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ZnO-Au Hybrid Metamaterial Thin Films with Tunable Optical Properties

ZnO-Au nanocomposite thin films have been previously reported as hybrid metamaterials with unique optical properties such as plasmonic resonance properties and hyperbolic behaviors. In this study, Au composition in the ZnO-Au nanocomposites has been effectively tuned by target composition variation and thus resulted in microstructure and optical property tuning. Specifically, all the ZnO-Au nanocomposite thin films grown through the pulsed laser deposition (PLD) method show obvious vertically aligned nanocomposite (VAN) structure with the Au nanopillars embedded in the ZnO matrix. Moreover, the average diameter of Au nanopillars increases as Au concentration increases, which also leads to the redshifts in the surface plasmon resonance (SPR) wavelength and changes in the hyperbolic behaviors of the films. As a whole, this work discusses how strain-driven tuning of optical properties and microstructure resulted through a novel Au concentration variation approach which has not been previously attempted in the ZnO-Au thin film system. These highly ordered films present great promise in the areas of sensing, waveguides, and nanophotonics to name a few.

Bhatt, Nirali A.↗

A comprehensive investigation of the strengthening effects of dislocations, texture and low and high angle grain boundaries in ultrafine grained AA6063 aluminum alloy

Highlights: • Evolution of microstructure and mechanical properties of AA6063 after severe plastic deformation was investigated. • Average cell size shows a more solid relationship with mechanical properties rather than the average grain size. • This indicates that in addition to high angle boundaries, cell boundaries play a strengthening role. - Abstract: The effect of equal channel angular pressing (ECAP) on the microstructure and mechanical properties of AA6063 aluminum alloy was investigated. For this purpose, samples of AA6063 aluminum alloy were deformed up to 10 passes using ECAP and the evolution of microstructure, texture and dislocation density was investigated. It was found that the dislocation density increased and cells mostly surrounded by low angle boundaries (LABs) formed after 2 passes ECAP. Increasing the dislocation density continued with further processing and reached a maximum at the 4th ECAP pass. With further deformation to 6 passes, the dislocation density reduced, the fraction of high angle boundaries (HABs) increased and the averages of cell size and grain size reduced, significantly, which indicated the occurrence of grain refinement. However, a slight increase in dislocation density, average cell size (ACS) and average grain size (AGS), indicating coarsening, occurred when 10 passes of ECAP are imposed. Hardness, yield (YS) and ultimate tensile strength (UTS) increased continuously although the most significant enhancement occurred after 2 passes of ECAP. Investigating the correlation between the microstructure and mechanical properties indicated that Hall-Petch relationship was valid for ultrafine grained AA6063 before the coarsening started provided that the property of interest was correlated to average cell size but not the average grain size.

36 MATERIALS SCIENCE↗

Development of a Novel Magnesium Alloy for Thixomolding® of Automotive Components (Final Report)

Magnesium (Mg) alloy die-castings are increasingly used in the automobile industry to achieve cost effective mass reduction, especially in systems where multiple components can be integrated into a single thin wall die-casting. However, there are several component quality restrictions in thin-walled Mg die castings, including variability in dimensional accuracy, part-to-part variation in mechanical properties, and porosity in the final part, which has limited the continued growth of die-cast components in the automobile industry. An alternative to die-casting is the process of thixomolding®. While the die-casting process relies on filling a mold at high speeds with the alloy in the completely molten state, the thixomolding® process fills a mold with a thixotropic alloy in a semi-solid slurry state at a temperature between the liquidus and solidus temperatures. Ideally, the material should be ~30–65% solid rather than being completely liquid at the beginning of the injection process. Advantages of the thixomolding® process include a finer grain structure, lower porosity, improved dimensional accuracy, improved part-to part consistency, improved mechanical properties, particularly ductility in the component, the ability to reduce wall thickness for mass savings, and longer tool life due to lower process temperatures. The objective of this collaborative project between Oak Ridge National Laboratory, FCA US LLC, and Leggera Technologies was to develop one or more novel Mg alloys more suitable for thixomolding® automotive structural components than the current die-casting alloys used for this process. The primary interest was to improve ductility while maintaining tensile and fatigue strengths, as these are properties that are critical for use in body and chassis structural applications. Since good corrosion resistance is also desirable for this application, this property was also considered when evaluating promising alloy compositions. An initial evaluation of existing components thixomolded® using AM60 was performed and microstructure, and tensile properties were evaluated for the baseline alloy. Targets were established for ease of processing (characterized by the melting range defined as the difference between the liquidus and the solidus), strength, and ductility. Computational modeling was used to identify promising alloys and selected alloys were cast in laboratory scale heats. Properties measured from laboratory scale heats were used to down-select two alloys for further evaluation and component fabrication. Two alloys were prepared in industrial scale heats, cut into small pieces (chips), and thixomolding® trials were initiated. Trial components were successfully fabricated using one alloy composition, but it was concluded that further refinement of the thixomolding® process parameters are required to successfully fabricate component using second alloy. Microstructure and mechanical properties were evaluated on the material removed from the fabricated component and properties were compared to the baseline alloy. Although mechanical properties of the alloys showed improvement over the baseline alloy, it was determined that modifications to the thixomolding® process would result in better microstructure control with further improvement in properties leading to successful commercialization. A provisional patent application has already been filed on the new alloys developed as part of the project.

36 MATERIALS SCIENCE↗

Properties of Rolled AZ31 Magnesium Alloy Sheet Fabricated by Continuous Variable Cross-Section Direct Extrusion

Rolling is currently a widely used method for manufacturing and processing high-performance magnesium alloy sheets and has received widespread attention in recent years. Here, we combined continuous variable cross-section direct extrusion (CVCDE) and rolling processes. The microstructure and mechanical properties of the resulting sheets rolled at different temperatures from CVCDE extrudate were investigated by optical microscopy, scanning electron microscope, transmission electron microscopy and electron backscatter diffraction. The results showed that a fine-grained microstructure was present with an average grain size of 3.62 μm in sheets rolled from CVCDE extrudate at 623 K. Dynamic recrystallization and a large strain were induced by the multi-pass rolling, which resulted in grain refinement. In the 573-673 K range, the yield strength, tensile strength and elongation initially increased and then declined as the CVCDE temperature increased. The above results provide an important scientific basis of processing, manufacturing and the active control on microstructure and property for high-performance magnesium alloy sheet.

36 MATERIALS SCIENCE↗

Mechanical and Microstructural Characterization of Low-Temperature Neutron Irradiated Zircaloy-4

Zr-based alloys, namely Zircaloy-2, Zircaloy-4, ZIRLO, or M5, have been used in light water reactors (LWRs) as structural materials (cladding, pressure tubes, and etc.). Under irradiation conditions, especially at harsh pressurized water reactor (PWR) conditions, these Zr alloys can undergo embrittlement due to corrosion, hydriding, and irradiation induced stresses. This ultimately leads to the severe degradation of Zr-alloys and increase the probability of fuel failure. While various research efforts have been conducted in developing better Zr-based alloys to withstand these harsh environments, there is a considerable amount of Zr-alloy characteristics, such as change in mechanical properties under irradiation conditions and its relationship to the materials microstructure, that need to be studied. This present study has focused on investigation of mechanical and microstructural properties of Zircaloy-4 under low temperature (80 - 100 deg. C) neutron irradiation conditions. Some of the samples studied were also hydrided to evaluate influence of hydride precipitates in the material. (authors)

36 MATERIALS SCIENCE↗

Machine-learning-based, online estimation of ceramic’s microstructure upon the laser spot brightness during laser sintering

The ceramic microstructure strongly influences its properties. During manufacturing, the online monitoring of microstructure is critical to ensure the desired material properties. So far, the microstructure on the relevant scale is usually characterized offline using scanning electron microscopy (SEM), which is time and cost-consuming. In this work, we demonstrate a cost-effective, machine learning (ML)-based approach to simulate the SEM micrographs in real-time from the laser spot brightness. We experimentally observed a strong correlation between the laser spot brightness and the corresponding microstructure at the exact locations. The brightness values obtained from thermal emission images and the corresponding SEM micrographs were used in the training datasets. The ML algorithm was a style-based conditional generative adversarial network (CGAN). After training, the ML model could generate high-fidelity microstructure images within 0.1 seconds based on in-situ captured brightness at the laser sintering spot. We used the average grain sizes as the metric to evaluate the accuracy of the ML-predicted micrographs. Here, the ML-predicted microstructures were in good agreement, with less than 5% in difference from the real SEM images. In conclusion, we demonstrate the cost-effective, online microstructure estimation during laser sintering with a simple setup (a camera, a regular computer, and the ML model).

08 HYDROGEN↗

Evaluating the bond strength and fracture mechanisms of cold-sprayed zinc coating on AZ91 magnesium substrate via a combined experimental and computational approach

Magnesium (Mg) alloys are ideal candidates for automotive applications due to their high strength to weight ratio, castability, recyclability etc., however, they lack corrosion and oxidation resistance. Solid-state deposition techniques, such as cold spray, have been demonstrated to enhance their corrosion resistance as it relies on the severe plastic deformation of powder particles upon impact with the substrate to form a metallurgical bond with the substrate and within the coating. At cold sprayed interfaces, a heterogeneous microstructure is formed that includes some porosity, oxides and intermetallics which can significantly affect coating performance. Thus, establishing a direct correlation between the interface microstructure and its properties can aid in designing optimal cold spray parameters. In this study, we investigated the microstructure and mechanical properties of a zinc (Zn) coating deposited on a high pressure die cast (HPDC) AZ91 Mg substrate via high resolution scanning transmission electron microscopy, in situ micro-tensile testing, and finite element method (FEM) modeling. Micro-tensile pillars fabricated using the plasma focused ion beam (PFIB) successfully isolates the coating-substrate interface within the gauge length. The average bond strength of Zn-Mg interface was determined to be ∼140 MPa with failure occurring partially at the interface and mostly into the coatings. A detailed microstructural characterization revealed evidence of a strong metallurgical bonding at the Zn-Mg interface and formation of the C14 MgZn 2 laves phase interlayer resulting in a mixed mode of fracture during the micro-tensile experiments. FEM modeling reveals the stress distribution along the interfaces and suggests that a MgZn 2 layer thickness between 200–400 nm is optimum to increase the bond strength and minimize the triaxiality. Such a site-specific interfacial analysis with correlative computational modeling provides crucial insight into the overall performance of cold spray interfaces.

Bond strength↗

Comparison of hardening and microstructures of ferritic/martensitic steels irradiated with fast neutrons and dual ions

Ferritic/martensitic steels T91 and HT9 were irradiated with neutrons (BOR-60 reactor) and dual ions (9 MeV Fe 3+ and 3.42 MeV energy degraded He 2+ ) from 369 to 520 °C and damage levels of 16.6 to 72 dpa to quantify the possibility of using ion irradiation to simulate neutron irradiation in terms of microstructures and mechanical properties. Nanoindentation testing was performed to obtain the bulk equivalent hardness of the dual-ion irradiated samples. For the neutron irradiated samples, both nanoindentation and Vickers hardness testing were conducted. Transmission Electron Microscopy (TEM) characterizations of the cavities, dislocation loops and precipitates were conducted to account for the strengthening contribution of each microstructure element. The good agreement between the microstructure-predicted (dispersed barrier hardening) and measured strength of the irradiated specimens demonstrated the accuracy of the strengthening model and the nanoindentation tests. Furthermore, the comparison of mechanical property and microstructure changes in ion and neutron irradiated structural materials indicated that ion irradiation replicated many neutron irradiation features. However, a single 70 °C temperature shift is insufficient to match all complex microstructures of neutron vs. ion irradiation over the irradiation temperature range of 369–520 °C.

36 MATERIALS SCIENCE↗

Material Characterization of Additively Manufactured Components for Rocket Propulsion

To advance Additive Manufacturing (AM) technologies for production of rocket propulsion components the NASA Glenn Research Center (GRC) is applying state of the art characterization techniques to interrogate microstructure and mechanical properties of AM materials and components at various steps in their processing. The materials being investigated for upper stage rocket engines include titanium, copper, and nickel alloys. Additive manufacturing processes include laser powder bed, electron beam powder bed, and electron beam wire fed processes. Various post build thermal treatments, including Hot Isostatic Pressure (HIP), have been studied to understand their influence on microstructure, mechanical properties, and build density. Micro-computed tomography, electron microscopy, and mechanical testing in relevant temperature environments has been performed to develop relationships between build quality, microstructure, and mechanical performance at temperature. A summary of GRCs Additive Manufacturing roles and experimental findings will be presented.

Additive Manufacturing↗

Materials Characterization of Additively Manufactured Components for Rocket Propulsion

To advance Additive Manufacturing (AM) technologies for production of rocket propulsion components the NASA Glenn Research Center (GRC) is applying state of the art characterization techniques to interrogate microstructure and mechanical properties of AM materials and components at various steps in their processing. The materials being investigated for upper stage rocket engines include titanium, copper, and nickel alloys. Additive manufacturing processes include laser powder bed, electron beam powder bed, and electron beam wire fed processes. Various post build thermal treatments, including Hot Isostatic Pressure (HIP), have been studied to understand their influence on microstructure, mechanical properties, and build density. Micro-computed tomography, electron microscopy, and mechanical testing in relevant temperature environments has been performed to develop relationships between build quality, microstructure, and mechanical performance at temperature. A summary of GRC's Additive Manufacturing roles and experimental findings will be presented.

Additive Manufacturing↗

Elaborating the phases and mechanical properties of multiphase alloy: Experimental two-dimensional mapping combined with theoretical calculations

Highlights: • Mechanical modulus and hardness distribution mapping is obtained for the first time by NanoBlitz 3D. • Phases mapping and exact element ratio are characterized for the nano multielement carbides by EPMA. • Carbides types are confirmed by acid etching and XRD refinement. • Young's modulus of multiple carbides is verified by DFT calculations and Voigt-Reuss-Hill model. - Abstract: The relationship between types of phases, microstructure and mechanical properties is always a critical challenge for the research and application of multiphase alloys. We report for the first time that NanoBlitz 3D method implemented in iNano is used to investigate the distribution of micro mechanical modulus and hardness for the entire complex multiphase alloy Fe-6.0W-5.0Mo-4.0Cr-2.0V-0.83C by constructing the two-dimensional mapping. In order to build the correlation between the microstructure and properties, the carbides in this tempering state steel are confirmed to be Fe{sub 3}(W, Mo){sub 3}C, Cr{sub 15.58}Fe{sub 7.42}C{sub 6} and V{sub 8}C{sub 7} by acid etching and XRD refinement. The phases mapping is obtained by electron probe micro-analysis. Exact element ratio is characterized for the nano-scale multielement carbides precipitates. The Young's modulus and hardness of the precipitated carbides are up to 330 GPa and 22 GPa, respectively. The distribution range of Young's modulus and hardness is during 150 to 250 GPa and 2.5 to 7.0 GPa for the matrix phases, respectively. The experimental Young's modulus and hardness results are verified by first-principles calculations combined with Voigt-Reuss-Hill approximation. In fact, this work provides a successful demonstration to three-dimensionally characterize the micro mechanical properties for all the ceramics and alloys.

36 MATERIALS SCIENCE↗

Machine-learning-assisted deciphering of microstructural effects on ionic transport in composite materials: A case study of Li 7 La 3 Zr 2 O 12 -LiCoO 2

The effective diffusivity of ionic species in multiphase materials is critical for the design and function of composite materials for electrochemical energy storage. In practice, effective diffusivity depends sensitively not only on the intrinsic diffusivities of constituting materials but also on their topological arrangement; nevertheless, these coupled contributions are oversimplified in most analytical models. Here, we combine atomistically informed mesoscale modeling and machine learning (ML) analysis to unravel how such features affect effective diffusivity in two-phase composites. Using the Li 7 La 3 Zr 2 O 12 -LiCoO 2 composite solid-state battery cathode as a model system, we compute effective diffusivity for 600 distinct dense polycrystalline microstructures with different topological configurations of grains, grain boundaries, and heterointerfaces. We verify that in addition to atomic-scale variabilities, microstructural feature diversity can significantly impact effective transport properties. Across the ensemble of test microstructures, this often results in bimodal distributions of effective diffusivity that encompass two qualitatively distinct operating mechanisms, which we identify via flux analysis. An ML approach reveals that the most critical determining factors for effective diffusivity are the connectivity of bulk phases and their heterointerfaces. The role of ionic mobility at the heterointerfaces is also discussed. These insights highlight the combined importance of microstructure and interface engineering in tuning the transport properties of ionic species in composite materials. In conclusion, our framework can also be extended for understanding generic microstructure-property relationships in other complex multiphase materials.

25 ENERGY STORAGE↗

Microstructural variation through weld thickness and mechanical properties of peened friction stir welded 6061 aluminum alloy joints

The current study examined the effect of microstructure variation on the development of mechanical properties in friction stir welded joints of 6061-T6 aluminum alloy, which were subsequently processed by shot peening (SP). Following to FSW, fatigue specimens were extracted perpendicularly to the welding direction. Surface Skimming to 0.5 mm from crown and root sides of the joint was made and SP was later applied on the two sides using ceramic shots of two different Almen intensities of 0.18 mmA and 0.24 mmA. Microstructural examination by electron back scattered diffraction (EBSD) indicated variation in the grain refinement of the weld zone, with coarsest grains (5 μm) at the crown side and finest grains (2 μm) at the root side. Reduction of microhardness to 60 HV occurred in the weld zone for samples in FSW condition. Application of SP promoted significant strain hardening at the crown side, with Almen intensities of 0.24 mmA providing maximum increase in microhardness to 120 HV. On the contrary, only a maximum microhardness of 75 HV was obtained at the root side. The difference in strain hardening capability at the two sides was strongly dependent on grain size. The two Almen intensities produced similar distribution of compressive residual stresses in the subsurface regions that led to enhance the fatigue strength to the level of base metal for N ≥ 10{sup 5} cycles. Yet, the increase in fatigue strength was more pronounced with increasing Almen intensity to 0.24 mmA, demonstrating further enhancement by strain hardening. - Highlights: • Grain refinement was observed after friction stir welding of AA 6061-T6. • Reduction in microhardness and fatigue strength were obtained after welding. • Variation in grain refinement led to different hardening behavior after peening. • Shot peening induced beneficial compressive residual stresses. • Shot peening and surface skimming markedly improved the fatigue performance.

36 MATERIALS SCIENCE↗

Strengthening mechanisms in directed energy deposited austenitic stainless steel

Microstructures and mechanical properties are evaluated in austenitic stainless steel structures fabricated by directed energy deposition (DED) considering the effects of applied loading orientation, build geometry, and distance from the deposition baseplate. Locations within an as-deposited build with different thermomechanical history display different yield strength, while those locations with similar history have approximately the same yield strength, regardless of test specimen orientation. Thermal expansion of deposited material near the baseplate is inhibited by the mechanical constraint imposed by the baseplate, promoting plastic deformation and producing a high density of dislocations. Concurrently, high initial cooling rates decrease away from the baseplate as the build is heated, causing an increased spacing of cellular solidification features. An analysis of strengthening mechanisms quantitatively established for the first time the important strengthening contribution of high dislocation densities in the materials (166–191 MPa) to yield strength that ranged from 438 to 553 MPa in the present DED fabricated structures. A newly adopted mechanistic relationship for microsegregation strengthening from the literature indicated an additional important contribution to strengthening (123–135 MPa) due to the cellular solidification features. These findings are corroborated by the measured evolution of microstructure and hardness caused by annealing the DED material. Finally, these results suggest that the mechanical properties of deposited austenitic stainless steels can be influenced by controlling thermomechanical history during the manufacturing process to alter the character of compositional microsegregation and the amount of induced plastic deformation.

36 MATERIALS SCIENCE↗

Additive Manufacturing of High-Entropy Alloys: A Review

Owing to the reduced defects, low cost, and high efficiency, the additive manufacturing (AM) technique has attracted increasingly attention and has been applied in high-entropy alloys (HEAs) in recent years. It was found that AM-processed HEAs possess an optimized microstructure and improved mechanical properties. However, no report has been proposed to review the application of the AM method in preparing bulk HEAs. Hence, it is necessary to introduce AM-processed HEAs in terms of applications, microstructures, mechanical properties, and challenges to provide readers with fundamental understanding. Specifically, we reviewed (1) the application of AM methods in the fabrication of HEAs and (2) the post-heat treatment effect on the microstructural evolution and mechanical properties. Compared with the casting counterparts, AM-HEAs were found to have a superior yield strength and ductility as a consequence of the fine microstructure formed during the rapid solidification in the fabrication process. The post-treatment, such as high isostatic pressing (HIP), can further enhance their properties by removing the existing fabrication defects and residual stress in the AM-HEAs. Furthermore, the mechanical properties can be tuned by either reducing the pre-heating temperature to hinder the phase partitioning or modifying the composition of the HEA to stabilize the solid-solution phase or ductile intermetallic phase in AM materials. Moreover, the processing parameters, fabrication orientation, and scanning method can be optimized to further improve the mechanical performance of the as-built-HEAs.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

An investigation of the microstructure and ductility of annealed cold-rolled tungsten

Tungsten is notoriously brittle metal at room temperature. Furthermore, contrary to most metals, plastic deformation increases ductility and recrystallization decreases ductility of tungsten. The fundamentals that govern this behavior have challenged academia and industry for decades. This paper focuses on understanding the controlling factors of ductility through a systematic investigation of the changes in microstructure and mechanical properties of cold-rolled tungsten that occur during annealing. Cold-rolled tungsten samples were annealed at temperatures up to 1400 °C, and mechanical testing and microstructural analysis was performed before and after annealing. Furthermore, a dislocation mobility model based on the Orowan equation was applied. The mechanisms of deformation are discussed within the context of deformed and annealed microstructures. The high fraction of low angle grain boundaries and high density of edge dislocations were found to be the most important factors for ductility. Although there were gradual changes in microstructure and mechanical properties, the ductility of cold-rolled tungsten was maintained up to 1300 °C. The material recrystallized when annealed above this temperature, had no ductility, and suffered brittle fracture. Microstructural characterizations of the as-rolled material revealed a typical BCC texture, with grains elongated in rolling direction and a large amount of edge dislocations and low angle grain boundaries. The level of texturing and the fraction of low angle grain boundaries diminished after recrystallization. It was found that, compared to the recrystallized material, as-rolled tungsten can accommodate over 7 orders of magnitude higher deformation velocity due to the high density of edge dislocations.

36 MATERIALS SCIENCE↗

Implementation Challenges for Ceramic Matrix Composites in High Temperature Applications

Ceramic matrix composites are leading candidate materials for a number of applications in aeronautics, space, energy, electronics, nuclear, and transportation industries. In the aeronautics and space exploration systems, these materials are being considered for applications in hot sections of jet engines such as the combustor liner, nozzle components, nose cones, leading edges of reentry vehicles and space propulsion components. Applications in the energy and environmental industries include radiant heater tubes, heat exchangers, heat recuperators, gas and diesel particulate filters (DPFs), and components for land based turbines for power generation. These materials are also being considered for use in the first wall and blanket components of fusion reactors. There are a number of critical issues and challenges related to successful implementation of composite materials. Fabrication of net and complex shape components with high density and tailorable matrix properties is quite expensive, and even then various desirable properties are not achievable. In this presentation, microstructure and thermomechanical properties of composites fabricated by two techniques (chemical vapor infiltration and melt infiltration), will be presented. In addition, critical need for robust joining and assembly technologies in successful implementation of these systems will be discussed. Other implementation issues will be discussed along with advantages and benefits of using these materials for various components in high temperature applications.

Singh, Mrityunjay↗