<p> In an era of advancing printed electronics, solution-processable organic semiconductors continue to make significant strides in electronic and optoelectronic applications. Electrochromic (EC) technology, which encompass reversible optical modulation under electrochemical biasing, has progressed rapidly over the past half-century and developed into niche commercial-scale devices for auto-tinting glasses as well as low-power, non-emissive displays. To utilize the advantages of organic electrochromic materials in next-generation devices, it is imperative to understand their fundamental material properties, interactions with other device components, and the underlying electrochemistry that governs the overall optical and electrochemical response of the complete electrochromic device. This dissertation presents a discussion on the synergistic role of organic electrochromes, charge-balancing layers and electrolytes in determining two key performance metrics, namely the optical contrast and operational stability, of an electrochromic device (ECD). The absorption features of colored-to-transmissive switching conjugated polymers have been investigated by exploring material design strategies in conjunction with analytical approaches to optimize and enhance the optical contrast. In parallel, transmissive redox-active radical polymer counter electrodes have been developed as compatible charge-balancing layers and integrated into devices by pairing with electrochromic polymers (ECPs) to achieve stable and high-contrast optical modulation. Electrochemical activity of both conjugated and radical polymer electrodes in different ionic and solvent environments have been further examined to understand material-electrolyte interactions governing mixed ionic-electronic conduction. Finally, a small molecular approach to realizing transparent-to-colored electrochromism is discussed, where distinct substituent-induced degradation pathways of conjugated radical cations were revealed. Overall, this research aims to assist future development of robust, ultra-high contrast organic electrochromic platforms.  </p>

<p dir="ltr">Thermal Barrier Coatings (TBC) represent the key technology enabling greater efficiency and performance in jet engines and gas turbines. In modern engines, TBCs allow gas temperatures to exceed 1700°C, well above the point at which the structural alloys lose their strength. By insulating the underlying nickel-alloy components from the extreme heat generated during combustion, TBCs support a larger temperature gradient. </p><p dir="ltr">As operating temperatures are further increased to improve performance, thermal radiation becomes a more substantial carrier of heat. However, conventional TBCs are designed to provide a single barrier against only the phonon-mediated conductive heat flux, leaving the photonic radiative heat transfer largely unmitigated. We propose a Thermal Dual Barrier Coating (TDBC) to simultaneously suppress the phononic and photonic heat transfer by integrating a reflective thermal metamaterial into an independent phonon-optimized TBC.</p><p dir="ltr">The main obstacle to achieving the TDBC is in the selection of adequate reflective materials in the metamaterial. Conventional refractory metals that demonstrate the greatest stability and functionality in thermal metamaterials show instability under harsher environments. In our work, we identified and studied the key ideas, metrics, and challenges in metamaterials based on alternating layers of refractory metals and oxides for TDBC applications.</p><p dir="ltr">Our work emphasizes oxidation as a crucial degradation factor that is unavoidable in our assessment of the metamaterials. In formulating this problem, we bring the concept of oxidation-resistance through passivation to the forefront of material selection. We emphasize the passivative and oxidative properties of the metallic layer as a critical determinant in overall stability. In our work, we assess the enhancements in stability brought via passivation through the Pilling-Bedworth Ratio. We then propose the use of metal silicides in metamaterials as an overlooked class of oxidation-resistant IR reflective materials that operate through a more complex passivation method. We demonstrate strong stability in the structural integrity as well as the infrared responses of the metamaterials at up to 1200°C in atmospheric and oxidative environments.</p><p dir="ltr">After establishing the viability of metal silicides in wide-area thin films, we explore their viability in more complex thermal structures. We fabricate metal silicide metasurfaces for directional thermal emission. We demonstrate a grating structure that exhibits enhanced structural stability and maintains directional modes in the mid-IR after annealing at 1000°C.</p>

A excelente resistência à corrosão dos aços inoxidáveis austeníticos é a principal característica de sua ampla gama de aplicações nas mais diversas indústrias. Entretanto, as limitadas propriedades mecânicas da austenita, restringem o uso dessas ligas em sistemas que requeiram melhor desempenho tribológico sem prejuízo de sua resistência à corrosão. Métodos de endurecimento superficial convencionais tendem a formar precipitados que reduzem a disponibilidade dos elementos responsáveis pela passivação da liga, favorecendo a ação de agentes corrosivos. A descoberta de uma fase supersaturada em intersticiais denominada austenita expandida, ou Fase-S, tem lançado novas perspectivas sobre as opções de endurecimento superficial dos aços inoxidáveis austeníticos. Produzida por modernas técnicas baseadas no emprego do plasma, a austenita expandida apresenta elevadíssima dureza, da ordem de 14 GPa, sem prejuízo de sua resistência à corrosão, uma vez que não ocorre precipitação observável por microscopia ótica ou de varredura. Caracterizações mecânicas das camadas de austenita expandida por ensaios que simulem situações mais próximas da real condição de trabalho do material fornecem um conjunto de dados empíricos relevantes para a compreensão e modelagem de fenômenos tribológicos atuantes em um dado sistema mecânico. Nesse sentido, a microesclerometria instrumentada aparece com excelente opção de ferramenta para os estudos direcionados à Engenharia de Superfície. O presente trabalho apresenta os resultados de uma série de ensaios de microesclerometria instrumentada realizados em amostras de aço AISI 316 nitretadas a plasma por 20 h em forno de corrente contínua, utilizando a tecnologia de tela ativa, temperatura de 400 ºC e atmosfera formada por três partes de nitrogênio para cada parte de hidrogênio (3N2:1H2), resultando na formação de austenita expandida na superfície. Também são discutidos a caracterização das amostras, o baixo coeficiente de atrito (< 0,1) verificado experimentalmente e a ausência de falha adesiva da camada durante o ensaio. / One of the main reasons for the common utilization of austenitic stainless steels by various industries remains on their great corrosion resistance. On the other hand, the poor mechanical properties of austenite restrict the use of these alloys in systems which require better tribological performance without decreasing their corrosion resistance. Conventional case hardening techniques promote precipitate formation, reducing availability of passivation elements in metallic matrix, what can ease the action of corrosive external agents. The discovery of a carbon and/or nitrogen supersaturated phase, called expanded austenite or S-phase, brought new perspectives over case hardening options for austenitic stainless steels. Obtained by recent techniques based on plasma, expanded austenite has very high hardness, around 14 GPa, without reducing corrosion resistance, since no precipitate is noticeable by optical or scanning electronic microscopy. Using testing apparatus that simulates real work conditions, mechanical characterization of expanded austenite layers gives an important set of empirical data. These data are useful for comprehension and modeling of tribological phenomena occurring in a given mechanical system. In this way, instrumented microscratch test appears as an interesting option to be used in studies oriented to the Surface Engineering field. This work presents results from a series of instrumented microscratch tests performed over AISI 316 stainless steel samples with an expanded austenite layer. Plasma nitriding surface treatment was carried out during 20 h, in an active screen DC reactor under 400 ºC and atmosphere compounded by three parts of nitrogen for each part of hydrogen (3N2:1H2). The tribological behavior of the expanded austenite layer was characterized in a series of linear scratch tests. The results show that in the beginning of the scratch test the coefficient of friction was kept smaller than 0,1. When the first cracks appear the apparent coefficient of friction steadily increases, indicating that cracking of the nitrided layer lead to an increase of the coefficient of friction. Although the expanded austenite layer cracks, no adhesive failure was observed, the hardened layer being preserved during the whole scratch test.

Ilhas de InxGa1-xAs são de grande interesse no desenvolvimento tecnológico de lasers de diodos e diodos emissores de luz. As ilhas de InxGa1-xAs investigadas neste trabalho foram crescidas sobre um substrato semi-isolante de GaAs (001) pelo método de auto-organização usando epitaxia de feixe molecular. Este tipo de ilha, quando isolada e de pequeno tamanho, é considerada um ponto quântico ou sistema zero-dimensional. As amostras foram caracterizadas através do uso da microscopia de força atômica. A densidade e o tamanho dos pontos aumenta com a diminuição da fração molar de In, resultando em uma maior cobertura para o caso de x = O, 25. As características principais dos espectros Raman são os picos que correspondem aos modos LO e TO do substrato de GaAs. Duas estruturas adicionais aparecem no espectro: um pico estreito em 222 cm- 1 e uma banda larga de mais alta energia, que só é resolvida para x = O, 25, centrada em 245 cm-1. O pico em 222 cm-1 é provavelmente devido ao fônon LA(X) do GaAs normalmente proibido, induzido por defeitos. Para identificar a banda larga foi construído um modelo que considera: (i) a frequência Raman do modo tipo- InAs com caráter de LO como constante com a variação de x no InGaAs 3-D; (ii) efeitos de confinamento não afetam a frequência Raman dado ao tamanho dos pontos quânticos das amostras deste trabalho; (iii) A tensão escala com x e o valor máximo ocorre para o composto binário InAs. Este modelo permite prever um intervalo de frequências para os pontos quânticos. O valor medido, 245 cm- 1, está dentro deste intervalo e portanto foi atribuído ao modo tipo-InAs dos pontos quânticos de In0,25Ga0,75As Considerações de simetria reforçam esta designação. Contribuições adicionais de fônons foram consideradas no intervalo de energia de interesse. Para analisar estas contribuições, foi feito um estudo detalhado dos fônons induzidos por desordem em camadas de GaAs, e espalhamento Raman de As cristalino e amorfo. A desordem foi produzida através da erosão por laser e a amostra de As foi formada por um processo de oxidação de um filme de AlAs. Comparação dos espectros Raman permitiu concluir que não houve contribuição de fônons induzidos por desordem no espectro do ponto quântico, seja de GaAs ou arsênio. / InxGa1-x As islands are interesting for use in Laser diode and light-emitting diode technology. The InxGa1-x As islands investigated in this work were grown on semi-insulating (001) GaAs substrates by the self-organization method using molecular beam epitaxy. This type of island, when isolated and of small size, is considered as a quantum dot or zero-dimensional system. The samples were characterized by use of atomic force microscopy. The dot density and size were seen to increase as the In molar fraction decreased, resulting in a large dot­ coverage in the case of x = 0.25. The Raman spectra main features were the peaks corresponding to the LO and TO modes of GaAs-substrate. Second order structures were also present around 520 cm-1 (160 cm-1) for optical (acoustic) vibration of GaAs. Two additional structures appear as a sharp peak at 222 cm- 1 and higher energy broad band, which is resolved only for x = 0.25, at 245 cm- 1. The peak in 222 cm-1 is probably due to the normally forbidden GaAs LA(X) phonon induced by defects. To assign the broad band a model was constructed that considers: (i) the Raman frequency of the InAs-like mode with LO character as constant with x in bulk I nGaAs; (ii) confinement effects for the large dots formed has negligible effects in the quantum dot Raman frequency; (iii) The strain scale with x, the maximun value corresponds to that obtained for InAs. This model allowed to predict a range of frequencies for the dots. The value measured, 245 cm- 1, fit into this range and is, thus, attributed to the InAs-like mode of the In0.25Ga0.75As quantum dots. Selection rules arguments reinforces this assignment. Several additional contributions in the frequency range of interest were considered. In order to analyze those contributions, a detailed study of disorder induced phonons in GaAs, and Raman scattering of As-crystaline and amorphous, was realized. The disorder was produced by laser ablation and the As sample was formed by an oxidation process of an A1As film. Comparison of the Raman spectra allowed to conclude that neither As or GaAs disorder induced phonons contribute to the quantum-dot spectrum.

Ilhas de InxGa1-xAs são de grande interesse no desenvolvimento tecnológico de lasers de diodos e diodos emissores de luz. As ilhas de InxGa1-xAs investigadas neste trabalho foram crescidas sobre um substrato semi-isolante de GaAs (001) pelo método de auto-organização usando epitaxia de feixe molecular. Este tipo de ilha, quando isolada e de pequeno tamanho, é considerada um ponto quântico ou sistema zero-dimensional. As amostras foram caracterizadas através do uso da microscopia de força atômica. A densidade e o tamanho dos pontos aumenta com a diminuição da fração molar de In, resultando em uma maior cobertura para o caso de x = O, 25. As características principais dos espectros Raman são os picos que correspondem aos modos LO e TO do substrato de GaAs. Duas estruturas adicionais aparecem no espectro: um pico estreito em 222 cm- 1 e uma banda larga de mais alta energia, que só é resolvida para x = O, 25, centrada em 245 cm-1. O pico em 222 cm-1 é provavelmente devido ao fônon LA(X) do GaAs normalmente proibido, induzido por defeitos. Para identificar a banda larga foi construído um modelo que considera: (i) a frequência Raman do modo tipo- InAs com caráter de LO como constante com a variação de x no InGaAs 3-D; (ii) efeitos de confinamento não afetam a frequência Raman dado ao tamanho dos pontos quânticos das amostras deste trabalho; (iii) A tensão escala com x e o valor máximo ocorre para o composto binário InAs. Este modelo permite prever um intervalo de frequências para os pontos quânticos. O valor medido, 245 cm- 1, está dentro deste intervalo e portanto foi atribuído ao modo tipo-InAs dos pontos quânticos de In0,25Ga0,75As Considerações de simetria reforçam esta designação. Contribuições adicionais de fônons foram consideradas no intervalo de energia de interesse. Para analisar estas contribuições, foi feito um estudo detalhado dos fônons induzidos por desordem em camadas de GaAs, e espalhamento Raman de As cristalino e amorfo. A desordem foi produzida através da erosão por laser e a amostra de As foi formada por um processo de oxidação de um filme de AlAs. Comparação dos espectros Raman permitiu concluir que não houve contribuição de fônons induzidos por desordem no espectro do ponto quântico, seja de GaAs ou arsênio. / InxGa1-x As islands are interesting for use in Laser diode and light-emitting diode technology. The InxGa1-x As islands investigated in this work were grown on semi-insulating (001) GaAs substrates by the self-organization method using molecular beam epitaxy. This type of island, when isolated and of small size, is considered as a quantum dot or zero-dimensional system. The samples were characterized by use of atomic force microscopy. The dot density and size were seen to increase as the In molar fraction decreased, resulting in a large dot­ coverage in the case of x = 0.25. The Raman spectra main features were the peaks corresponding to the LO and TO modes of GaAs-substrate. Second order structures were also present around 520 cm-1 (160 cm-1) for optical (acoustic) vibration of GaAs. Two additional structures appear as a sharp peak at 222 cm- 1 and higher energy broad band, which is resolved only for x = 0.25, at 245 cm- 1. The peak in 222 cm-1 is probably due to the normally forbidden GaAs LA(X) phonon induced by defects. To assign the broad band a model was constructed that considers: (i) the Raman frequency of the InAs-like mode with LO character as constant with x in bulk I nGaAs; (ii) confinement effects for the large dots formed has negligible effects in the quantum dot Raman frequency; (iii) The strain scale with x, the maximun value corresponds to that obtained for InAs. This model allowed to predict a range of frequencies for the dots. The value measured, 245 cm- 1, fit into this range and is, thus, attributed to the InAs-like mode of the In0.25Ga0.75As quantum dots. Selection rules arguments reinforces this assignment. Several additional contributions in the frequency range of interest were considered. In order to analyze those contributions, a detailed study of disorder induced phonons in GaAs, and Raman scattering of As-crystaline and amorphous, was realized. The disorder was produced by laser ablation and the As sample was formed by an oxidation process of an A1As film. Comparison of the Raman spectra allowed to conclude that neither As or GaAs disorder induced phonons contribute to the quantum-dot spectrum.

A excelente resistência à corrosão dos aços inoxidáveis austeníticos é a principal característica de sua ampla gama de aplicações nas mais diversas indústrias. Entretanto, as limitadas propriedades mecânicas da austenita, restringem o uso dessas ligas em sistemas que requeiram melhor desempenho tribológico sem prejuízo de sua resistência à corrosão. Métodos de endurecimento superficial convencionais tendem a formar precipitados que reduzem a disponibilidade dos elementos responsáveis pela passivação da liga, favorecendo a ação de agentes corrosivos. A descoberta de uma fase supersaturada em intersticiais denominada austenita expandida, ou Fase-S, tem lançado novas perspectivas sobre as opções de endurecimento superficial dos aços inoxidáveis austeníticos. Produzida por modernas técnicas baseadas no emprego do plasma, a austenita expandida apresenta elevadíssima dureza, da ordem de 14 GPa, sem prejuízo de sua resistência à corrosão, uma vez que não ocorre precipitação observável por microscopia ótica ou de varredura. Caracterizações mecânicas das camadas de austenita expandida por ensaios que simulem situações mais próximas da real condição de trabalho do material fornecem um conjunto de dados empíricos relevantes para a compreensão e modelagem de fenômenos tribológicos atuantes em um dado sistema mecânico. Nesse sentido, a microesclerometria instrumentada aparece com excelente opção de ferramenta para os estudos direcionados à Engenharia de Superfície. O presente trabalho apresenta os resultados de uma série de ensaios de microesclerometria instrumentada realizados em amostras de aço AISI 316 nitretadas a plasma por 20 h em forno de corrente contínua, utilizando a tecnologia de tela ativa, temperatura de 400 ºC e atmosfera formada por três partes de nitrogênio para cada parte de hidrogênio (3N2:1H2), resultando na formação de austenita expandida na superfície. Também são discutidos a caracterização das amostras, o baixo coeficiente de atrito (< 0,1) verificado experimentalmente e a ausência de falha adesiva da camada durante o ensaio. / One of the main reasons for the common utilization of austenitic stainless steels by various industries remains on their great corrosion resistance. On the other hand, the poor mechanical properties of austenite restrict the use of these alloys in systems which require better tribological performance without decreasing their corrosion resistance. Conventional case hardening techniques promote precipitate formation, reducing availability of passivation elements in metallic matrix, what can ease the action of corrosive external agents. The discovery of a carbon and/or nitrogen supersaturated phase, called expanded austenite or S-phase, brought new perspectives over case hardening options for austenitic stainless steels. Obtained by recent techniques based on plasma, expanded austenite has very high hardness, around 14 GPa, without reducing corrosion resistance, since no precipitate is noticeable by optical or scanning electronic microscopy. Using testing apparatus that simulates real work conditions, mechanical characterization of expanded austenite layers gives an important set of empirical data. These data are useful for comprehension and modeling of tribological phenomena occurring in a given mechanical system. In this way, instrumented microscratch test appears as an interesting option to be used in studies oriented to the Surface Engineering field. This work presents results from a series of instrumented microscratch tests performed over AISI 316 stainless steel samples with an expanded austenite layer. Plasma nitriding surface treatment was carried out during 20 h, in an active screen DC reactor under 400 ºC and atmosphere compounded by three parts of nitrogen for each part of hydrogen (3N2:1H2). The tribological behavior of the expanded austenite layer was characterized in a series of linear scratch tests. The results show that in the beginning of the scratch test the coefficient of friction was kept smaller than 0,1. When the first cracks appear the apparent coefficient of friction steadily increases, indicating that cracking of the nitrided layer lead to an increase of the coefficient of friction. Although the expanded austenite layer cracks, no adhesive failure was observed, the hardened layer being preserved during the whole scratch test.

<p>Functional oxide-based thin films have attracted much attention owing to their broad applications in modern society. The multifunction tuning in oxide thin films is critical for obtaining enhanced properties. In this dissertation, four new nanocomposite thin film systems with highly textured growth have been fabricated by pulsed laser deposition technique. The functionalities including ferromagnetism, ferroelectricity, multiferroism, magnetoelectric coupling, low-field magnetoresistance, transmittance, optical bandgap and dielectric constants have been demonstrated. Besides, the tunability of the functionalities have been studied via different approaches.</p> <p>First, varies deposition frequencies have been used in vertically aligned nanocomposite BaTiO₃:YMnO₃ (BTO:YMO) and BaTiO₃:La_0.7Sr_0.3Mn₃(BTO:LSMO) thin films. In both systems, the strain coupling effect between the phases are affected by the density of grain boundaries. Increasing deposition frequency generates thinner columns in BTO:YMO thin films, which enhances the anisotropic ferromagnetic response in the thin films. In contrast, the columns in BTO:LSMO thin films become discontinuous as the deposition frequency increases, leading to the diminished anisotropic ferromagnetic response. Coupling with the ferroelectricity in BTO, the room temperature multiferroic properties have been obtained in these two systems.</p> <p> Second, the impact of the film composition has been demonstrated in La_0.7Ca_0.3MnO₃ (LCMO):CeO₂thin film system, which has an insulating CeO₂in ferromagnetic conducting LCMO matrix structure. As the atomic percentage of the CeO₂increases, enhanced low-field magnetoresistance and increased metal-to-insulator transition temperature are observed. The thin films also show enhanced anisotropic ferromagnetic response comparing with the pure LCMO film.</p> <p> Third, the transition metal element in Bi₃MoM_TO₉(M_T, transition metals of Mn, Fe, Co and Ni) thin films have been varied. The thin films have a multilayered structure with M_T-rich pillar-like domains embedded in Mo-rich matrix structure. The anisotropic magnetic easy axis and optical properties have been demonstrated. By the element variation, the optical bandgaps, dielectric constants as well as anisotropic ferromagnetic properties have been achieved. </p> <p> The studies in this dissertation demonstrate several examples of tuning the multifunctionalities in oxide-based nanocomposite thin films. These enhanced properties can broaden the applications of functional oxides for advanced nanoscale devices.</p><br>

<p>Aluminum alloys have broad applications in aerospace, automotive, and defense industries as structural material due to the low density, high-specific strength, good castability and formability. However, aluminum alloys commonly suffer from problems such as low yield strength, low stiffness, and poor wear and tear resistance, and therefore are restricted to certain advanced industrial applications. To overcome the problems, one promising method is the fabrication of aluminum matrix composites (AMCs) by introducing ceramic reinforcements (fibers, whiskers or particles) in the metal matrix. AMCs typically possess advanced properties than the matrix alloys such as high specific modulus, strength, wear resistance, thermal stability, while remain the low density. Among the AMCs, particulate reinforced aluminum matrix composites (PRAMCs) are advantageous for their isotropic properties, ease of fabrication, and low costs. Particularly, the PRAMCs with in-situ particulate reinforcements have received great interest recent years. The in-situ fabricated particles are synthesized in an aluminum matrix via chemical reactions. They are more stable and finer in size, and have a more uniform distribution in the aluminum matrix and stronger interface bonding with aluminum matrix, compared to the ex-situ particulate reinforcements. As a consequence, the in-situ PRAMCs have superior strength and mechanical properties as advanced engineering materials for a broad range of industrial applications.</p> <p>This dissertation focuses on the investigation of high strength aluminum matrix composites reinforced with in-situ particulates. The first chapter provides a brief introduction for the studied materials in the dissertation, including the background, the scope, the significance and the research questions of the study. The second chapter presents the literature review on the basic knowledge, the fabrication methods, the mechanical properties of in-situ PRAMCs. The strengthening mechanisms and strategies of in-situ PRAMCs are summarized. Besides, the micromechanical simulation is introduced as a complementary methodology for the investigation of the microstructure-properties relationship of the in-situ PRAMCs. The third chapter shows the framework and methodology of this dissertation, including material preparation and material characterization methods, phase diagram method and finite element modelling. </p> <p>In Chapter 4, the microstructures and mechanical properties of in-situ Al₃Ti particulate reinforced A356 composites are investigated. The microstructure and mechanical properties of in-situ 5 vol. % Al₃Ti/A356 composites are studied either taking account of the effects of T6 heat treatment and strontium (Sr) addition or not. Chapter 5 studies the evolution of intermetallic phases in the Al-Si-Ti alloy during solution treatment, based on the work of Chapter 4. The as-cast Al-Si-Ti alloy is solution treated at 540 °C for different periods between 0 to 72 h to understand the evolution of intermetallic phases. In Chapter 6, a three-dimensional (3D) micromechanical simulation is conducted to study the effects of particle size, fraction and distribution on the mechanical behavior of the in-situ Al₃Ti/A356 composite. The mechanical behavior of the in-situ Al₃Ti/A356 composite is studied by three-dimensional (3D) micromechanical simulation with microstructure-based Representative Volume Element (RVE) models. The effects of hot rolling and heat treatment on the microstructure and mechanical properties of an in-situ TiB₂/Al2618 composite with minor Sc addition are investigated in Chapter 7. TiB₂/Al2618 composites ingots were fabricated <i>in-situ</i> via salt-melt reactions and subjected to hot rolling. The microstructure and mechanical properties of the TiB₂/Al2618 composite are investigated by considering the effects of particle volume fraction, hot rolling thickness reduction, and heat treatment. </p>

<p> Environmental Barrier Coatings (EBCs) protect ceramic gas turbine engine components from corrosion by high temperature water vapor, but the coatings often form complex metastable microstructures upon plasma spray deposition. In ytterbium disilicate (YbDS) and its yttrium-doped counterpart (Y/YbDS), two coatings compatible with SiC/SiC parts, plasma spray forms a largely cracked, mechanically weak amorphous phase comprising up to ~80% of the coating’s volume. Therefore, the coatings must undergo a pre-service heat treatment to crystallize into stable phases and heal cracks. During the treatment, however, interplay between thermal expansion and crystallization contraction can cause vertical cracks which expose the component to the corrosive atmosphere. Remedial treatments with long, high temperature holds (~1300 ºC) can both crystallize the coating and heal existing cracks. However, these temperatures cause unnecessary grain growth that reduces the structural integrity of the coating over its lifetime.</p> <p>Here we propose an alternate heat treatment informed by experiments and modelling that removes metastable phases, heals cracks, and reduces time at temperature to prevent significant grain growth. First, we determine crystallization and phase change kinetics by applying the Ozawa-Flynn-Wall and Vyazovkin kinetic methods to differential scanning calorimetry (DSC) data. Next, we track locations and microstructural effects of phase evolution using correlative Raman spectroscopic mapping, scanning electron microscopy (SEM), and X-Ray diffraction (XRD). We interpret the formation of three distinct phases – a major phase of stable β-YbDS, and minor phases of stable Χ2-YbMS and metastable α-YbDS – within the existing framework of kinetic theory and quantify differences in their transformations between YbDS and Y/YbDS. We find that cracks in the coating heal through the crystallization of the amorphous phase and the transformation of the metastable phase although the mechanisms remain unclear. Each phase transformation causes a bulk volumetric change which we measure using dilatometry and use to calculate delamination stresses during a simulated heat treatment. Lastly, we determine the viability of our heat treatment compared to the industry standard.</p>

<p dir="ltr">The process of metal additive manufacturing is characterized by the layer-by-layer construction of components, where each individual layer may be subjected to distinct thermal variations, resulting in differences in cooling rates and thermal gradients. These variations can impact the microstructure and, subsequently, mechanical properties of the final product, especially as the height of the build increases. In the present investigation, an evaluation was undertaken to ascertain the impact of build height on the structural integrity of Ti-6Al-4V samples produced using the laser powder bed fusion (LPBF) technique. The study encompassed a comprehensive examination of microstructural features, the microhardness measurement, as well as an evaluation of defect characteristics including size, location, and distribution, with respect to the build height. Tensile and fatigue tests were conducted to elucidate the potential dependence of fatigue and tensile failures on the build height. Two groups of specimens were fabricated: the first, underwent continuous fabrication, while the second involved a pause at the half height, with the process resuming after a 24-hour interval. The results of this investigation unveiled a discernible influence of the height of the build on the structural integrity of components under cyclic loading. Most fatigue specimens were observed to exhibit failure in the upper portion of the gage section with respect to the build direction. Analyses of microstructure revealed a consistent grain morphology in alignment with the build direction, and a uniform distribution of hardness throughout the build height was noted. However, for the specimens in the first group, more process-induced defects were detected within the top half of the gage section in comparison to the bottom half, while there was no noticeable difference in the distribution of defects in the second group. The results suggest that in LPBF process, as the build height is increased, there is a higher likelihood of process-induced defect formation, ultimately resulting in a reduction in structural integrity at greater build heights.</p>