Additive manufacturing of micro-architected metals via hydrogel infusion.

Metal additive manufacturing (AM) enables the production of high value and high performance components1 with applications from aerospace2 to biomedical3 fields. Layer-by-layer fabrication circumvents the geometric limitations of traditional metalworking techniques, allowing topologically optimized parts to be made rapidly and efficiently4,5. Existing AM techniques rely on thermally initiated melting or sintering for part shaping, a costly and material-limited process6-8. We report an AM technique that produces metals and alloys with microscale resolution via vat photopolymerization (VP). Three-dimensional-architected hydrogels are infused with metal precursors, then calcined and reduced to convert the hydrogel scaffolds into miniaturized metal replicas. This approach represents a paradigm shift in VP; the material is selected only after the structure is fabricated. Unlike existing VP strategies, which incorporate target materials or precursors into the photoresin during printing9-11, our method does not require reoptimization of resins and curing parameters for different materials, enabling quick iteration, compositional tuning and the ability to fabricate multimaterials. We demonstrate AM of metals with critical dimensions of approximately 40 µm that are challenging to fabricate by using conventional processes. Such hydrogel-derived metals have highly twinned microstructures and unusually high hardness, providing a pathway to create advanced metallic micromaterials.

Electrochemically reconfigurable architected materials.

Architected materials can actively respond to external stimuli-such as mechanical forces, hydration and magnetic fields-by changing their geometries and thereby achieve novel functionalities. Such transformations are usually binary and volatile because they toggle between 'on' and 'off' states and require persistent external stimuli. Here we develop three-dimensional silicon-coated tetragonal microlattices that transform into sinusoidal patterns via cooperative beam buckling in response to an electrochemically driven silicon-lithium alloying reaction. In situ microscopy reveals a controllable, non-volatile and reversible structural transformation that forms multiple ordered buckling domains separated by distorted domain boundaries. We investigate the mechanical dynamics of individual buckling beams, cooperative coupling among neighbouring beams, and lithiation-rate-dependent distributions of domain sizes through chemo-mechanical modelling and statistical mechanics analysis. Our results highlight the critical role of defects and energy fluctuations in the dynamic response of architected materials. We further demonstrate that domain boundaries can be programmed to form particular patterns by pre-designing artificial defects, and that a variety of reconfigurational degrees of freedom can be achieved through micro-architecture design. This framework enables the design, fabrication, modelling, behaviour prediction and programming of electrochemically reconfigurable architected materials, and could open the way to beyond-intercalation battery electrodes, tunable phononic crystals and bio-implantable devices.

Carbon-Related Quantum Emitter in Hexagonal Boron Nitride with Homogeneous Energy and 3-Fold Polarization.

Most hexagonal boron nitride (hBN) single-photon emitters (SPEs) studied to date suffer from variable emission energy and unpredictable polarization, two crucial obstacles to their application in quantum technologies. Here, we report an SPE in hBN with an energy of 2.2444 ± 0.0013 eV created via carbon implantation that exhibits a small inhomogeneity of the emission energy. Polarization-resolved measurements reveal aligned absorption and emission dipole orientations with a 3-fold distribution, which follows the crystal symmetry. Photoluminescence excitation (PLE) spectroscopy results show the predictability of polarization is associated with a reproducible PLE band, in contrast with the non-reproducible bands found in previous hBN SPE species. Photon correlation measurements are consistent with a three-level model with weak coupling to a shelving state. Our ab initio excited-state calculations shed light on the atomic origin of this SPE defect, which consists of a pair of substitutional carbon atoms located at boron and nitrogen sites separated by a hexagonal unit cell.

Suppressed Size Effect in Nanopillars with Hierarchical Microstructures Enabled by Nanoscale Additive Manufacturing.

Studies on mechanical size effects in nanosized metals unanimously highlight both intrinsic microstructures and extrinsic dimensions for understanding size-dependent properties, commonly focusing on strengths of uniform microstructures, e.g., single-crystalline/nanocrystalline and nanoporous, as a function of pillar diameters, D. We developed a hydrogel infusion-based additive manufacturing (AM) technique using two-photon lithography to produce metals in prescribed 3D-shapes with ∼100 nm feature resolution. We demonstrate hierarchical microstructures of as-AM-fabricated Ni nanopillars (D ∼ 130-330 nm) to be nanoporous and nanocrystalline, with d ∼ 30-50 nm nanograins subtending each ligament in bamboo-like arrangements and pores with critical dimensions comparable to d. In situ nanocompression experiments unveil their yield strengths, σ, to be ∼1-3 GPa, above single-crystalline/nanocrystalline counterparts in the D range, a weak size dependence, σ ∝ D-0.2, and localized-to-homogenized transition in deformation modes mediated by nanoporosity, uncovered by molecular dynamics simulations. This work highlights hierarchical microstructures on mechanical response in nanosized metals and suggests small-scale engineering opportunities through AM-enabled microstructures.

Microstructure-driven mechanical and electromechanical phenomena in additively manufactured nanocrystalline zinc oxide.

Advances in nanoscale additive manufacturing (AM) offer great opportunities to expand nanotechnologies; however, the size effects in these printed remain largely unexplored. Using bothin situnanomechanical and electrical experiments and molecular dynamics (MD) simulations, this study investigates additively manufactured nano-architected nanocrystalline ZnO (nc-ZnO) with ∼7 nm grains and dimensions spanning 0.25-4µm. These nano-scale ceramics are fabricated through printing and subsequent burning of metal ion-containing hydrogels to produce oxide structures. Electromechanical behavior is shown to result from random ordering in the microstructure and can be modeled through a statistical treatment. A size effect in the failure behavior of AM nc-ZnO is also observed and characterized by the changes in deformation behavior and suppression of brittle failure. MD simulations provide insights to the role of grain boundaries and grain boundary plasticity on both electromechanical behavior and failure mechanisms in nc-ZnO. The frameworks developed in this paper extend to other AM nanocrystalline materials and provide quantification of microstructurally-drive limitations to precision in materials property design.

Extreme mechanical resilience of self-assembled nanolabyrinthine materials.

Low-density materials with tailorable properties have attracted attention for decades, yet stiff materials that can resiliently tolerate extreme forces and deformation while being manufactured at large scales have remained a rare find. Designs inspired by nature, such as hierarchical composites and atomic lattice-mimicking architectures, have achieved optimal combinations of mechanical properties but suffer from limited mechanical tunability, limited long-term stability, and low-throughput volumes that stem from limitations in additive manufacturing techniques. Based on natural self-assembly of polymeric emulsions via spinodal decomposition, here we demonstrate a concept for the scalable fabrication of nonperiodic, shell-based ceramic materials with ultralow densities, possessing features on the order of tens of nanometers and sample volumes on the order of cubic centimeters. Guided by simulations of separation processes, we numerically show that the curvature of self-assembled shells can produce close to optimal stiffness scaling with density, and we experimentally demonstrate that a carefully chosen combination of topology, geometry, and base material results in superior mechanical resilience in the architected product. Our approach provides a pathway to harnessing self-assembly methods in the design and scalable fabrication of beyond-periodic and nonbeam-based nano-architected materials with simultaneous directional tunability, high stiffness, and unsurpassed recoverability with marginal deterioration.

Supersonic impact resilience of nanoarchitected carbon.

Architected materials with nanoscale features have enabled extreme combinations of properties by exploiting the ultralightweight structural design space together with size-induced mechanical enhancement at small scales. Apart from linear waves in metamaterials, this principle has been restricted to quasi-static properties or to low-speed phenomena, leaving nanoarchitected materials under extreme dynamic conditions largely unexplored. Here, using supersonic microparticle impact experiments, we demonstrate extreme impact energy dissipation in three-dimensional nanoarchitected carbon materials that exhibit mass-normalized energy dissipation superior to that of traditional impact-resistant materials such as steel, aluminium, polymethyl methacrylate and Kevlar. In-situ ultrahigh-speed imaging and post-mortem confocal microscopy reveal consistent mechanisms such as compaction cratering and microparticle capture that enable this superior response. By analogy to planetary impact, we introduce predictive tools for crater formation in these materials using dimensional analysis. These results substantially uncover the dynamic regime over which nanoarchitecture enables the design of ultralightweight, impact-resistant materials that could open the way to design principles for lightweight armour, protective coatings and blast-resistant shields for sensitive electronics.

Lightweight, flaw-tolerant, and ultrastrong nanoarchitected carbon.

It has been a long-standing challenge in modern material design to create low-density, lightweight materials that are simultaneously robust against defects and can withstand extreme thermomechanical environments, as these properties are often mutually exclusive: The lower the density, the weaker and more fragile the material. Here, we develop a process to create nanoarchitected carbon that can attain specific strength (strength-to-density ratio) up to one to three orders of magnitude above that of existing micro- and nanoarchitected materials. We use two-photon lithography followed by pyrolysis in a vacuum at 900 °C to fabricate pyrolytic carbon in two topologies, octet- and iso-truss, with unit-cell dimensions of ∼2 µm, beam diameters between 261 nm and 679 nm, and densities of 0.24 to 1.0 g/cm3 Experiments and simulations demonstrate that for densities higher than 0.95 g/cm3 the nanolattices become insensitive to fabrication-induced defects, allowing them to attain nearly theoretical strength of the constituent material. The combination of high specific strength, low density, and extensive deformability before failure lends such nanoarchitected carbon to being a particularly promising candidate for applications under harsh thermomechanical environments.

Failure Mechanisms in Vertically Aligned Dense Nanowire Arrays.

Nanowires are an increasingly prevalent class of nanomaterials in composites and devices, with arrays and other complex geometries used in various applications. Little investigation has been done regarding the mechanical behavior of micron-sized nanowire structures. We conduct in situ microcompression experiments on vertically aligned dense microbundles of 300 nm diameter single-crystalline zinc oxide nanowires to gain insights into their structural failure. Experiments demonstrate that bundles containing approximately 10-130 nanowires experience two failure regimes: (1) localized noncatastrophic interfacial splitting and (2) global structural failure. Utilizing Weibull statistics and experimental results, we develop a technique for analyzing flaw distribution and use it to predict the expected range of bundle failure stress. This analysis provides guidelines for nanowire arrays' susceptibility to failure, sensitivity to flaw size, interfacial interactions of constituents, and degree of alignment. This work develops insights to understand and predict fundamental failure mechanisms in highly aligned, dense structures.

Dispersion Mapping in 3-Dimensional Core-Shell Photonic Crystal Lattices Capable of Negative Refraction in the Mid-Infrared.

Engineering of the dispersion properties of a photonic crystal (PhC) opens a new paradigm for the design and function of PhC devices. Exploiting the dispersion properties of PhCs allows control over wave propagation within a PhC. We describe the design, fabrication, and experimental observation of photonic bands for 3D PhCs capable of negative refraction in the mid-infrared. Band structure and equifrequency contours were calculated to inform the design of 3D polymer-germanium core-shell PhCs, which were fabricated using two-photon lithography direct laser writing and sputtering. We successfully characterized a polymer-Ge core-shell lattice and mapped its band structure, which we then used to calculate the PhC refraction behavior. An analysis of wave propagation revealed that this 3D core-shell PhC refracts light negatively and possesses an effective negative index of refraction in the experimentally observed region. These results suggest that architected nanolattices have the potential to serve as new optical components and devices across infrared frequencies.

Additive Manufacturing of High-Refractive-Index, Nanoarchitected Titanium Dioxide for 3D Dielectric Photonic Crystals.

Additive manufacturing at small scales enables advances in micro- and nanoelectromechanical systems, micro-optics, and medical devices. Materials that lend themselves to AM at the nanoscale, especially for optical applications, are limited. State-of-the-art AM processes for high-refractive-index materials typically suffer from high porosity and poor repeatability and require complex experimental procedures. We developed an AM process to fabricate complex 3D architectures out of fully dense titanium dioxide (TiO2) with a refractive index of 2.3 and nanosized critical dimensions. Transmission electron microscopy (TEM) analysis proves this material to be rutile phase of nanocrystalline TiO2, with an average grain size of 110 nm and <1% porosity. Proof-of-concept woodpile architectures with 300-600 nm beam dimensions exhibit a full photonic band gap centered at 1.8-2.9 µm, as revealed by Fourier-transform infrared spectroscopy (FTIR) and supported by plane wave expansion simulations. The developed AM process enables advances in 3D MEMS, micro-optics, and prototyping of 3D dielectric PhCs.

Enhanced strength and temperature dependence of mechanical properties of Li at small scales and its implications for Li metal anodes.

Most next-generation Li ion battery chemistries require a functioning lithium metal (Li) anode. However, its application in secondary batteries has been inhibited because of uncontrollable dendrite growth during cycling. Mechanical suppression of dendrite growth through solid polymer electrolytes (SPEs) or through robust separators has shown the most potential for alleviating this problem. Studies of the mechanical behavior of Li at any length scale and temperature are limited because of its extreme reactivity, which renders sample preparation, transfer, microstructure characterization, and mechanical testing extremely challenging. We conduct nanomechanical experiments in an in situ scanning electron microscope and show that micrometer-sized Li attains extremely high strengths of 105 MPa at room temperature and of 35 MPa at 90 °C. We demonstrate that single-crystalline Li exhibits a power-law size effect at the micrometer and submicrometer length scales, with the strengthening exponent of -0.68 at room temperature and of -1.00 at 90 °C. We also report the elastic and shear moduli as a function of crystallographic orientation gleaned from experiments and first-principles calculations, which show a high level of anisotropy up to the melting point, where the elastic and shear moduli vary by a factor of ∼4 between the stiffest and most compliant orientations. The emergence of such high strengths in small-scale Li and sensitivity of this metal's stiffness to crystallographic orientation help explain why the existing methods of dendrite suppression have been mainly unsuccessful and have significant implications for practical design of future-generation batteries.

Recoverable Electrical Breakdown Strength and Dielectric Constant in Ultralow-k Nanolattice Capacitors.

The dielectric reliability of low-k materials during mechanical deformation attracts tremendous attention, owing to the increasing demand for thin electronics to meet the ever-shrinking form factor of consumer products. However, the strong coupling between dielectric/electric and mechanical properties limits the use of low-k dielectrics in industrial applications. We report the leakage current and dielectric properties of a nanolattice capacitor during compressive stress cycling. Electrical breakdown measurements during the stress cycling, combined with a theoretical model and in situ mechanical experiments, provide insights to key breakdown mechanisms. Electrical breakdown occurs at nearly 50% strain, featuring a switch-like binary character, correlated with a transition from beam bending and buckling to collapse. Breakdown strength appears to recover after each cycle, concomitant with nanolattice's shape recovery. The compressive displacement at breakdown decreases with cycling due to permanently buckled beams, transforming the conduction mechanism from Schottky to Poole-Frankel emission. Remarkably, our capacitor with 99% porosity, k ∼ 1.09, is operative up to 200 V, whereas devices with 17% porous alumina films breakdown upon biasing based on a percolation model. Similarly with electrical breakdown, the dielectric constant of the capacitor is recoverable with five strain cycles and is stable under 25% compression. These outstanding capabilities of the nanolattice are essential for revolutionizing future flexible electronics.

Yield Precursor Dislocation Avalanches in Small Crystals: The Irreversibility Transition.

The transition from elastic to plastic deformation in crystalline metals shares history dependence and scale-invariant avalanche signature with other nonequilibrium systems under external loading such as colloidal suspensions. These other systems exhibit transitions with clear analogies to work hardening and yield stress, with many typically undergoing purely elastic behavior only after "training" through repeated cyclic loading; studies in these other systems show a power-law scaling of the hysteresis loop extent and of the training time as the peak load approaches a so-called reversible-to-irreversible transition (RIT). We discover here that deformation of small crystals shares these key characteristics: yielding and hysteresis in uniaxial compression experiments of single-crystalline Cu nano- and micropillars decay under repeated cyclic loading. The amplitude and decay time of the yield precursor avalanches diverge as the peak stress approaches failure stress for each pillar, with a power-law scaling virtually equivalent to RITs in other nonequilibrium systems.

Microstructure provides insights into evolutionary design and resilience of Coscinodiscus sp. frustule.

We conducted in situ three-point bending experiments on beams with roughly square cross-sections, which we fabricated from the frustule of Coscinodiscus sp. We observe failure by brittle fracture at an average stress of 1.1 GPa. Analysis of crack propagation and shell morphology reveals a differentiation in the function of the frustule layers with the basal layer pores, which deflect crack propagation. We calculated the relative density of the frustule to be ∼30% and show that at this density the frustule has the highest strength-to-density ratio of 1,702 kN⋅m/kg, a significant departure from all reported biologic materials. We also performed nanoindentation on both the single basal layer of the frustule as well as the girdle band and show that these components display similar mechanical properties that also agree well with bending tests. Transmission electron microscopy analysis reveals that the frustule is made almost entirely of amorphous silica with a nanocrystalline proximal layer. No flaws are observed within the frustule material down to 2 nm. Finite element simulations of the three-point bending experiments show that the basal layer carries most of the applied load whereas stresses within the cribrum and areolae layer are an order of magnitude lower. These results demonstrate the natural development of architecture in live organisms to simultaneously achieve light weight, strength, and exceptional structural integrity and may provide insight into evolutionary design.

Ultralow Thermal Conductivity and Mechanical Resilience of Architected Nanolattices.

Creating materials that simultaneously possess ultralow thermal conductivity, high stiffness, and damage tolerance is challenging because thermal and mechanical properties are coupled in most fully dense and porous solids. Nanolattices can fill this void in the property space because of their hierarchical design and nanoscale features. We report that nanolattices composed of 24- to 182-nm-thick hollow alumina beams in the octet-truss architecture achieved thermal conductivities as low as 2 mW m-1 K-1 at room temperature while maintaining specific stiffnesses of 0.3 to 3 MPa kg-1 m3 and the ability to recover from large deformations. These nanoarchitected materials possess the same ultralow thermal conductivities as aerogels while attaining specific elastic moduli that are nearly 2 orders of magnitude higher. Our work demonstrates a general route to realizing multifunctional materials that occupy previously unreachable regions within the material property space.

Resilient 3D hierarchical architected metamaterials.

Hierarchically designed structures with architectural features that span across multiple length scales are found in numerous hard biomaterials, like bone, wood, and glass sponge skeletons, as well as manmade structures, like the Eiffel Tower. It has been hypothesized that their mechanical robustness and damage tolerance stem from sophisticated ordering within the constituents, but the specific role of hierarchy remains to be fully described and understood. We apply the principles of hierarchical design to create structural metamaterials from three material systems: (i) polymer, (ii) hollow ceramic, and (iii) ceramic-polymer composites that are patterned into self-similar unit cells in a fractal-like geometry. In situ nanomechanical experiments revealed (i) a nearly theoretical scaling of structural strength and stiffness with relative density, which outperforms existing nonhierarchical nanolattices; (ii) recoverability, with hollow alumina samples recovering up to 98% of their original height after compression to ≥ 50% strain; (iii) suppression of brittle failure and structural instabilities in hollow ceramic hierarchical nanolattices; and (iv) a range of deformation mechanisms that can be tuned by changing the slenderness ratios of the beams. Additional levels of hierarchy beyond a second order did not increase the strength or stiffness, which suggests the existence of an optimal degree of hierarchy to amplify resilience. We developed a computational model that captures local stress distributions within the nanolattices under compression and explains some of the underlying deformation mechanisms as well as validates the measured effective stiffness to be interpreted as a metamaterial property.

Enabling Simultaneous Extreme Ultra Low-k in Stiff, Resilient, and Thermally Stable Nano-Architected Materials.

Low dielectric constant (low-k) materials have gained increasing popularity because of their critical role in developing faster, smaller, and higher performance devices. Their practical use has been limited by the strong coupling among mechanical, thermal, and electrical properties of materials and their dielectric constant; a low-k is usually attained by materials that are very porous, which results in high compliance, that is, silica aerogels; high dielectric loss, that is, porous polycrystalline alumina; and poor thermal stability, that is, Sr-based metal-organic frameworks. We report the fabrication of 3D nanoarchitected hollow-beam alumina dielectrics which k is 1.06-1.10 at 1 MHz that is stable over the voltage range of -20 to 20 V and a frequency range of 100 kHz to 10 MHz. This dielectric material can be used in capacitors and is mechanically resilient, with a Young's modulus of 30 MPa, a yield strength of 1.07 MPa, a nearly full shape recoverability to its original size after >50% compressions, and outstanding thermal stability with a thermal coefficient of dielectric constant (TCK) of 2.43 × 10-5 K-1 up to 800 °C. These results suggest that nanoarchitected materials may serve as viable candidates for ultra low-k materials that are simultaneously mechanically resilient and thermally and electrically stable for microelectronics and devices.

The nanocomposite nature of bone drives its strength and damage resistance.

In human bone, an amorphous mineral serves as a precursor to the formation of a highly substituted nanocrystalline apatite. However, the precise role of this amorphous mineral remains unknown. Here, we show by using transmission electron microscopy that 100-300 nm amorphous calcium phosphate regions are present in the disordered phase of trabecular bone. Nanomechanical experiments on cylindrical samples, with diameters between 250 nm and 3,000 nm, of the bone's ordered and disordered phases revealed a transition from plastic deformation to brittle failure and at least a factor-of-2 higher strength in the smaller samples. We postulate that this transition in failure mechanism is caused by the suppression of extrafibrillar shearing in the smaller samples, and that the emergent smaller-is-stronger size effect is related to the sample-size scaling of the distribution of flaws. Our findings should help in the understanding of the multi-scale nature of bone and provide insights into the biomineralization process.

Probing Microplasticity in Small-Scale FCC Crystals via Dynamic Mechanical Analysis.

In small-scale metallic systems, collective dislocation activity has been correlated with size effects in strength and with a steplike plastic response under uniaxial compression and tension. Yielding and plastic flow in these samples is often accompanied by the emergence of multiple dislocation avalanches. Dislocations might be active preyield, but their activity typically cannot be discerned because of the inherent instrumental noise in detecting equipment. We apply alternate current load perturbations via dynamic mechanical analysis during quasistatic uniaxial compression experiments on single crystalline Cu nanopillars with diameters of 500 nm and compute dynamic moduli at frequencies 0.1, 0.3, 1, and 10 Hz under progressively higher static loads until yielding. By tracking the collective aspects of the oscillatory stress-strain-time series in multiple samples, we observe an evolving dissipative component of the dislocation network response that signifies the transition from elastic behavior to dislocation avalanches in the globally preyield regime. We postulate that microplasticity, which is associated with the combination of dislocation avalanches and slow viscoplastic relaxations, is the cause of the dependency of dynamic modulus on the driving rate and the quasistatic stress. We construct a continuum mesoscopic dislocation dynamics model to compute the frequency response of stress over strain and obtain a consistent agreement with experimental observations. The results of our experiments and simulations present a pathway to discern and quantify correlated dislocation activity in the preyield regime of deforming crystals.