Recent progress in acoustic field-assisted 3D-printing of functional composite materials.

Acoustic forces are an attractive pathway to achieve directed assembly for multi-phase materials via additive processes. Programmatic integration of microstructure and structural features during deposition offers opportunities for optimizing printed component performance. We detail recent efforts to integrate acoustic focusing with a direct-ink-write mode of printing to modulate material transport properties (e.g. conductivity). Acoustic field-assisted printing, operating under a multi-node focusing condition, supports deposition of materials with multiple focused lines in a single-pass printed line. Here, we report the demonstration of acoustic focusing in concert with diffusive self-assembly to rapidly assembly and print multiscale, mm-length colloidal solids on a timescale of seconds to minutes. These efforts support the promising capabilities of acoustic field-assisted deposition-based printing to achieve spatial control of printed microstructures with deterministic, long-range ordering across multiple length scales.

Electron backscattered diffraction using a new monolithic direct detector: High resolution and fast acquisition.

A monolithic active pixel sensor based direct detector that is optimized for the primary beam energies in scanning electron microscopes is implemented for electron back-scattered diffraction (EBSD) applications. The high detection efficiency of the detector and its large array of pixels allow sensitive and accurate detection of Kikuchi bands arising from primary electron beam excitation energies of 4 keV to 28 keV, with the optimal contrast occurring in the range of 8-16 keV. The diffraction pattern acquisition speed is substantially improved via a sparse sampling mode, resulting from the acquisition of a reduced number of pixels on the detector. Standard inpainting algorithms are implemented to effectively estimate the information in the skipped regions in the acquired diffraction pattern. For EBSD mapping, an acquisition speed as high as 5988 scan points per second is demonstrated, with a tolerable fraction of indexed points and accuracy. The collective capabilities spanning from high angular resolution EBSD patterns to high speed pattern acquisition are achieved on the same detector, facilitating simultaneous detection modalities that enable a multitude of advanced EBSD applications, including lattice strain mapping, structural refinement, low-dose characterization, 3D-EBSD and dynamic in situ EBSD.

Multiplicity of dislocation pathways in a refractory multiprincipal element alloy.

Refractory multiprincipal element alloys (MPEAs) are promising materials to meet the demands of aggressive structural applications, yet require fundamentally different avenues for accommodating plastic deformation in the body-centered cubic (bcc) variants of these alloys. We show a desirable combination of homogeneous plastic deformability and strength in the bcc MPEA MoNbTi, enabled by the rugged atomic environment through which dislocations must navigate. Our observations of dislocation motion and atomistic calculations unveil the unexpected dominance of nonscrew character dislocations and numerous slip planes for dislocation glide. This behavior lends credence to theories that explain the exceptional high temperature strength of similar alloys. Our results advance a defect-aware perspective to alloy design strategies for materials capable of performance across the temperature spectrum.

Microscopic origin of shear banding as a localized driven glass transition in compressed colloidal pillars.

Here we report on compression experiments of colloidal pillars in which the evolution of a shear band can be followed at the particle level during deformation. Quasistatic deformation results in dilation and anisotropic changes in coordination in a localized band of material. Additionally, a transition from solid- to liquidlike mechanical response accompanies the structural change in the band, as evidenced by saturation of the packing fraction at the glass transition point, a diminishing ability to host anelastic strains, and a rapid decay in the long-range strain correlations. Overall, our results suggest that shear banding quantitatively resembles a localized, driven glass transition.

Strong, Ultralight Nanofoams with Extreme Recovery and Dissipation by Manipulation of Internal Adhesive Contacts.

Advances in three-dimensional nanofabrication techniques have enabled the development of lightweight solids, such as hollow nanolattices, having record values of specific stiffness and strength, albeit at low production throughput. At the length scales of the structural elements of these solids-which are often tens of nanometers or smaller-forces required for elastic deformation can be comparable to adhesive forces, rendering the possibility to tailor bulk mechanical properties based on the relative balance of these forces. Herein, we study this interplay via the mechanics of ultralight ceramic-coated carbon nanotube (CNT) structures. We show that ceramic-CNT foams surpass other architected nanomaterials in density-normalized strength and that, when the structures are designed to minimize internal adhesive interactions between CNTs, more than 97% of the strain after compression beyond densification is recovered. Via experiments and modeling, we study the dependence of the recovery and dissipation on the coating thickness, demonstrate that internal adhesive contacts impede recovery, and identify design guidelines for ultralight materials to have maximum recovery. The combination of high recovery and dissipation in ceramic-CNT foams may be useful in structural damping and shock absorption, and the general principles could be broadly applied to both architected and stochastic nanofoams.

Bridging functional nanocomposites to robust macroscale devices.

At the intersection of the outwardly disparate fields of nanoparticle science and three-dimensional printing lies the promise of revolutionary new "nanocomposite" materials. Emergent phenomena deriving from the nanoscale constituents pave the way for a new class of transformative materials with encoded functionality amplified by new couplings between electrical, optical, transport, and mechanical properties. We provide an overview of key scientific advances that empower the development of such materials: nanoparticle synthesis and assembly, multiscale assembly and patterning, and mechanical characterization to assess stability. The focus is on recent illustrations of approaches that bridge these fields, facilitate the design of ordered nanocomposites, and offer clear pathways to device integration. We conclude by highlighting the remaining scientific challenges, including the critical need for assembly-compatible particle-fluid systems that ultimately yield mechanically robust materials. The role of domain boundaries and/or defects emerges as an important open question to address, with recent advances in fabrication setting the stage for future work in this area.

Transmission scanning electron microscopy: Defect observations and image simulations.

The new capabilities of a FEG scanning electron microscope (SEM) equipped with a scanning transmission electron microscopy (STEM) detector for defect characterization have been studied in parallel with transmission electron microscopy (TEM) imaging. Stacking faults and dislocations have been characterized in strontium titanate, a polycrystalline nickel-base superalloy and a single crystal cobalt-base material. Imaging modes that are similar to conventional TEM (CTEM) bright field (BF) and dark field (DF) and STEM are explored, and some of the differences due to the different accelerating voltages highlighted. Defect images have been simulated for the transmission scanning electron microscopy (TSEM) configuration using a scattering matrix formulation, and diffraction contrast in the SEM is discussed in comparison to TEM. Interference effects associated with conventional TEM, such as thickness fringes and bending contours are significantly reduced in TSEM by using a convergent probe, similar to a STEM imaging modality, enabling individual defects to be imaged clearly even in high dislocation density regions. Beyond this, TSEM provides significant advantages for high throughput and dynamic in-situ characterization.

High-strength magnetically switchable plasmonic nanorods assembled from a binary nanocrystal mixture.

Next-generation 'smart' nanoparticle systems should be precisely engineered in size, shape and composition to introduce multiple functionalities, unattainable from a single material. Bottom-up chemical methods are prized for the synthesis of crystalline nanoparticles, that is, nanocrystals, with size- and shape-dependent physical properties, but they are less successful in achieving multifunctionality. Top-down lithographic methods can produce multifunctional nanoparticles with precise size and shape control, yet this becomes increasingly difficult at sizes of ∼10 nm. Here, we report the fabrication of multifunctional, smart nanoparticle systems by combining top-down fabrication and bottom-up self-assembly methods. Particularly, we template nanorods from a mixture of superparamagnetic Zn0.2Fe2.8O4 and plasmonic Au nanocrystals. The superparamagnetism of Zn0.2Fe2.8O4 prevents these nanorods from spontaneous magnetic-dipole-induced aggregation, while their magnetic anisotropy makes them responsive to an external field. Ligand exchange drives Au nanocrystal fusion and forms a porous network, imparting the nanorods with high mechanical strength and polarization-dependent infrared surface plasmon resonances. The combined superparamagnetic and plasmonic functions enable switching of the infrared transmission of a hybrid nanorod suspension using an external magnetic field.

Linking stress-driven microstructural evolution in nanocrystalline aluminium with grain boundary doping of oxygen.

The large fraction of material residing at grain boundaries in nanocrystalline metals and alloys is responsible for their ultrahigh strength, but also undesirable microstructural instability under thermal and mechanical loads. However, the underlying mechanism of stress-driven microstructural evolution is still poorly understood and precludes rational alloy design. Here we combine quantitative in situ electron microscopy with three-dimensional atom-probe tomography to directly link the mechanics and kinetics of grain boundary migration in nanocrystalline Al films with the excess of O atoms at the boundaries. Site-specific nanoindentation leads to grain growth that is retarded by impurities, and enables quantification of the critical stress for the onset of grain boundary migration. Our results show that a critical excess of impurities is required to stabilize interfaces in nanocrystalline materials against mechanical driving forces, providing new insights to guide control of deformation mechanisms and tailoring of mechanical properties apart from grain size alone.

Thermomechanical Behavior of Molded Metallic Glass Nanowires.

Metallic glasses are disordered materials that offer the unique ability to perform thermoplastic forming operations at low thermal budget while preserving excellent mechanical properties such as high strength, large elastic strain limits, and wear resistance owing to the metallic nature of bonding and lack of internal defects. Interest in molding micro- and nanoscale metallic glass objects is driven by the promise of robust and high performance micro- and nanoelectromechanical systems and miniature energy conversion devices. Yet accurate and efficient processing of these materials hinges on a robust understanding of their thermomechanical behavior. Here, we combine large-scale thermoplastic tensile deformation of collections of Pt-based amorphous nanowires with quantitative thermomechanical studies of individual nanowires in creep-like conditions to demonstrate that superplastic-like flow persists to small length scales. Systematic studies as a function of temperature, strain-rate, and applied stress reveal the transition from Newtonian to non-Newtonian flow to be ubiquitous across the investigated length scales. However, we provide evidence that nanoscale specimens sustain greater free volume generation at elevated temperatures resulting in a flow transition at higher strain-rates than their bulk counterparts. Our results provide guidance for the design of thermoplastic processing methods and methods for verifying the flow response at the nanoscale.

Orthogonal Control of Stability and Tunable Dry Adhesion by Tailoring the Shape of Tapered Nanopillar Arrays.

Tapered nanopillar structures of different cross-sectional geometries including cone-, pencil-like, and stepwise are prepared from anodized aluminum oxide templates. The shape effect on the adhesion strength is investigated in experiments and simulation. Cone-shaped nanopillars are highly bendable under load and can recover after unloading, thus, warranting high adhesion strength, 34 N cm(-2) . The pencil-like and stepwise nano-pillars are, however, easily fractured and are not recoverable under the same conditions.

Measuring surface dislocation nucleation in defect-scarce nanostructures.

Linear defects in crystalline materials, known as dislocations, are central to the understanding of plastic deformation and mechanical strength, as well as control of performance in a variety of electronic and photonic materials. Despite nearly a century of research on dislocation structure and interactions, measurements of the energetics and kinetics of dislocation nucleation have not been possible, as synthesizing and testing pristine crystals absent of defects has been prohibitively challenging. Here, we report experiments that directly measure the surface dislocation nucleation strengths in high-quality 〈110〉 Pd nanowhiskers subjected to uniaxial tension. We find that, whereas nucleation strengths are weakly size- and strain-rate-dependent, a strong temperature dependence is uncovered, corroborating predictions that nucleation is assisted by thermal fluctuations. We measure atomic-scale activation volumes, which explain both the ultrahigh athermal strength as well as the temperature-dependent scatter, evident in our experiments and well captured by a thermal activation model.

A robust smart window: reversibly switching from high transparency to angle-independent structural color display.

A smart window is fabricated from a composite consisting of elastomeric poly(dimethylsiloxane) embedded with a thin layer of quasi-amorphous silica nanoparticles. The smart window can be switched from the initial highly transparent state to opaqueness and displays angle-independent structural color via mechanical stretching. The switchable optical property can be fully recovered after 1000 stretching/releasing cycles.

Robust scaling of strength and elastic constants and universal cooperativity in disordered colloidal micropillars.

We study the uniaxial compressive behavior of disordered colloidal free-standing micropillars composed of a bidisperse mixture of 3- and 6-µm polystyrene particles. Mechanical annealing of confined pillars enables variation of the packing fraction across the phase space of colloidal glasses. The measured normalized strengths and elastic moduli of the annealed freestanding micropillars span almost three orders of magnitude despite similar plastic morphology governed by shear banding. We measure a robust correlation between ultimate strengths and elastic constants that is invariant to relative humidity, implying a critical strain of ∼0.01 that is strikingly similar to that observed in metallic glasses (MGs) [Johnson WL, Samwer K (2005) Phys Rev Lett 95:195501] and suggestive of a universal mode of cooperative plastic deformation. We estimate the characteristic strain of the underlying cooperative plastic event by considering the energy necessary to create an Eshelby-like ellipsoidal inclusion in an elastic matrix. We find that the characteristic strain is similar to that found in experiments and simulations of other disordered solids with distinct bonding and particle sizes, suggesting a universal criterion for the elastic to plastic transition in glassy materials with the capacity for finite plastic flow.

Strain- and defect-mediated thermal conductivity in silicon nanowires.

The unique thermal transport of insulating nanostructures is attributed to the convergence of material length scales with the mean free paths of quantized lattice vibrations known as phonons, enabling promising next-generation thermal transistors, thermal barriers, and thermoelectrics. Apart from size, strain and defects are also known to drastically affect heat transport when introduced in an otherwise undisturbed crystalline lattice. Here we report the first experimental measurements of the effect of both spatially uniform strain and point defects on thermal conductivity of an individual suspended nanowire using in situ Raman piezothermography. Our results show that whereas phononic transport in undoped Si nanowires with diameters in the range of 170-180 nm is largely unaffected by uniform elastic tensile strain, another means of disturbing a pristine lattice, namely, point defects introduced via ion bombardment, can reduce the thermal conductivity by over 70%. In addition to discerning surface- and core-governed pathways for controlling thermal transport in phonon-dominated insulators and semiconductors, we expect our novel approach to have broad applicability to a wide class of functional one- and two-dimensional nanomaterials.

Tailoring and understanding the mechanical properties of nanoparticle-shelled bubbles.

One common approach to generate lightweight materials with high specific strength and stiffness is the incorporation of stiff hollow microparticles (also known as bubbles or microballoons) into a polymeric matrix. The mechanical properties of these composites, also known as syntactic foams, greatly depend on those of the hollow microparticles. It is critical to precisely control the properties of these bubbles to fabricate lightweight materials that are suitable for specific applications. In this paper, we present a method to tailor the mechanical properties and response of highly monodisperse nanoparticle-shelled bubbles using thermal treatment. We characterize the mechanical properties of individual as-assembled bubbles as well as those of thermally treated ones using nanoindentation and quantitative in situ compression tests. As-assembled bubbles display inelastic response, whereas thermally treated bubbles behave elastically. We also show that the stiffness and strength of bubbles are enhanced significantly, as much as 12 and 14 times that of the as-assembled bubbles, respectively, via thermal treatment. We complement the experimental results with finite element analysis (FEA) to understand the effect of shell thickness nonuniformity as well as the inelasticity on the mechanical response and fracture behavior of these bubbles. We demonstrate that the failure mechanism of bubbles incorporated into a polymer composite depends on the structure of the bubbles.

Synthesis and mechanical response of disordered colloidal micropillars.

We present a new approach for studying the uniaxial compressive behavior of colloidal micropillars as a function of the initial defect population, pillar and colloid dimension, and particle-particle interaction. Pillars composed of nanometer scale particles develop cracks during drying, while pillars composed of micron scale particles dry crack-free. We subject the free-standing pillars, with diameters of 580 µm and 900 µm, to uniaxial compression experiments using a custom-built micromechanical testing apparatus. In pillars with pre-existing cracks, compression activates the macroscopic defects, leading to fracture and stochastic mechanical response as a result of the flaw distribution. Pillars that dry crack-free fail by shear bands that initiate near the punch face. While macroscopically identical, pillar-to-pillar mechanical response varies significantly. We attribute the disparate response to varying structure and environmental conditions. To isolate the effects of environment, we performed controlled experiments over a range of relative humidity levels (<2% to >98% RH). The level of atmospheric humidity affects particle-particle cohesion and friction, resulting in dramatically different mechanical responses. We discuss the results in the context of underlying particle rearrangements leading to mesoscopic shear localization and examine comparisons with atomic disordered systems such as metallic glasses.

Temperature controlled tensile testing of individual nanowires.

We present a novel experimental method for quantitatively characterizing the temperature-dependent mechanical behavior of individual nanostructures during uniaxial straining. By combining a microelectromechanical tensile testing device with a low thermal mass and digital image correlation providing nm-level displacement resolution, we show successful incorporation of a testing platform in a vacuum cryostat system with an integrated heater and temperature control. Characterization of the local sample temperature and time-dependent response at both low and high temperature demonstrates a testing range of ∼90-475 K and steady-state drift rates less than 0.04 K/min. In situ operation of the tensile testing device employing resistively heated thermal actuators while imaging with an optical microscope enables high-resolution displacement measurements, from which stress-strain behavior of the nanoscale specimens is deduced. We demonstrate the efficacy of our approach in measuring the temperature dependence of tensile strength in nominally defect-free ⟨110⟩ Pd nanowhiskers. We uncover a pronounced sensitivity of the plastic response to testing temperature over a range of ∼300 K, with an ultimate strength in excess of 6 GPa at low temperature. The results are discussed in the context of thermally activated deformation mechanisms and defect nucleation in defect-free metallic nanostructures.

Effect of organometallic clamp properties on the apparent diversity of tensile response of nanowires.

The influence of the experimental boundary conditions used for tensile testing of individual nanowires on the measured apparent mechanical response is reported. Using a microelectromechanical platform designed for in situ tensile testing, in combination with digital image correlation of sequences of scanning electron microscope images, the mechanical behavior of single crystalline Si, Pd, and Ge2Sb2Te5 nanowires was measured during load-unload cycles. In situ testing enables direct determination of the nanowire strain. Comparison of the direct strain with common metrics for apparent strain that include any compliance or slipping of the clamping materials (electron-beam induced Pt-containing deposits) highlights several different artifacts that may be manifested. Calculation of the contact stiffness is thus enabled, providing guidelines for both proper strain measurement and selection of clamping materials and geometries that facilitate elucidation of intrinsic material response. Our results suggest that the limited ability to tailor the stiffness of electron-beam induced deposits results from the predominance of the organic matrix in controlling its mechanical properties owing to relatively low Pt content and sparse morphology.