Student Number : 0109917P - PhD thesis - School of Process and Materials Engineering - Faculty of Engineering and the Built Environment / The aim of this project was to characterise new WC-10VC-Co powders, and to deposit WC-10VC-Co thermal spray coatings from these powders for characterisation and testing in adhesion, wear and corrosion tests. Throughout the project, the new powders and coatings were compared to commercial WC-Co powders of the same binder content and commercial WC-Co thermal spray coatings. All the powders i.e WC-10VC-Co and WC-Co powders, were produced by agglomeration (by spray drying) and sintering and characaterised by determining the sizes and size distributions of the powders' particles, the morphology, the flowability and the phase composition and grain size and size distribution of carbide grains. The vanadium carbide in the WC-10VC-Co powders occurred in the solution as the double carbide (V,W)C and the carbides present in the WC-10VC-Co powders were WC and (V,W)C. None of the starting VC was left in the powders. Coatings were deposited using high pressure high velocity oxy-fuel (HP/HVOF) spraying systems, and characterized by determining the microstructures, the phase compositions and the carbide grain sizes, as had been done for the powders. Three types of tests were done on the coatings: adhesion tests, (according to standard SNECMA 14 -008); dry abrasion, wet abrasion and slurry erosion tests; and corrosion tests, in synthetic mione water. Thermal spraying lead to some WC decarburization to W2C and eta phase, and to the formation of amorphous binder. The W2C grains from the WC decarburization formed in the amorphous binder matrix of coatings. All the coatinge were porous, but the new WC-10VC-Co coatings were more porous than the commercial Wc-Co coatings because the spray parameters had only been optimized for the WC-Co coatings. The carbide grains decreased in size by as much as 50% during decomposition. Evidence suggested that the WC grains in the coatings were subjected to different residual stresses that in the powders, probably due to the formation of the amorphous binder. Vanadium carbide in the Wc-10VC-Co coatings occurred as (V,W)C, just as in the powders, with as distribution that was reasonably homogeneous. The apparent hardness of the new Wc-10VC-Co coatings was slightly lower than that of WC-Co coatings of the same cobalt content, due to their higher porosity. The adhesion of the new Wc-10VC-Co coatings was as good as that of the Wc-Co coatings. The dry and wet abrasion resistance of the new Wc-10VC-Co coatings was better that for the Wc-Co coatings of equal Co wt%, on account of the Wc-10VC-Co coatings having a lower binder volume fraction, finer carbide grains, and (V,W)C grains. The (V,W)C grains are harder than WC grains and apparently slowed down the overall abrasion rate. In slurry erosion, the best performance of the Wc-10VC-Co coatings was as good as that of the commercial WC-Co coatings at equal cobalt mass content, due to the higher porosity of the Wc-10VC-Co coatings, apparent faster erosion of the harder but brittle (V,W)C grains, and, from what evidence appreared to suggest, generally slightly poorer erosion resistance of the fine WC grains under the test conditions used. Polishing the slurry erosion test specimens reduced mass losses in slurry erosion by factor of up to 10 compared to the unpolished specimens, and led to better erosion resistance of the WC-10VC-Co coating compared to the WC-12Co coating. The results of the tests done to investigate the corrosion properties of the coatings were conclusive. This is because the effects of cleaning procedures on mass loss after immersion corrosion were not explored, and it appeared, for some coatings, that the corrosion mechanisms in immersion corrosion could not be reproduced in electrochemical testing.

The purpose of this study is to characterize the plasma spray deposits used for attaching intrinsic Fabry-Perot interferometric fiber optic strain sensors. The deposits must maintain adhesion at elevated temperatures without distorting the sensors' signals. Two different material systems were tested and modeled, a nickel based alloy and yttria-stabilized zirconia. The material properties of the deposits and the thermal stresses in the system were evaluated to determine attachment lifetime of the sensors. The encapsulated sensors' signals were collected before and after plasma spraying and at elevated temperatures. The material properties of the deposits were evaluated by electron microscopy, energy dispersive x-ray spectroscopy, scratch testing, thermal fatigue testing, and nanoindentation. The thermal stresses were evaluated by Raman spectroscopy and from finite element analysis in COMSOL® Multiphysics®. Several of the sensors broke during encapsulation due to the plasma spray processing conditions and the signals experienced distortion at elevated temperatures. The sensors can be treated to remove this interference to allow for this deposit attachment. The nickel based alloy's ductility and lamellar microstructure allowed for non catastrophic relaxation mechanisms to relieve induced thermal stresses. The yttria stabilized zirconia failed catastrophically at elevated temperatures due its lack of compliance to mismatches in thermal expansion. A high melting point metallic deposit, similar to the nickel based alloy, is desirable for fiber optic sensor attachment due to its ductility, thermal expansion, and dominant relaxation mechanisms. The processing conditions may need to be optimized to allow for the sensors' protection during encapsulation. / Master of Science

Made available in DSpace on 2016-12-08T17:19:23Z (GMT). No. of bitstreams: 1 Matheus Machado de Souza.pdf: 5533626 bytes, checksum: a5f582284c7919cc899d81e7de2c62c8 (MD5) Previous issue date: 2014-08-25 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The use of coatings based in electrolytic chromium deposition causes damages to the environment, since during the process, hexavalent chromium ions are released and these are extremely toxic to nature and man. However, other technologies have been studied as alternatives to the traditional chromium electroplating process. The thermal spray high velocity oxy-fuel (HVOF) is a technique that has shown the best results considering coating quality, porosity, wear resistance, mechanical and adhesive properties. In this work, a comparative study between the hard chromium electroplated and HVOF sprayed coatings was performed, in a condition which the substrate surface has been rectified. Surface properties were checked in terms of adhesion, hardness and microstructure, while the tribological behavior was obtained by pin on disk wear tests, considering the evaluation of wear resistance, friction coefficient and wear mechanisms. The material used as substrate was the SAE 4140 steel; the coatings sprayed by HVOF were WC-Co-Cr and 316L Stainless Steel. As the conditions studied, no adhesion on substrate of 316L coating was observed. For coatings which obtained satisfactory adherence, the tungsten carbide was harder (1750 HV0,1) than chromium (1050 HV0,1). This result was attributed to the low porosity and high hardness of WC and W2C phases contained into sprayed coating. The coat WC-Co-Cr had a better performance and wear resistance, possibly, due to the formation of a great wear resistant tribofilm and the high hardness of the layer. For chromium, the delamination of a fragile tribofilm aggregated with a big quantity of cracks inside the microstructure might explain the pronounced wear. / A utilização de revestimentos a base de cromo eletrolítico traz prejuízos ao meio ambiente, uma vez que durante o processo são liberados íons de cromo extremamente tóxicos à natureza e ao homem. Outras tecnologias vêm sendo estudadas como alternativas ao processo tradicional de cromagem. A aspersão térmica por oxi- ombustível de alta velocidade (HVOF) é a técnica que tem apresentado os melhores resultados sob as óticas de qualidade de revestimento, porosidade, resistência ao desgaste, propriedades mecânicas e adesivas. Neste trabalho foi realizado um estudo comparativo entre o cromo duro eletrodepositado e revestimentos aspergidos (WC-Co-Cr e o Inox 316L) pela técnica de HVOF em uma condição em que a superfície do substrato (aço SAE 4140) foi retificada. As propriedades de superfície foram verificadas em função da adesão, dureza e microestrutura, enquanto que o comportamento tribológico foi obtido por meio de ensaios de desgaste por deslizamento pino sobre disco, com avaliação da resistência ao desgaste, coeficiente de atrito e mecanismos de desgaste. Verificou-se a não adesão ao substrato do revestimento de Inox 316L para as condições estudadas. Quanto a dureza o carbeto de tungstênio apresentou maior valor (1750 HV0,1), bastante superior ao cromo (1050 HV0,1). Resultado atribuído a baixa porosidade e a elevada dureza das fases WC e W2C contidas no revestimento aspergido. O revestimento de WC-Co-Cr teve um melhor desempenho quanto a resistência ao desgaste, possivelmente, em função da formação de um tribofilme resistente ao desgaste e a elevada dureza da camada. Para o cromo, a delaminação de um tribofilme de natureza frágil somada a uma microestrutura com elevada densidade de trincas foram fatores que puderam explicar seu desgaste mais acentuado.

Mechanical properties of thermal spray deposited coatings are highly influenced by their microstructural characteristics. The objective of this investigation is to evaluate the mechanical properties of thermally sprayed coatings consisted of aluminum and zinc based on the coating microstructure, using an image based computational scheme. Microstructural images of coating samples were subjected to image-based finite element analysis and the results were validated by experimental tests and analytical models. Comparison of the experimental data with FEA was used to explain the microstructural basis of the mechanical characteristics of Al-Zn coatings and the differences between two methods of thermal spray techniques. It was concluded that the cold spraying technique produces higher-quality coatings with less porosity and higher hardness compared to wire arc deposition. An isotropic behavior was observed in the cold sprayed coating. Finally, the electrochemical tests showed that the coating with a higher amount of zinc had better anti-corrosion properties.

<p> Cellulose-based materials have been attracting significant attention in recent years for their potential as renewable and biodegradable materials. Cellulose nanofibrils (CNFs) in particular are readily attainable from woody biomass in high purity and without harsh chemical processes. These CNFs can undergo chemical surface modifications after a simple workup, imbuing them with new attributes that differ from their naturally paper-like structure and properties. In this research, CNFs are modified with oleic acid—another common biomass found in high concentrations in some vegetable oils—which transforms the naturally hydrophilic cellulose into a superhydrophobic material. This transformation can be carried out using solventless mechanochemistry and worked up in ethanol, supporting a green process from start to finish.</p> <p><br></p> <p>Since cellulose contains many free, exposed hydroxyl groups, carboxylic acids can be condensed onto exposed hydroxyls to form esters. In this research, we focus specifically on the oleic acid moiety because its internal alkene has potential for further reactivity. Here we explore methods to introduce crosslinks into esterified CNF (eCNF) for structural and mechanical reinforcement between fibrils. Several methods are attempted, including methods involving thiolene chemistry and epoxide ring opening.</p> <p><br></p> <p>Additionally, efforts have been made to develop a method to disperse eCNF materials in ethyl acetate for deposition by spray coating. Dispersions of eCNF in ethyl acetate are sufficiently stable to enable deposition using simple airbrushing tools. The eCNF coatings are homogenous, superhydrophobic, and have good adhesion to a wide variety of surfaces. </p>

Coatings utilizing the piezospectroscopic (PS) effect of alpha alumina could enable on the fly stress sensing for structural health monitoring applications. While the PS effect has been historically utilized in several applications, here by distributing the photo-luminescent material in nanoparticle form within a matrix, a stress sensing coating is created. Parallel to developing PS coatings for stress sensing, the multi-scale mechanics associated with the observed PS response of nanocomposites and their coatings has been applied to give material property measurements, providing an understanding of particle reinforced composite behavior. Understanding the nanoparticle-coating-substrate mechanics is essential to interpreting the spectral shifts for stress sensing of structures. In the past, methods to experimentally measure the mechanics of these embedded nano inclusions have been limited, and much of the design of these composites depend on computational modeling and bulk response from mechanical testing. The PS properties of Chromium doped alumina allow for embedded inclusion mechanics to be revisited with unique experimental setups that probe the particles state of stress under applied load to the composite. These experimental investigations of particle mechanics will be compared to the Eshelby theory and its derivative theories in addition to the nanocomposite coating mechanics. This work discovers that simple nanoparticle load transfer theories are adequate for predicting PS properties in an intermediate volume fraction range. With fundamentals of PS nanocomposites established, the approach was applied to selected experiments to prove its validity. In general it was observed that the elastic modulus values calculated from the PS response were similar to that observed from macroscale strain measurements such as a strain gage. When simple damage models were applied to monitor the elastic modulus, it was observed that the rate of decay for the elastic modulus was much higher for the PS measurements than for the strain gage. A novel experiment including high resolution PS maps with secondary strain maps from digital image correlation is reviewed on an open hole tension, composite coupon. The two complementary measurements allow for a unique PS response for every location around the hole with a spatial resolution of 400 microns. Progression of intermediate damage mechanisms was observed before digital image correlation indicated them. Using the PS nanocomposite model, elastic modulus values were calculated. Introducing an elastic degradation model with some plastic deformation allows for estimation of material properties during the progression of failure. This work is part of a continuing effort to understand the mechanics of a stress sensing PS coating. The mechanics were then applied to various experimental data that provided elastic property calculations with high resolution. The significance is in the experimental capture of stress transfer in particulate composites. These findings pave the way for the development of high resolution stress-sensing coatings.