Ti2AlC coatings have been fabricated by cold-spray deposition. The microstructure evolution as a function of basic spray parameters temperature and pressure onto AA6060 aluminium alloy and 1.0037 steel substrates has been studied. Adherent and dense 50–80 μm thick Ti2AlC coatings were deposited on soft AA6060 substrates under gas temperature and pressure of 600 °C and 3.4 MPa, respectively, whilst comparable results were obtained on harder 1.0037 steel by using higher temperature (800 °C) and pressure (3.9 MPa).

abstract: Polycrystalline magnetite thin films were deposited on large area polymer substrates using aqueous solution based spin-spray deposition (SSD). This technique involved the hydrolysis of precursor salt solutions at low temperatures (70-100°C). The fundamental mechanisms and pathways in crystallization and evolution of the film microstructures were studied as a function of reactant chemistry and reactor conditions (rotation rate, flow rates etc.). A key feature of this method was the ability to constantly supply fresh solutions throughout deposition. Solution flow due to substrate rotation ensured that reactant depleted solutions were spun off. This imparted a limited volume, near two-dimensional restriction on the growth process. Film microstructure was studied as a function of process parameters such as liquid flow rate, nebulizer configuration, platen rotation rate and solution chemistry. It was found that operating in the micro-droplet regime of deposition was a crucial factor in controlling the microstructure. Film porosity and substrate adhesion were linked to the deposition rate, which in-turn depended on solution chemistry. Films exhibited a wide variety of hierarchically organized microstructures often spanning length scales from tens-of-nanometers to a few microns. These included anisotropic morphologies such as nanoplates and nanoblades, that were generally unexpected from magnetite (a high symmetry cubic solid). Time resolved studies showed that the reason for complex hierarchy in microstructure was the crystallization via non-classical pathways. SSD of magnetite films involved formation of precursor phases that subsequently underwent solid-state transformations and nanoparticle self-assembly. These precursor phases were identified and possible reaction mechanisms for the formation of magnetite were proposed. A qualitative description of the driving forces for self-assembly was presented. / Dissertation/Thesis / Doctoral Dissertation Materials Science and Engineering 2018

abstract: The overall objective of this project is to optimize the development of magnetic ferrite thin films targeted for enabling low-loss broadband communication devices, miniaturized low-microwave inductors and electromagnetic noise suppressors. The focus of this objective is to design and build a reactor and improve the spin-spray process. Each film is then characterized and optimized to have a high permeability and high frequency in the range of 500 MHz - 3 GHz. Films produced by the µ-droplet deposition regime yields a higher Snoek's product than the continuous liquid layer regime. The highest Snoek's product occurs when it is deposited at an oxidant pH of 8.28. The Ni-Zn-Co ferrite magnetic domains were imaged using the Lorentz TEM in which multi-grain domains are experimentally observed for the first time. / Dissertation/Thesis / Ph.D. Materials Science and Engineering 2013

This thesis presents work relating to the fabrication of novel thin film electrodes for energy storage applications, with a focus on low cost, nanostructured transition metal oxides, and electrode manufacture by atomised spray deposition. Iron oxide (FeO_x) nanowires were synthesised hydrothermally and combined with multi-walled carbon nanotubes (MWNT) in sprayed electrodes, which provided the necessary conductivity enhancement for effective energy storage. The spray processing technique allowed for facile control over the relative fraction of MWNTs in the sprayed electrodes. Optimised electrodes were investigated in a range of aqueous electrolytes, and the best energy storage behaviour occurred in Na₂SO₃ with a maximum capacitance from cyclic voltammetry of 312 Fg^-1 at a scan rate of 2 mVs^-1. The FeO_x/MWNT electrodes were investigated for their suitability as lithium-ion battery anodes and showed reasonable energy storage behaviour. Nickel oxide (NiO) electrodes were manufactured by hydrothermal synthesis and annealing followed atomised spray deposition. The performance of the NiO electrodes was enhanced though combination with aqueous graphene suspensions, produced in-house by ultrasonic exfoliation of graphite. The processing route used to combine the nanomaterials was considered and a co-synthesis route resulted in the best performing electrodes. Different substrates were investigated, as the most commonly used Ni-foam substrate reacted with the basic electrolytes necessary for electrochemical activity of NiO. NiO/graphene electrodes showed charge/discharge capacitances of up to 571 Fg^-1 at a current density of 10 Ag^-1, which was maintained at over 300 F/g at a very high current density of 100 Ag^-1. Asymmetric supercapacitor devices were constructed using various combinations of FeO_x, NiO, and commercial carbon black electrodes to extend the operating potential window beyond the ~1.23 V limit of symmetric aqueous-electrolyte devices. Power densities of over 20 kWkg^-1 were achieved for an FeO_x/MWNT-carbon device, which was comparable with current commercial carbon-only supercapacitors.

O presente trabalho teve por objetivo avaliar e comparar dois sistemas de aplicação de agrotóxicos em citros visando à redução do volume de aplicação com base no estudo da quantidade de produto que permanece no alvo (deposição) e análise das gotas. Na citricultura utilizam-se altos volumes de aplicação (de 2000 a 5000 L.ha-1) para o controle de pragas e doenças incrementando os custos operacionais, por esse motivo, atualmente vem-se desenvolvendo diversos sistemas de aplicação com tecnologia sofisticada visando diminuir esses volumes para 200 ou 500 L.ha-1 mas permitindo que a quantidade de produto depositado no alvo seja eficaz no controle de pragas e doenças. Procuramos avaliar dois sistemas de aplicação de agrotóxicos com um pulverizador de jato transportado. Os sistemas de aplicação utilizaram os atomizadores rotativos de discos e os bicos hidráulicos para efeito comparativo do desempenho. Foi realizada uma pulverização em duas passadas para cada sistema sobre uma amostra de quatro árvores. Utilizaram-se papéis hidrosensíveis, folhas e placas de vidro para a coleta dos dados. Para a análise da gota utilizou-se o software de leitura visual e-Sprinkle e a análise de deposição foi realizada com cromatografia gasosa e cromatografia de permeação em gel. Concluiu-se que o sistema de aplicação com atomizadores rotativos mostrou resultados favoráveis de deposição quando comparado com o sistema de aplicação com bicos hidráulicos, uma vez que esses resultados não foram significativamente diferentes. O que resulta bastante importante é que o sistema de aplicação com atomizadores rotativos utilizou um quinto do volume de aplicação quando comparado ao sistema com bicos hidráulicos, pelo que se deve considerar de vital importância o aspecto econômico para trabalhos complementares. / The aim of the work was to evaluate and compare two application spray systems of pesticides in citrus, aiming the reduction of the application volume rate in based in the amount of product that remains in the target (spray deposition) and distribution of the drops. Actually in the citrus orchard high application volumes rates for the pest control are used increasing the operational costs. The application system must be based in sophisticated technology to reduce the application volumes rates and also be efficient in the pest control. For such we evaluated two pesticides application systems with an air carrier sprayer. The application systems used were the rotary discs atomizers and the hydraulic nozzles, to compare the performance based in the applied volume rates, spray deposition and droplets distribution. A spraying run for each system was performed on a random sample of four trees for each system, water-sensitive papers, leaves and glass slides had been used for data collection. The water-sensitive papers were analyzed with visual imaging software (e-Sprinkle) and the spray deposition was analyzed with gas chromatography and gel permeation chromatography. The application system with rotary discs atomizers used reduced application volumes rates and had less deposit than hydraulic nozzles but did not significantly differents. Those results were important because the application system with rotary discs atomizers only used fifth of the application volume rate compared with hydraulic nozzles, must be consider of vital importance the economical aspect to complementary works.

O presente trabalho teve por objetivo avaliar e comparar dois sistemas de aplicação de agrotóxicos em citros visando à redução do volume de aplicação com base no estudo da quantidade de produto que permanece no alvo (deposição) e análise das gotas. Na citricultura utilizam-se altos volumes de aplicação (de 2000 a 5000 L.ha-1) para o controle de pragas e doenças incrementando os custos operacionais, por esse motivo, atualmente vem-se desenvolvendo diversos sistemas de aplicação com tecnologia sofisticada visando diminuir esses volumes para 200 ou 500 L.ha-1 mas permitindo que a quantidade de produto depositado no alvo seja eficaz no controle de pragas e doenças. Procuramos avaliar dois sistemas de aplicação de agrotóxicos com um pulverizador de jato transportado. Os sistemas de aplicação utilizaram os atomizadores rotativos de discos e os bicos hidráulicos para efeito comparativo do desempenho. Foi realizada uma pulverização em duas passadas para cada sistema sobre uma amostra de quatro árvores. Utilizaram-se papéis hidrosensíveis, folhas e placas de vidro para a coleta dos dados. Para a análise da gota utilizou-se o software de leitura visual e-Sprinkle e a análise de deposição foi realizada com cromatografia gasosa e cromatografia de permeação em gel. Concluiu-se que o sistema de aplicação com atomizadores rotativos mostrou resultados favoráveis de deposição quando comparado com o sistema de aplicação com bicos hidráulicos, uma vez que esses resultados não foram significativamente diferentes. O que resulta bastante importante é que o sistema de aplicação com atomizadores rotativos utilizou um quinto do volume de aplicação quando comparado ao sistema com bicos hidráulicos, pelo que se deve considerar de vital importância o aspecto econômico para trabalhos complementares. / The aim of the work was to evaluate and compare two application spray systems of pesticides in citrus, aiming the reduction of the application volume rate in based in the amount of product that remains in the target (spray deposition) and distribution of the drops. Actually in the citrus orchard high application volumes rates for the pest control are used increasing the operational costs. The application system must be based in sophisticated technology to reduce the application volumes rates and also be efficient in the pest control. For such we evaluated two pesticides application systems with an air carrier sprayer. The application systems used were the rotary discs atomizers and the hydraulic nozzles, to compare the performance based in the applied volume rates, spray deposition and droplets distribution. A spraying run for each system was performed on a random sample of four trees for each system, water-sensitive papers, leaves and glass slides had been used for data collection. The water-sensitive papers were analyzed with visual imaging software (e-Sprinkle) and the spray deposition was analyzed with gas chromatography and gel permeation chromatography. The application system with rotary discs atomizers used reduced application volumes rates and had less deposit than hydraulic nozzles but did not significantly differents. Those results were important because the application system with rotary discs atomizers only used fifth of the application volume rate compared with hydraulic nozzles, must be consider of vital importance the economical aspect to complementary works.

This thesis deals with the heat evolution duringsolidification and its relation to the formation of porosity.It intends to improve the current understanding of theformation of porosity in cast materials with special interestin nodular cast iron and the spray forming process. Twodifferent systems, a Fe-based alloy, Cast iron, and a Ni-basedalloy, Inconel 625, are examined. The effect on the heatevolution of the morphology and the processing parameters inspray forming are treated. An evaluation of the microstructural features, segregationbehavior and physical properties such as latent heat of fusionis performed byusing thermal analysis under cooling ratesranging from 0.1 to 104 K/s. In order to achieve this amodified differential thermal analysis (DTA) equipment, amirror furnace and levitation casting are used. Results arepresented in terms of the fraction of solidified, the coolingrate and the microstructure observed. The measured latent heatof fusion is not constant throughout the solidificationprocess. Variations in morphology and cooling rate affect therelease of the latent heat. A thermodynamic model is used to describe the experimentalobservations and to explain the formation of pores in nodularcast iron by taking into consideration the formation of latticedefects during the liquid/solid transformation. In this casethe formation of porosity is regarded as a consequence ofchanges in the volume fraction ratio graphite/ during thesolidification process. A numerical model of the spray forming process is developedby means of CFD modelling and compared with experimentalmeasurements performed in an industrial facility. Stagnationpressure measurements provided information about the gas flowvelocity and an analysis of the overspray powder providedinformation about the particle thermal history. Evaluation ofthe deposit was also performed. It is observed that the processconditions in spray forming promote non-equilibriumsolidification even though solidification at the deposit occursat a lower rate. In this case the porosity formed near theinterface substrate/deposit depends largely on the substratetemperature. The presence of certain reactive elements, such astitanium, affects the porosity levels in the rest of thedeposit. <b>Keywords:</b>Thermal Analysis, Nodular Cast Iron, Inconel625, CFD, Flow Assesment, Multiphase Flow, Spray Deposition,Microporosity, Superalloys

Reactive spray deposition technology (RSDT) is a method of depositing films or producing nanopowders through combustion of metal-organic compounds dissolved in a solvent. This technology produces powders of controllable size and quality by changing process parameters to control the stoichiometry of the final product. This results in a low-cost, continuous production method suitable for producing a wide range of fuel cell related catalyst films or powders. In this work, the system is modified for direct deposition of both unsupported and carbon supported layers on proton exchange membrane (PEM) fuel cells. The cell performance is investigated for platinum loadings of less than 0.15 mg/cm² using a heterogeneous bi-layer consisting of a layer of unsupported platinum followed by a composite layer of Nafion®, carbon and platinum. Comparison to more traditional composite cathode architectures is made at loadings of 0.12 and 0.05 mg platinum/cm². The composition and phase of the platinum catalyst is confirmed by XPS and XRD analysis while the particle size is analyzed by TEM microscopy. Cell voltages of 0.60 V at 1 A/cm² using H₂/O₂ at a loading of 0.053 mg platinum/cm² have been achieved.

<p>This thesis deals with the heat evolution duringsolidification and its relation to the formation of porosity.It intends to improve the current understanding of theformation of porosity in cast materials with special interestin nodular cast iron and the spray forming process. Twodifferent systems, a Fe-based alloy, Cast iron, and a Ni-basedalloy, Inconel 625, are examined. The effect on the heatevolution of the morphology and the processing parameters inspray forming are treated.</p><p>An evaluation of the microstructural features, segregationbehavior and physical properties such as latent heat of fusionis performed byusing thermal analysis under cooling ratesranging from 0.1 to 104 K/s. In order to achieve this amodified differential thermal analysis (DTA) equipment, amirror furnace and levitation casting are used. Results arepresented in terms of the fraction of solidified, the coolingrate and the microstructure observed. The measured latent heatof fusion is not constant throughout the solidificationprocess. Variations in morphology and cooling rate affect therelease of the latent heat.</p><p>A thermodynamic model is used to describe the experimentalobservations and to explain the formation of pores in nodularcast iron by taking into consideration the formation of latticedefects during the liquid/solid transformation. In this casethe formation of porosity is regarded as a consequence ofchanges in the volume fraction ratio graphite/ during thesolidification process.</p><p>A numerical model of the spray forming process is developedby means of CFD modelling and compared with experimentalmeasurements performed in an industrial facility. Stagnationpressure measurements provided information about the gas flowvelocity and an analysis of the overspray powder providedinformation about the particle thermal history. Evaluation ofthe deposit was also performed. It is observed that the processconditions in spray forming promote non-equilibriumsolidification even though solidification at the deposit occursat a lower rate. In this case the porosity formed near theinterface substrate/deposit depends largely on the substratetemperature. The presence of certain reactive elements, such astitanium, affects the porosity levels in the rest of thedeposit.</p><p><b>Keywords:</b>Thermal Analysis, Nodular Cast Iron, Inconel625, CFD, Flow Assesment, Multiphase Flow, Spray Deposition,Microporosity, Superalloys</p>

Reactive spray deposition technology (RSDT) is a method of depositing films or producing nanopowders through combustion of metal-organic compounds dissolved in a solvent. This technology produces powders of controllable size and quality by changing process parameters to control the stoichiometry of the final product. This results in a low-cost, continuous production method suitable for producing a wide range of fuel cell related catalyst films or powders. In this work, the system is modified for direct deposition of both unsupported and carbon supported layers on proton exchange membrane (PEM) fuel cells. The cell performance is investigated for platinum loadings of less than 0.15 mg/cm² using a heterogeneous bi-layer consisting of a layer of unsupported platinum followed by a composite layer of Nafion®, carbon and platinum. Comparison to more traditional composite cathode architectures is made at loadings of 0.12 and 0.05 mg platinum/cm². The composition and phase of the platinum catalyst is confirmed by XPS and XRD analysis while the particle size is analyzed by TEM microscopy. Cell voltages of 0.60 V at 1 A/cm² using H₂/O₂ at a loading of 0.053 mg platinum/cm² have been achieved.