Negative enthalpy alloys and local chemical ordering: a concept and route leading to synergy of strength and ductility.

Solid solutions are ubiquitous in metals and alloys. Local chemical ordering (LCO) is a fundamental sub-nano/nanoscale process that occurs in many solid solutions and can be used as a microstructure to optimize strength and ductility. However, the formation of LCO has not been fully elucidated, let alone how to provide efficient routes for designing LCO to achieve synergistic effects on both superb strength and ductility. Herein, we propose the formation and control of LCO in negative enthalpy alloys. With engineering negative enthalpy in solid solutions, genetic LCO components are formed in negative enthalpy refractory high-entropy alloys (RHEAs). In contrast to conventional 'trial-and-error' approaches, the control of LCO by using engineering negative enthalpy in RHEAs is instructive and results in superior strength (1160 MPa) and uniform ductility (24.5%) under tension at ambient temperature, which are among the best reported so far. LCO can promote dislocation cross-slip, enhancing the interaction between dislocations and their accumulation at large tensile strains; sustainable strain hardening can thereby be attained to ensure high ductility of the alloy. This work paves the way for new research fields on negative enthalpy solid solutions and alloys for the synergy of strength and ductility as well as new functions.

Negative mixing enthalpy solid solutions deliver high strength and ductility.

Body-centred cubic refractory multi-principal element alloys (MPEAs), with several refractory metal elements as constituents and featuring a yield strength greater than one gigapascal, are promising materials to meet the demands of aggressive structural applications1-6. Their low-to-no tensile ductility at room temperature, however, limits their processability and scaled-up application7-10. Here we present a HfNbTiVAl10 alloy that shows remarkable tensile ductility (roughly 20%) and ultrahigh yield strength (roughly 1,390 megapascals). Notably, these are among the best synergies compared with other related alloys. Such superb synergies derive from the addition of aluminium to the HfNbTiV alloy, resulting in a negative mixing enthalpy solid solution, which promotes strength and favours the formation of hierarchical chemical fluctuations (HCFs). The HCFs span many length scales, ranging from submicrometre to atomic scale, and create a high density of diffusive boundaries that act as effective barriers for dislocation motion. Consequently, versatile dislocation configurations are sequentially stimulated, enabling the alloy to accommodate plastic deformation while fostering substantial interactions that give rise to two unusual strain-hardening rate upturns. Thus, plastic instability is significantly delayed, which expands the plastic regime as ultralarge tensile ductility. This study provides valuable insights into achieving a synergistic combination of ultrahigh strength and large tensile ductility in MPEAs.

Ultrahigh Permeability at High Frequencies via A Magnetic-Heterogeneous Nanocrystallization Mechanism in an Iron-Based Amorphous Alloy.

The prevalence of wide-bandgap (WBG) semiconductors allows modern electronic devices to operate at much higher frequencies. However, development of soft magnetic materials with high-frequency properties matching the WBG-based devices remains challenging. Here, a promising nanocrystalline-amorphous composite alloy with a normal composition Fe75.5 Co0.5 Mo0.5 Cu1 Nb1.5 Si13 B8 in atomic percent is reported, which is producible under industrial conditions, and which shows an exceptionally high permeability at high frequencies up to 36 000 at 100 kHz, an increase of 44% compared with commercial FeSiBCuNb nanocrystalline alloy (25 000 ± 2000 at 100 kHz), outperforming all existing nanocrystalline alloy systems and commercial soft magnetic materials. The alloy is obtained by a unique magnetic-heterogeneous nanocrystallization mechanism in an iron-based amorphous alloy, which is different from the traditional strategy of nanocrystallization by doping nonmagnetic elements (e.g., Cu and Nb). The induced magnetic inhomogeneity by adding Co atoms locally promotes the formation of highly ordered structures acting as the nuclei of nanocrystals, and Mo atoms agglomerate around the interfaces of the nanocrystals, inhibiting nanocrystal growth, resulting in an ultrafine nanocrystalline-amorphous dual-phase structure in the alloy. The exceptional soft magnetic properties are shown to be closely related to the low magnetic anisotropy and the unique spin rotation mechanism under alternating magnetic fields.

Machine Learning Customized Novel Material for Energy-Efficient 4D Printing.

Existing commercial powders for laser additive manufacturing (LAM) are designed for traditional manufacturing methods requiring post heat treatments (PHT). LAM's unique cyclic thermal history induces intrinsic heat treatment (IHT) on materials during deposition, which offers an opportunity to develop LAM-customized new materials. This work customized a novel Fe-Ni-Ti-Al maraging steel assisted by machine learning to leverage the IHT effect for in situ forming massive precipitates during LAM without PHT. Fast precipitation kinetics in steel, tailored intermittent deposition strategy, and the IHT effect facilitate the in situ Ni3 Ti precipitation in the martensitic matrix via heterogeneous nucleation on high-density dislocations. The as-built steel achieves a tensile strength of 1538 MPa and a uniform elongation of 8.1%, which is superior to a wide range of as-LAM-processed high-strength steel. In the current mainstream ex situ 4D printing, the time-dependent evolutions (i.e., property or functionality changes) of a 3D printed structure occur after part formation. This work highlights in situ 4D printing via the synchronous integration of time-dependent precipitation hardening with 3D geometry shaping, which shows high energy efficiency and sustainability. The findings provide insight into developing LAM-customized materials by understanding and utilizing the IHT-materials interaction.

Creating two-dimensional solid helium via diamond lattice confinement.

The universe abounds with solid helium in polymorphic forms. Therefore, exploring the allotropes of helium remains vital to our understanding of nature. However, it is challenging to produce, observe and utilize solid helium on the earth because high-pressure techniques are required to solidify helium. Here we report the discovery of room-temperature two-dimensional solid helium through the diamond lattice confinement effect. Controllable ion implantation enables the self-assembly of monolayer helium atoms between {100} diamond lattice planes. Using state-of-the-art integrated differential phase contrast microscopy, we decipher the buckled tetragonal arrangement of solid helium monolayers with an anisotropic nature compressed by the robust diamond lattice. These distinctive helium monolayers, in turn, produce substantial compressive strains to the surrounded diamond lattice, resulting in a large-scale bandgap narrowing up to ~2.2 electron volts. This approach opens up new avenues for steerable manipulation of solid helium for achieving intrinsic strain doping with profound applications.

Metal-carbide eutectics with multiprincipal elements make superrefractory alloys.

Materials with excellent high-temperature strength are now sought for applications in hypersonics, fusion reactors, and aerospace technologies. Conventional alloys and eutectic multiprincipal-element alloys (MPEAs) exhibit insufficient strengths at high temperatures due to low melting points and microstructural instabilities. Here, we report a strategy to achieve exceptional high-temperature microstructural stability and strength by introducing eutectic carbide in a refractory MPEA. The synergistic strengthening effects from the multiprincipal-element mixing and strong dislocation blocking at the interwoven metal-carbide interface make the eutectic MPEA not only have outstanding high-temperature strength (>2 GPa at 1473 K) but also alleviate the room-temperature brittleness through microcrack tip blunting by layered metallic phase. This strategy offers a paradigm for the design of the next-generation high-temperature materials to bypass the low-melting point limitation of eutectic alloys and diffusion-dominated softening in conventional superalloys.

Spinodal-modulated solid solution delivers a strong and ductile refractory high-entropy alloy.

Body-centered-cubic (BCC) refractory high-entropy alloys (RHEAs) are being actively pursued due to their potential to outperform existing superalloys at elevated temperatures. One bottleneck problem, however, is that these RHEAs lack tensile ductility and, hence, processability at room temperature. The strategy previously invoked to sustain ductility in high-strength HEAs is to manage dislocation movements via incorporating dispersed obstacles; this, however, may also have embrittlement ramifications. Here, a new strategy is demonstrated to achieve ductile BCC HfNbTiV, via decomposing the BCC arrangement (ß phase) into a ß(BCC1) + ß*(BCC2) arrangement via spinodal decomposition, producing chemical composition modulations and, more importantly, elastic strain on a length scale of a few tens of nanometers. The periodically spaced ß*, with large lattice distortion, is particularly potent in heightening the ruggedness of the terrain for the passage of dislocations. This makes the motion of dislocations sluggish, causing a traffic jam and cross-slip, facilitating dislocation interactions, multiplication, and accumulation. Wavy dislocations form walls that entangle with slip bands, promoting strain hardening and delocalizing plastic strain. A simultaneous combination of high yield strength (1.1 GPa) and tensile strain to failure (28%) is achieved; these values are among the best reported so far for refractory high-entropy alloys.

Nanoprecipitate-Strengthened High-Entropy Alloys.

Multicomponent high-entropy alloys (HEAs) can be tuned to a simple phase with some unique alloy characteristics. HEAs with body-centered-cubic (BCC) or hexagonal-close-packed (HCP) structures are proven to possess high strength and hardness but low ductility. The faced-centered-cubic (FCC) HEAs present considerable ductility, excellent corrosion and radiation resistance. However, their strengths are relatively low. Therefore, the strategy of strengthening the ductile FCC matrix phase is usually adopted to design HEAs with excellent performance. Among various strengthening methods, precipitation strengthening plays a dazzling role since the characteristics of multiple principal elements and slow diffusion effect of elements in HEAs provide a chance to form fine and stable nanoscale precipitates, pushing the strengths of the alloys to new high levels. This paper summarizes and review the recent progress in nanoprecipitate-strengthened HEAs and their strengthening mechanisms. The alloy-design strategies and control of the nanoscale precipitates in HEAs are highlighted. The future works on the related aspects are outlined.

In situ design of advanced titanium alloy with concentration modulations by additive manufacturing.

Additive manufacturing is a revolutionary technology that offers a different pathway for material processing and design. However, innovations in either new materials or new processing technologies can seldom be successful without a synergistic combination. We demonstrate an in situ design approach to make alloys spatially modulated in concentration by using laser-powder bed fusion. We show that the partial homogenization of two dissimilar alloy melts­Ti-6Al-4V and a small amount of 316L stainless steel­allows us to produce micrometer-scale concentration modulations of the elements that are contained in 316L in the Ti-6Al-4V matrix. The corresponding phase stability modulation creates a fine scale­modulated ß + α' dual-phase microstructure that exhibits a progressive transformation-induced plasticity effect, which leads to a high tensile strength of ~1.3 gigapascals with a uniform elongation of ~9% and an excellent work-hardening capacity of >300 megapascals. This approach creates a pathway for concentration-modulated heterogeneous alloy design for structural and functional applications.

A medium-range structure motif linking amorphous and crystalline states.

Amorphous materials have no long-range order, but there are ordered structures at short range (2-5 Å), medium range (5-20 Å) 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 Å. 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.

Self-Assembled Hydrophobic/Hydrophilic Porphyrin-Ti3C2Tx MXene Janus Membrane for Dual-Functional Enabled Photothermal Desalination.

Photothermal desalination is a promising approach for seawater purification by harvesting solar energy. Titanium carbide (Ti3C2Tx MXene) membranes have been regarded as potential materials for photothermal desalination by virtue of their excellent light-to-heat conversion. However, achieving a well-balanced synergy between high evaporation rate and good salt resistance remains a significant challenge due to their limited solar absorption and inferior stability. Herein, we report a self-assembled flexible porphyrin-Ti3C2Tx MXene Janus membrane (Janus PMX membrane) for dual-functional enabled photothermal desalination. The self-assembly of porphyrin on MXene not only effectively creates a favorable hydrophobic surface but also simultaneously enables efficient solar utilization. The significant interactions and charge redistribution between MXene and porphyrin lead to a stable hydrophobic/hydrophilic Janus structure with synergistically enhanced photothermal conversion. As a result, the Janus PMX membrane demonstrates highly efficient water pumping, heat localization, vapor generation, and salt resistance during photothermal desalination. This work presents an effective and facile strategy toward advancing a well-performing MXene membrane for efficient seawater desalination.

Stacking Fault Driven Phase Transformation in CrCoNi Medium Entropy Alloy.

Phase transformation is an effective means to increase the ductility of a material. However, even for a commonly observed face-centered-cubic to hexagonal-close-packed (fcc-to-hcp) phase transformation, the underlying mechanisms are far from being settled. In fact, different transformation pathways have been proposed, especially with regard to nucleation of the hcp phase at the nanoscale. In CrCoNi, a so-called medium-entropy alloy, an fcc-to-hcp phase transformation has long been anticipated. Here, we report an in situ loading study with neutron diffraction, which revealed a bulk fcc-to-hcp phase transformation in CrCoNi at 15 K under tensile loading. By correlating deformation characteristics of the fcc phase with the development of the hcp phase, it is shown that the nucleation of the hcp phase was triggered by intrinsic stacking faults. The confirmation of a bulk phase transformation adds to the myriads of deformation mechanisms available in CrCoNi, which together underpin the unusually large ductility at low temperatures.

Ultrahigh strength and ductility in newly developed materials with coherent nanolamellar architectures.

Nano-lamellar materials with ultrahigh strengths and unusual physical properties are of technological importance for structural applications. However, these materials generally suffer from low tensile ductility, which severely limits their practical utility. Here we show that markedly enhanced tensile ductility can be achieved in coherent nano-lamellar alloys, which exhibit an unprecedented combination of over 2 GPa yield strength and 16% uniform tensile ductility. The ultrahigh strength originates mainly from the lamellar boundary strengthening, whereas the large ductility correlates to a progressive work-hardening mechanism regulated by the unique nano-lamellar architecture. The coherent lamellar boundaries facilitate the dislocation transmission, which eliminates the stress concentrations at the boundaries. Meanwhile, deformation-induced hierarchical stacking-fault networks and associated high-density Lomer-Cottrell locks enhance the work hardening response, leading to unusually large tensile ductilities. The coherent nano-lamellar strategy can potentially be applied to many other alloys and open new avenues for designing ultrastrong yet ductile materials for technological applications.

A Novel Multinary Intermetallic as an Active Electrocatalyst for Hydrogen Evolution.

Electrochemical water splitting offers an attractive approach for hydrogen production. However, the lack of high-performance cost-effective electrocatalyst severely hinders its applications. Here, a multinary high-entropy intermetallic (HEI) that possesses an unusual periodically ordered structure containing multiple non-noble elements is reported, which can serve as a highly efficient electrocatalyst for hydrogen evolution. This HEI exhibits excellent activities in alkalinity with an overpotential of 88.2 mV at a current density of 10 mA cm-2 and a Tafel slope of 40.1 mV dec-1 , which are comparable to those of noble catalysts. Theoretical calculations reveal that the chemical complexity and surprising atomic configurations provide a strong synergistic function to alter the electronic structure. Furthermore, the unique L12 -type ordered structure enables a specific site-isolation effect to further stabilize the H2 O/H* adsorption/desorption, which dramatically optimizes the energy barrier of hydrogen evolution. Such an HEI strategy uncovers a new paradigm to develop novel electrocatalyst with superior reaction activities.

Hierarchical nanostructured aluminum alloy with ultrahigh strength and large plasticity.

High strength and high ductility are often mutually exclusive properties for structural metallic materials. This is particularly important for aluminum (Al)-based alloys which are widely commercially employed. Here, we introduce a hierarchical nanostructured Al alloy with a structure of Al nanograins surrounded by nano-sized metallic glass (MG) shells. It achieves an ultrahigh yield strength of 1.2 GPa in tension (1.7 GPa in compression) along with 15% plasticity in tension (over 70% in compression). The nano-sized MG phase facilitates such ultrahigh strength by impeding dislocation gliding from one nanograin to another, while continuous generation-movement-annihilation of dislocations in the Al nanograins and the flow behavior of the nano-sized MG phase result in increased plasticity. This plastic deformation mechanism is also an efficient way to decrease grain size to sub-10 nm size for low melting temperature metals like Al, making this structural design one solution to the strength-plasticity trade-off.

Innovative approach to the design of low-cost Zr-based BMG composites with good glass formation.

The high manufacturing cost for metallic glasses hampers actual commercial applications of this class of fascinating materials. In this letter, the effect of oxygen impurity on the glass forming ability and tensile properties of Zr-BMG composites were studied. Our results have demonstrated that oxygen was absorbed and concentrated only in the precipitated ß-Zr phase, leading that the remainder molten metal retains good glass forming ability. The high oxygen concentration in the ß-Zr phase induces a significant solid-solution strengthening effect, this resulting in an enhanced strength of the BMG composites without sacrificing their overall ductility. Based on this alloying strategy, we have successfully developed the low-cost Zr-based BMG composites with excellent tensile properties and good glass forming ability, using the low grade industrial raw materials processed under industrial vacuum systems. This finding is expected to greatly cut down the manufacturing cost and greatly promote the commercial applications of the BMG composites.

A nanoscale co-precipitation approach for property enhancement of Fe-base alloys.

Precipitate size and number density are two key factors for tailoring the mechanical behavior of nanoscale precipitate-hardened alloys. However, during thermal aging, the precipitate size and number density change, leading to either poor strength or high strength but significantly reduced ductility. Here we demonstrate, by producing nanoscale co-precipitates in composition-optimized multicomponent precipitation-hardened alloys, a unique approach to improve the stability of the alloy against thermal aging and hence the mechanical properties. Our study provides compelling experimental evidence that these nanoscale co-precipitates consist of a Cu-enriched bcc core partially encased by a B2-ordered Ni(Mn, Al) phase. This co-precipitate provides a more complex obstacle for dislocation movement due to atomic ordering together with interphases, resulting in a high yield strength alloy without sacrificing alloy ductility.