode, chloride ions preferentially adsorb directly onto the surface of Ru atoms on Ru-O4 SAM, thereby leading to a reduction in Gibbs free-energy barrier and an improvement in Cl2 selectivity during CER. This finding not only offers fundamental insights into the mechanisms of electrocatalysis but also provides a promising avenue for the electrochemical synthesis of chlorine from seawater electrocatalysis.

Formation of Head/Tail-to-Body Charged Domain Walls by Mechanical Stress.

Domain walls (DWs) in ferroelectric materials are interfaces that separate domains with different polarizations. Charged domain walls (CDWs) and neutral domain walls are commonly classified depending on the charge state at the DWs. CDWs are particularly attractive as they are configurable elements, which can enhance field susceptibility and enable functionalities such as conductance control. However, it is difficult to achieve CDWs in practice. Here, we demonstrate that applying mechanical stress is a robust and reproducible approach to generate CDWs. By mechanical compression, CDWs with a head/tail-to-body configuration were introduced in ultrathin BaTiO3, which was revealed by in-situ transmission electron microscopy. Finite element analysis shows strong strain fluctuation in ultrathin BaTiO3 under compressive mechanical stress. Molecular dynamics simulations suggest that the strain fluctuation is a critical factor in forming CDWs. This study provides insight into ferroelectric DWs and opens a pathway to creating CDWs in ferroelectric materials.

Ultrahigh Energy Storage Density in Glassy Ferroelectric Thin Films under Low Electric Field.

The current approach to achieving superior energy storage density in dielectrics is to increase their breakdown strength, which often incurs heat generation and unexpected insulation failures, greatly deteriorating the stability and lifetime of devices. Here, a strategy is proposed for enhancing recoverable energy storage density (Wr ) while maintaining a high energy storage efficiency (η) in glassy ferroelectrics by creating super tetragonal (super-T) nanostructures around morphotropic phase boundary (MPB) rather than exploiting the intensely strong electric fields. Accordingly, a giant Wr of ≈86 J cm-3 concomitant with a high η of ≈81% is acquired under a moderate electric field (1.7 MV cm-1 ) in thin films having MPB composition, namely, 0.94(Bi, Na)TiO3 -0.06BaTiO3 (BNBT), where the local super-T polar clusters (tetragonality ≈1.25) are stabilized by interphase strain. To the knowledge of the authors, the Wr of the engineered BNBT thin films represents a new record among all the oxide perovskites under a similar strength of electric field to date. The phase field simulation results ascertain that the improved Wr is attributed to the local strain heterogeneity and the large spontaneous polarization primarily is originated from the super-T polar clusters. The findings in this work present a genuine opportunity to develop ultrahigh-energy-density thin-film capacitors for low-electric-field-driven nano/microelectronics.

Uniting tensile ductility with ultrahigh strength via composition undulation.

Metals with nanocrystalline grains have ultrahigh strengths approaching two gigapascals. However, such extreme grain-boundary strengthening results in the loss of almost all tensile ductility, even when the metal has a face-centred-cubic structure-the most ductile of all crystal structures1-3. Here we demonstrate that nanocrystalline nickel-cobalt solid solutions, although still a face-centred-cubic single phase, show tensile strengths of about 2.3 gigapascals with a respectable ductility of about 16 per cent elongation to failure. This unusual combination of tensile strength and ductility is achieved by compositional undulation in a highly concentrated solid solution. The undulation renders the stacking fault energy and the lattice strains spatially varying over length scales in the range of one to ten nanometres, such that the motion of dislocations is thus significantly affected. The motion of dislocations becomes sluggish, promoting their interaction, interlocking and accumulation, despite the severely limited space inside the nanocrystalline grains. As a result, the flow stress is increased, and the dislocation storage is promoted at the same time, which increases the strain hardening and hence the ductility. Meanwhile, the segment detrapping along the dislocation line entails a small activation volume and hence an increased strain-rate sensitivity, which also stabilizes the tensile flow. As such, an undulating landscape resisting dislocation propagation provides a strengthening mechanism that preserves tensile ductility at high flow stresses.

Cation-Vacancy-Enriched Nickel Phosphide for Efficient Electrosynthesis of Hydrogen Peroxides.

Electrocatalytic hydrogen peroxide (H2 O2 ) synthesis via the two-electron oxygen reduction reaction (2e ORR) pathway is becoming increasingly important due to the green production process. Here, cationic vacancies on nickel phosphide, as a proof-of-concept to regulate the catalyst's physicochemical properties, are introduced for efficient H2 O2 electrosynthesis. The as-fabricated Ni cationic vacancies (VNi )-enriched Ni2- x P-VNi electrocatalyst exhibits remarkable 2e ORR performance with H2 O2 molar fraction of >95% and Faradaic efficiencies of >90% in all pH conditions under a wide range of applied potentials. Impressively, the as-created VNi possesses superb long-term durability for over 50 h, suppassing all the recently reported catalysts for H2 O2 electrosynthesis. Operando X-ray absorption near-edge spectroscopy (XANES) and synchrotron Fourier transform infrared (SR-FTIR) combining theoretical calculations reveal that the excellent catalytic performance originates from the VNi -induced geometric and electronic structural optimization, thus promoting oxygen adsorption to the 2e ORR favored "end-on" configuration. It is believed that the demonstrated cation vacancy engineering is an effective strategy toward creating active heterogeneous catalysts with atomic precision.

Deformation-Induced Phase Transformations in Gold Nanoribbons with the 4H Phase.

The mechanical stability of metallic nanomaterials has been intensively studied due to their unique structures and promising applications. Although extensive investigations have been carried out on the deformation behaviors of metallic nanomaterials, the atomic-scale deformation mechanism of metallic nanomaterials with unconventional hexagonal structures remains unclear because of the lack of direct experimental observation. Here, we conduct an atomic-resolution in situ tensile-straining transmission electron microscopy investigation on the deformation mechanism of gold nanoribbons with the 4H (hexagonal) phase. Our results reveal that plastic deformation in the 4H gold nanoribbons comprises three stages, in which both full and partial dislocations are involved. At the early deformation stage, plastic deformation is governed by full dislocation activities. Partial dislocations are subsequently activated in regions that have undergone full dislocation gliding, leading to phase transformation from the 4H phase to the face-centered cubic (FCC) phase. At the last stage of the deformation process, the volume fraction of the FCC phase increases, and full dislocation activities in the FCC regions also play an important role.

Giant room temperature compression and bending in ferroelectric oxide pillars.

Plastic deformation in ceramic materials is normally only observed in nanometre-sized samples. However, we have observed high levels of plasticity (>50% plastic strain) and excellent elasticity (6% elastic strain) in perovskite oxide Pb(In1/2Nb1/2)O3-Pb(Mg1/3Nb2/3)O3-PbTiO3, under compression along <100>pc pillars up to 2.1 µm in diameter. The extent of this deformation is much higher than has previously been reported for ceramic materials, and the sample size at which plasticity is observed is almost an order of magnitude larger. Bending tests also revealed over 8% flexural strain. Plastic deformation occurred by slip along {110} <1[Formula: see text]0 > . Calculations indicate that the resulting strain gradients will give rise to giant flexoelectric polarization. First principles models predict that a high concentration of oxygen vacancies weaken the covalent/ionic bonds, giving rise to the unexpected plasticity. Mechanical testing on oxygen vacancies-rich Mn-doped Pb(In1/2Nb1/2)O3-Pb(Mg1/3Nb2/3)O3-PbTiO3 confirmed this prediction. These findings will facilitate the design of plastic ceramic materials and the development of flexoelectric-based nano-electromechanical systems.

Manipulating ferroelectric behaviors via electron-beam induced crystalline defects.

Ferroelectric nanoplates are attractive for applications in nanoelectronic devices. Defect engineering has been an effective way to control and manipulate ferroelectric properties in nanoscale devices. Defects can act as pinning centers for ferroelectric domain wall motion, altering the switching properties and domain dynamics of ferroelectrics. However, there is a lack of detailed investigation on the interactions between defects and domain walls in ferroelectric nanoplates due to the limitation of previous characterization techniques, which impedes the development of defect engineering in ferroelectric nanodevices. In this study, we applied in situ biasing transmission electron microscopy to explore how dislocation loops, which were judiciously introduced into barium titanate nanoplates via electron beam irradiation, affect the motion of ferroelectric domain walls. The results show that the motion was dramatically suppressed by these localized defects, because of the local strain fields induced by the defects. The pinning effect can be further enhanced by multiple domain walls embedded with defect arrays. These results indicate the possibility of manipulating domain switching in ferroelectric nanoplates via the electron beam.

Ultrahigh specific strength in a magnesium alloy strengthened by spinodal decomposition.

Strengthening of magnesium (Mg) is known to occur through dislocation accumulation, grain refinement, deformation twinning, and texture control or dislocation pinning by solute atoms or nano-sized precipitates. These modes generate yield strengths comparable to other engineering alloys such as certain grades of aluminum but below that of high-strength aluminum and titanium alloys and steels. Here, we report a spinodal strengthened ultralightweight Mg alloy with specific yield strengths surpassing almost every other engineering alloy. We provide compelling morphological, chemical, structural, and thermodynamic evidence for the spinodal decomposition and show that the lattice mismatch at the diffuse transition region between the spinodal zones and matrix is the dominating factor for enhancing yield strength in this class of alloy.

Deformation-induced crystalline-to-amorphous phase transformation in a CrMnFeCoNi high-entropy alloy.

The Cantor high-entropy alloy (HEA) of CrMnFeCoNi is a solid solution with a face-centered cubic structure. While plastic deformation in this alloy is usually dominated by dislocation slip and deformation twinning, our in situ straining transmission electron microscopy (TEM) experiments reveal a crystalline-to-amorphous phase transformation in an ultrafine-grained Cantor alloy. We find that the crack-tip structural evolution involves a sequence of formation of the crystalline, lamellar, spotted, and amorphous patterns, which represent different proportions and organizations of the crystalline and amorphous phases. Such solid-state amorphization stems from both the high lattice friction and high grain boundary resistance to dislocation glide in ultrafine-grained microstructures. The resulting increase of crack-tip dislocation densities promotes the buildup of high stresses for triggering the crystalline-to-amorphous transformation. We also observe the formation of amorphous nanobridges in the crack wake. These amorphization processes dissipate strain energies, thereby providing effective toughening mechanisms for HEAs.

Direct observation of nanoscale dynamics of ferroelectric degradation.

Failure of polarization reversal, i.e., ferroelectric degradation, induced by cyclic electric loadings in ferroelectric materials, has been a long-standing challenge that negatively impacts the application of ferroelectrics in devices where reliability is critical. It is generally believed that space charges or injected charges dominate the ferroelectric degradation. However, the physics behind the phenomenon remains unclear. Here, using in-situ biasing transmission electron microscopy, we discover change of charge distribution in thin ferroelectrics during cyclic electric loadings. Charge accumulation at domain walls is the main reason of the formation of c domains, which are less responsive to the applied electric field. The rapid growth of the frozen c domains leads to the ferroelectric degradation. This finding gives insights into the nature of ferroelectric degradation in nanodevices, and reveals the role of the injected charges in polarization reversal.

The mechanism for the enhanced piezoelectricity in multi-elements doped (K,Na)NbO3 ceramics.

(K,Na)NbO3 based ceramics are considered to be one of the most promising lead-free ferroelectrics replacing Pb(Zr,Ti)O3. Despite extensive studies over the last two decades, the mechanism for the enhanced piezoelectricity in multi-elements doped (K,Na)NbO3 ceramics has not been fully understood. Here, we combine temperature-dependent synchrotron x-ray diffraction and property measurements, atomic-scale scanning transmission electron microscopy, and first-principle and phase-field calculations to establish the dopant-structure-property relationship for multi-elements doped (K,Na)NbO3 ceramics. Our results indicate that the dopants induced tetragonal phase and the accompanying high-density nanoscale heterostructures with low-angle polar vectors are responsible for the high dielectric and piezoelectric properties. This work explains the mechanism of the high piezoelectricity recently achieved in (K,Na)NbO3 ceramics and provides guidance for the design of high-performance ferroelectric ceramics, which is expected to benefit numerous functional materials.

Giant tuning of ferroelectricity in single crystals by thickness engineering.

Thickness effect and mechanical tuning behavior such as strain engineering in thin-film ferroelectrics have been extensively studied and widely used to tailor the ferroelectric properties. However, this is never the case in freestanding single crystals, and conclusions from thin films cannot be duplicated because of the differences in the nature and boundary conditions of the thin-film and freestanding single-crystal ferroelectrics. Here, using in situ biasing transmission electron microscopy, we studied the thickness-dependent domain switching behavior and predicted the trend of ferroelectricity in nanoscale materials induced by surface strain. We discovered that sample thickness plays a critical role in tailoring the domain switching behavior and ferroelectric properties of single-crystal ferroelectrics, arising from the huge surface strain and the resulting surface reconstruction. Our results provide important insights in tuning polarization/domain of single-crystal ferroelectric via sample thickness engineering.

Constructing phase boundary in AgNbO3 antiferroelectrics: pathway simultaneously achieving high energy density and efficiency.

Dielectric capacitors with high energy storage density (Wrec) and efficiency (η) are in great demand for high/pulsed power electronic systems, but the state-of-the-art lead-free dielectric materials are facing the challenge of increasing one parameter at the cost of the other. Herein, we report that high Wrec of 6.3 J cm-3 with η of 90% can be simultaneously achieved by constructing a room temperature M2-M3 phase boundary in (1-x)AgNbO3-xAgTaO3 solid solution system. The designed material exhibits high energy storage stability over a wide temperature range of 20-150 °C and excellent cycling reliability up to 106 cycles. All these merits achieved in the studied solid solution are attributed to the unique relaxor antiferroelectric features relevant to the local structure heterogeneity and antiferroelectric ordering, being confirmed by scanning transmission electron microscopy and synchrotron X-ray diffraction. This work provides a good paradigm for developing new lead-free dielectrics for high-power energy storage applications.

3D electron backscatter diffraction study of α lath morphology in additively manufactured Ti-6Al-4V.

Titanium alloys exhibit complex, multi-phase microstructures which form during liquid-solid and solid-solid phase transformations. These phase transformations govern the microstructural evolution and are potentially more complex during additive manufacturing due to large thermal gradients and inhomogeneities. The prototypical fundamental unit of titanium microstructures are the α laths, and investigations into their three-dimensional morphology may provide new insights. A prior ß-grain boundary, 3-variant clusters and interconnected laths were studied in 3D in electron-beam printed Ti-6Al-4V using a plasma FIB. These key features are of interest for studying variant selection in additive manufacturing.

Effect of Ion Irradiation Introduced by Focused Ion-Beam Milling on the Mechanical Behaviour of Sub-Micron-Sized Samples.

The development of xenon plasma focused ion-beam (Xe+ PFIB) milling technique enables site-specific sample preparation with milling rates several times larger than the conventional gallium focused ion-beam (Ga+ FIB) technique. As such, the effect of higher beam currents and the heavier ions utilized in the Xe+ PFIB system is of particular importance when investigating material properties. To investigate potential artifacts resulting from these new parameters, a comparative study is performed on transmission electron microscopy (TEM) samples prepared via Xe+ PFIB and Ga+ FIB systems. Utilizing samples prepared with each system, the mechanical properties of CrMnFeCoNi high-entropy alloy (HEA) samples are evaluated with in situ tensile straining TEM studies. The results show that HEA samples prepared by Xe+ PFIB present better ductility but lower strength than those prepared by Ga+ FIB. This is due to the small ion-irradiated volumes and the insignificant alloying effect brought by Xe irradiation. Overall, these results demonstrate that Xe+ PFIB systems allow for a more efficient material removal rate while imparting less damage to HEAs than conventional Ga+ FIB systems.

Electronic Modulation of Nickel Disulfide toward Efficient Water Electrolysis.

Developing highly efficient earth-abundant nickel-based compounds is an important step to realize hydrogen generation from water. Herein, the electronic modulation of the semiconducting NiS2 by cation doping for advanced water electrolysis is reported. Both theoretical calculations and temperature-dependent resistivity measurements indicate the semiconductor-to-conductor transition of NiS2 after Cu incorporation. Further calculations also suggest the advantages of Cu dopant to cathodic water electrolysis by bringing Gibbs free energy of H adsorption at both Ni sites and S sites much closer to zero. It is noteworthy that water dissociation on Cu-doped NiS2 (Cu-NiS2 ) surface is even more favorable than those on NiS2 and Pt(111). Thus, the prepared Cu-NiS2 shows noticeably improved performance toward alkaline hydrogen and oxygen evolution reactions (HER and OER). Specifically, it requires merely 232 mV OER overpotential to drive 10 mA cm-2 ; in parallel with Tafel slopes of 46 mV dec-1 . Regarding HER, an onset overpotential of only 68 mV is achieved. When integrated as both electrodes for water electrolysis, Cu-NiS2 needs only 1.64 V to drive 10 mA cm-2 , surpassing the state-of-the-art Ir/C-Pt/C couple (1.71 V). This work opens up an avenue to engineer low-cost and earth-abundant catalysts performing on par with the noble-metal-based one for water splitting.

Atomistic Mechanism of Stress-Induced Combined Slip and Diffusion in Sub-5 Nanometer-Sized Ag Nanowires.

With continuous minimization of nanodevices, the dimensions of metallic materials used in nanodevices decrease to a few nanometers. Understanding the structural stability and deformation behavior of these small-sized metallic materials is important for their practical applications. Here we report our atomic-resolution observation of the deformation processes of Ag nanowires with widths of ∼3 nm. The nanowires under tension experienced plastic deformation via partial dislocation activities, which led to deformation twinning in and homogeneous elongation of the nanowires, and surface atom diffusion that reduced the nanowires' width but did not contribute to the nanowire elongation. The diffusion of surface atoms was initiated at surface steps introduced by the partial dislocation activities, leading to fracture of the nanowires with relatively low homogeneous elongation.