In the present study both fusion based - laser powder bed fusion (LPBF), and solid state - additive friction stir deposition (AFSD) additive manufacturing processes were employed for the manufacturing of a metastable high entropy alloy (HEA), Fe40Mn20Co20Cr15Si5 (CS-HEA). A processing window was developed for the LPBF and AFSD processings of CS-HEA. In case of LPBF, formation of solidification related defects such as lack of fusion pores (for energy density ≤ 31.24 J/mm3) and keyhole pores (for energy density ≥ 75 J/mm3) were observed. Variation in processing conditions affected the microstructural evolution of the metastable CS-HEA; correlation between processing conditions and microstructure of the alloy is developed in the current study. The tendency to transform and twin near stress concentration sites provided excellent tensile and fatigue properties of the material despite the presence of defects in the material. Moreover, solid state nature of AFSD process avoids formation of solidification related defects. Defect free builds of CS-HEA using AFSD resulted in higher work hardening in the material. In summary, the multi-processing techniques used for CS-HEA in the present study showcase the capability of the AM process in tailoring the microstructure, i.e., grain size and phase fractions, both of which are extremely …

In this study, we have investigated the relationship between the process-microstructure to predict and modify the material's properties. Understanding these relationships allows the identification and correction of processing deficiencies when the desired properties are not achieved, depending on the microstructure. Hence, the co-relation between process-microstructure-properties helped reduce the number of experiments, materials & tool costs and saved much time. In the case of high entropy alloys, friction stir welding (FSW) causes improved strength due to the formation of fine grain structure and phase transformation from f.c.c to h.c.p. The phase transformation is temperature sensitive and is studied with the help of differential scanning calorimetry (DSC) to calculate the enthalpy experimentally to obtain ΔGγ→ε. The second process discussed is heat treatment causing precipitation evolution. Fundamental investigations aided in understanding the influence of strengthening precipitates on mechanical properties due to the aging kinetics – solid solution and variable artificial aging temperature and time. Finally, in the third case, the effect of FSW parameters causes the thermal profile to be generated, which significantly influences the final microstructure and weld properties. Therefore, a computational model using COMSOL Multiphysics and TC-Prisma is developed to generate the thermal profile for different weld parameters to understand its …

Chalcogen-rich transition-metal dichalcogenide (TMD) magnetron sputtering targets were custom manufactured via ball milling and sintering in the interest of depositing p-type chalcogen-rich films. Room temperature radio frequency (RF) magnetron sputtering produced ultra-thin amorphous precursor of WSx and MoSx (where x is between 2-3) on several different substrates. The influence of working pressure on the MoS3 content of the amorphous films was explored with X-ray photoelectron spectroscopy (XPS), while the physical and chemical effects of sputtering were investigated for the WSx target itself. The amorphous precursor films with higher chalcogenide content were chosen for laser annealing, and their subsequent laser annealing induced phase transformations were investigated for the synthesis of polycrystalline 2H-phase semiconducting thin films. The role of laser fluence and the number of laser pulses during annealing on phase transformation and film mobility was determined from Raman spectroscopy and Hall effect measurement, respectively. Hall effect measurements were used to identify carrier type and track mobility between amorphous precursors and crystalline films. The p-type 2H-TMD films demonstrates the ability to produce a scalable processing criterion for quality ultra-thin TMD films on various substrates and in a method which is also compatible for flexible, stretchable, transparent, and bendable substrates.

To design high pressure fuel system components that resist wear and scuffing failure when operated in low viscosity fuels, a comprehensive study on the tribological performance of various existing coating materials is necessary. This thesis aims to provide the relative performance of a variety of coating materials across different fuel environments by testing them in conditions that model those experienced in fuel pumps. The relative performance of these coatings are then indexed across a variety of material properties, including hardness, elastic modulus, wettability, and the interaction between the surface and the various types of fuel molecules.

In the first study, superconducting 2D NbSe₂ was examined towards its prototypical demonstration as a transition-edge sensor, where photoexcitation caused a thermodynamic phase transition in NbSe₂ from the superconducting state to the normal state. The efficacy of the optical absorption was found to depend on the wavelength of the incoming radiation used, which ranged from the ultra-violet (405 nm), visible (660 nm), to the infrared (1060 nm). In the second case involving WSe₂, the UV-ozone treatment revealed the presence of localized excitonic emission in 1L WSe₂ that was robust and long-lived. Our third material platform dealt with hybrid 0D-2D ensembles based on graphene and WSe₂, specifically graphene–endohedral, WSe₂–fullerene (C₆₀), and WSe₂–Au nanoparticles, and exhibited exceptional performance gains achieved with both types of hybrid structures. Next, we investigated WSe₂ based mixed dimensional hybrids. Temperature T-dependent and wavelength λ-dependent optoelectronic transport measurements showed a shift in the spectral response of 1L WSe₂ towards the SPR peak locations of Au-Sp and Au-BP, fostered through the plexciton interactions. Models for the plexcitonic interactions are proposed that provide a framework for explaining the photoexcited hot charge carrier injection from AuNPs to WSe₂ and its influence on the carrier dynamics in these hybrid systems. Last, we …

Traditional lightweight armor ceramics such as boron carbide (B4C) and silicon carbide (SiC) are used alone or together in varying amounts to create monolithic protective plates. These materials exhibit relatively small differences in hardness, flexure strength, and fracture toughness. Many of the routes taken during the synthesis of the powder and sintering of the plates using traditional ceramic processing techniques have long processing times, tend to leave asperities within the microstructure, and have unwanted secondary phases that lower the performance of these materials. In lieu of the incremental changes in the above properties, it is thought that adding diamond particulates to the ceramic matrix will dramatically improve the mechanical properties and overall performance. With the reduced cost of synthetic diamond and the commercial development of more rapid spark plasma sintering (SPS), this work develops a novel reactive SPS process to fabricate near fully dense SiC-TiC-diamond composites at various processing temperatures with minimal graphitization and full adhesion to the ceramic matrix. It was found that samples with up to ~97% theoretical density can be fabricated with no quantifiable graphite content within the characterization ability using advanced X-ray diffraction and microscopy techniques.

Ceramics have a wide variety of applications due to their unique properties; however, the low fracture toughness leads the formation and propagation of unpredictable cracks, and reduces their reliability. To solve this problem, self-healing adaptive oxides were developed. The aim of the work is to gain new insights into self-healing mechanisms of ceramics and their application. Binary oxide systems were investigated that are at least partially healed through the extrinsic or intrinsic addition of silver or silver oxide to form ternary oxides (e.g., Nb2O5 + Ag → AgNbO3). Sintered pellets and coatings were tested. For self-healing TBCs, model systems that were studied include YSZ-Al2O3-SiC, YSZ-Al2O3-TiC, YSZ-Al2O3-Nb2O5, and YSZ-Al2O3-Ta2O5. Laser cladded samples and sintered pellets were produced to test. The healing process occurs due to the formation of oxidation products and glassy phases depending on the self-healing mechanism. X-ray diffraction was used to explore phase evolution, chemical compositions, and structural properties of these samples. SEM equipped with EDS was used to investigate the chemical and morphological properties for the cross-sectional area. Pin-on-disc test was applied to test tribology performance for Nb2O5-Ag2O system, and infiltration test was applied to test CMAS-resistance for TBCs at elevated temperature. The improvements in the performance of …

The current work investigates how the interactions among constituent elements in high entropy alloys or complex concentrated alloys (HEA/CCAs) can lead to lattice instability and local chemical ordering which in turn affects the microstructure and properties of these alloys. Using binary enthalpies of mixing, the degree of ordering in concentrated multi-component solid solutions was successfully tailored by introducing Cr, Al and Ti in a CoFeNi HEA/CCA. CoFeNi was selected as the base alloy to achieve a close to random solid solution as indicated by the near-zero binary enthalpies in CoFeNi alloy system. The room temperature tensile properties of these alloys with varied degree of ordering follow a consistent trend where yield stress increased with degree of ordering. This novel approach provides a new alloy design strategy to obtain controlled ordering tendencies and consequently targeted mechanical properties. Further studies on specific alloys have been conducted to utilize this ordering tendency in attaining precipitation strengthening. For this purpose, Al, Ti and Ni were selected to promote ordering and Co, Fe, and Cr were chosen to strengthen the solid solution matrix. In Al0.25CoFeNi HEA/CCA, the ordering tendency between Al and Ni results in a competition between two long-range ordered phases, L12 and B2. …

Ti and Ti-based alloys are used in many aerospace and automotive components due to their high strength-to-weight ratio and corrosion resistance. However, room and elevated temperature wear resistance remain an issue, thus requiring some form of secondary hard phase, e.g., refractory carbides and oxides, as well as solid lubrication to mitigate wear. In this study, Ti-TiC (14, 24 and 35 vol% TiC) composite coatings were deposited on mild steel substrates using cold spray with comparisons made to baseline cold-sprayed Ti. The dry sliding friction and wear behavior were studied from 25°C to 575°C and during thermal cycling in this temperature range. While the room temperature friction coefficient of all the coatings remained relatively constant at ~0.5, the wear rate continually decreased from ~1x10-3 to ~2x10-5 mm3/N-m with increasing the TiC loading. Raman spectroscopy measurements determined that the same TiO2 tribochemical phases (rutile and anatase) were present on the room temperature sliding wear surfaces, thus responsible for similar friction coefficients. With increasing sliding temperatures to 575°C, the Ti-35%TiC composite coating exhibited the best overall tribological behavior, i.e., the friction coefficient decreased to ~0.3 along with a negative wear rate of -6.6x10-5 mm3/N-m (material gain on the wear track was recorded due …

To study the effect of the substrate support on the nanoscale contact, three different regimes, i.e., graphene on rigid (ultra-crystalline diamond) and on elastic (Polydimethylsiloxane) supports and free-standing graphene, were considered. The contribution of the graphene support to the mechanical and electrical characteristics of the graphene/metal contact was studied using the conductive atomic force microscopy (AFM) technique.The results revealed that the electrical conductivity of the graphene/metal contact highly depends on the nature of the graphene support. The conductivity increased when transitioning from suspended to elastic and then to rigid substrates, which is attributed to the changes in the contact area being higher for the suspended graphene and lower for the rigid substrate. The experimental observations showed good agreement with theoretical results obtained from modeling of the studied material systems. Further, the results indicated that in addition to the substrate support, the nature of the contact, static or dynamic, results in large variations of the electrical conductivity of the graphene/metal contacts. In case of the static mode, the contact made with supported graphene was very stable for a wide range of applied normal loads. Transitioning to the dynamic mode led to instability of the graphene/metal contact as demonstrated by lowering in …

Sintering parameter effects on the microstructure of boron carbide and boron carbide/titanium diboride composites are investigated. The resulting microstructure and composition are characterized by scanning electron microscopy (SEM), x-ray microscopy (XRM) and x-ray diffraction (XRD). Starting powder size distribution effects on microstructure are present and effect the mechanical properties. Reactive spark plasma sintering introduces boron nitride (BN) intergranular films (IGF's) and their effects on fracture toughness, hardness and flexural strength are shown. Mechanical testing of Vickers hardness, 3-point bend and Chevron notch was done and the microstructural effects on the resulting mechanical properties are investigated.

High entropy alloys (HEAs) are a new class of solid solution alloys that contain multiple principal elements and possess excellent mechanical properties, from corrosion resistance to fatigue and wear resistance. Even more recently, twinning induced plasticity (TWIP) and transformation induced plasticity (TRIP) non-equiatomic high entropy alloys have been engineered, promising increased strength and ductility as compared to their equiatomic counterparts. However, impact and fracture resistance of these HEAs has not been studied as much as their other mechanical properties. In this thesis, the hardness, tensile properties, and Charpy impact energy of Al0.3CoCrFeNi, a TWIP HEA, and 50Fe-30Mn-10Co-10Cr (at.%), a TRIP HEA, was explored. First, three processing conditions, (1) as-received, (2) recrystallized, and (3) peak hardness, were chosen for each alloy and verified with Vickers microhardness measurements. Next, the tensile properties of each alloy and condition were investigated. Charpy impact specimen size was then selected based on the final plate thickness, and the machined samples were tested. Plastic zone size and change in sample thickness in the deformed region of each condition after testing was measured. Post-impact test inspection of the samples in all conditions showed that the samples were in tension near the V-notch root and in compression at the …

Structural material fatigue is a leading cause of failure and has motivated fatigue-resistant design to eliminate risks to human lives. Intrinsic microstructural features alter fatigue deformation mechanisms so profoundly that, essentially, fatigue properties of structural materials become deviant. With this in mind, we initiated this project to investigate the microstructural effect on fatigue behavior of potential structural high entropy alloys. With a better understanding of the effect of microstructure features on fatigue properties, the ultimate goal was to engineer the microstructure to enhance the fatigue life of structural materials. The effects of two major deformation mechanisms presented here are twinning-induced fatigue crack retardation, and transformation-induced fatigue crack retardation. The fundamental principle of both mechanisms is to delay the fatigue crack propagation rate by altering the work hardening ability locally within the crack plastic zone. In ultrafine grained triplex Al0.3CoCrFeNi, nano-sized deformation twins were observed during cyclic loading in FCC matrix due to low stacking fault energy (SFE). The work-hardening ability of the material near the crack was sustained with the formation of twins according to Considere's criteria. Further, due to the ultrafine-grained (UFG) nature of the material, fatigue runout stress was enhanced. In a coarse-grained, dual-phase high entropy alloy, persistent …

This dissertation tested the hypothesis that pulsed laser deposition (PLD) could be used to create targeted dopant profiles in few layered WS2 films based on congruent evaporation of the target. At the growth temperatures used, 3D Volmer-Weber growth was observed. Increased energy transfer from the PLD plume to the growing films degraded stoichiometry (desorption of sulfur) and mobility. Sulfur vacancies act as donors and produce intrinsic n-type conductivity. Post deposition annealing significantly improved the crystallinity, which was accompanied by a mobility increase from 6.5 to 19.5 cm2/Vs. Preparation conditions that resulted in excess sulfur, possibly in the form of interstitials, resulted in p-type conductivity. Current-voltage studies indicated that Ohmic contacts were governed by surface properties and tunneling. Extrinsic p-type doping of few layered WS2 films with Nb via pulsed laser deposition using ablation targets fabricated from WS2, S and Nb powders is demonstrated. The undoped controls were n-type, and exhibited a Hall mobility of 0.4 cm2/Vs. Films doped at 0.5 and 1.1 atomic percentages niobium were p-type, and characterized by Fermi levels at 0.31 eV and 0.18 eV from the valence band edge. That is, the Fermi level moved closer to the valence band edge with increased doping. With increased …

The current understanding of the mechanical properties and deformation behavior of some individual phases in titanium alloys is limited due to the fine scale at which these phases precipitate within the β-phase matrix. The α and ω phases represent the most widely observed phases in titanium alloys depending on the alloy composition and also the heat treatment procedure adopted during processing. The possibility of precipitating ω-phase depends on the content of the β-stabilizers within the system. Although a significant compositional partitioning occurs within ω-phase upon aging treatment, the knowledge of ω-phase mechanical properties as a function of composition is very limited. The initial part of the current work focuses on the effect of common β-stabilizers elements on the phase stability and mechanical properties of the ω-phase using first-principles calculations. A relation between the bonding nature, the phase stability, and elastic properties was proposed. Thereafter αʺ martensitic phase was investigated in Ti-Nb and Ti-Nb-O alloys. The phase stability and martensitic start temperature of αʺ-phase was studied as a function of Nb and oxygen content. Also, the effect of the lattice shear distortion induced by oxygen atom on stabilizing β-phase was investigated. Subsequently the effect of the β-stabilizers' elements on stacking faults …

In the current study, we have investigated the cyclic loading behavior of conventional as well as novel alloy system exhibiting fine and ultrafine-grained structure. While in case of conventional alloy systems (here aluminum alloy AA5024), the effect of three different grain sizes was investigated. Improvement in fatigue properties was observed with decreasing grain size. The unique microstructure produced via Friction stir processing was responsible for the improved fatigue response. Additionally, microstructures consisting of a high fraction of special boundaries within the fine and ultrafine-grained regime were also subjected to cyclic loading. The hierarchical features introduced in the eutectic high entropy alloy deflected the persistent slip bands, responsible for fatigue cracking, thus resulted in delayed crack initiation and improved fatigue life. The selective nature of fatigue was learnt in the fine grain Al0.5CoCrFeNi, where the introduction of hierarchical features did not result in improved fatigue properties. The weak links in the microstructure, while not affecting the tensile properties, got exposed during cyclic loading. Further study on the medium entropy alloy revealed the inherent reason for the improved fatigue properties. The medium entropy alloys utilized the benefit of UFG single-phase FCC matrix. The UFG matrix showed signs of transformation of FCC phase …

High entropy alloys (HEAs) based on refractory elements have shown a great potential for high temperature structural applications. In particular, the ones containing Al, exhibits a microstructure similar to the γ-γ' in Ni-based superalloys. While these alloys exhibit impressive strengths at room temperature (RT) and at elevated temperatures, the continuous B2 matrix in these alloys is likely to be responsible for their brittle behavior at RT. Phase stability of five such alloys are studied by thermo-mechanical treatments and characterization techniques using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Two of these alloys showed an inverted microstructure, where the disordered BCC phase becomes continuous, and therefore, they were characterized in detail using SEM, TEM, atom probe tomography (APT) and synchrotron x-ray diffraction experiments. The phenomenon of phase inversion lead to a better combination of strength and ductility as compared to the non-inverted microstructure.To enhance the stability of B2 intermetallic phase which provides the strength when present in a BCC matrix, multicomponent B2 phase compositions stable at 1000°C in some of the above studied alloys, were melted separately. The aim was to establish a single phase B2 at 1000°C and understand the mechanical behavior of these single-phase multicomponent B2 intermetallic …

High entropy alloys (HEAs) are a relatively new class of solid solution alloys that contain multiple principal elements to take advantage of their high configurational entropy, sluggish diffusion, lattice distortion, and the cocktail effect. In recent development, work hardening mechanisms known as twinning induced plasticity (TWIP) and transformation induced plasticity (TRIP) have been found active in Al0.3CoCrFeNi (molar fraction) and Fe50Mn30Co10Cr10 (at %) HEA compositions. Friction-stir processing was done to increase the mechanical properties and improve the microstructure of the alloys for the purpose of high strain rate performance. Quasi-static tensile tests as well as top-hat geometry Split-Hopkinson pressure bar tests were conducted to view the mechanical properties as well as view the microstructural evolution at dynamic strain rates. Overall, the Al0.3CoCrFeNi condition after friction-stir processing and heat treatment has proved to have the best mechanical properties, and selecting from the conditions in this study, Al0.3CoCrFeNi has better shear localization resistance.

Lithium-sulfur (Li-S) batteries are faced with practical drawbacks of poor cycle life and low charge efficiency which hinder their advancements. Those drawbacks are primarily caused by the intrinsic issues of the cathodes (sulfur) and the anodes (Li metal). In attempt to resolve the issues found on the cathodes, this work discusses the method to prepare a binder-free three-dimensional carbon nanotubes-sulfur (3D CNTs-S) composite cathode by a facile and a scalable approach. Here, the 3D structure of CNTs serves as a conducting network to accommodate high loading amounts of active sulfur material. The efficient electron pathway and the short Li ions (Li+) diffusion length provided by the 3D CNTs offset the insulating properties of sulfur. As a result, high areal and specific capacities of 8.8 mAh cm−2 and 1068 mAh g−1, respectively, with the sulfur loading of 8.33 mg cm−2 are demonstrated; furthermore, the cells operated at a current density of 1.4 mA cm−2 (0.1 C) for up to 150 cycles. To address the issues existing on the anode part of Li-S batteries, this work also covers the novel approach to protect a Li metal anode with a thin layer of two-dimensional molybdenum disulfide (MoS2). With the protective layer of MoS2 …

Thermoelectric (TE) devices can undergo degradation from reactions in corrosive environments and at higher operating temperatures by sublimation and oxidation. To prevent the degradation, we have applied two high temperature polymers (HTPs) as coatings for TE materials. Sintering temperatures were from 250°C to 400°C. We explain why dip coating is better technique in our study and had two potential HTPs for tests. By applying TGA (thermogravimetric analysis), we were able to figure out which HTPs have better thermal resistivity. Besides, TGA also help us to find proper curing cycles for HTPs. EDS and SEM results show that the coatings prevent oxidation and sublimation of TE materials. We also shorten HTP curing cycle time and lower the energy costs.

Magnesium and its alloys are considered as the potential biomaterials due to their biocompatibility and biodegradable characteristics but suffer from poor corrosion performance. Various surface modification techniques are employed to improve their corrosion resistance. In present case, laser surface melting was carried out on AZ31B Mg alloy with various laser energy densities using a continuous wave ytterbium laser. Effect of laser treatment on phase and microstructure evolution was evaluated by X ray diffraction and scanning electron microscopy. Multi-physics thermal model predicted time temperature evolution along the depth of the laser treatment zone. Additionally, electrochemical method and bio-immersion test were employed to evaluate the corrosion behavior in simulated body fluid medium. Microstructure revealed grain refinement and even distribution of Mg17Al12 phase along the grain boundary for laser treated samples leading to substantial enhancement in the corrosion resistance of the laser treated samples compared to the untreated alloy. The laser processed samples also possessed a superior wettability in SBF solution than the untreated sample. This was further reflected in enhanced bio-integration behavior of laser processed samples. By changing the parameters of laser processing such as power, scanning speed, and fill spacing, a controllable corrosion resistance and bioactivity/biocompatibility of the implant material was …

The tribological properties of cold sprayed Ni-WC metal matrix composite (MMC) coatings were investigated under dry sliding conditions from room temperature (RT) up to 400°C, and during thermal cycling to explore their temperature adaptive friction and wear behavior. Characterization of worn surfaces was conducted using scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), and Raman spectroscopy to determine the chemical and microstructural evolution during friction testing. Data provided insights into tribo-oxide formation mechanisms controlling friction and wear. It was determined that the steady-state coefficient of friction (CoF) decreased from 0.41 at RT to 0.32 at 400˚C, while the wear rate increased from 0.5×10-4 mm3/N·m at RT to 3.7×10-4 mm3/N·m at 400˚C. The friction reduction is attributed primarily to the tribochemical formation of lubricious NiO on both the wear track and transfer film adhered to the counterface. The increase in wear is attributed to a combination of thermal softening of the coating and a change in the wear mechanism from adhesive to more abrasive. In addition, the coating exhibited low friction behavior during thermal cycling by restoring the lubricious NiO phase inside the wear track at high temperature intervals. Therefore, cold sprayed Ni-WC coatings are potential candidates for elevated temperature and …

Acoustics is the study of all sound waves, with ultrasound classified as those frequencies above 20,000 Hz. Currently, ultrasound is being used in many industries for a variety of purposes such as ultrasonic imaging, ultrasonic assisted friction stir welding, and ultrasonic spot welding. Despite these uses, the effects of ultrasound on phase stability and resultant mechanical properties has been minimally analyzed. Here we study the impact waves play in ultrasonic welding and design an apparatus to maximize waves entering aluminum alloy samples. Aluminum 2139 and 7050 are used because they are precipitation strengthened by metastable phases so temperature change, and the corresponding phase stability, can greatly impact their strength. Results suggest that the ultrasonic welder primarily imposes a localized temperature spike due to friction, averaging over 200°C in a few seconds, which generally lowers the Vickers hardness due to coarsening or even dissolution of strengthening precipitates. Conversely, the new design increases the Vickers hardness by up to 30% over the initial hardness of approximately 63HV for aluminum 2139 and 83HV for aluminum 7050, respectively, while only increasing the temperature by an average of approximately 10°C. This new design was unable to achieve peak hardness, but the strengthening it achieved in …

Additive manufacturing processes of many alloys are known to develop texture during the deposition process due to the rapid reheating and the directionality of the dissipation of heat. Titanium alloys and with respect to this study beta titanium alloys are especially susceptible to these effects. This work examines Ti-20wt%V and Ti-12wt%Mo deposited under normal additive manufacturing process parameters to examine the texture of these beta-stabilized alloys. Both microstructures contained columnar prior beta grains 1-2 mm in length beginning at the substrate with no visible equiaxed grains. This microstructure remained constant in the vanadium system throughout the build. The microstructure of the alloy containing molybdenum changed from a columnar to an equiaxed structure as the build height increased. Eighteen additional samples of the Ti-Mo system were created under different processing parameters to identify what role laser power and travel speed have on the microstructure. There appears to be a correlation in alpha lath size and power density. The two binary alloys were again deposited under the same conditions with the addition of 0.5wt% boron to investigate the effects an insoluble interstitial alloying element would have on the microstructure. The size of the prior beta grains in these two alloys were reduced …