The dissertation thesis deals with the modification of the surface of advanced magnesium alloys with Ni-P based coatings. At the beginning of the theoretical part, the structures of the used magnesium alloys and the influence of individual alloying elements on their properties are characterized. In the following part of the thesis the current knowledge in the field of electroless deposition on metal substrates is summarized. The theoretical part of the thesis is closed with contemporary research study in the field of clarification and determination of possible mechanism of electroless deposition. For the subsequent investigation of the mechanism of electroless deposition on magnesium alloys, it was necessary to characterize the microstructure and composition of individual magnesium alloys in the first phase of the experimental part. The exact composition of elements was determined using glow discharge optical emission spectroscopy and scanning electron microscopy with EDS was used for composition of phases of magnesium alloys. Using scanning electron microscopy and detailed elemental analysis of the coated magnesium substrate, it was found that for optimal Ni-P coating deposition on magnesium alloys, acid pickling prior coating is required in a mixture of acetic acid and sodium nitrate. Using the XPS method, it was found that the phosphorus atom in the sodium dihydride-diphosphate reducing agent has a + V charge. 4 At the end of the experimental part scanning electron microscopy and detailed elemental analyses were used for monitoring of the Ni-P particles nucleation and growth in the first 120 seconds of the coating process.

The growing demand in the industry towards sustainability and the globalization of manufacturing lead to an industrial climate of constant development and improvements, and automotive interior design is not excluded. In 2017 the European Union declared that the material used to generate the bright chrome surfaces of car interiors (CR VI) is toxic and carcinogenic. This implies that Volvo will ban the use of Chrome VI for decorative parts from September 2024.  Finding a more eco-friendly alternative to replace CR VI not only functionally but also in terms of perceived quality and user experience will be an urgent and decisive action.  In this project, the parameters of gloss, haze, color temperature, and metallic depth are investigated in order to figure out which elements ensure the perceived quality of chrome surfaces.  For this purpose, a user study based on different sensory tests and soft metrology was carried out with 48 people, as well as seven samples, five of them more eco-friendly alternatives. This project aims to introduce a set of tools to assess and guarantee the perception of quality by supporting the development of "chrome-look" surfaces in the automotive interior with new sustainable materials. Through this study, correlating soft and hard metrology, it is observed what makes a surface perceived as "high-quality" and which of the more eco-friendly alternatives could be the most optimal to replace Chrome VI in Volvo's car interiors.

Die vorliegende Arbeit liefert einen Beitrag zum Verständnis der elektrochemischen Prozesse an der Elektrodengrenzfläche und im Festkörper graphitischer Anoden für Lithium-Ionen-Batterien. Der Zusammenhang zwischen den intrinsischen Eigenschaften des Aktivmaterials und den resultierenden Eigenschaften von Kompositelektroden stand dabei im Fokus der Untersuchungen. Die Temperaturabhängigkeit von Materialeigenschaften (Diffusionskoeffizient, Austauschstromdichte) und Elektrodeneigenschaften (Verhalten unter Strombelastung) wurde in einem Bereich von 40 °C bis -10 °C erfasst. Dazu werden elektrochemische Charakterisierungsmethoden aus der Literatur vorgestellt und hinsichtlich ihrer Gültigkeit für die Anwendung an realen Elektroden evaluiert. Die elektrochemisch aktive Oberfläche wurde bestimmt und stellte sich als ausschlaggebender Parameter für die Bewertung der Elektrodenprozesse heraus. Auf Basis korrigierter Elektrodenoberflächen konnten Austauschstromdichten für die konkurrierenden Prozesse Lithium-Interkalation und -Abscheidung ermittelt werden. Zusammen mit Kennwerten zur Keimbildungsüberspannung für Lithium-Abscheidung flossen die ermittelten Kennwerte in eine theoretische Berechnung des Zellstroms ein. Es konnte gezeigt werden, dass die Lithium-Abscheidung kinetisch deutlich gegenüber der Lithium-Interkalation bevorzugt ist, nicht nur bei niedriger Temperatur. Die Übertragbarkeit wissenschaftlicher Grundlagenexperimente auf kommerzielle Systeme war bei allen Versuchen Gegenstand der Untersuchungen. In einem separaten Beispiel einer Oberflächenmodifikation mit Zinn wurde diese Problematik besonders verdeutlicht. Zusätzlich wurde die parasitäre Abscheidung von Lithium auf graphitischen Anoden hinsichtlich der Nachweisbarkeit und Quantifizierung evaluiert. Hierfür wurde eine neue Untersuchungsmethode im Bereich der Lithium-Ionen-Batterie zur besseren Detektion von Lithium-Abscheidung und Grenzflächen-Morphologie mittels Elektronenmikroskopie entwickelt. Die Osmiumtetroxid (OsO4) Färbung ermöglichte eine deutliche Verbesserung des Materialkontrasts und erlaubte somit eine gezielte Untersuchung von graphitischen Anoden nach erfolgter Lithium-Abscheidung. Darüber hinaus konnte die selektive Reaktion des OsO4 für eine genauere Betrachtung der Solid Electrolyte Interphase genutzt werden. Eine Stabilisierung der Proben an Luft und im Elektronenstrahl konnte erreicht werden. / This work sheds light on the electrochemical processes occurring at commercially processed graphitic anodes. It raises the question whether values published in literature for mostly ideal electrode systems can be readily taken for simulation and design of real electrodes in high-energy cells. A multiple step approach is given, evaluating different methods to determine electrode and material properties independently. The electrochemically active surface area was shown to be a crucial parameter for the calculation of electrode kinetics. Using exchange current densities corrected for the electrode surface area, the overall charging current in a cell could be calculated. The resulting part of lithium deposition in the charging process is strikingly high, not only at low temperatures. To further investigate lithium deposition in terms of morphology and quantity, a method was developed for graphitic anodes. Osmium tetroxide (OsO4) staining serves well as a tool to strongly increase material contrast in electron microscopy. Thus lithium dendrites could be made visible in an unprecedented manner. Furthermore, the selective chemical reaction of osmium tetroxide allows for a better investigation of the multi-layer solid electrolyte interphase as was shown in transmission electron microscopy. Using the staining method, a stabilization of the sample under air and in the electron beam could be achieved.

<p>Micro- and nanoparticles (MNP) attract much attention owing to their unique properties, structural tunability, and wide range of practical applications. To deposit these important materials on surfaces for generating functional coatings, a variety of special delivery systems and coating/printing techniques have been explored. Herein, spray coating technique is a promising candidate to advance the field of nanotechnology due to its low-cost, high-deposition rate, manufacturing flexibility, and compatibility with roll-to-roll processing. Despite great advances, direct scalable spray writing of functional materials at high-spatial resolution through fine patterning without a need of vacuum and mask equipment still remains challenging. Addressing these limitations requires the development of efficient spray deposition techniques and novel manufacturing approaches to effectively fabricate functional coatings. To this end, this dissertation employs three different spray coating methods of (1) cold spray; (2) atomization-assisted supersonic spray, and (3) dual velocity regime spray to address the aforementioned limitations. A comprehensive set of coating materials, design principles, and operational settings for each spray system are tailored for rapid, direct, and sustainable deposition of MNP on various substrates. Besides, through the two-phase flow modeling, droplets dispersion and deposition characteristics were investigated under both subsonic and supersonic flow conditions to uncover the process-structure-property relationships of the established spray systems. Moreover, novel spray-based manufacturing approaches are developed to fabricate functional coatings in various applications, including (i) functional polymer metallization, (ii) printed flexible electronics, (iii) advanced thin-film nanocoating, (iv) laser direct writing, and (v) electronic textiles.</p>

The rate of degradation of a lithium-ion battery depends on its use i.e. how it is charged and discharged. Physics-based models are used to represent the processes inside a cell as well as the degradation mechanisms. This thesis aimed to compare how the battery lifetime is affected when charging with different charging protocols using different battery models and degradation mechanisms. The investigated models are the Single Particle Model (SPM), the Single Particle Model with electrolyte (SPMe), and the Doyle-Fuller Newman model (DFN). The degradation mechanisms are solid electrolyte interphase (SEI), and lithium plating (LP). The used charging protocols are constant-current constant voltage(CCCV), positive pulsed current (PPC), and constant current (CC). Pulsed charging was included to investigate if the battery lifetime can be improved as in an experiment by Huang where pulsed charging increased the battery lifetime by 60%. To perform the simulations using the physics-based models, PyBaMM (PythonBattery Mathematical Modeling) was used. The simulations were performed for a lithium cobalt oxide (LCO) cell. Two types of SEI were implemented, solvent-diffusion limited and reaction limited. For the LP only irreversible LP was used.1200 cycles were simulated. Comparing the PPC and CC protocols, there were no significant changes between the degradation mechanisms for the different protocols. The results were the same for all the models, except for the results of the internal resistance. The conclusion is that for the PPC and CC protocols, the cell degrades the same although the PPC protocol used twice the C-rate. The PPC charging did not increase the battery lifetime. For the CCCV and CC protocols, there were some bigger differences between the protocols, but between the different models, there weren’t any significant differences. The CCCV degrades the cell faster for all degradation mechanisms and all models. Simulating one degradation submodel at a time resulted in a very small capacity fade for some submodels. Therefore, for future work, it is suggested to use several degradation submodels at the same time but also to try other degradation mechanisms or try PPC protocols with different frequencies and duty cycles. / Hur snabbt litiumjonbatterier degraderas beror på hur de används, laddas och laddas ur. Fysikbaserde modeller används för att representera processerna inuti cellen och även degraderingsmekanismerna. Denna studie har genomförts för att undersöka hur batteriets livslängd påverkas av olika laddningsprotokoll genom att använda olika batterimodeller och degraderingsmekanismer. Modellerna som användes är Singel-partikelmodellen (SPM), Singel-partikelmodellen med elektrolyt (SPMe) och Doyle-Fuller Newman-modellen (DFN). Degraderingsmekanismerna är fast elektrolytinterfas (SEI) och litiumplätering (LP). Laddningsprotokollen som användes är konstant ström konstant spänning (CCCV), positiv pulserande ström (PPC) och konstant ström konstant (CC). Protokollet för pulsad laddning inkluderades för att undersöka om batteriets livslängd kan förbättras som i ett experiment av Huang, där pulsad laddning ökade batteriets livslängdmed 60%. För att utföra simuleringar med fysikbaserade modeller användes PyBaMM(Pyhton Battery Mathematical Modeling). Simuleringarna utfördes för en lithiumkobaltoxid-cell (LCO). Två typer av SEI implementerades, lösningsmedelsdiffusion-begränsad och reaktions-begränsad SEI. För LP användes endast irreversibel LP.1200 cykler simulerades. Jämförande PPC- och CC-protokollen fanns det inga signifikanta förändringar mellan degraderingsmekanismerna för de olika protokollen. Resultaten vardesamma för alla modellerna, förutom resultaten av den interna resistansen. Slutsatsen är att för både PPC- och CC-protokollen så degraderades cellen på samma sätt, trots att PPC-protokollet använde dubbelt så hög C-faktor. PPC-protokollet ökade inte batteriets livslängd. För CCCV- och CC-protokollen fanns det några större skillnader mellan protokollen, men mellan de olika modellerna fanns det inga signifikanta skillnader. CCCV-protokollet försämrade cellen snabbare för alla degraderingsmekanismer och alla modeller. Att simulera en degraderingsmodell i taget resulterade i mycket små kapacitetsförluster. Därmed föreslås det att i framtida arbete använda flera degraderingsmodeller samtidigt men även testa andra degraderingsmekanismer eller PPC-protokoll med olika frekvenser och arbetscykler

<p dir="ltr">Additive manufacturing has introduced new possibilities for the design and manufacturing of monolith catalyst beds. Many hydrogen peroxide monolith catalyst beds are made of ceramics and washcoated through a complex process. However, creating a metal monolith bed with the tried-and-true silver catalyst could provide an alternative decomposition method for 90 wt.% hydrogen peroxide with easier manufacturing methods and similar or better decomposition efficiency. 91.2 wt.% hydrogen peroxide was decomposed with a lattice-type monolithic catalyst bed additively manufactured out of 316L stainless steel that was electroplated with pure silver. The variables investigated included the catalyst bed’s mass loading, chamber pressure, pressure drop, and length-to-diameter ratio (L/D). The catalyst bed had loadings of 0.1 lb_m/s/inch², 0.25 lb_m/s/inch², and 0.4 lb_m/s/inch². One catalyst bed configuration had an L/D of 2.6, while the other configuration had an L/D of 0.85. A modular throat controlled the chamber pressures for each catalyst bed loading case. The decomposition efficiency was calculated with the theoretical and expected characteristic velocity (c*) of the catalyst beds. The chamber pressures for the lowest bed loading and highest L/D ratio varied from 52 psia to 202 psia. The hydrogen peroxide decomposition efficiency was approximately 85% for the lowest chamber pressure and approximately 100% for the highest chamber pressure. The chamber pressures for the middle and highest bed loading and high L/D were 193 psia at the lowest to 325 psia at the highest. The decomposition efficiencies for all middle and highest bed loading tests with high L/D were 90% or higher for all tests. For all of the highest L/D tests, decomposition was also confirmed by observing videos of the exhaust plume, which was clear and showed no sign of flow channeling. For all of the highest L/D tests, the pressure drops in all of the middle bed loading cases were at or below 30% of the chamber pressure. The high chamber pressure, highest bed loading cases also had a pressure loss below 30% of the chamber pressure. The smallest L/D configuration performed significantly worse than expected, with efficiencies between 15-25% at chamber pressures between 33-75 psi. The silver electroplated on the stainless steel survived the 143 s of lifetime on the catalyst bed during testing with minimal to no silver loss determined by weight and visual inspection with a microscope post-test. The higher L/D catalyst bed tests prove that silver electroplated on to an additively manufactured stainless steel monolith is a viable method for creating a catalyst bed. More research is required to determine the lowest L/D possible, which resides somewhere between the two L/D cases studied, and higher bed loadings also require investigation.</p>

No description available.

台灣的連接器產業雖然有很優良的研發能力及快速且專業的模具技術，但綜觀當今的連接器產業產品規格的制定及材料的要求多由在世界級連接器大廠來訂定規範。大部分的台灣連接器工廠都屬於產品的跟隨者，所以在模具技術日趨成熟、材料環保訴求高、大量機器化組裝的情況下，連接器的製造門檻已不像往日那麼的高。再加上1997年後大陸開放投資，台商大舉進陸投資，也將大陸的連接器產品之技術及生產水平大幅提昇，台灣連接器的製造工廠所面對的競爭不僅是先進的歐美大廠、鄰近日本、韓國工廠，以及國內工廠競爭者，其實最近幾年大陸的連接器廠如雨後春筍般的蓬勃發展，更加遽連接器工廠經營的困難及艱苦。 本研究之個案以糧德精密公司為例，先由全球連接器技術之比較與發展現況之介紹，進而討論全球連接器市場之概況，再以4C策略行銷架構為研究基礎。針對個案進行對「中小企業連接器製造廠國際市場進入之行銷策略」加以分析研究。讓糧德精密藉由此研究得以明瞭進入國際市場過程中如何透過外顯單位效益成本、資訊搜尋成本、道德危機成本，及專屬陷入成本，找出在連接器產業的定位。 在4C架構下，分析出業界大廠及二家上市櫃公司對產品、研發的作法，以及經營客戶群的策略。幫助個案之公司能夠發展出一塊小眾的經營規模市場，藉以走出連接器之紅海市場，找到屬於連接器市場之湛藍海洋。讓台灣的連接器工廠得以透過產品及供應商的整合，推廣自有品牌至國際市場。

Indiana University-Purdue University Indianapolis (IUPUI) / The purpose of this study was to evaluate the fracture resistance of three post and core systems in endodontically treated teeth by loading to failure, and to measure marginal gaps before and after cyclic loading. Sixty extracted canines were assigned to three groups. The groups tested were: 1) Single cast post and core (Group CP). 2) Prefabricated metal post and composite resin core (Group MR). 3) Glass fiber post and composite resin core (Group FR). All teeth were obturated and prepared to receive a post and core with a coping. Thirty teeth (10 from each group) were loaded to failure, and the other 30 teeth were fatigue-loaded. The marginal gaps on the facial and lingual surface of the fatigue-loaded group were measured before and after cyclic loading. There were two hypotheses for this study. The first was that the FR group would have less marginal gap opening on the lingual surface than the other groups. The second was that the CP group would have a higher load at failure than the other groups. Group CP was found to have a significantly smaller pre-loading marginal gap than group FR (p = 0.0265) and group MR (p = 0.0273), while groups FR and MR did not have a significantly different pre-loading marginal gaps (p = 0.86). Group FR had significantly less change in marginal gap than group MR (p = 0.0013). Groups CP and MR did not have significantly different changes in marginal gap (p = 0.09). Groups CP and FR did not have significantly different changes in marginal gap (p = 0.11). The three post types did not have significantly different maximum loads to failure (p= 0.49), moments of inertia at cervical area (p = 0.75), or moments of inertia at fracture site (p=0.12). There was no significant difference between groups CP, FR, and MR in the load-to-failure test. Group CP demonstrated the highest load-to-failure values; however, the highest load-to-failure mean was for group MR. All fractures observed in this study were catastrophic. Group FR demonstrated better stress distribution and caused no early fractures in the fatigue-loading group. All groups demonstrated significant marginal gap changes on the lingual surface after fatigue loading; however, group FR demonstrated <45 μm marginal gap opening. In group FR, the reduced marginal gap opening was attributed to the use of Panavia 21 with the proper surface treatments to bond to the tooth structure, the resin composite, and the metal coping.

Sélectionner des traitements de surface pour l’industrie nécessite de prendre en compte : les propriétés à conférer au substrat, la nature et la géométrie de celui-ci et les caractéristiques du milieu extérieur. Certaines combinaisons de ces paramètres rendent difficile la sélection d’un traitement unique, d’où le recours à des multitraitements de surface. Dès lors, se posent les questions suivantes : - Utiliser des multitraitements de surface peut se faire en scindant les différentes requêtes en sous-ensembles, de manière à ce que chaque traitement réponde à l’un d’eux. Dans quel ordre ces requêtes doivent-elles être introduites par rapport au substrat ? - Comment sélectionner les traitements de surface répondant à chaque requête individuelle ? - Comment classer des multitraitements en termes d’adéquation au problème posé ? Dans ce travail, les première et troisième questions sont abordées, en explorant les requêtes concernant habituellement les dispositifs de moulage de l’aluminium : - Résistance aux contraintes d’origine thermique. - Résistance à la corrosion par les métaux fondus. - Résistance au frottement. L’analyse de la bibliographie relative aux traitements de surface utilisés dans ces systèmes a été analysée et des « architectures »-types ont été identifiées (chapitre 3). On prévoit, par exemple, un traitement conférant la résistance à la fatigue superficielle, ainsi qu’un revêtement étanche et résistant à l’aluminium fondu. Une barrière thermique est parfois préconisée. Pour chacune des architectures, des traitements de surface individuels peuvent être sélectionnés. Un « facteur de performance » permettant de classer les solutions par rapport au problème de la fatigue thermique a été construit (chapitre 4) et discuté dans deux situations : - Lorsqu’un revêtement est présent, et que les contraintes d’origine thermique (différence de dilatation thermique couche-substrat) menacent de le rompre lors de l’immersion dans un milieu corrosif à haute température. Des essais de corrosion dans de l’aluminium fondu ont été réalisés sur un acier revêtu par du nitrure de chrome dopé à l’aluminium, synthétisé par déposition physique en phase vapeur (chapitre 5 – collaboration : Inasmet). - Lorsque des variations thermiques rapides menacent de rompre le substrat et la (les) couches. Des essais de fatigue thermique ont été réalisés sur de l’acier à outils pour travail à chaud non traité, boruré ou recouvert d’un multitraitements (zircone yttriée / NiCrAlY / boruration / acier). Le revêtement en zircone yttriée a été obtenu par projection par plasma. L’essai de fatigue thermique a été modélisé et le facteur de performance, discuté (chapitre 6). Au chapitre 7, les architectures-types ont été introduites dans une méthodologie de sélection des multi-traitements de surface, qui a été appliquée dans deux cas : - Celui des moules de fonderie, devant résister à la fatigue thermique et à la corrosion par l’aluminium fondu. Le facteur de performance a été extrapolé à d’autres situations qu’aux chapitres 5 et 6. Les solutions habituellement proposées pour résoudre ce problème sont retrouvées. - Celui de deux pièces en acier frottant l’une contre l’autre en présence d’aluminium fondu. To select surface treatments, one must account for the required functional properties, the substrate features and the solicitations the substrate must endure. Certain combinations of these parameters make it difficult to select a single surface treatment, a reason why several successive treatments are preferred. To select them, one needs to determine: - How to divide the several requests into groups and how to stack up these groups from the substrate to the outer surface, so that each treatment deals with one specific group of requests/properties. - How to select individual layers for each group of properties. - How to rank the multi-treatments in terms of relevance for a given application. In this work, one tries to answer the first and the third questions, by studying the case of aluminium foundry, in which the industrial devices frequently face the following solicitations: - Thermal stress (thermal fatigue, thermal expansion mismatch). - Presence of corrosive molten metal. - Sliding wear. In the literature, several “standard” architectures are proposed (chapter 3), like a diffusion layer reducing superficial fatigue plus a corrosion barrier layer. A thermal barrier coating is also sometimes proposed. For each of these architectures, one can select individual treatments. To rank them, one devised a “performance index” for thermal stress (chap.4), which is discussed for two cases: - For large differences between layer and substrate thermal expansion coefficients, when both are put into contact with a high temperature corrosive medium, the layer may be damaged. One discusses this case by examining the corrosion caused by molten aluminium for a steel substrate coated by anticorrosive chromium nitride doped with aluminium. The layer is produced by physical vapour deposition (chap. 5 – cooperation: Inasmet). - Repeated fast surface temperature transients can also damage the substrate and/or the layer by thermal fatigue. One conducted thermal fatigue tests with samples of hot work tool steel, respectively untreated, simply borided and protected by a multilayer. In the last case, top coat is yttria stabilised zirconia, followed by a nickel superalloy and then a borided layer (undercoat). One synthesized the zirconia coating by plasma spray and one modelled the thermal fatigue (chap. 6). In chap. 7, architectures from chap. 2 are introduced in a multi-treatment selection routine, which is applied in two cases: - Foundry moulds for molten aluminium, withstanding both thermal fatigue and corrosion. The devised performance index is extrapolated beyond the tests of chap. 5 and 6 to treatments for this industrial application, thereby quantifying their respective merits. - A foundry device exposed to molten metal and sliding wear.