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A low cost and scalable powder-based method for producing nanoporous Ni is demonstrated, and the only processing byproduct is water vapor. This is achieved by creating a metal-matrix composite of Ni and NiO that is then reduced under dilute hydrogen to create pure Ni with nanocrystalline structure and nanoscale porosity. The technique is demonstrated in loose powder and in thin and bulk compacts with centimeter dimensions. These compacts can withstand extensive deformation without disintegrating, performing similarly to wrought Ni in specific strength. The unique processing strategy and resulting material can be readily extended to other metals and alloys. Accepted version

Mechanical alloying has been repeatedly demonstrated as an effective means to create unique structural materials, but it is comparatively rare that functional alloys are produced. Multi-phase functional alloy production is demonstrated with an oxide-dispersed Ni–Cu catalyst. These catalyst particles are designed to form porosity and catalyze carbon nanofiber deposition in situ, which results in a six-fold increase in deposition rate over traditional preparation methods. This technique serves as a template for many other systems possible with MA.

Surface oxidation of metal powders is a common challenge in powder metallurgy processing, and the oxides must eventually be broken up to produce high-quality, structural components. Here it is proposed that surface oxidation may be beneficial in the creation of porous metals through intraparticle expansion, which creates porosity by the reduction of oxides which are distributed within a metallic matrix. Previous work utilized the addition of separate oxides to the metal as a two-component (Cu powder + CuO powder) cryogenic ball milling process. The feasibility of controlling pore formation by directly oxidizing copper powder before milling is examined, and it is then extended to room temperature processing. Both pore distribution and morphology vary greatly with oxygen content, which can be controlled during processing. The pore volume and interconnectedness are maximized at intermediate oxygen concentration, indicating competing effects of the oxide loading. When room temperature high-energy ball milling is applied, the oxidized powder was found to exhibit even greater expansion upon annealing and larger pore size, though cold welding of the copper was encountered at short milling times. Using a single-component method at room temperature may prove valuable to reduce the cost and complexity of large scale production of expandable powder feedstock, and key considerations are discussed.

Predicting grain growth in nanocrystalline materials requires modeling approaches that incorporate grain boundary thermodynamics and kinetics. In this work, the thermokinetic model of Chen et al. (2012) for grain growth was applied to experimental X-ray diffraction measurements from a binary nanocrystalline alloy in an effort (1) to understand the influence of thermodynamic, kinetic, and material parameters in the model; and (2) to extend the thermokinetic model by incorporating temperature dependence. The model performs well for the grain boundary saturated case in the binary nanocrystalline alloy, where it is assumed that solute segregates to the grain boundaries and thermodynamically/kinetically reduces the driving force for grain growth. In this work, a sensitivity analysis of parameters (Monte Carlo global sensitivity analysis) identifies the important thermodynamic/kinetic parameters and their correlation with one another for the present model. This model was then extended to include the change in these independent thermodynamic/kinetic parameters as a function of temperature and to model the effect of initial grain size distribution. This research shows that the thermodynamic and kinetic contributions can describe grain growth in nanocrystalline materials and this extended model can be parameterized for grain size evolution and stabilization with temperature for nanocrystalline systems.

Microscale and nanoscale CuO was dispersed in Cu using room temperature high-energy ball milling over time intervals of 5, 30, 60, 120, and 240 min. These samples were then annealed under a reducing atmosphere for 1 h at temperatures of 400, 600, 800 and 1000 °C to create porosity by the reduction of the entrained oxides. Increases in porosity exceeding 40% were achieved using intermediate milling times and annealing temperatures. When considered cumulatively, the most effective processing conditions were a milling time of 30 min and expansion at 800 °C, but variations exist within each sample type. The complex relationship between milling time and annealing temperature is investigated in terms of particle size, morphology and microstructure. The findings indicate that room temperature milling is more efficient at producing porosity than comparable cryogenic methods, and this may enable industrial scaling of the process.

Porous metals can be created through a wide variety of processing techniques, and the pore morphology resulting from these processes is equally diverse. The structural and functional properties of metal foams are directly dependent on the size, shape, interconnectedness and volume fraction of pores, so accurately quantifying the pore characteristics is of great importance. Methods for analyzing porous materials are presented here and applied to a copper-based metallic foam generated through solid state foaming via oxide reduction and expansion. This process results in large voids (10s of microns) between sintered particles and small pores (10 microns to less than 50 nm) within particles. Optical and electron microscopy were used to image the porosity over this wide range, and the pore characteristics were quantified using image segmentation and statistical analysis. Two-dimensional pore analysis was performed using the Chan-Vese method, and two-point correlation and lineal path functions were used to assess three-dimensional reconstructions from FIB tomography. Two-dimensional analysis reveals distinct size and morphological differences in porosity between particles and within them. Three-dimensional analysis adds further information on the high level interconnectedness of the porosity and irregular shape it takes, forming tortuous pathways rather than spherical cells. Mechanical polishing and optical microscopy allow large areas to be created and analyzed quickly, but methods such as focused ion beam (FIB) sectioning can provide additional insight about microstructural features. In particular, after FIB milling is used to create a flat surface, that surface can be analyzed for structural and compositional information.

Mechanical alloying (MA) has been and continues to be thoroughly examined for creating structural materials, but the production of catalysts is relatively rare. This is especially true for catalysts used in the production of carbon nanofibers (CNFs), a versatile material for applications such as energy storage, catalyst support, advanced composites and others. The application of MA to create CNFs presents a valuable tool in reducing their cost and complexity, and thereby may increase their commercial potential. In this study, the effects of milling duration on CNF deposition are studied by the complementary methods of X-ray diffraction, compositional mapping, electron microscopy, particle size analysis and surface area analysis. These were used to determine microstructural and macroscale evolution of the catalyst powder and its effects on the kinetics and characteristics of carbon deposition using Ni and Ni 30 at % Cu. The results have important implications for low cost catalyst production and provide general guidance on the development of catalytic materials in miscible systems.

Pore expansion in solid metals is typically driven by an entrapped gas phase, such that temperature directly determines both the pressure within the pores and the ability of the matrix to plastically deform. This approach fundamentally limits the total porosity, as all pores are active simultaneously, which quickly results in coalescence and percolation. The method introduced here converts dispersed oxide particles to a gaseous reactant using reduction, such that independent stages of pore formation and expansion can be achieved by using more than one oxide chemistry. This is demonstrated using silver and copper oxides distributed within a silver matrix. As the temperature is raised, the silver oxide reduces first and creates porosity. As the temperature is raised further, the copper oxide reduces and creates additional porosity. This allows the pore morphology and grain size to be uniquely controlled while still maintaining the simplicity and scalability of the process. The microstructural development is studied through a combination of isothermal annealing, optical dilatometry, and focused ion beam cross-sectioning, and implications and strategies for other alloy systems are discussed. Keywords: Porous metals, Solid state foaming, Mechanical alloying, Dilatometry, Microstructure, Grain boundary pinning

In this study, we demonstrate the feasibility of forming a bulk consolidated, low-density high-entropy alloy, namely AlFeMgTiZn, which shows reasonable mechanical properties and high hardness. The fabrication of the high-entropy alloy from powdered precursors via high-energy mechanical alloying as a function of milling time is presented. In turn, the evolution of the alloy microstructure with postmilling anneal treatment is elucidated. Last, the severe plastic deformation processing methodology, i.e., equal-channel angular extrusion, chosen for consolidation, is described and shown to result in a bulk product with good results.

Entangled networks of carbon nanofibers are characterized both mechanically and electrically. Results for both tensile and compressive loadings of the entangled networks are presented for various densities. Mechanically, the nanofiber ensembles follow the micromechanical model originally proposed by van Wyk nearly 70 years ago. Interpretations are given on the mechanisms occurring during loading and unloading of the carbon nanofiber components.

Mitigating grain growth at high temperatures in binary nanocrystalline alloys is important for processing nanocrystalline alloy systems. The objective of this research is to develop a methodical design-based approach for selecting solutes in binary nanocrystalline alloys by revisiting grain boundary thermodynamics and the internal processes of grain growth and solute segregation in a closed system. In this work, the grain boundary energy is derived and systematically studied in terms of temperature, grain size, concentration, and solute segregation for binary systems of 44 solvents and 52 solutes, using readily-available elemental data, such as moduli and liquid enthalpy of mixing. It is shown that through solute segregation, the grain boundary energies of some binary systems can be reduced, resulting in thermodynamically stable grain structures and successful prediction of solutes that inhibit grain growth in some nanocrystalline alloys. Parametric studies reveal trends between equilibrium grain size, solute distribution and temperature for various binary systems culminating in the generation of nanocrystalline thermodynamic stability maps as a tool for solute selection in binary nanocrystalline alloys.

Cryogenic high energy ball milling was used to synthesize nanocrystalline Cu and Cu 99.5 Zr 0.5 alloys by mechanical alloying and consolidation by hot pressing at 550 °C temperature. The grain size stability of nanocrystalline Cu is improved by the Zr addition. Microstructural characterization using X-ray diffraction and transmission electron microscopy provided evidence for the formation of a Cu–Zr alloy solid solution with nanocrystalline size after hot pressing. The alloy exhibited a higher hardness (3.31 GPa), and shear strength (550 MPa) than nano-crystalline pure Cu however, the electrical resistivity is increased in the alloy.

Widespread adoption of carbon nanomaterials has been hindered by inefficient production and utilization. A recently developed method has shown possibility to directly synthesize bulk nanostructured nonwoven materials from catalytically deposited carbon nanofibers (CNFs). The basic manufacturing scheme involves constraining carbon nanofiber growth to create three-dimensionally featured, macroscale products. Although previously demonstrated as a proof of concept, the possibilities and pitfalls of the method at a larger scale have not yet been explored. In this work, the basic foundation for using the constrained formation of fibrous nanostructures (CoFFiN) process is established by testing feasibility in larger volumes (as much as 2000% greater than initial experiments) and by noting the macroscale carbon growth characteristics. It has been found that a variety of factors contribute to determining the basic qualities of the macroscale fiber collection (nonwoven material), and there are tunable parameters at the catalytic and constraint levels. The results of this work have established that monolithic structures of nonwoven carbon nanofibers can be created with centimeter dimensions in a variety of cross-sectional shapes. The only limit to scale noted is the tendency for nanofibers to entangle with one another during growth and self-restrict outward expansion to the mold walls. This may be addressed by pregrowing carbon before placement or selective placement of the catalyst in the mold.

The thermal stability of nanocrystalline cartridge brass (Cu–30 at.% Zn) and brass–Zr alloys were investigated. The alloys were produced by cryogenic ball milling and subsequently heat treated to a maximum temperature of 800 °C. The grain size of pure brass was found to be relatively stable in comparison to pure copper, and a high hardness was retained up to 600 °C. When 1 at.% zirconium was alloyed with the brass, the grain size was stabilized near 100 nm even at 800 °C. At the highest temperature, hardness was retained above 2.5 GPa for 1 and 5 at.% zirconium alloys, but the pure brass softened significantly. The stabilization is believed to be dominated by Zn–Zr interactions as a second phase of these two was observed in X-ray diffraction and transmission electron microscopy. Thermodynamic modeling indicates a zero grain boundary energy may be achieved depending on the mixing enthalpy value used (i.e., calculated vs. experimental) under ideal conditions, but microstructural features such as twinning and second phase particles are thought to be the dominant stabilization mechanism. Zr worked well in stabilizing the brass in the nanocrystalline state to nearly 90 % of its melting temperature.

Nanocrystalline Cu–30% Zn samples were produced by high energy ball milling at 77 K and room temperature. Cryomilled flakes were further processed by ultrahigh strain high pressure torsion (HPT) or room temperature milling to produce bulk artifact-free samples. Deformation-induced grain growth and a reduction in twin probability were observed in HPT consolidated samples. Investigations of the mechanical properties by hardness measurements and tensile tests revealed that at small grain sizes of less than ∼35 nm Cu–30% Zn deviates from the classical Hall–Petch relation and the strength of nanocrsytalline Cu–30% Zn is comparable with that of nanocrystalline pure copper. High resolution transmission electron microscopy studies show a high density of finely spaced deformation nanotwins, formed due to the low stacking fault energy of 14 mJ m –2 and low temperature severe plastic deformation. Possible softening mechanisms proposed in the literature for nanotwin copper are addressed and the twin-related softening behavior in nanotwinned Cu is extended to the Cu–30% Zn alloy based on detwinning mechanisms.

The characteristics of carbonaceous materials deposited in fuel rich ethylene–oxygen mixtures on three types of palladium: foil, sputtered film, and nanopowder, are reported. It was found that the form of palladium has a dramatic influence on the morphology of the deposited carbon. In particular, on sputtered film and powder, tight ‘weaves’ of sub-micron filaments formed quickly. In contrast, on foils under identical conditions, the dominant morphology is carbon thin films with basal planes oriented parallel to the substrate surface. Temperature, gas flow rate, reactant flow ratio (C2H4:O2), and residence time (position) were found to influence both growth rate and type for all three forms of Pd. X-ray diffraction, high resolution transmission electron microscopy, temperature-programmed oxidation, and Raman spectroscopy were used to assess the crystallinity of the as-deposited carbon, and it was determined that transmission electron microscopy and X-ray diffraction were the most reliable methods for determining crystallinity. The dependence of growth on reactor position, and the fact that no growth was observed in the absence of oxygen support the postulate that the carbon deposition proceeds by combustion generated radical species.

Carbon nanofibers were generated over bimetallic catalysts in an atmospheric pressure chemical vapor deposition (APCVD) reactor. Catalyst compositions of Fe 30 at%, Cu and Ni 30 at% and Cu were mechanically alloyed using high-energy ball milling over durations of 4, 8, 12, 16, and 20 h. The catalyst powders were then used to produce carbon nanofibers in ethylene and hydrogen (4:1) at temperatures of 500, 550, and 600 °C. The microstructures of the catalysts were characterized as a function of milling time as well as at deposition temperature. The corresponding carbon deposition rates were assessed and are correlated to the microstructural features of each catalyst. The milling process directly determines the performance of each catalyst toward carbon deposition, and both catalysts performed comparably to those made by traditional co-precipitation methods. Considerations in miscible and immiscible nanostructured alloy systems are discussed.

Extinction coefficients of gold nanoparticles with core size ranging from approximately 4 to 40 nm were determined by high resolution transmission electron microscopy analysis and UV-vis absorption spectroscopic measurement. Three different types of gold nanoparticles were prepared and studied: citrate-stabilized nanoparticles in five different sizes; oleylamide-protected gold nanoparticles with a core diameter of 8 nm, and a decanethiol-protected nanoparticle with a diameter of around 4 nm. A linear relationship between the logarithms of extinction coefficients and core diameters of gold particles was found independent of the capping ligands on the particle surface and the solvents used to dissolve the nanoparticles. This linear relation may be used as a calibration curve to determine the concentration or average size of an unknown nanoparticle or nanoparticle-biomolecule conjugate sample.

Carbon nanofibres were grown at low temperatures on a novel fibre catalyst, palladium particles, using a novel method, growth in fuel rich combustion conditions. The growth of carbon filaments by this process was found to be remarkably rapid. Preliminary analysis of how changes in operating parameters, for example gas flow rate and reactant ratio, showed that fibre diameter and other factors such as helicity are very sensitive to the precise conditions employed, suggesting simple means to impact overall properties of the fibres. The ability to control diameter, helicity, and surface roughness are discussed with possible importance to advanced composites.