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At least 199 records · Page 11

Heterogeneous doping via nanoscale coating impacts the mechanics of Li intrusion in brittle solid electrolytes

Lithium dendrite intrusion in solid-state batteries limits fast charging and causes short-circuiting, yet the underlying regulating mechanisms are not well-understood. Here, in this work, we discover that heterogeneous Ag + doping dramatically affects lithium intrusion into Li 6.6 La 3 Zr 1.6 Ta 0.4 O 12 (LLZO), a brittle solid electrolyte. Nanoscale Ag + doping is achieved by thermally annealing a 3-nm-thick metallic coating on LLZO, inducing Ag–Li ion exchange and Ag diffusion into grains and grain boundaries. Density functional theory calculations and experimental characterization show negligible impact on the electronic properties and surface wettability from Ag + incorporation. Mechanically, nanoindentation experiments show a fivefold increase in the mechanical force required to fracture the surface Ag + -doped LLZO, indicating substantial doping-induced surface toughening. Operando microprobe scanning electron microscopy experiments show that the Ag + -doped LLZO surface exhibits improved lithium plating at >250 mA cm −2 and an electroplating diameter that is expanded by over fourfold, even under an extreme indentation stress of 3 GPa. This demonstrates enhanced defect tolerance in LLZO, rather than electronic or adhesion effects. Our study reveals a chemo-mechanical mechanism via surface heterogeneous doping, complementing present bulk design rules to minimize mechanical failures in solid-state batteries.

36 MATERIALS SCIENCE↗

Improving the Fracture Toughness and Ductility of Liquid-Phase Sintered WNiFe Tungsten Heavy Alloys by High-Temperature Annealing

Tungsten heavy alloys (WHAs) are candidates for use in fusion reactor divertors. Here, we characterize liquid-phase sintered WHAs with 90, 92.5, 95, and 97 (wt.%) tungsten (W), with a balance of a 0.7Ni–0.3Fe ductile phase. These WHAs show remarkable room temperature (RT) fracture toughness at the maximum load, K Jm , ranging from ≈ 38 to 107 MPa√m, compared to a monolithic W toughness of ≈ 8 MPa√m. In most cases, the fracture of WHAs occurs through stable crack tearing. However, the 97W WHA has the lowest toughness and fracture elastically in all but the smallest specimens. As lower Ni contents are desirable for fusion application, we explore the potential for improving the ductility and K Jm of WHAs using vacuum annealing at 1300 °C for 24 h. The microstructural observations reveal negligible changes in the WHA microstructure and constituent compositions. While annealing reduces the Vickers microhardness (HV), it does not significantly change the RT yield (σ y ) and ultimate (σ u ) strengths but results in beneficial increases in total elongation in the 95 and 97W WHAs by a factor of 2. RT tests on the precracked three-point-bend (3PB) bars show that annealing increases the K Jm of these WHAs, and in the case of the 97W WHA, the increase is from 42 to 92%, depending on the size of the specimen. Toughening is due to enhanced crack tip process zone microcracking and dilatation.

36 MATERIALS SCIENCE↗

Engineered Polymer Composites Through Electrospun Nanofiber Coating of Fiber Tows

Toughening and other property enhancements of composite materials are typically implemented by-modifying the bulk properties of the constituents, either the fiber or matrix materials. This often leads to difficulties in processing and higher material costs. Many composites consist of tows or yarns (thousands of individual fibers) that are either filament wound or processed into a fabric by weaving or braiding. The matrix material can be added to the tow or fabric before final processing, resulting in a prepreg material, or infused into the fiber material during final processing by a variety of methods. By using a direct electrospun deposition method to apply thermoplastic nanofiber to the surface of the tows, the tow-tow interface in the resulting composite can be modified while using otherwise conventional materials and handling processes. Other materials of interest could also be incorporated into the electrospun precursor.

toughening↗

Engineered Polymer Composites Through Electrospun Nanofiber Coating of Fiber Tows

Composite materials offer significant weight savings in many aerospace applications. The toughness of the interface of fibers crossing at different angles often determines failure of composite components. A method for toughening the interface in fabric and filament wound components using directly electrospun thermoplastic nanofiber on carbon fiber tow is presented. The method was first demonstrated with limited trials, and then was scaled up to a continuous lab scale process. Filament wound tubes were fabricated and tested using unmodified baseline towpreg material and nanofiber coated towpreg.

toughening↗

Formation of Composite SiC/SiC Joints by Embedded Wire Chemical Vapor Deposition

The joining of ceramic monoliths or composites to date has primarily been limited to the formation of brittle monolithic joints using heterogeneous (dissimilar) materials, similar to brazing in metals. The development of a damage-tolerant joint layer by SiC fiber reinforcements is demonstrated here. Tube workpieces made of SiC fiber-SiC matrix composite are joined using a nonwoven SiC fiber mat densified by embedded wire chemical vapor deposition (EWCVD), creating a fiber-reinforced weld-like joint by homogeneous joining. EWCVD uses a localized heating method to target deposition and growth to the joint region specifically, while minimizing thermal damage to the surrounding composite tube material. X-ray computed tomography (XCT) is used to nondestructively characterize as-made joints for relative density, adhesion, and composition. In situ XCT analysis during mechanical testing revealed crack deflections in the bonding layer, which indicates a toughening mechanism typical of ceramic matrix composite phase. Gas permeation testing of these proof-of-concept composite joints identified relatively high leak rates in comparison to fully coated SiC/SiC composite tube workpieces. In conclusion, the novelty of the composite joining method and current technology challenges, including gas permeability, are discussed in comparison with traditional ceramic joints and materials.

SiC↗

Grain Boundary and Lattice Fracture Toughness of UO 2 Measured Using Small-Scale Mechanics

Small-scale mechanical testing has been used to isolate the properties of individual grain boundaries and regions of the lattice in undoped UO 2 polycrystals. Notched microcantilever specimens were prepared by focused ion beam milling and tested in bending. Fracture toughness values were calculated from finite element analysis of the sample geometry at fracture load using the J-integral method. Lattice and grain boundary fracture toughness values of 1.17 ± 0.16 MPa m 1/2 and 1.08 ± 0.08 MPa m 1/2 , respectively, were obtained. The similarity between the lattice and grain boundary fracture toughness values is consistent with the preference for transgranular room-temperature fracture in UO 2 . The grain boundary and lattice fracture toughness values also agree well with the toughness of dense polycrystals, which suggests that microstructural-scale toughening mechanisms are limited in such samples.

36 MATERIALS SCIENCE↗

Evading strength and ductility trade-off in an inverse nacre structured magnesium matrix nanocomposite

Mimicking nacre structure is an often-used strategy for developing materials which combine high strength and high toughness. Here, a novel strategy, named inverse nacre structure, is proposed where elongated and curled soft constituents are embedded in a matrix of hard constituent to form an ordered brick-and-mortar arrangement. This strategy is demonstrated in a particle reinforced metal matrix composite, using pure Mg as the soft phase and SiC nanoparticle reinforced Mg as the hard phase. In this work, the resulting nanocomposite yields high strength, and especially high tensile elongation which is five times that of the homogeneous counterpart. The superior comprehensive strengthening-toughening effect originates from the tailored inverse nacre structure which enables a stable microcrack-multiplication process by sufficiently promoting strain hardening so as to avoid any significant decrease in post-ultimate tensile strength. This strategy, while demonstrated here for the specific case of particle reinforced Mg, is not restricted to any particular material system but constitutes a generic pathway for the development of high-performance materials for engineering applications.

36 MATERIALS SCIENCE↗

Enhanced flexibility and thermal conductivity of HfC decorated carbon nanofiber mats

Future-generation spacecraft components allude discovery of novel materials that can withstand extreme environments (>2000 °C). The combined effect of ultra-high temperature ceramics (UHTCs) and carbon fibers (C f ) can satisfy the demanding requirements of aerospace applications. A novel, hybrid, and flexible hafnium carbide (HfC)-decorated carbon nanofiber (C nf ) mat was fabricated via electrospinning. Enhanced thermal stability of the flexible HfC decorated C nf over C nf can be elucidated from the 20-fold increment in thermal conductivity and the onset of degradation at higher temperatures (840 °C). Successful integration of multi-layered sandwich lattice using in-housed fabricated HfC decorated C nf showed retention of the fibrous structure even after extreme spark plasma sintering (SPS) process at 1850 °C. Fabricating a similar multi-layered structure using procured C f was unsuccessful due to bundled agglomeration and micron-sized fibers. High-load indentation suggests that HfC decorated C nf interlayer is stronger (~2.3 times) than the parent UHTC with no cracking at the interface. Compared with the HfC matrix, the indentation-damaged area at the interface reduced up to ~56% due to toughening mechanisms such as C nf , fiber pull-out and bridging. The synthesized HfC decorated Cnf mat is proposed as an ultra-thin filler material for joining similar or dissimilar UHTCs while maintaining similar chemistry and better mechanical integrity at the interface. Furthermore, the findings insinuate a new paradigm in designing hybrid and flexible ceramic-containing materials for thermal protection systems (TPS) of future-generation spacecraft components that can mitigate failure in extreme environments (>2000 °C).

36 MATERIALS SCIENCE↗

Hemp fiber reinforced dual dynamic network vitrimer biocomposites with direct incorporation of amino silane

Natural fiber composites are inexpensive and renewable alternatives to traditional fiber reinforced polymers (FRPs). However, existing natural fiber composites primarily rely on petrochemical based thermosetting matrices, which are difficult to recycle due to their stable crosslinked network structures. To address this challenge, it is desirable to develop natural fiber composites with inherently recyclable biobased matrices. In this study, we developed a dual dynamic network vitrimer matrix from hempseed oil and limonene derivatives and demonstrated its application in hemp fiber reinforced composites. To improve the weak interface between hemp fiber and the polymer matrix, a common challenge in the realm of natural fiber composites, we directly incorporated amino silane into the vitrimer matrix. The amino silane participated in the polymer network, increasing the crosslink density and toughening the matrix, as evidenced by a significantly improved impact strength from 3.5 kJ/m 2 to 10.3 kJ/m 2 . Moreover, the incorporation of amino silane resulted in a lower water absorption by 11% in 7-day soaking for the composites, demonstrating improved fiber/matrix interfacial interaction. Furthermore, our biobased vitrimer matrix exhibits both imine and hydroxy-ester dynamic bonds, which enable the recycling of the biocomposite through a mild and cost-effective aminolysis process (100°C, 3h, ambient pressure). The decomposed polymer matrix was successfully reused as a polyol for polyurethane adhesives, and the surface morphology of recovered hemp fibers was analyzed and compared with that of the original fibers. Furthermore, these findings will help broaden the use of vitrimers for practical natural fiber composite applications, raise awareness of the problem of recycling natural fiber composite waste, and shed light on the interfacial challenge of natural fiber reinforced vitrimer composites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Strain hardening magnesium-silicate-hydrate composites (SHMSHC) reinforced with short and randomly oriented polyvinyl alcohol microfibers

Magnesium-silicate-hydrate (M-S-H) cement has emerged as an alternative binder with potentially lower energy requirements and emissions. Due to the intrinsically low pH values of its matrix, however, normal steel reinforcement is not appropriate for M-S-H system. To toughen the matrix and to overcome the brittle nature of the material, a new strain hardening magnesium-silicate-hydrate composite (SHMSHC) is developed for the first time by incorporating 2 vol% short and randomly oriented polyvinyl alcohol (PVA) microfibers. The resulting SHMSHC exhibits significant strain hardening with a tensile strain capacity of more than 3%, a compressive strength beyond 50 MPa and a tensile strength of around 3 MPa. Remarkably, saturated multiple cracking with a tight crack width less than 10 μm invisible to the human naked eyes was observed. The newly developed SHMSHC addresses the fundamental challenge of M-S-H binder and is expected to widen possible application areas of M-S-H system.

36 MATERIALS SCIENCE↗

3D-printable engineered cementitious composites (3DP-ECC): Fresh and hardened properties

3D printing (3DP) is an emerging digital construction method for concrete materials. A major impediment to efficient 3D concrete printing (3DCP) is the need for steel reinforcement, the placement of which is incompatible with the 3DP process. Unlike plain concrete, ductile self-reinforced engineered cementitious composite (ECC) holds promise to remove the dependence on steel reinforcement. The objective of this research is to develop a 3D-printable ECC (3DP-ECC). The fresh rheological and hardened mechanical properties of 3DP-ECC are investigated. The robotically printed tensile specimens demonstrated the familiar multiple microcracking and strain-hardening behavior of conventionally cast ECC. Significant orthotropy is revealed in the compressive properties. The interface between printed layers is found to be toughened by a printed groove-tongue joint. The developed 3DP-ECC was used to print a twisted column with 150 layers, reaching a height of 1.5 m. This research lays the groundwork for efficient robotically 3D-printed structures of complex shapes.

36 MATERIALS SCIENCE↗

The effect of loading direction on the fracture behaviors of cortical bone at a dynamic loading rate

Here, the dynamic cracking processes in porcine cortical bone were visualized in real-time using the high-speed synchrotron X-ray phase-contrast imaging (PCI) technique in three osteon orientations: in-plane transverse, out-of-plane transverse and in-plane longitudinal. The dynamic flexural loading applied on the pre-notched bone specimens was introduced by a modified Kolsky compression bar. High-speed X-ray images of the entire loading events were documented with a high-speed camera. Three-dimensional X-ray micro-computed tomography was conducted to examine the intact microstructures and obtain the basic material properties of the bone material used for mechanical characterizations. The onset location, where crack initiated, and the subsequent direction, along which the incipient crack propagated, were measured quantitatively using the high-speed X-ray images and the latter was found dependent on the osteon direction significantly. The crack propagation velocities were dependent on crack extension over the entire crack path significantly for all the three directions while the initial velocity for in-plane longitudinal direction was lower than the other two directions. Straight-through crack paths were observed for in-plane longitudinal specimens while the cracks were deflected and twisted in the in-plane transverse direction. For out-of-plane transverse direction, the cracks follow paths with tortuosity fall in between the other two directions, showing a mixed mode of fractures of the former two extreme cases. The toughening mechanisms, visualized by the high-speed X-ray images, and the corresponding fracture toughness, evaluated in terms of fracture initiation toughness and crack growth resistance curve (R-curve), were also found significantly different among the three osteon directions, suggesting an overall transition from brittle to ductile-like fracture behaviors at the dynamic displacement rate (5.4 m/s) as the osteon orientation varies from in-plane longitudinal to out-of-plane transverse, and to in-plane transverse eventually.

42 ENGINEERING↗

Through-thickness fracture behavior of neutron-irradiated nuclear graphite NBG-17 Using X-ray micro-CT

Achieving precise control over crack propagation in nuclear graphite and conducting quantitative analysis remain challenging. In this study, the through-thickness fracture behavior of pristine and neutron-irradiated (700 °C, ∼7 dpa) NBG-17 nuclear graphite was investigated using split-disc testing coupled with micro-computed tomography (micro-CT). A notably lower number of micropores was observed in the neutron-irradiated specimen. The fracture toughness of neutron-irradiated NBG-17 was measured to be 1.45 MPa√m, compared to 1.17 ± 0.05 MPa√m for the pristine specimen. In both materials, cracks were found to initiate at the filler–binder interface, and often correlated with microstructural features such as pores and thermal cracks. Crack bridging and deflections emerged as the primary toughening mechanisms in both unirradiated and irradiated NBG-17. However, compared with the pristine specimen, the cracks in the neutron-irradiated specimen were more likely to grow trans granularly, resulting in less deflected crack paths. The reduced micro-porosity and strengthened filler–binder boundaries were considered to be the cause of the observed differences in crack morphologies. In conclusion, this study provides a qualitative analysis of the fracture behavior of neutron-irradiated nuclear graphite in the absence of radiolytic oxidation.

36 - MATERIALS SCIENCE↗

Structure and Mechanical Adaptability of a Modern Elasmoid Fish Scale from the Common Carp

The carp (Cyprinus carpio) has typical elasmoid scales commonly found on teleosts. They provide protection while retaining flexibility and maneuverability of the fish. The exterior surface of the scale consists of an ultrathin discontinuous mineral layer on top of mineralized woven collagen fibrils. The underlying foundation is composed of two collagenous components. The major one consists of a single-twisted ‘‘Bouligand’’ structure with a twisting angle of 36°. A secondary ‘‘sheet-like’’ structure, formed by thinner collagen fibrils oriented along the thickness direction, acts to increase the integrity of the scale. In this work, we identify the deformation and failure mechanisms of the carp scale, revealing slight tensile anisotropy. Using in situ small-angle X-ray scattering during tensile testing, the toughening mechanisms of the scale, including the adaptive structural reorientation of lamellae as well as fibrillar sliding and elastic deformation, are quantified and compared with those of other fish scales.

59 BASIC BIOLOGICAL SCIENCES↗

Modeling and experimental validation of a W f /W-fabrication by chemical vapor deposition and infiltration

Tungsten (W) has a unique combination of excellent thermal properties, low sputter yield, low hydrogen retention, and acceptable activation. Therefore, W is presently the main candidate for the first wall material in future fusion devices. However, its intrinsic brittleness and its further embrittlement during operation bears the risk of a sudden and catastrophic component failure. As a countermeasure, tungsten fiber-reinforced tungsten (W f /W) with extrinsic toughening is being developed. A possible synthesis route is chemical vapor deposition (CVD) using heated W fabrics as substrate. The challenge is that the growing CVD-W can isolate domains from precursor access leading to strength-reducing pores. To deepen the process understanding and to optimize the CVD parameters, models were developed with COMSOL Multiphysics and validated experimentally. W deposition rate equations as function of the temperature and the partial pressures of the precursors H 2 and WF 6 were experimentally validated in previous work. In the present article, these equations are applied to obtain partial pressures within the CVD reactor. The results are taken as input for transient simulations in the microscale, in which W coatings, growing onto multiple adjacent W fibers, were simulated via mesh deformation and remeshing. The surface-to-surface contact of the W coatings and the corresponding potential pore formation were simulated by implementing sophisticated deposition rate stop conditions. Within the measuring uncertainties of ≃ ±1%, the models are validated successfully by experimental comparison regarding the deposition rate, pore structure, and relative densities ranging from 0.6 to 0.9.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Nanolatticed Architecture Mitigates Damage in Shark Egg Cases

Structural versatility and multifunctionality of biological materials have resulted in countless bioinspired strategies seeking to emulate the properties of nature. The nanostructured egg case of swell sharks is one of the toughest permeable membranes known and, thus, presents itself as a model system for materials where the conflicting properties, strength and porosity, are desirable. The egg case possesses an intricately ordered structure that is designed to protect delicate embryos from the external environment while enabling respiratory and metabolic exchange, achieving a tactical balance between conflicting properties. Herein, structural analyses revealed an enabling nanolattice architecture that constitutes a Bouligand-like nanoribbon hierarchical assembly. Three distinct hierarchical architectural adaptations enhance egg case survival: Bouligand-like organization for in-plane isotropic reinforcement, noncylindrical nanoribbons maximizing interfacial stress distribution, and highly ordered nanolattices enabling permeability and lattice-governed toughening mechanisms. Furthermore, these discoveries provide fundamental insights for the improvement of multifunctional membranes, fiber-reinforced soft composites, and mechanical metamaterials.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Connecting Interfacial Mechanical Adhesion, Efficiency, and Operational Stability in High Performance Inverted Perovskite Solar Cells

Carbazole-based self-assembled monolayers (SAMs) at the interface between the metal-halide perovskite (MHP) and the transparent conducting oxide (TCO) serve the function of hole-transport layers in p-i-n "inverted" perovskite solar cells (PSCs). In this report we show that the use of an iodine-terminated carbazole-based SAM increases the interfacial mechanical adhesion dramatically (2.6-fold) and that this is responsible for substantial improvements in the interfacial morphology, photocarrier transport, and operational stability. While the improved morphology and optoelectronic properties impart high efficiency (up to 25.39%) to the PSCs, the enhanced adhesion suppresses nucleation and propagation of pores/cracks during PSC operation, resulting in the retention of 96% of the initial efficiency after 1000 h of continuous-illumination testing at the maximum power-point. This demonstrates the strong connection between judicious interfacial adhesion toughening and simultaneous enhancement in the efficiency and operational stability of p-i-n PSCs, with broader implications for the reliability and durability of perovskite photovoltaics before they can be commercialized.

14 SOLAR ENERGY↗

Bioinspired mechanical mineralization of organogels

Mineralization is a long-lasting method commonly used by biological materials to selectively strengthen in response to site specific mechanical stress. Achieving a similar form of toughening in synthetic polymer composites remains challenging. In previous work, we developed methods to promote chemical reactions via the piezoelectrochemical effect with mechanical responses of inorganic, ZnO nanoparticles. Herein, we report a distinct example of a mechanically-mediated reaction in which the spherical ZnO nanoparticles react themselves leading to the formation of microrods composed of a Zn/S mineral inside an organogel. The microrods can be used to selectively create mineral deposits within the material resulting in the strengthening of the overall resulting composite.

59 BASIC BIOLOGICAL SCIENCES↗