High fatigue resistance in a titanium alloy via near-void-free 3D printing.

The advantage of 3D printing-that is, additive manufacturing (AM) of structural materials-has been severely compromised by their disappointing fatigue properties1,2. Commonly, poor fatigue properties appear to result from the presence of microvoids induced by current printing process procedures3,4. Accordingly, the question that we pose is whether the elimination of such microvoids can provide a feasible solution for marked enhancement of the fatigue resistance of void-free AM (Net-AM) alloys. Here we successfully rebuild an approximate void-free AM microstructure in Ti-6Al-4V titanium alloy by development of a Net-AM processing technique through an understanding of the asynchronism of phase transformation and grain growth. We identify the fatigue resistance of such AM microstructures and show that they lead to a high fatigue limit of around 1 GPa, exceeding the fatigue resistance of all AM and forged titanium alloys as well as that of other metallic materials. We confirm the high fatigue resistance of Net-AM microstructures and the potential advantages of AM processing in the production of structural components with maximum fatigue strength, which is beneficial for further application of AM technologies in engineering fields.

Functional composites by programming entropy-driven nanosheet growth.

Nanomaterials must be systematically designed to be technologically viable1-5. Driven by optimizing intermolecular interactions, current designs are too rigid to plug in new chemical functionalities and cannot mitigate condition differences during integration6,7. Despite extensive optimization of building blocks and treatments, accessing nanostructures with the required feature sizes and chemistries is difficult. Programming their growth across the nano-to-macro hierarchy also remains challenging, if not impossible8-13. To address these limitations, we should shift to entropy-driven assemblies to gain design flexibility, as seen in high-entropy alloys, and program nanomaterial growth to kinetically match target feature sizes to the mobility of the system during processing14-17. Here, following a micro-then-nano growth sequence in ternary composite blends composed of block-copolymer-based supramolecules, small molecules and nanoparticles, we successfully fabricate high-performance barrier materials composed of more than 200 stacked nanosheets (125 nm sheet thickness) with a defect density less than 0.056 µm-2 and about 98% efficiency in controlling the defect type. Contrary to common perception, polymer-chain entanglements are advantageous to realize long-range order, accelerate the fabrication process (<30 min) and satisfy specific requirements to advance multilayered film technology3,4,18. This study showcases the feasibility, necessity and unlimited opportunities to transform laboratory nanoscience into nanotechnology through systems engineering of self-assembly.

Near-complete depolymerization of polyesters with nano-dispersed enzymes.

Successfully interfacing enzymes and biomachinery with polymers affords on-demand modification and/or programmable degradation during the manufacture, utilization and disposal of plastics, but requires controlled biocatalysis in solid matrices with macromolecular substrates1-7. Embedding enzyme microparticles speeds up polyester degradation, but compromises host properties and unintentionally accelerates the formation of microplastics with partial polymer degradation6,8,9. Here we show that by nanoscopically dispersing enzymes with deep active sites, semi-crystalline polyesters can be degraded primarily via chain-end-mediated processive depolymerization with programmable latency and material integrity, akin to polyadenylation-induced messenger RNA decay10. It is also feasible to achieve processivity with enzymes that have surface-exposed active sites by engineering enzyme-protectant-polymer complexes. Poly(caprolactone) and poly(lactic acid) containing less than 2 weight per cent enzymes are depolymerized in days, with up to 98 per cent polymer-to-small-molecule conversion in standard soil composts and household tap water, completely eliminating current needs to separate and landfill their products in compost facilities. Furthermore, oxidases embedded in polyolefins retain their activities. However, hydrocarbon polymers do not closely associate with enzymes, as their polyester counterparts do, and the reactive radicals that are generated cannot chemically modify the macromolecular host. This study provides molecular guidance towards enzyme-polymer pairing and the selection of enzyme protectants to modulate substrate selectivity and optimize biocatalytic pathways. The results also highlight the need for in-depth research in solid-state enzymology, especially in multi-step enzymatic cascades, to tackle chemically dormant substrates without creating secondary environmental contamination and/or biosafety concerns.

Short-range order and its impact on the CrCoNi medium-entropy alloy.

Traditional metallic alloys are mixtures of elements in which the atoms of minority species tend to be distributed randomly if they are below their solubility limit, or to form secondary phases if they are above it. The concept of multiple-principal-element alloys has recently expanded this view, as these materials are single-phase solid solutions of generally equiatomic mixtures of metallic elements. This group of materials has received much interest owing to their enhanced mechanical properties1-5. They are usually called medium-entropy alloys in ternary systems and high-entropy alloys in quaternary or quinary systems, alluding to their high degree of configurational entropy. However, the question has remained as to how random these solid solutions actually are, with the influence of short-range order being suggested in computational simulations but not seen experimentally6,7. Here we report the observation, using energy-filtered transmission electron microscopy, of structural features attributable to short-range order in the CrCoNi medium-entropy alloy. Increasing amounts of such order give rise to both higher stacking-fault energy and hardness. These findings suggest that the degree of local ordering at the nanometre scale can be tailored through thermomechanical processing, providing a new avenue for tuning the mechanical properties of medium- and high-entropy alloys.

Effect of local chemical order on the irradiation-induced defect evolution in CrCoNi medium-entropy alloy.

High- (and medium-) entropy alloys have emerged as potentially suitable structural materials for nuclear applications, particularly as they appear to show promising irradiation resistance. Recent studies have provided evidence of the presence of local chemical order (LCO) as a salient feature of these complex concentrated solid-solution alloys. However, the influence of such LCO on their irradiation response has remained uncertain thus far. In this work, we combine ion irradiation experiments with large-scale atomistic simulations to reveal that the presence of chemical short-range order, developed as an early stage of LCO, slows down the formation and evolution of point defects in the equiatomic medium-entropy alloy CrCoNi during irradiation. In particular, the irradiation-induced vacancies and interstitials exhibit a smaller difference in their mobility, arising from a stronger effect of LCO in localizing interstitial diffusion. This effect promotes their recombination as the LCO serves to tune the migration energy barriers of these point defects, thereby delaying the initiation of damage. These findings imply that local chemical ordering may provide a variable in the design space to enhance the resistance of multi-principal element alloys to irradiation damage.

Tuning element distribution, structure and properties by composition in high-entropy alloys.

High-entropy alloys are a class of materials that contain five or more elements in near-equiatomic proportions1,2. Their unconventional compositions and chemical structures hold promise for achieving unprecedented combinations of mechanical properties3-8. Rational design of such alloys hinges on an understanding of the composition-structure-property relationships in a near-infinite compositional space9,10. Here we use atomic-resolution chemical mapping to reveal the element distribution of the widely studied face-centred cubic CrMnFeCoNi Cantor alloy2 and of a new face-centred cubic alloy, CrFeCoNiPd. In the Cantor alloy, the distribution of the five constituent elements is relatively random and uniform. By contrast, in the CrFeCoNiPd alloy, in which the palladium atoms have a markedly different atomic size and electronegativity from the other elements, the homogeneity decreases considerably; all five elements tend to show greater aggregation, with a wavelength of incipient concentration waves11,12 as small as 1 to 3 nanometres. The resulting nanoscale alternating tensile and compressive strain fields lead to considerable resistance to dislocation glide. In situ transmission electron microscopy during straining experiments reveals massive dislocation cross-slip from the early stage of plastic deformation, resulting in strong dislocation interactions between multiple slip systems. These deformation mechanisms in the CrFeCoNiPd alloy, which differ markedly from those in the Cantor alloy and other face-centred cubic high-entropy alloys, are promoted by pronounced fluctuations in composition and an increase in stacking-fault energy, leading to higher yield strength without compromising strain hardening and tensile ductility. Mapping atomic-scale element distributions opens opportunities for understanding chemical structures and thus providing a basis for tuning composition and atomic configurations to obtain outstanding mechanical properties.

Helical van der Waals crystals with discretized Eshelby twist.

The ability to manipulate the twisting topology of van der Waals structures offers a new degree of freedom through which to tailor their electrical and optical properties. The twist angle strongly affects the electronic states, excitons and phonons of the twisted structures through interlayer coupling, giving rise to exotic optical, electric and spintronic behaviours1-5. In twisted bilayer graphene, at certain twist angles, long-range periodicity associated with moiré patterns introduces flat electronic bands and highly localized electronic states, resulting in Mott insulating behaviour and superconductivity3,4. Theoretical studies suggest that these twist-induced phenomena are common to layered materials such as transition-metal dichalcogenides and black phosphorus6,7. Twisted van der Waals structures are usually created using a transfer-stacking method, but this method cannot be used for materials with relatively strong interlayer binding. Facile bottom-up growth methods could provide an alternative means to create twisted van der Waals structures. Here we demonstrate that the Eshelby twist, which is associated with a screw dislocation (a chiral topological defect), can drive the formation of such structures on scales ranging from the nanoscale to the mesoscale. In the synthesis, axial screw dislocations are first introduced into nanowires growing along the stacking direction, yielding van der Waals nanostructures with continuous twisting in which the total twist rates are defined by the radii of the nanowires. Further radial growth of those twisted nanowires that are attached to the substrate leads to an increase in elastic energy, as the total twist rate is fixed by the substrate. The stored elastic energy can be reduced by accommodating the fixed twist rate in a series of discrete jumps. This yields mesoscale twisting structures consisting of a helical assembly of nanoplates demarcated by atomically sharp interfaces with a range of twist angles. We further show that the twisting topology can be tailored by controlling the radial size of the structure.

Magnetically driven short-range order can explain anomalous measurements in CrCoNi.

The presence, nature, and impact of chemical short-range order in the multi-principal element alloy CrCoNi are all topics of current interest and debate. First-principles calculations reveal that its origins are fundamentally magnetic, involving repulsion between like-spin Co-Cr and Cr-Cr pairs that is complemented by the formation of a magnetically aligned sublattice of second-nearest-neighbor Cr atoms. Ordering models following these principles are found to predict otherwise anomalous experimental measurements concerning both magnetization and atomic volumes across a range of compositions. In addition to demonstrating the impact of magnetic interactions and resulting chemical rearrangement, the possible explanation of experiments would imply that short-range order of this type is far more prevalent than previously realized.

Bone manganese is a sensitive biomarker of ongoing elevated manganese exposure, but does not accumulate across the lifespan.

Studies have established associations between environmental and occupational manganese (Mn) exposure and executive and motor function deficits in children, adolescents, and adults. These health risks from elevated Mn exposure underscore the need for effective exposure biomarkers to improve exposure classification and help detect/diagnose Mn-related impairments. Here, neonate rats were orally exposed to 0, 25, or 50 mg Mn/kg/day during early life (PND 1-21) or lifelong through âˆ¼ PND 500 to determine the relationship between oral Mn exposure and blood, brain, and bone Mn levels over the lifespan, whether Mn accumulates in bone, and whether elevated bone Mn altered the local atomic and mineral structure of bone, or its biomechanical properties. Additionally, we assessed levels of bone Mn compared to bone lead (Pb) in aged humans (age 41-91) living in regions impacted by historic industrial ferromanganese activity. The animal studies show that blood, brain, and bone Mn levels naturally decrease across the lifespan without elevated Mn exposure. With elevated exposure, bone Mn levels were strongly associated with blood Mn levels, bone Mn was more sensitive to elevated exposures than blood or brain Mn, and Mn did not accumulate with lifelong elevated exposure. Elevated early life Mn exposure caused some changes in bone mineral properties, including altered local atomic structure of hydroxyapatite, along with some biomechanical changes in bone stiffness in weanlings or young adult animals. In aged humans, blood Mn ranged from 5.4 to 23.5 ng/mL; bone Mn was universally low, and decreased with age, but did not vary based on sex or female parity history. Unlike Pb, bone Mn showed no evidence of accumulation over the lifespan, and may not be a biomarker of cumulative long-term exposure. Thus, bone may be a useful biomarker of recent ongoing Mn exposure in humans, and may be a relatively minor target of elevated exposure.

Toughening materials: enhancing resistance to fracture.

It has been said that 'God invented plasticity, but the Devil invented fracture!' Both mechanisms represent the two prime modes of structural failure, respectively, plastic collapse and the rupture/breaking of a component, but the concept of developing materials with enhanced resistance to fracture can be difficult. This is because fracture resistance invariably involves a compromise-between strength and ductility, between strength and toughness-fundamentally leading to a 'conflict' between nano-/micro-structural damage and the mechanisms of toughening. Here, we examine the two major classes of such toughening: (i) intrinsic toughening, which occurs ahead of a crack tip and is motivated by plasticity-this is the principal mode of fracture resistance in ductile materials, and (ii) extrinsic toughening, which occurs at, or in the wake of, a crack tip and is associated with crack-tip shielding-this is generally the sole mode of fracture resistance in brittle materials. We briefly examine how these distinct mechanistic processes have been used to toughen synthetic materials-intrinsically in gradient materials and in multiple principal-element metallic alloys with the example of metallic glasses and high-entropy alloys, and extrinsically in ceramics with the example of ceramic-matrix composites-in comparison to Nature which has been especially adept in creating biological/natural materials which are toughened by one or both mechanistic classes, despite often consisting of constituents with meagre mechanical properties. The success of Nature has been driven by its ability to cultivate the development of materials with multiple length-scale hierarchical structures that display ingenious gradients and structural adaptability, a philosophy which we need to emulate and more importantly learn to synthesize to make structural materials of the future with unprecedented combinations of mechanical properties. This article is part of a discussion meeting issue 'A cracking approach to inventing new tough materials: fracture stranger than friction'.

Tunable stacking fault energies by tailoring local chemical order in CrCoNi medium-entropy alloys.

High-entropy alloys (HEAs) are an intriguing new class of metallic materials due to their unique mechanical behavior. Achieving a detailed understanding of structure-property relationships in these materials has been challenged by the compositional disorder that underlies their unique mechanical behavior. Accordingly, in this work, we employ first-principles calculations to investigate the nature of local chemical order and establish its relationship to the intrinsic and extrinsic stacking fault energy (SFE) in CrCoNi medium-entropy solid-solution alloys, whose combination of strength, ductility, and toughness properties approaches the best on record. We find that the average intrinsic and extrinsic SFE are both highly tunable, with values ranging from -43 to 30 mJ⋅m-2 and from -28 to 66 mJ⋅m-2, respectively, as the degree of local chemical order increases. The state of local ordering also strongly correlates with the energy difference between the face-centered cubic (fcc) and hexagonal close-packed (hcp) phases, which affects the occurrence of transformation-induced plasticity. This theoretical study demonstrates that chemical short-range order is thermodynamically favored in HEAs and can be tuned to affect the mechanical behavior of these alloys. It thus addresses the pressing need to establish robust processing-structure-property relationships to guide the science-based design of new HEAs with targeted mechanical behavior.

Multi-Step Crystallization of Self-Organized Spiral Eutectics.

A method for the solidification of metallic alloys involving spiral self-organization is presented as a new strategy for producing large-area chiral patterns with emergent structural and optical properties, with attention to the underlying mechanism and dynamics. This study reports the discovery of a new growth mode for metastable, two-phase spiral patterns from a liquid metal. Crystallization proceeds via a non-classical, two-step pathway consisting of the initial formation of a polytetrahedral seed crystal, followed by ordering of two solid phases that nucleate heterogeneously on the seed and grow in a strongly coupled fashion. Crystallographic defects within the seed provide a template for spiral self-organization. These observations demonstrate the ubiquity of defect-mediated growth in multi-phase materials and establish a pathway toward bottom-up synthesis of chiral materials with an inter-phase spacing comparable to the wavelength of infrared light. Given that liquids often possess polytetrahedral short-range order, our results are applicable to many systems undergoing multi-step crystallization.

On the question of fractal packing structure in metallic glasses.

This work addresses the long-standing debate over fractal models of packing structure in metallic glasses (MGs). Through detailed fractal and percolation analyses of MG structures, derived from simulations spanning a range of compositions and quenching rates, we conclude that there is no fractal atomic-level structure associated with the packing of all atoms or solute-centered clusters. The results are in contradiction with conclusions derived from previous studies based on analyses of shifts in radial distribution function and structure factor peaks associated with volume changes induced by pressure and compositional variations. The interpretation of such shifts is shown to be challenged by the heterogeneous nature of MG structure and deformation at the atomic scale. Moreover, our analysis in the present work illustrates clearly the percolation theory applied to MGs, for example, the percolation threshold and characteristics of percolation clusters formed by subsets of atoms, which can have important consequences for structure-property relationships in these amorphous materials.

Atypical fracture with long-term bisphosphonate therapy is associated with altered cortical composition and reduced fracture resistance.

Bisphosphonates are the most widely prescribed pharmacologic treatment for osteoporosis and reduce fracture risk in postmenopausal women by up to 50%. However, in the past decade these drugs have been associated with atypical femoral fractures (AFFs), rare fractures with a transverse, brittle morphology. The unusual fracture morphology suggests that bisphosphonate treatment may impair toughening mechanisms in cortical bone. The objective of this study was to compare the compositional and mechanical properties of bone biopsies from bisphosphonate-treated patients with AFFs to those from patients with typical osteoporotic fractures with and without bisphosphonate treatment. Biopsies of proximal femoral cortical bone adjacent to the fracture site were obtained from postmenopausal women during fracture repair surgery (fracture groups, n = 33) or total hip arthroplasty (nonfracture groups, n = 17). Patients were allocated to five groups based on fracture morphology and history of bisphosphonate treatment [+BIS Atypical: n = 12, BIS duration: 8.2 (3.0) y; +BIS Typical: n = 10, 7.7 (5.0) y; +BIS Nonfx: n = 5, 6.4 (3.5) y; -BIS Typical: n = 11; -BIS Nonfx: n = 12]. Vibrational spectroscopy and nanoindentation showed that tissue from bisphosphonate-treated women with atypical fractures was harder and more mineralized than that from bisphosphonate-treated women with typical osteoporotic fractures. In addition, fracture mechanics measurements showed that tissue from patients treated with bisphosphonates had deficits in fracture toughness, with lower crack-initiation toughness and less crack deflection at osteonal boundaries than that of bisphosphonate-naïve patients. Together, these results suggest a deficit in intrinsic and extrinsic toughening mechanisms, which contribute to AFFs in patients treated with long-term bisphosphonates.

Bioinspired Nacre-Like Alumina with a Metallic Nickel Compliant Phase Fabricated by Spark-Plasma Sintering.

Many natural materials present an ideal "recipe" for the development of future damage-tolerant lightweight structural materials. One notable example is the brick-and-mortar structure of nacre, found in mollusk shells, which produces high-toughness, bioinspired ceramics using polymeric mortars as a compliant phase. Theoretical modeling has predicted that use of metallic mortars could lead to even higher damage-tolerance in these materials, although it is difficult to melt-infiltrate metals into ceramic scaffolds as they cannot readily wet ceramics. To avoid this problem, an alternative ("bottom-up") approach to synthesize "nacre-like" ceramics containing a small fraction of nickel mortar is developed. These materials are fabricated using nickel-coated alumina platelets that are aligned using slip-casting and rapidly sintered using spark-plasma sintering. Dewetting of the nickel mortar during sintering is prevented by using NiO-coated as well as Ni-coated platelets. As a result, a "nacre-like" alumina ceramic displaying a resistance-curve toughness up to ≈16 MPa m½ with a flexural strength of ≈300 MPa is produced.

Influence of three-dimensional nanoparticle branching on the Young's modulus of nanocomposites: Effect of interface orientation.

With the availability of nanoparticles with controlled size and shape, there has been renewed interest in the mechanical properties of polymer/nanoparticle blends. Despite the large number of theoretical studies, the effect of branching for nanofillers tens of nanometers in size on the elastic stiffness of these composite materials has received limited attention. Here, we examine the Young's modulus of nanocomposites based on a common block copolymer (BCP) blended with linear nanorods and nanoscale tetrapod Quantum Dots (tQDs), in electrospun fibers and thin films. We use a phenomenological lattice spring model (LSM) as a guide in understanding the changes in the Young's modulus of such composites as a function of filler shape. Reasonable agreement is achieved between the LSM and the experimental results for both nanoparticle shapes--with only a few key physical assumptions in both films and fibers--providing insight into the design of new nanocomposites and assisting in the development of a qualitative mechanistic understanding of their properties. The tQDs impart the greatest improvements, enhancing the Young's modulus by a factor of 2.5 at 20 wt.%. This is 1.5 times higher than identical composites containing nanorods. An unexpected finding from the simulations is that both the orientation of the nanoscale filler and the orientation of X-type covalent bonds at the nanoparticle-ligand interface are important for optimizing the mechanical properties of the nanocomposites. The tQD provides an orientational optimization of the interfacial and filler bonds arising from its three-dimensional branched shape unseen before in nanocomposites with inorganic nanofillers.