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.

In Situ Atomic-Scale Quantitative Evidence of Plastic Activities Resulting in Reparable Deformation in Ultrasmall-Sized Ag Nanocrystals.

Permanent structural changes in pure metals that are caused by plastic activity are normally irreparable after unloading. Because of the lack of experimental evidence, it is unclear whether the plastic activity can be repaired as the size of the pure metals decreases to several nanometers; it is also unclear how the metals accommodate the plastic deformation. In this study, the in situ atomic-scale loading and unloading of ∼2 nm Ag nanocrystals was investigated, and three modes of plastic deformation were observed: (i) the phase transition from the face-centered cubic (fcc) phase to the hexagonal close-packed (hcp) phase, (ii) stacking faults, and (iii) deformation twin nucleation. We show that all three modes resulted in structural changes that were reparable, and their generation and restoration during loading and unloading were observed in situ. We discovered that the deformation modes of nanosized metals can be predicted from the ratio of the energy barriers of the fcc-hcp phase transition (ΔγH) and the deformation twin nucleation (ΔγT), which differ from those of the theoretical modes of relatively large-sized metals. The proposed ΔγH/ΔγT criterion provides insights into the deformation mechanism of nanometals.

Nanoscale ductile fracture and associated atomistic mechanisms in a body-centered cubic refractory metal.

Understanding the competing modes of brittle versus ductile fracture is critical for preventing the failure of body-centered cubic (BCC) refractory metals. Despite decades of intensive investigations, the nanoscale fracture processes and associated atomistic mechanisms in BCC metals remain elusive due to insufficient atomic-scale experimental evidence. Here, we perform in situ atomic-resolution observations of nanoscale fracture in single crystals of BCC Mo. The crack growth process involves the nucleation, motion, and interaction of dislocations on multiple 1/2 < 111 > {110} slip systems at the crack tip. These dislocation activities give rise to an alternating sequence of crack-tip plastic shearing, resulting in crack blunting, and local separation normal to the crack plane, leading to crack extension and sharpening. Atomistic simulations reveal the effects of temperature and strain rate on these alternating processes of crack growth, providing insights into the dislocation-mediated mechanisms of the ductile to brittle transition in BCC refractory metals.

Liquid-phase scanning electron microscopy for single membrane protein imaging.

Liquid-phase electron microscopy is highly desirable for observing biological samples in their native liquid state at high resolution. We developed liquid imaging approaches for biological cells using scanning electron microscopy. Novel approaches included scanning transmission electron imaging using a liquid-cell apparatus (LC-STEM), as well as correlative cathodoluminescence and electron microscopy (CCLEM) imaging. LC-STEM enabled imaging at a ∼2 nm resolution and excellent contrast for the precise recognition of localization, distribution, and configuration of individually labeled membrane proteins on the native cells in solution. CCLEM improved the resolution of fluorescent images down to 10 nm. Liquid SEM technologies will bring unique and wide applications to the study of the structure and function of cells and membrane proteins in their near-native states at the monomolecular level.

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.

Timely and atomic-resolved high-temperature mechanical investigation of ductile fracture and atomistic mechanisms of tungsten.

Revealing the atomistic mechanisms for the high-temperature mechanical behavior of materials is important for optimizing their properties for service at high-temperatures and their thermomechanical processing. However, due to materials microstructure's dynamic recovery and the absence of available in situ techniques, the high-temperature deformation behavior and atomistic mechanisms of materials are difficult to evaluate. Here, we report the development of a microelectromechanical systems-based thermomechanical testing apparatus that enables mechanical testing at temperatures reaching 1556 K inside a transmission electron microscope for in situ investigation with atomic-resolution. With this unique technique, we first uncovered that tungsten fractures at 973 K in a ductile manner via a strain-induced multi-step body-centered cubic (BCC)-to-face-centered cubic (FCC) transformation and dislocation activities within the strain-induced FCC phase. Both events reduce the stress concentration at the crack tip and retard crack propagation. Our research provides an approach for timely and atomic-resolved high-temperature mechanical investigation of materials at high-temperatures.

Single Tungsten Atom-Modified Cotton Fabrics for Visible-Light-Driven Photocatalytic Degradation and Antibacterial Activity.

Various single-atom materials exhibit distinguished performances in catalysis and biology. To boost their applications, single-atom-based strategies are highly demanded to exhibit repeatable functions on advanced wearable substrates. However, single-atom approaches are rarely reported to anchor on wearable materials, i.e., widely applied cotton fabrics. Here, we developed a simple method of loading uniformly dispersed single tungsten atoms on cotton via ordinary direct-dye processing to exhibit superior sustainable functions. The single sites of tungsten atom centers are constructed by binding oxygen-coordinated single tungsten atom on the cotton fabric surface via -COOH groups. Consequently, the band gap of single sites decreases significantly to 2.75 from 3.03 eV. Therefore, the single-site-modified cotton exhibits excellent visible-light-driven (>420 nm) photocatalytic degradation efficiency of organic dyes, which exceeds other reported cotton-based materials by nearly two orders of magnitude. Furthermore, the single-site-modified cotton also exhibits great antibacterial performance due to reactive oxygen species. Moreover, the cotton with anchored single sites possesses great washing-resistance ability during 20 laundry cycles under soap-washing conditions. After recycling, the single sites on cotton have no obvious changes in the microstructure, which demonstrates the success of our sustainable strategy of single sites anchored on cotton. The single-site technique can be extended to many other elemental atoms on various wearable devices, providing a playground for functional material communities.

Investigations of EGFR configurations on tumor cell surface by high-resolution electron microscopy.

Epidermal growth factor receptor (EGFR) is an important target for tumor therapy in various tumors. The current understanding of EGFR conformations on the cell surface is based on X-ray structural data, molecular dynamic simulations, and fluorescence-localization imaging. Using scanning electron microscope (SEM) and transmission electron microscope (TEM) with the resolution at sub-nanometers, we successfully recognized individual molecules of EGFRs and their assembly details on the surface of triple-negative breast cancer (TNBC) upon one-to-one labeling by Au nanoparticles. Based on our results, we have proposed the possible configurations, structural models, and conformational transitions of EGFR oligomers. Our study shows that the high-resolution electron imaging is an invaluable tool to provide direct evidence of EGFR configuration on tumor cell surfaces, and may play a pivotal role in further understanding of EGFR-associated signaling and tumor therapy.

"Lattice Strain Matching"-Enabled Nanocomposite Design to Harness the Exceptional Mechanical Properties of Nanomaterials in Bulk Forms.

Nanosized materials are known to have the ability to withstand ultralarge elastic strains (4-10%) and to have ultrahigh strengths approaching their theoretical limits. However, it is a long-standing challenge to harnessing their exceptional intrinsic mechanical properties in bulk forms. This is commonly known as "the valley of death" in nanocomposite design. In 2013, a breakthrough was made to overcome this challenge by using a martensitic phase transforming matrix to create a composite in which ultralarge elastic lattice strains up to 6.7% are achieved in Nb nanoribbons embedded in it. This breakthrough was enabled by a novel concept of phase transformation assisted lattice strain matching between the uniform ultralarge elastic strains (4-10%) of nanomaterials and the uniform crystallographic lattice distortion strains (4-10%) of the martensitic phase transformation of the matrix. This novel concept has opened new opportunities for developing materials of exceptional mechanical properties or enhanced functional properties that are not possible before. The work in progress in this research over the past six years is reported.

Ultrahigh Photocatalytic Rate at a Single-Metal-Atom-Oxide.

Metal oxides, as one of the mostly abundant and widely utilized materials, are extensively investigated and applied in environmental remediation and protection, and in energy conversion and storage. Most of these diverse applications are the result of a large diversity of the electronic states of metal oxides. Noticeably, however, many metal oxides present obstacles for applications in catalysis, mainly due to the lack of efficient active sites with desired electronic states. Here, the fabrication of single-tungsten-atom-oxide (STAO) is demonstrated, in which the metal oxide's volume reaches its minimum as a unit cell. The catalytic mechanism in the STAO is determined by a new single-site physics mechanism, named as quasi-atom physics. The photogenerated electron transfer process is enabled by an electron in the spin-up channel excited from the highest occupied molecular orbital to the lowest unoccupied molecular orbital +1 state, which can only occur in STAO with W5+ . STAO results in a record-high and stable sunlight photocatalytic degradation rate of 0.24 s-1 , which exceeds the rates of available photocatalysts by two orders of magnitude. The fabrication of STAO and its unique quasi-atom photocatalytic mechanism lays new ground for achieving novel physical and chemical properties using single-metal-atom oxides (SMAO).

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.

In situ atomic scale mechanisms of strain-induced twin boundary shear to high angle grain boundary in nanocrystalline Pt.

Twin boundary can both strengthen and soften nanocrystalline metals and has been an important path for improving the strength and ductility of nano materials. Here, using in-lab developed double-tilt tensile stage in the transmission electron microscope, the atomic scale twin boundary shearing process was in situ observed in a twin-structured nanocrystalline Pt. It was revealed that the twin boundary shear was resulted from partial dislocation emissions on the intersected {111} planes, which accommodate as large as 47% shear strain. It is uncovered that the partial dislocations nucleated and glided on the two intersecting {111} slip planes lead to a transition of the original <110> symmetric tilt ∑3/(111) coherent twin boundary into a <110> symmetric tilt ∑9/(114) high angle grain boundary. These results provide insight of twin boundary strengthening mechanisms for accommodating plasticity strains in nanocrystalline metals.

Heterostructure TiO2 polymorphs design and structure adjustment for photocatalysis.

Atomic composite-structure materials play an important role in energy generation and storage application fields for their advanced performance. Constructing heterostructured semiconductors is a promising strategy to devise photocatalytic systems with high activity. However, most studied hererostructures are those semiconductors with different materials formed by multi-steps, researches on in-situ formed hererostructure originated from the same precursor are few reported, and the effects of different structure ratios on photocatalytic performance are ambiguous. Here, according to in-situ temperature X-ray diffraction and transmission electron microscope techniques, a nano-sized in-situ formed heterostructure of TiO2 semiconductors with anatase and TiO2-B crystalline structures were designed, their structure ratios were adjusted, the heterostructure interface and photocatalytic reaction mechanism were also detected. Results show that high-quality heterojunction and optimum structure ratios have vital influence on photocatalytic performance, there is an obvious synergetic effect between anatase and TiO2-B structure, degradation reactions on methyl orange (MO) under ultraviolet light irradiation prove that the highest activity toward MO removal can be obtained for material with 82.5% anatase structure.

Elemental preference and atomic scale site recognition in a Co-Al-W-base superalloy.

Using state-of-the-art atomic scale super energy dispersive X-ray spectroscopy and high angle annular dark field imaging this study reveals the elemental partitioning preference between the γ' and γ phases in a Co-Al-W-Ti-Ta superalloy and the site preference of its alloying elements in the ordered L12 γ' phase. A semi-quantitative analysis of atomic column compositions in the ordered L12 γ' structure is provided. Co atoms were found to occupy the {1/2, 1/2, 0} face-center positions whereas Al, W, Ti and Ta atoms prefer to occupy the {0, 0, 0} cube corner positions in the L12 γ phase. These findings agree well with predictions from first principles simulations in the literature.

Size effect on the deformation mechanisms of nanocrystalline platinum thin films.

This paper reports a study of time-resolved deformation process at the atomic scale of a nanocrystalline Pt thin film captured in situ under a transmission electron microscope. The main mechanism of plastic deformation was found to evolve from full dislocation activity-enabled plasticity in large grains (with grain size d > 10 nm), to partial dislocation plasticity in smaller grains (with grain size 10 nm < d < 6 nm), and grain boundary-mediated plasticity in the matrix with grain sizes d < 6 nm. The critical grain size for the transition from full dislocation activity to partial dislocation activity was estimated based on consideration of stacking fault energy. For grain boundary-mediated plasticity, the possible contributions to strain rate of grain creep, grain sliding and grain rotation to plastic deformation were estimated using established models. The contribution of grain creep is found to be negligible, the contribution of grain rotation is effective but limited in magnitude, and grain sliding is suggested to be the dominant deformation mechanism in nanocrystalline Pt thin films. This study provided the direct evidence of these deformation processes at the atomic scale.

Cloning Nacre's 3D Interlocking Skeleton in Engineering Composites to Achieve Exceptional Mechanical Properties.

Ceramic/polymer composite equipped with 3D interlocking skeleton (3D IL) is developed through a simple freeze-casting method, exhibiting exceptionally light weight, high strength, toughness, and shock resistance. Long-range crack energy dissipation enabled by 3D interlocking structure is considered as the primary reinforcing mechanism for such superior properties. The smart composite design strategy should hold a place in developing future structural engineering materials.

Strongly enhanced ultraviolet emission of an Au@SiO2/ZnO plasmonic hybrid nanostructure.

We present the surface plasmon polariton (SPP)-enhanced ultraviolet (UV) emission of an Au@SiO2/ZnO hybrid nanostructure. We achieved approximately 20- and 8-fold enhancements of the UV-emitting intensities from Au-SPP coupled nanometre- and micrometre-scaled ZnO wires through an optimized 5 nm-thick SiO2 spacer compared to that obtained from bare ZnO on a Si substrate without SPP coupling. Cathodoluminescence measurements and simulations demonstrated that the plasmonic hybrid nanostructure enables the strong localization of the SPP field, resulting in significantly enhanced UV emission. This plasmonic structure paves the way to nanoscale UV-optical lasers and sensors.

Revealing ultralarge and localized elastic lattice strains in Nb nanowires embedded in NiTi matrix.

Freestanding nanowires have been found to exhibit ultra-large elastic strains (4 to 7%) and ultra-high strengths, but exploiting their intrinsic superior mechanical properties in bulk forms has proven to be difficult. A recent study has demonstrated that ultra-large elastic strains of ~6% can be achieved in Nb nanowires embedded in a NiTi matrix, on the principle of lattice strain matching. To verify this hypothesis, this study investigated the elastic deformation behavior of a Nb nanowire embedded in NiTi matrix by means of in situ transmission electron microscopic measurement during tensile deformation. The experimental work revealed that ultra-large local elastic lattice strains of up to 8% are induced in the Nb nanowire in regions adjacent to stress-induced martensite domains in the NiTi matrix, whilst other parts of the nanowires exhibit much reduced lattice strains when adjacent to the untransformed austenite in the NiTi matrix. These observations provide a direct evidence of the proposed mechanism of lattice strain matching, thus a novel approach to designing nanocomposites of superior mechanical properties.