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In this study, GdBa2Cu3O7−ẟ (GdBCO) sol with ultraviolet (UV) sensitivity was prepared using Gd(OAC)3, Ba(OAC)2, and Cu(OAC)2 as the starting materials, methanol as the solvent, and 2,2′-bipyridine as the chemical modifier. Furthermore, chelation mechanism of the chemical modifier and metal ions in the sol was analyzed by infrared and UV absorption spectroscopy. Cu2+ in the sol was found to chelate with the chemical modifier to form a photosensitive chelate, rendering UV sensitivity to the sol. Next, the photosensitive chelate was decomposed by exposing it to UV light, and the decomposition product was barely soluble in organic solvents. By exploiting the self-sensitivity of GdBCO, fine patterns of its films were obtained (without photoresist throughout) with micron scale resolution. XRD and superconductivity performance tests revealed that compared to the GdBCO film without fine patterns, fine-patterned GdBCO fabricated herein does not exhibit significant degradation in terms of its crystal structure and superconductivity. This result indicates that fine-pattern technology developed for chemical film formation is simple in terms of process and equipment, and it does not affect the performance of the GdBCO film. Therefore, “chemically modified self-photosensitive” photolithography can be applied for the preparation of the GdBCO-based inorganic microstructure, which exhibits specific significance for the research and application of high-temperature superconductor electronic devices. In addition, during heat treatment, the technology of first introducing carbon dioxide and then water vapor also was adopted in this paper, which reduced the surface roughness of the GdBCO film.

Developing a highly active and durable non-noble metal catalyst for aqueous-phase levulinic acid (LA) hydrogenation to γ-valerolactone (GVL) is an appealing yet challenging task. Herein, we report well-dispersed Co nanoparticles (NPs) embedded in nitrogen-doped mesoporous carbon nanofibers as an efficient catalyst for aqueous-phase LA hydrogenation to GVL. The Co zeolitic imidazolate framework (ZIF-67) nanocrystals were anchored on the sodium dodecyl sulfate modified wipe fiber (WF-S), yielding one-dimensional (1-D) structured composite (ZIF-67/WF-S). Subsequently, Co NPs were uniformly embedded in nitrogen-doped mesoporous carbon nanofibers (CoRNC/SMCNF) through a pyrolysis-reduction strategy using ZIF-67/WF-S as the precursor. Benefiting from introducing modified wipe fiber WF-S to enhance the dispersion of Co NPs, and Co0 with Co-Nx dual active sites, the resulting CoRNC/SMCNF catalyst shows brilliant catalytic activity (206 h−1 turnover frequency). Additionally, the strong metal–support interactions greatly inhibited the Co NPs from aggregation and leaching from the mesoporous carbon nanofibers, and thus increasing the reusability of the CoRNC/SMCNF catalyst (reusable nine times without notable activity loss).

Graphite, a robust host for reversible lithium storage, enabled the first commercially viable lithium-ion batteries. However, the thermal degradation pathway and the safety hazards of lithiated graphite remain elusive. Here, solid-electrolyte interphase (SEI) decomposition, lithium leaching, and gas release of the lithiated graphite anode during heating were examined by in situ synchrotron X-ray techniques and in situ mass spectroscopy. The source of flammable gas such as H2 was identified and quantitively analyzed. Also, the existence of highly reactive residual lithium on the graphite surface was identified at high temperatures. Our results emphasized the critical role of the SEI in anode thermal stability and uncovered the potential safety hazards of the flammable gases and leached lithium. The anode thermal degradation mechanism revealed in the present work will stimulate more efforts in the rational design of anodes to enable safe energy storage., The role of the lithiated graphite anode in battery thermal runaway failure remains under intense investigation. In this work, with multiple in situ synchrotron X-ray characterizations, the phase evolution, gas release, and lithium leaching of lithiated graphite anode are illustrated in detail.

The addition of a small amount of oxygen improves the mechanical properties, especially plasticity, of Ti45.7Zr33Ni3Cu5.8Be12.5 amorphous alloy composites (AACs) at room temperature (298 K). Compared to the plasticity of AACs without added O (5%), the plasticity of the composites with 0.73 at.% O (nominal composition) was much higher (11 %). Even at O content higher than 0.73 at.%, the AACs exhibited good plasticity. The highest plasticity of ∼12.3 % was observed with 2.87 at.% O. Two distinct mechanisms are proposed to explain the enhanced plasticity of the AACs. At low O content, although deformation-induced phase transformation was suppressed, a substantial amount of α’’ martensite was formed. The microstructural features of α’’ martensite, such as thinner laths and homogeneous distribution, induced the formation of multiple shear bands in the amorphous matrix. At high O content, deformation-induced phase transformation was seriously suppressed. A dispersed nano ω phase was formed during rapid solidification in AACs with O content higher than 1.45 at.%. This resulted in a weakening in the anisotropy of β dendrites and led to their homogenous deformation. Furthermore, multiple shear bands were formed in the amorphous matrix. Apart from plasticity, the strength of the AACs also increased with an increase in the O content. This phenomenon was explained in terms of three mechanisms, viz. the solid-solution-strengthening effect of O, fine-grain strengthening of β dendrites, and secondary phase strengthening by the nano ω phase.

Amorphous materials have no long-range order, but there are ordered structures at short range (2–5 A), medium range (5–20 A) and even longer length scales1–5. While regular6,7 and semiregular polyhedra8–10 are often found as short-range ordering in amorphous materials, the nature of medium-range order has remained elusive11–14. Consequently, it is difficult to determine whether there exists any structural link at medium range or longer length scales between the amorphous material and its crystalline counterparts. Moreover, an amorphous material often crystallizes into a phase of different composition15, with very different underlying structural building blocks, further compounding the issue. Here, we capture an intermediate crystalline cubic phase in a Pd-Ni-P amorphous alloy and reveal the structure of the medium-range order, a six-membered tricapped trigonal prism cluster (6M-TTP) with a length scale of 12.5 A. We find that the 6M-TTP can pack periodically to several tens of nanometres to form the cube phase. Our experimental observations provide evidence of a structural link between the amorphous and crystalline phases in a Pd-Ni-P alloy at the medium-range length scale and suggest that it is the connectivity of the 6M-TTP clusters that distinguishes the crystalline and amorphous phases. These findings will shed light on the structure of amorphous materials at extended length scales beyond that of short-range order. An intermediate cube phase with a medium-range order structure is identified in Pd-Ni-P metallic glass, which links the amorphous and crystalline phases.

Ferromagnetic transitions, the magnetocaloric effect, and the atomic-scale microstructure in an annealed bulk material of LaFe11.5Si1.5 were investigated using magnetic measurements, Mossbauer spec...

The temperature-dependent structure and properties of a liquid GaInSn eutectic alloy have been investigated by using in situ high-energy X-ray diffraction, thermal expansion, and heat capacity meas...

Iron-based electrodes have attracted great attention for sodium storage because of the distinct cost effectiveness. However, exploring suitable iron-based electrodes with high power density and long duration remains a big challenge. Herein, a spray-drying strategy is adopted to construct graphene-coated Na2.4Fe1.8(SO4)3 nanograins in a 3D graphene microsphere network. The unique structural and compositional advantages endow these electrodes to exhibit outstanding electrochemical properties with remarkable rate performance and long cycle life. Mechanism analyses further explain the outstanding electrochemical properties from the structural aspect.

Rapid solidification of the intermetallic Ni3Sn compound from an undercooled liquid was investigated using time-resolved synchrotron X-ray diffraction. Primary growth of an ordered and a disordered cubic solid was observed in situ at a low and a high undercooling, respectively. The disordered cubic solid was reordered after rapid solidification and experienced a solid-state transformation in cooling. A HRTEM study revealed high density of crystal defects and nanodomains in the transformed matrix. A HAADF-STEM study determined that the nanodomains are antiphase domains with chemical disorder. These observations indicated a possibility of online control of mechanical properties in additively manufactured intermetallics.

Current bottlenecks in cobalt (Co) supply have negatively impacted commercial battery production and inspired the development of cathode materials that are less reliant on Co. However, complete Co elimination is prevented by the lack of fundamental understanding of the impact of Co on cathode capacity and structural stability, as well as the lack of effective substitute components in practice. Here we investigate the roles of Co in purposely designed systems that include both Co-rich and Mn-substituted Co-free cathodes. Our results affirmed that Co plays an undeniable role in fast capacity and/or structural degradation, and found that Co is more destructive than Ni at high potentials, which offers unexpected but encouraging perspectives for Co reduction. Moreover, Mn substitution effectively alleviates the destructive effects of Co and enables a high potential functionality. With these fundamental discoveries, we demonstrated a series of LiNiαMnβXγO2 (X = single or multiple dopants) as a promising candidate for Co-free cathodes. Reduction on cobalt reliance is an urgent requirement in the development of sustainable cathode materials for Li-ion batteries. Here the authors analyse the roles of cobalt and its interplay with other ions in high-nickel layered oxides, and deduce a material formula for promising cobalt-free cathodes.

Grain size effect plays a vital role in piezoelectric performance from both scientific and technological view. However, the underlying structural mechanism related to grain size is still unclear. In the present study, the structural mechanism of grain size effect on piezoelectric performance has been revealed in the prototype Pb(Zr,Ti)O3 system by using in-situ synchrotron X-ray diffraction. The miniaturization of grain size tends to favor the appearance of higher symmetric tetragonal phase, while a single monoclinic phase is determined in the coarse-grained ceramics. The direct structural evidence reveals that both tetragonal and monoclinic phases in the fine-grained ceramics are less sensitive to the electric field, corresponding to the inferior piezoelectric performance, while the single monoclinic phase in the coarse-grained ceramics is more active to be driven by the electric field, generating good piezoelectric behavior. Both domain switching ability and lattice strain are suppressed with decreasing grain size, which directly leads to the deterioration in piezoelectric performance. The current results will benefit the structural understanding of the size effect of piezoelectric and other related systems.

The simple ABO3 and A-site-ordered AA′3B4O12 perovskites represent two types of classical perovskite functional materials. There are well-known simple perovskites with ferroelectric properties, while there is still no report of ferroelectricity due to symmetry breaking transition in A-site-ordered quadruple perovskites. Here we report the high pressure synthesis of an A-site-ordered perovskite PbHg3Ti4O12, the only known quadruple perovskite that transforms from high-temperature centrosymmetric paraelectric phase to low-temperature non-centrosymmetric ferroelectric phase. The coordination chemistry of Hg2+ is changed from square planar as in typical A-site-ordered quadruple perovskite to a rare stereo type with 8 ligands in PbHg3Ti4O12. Thus PbHg3Ti4O12 appears to be a combinatory link from simple ABO3 perovskites to A-site-ordered AA′3Ti4O12 perovskites, sharing both displacive ferroelectricity with former and structure coordination with latter. This is the only example so far showing ferroelectricity due to symmetry breaking phase transition in AA′3B4O12-type A-site-ordered perovskites, and opens a direction to search for ferroelectric materials.

Sodium-ion batteries are promising candidates for energy storage application, but the absence of high-capacity and low-cost anode materials significantly limits their practical specific energy and ...

The deformation behaviors of W nanowires embedded in a TiNi matrix were investigated by means of in-situ synchrotron high energy X-ray diffraction (HEXRD) and in-situ transmission electron microscopy (TEM) analysis during tensile deformation. The HEXRD measurement indicated that the W nanowires exhibited an average lattice strain of about 1.50 %, whereas the TEM examination revealed a local elastic strain of about 4.59 % in areas adjacent to the TiNi matrix where stress-induced martensitic transformation occurred. This strain corresponds to a stress of ∼15 GPa for the W nanowires. In addition, in areas adjacent to the TiNi matrix where plastic deformation and cracking were generated, the W nanowire showed significant ductile necking with ∼80 % reduction in cross-section area. The ductile necking of W nanowire is attributed to the lack of protection from the stress-induced martensitic transformation of the TiNi matrix.

Owing to their high specific capacity and suitably low operating potential, silicon-based anodes are an attractive alternative to graphite in next-generation lithium-ion batteries. However, silicon anodes suffer from low initial coulombic efficiency and fast capacity decay, limiting their widespread application. Pre-lithiation strategies are highly appealing to compensate for irreversible active lithium loss and to boost the cell energy density. In this work, we maximize the cell energy density by direct pre-lithiation of the NMC (LiNi0.5Mn0.3Co0.2O2) cathode to Li1+xNMCO2 without introducing inactive deadweight to either electrode. First, we demonstrate that Li1+xNMCO2 can be synthesized chemically, via reaction between NMC and lithium napthalide, and electrochemically. The NMC cathode is tolerant of a one-time over-lithiation up to 60 mA h gNMC−1, giving capacity retention on par with untreated NMC in half cell electrochemical cycling. Using synchrotron X-ray absorption spectroscopy (ex situ) and diffraction (in situ), we demonstrate that higher amounts of over-lithiation lead to local structure distortion – driven by transition metal reduction to Jahn–Teller active Mn3+ and Co2+ – as well as bulk structural hysteresis during over-lithiation and layer “buckling” that increases the amount of lithium extracted from the structure in the charged state. The Li1+xNMCO2 with low-to-moderate over-lithiation capacity (23, 46, and 70 mA h gNMC−1) is proven to be a highly effective dual-purpose lithium source and cathode material in full cell tests with a commercially relevant Si–graphite anode. These cells show higher capacity, superior cycle life, and improved coulombic efficiencies when compared to those with stoichiometric NMC cathodes. This study introduces a new and simple method to pre-lithiate layered transition metal oxide cathodes, opening up new possibilities for the development of high energy density lithium-ion batteries with next-generation anodes.

The realization of high piezoelectric performance and excellent temperature stability simultaneously in Pb-free ceramics is the key for replacing Pb-containing perovskites in the industry. In this study, large piezoelectric performance (d33 = 354 pC N−1) was achieved in a wide temperature sinterable potassium-free NaNbO3–BaTiO3–BaSnO3 system, which is twice more than the piezoelectricity found in NaNbO3–BaTiO3 binary ceramics. Structural refinement of high-energy synchrotron powder diffraction data suggests a single tetragonal structure with P4bm symmetry for the studied NaNbO3-based Pb-free ceramic. The results indicate that the small axial ratio favoring polarization reorientation benefits strong piezoelectricity, while the large oxygen octahedron tilt enhances the stability of the P4bm structure during the changing temperature according to the in situ high-energy synchrotron X-ray diffraction measurements and provides the foundation for the excellent thermal stability (20–100 °C) of the piezoelectric properties. A single tetragonal phase with a tiny axial ratio and large oxygen octahedron tilt effectively balances the piezoelectricity and thermal stability in Pb-free systems.

High-entropy alloys (HEAs) provide a new perspective to design metastable alloys with the stress-induced martensitic transformation (SIMT) for overcoming the strength-ductility trade-off. Here, we report a novel SIMT, orthorhombic to hexagonal close-packed martensite, in a single orthorhombic refractory HEA (Ti16Zr35Hf35Ta14 RHEA), showing a good yield strength-ductility matching. The analysis of the elastic distortion energy (∆Eels) of Ti16Zr35Hf35Ta14 and several other RHEAs reveals that severe lattice distortion is a key factor which causes this SIMT. Combined the “d-electron alloy design” approach with the ∆Eels, the phase configuration and SIMT path in RHEAs can be well predicted. Our work brings new insights between the lattice distortion and SIMT of RHEAs, benefiting the metastable alloy development.

Sodium-ion batteries (SIBs) have been attracting an ever-growing research interest, mainly ascribed to their cost-effectiveness. However, SIBs have been significantly hindered by lack of a suitable anode. Herein, an exceptional Cu2S-based composite anode is developed via a facile ball-milling method, in which Cu2S particles are wrapped by nitrogen-doped graphene sheets (Cu2S@NG). This Cu2S@NG composite anode enables extremely long cycling life, ultra-stable cyclability with high capacity, and excellent rate capability. The superior performance of the Cu2S@NG composite is owing to its intriguing core-shell structure and the exceptional properties of both the Cu2S and NG. In this study, it is found that the NG shell yields multiple merits in improving the performance of Cu2S: (i) mitigating the loss of active materials, (ii) constituting a stable interface, (iii) providing improved electrical conductivity and good ionic transfer, and (iv) enhancing mechanical integrity. Additionally, the vital effects of different voltage windows and a surface coating via atomic layer deposition on further enhancing performance are clarified. Significantly, the electrochemical mechanism of Cu2S during sodiation/desodiation is unveiled using advanced synchrotron-based in-situ X-ray diffraction and X-ray adsorption spectroscopy. This work represents a great advance in seeking high-performance anodes in SIBs.

The Advanced Photon Source (APS) at Argonne National Laboratory (ANL) was designed and built as one of the first large third-generation synchrotrons operated at 7 GeV. The United States Department ...

Thermoelectric materials enable the mutual energy conversion of waste heat and electricity, critical to relieve global energy crisis. Hightemperature thermoelectric materials are special species due to their high-temperature stability and noticeable energy conversion efficiency. Here, we report a systematic investigation on high-temperature thermoelectric gadolinium selenides, cubic Gd3-xSe4 (x = 0.16, 0.21 and 0.25) and orthorhombic Gd2Se3-y (y = 0.02, 0.06 and 0.08). High energy synchrotron x-ray diffraction and total scattering are used to investigate the crystallographic and local structures. The atomic-scale cluster of Gd vacancy in cubic Gd2.84Se4 is observed by employing the reverse Monte Carlo simulation. For cubic Gd3-xSe4, its carrier concentration is tuned and multiple conduction bands are incorporated by adjusting Gd vacancy. Experimentally, the gradual increase in effective masses is evidently observed in cubic Gd3-xSe4, which is consistent with the density functional theory (DFT) calculation. A reasonable peak zT value of 0.27 is achieved at 850 K for Gd2.84Se4. On the other hand, adjusting Se vacancy enables the optimization of electron concentration for orthorhombic Gd2Se3-y phase. Its low deformation potential (Ξ = 12eV) with single conduction band gives rise to enhanced electron mobility and higher peak zT value of 0.54 at 850 K for Gd2Se2.98. In addition, a higher zT of 1.2 at1200 K is reasonably predicted for Gd2Se2.98 by using quality factor analysis. This work not just presents a systematic crystallographic investigation of gadolinium selenides, but also provides a deep insight into the charge transport and phonon scattering mechanisms. This study facilitates the exploration of more high-temperature thermoelectric materials. Ministry of Education (MOE) Accepted version The authors would like to acknowledge EFRC Solid-State-Thermal Energy Conversion Center (S3TEC), Grant DE-SC000XXXX. This work is also supported by Japan Society for the Promotion of Science (JSPS) KAKENHI, Grant JP 19F19057. L. H. acknowledge the International Research Fellow of JSPS. Q. F. Y. acknowledge the Chinese Scholarship Council (CSC) for the scholarship in Tokyo Institute of Technology. A. Q. Yan acknowledges Singapore MOE Tier 2 under Grant MOE2018-T2-1- 010. Use of the Advanced Photon Source was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Science, under Contract No. DE-AC02-06CH11357.

Lithium–sulfur batteries are attractive alternatives to lithium-ion batteries because of their high theoretical specific energy and natural abundance of sulfur. However, the practical specific energy and cycle life of Li–S pouch cells are significantly limited by the use of thin sulfur electrodes, flooded electrolytes and Li metal degradation. Here we propose a cathode design concept to achieve good Li–S pouch cell performances. The cathode is composed of uniformly embedded ZnS nanoparticles and Co–N–C single-atom catalyst to form double-end binding sites inside a highly oriented macroporous host, which can effectively immobilize and catalytically convert polysulfide intermediates during cycling, thus eliminating the shuttle effect and lithium metal corrosion. The ordered macropores enhance ionic transport under high sulfur loading by forming sufficient triple-phase boundaries between catalyst, conductive support and electrolyte. This design prevents the formation of inactive sulfur (dead sulfur). Our cathode structure shows improved performances in a pouch cell configuration under high sulfur loading and lean electrolyte operation. A 1-A-h-level pouch cell with only 100% lithium excess can deliver a cell specific energy of >300 W h kg−1 with a Coulombic efficiency >95% for 80 cycles. The shuttling effect in Li–S batteries can be drastically suppressed by using a single-atom Co catalyst and polar ZnS nanoparticles embedded in a macroporous conductive matrix as a cathode. Using this strategy, Li–S pouch cells show stable cycling and high energy performances.

This study investigated the microstructure, residual stress, and tensile properties of directed energy deposited stainless steel 316L (SS316L) under thermal annealing. Microstructure characterization shows the as-printed sample has laser-generated patterns where dendritic structure is observed at the edge of the patterns and cellular structure dominates the interior region. The thermal annealing at 983 and 1093°C effectively removes the dendritic/cellular structures. Synchrotron x-ray diffraction reveals that the as-printed SS316L exhibits compressive residual stress of − 197.4 MPa, which is greatly relieved to − 53.8 MPa after annealing at 1093°C. The room temperature tensile testing indicates that the yield strength and ultimate tensile strength drop from 378 MPa and 502 MPa in the as-printed sample to 258 MPa and 446 MPa in the annealed samples (1093°C), respectively. Our study provides insights into the relationship among microstructure, residual stress, and tensile properties of laser additive manufactured SS316L.

Many shape memory alloys can support large recoverable strains of a few percent by reversible stress-induced martensite transformation, yet they behave non-linear within a narrow operating temperature range. Developing the bulk metallic materials with ultra-large linear elasticity over a wide temperature range has proven to be difficult. In this work, a material design concept was proposed, that is true elastic deformation and reversible twinning-detwinning deformation run in parallel to overcome this challenge. By engineering the residual internal stress to realize the concurrency of true elastic deformation and twinning-detwinning deformation, a bulk nanocrystalline NiTi that possesses an ultra-large linear elastic strain up to 5.1 % and a high yield stress of 2.16 GPa over a wide temperature range of 270 °C was developed. This study offers a new avenue for developing the metallic materials with ultra-large linear elasticity over a wide temperature range of 270 °C (from 70 °C to −197 °C).

The multiscale structures in a Pd82Si18 binary bulk metallic glass before and after deformation were studied using electron microscopies, high-energy synchrotron X-ray diffraction, and small-angle scattering techniques. The experimental results revealed an enhancement of hierarchical structure heterogeneities on multiple length scales after deformation. Hierarchical multiple shear bands of high number density were observed after bending, introducing complex but periodically distributed residual strain. Pair distribution function analysis revealed that the connectivity of the short-range clusters on the medium-range scale determines the packing density difference between the tension side and the compression side in the sample after bending. In-situ synchrotron X-ray diffraction study also revealed a transformation of connection modes among short-range clusters under uniaxial tension and compression, which is consistent with those of triaxial tension/compression parts upon bending in Pd82Si18 glassy alloys. The nanoscale heterogeneities for metallic glasses after deformation observed by small-angle scattering and transmission electron microscopy may be attributed to the nanoscale amorphous phase separation and interacting multiple shear bands enhanced by plastic deformation. Our findings suggested that the enhancement of hierarchical heterogeneous structure on multiple length scales may explain the excellent plasticity of Pd-Si glassy alloys, deepening the understanding of structure-property relation during plastic deformation in metallic glasses.

Bismuth-Yttrium Oxide Bi3YO6 (BYO) is well-known among researchers for its potential applications in different fields but its use as an electrode for asymmetric supercapacitor (ASC) has not yet been discussed and uncovered. As high energy and power densities could be well achieved with the aid of optimum potential. In the current scenario, BYO is used as an electrode material for ASCs for the first time. The material is prepared by a solid-state reaction method and its structural, morphological, and electrochemical properties have been explored by using different characterization tools. Structural analysis declared the flourite based structure of BYO having a cubic phase without any visible impurity. In a morphological analysis, a mesoporous thin film with a high surface area (~ 36.6 m2 g−1) with a narrow pore width of (~ 5–18 nm) has been observed. The as-prepared BYO employed as an electrode material for SCs delivers a high specific capacitance of (388 F g−1 at 100 m Vs−1 in the three-electrode system) with excellent cycling stability (5% loss after 6000 cycles). Essentially, an ASC is assembled using BYO and rGO as a positive and negative electrodes operating in a stable and wide potential window up to 2.2 V. Moreover, a high energy density of 11 Wh kg−1 along with a power density of 648 W kg−1 is obtained and maintained a high power density of 888 W kg−1 with the downfall of energy density to 3.7 Wh kg−1. The results prove electrode material as an alternative promising candidate for ASCs.

In many ferroelectrics, large electromechanical strains are observed near regions of composition- or temperature- driven phase coexistence. Phenomenologically, this is attributed to easy re-orientation of the polarization vector and/or phase transition, although their effects are highly convoluted and difficult to distinguish experimentally. Here, we used synchrotron X-ray scattering and digital image correlation to differentiate between the microscopic mechanisms leading to large electrostrains in an exemplary Pb-free piezoceramic Sn-doped barium calcium zirconate titanate. Large electrostrains of ~0.2% measured at room-temperature are attributed to an unconventional effect, wherein polarization switching is aided by a reversible phase transition near the tetragonal-orthorhombic phase boundary. Additionally, electrostrains of ~0.1% or more could be maintained from room temperature to 140 °C due to a succession of different microscopic mechanisms. In situ X-ray diffraction elucidates that while 90° domain reorientation is pertinent below the Curie temperature (TC), isotropic distortion of polar clusters is the dominant mechanism above TC. Piezoelectric materials are used for a broad range of industrial and research applications. The authors use synchrotron X-ray scattering and digital imaging correlation to investigate the microscopic mechanisms behind electromechanical strains in a lead-free piezoceramic material, which suggests an unconventional domain switching mechanism and ability to enhance the temperature range of operation by suitable doping strategies.

In the present study, the composites have been prepared using vacuum hot pressing process technique. The influence of 2.0 wt.% nanometric SiC particles (n-SiCp) on the microstructure and fracture mechanism of 7075 aluminum alloy was studied by means of metallographic microscope, scanning electron microscope (SEM), energy-dispersive spectrometer (EDS), X-ray diffraction (XRD), laser scanning confocal (LSC). The results indicate that SiCp fill at grain boundaries dispersing evenly and nail to aluminum grains which sizes have been reduced successfully, that making the organization tighter, the gaps fewer and the surface rougher. Meanwhile, phases (MgZn2) precipitated from the 7075 aluminum alloy were been detected. The grain bonding states of matrix alloys are strengthened by the combination of fine grains strengthening and dispersion strengthening and thus affect the fracture morphology. The micro-fracture mechanism of 7075 aluminum alloy is micro-porous aggregation fracture, however, the 7075 aluminum matrix composites (AMCs) are quasi cleavage fracture.

This study investigated the mechanisms and temperature dependence of the R phase variant reorientation deformation in a nanocrystalline NiTi wire by means of in-situ synchrotron high-energy X-ray diffraction technique during tensile deformation. The NiTi wire exhibited a single stage B2 → R transformation upon cooling with the R → B19′ martensitic transformation completely suppressed down to the liquid nitrogen temperature. The R phase variant reorientation deformation in tension was revealed to proceed in a Luders-manner, as evidenced by sudden changes of diffraction peak intensity and increases of lattice elastic strains of the R phase during the deformation. The variant reorientation obeys the principles to yield maximum crystallographic strain in the direction of the applied load. Thus, the variants with larger d-spacing values aligned to the axis of tension grew at the expense of those of lower d-spacing values. The increases of lattice elastic strains are attributed to the internal load transfer among the different crystallographic variants during the R phase reorientation. The crystallographic strain of R phase reorientation was found to increase with decreasing the deformation temperature. This corresponds directly to the continued evolution of the structure of the R phase of increased structural distortion relative the B2 phase with decreasing the temperature. This reflects the second order nature of the R phase.

Low cycle fatigue of lamellar TiAl with 8.5 at.-%Nb was studied with a total strain amplitude of 0.28% at three temperatures: room temperature, 750°C and 900°C. At room temperature, the material exhibited cyclic hardening and the fracture mode was mainly interlamellar. At 750°C and 900°C, the material showed cyclic softening and the fracture mode was translamellar. The lattice strain in γ phase was almost tensile and larger tensile lattice strain in γ phase seems detrimental. Besides, the opposite direction of {201}γ and {100}α2 lead to crack propagation along α2/γ interfaces. B2/βo phase always suffered compressive lattice strain in the tests. The destruction of lamellar microstructure was the reason for colony refinement at 750°C and 900°C. Accepted version

Lacking of forest hardening makes low ductility in steels long challenge particularly at high yield strength. Here, we report to make good use of hetero-structuring for superior strength-ductility synergy in high manganese steel. The point is to retain original deformed structure of large quantity, along with recrystallized ultrafine-grains and fine grains, jointly for most effective heterogeneous deformation-induced (HDI) hardening especially at high strength. The residual plastic strain of larger than 0.2% and large proportion of HDI stress over 60% indicate the crucial role in ductility by HDI hardening. This renders a significantly upgraded strength-ductility combination within high strength scope.

Metastable spiral MgZn2/Zn eutectics grow in binary Zn-3 wt.% Mg alloys at small liquid undercooling. In this article, we report growth of a new class of three-phase spiral structures in metastable solidification of Ni-doped Zn-3Mg alloys. Thermodynamic calculations demonstrated that a minor Ni substitution for Zn allows for peritectic growth of the Mg2Zn11 phase following secondary MgZn2 growth. In situ synchrotron x-ray diffraction confirmed such metastable solidification reactions and suggested concomitant growth of MgZn2, Mg2Zn11 and Zn close to the end of solidification. Synchrotron x-ray nano-tomography revealed a localized three-phase spiral structure, wherein Mg2Zn11 grows at the phase-interface of the metastable eutectic. Such a novel spiral structure can be attributed to competitive growth of a metastable binary eutectic and a peritectic phase in metastable solidification. Ni doping increases the nucleation rate of MgZn2 and the driving force for peritectic growth of Mg2Zn11, thus leading to the formation of the three-phase spiral structure.

Melting, solidification and solid-state transformation of the intermetallic Ni3Sn compound were investigated in situ using synchrotron high-energy X-ray diffraction. It was observed that the compound undergoes a hexagonal to cubic transition before melting. In solidification, a disordered cubic phase crystallizes from the liquid at a large undercooling but it is reordered prior to bulk solidification. In melting and solidification, forced or natural flows are active bringing about significant changes of crystal orientations. These in situ observations provided insights into phase transformations of Ni3Sn at elevated temperatures and their roles in formation of metastable microstructure consisting of coarse grains and subgrains.

An intrinsic two-way shape memory effect with a fully recoverable strain of 1.0 % was achieved in an as-prepared Ni50Mn37.5Sn12.5 metamagnetic shape memory microwire fabricated by Taylor-Ulitovsky method. This two-way shape memory effect is mainly owing to the internal stress caused by the retained martensite in austenite matrix, as revealed by transmission electron microscopy observations and high-energy X-ray diffraction experiments. After superelastic training for 30 loading/unloading cycles at room temperature, the amount of retained martensite increased and the recoverable strain of two-way shape memory effect increased significantly to 2.2 %. Furthermore, a giant recoverable strain of 11.2 % was attained under a bias stress of 300 MPa in the trained microwire. These properties confer this microwire great potential for micro-actuation applications.

Polyamorphs are often observed in amorphous matters, and a representative example is the reentrant glass transition in colloid systems. For metallic amorphous alloys, however, the cases reported so far are limited to metallic glasses (MGs) that undergo electronic transitions under gigapascal applied pressure, or the presence of two liquids at the same composition. Here we report the first observation of a reentrant glass transition in MGs. This unusual reentrant glass transition transforms an MG from its as-quenched state (Glass I) to an ultrastable state (Glass II), mediated by the supercooled liquid of Glass I. Specifically, upon heating to above its glass transition temperature under ambient pressure, Glass I first transitions into its supercooled liquid, which then transforms into a new Glass II, accompanied by an exothermic peak in calorimetric scan, together with a precipitous drop in volume, electrical resistance and specific heat, as well as clear evidence of local structural ordering on the short-to-medium-range scale revealed via in-situ synchrotron X-ray scattering. Atomistic simulations indicate enhanced ordering of locally favored motifs to establish correlations in the medium range that resemble those in equilibrium crystalline compounds. The resulting lower-energy Glass II has its own glass transition temperature higher than that of Glass I by as much as 50 degrees. This route thus delivers a thermodynamically and kinetically ultrastable MG that can be easily retained to ambient conditions.

Superelasticity associated with the martensitic transformation has found a broad range of engineering applications1,2. However, the intrinsic hysteresis3 and temperature sensitivity4 of the first-order phase transformation significantly hinder the usage of smart metallic components in many critical areas. Here, we report a large superelasticity up to 15.2% strain in [001]-oriented NiCoFeGa single crystals, exhibiting non-hysteretic mechanical responses, a small temperature dependence and high-energy-storage capability and cyclic stability over a wide temperature and composition range. In situ synchrotron X-ray diffraction measurements show that the superelasticity is correlated with a stress-induced continuous variation of lattice parameter accompanied by structural fluctuation. Neutron diffraction and electron microscopy observations reveal an unprecedented microstructure consisting of atomic-level entanglement of ordered and disordered crystal structures, which can be manipulated to tune the superelasticity. The discovery of the large elasticity related to the entangled structure paves the way for exploiting elastic strain engineering and development of related functional materials. NiCoFeGa single crystals exhibit large non-hysteretic superelasticity over broad temperature and composition ranges. It is attributed to the continuous phase transition with applied stress, which is related to the fluctuation of entangled ordered and disordered crystal structures.

Laser shock peening (LSP) is a mechanical surface treatment which can induce large compressive residual stresses and microstructural changes in a material by using repetitive shocks from laser pulses. In this work, the surface integrity (surface microstructure, topography, hardness and residual stress) of a LSP-treated powder metallurgy Ni-based superalloy was investigated for the first time. LSP treatment introduced large plastic deformation especially at a depth of about 100 μm from the surface, which increased the local hardness. The residual stress from the surface to the interior of the sample was investigated by synchrotron x-ray diffraction. The maximum compressive stress reached 400 MPa at the surface, while the depth of the compressive stress is about 0.7 mm. Lastly, the oxidation behavior of the treated and untreated samples was evaluated by thermal exposure at 700°C for 312 h. The LSP treatment decreased the thickness of the oxide layer, thereby showing improved oxidation resistance.

Antiferroelectrics (AFEs) have a great potential for modern electronic devices by virtue of the large strain during the antiferroelectric-to-ferroelectric (AFE-FE) phase transition under external electric fields. Although the fascinating macroscopic properties of AFE materials have been extensively studied, it is still unclear how the underlying structure evolution engenders their defining properties. Here we employ an electric biasing in-situ high-energy synchrotron X-ray diffraction technique to reveal the phase, domain texture, and lattice evolution in a high performance PbZrO3-based AFE material. During the reversible AFE-FE transition triggered by electric fields, the evolution of the superstructure for AFE pseudo-tetragonal and FE rhombohedral phase is found to display strong dependence on the angle with respect to the field direction. In contrast to previous prediction, it is found that there is no obvious domain reorientation in the AFE phase, when the system is far away from the AFE-FE transitions. The electric-field-induced FE rhombohedral phase exhibits an unusual microscopic behavior, distinguished from the normal one, presenting small changes in domain texture and lattice strain with electric field, and leading to a small piezoelectric response. The longitudinal, transverse, and volume strains estimated from the XRD peak profiles are well consistent with the macroscopic strain measurements. It is demonstrated that the large strain arises from the structural change associated with anisotropic lattice strain and highly preferential domain reorientation during the AFE-FE transitions. The AFE-FE switching sequence is constructed based on the present study, which provides a further understating of AFE materials.

To understand the effect of selenium doping on the good cycling performance and rate capability of a Ge0.9Se0.1 electrode, the dynamic morphological and phase changes of the Ge0.9Se0.1 electrode were investigated by synchrotron-based operando transmission X-ray microscopy (TXM) imaging, X-ray diffraction (XRD), and X-ray absorption spectroscopy (XAS). The TXM results show that the Ge0.9Se0.1 particle retains its original shape after a large volume change induced by (de)lithiation and undergoes a more sudden morphological and optical density change than pure Ge. The difference between Ge0.9Se0.1 and Ge is attributed to a super-ionically conductive Li–Se–Ge network formed inside Ge0.9Se0.1 particles, which contributes to fast Li-ion pathways into the particle and nano-structuring of Ge as well as buffering the volume change of Ge. The XRD and XAS results confirm the formation of a Li–Se–Ge network and reveal that the Li–Se–Ge phase forms during the early stages of lithiation and is an inactive phase. The Li–Se–Ge network also can suppress the formation of the crystalline Li15Ge4 phase. These in situ and operando results reveal the effect of the in situ formed, super-ionically conductive, and inactive network on the cycling performance of Li-ion batteries and shed light on the design of high capacity electrode materials.

Nanoscale oxide-based negative electrodes are of great interest for lithium ion batteries due to their high energy density, power density and enhanced safety. In this work, we conducted a case study on mesoporous TiO2 nanoparticle negative electrodes with uniform size and varying crystallinity in order to investigate the trend in the electrochemical properties of oxide-based nanoscale negative electrodes with varying crystallinity. Mesoporous solid spherical TiO2 nanoparticles with a uniform particle size and varying crystallinity, i.e., amorphous TiO2 (A-TiO2), partially crystalline TiO2 (PC-TiO2) and fully crystalline TiO2 (FC-TiO2) nanoparticles were studied. At low current rate (quasi steady-state), the specific capacity of the samples drops with the decrease of crystallinity. Ex situ synchrotron pair distribution function analysis reveals that the 1D zigzag Li ion diffusion pathway becomes expanded with the increase of crystallinity, which promotes ion mobility and charge storage. At high current rates (away from equilibrium states), however, the A-TiO2 sample demonstrates slightly larger capacity than the FC-TiO2 sample, both of which show larger capacities than that of the PC-TiO2 sample. Both A-TiO2 and FC-TiO2 samples exhibit higher capacitive contribution to the charge storage and larger Li+ diffusivity than those of the PC-TiO2 sample, which explains their better rate capability. Moreover, the larger Li+ diffusivity of the A-TiO2 sample leads to the slightly larger specific capacity than the FC-TiO2 sample at the highest current rate.

The configuration of electric or magnetic dipoles embedded into a crystal lattice gives rise to the defining physical properties of a functional material. The prevailing antiferroelectric materials have so far been allusively assumed to be in a strict antiparallel electric polarization configuration, although they have shown huge potential applications for use in electronic devices. Herein, we have revealed for the first time the complex crystal structure of an intermediate state between the two conventional antiferroelectric (AFE) and ferroelectric (FE) states in PbZrO3-based perovskites by employing a combination of advanced synchrotron X-ray, neutron and three-dimensional (3D) electron diffraction techniques. We found that the intermediate state displays an intriguing flexible configuration of a sinusoidal wave functional with imbalanced polarization, different to the commonly believed antiparallel and balanced polarization. Such an intermediate state was concluded to act as a bridge between the conventional AFE and FE states. Our observations offer new insight into the AFE state and its transformation into the FE state. Such an intermediate state with a unique polarization configuration is believed to be a common feature that occurs in high-performance AFE perovskite materials.

Strain glass is a frozen disordered strain state with local strain order manifested by nano-sized strain domains, which is formed as a result of doping sufficient point defects into the normal martensitic system. Exploration of the transition between strain glass and long-range strain-ordered martensite is of both great fundamental importance and practical interest. However, it remains a mystery whether magnetic field can induce a transition from strain glass to martensite. Here, we report for the first time the magnetic-field-induced strain-glass-to-martensite transition, in a model system Fe-Mn-Ga. It was found that the martensitic transformation temperature of the Fe43-xMn28Ga29+x alloys decreases rapidly with increasing x and the martensitic transformation disappears when x reaches the critical value xc = 2.0. Strain glass transition occurs in the alloy with x = 2.0 (Fe41Mn28Ga31), which is confirmed by the invariance of the average structure during cooling, the frequency dispersion of the ac storage modulus and internal friction following the Vogel–Fulcher relation, and the formation of nanodomains. The magnetic-field-induced transition from strain glass to non-modulated tetragonal martensite in Fe41Mn28Ga31 was indicated by the abrupt magnetization jump on the M(H) curve and directly evidenced by the crystal structure evolution with magnetic field change revealed by in-situ neutron diffraction experiments. The microscopic mechanism for this magnetic-field-induced strain-glass-to-martensite transition is discussed. The present study may not only help establish the unified theory for strain-glass-to-martensite transition under external fields but also open a new avenue for designing advanced materials with novel functional properties.

We observed exotic hysteresis behavior in the ferrimagnetic transition of a Laves compound TbCo2. While positive thermal hysteresis was observed in zero-field calorimetric measurements, inverse thermal hysteresis was observed in thermomagnetic measurements as a rare phenomenon. These observations confirmed a first order of the ferrimagnetic transition and revealed a lowering of this order by an external magnetic field. Elastic measurements and high-resolution synchrotron X-ray diffraction measurements suggested that the rare inverse thermal hysteresis can be related to microscopic lattice strains. Those strains are induced by a spontaneous magnetoelastic coupling and are modified by the external magnetic field.

Organic cathode materials are promising for developing high-energy and high-power Li-ion batteries (LIBs). However, the energy storage of most organic cathodes relies on the electron transfer of a ...

Heusler-type ferromagnetic shape memory alloys possess attractive multifunctional properties, including magnetic field induced shape memory effect, magnetoresistance and magnetocaloric effect, owing to the unique concurrent magnetic and martensitic transformations. However, these intermetallics generally exhibit intrinsic high brittleness and low strength, which severely impede their workability for processing and applicability in real use. In this study, we demonstrate a new grain refining strategy by means of eutectic solidification to improve the mechanical properties in Ni–Mn–Sn–Fe alloys. In a fully eutectic microstructure, the average γ lamellae thickness was refined to ∼170 nm and the composite showed a compressive strength of 1950 MPa, ductility of 19.5%, Young's Modulus of 38 GPa, pseudoelasticity of 3.2% and high mechanical cyclic stability. The high mechanical performance is attributed to the effect of departmentalisation of the brittle Heusler alloy by the densely distributed γ phase fine lamellae in resisting crack propagation. The eutectic Heusler composite exhibited a metamagnetic phase transformation, with a magnetic entropy change of 10.2 J/kg·K and a refrigeration capacity of 181 J/kg in a field change of 5 T.

The temperature effect on the mechanical behavior of the HfNbTaTiZr high entropy alloy (HEA) was investigated at 77–673 K. The decrease of the yield strength with increasing the temperature was mechanistically analyzed by considering contributions from various strengthening mechanisms. An anomalous dependence of strain hardening on temperature was observed and was justified to be caused by dynamic strain aging (DSA) as an extra strengthening mechanism at elevated temperatures. A model was constructed to split the overall strain hardening into forest hardening and DSA hardening, both of which were theoretically quantified at all temperatures considered.

Piezoelectric materials, which mechanically respond to electrical stimulation and vice versa, typically exhibit high piezoelectricity at a morphotropic phase boundary (MPB). A thorough structural description is essential for understanding the origin of excellent piezoelectric properties. Herein, a comparative study of electric-field-driven structure and phase evolution has been conducted on MPB and non-MPB tetragonal composition in high performance system of PbTiO3–Bi(Ni1/2Hf1/2)O3 piezoceramics using in situ high-energy synchrotron X-ray diffraction. The results show that the MPB composition exhibits electric-field-driven reversible tetragonal-to-monoclinic transformation, whereas non-MPB composition does not. Direct evidence shows that the extensive phase transformation triggers multiple contributions to enhancing piezoelectric performance. Namely, it not only enables the unit cell parameters of coexisting phases easily change with an external electric field, but also enhances the domain switching and lattice strain. These results offer a unique perspective on MPB associated piezoelectricity enhancement, and will be helpful for developing high performance piezoelectric materials.

Architected metallic materials generally suffer from a serious engineering problem of mechanical instability manifested as the emergence of localized deformation bands and collapse of strength. They usually cannot exhibit satisfactory shape recoverability due to the little recoverable strain of metallic constituent material. After yielding, the metallic constituent material usually exhibits a continuous low strain-hardening capacity, giving the local yielded regions of architecture low load resistance and easily developing into excessive deformation bands, accompanied by the collapse of strength. Here, a novel constituent material deformation design strategy has been skillfully proposed, where the low load resistance of yielded regions of the architecture can be effectively compensated by the significant self-strengthening behavior of constituent material, thus avoiding the formation of localized deformation bands and collapse of strength. To substantiate this strategy, shape-memory alloys (SMAs) are considered as suitable constituent materials for possessing both self-strengthening behavior and shape-recovery function. A 3D-printing technique was adopted to prepare various NiTi SMA architected materials with different geometric structures. It is demonstrated that all of these architected metallic materials can be stably and uniformly compressed by up to 80% without the formation of localized bands, collapse of strength, and structural failure, exhibiting ultrahigh damage tolerance. Furthermore, these SMA architected materials can display more than 98% shape recovery even after 80% deformation and excellent cycle stability during 15 cycles. This work exploits the amazing impact of constituent materials on constructing supernormal properties of architected materials and will open new avenues for developing high-performance architected metallic materials.

TiNi-based shape-memory alloys are known to exhibit a strain glass state under certain conditions, generally in the presence of high-density defects such as excess solute atoms or alloying elements, dislocations, and nanoprecipitates. In this paper, we report a strain glass transition in a nanocrystalline ${\mathrm{Ti}}_{50}{\mathrm{Ni}}_{35}{\mathrm{Pt}}_{15}$ alloy. The nanocrystalline strain glass state is achieved by a combined effect of high-density grain boundaries and high concentration doping of Pt atoms in the B2 matrix. The nanocrystalline ${\mathrm{Ti}}_{50}{\mathrm{Ni}}_{35}{\mathrm{Pt}}_{15}$ strain glass alloy showed a large near-complete progressive superelasticity with a recovery strain of about 6% and a low apparent Young's modulus of about 30 GPa in a wide temperature range of over 200 \ifmmode^\circ\else\textdegree\fi{}C. In situ synchrotron x-ray diffraction measurement showed that the strain glass B2 [B2(SG)] phase experienced B2(SG)\ensuremath{\rightarrow}R\ensuremath{\rightarrow}B19 transformation upon loading and B19\ensuremath{\rightarrow}B2(SG) upon unloading. The findings of this study provide insight for the development of nanocrystalline strain glass shape-memory alloys.

Developing affordable and light high-temperature materials alternative to Ni-base superalloys has significantly increased the efforts in designing advanced ferritic superalloys. However, currently developed ferritic superalloys still exhibit low high-temperature strengths, which limits their usage. Here we use a CALPHAD-based high-throughput computational method to design light, strong, and low-cost high-entropy alloys for elevated-temperature applications. Through the high-throughput screening, precipitation-strengthened lightweight high-entropy alloys are discovered from thousands of initial compositions, which exhibit enhanced strengths compared to other counterparts at room and elevated temperatures. The experimental and theoretical understanding of both successful and failed cases in their strengthening mechanisms and order-disorder transitions further improves the accuracy of the thermodynamic database of the discovered alloy system. This study shows that integrating high-throughput screening, multiscale modeling, and experimental validation proves to be efficient and useful in accelerating the discovery of advanced precipitation-strengthened structural materials tuned by the high-entropy alloy concept., Advanced screening strategies for the design of high-entropy alloys are highly desirable. Here the authors use the project-oriented design strategy and CALPHAD-based high-throughput calculation tool to rapidly screen promising Al-Cr-Fe-Mn-Ti structural HEAs for high-temperature applications.

Zinc-blende CdS nanoplatelets with atomically flat and very large {100} basal planes terminated solely by one type of element (either Cd or S atoms) are synthesized. Optical spectroscopy, X-ray diffraction, X-ray absorption, and transmission electron microscopy confirm that the surface structures of newly developed S-terminated CdS nanoplatelets are at least as well-defined as the original Cd-terminated nanoplatelets. Band gaps of the nanoplatelets are found to depend on not only the quantum-confined dimension (thickness) but also the nature of the surface termination. The facet structure dictates the packing of the ligands (carboxylate for Cd-terminated nanoplatelets and alkyl for S-terminated nanoplatelets), which causes a difference in the lattice strain and significantly affects the optical spectral width. Experimental and theoretical results reveal that engineering the exciton spatial distribution by the tailored synthesis of semiconductor nanocrystals with a precisely controlled surface structure is fully possible, which should open a new door for delivering the long-promised potential of semiconductor nanocrystals.