Au cours des procédés de mise en forme du verre creux, les outillages de verrerie sont soumis à des conditions extrêmes avec des températures pouvant dépasser largement 650 °C. De plus, ces derniers sont exposés à des phénomènes d'abrasion sévères et à des réactions physico-chimiques complexes avec le verre fondu. Ceci est particulièrement accentué par les cycles thermiques dus aux contacts répétés avec le verre. L'objectif de ce travail de thèse est de proposer des solutions innovantes de dépôts de superalliages et/ou traitements de surface destinés à augmenter la durée de vie des outillages. Trois axes d'innovation sont présentés dans ce mémoire. Le premier concerne l'étude du dépôt de poudre composite Co/NiB par soudure PTA (Plasma Transfered Arc) sur des moules en alliage cuivreux. Le second est dédié à l'étude de la faisabilité technique d'un dépôt PVD (Physical Vapor Deposition) multicouche à gradient fonctionnel, présentant des caractéristiques intéressantes pour des applications verrières en termes de dureté et de stabilité thermique, sur des poinçons en acier AISI 431. Enfin, le troisième axe de recherche fait l'objet d'une analyse plus approfondie et concerne l'étude de la nitruration par implantation d'ions azotes multichargés, également sur un acier AISI 431. On observe après implantation une augmentation significative de la dureté (+ 240 %). Une approche multi-expérimentale et multi-échelle est alors proposée afin d'étudier la microstructure du matériau implanté ainsi que son évolution après un recuit de 1h à 650 °C de manière à anticiper le comportement du matériau en production, et de corréler ceci aux propriétés de dureté / Glass moulds have to withstand very high temperatures which can far exceed 650 °C during the glass forming process. They are exposed to very tough conditions such as abrasive wear and physico-chemical reactions, accentuated by thermal shocks due to high speed contact with hot glass melt. The aim of this work is to find innovative solutions for superalloy coating or surface treatments in order to increase the service life of glass tools. Three innovation projects are presented in this report. The first one is dedicated to PTA (Plasma Transferred Arc) welded coating of composite Co/NiB powder on copper alloy moulds. The second one is about technical feasibility of a multilayer PVD (Physical Vapor Deposition) coating with properties congruent to glass production in term of hardness and thermal stability, on AISI 431 plunger stainless steel. Last but not least, the third innovative project is about nitriding by ion implantation with multicharged nitrogen ions on AISI 431 stainless steel. We notice after ion implantation a significant hardness increase (+ 240 %). A multi-experimental and multi-scale approach was carried out in order to study the implanted material microstructure and its evolution after annealing at 650 °C during 1h to predict the material behavior during production and correlate it to hardness properties

The usage of titanium alloys in many industries has increased significantly over the years due to their superior properties. However, they are extremely difficult to machine because of their distinctive characteristics such as their high temperature strength, low thermal conductivity, and high chemical affinity for tool materials. Hence, despite their increased usage, they are still expensive to machine when compared to other metals. The current research aims to address the machinability issues of titanium alloys by developing novel compositions of a new generation of self-adaptive Physical Vapor Deposition (PVD) coatings that function by forming beneficial tribo-films through their interaction with the environment. These tribo-films form during cutting and provide enhanced lubricity, hardness, strength, and thermal barrier characteristics to the cutting tool. It was found that during Ti6Al4V machining, significant BUE and crater wear formation occurs; however, one is dominant over the other depending on the cutting conditions. Therefore, the coatings investigated were designed by taking into consideration the dominant tool wear mechanisms and the complex tribological phenomena that occur in the cutting zone. The current research investigated monolayer TiB2 and CrN self-adaptive PVD coatings for the rough (cutting speed - 45 m/min, feed -0.15 mm/rev, and depth of cut – 2 mm) and finish (cutting speed - 150 m/min, feed -0.1225 mm/rev, and depth of cut – 0.25 mm) turning of Ti6Al4V alloy. Detailed experimental studies were performed to study the effectiveness of the coatings during machining. Micro-mechanical characteristics of the coatings were also studied to understand how coating properties affect the coatings performance in machining and tribo-film formation. The results obtained show that both the TiB2 and CrN coatings significantly improve tool performance during the rough turning of Ti6Al4V alloy compared to the current industrial standard, which is due to certain micro-mechanical coating properties and the beneficial tribo-films formed. A coating of CrN coating was found to increase tool life during finish turning. It was also established that for machining applications where intensive adhesive interaction occurs at the tool-chip interface, coatings with lower hardness values perform significantly better than harder ones. / Thesis / Doctor of Philosophy (PhD) / Titanium alloys are increasingly becoming the material of choice for many industrial applications due to their superior properties. However, they are very difficult to machine since they have high chemical affinity towards tool materials, low thermal conductivity, and high temperature strength. These properties cause rapid failure of the tool. The objective of the current research is to address machinability issues during Ti6Al4V machining and improve tool performance. One effective strategy to minimize tool wear is to apply self-adaptive PVD tool coatings that can form beneficial tribo-films through their interaction with the environment and provide enhanced lubricity, hardness, strength, and thermal barrier characteristics to the cutting tool. In the current research, two self-adaptive PVD coatings were developed that offset the dominant tool wear mechanisms prevalent during the rough and finish turning of Ti6Al4V alloy and reduced the tool wear rate by more than 60% compared to the current industrial standard.

Various nitrides, such as chromium nitride and titanium nitride, find extensive use in cutting tools, micromechanical devices, and medical implants due to their exceptional physical, mechanical, and chemical properties. These coatings exhibit superior hardness compared to high-speed steel and cemented carbide along with notable protective capabilities against corrosion and wear. These coatings have been successfully used to enhance the properties of cemented carbide and steel tools while safeguarding their surfaces. By adjusting deposition parameters like N2 gas pressure, the properties of PVD coatings can be tailored to effectively withstand specific dominant wear modes during machining. The study investigates and demonstrates that CrN coatings can be specifically engineered to have distinct mechanical and tribological properties by adjusting the N2 gas pressure, which enhances machining performance in cases where BUE formation occurs. A comprehensive coating characterization was conducted for each CrN coating studied. Wear performance assessments of the various CrN-coated WC tools were carried out during dry finish turning of SS 304. Additionally, high temperature coating characterization was performed for the best-performing in house deposited coating (nitrogen gas pressure of 4 Pa, bias voltage of -50 V) and a commercial coating, up to 450°C. The results highlighted the influence of N2 gas pressure on the structural, mechanical, and tribological properties of CrN coatings. The findings indicate that coatings with a comparatively low H/E ratio (while maintaining higher elastic modulus values), low roughness, moderate residual stress, high plasticity index, and high toughness exhibited superior performance when machining sticky materials and in high-temperature applications prone to adhesive wear and built-up edge (BUE) formation. Furthermore, high-temperature studies confirmed that the in-house coating retained a low H/E ratio, high plasticity index, high toughness, and low roughness, without compromising the hardness or elastic modulus values. In contrast, the commercial coating failed to retain its properties at higher temperatures. These high-temperature studies provide valuable insights for selecting CrN coatings tailored for machining materials that tend to adhere to the cutting tool and for high-temperature applications. / Dissertation / Master of Applied Science (MASc) / Coating properties such as hardness, residual stress, adhesive behaviour, elastic modulus, and roughness significantly affect tool performance and wear patterns, besides machining parameters and conditions. This research focuses on CrN coatings deposited by PVD cathodic arc deposition, adjusting the N2 gas pressure while keeping bias voltage constant. The research investigates and illustrates that CrN coatings can be specifically tailored (by adjusting the N2 gas pressure) to possess unique mechanical, and tribological properties that ameliorate machining performance in scenarios involving BUE formation. Three CrN coatings were deposited using the PVD technique by varying the N2 gas pressure. A thorough coating characterization was conducted for each of three in house deposited coatings and one commercially available coating. The wear behaviour of different CrN-coated WC tools was evaluated during dry finish turning of SS 304 to identify the best-performing coating. Lastly, high-temperature coating characterization was performed up to 450 ˚C for one in-house deposited coating (nitrogen gas pressure of 4 Pa, bias voltage of -50 V) and one commercial coating. The results showed that a coating that has low H/E ratio (without compromising elastic modulus), high plasticity index, high toughness, moderate residual stress and low roughness effectively minimizes issues related to sticking and BUE formation and retains coating properties at high temperatures.

Gegenstand der wissenschaftlichen Arbeit ist der technologische Nachweis für die Erzeugbarkeit haftfester metallischer und keramischer Schichten auf textilen Flächengebilden mit den PVD-Technologien reaktives Magnetron-Sputtern und reaktives Vakuumbogen-Verdampfen. Basis für die Realisierung der experimentellen Untersuchungen sind sowohl vorhandene industrielle PVD-Beschichtungsanlagen, die im Batchbetrieb arbeiten, als auch Rollcoater als Bindeglied zwischen einer Labor- und einer Industrieanlage. Kern des Vorhabens sind umfangreiche Batchbeschichtungen auf Basis einer breit angelegten Experimentalmatrix bezüglich Substrat- und Schichtauswahl. Gängige Targetmaterialien sind Kupfer, Aluminium und Silber. Um zu zeigen, dass über das thermische Bedampfen hinaus neue Schichten und Schichtsysteme auf textilen Faserstoffen abgeschieden werden können, wurden zusätzlich die Targetmaterialien Titan und Zirkonium in die Untersuchungen einbezogen. Zur Herstellung sowohl metallischer als auch keramischer Schichten wird neben den technologischen Parametern Beschichtungszeit und Schichtmaterial der Reaktivgasfluss variiert. Als Substrate kamen zwei leichtgewichtige PA 6.6-Gewebe mit unterschiedlicher Bindung, ein kalanderverfestigter Vliesstoff aus PES und ein Spinnvliesstoff aus Kern-Mantel-Fasern mit einem PA 6 Mantel zum Einsatz. Zur Verbesserung der Schichthaftungen wurden Versuche zur Vorbehandlung mittels Plasmabehandlung in Argon und Sauerstoff, mit Gasphasenfluorierung sowie HMDSO-Behandlung mit einem PA 6.6-Gewebe durchgeführt. Im Anschluss an die Vorbehandlung wurden die Proben mit Titan und Titannitrid metallisiert. Die Charakterisierung der Substrat-Schicht-Verbunde erfolgt hinsichtlich - der chemischen Zusammensetzungen der Schichten mittels ESCA (Electron Spectroscopy for Chemical Analysis), - der Schichtstrukturen und Fasermorphologien mittels Rasterelektronenmikroskopie, - der E-Moduln an Referenzprobekörpern aus Edelstahl mittels Härtemessung, - der Schichthaftungen durch Waschversuche, Martindale-Scheuertest, Peel-Test und - der funktionellen Schichteigenschaften wie Oberflächenwiderstände, elektromagnetische Schirmdämpfung, Wärmedämmeigenschaften Im Ergebnis der experimentellen Untersuchungen werden grundlegende Erkenntnisse zum Einfluss der PVD-Technologien und der Prozessparameter auf genannte Schicht- und Fasereigenschaften aufgezeigt. Des Weiteren werden die Zusammenhänge zwischen Schichtstruktur, Fasermorphologie und Schichthaftung dargelegt. Aus den Ergebnissen werden Schlussfolgerungen für eine gezielte industrielle Anwendung und Vorschläge für weiterführende wissenschaftliche Arbeiten abgeleitet. Die PVD-Verfahren werden bezüglich ihrer Eignung für die Textilbeschichtung bewertet. / Subject of the scientific study is the technological proof for the possibility to generate well adherent metallic and ceramic layers on textile fabrics with the PVD technologies reactive magnetron sputtering and reactive arc evaporation. Basis for the experimental investigations were both an industrial PVD coating device of the batch-type and a roll-coater which is a connective link between a laboratory and an industrial coating device. Extensive batch coatings on basis of a broadly applied experimental matrix in terms of the choice of the substrate and layer material are basis of the project. Usual target materials were copper, aluminium and silver. Additionally, the target materials titanium and zirconium were included in the investigations in order to show that new layers and layer systems can be deposited on textile fabrics by means of the investigated PVD technologies in comparison with thermal evaporation. Apart from the technological parameters coating time and layer material, the reactive gas flow were varied to deposit both metallic and ceramic layers. Substrates used in this study were lightweight Pa 6.6 fabrics with different weaves of the fabric, a calender bonded nonwoven of PES and a spunbonded nonwoven consisting of sheath-core fibers of PES (sheath) and Pa 6 (core). In order to improve the adhesion of layers, different pretreatments of the PA 66 fabric were carried out by means of plasma treatment with argon and oxygen, gas phase fluorination and treatment with HMDSO respectively. Subsequently, the pretreated samples were metallized with titanium and titanium nitride. The characterisation of the substrate layer combinations were carried out regarding - the chemical compositions of the layers by means of ESCA (Electron Spectroscopy for Chemical Analysis), - the layer structures and fiber morphologies by means of raster electron microscopy, - the modulus of elasticity on reference specimens consisting of stainless steel by means of hardness measurement, - the layer adhesion by wash tests, Martindale abrasion test, peel tests and - the functional layer characteristics such as surface resistances, electromagnetic shielding, heat insulating characteristics In the result of the experimental investigations, extensive knowledge to the influence of the PVD technologies and process parameters on layer and fiber characteristics are presented. Furthermore, the correlation of layer structure, fiber morphology and layer adhesion are explained. Conclusions for a selective industrial application and suggestions for further scientific investigations are derived from the results. The PVD procedures are evaluated concerning their suitability for the coating of textiles.

L’objectif de ces travaux de thèse est l’optimisation par une approche expérimentale d’un modèle de micro-fraise hémisphérique en carbure de tungstène revêtu, de diamètre 0,5 mm, destiné à l’usinage des aciers durs. Les données expérimentales obtenues résultent donc de l’usinage d’un acier 40NiCrMo16 à l’état trempé (54 HRC). Les résultats permettent de mettre en évidence certains phénomènes de coupe, d’usure et de comportement dynamique de l’outil liés au procédé, et leur évolution en fonction du type de fraise considéré et des conditions de coupe choisies. La géométrie de l’outil et son comportement dynamique sont ici principalement commentés. Dans un premier temps, l’étude de différentes nuances de carbure, préparation de surface ainsi que l’optimisation des géométries globale et locale des micro-fraises a permis de proposer un modèle optimisé pour notre partenaire outilleur Magafor. Dans un second temps, une approche numérique du micro-fraisage a été utilisée. Un premier modèle de calcul analytique des efforts de coupe a été testé et il a été mis en évidence les limites d’identification des coefficients spécifiques de coupe dans notre cas. Ensuite, une modélisation numérique par éléments finis du micro-fraisage a été réalisée afin d’appréhender l’étude du comportement dynamique des micro-fraises en fonction de la géométrie globale de l’outil développé. / The aim of this PhD work is optimized by experimental approach with 0.5 mm diameter micro-ball-end mills made from micro-grain tungsten carbide and PVD coated for hardened tool steels machining. The experimental data are obtained on machining of hardened steel (54/55HRC), typically used for the production of plastic injection molds. Results permit to highlight some cutting phenomena of wear and dynamic behavior of the process related tool, and changes depending on the type of milling considered and selected cutting conditions. The geometry of the tool and dynamic behavior are primarily discussed here. As a first step, the study of different carbide grades, surface preparation and optimization of global and local geometries of micro-cutters helped provide an efficient model for our partner Magafor toolmaker. In a second step, the modelling of micro-milling is discussed and an analytical model for cutting forces calculation is introduced. It was demonstrated the identifying limits of the specific cutting coefficients in our case. Then, a test of finite element modelling of micro-milling is made in order to estimate the potential of such a method for the study of the dynamic behaviour of micro-mills.

Dissertation thesis is focused on development, design and production of the new milling cutter which is used for roughing operations. High-speed steels, coating technology and milling technology are described in first chapters of dissertation thesis. The main part of this thesis is the design of the new milling cutter that has been designed on the basis of the machining simulation. The milling cutter is designed as a three-flute cylindrical end mill made of high speed steel. The each flute is composed of two special compensation edges. The compensation edges are used for reducing (at best suppression) tensile stress in the heel of the tooth. The milling cutter was made by lost wax technology, followed by grinding and thermal treatment. New designed tools were deposited by PVD coatings (e.g. (Al,Ti)N). Standard catalog milling cutters (producer ZPS - milling tools, Zlín, Czech Republic) were used for comparison the designed milling cutter. Carbon steel CSN 41 2050 (DIN 1.1191) was used for milling, which was carried out with using process liquid. The monitored parameters were force loading, flank wear and tensile stress during milling. The dynamometer Kistler was used for measuring force loading and data obtained during machining was used for stress analysis.

Gegenstand der wissenschaftlichen Arbeit ist der technologische Nachweis für die Erzeugbarkeit haftfester metallischer und keramischer Schichten auf textilen Flächengebilden mit den PVD-Technologien reaktives Magnetron-Sputtern und reaktives Vakuumbogen-Verdampfen. Basis für die Realisierung der experimentellen Untersuchungen sind sowohl vorhandene industrielle PVD-Beschichtungsanlagen, die im Batchbetrieb arbeiten, als auch Rollcoater als Bindeglied zwischen einer Labor- und einer Industrieanlage. Kern des Vorhabens sind umfangreiche Batchbeschichtungen auf Basis einer breit angelegten Experimentalmatrix bezüglich Substrat- und Schichtauswahl. Gängige Targetmaterialien sind Kupfer, Aluminium und Silber. Um zu zeigen, dass über das thermische Bedampfen hinaus neue Schichten und Schichtsysteme auf textilen Faserstoffen abgeschieden werden können, wurden zusätzlich die Targetmaterialien Titan und Zirkonium in die Untersuchungen einbezogen. Zur Herstellung sowohl metallischer als auch keramischer Schichten wird neben den technologischen Parametern Beschichtungszeit und Schichtmaterial der Reaktivgasfluss variiert. Als Substrate kamen zwei leichtgewichtige PA 6.6-Gewebe mit unterschiedlicher Bindung, ein kalanderverfestigter Vliesstoff aus PES und ein Spinnvliesstoff aus Kern-Mantel-Fasern mit einem PA 6 Mantel zum Einsatz. Zur Verbesserung der Schichthaftungen wurden Versuche zur Vorbehandlung mittels Plasmabehandlung in Argon und Sauerstoff, mit Gasphasenfluorierung sowie HMDSO-Behandlung mit einem PA 6.6-Gewebe durchgeführt. Im Anschluss an die Vorbehandlung wurden die Proben mit Titan und Titannitrid metallisiert. Die Charakterisierung der Substrat-Schicht-Verbunde erfolgt hinsichtlich - der chemischen Zusammensetzungen der Schichten mittels ESCA (Electron Spectroscopy for Chemical Analysis), - der Schichtstrukturen und Fasermorphologien mittels Rasterelektronenmikroskopie, - der E-Moduln an Referenzprobekörpern aus Edelstahl mittels Härtemessung, - der Schichthaftungen durch Waschversuche, Martindale-Scheuertest, Peel-Test und - der funktionellen Schichteigenschaften wie Oberflächenwiderstände, elektromagnetische Schirmdämpfung, Wärmedämmeigenschaften Im Ergebnis der experimentellen Untersuchungen werden grundlegende Erkenntnisse zum Einfluss der PVD-Technologien und der Prozessparameter auf genannte Schicht- und Fasereigenschaften aufgezeigt. Des Weiteren werden die Zusammenhänge zwischen Schichtstruktur, Fasermorphologie und Schichthaftung dargelegt. Aus den Ergebnissen werden Schlussfolgerungen für eine gezielte industrielle Anwendung und Vorschläge für weiterführende wissenschaftliche Arbeiten abgeleitet. Die PVD-Verfahren werden bezüglich ihrer Eignung für die Textilbeschichtung bewertet. / Subject of the scientific study is the technological proof for the possibility to generate well adherent metallic and ceramic layers on textile fabrics with the PVD technologies reactive magnetron sputtering and reactive arc evaporation. Basis for the experimental investigations were both an industrial PVD coating device of the batch-type and a roll-coater which is a connective link between a laboratory and an industrial coating device. Extensive batch coatings on basis of a broadly applied experimental matrix in terms of the choice of the substrate and layer material are basis of the project. Usual target materials were copper, aluminium and silver. Additionally, the target materials titanium and zirconium were included in the investigations in order to show that new layers and layer systems can be deposited on textile fabrics by means of the investigated PVD technologies in comparison with thermal evaporation. Apart from the technological parameters coating time and layer material, the reactive gas flow were varied to deposit both metallic and ceramic layers. Substrates used in this study were lightweight Pa 6.6 fabrics with different weaves of the fabric, a calender bonded nonwoven of PES and a spunbonded nonwoven consisting of sheath-core fibers of PES (sheath) and Pa 6 (core). In order to improve the adhesion of layers, different pretreatments of the PA 66 fabric were carried out by means of plasma treatment with argon and oxygen, gas phase fluorination and treatment with HMDSO respectively. Subsequently, the pretreated samples were metallized with titanium and titanium nitride. The characterisation of the substrate layer combinations were carried out regarding - the chemical compositions of the layers by means of ESCA (Electron Spectroscopy for Chemical Analysis), - the layer structures and fiber morphologies by means of raster electron microscopy, - the modulus of elasticity on reference specimens consisting of stainless steel by means of hardness measurement, - the layer adhesion by wash tests, Martindale abrasion test, peel tests and - the functional layer characteristics such as surface resistances, electromagnetic shielding, heat insulating characteristics In the result of the experimental investigations, extensive knowledge to the influence of the PVD technologies and process parameters on layer and fiber characteristics are presented. Furthermore, the correlation of layer structure, fiber morphology and layer adhesion are explained. Conclusions for a selective industrial application and suggestions for further scientific investigations are derived from the results. The PVD procedures are evaluated concerning their suitability for the coating of textiles.

The submerged entry nozzle (SEN) is used to transport the molten steel from a tundish to a mould. The main purpose of its usage is to prevent oxygen and nitrogen pick-up by molten steel from the gas. Furthermore, to achieve the desired flow conditions in the mould. Therefore, the SEN can be considered as a vital factor for a stable casting process and the steel quality. In addition, the steelmaking processes occur at high temperatures around 1873 K, so the interaction between the refractory materials of the SEN and molten steel is unavoidable. Therefore, the knowledge of the SEN behaviors during preheating and casting processes is necessary for the design of the steelmaking processes  The internal surfaces of modern SENs are coated with a glass/silicon powder layer to prevent the SEN graphite oxidation during preheating. The effects of the interaction between the coating layer and the SEN base refractory materials on clogging were studied. A large number of accretion samples formed inside alumina-graphite clogged SENs were examined using FEG-SEM-EDS and Feature analysis. The internal coated SENs were used for continuous casting of stainless steel grades alloyed with Rare Earth Metals (REM). The post-mortem study results clearly revealed the formation of a multi-layer accretion. A harmful effect of the SENs decarburization on the accretion thickness was also indicated. In addition, the results indicated a penetration of the formed alkaline-rich glaze into the alumina-graphite base refractory. More specifically, the alkaline-rich glaze reacts with graphite to form a carbon monoxide gas. Thereafter, dissociation of CO at the interface between SEN and molten metal takes place. This leads to reoxidation of dissolved alloying elements such as REM (Rare Earth Metal). This reoxidation forms the “In Situ” REM oxides at the interface between the SEN and the REM alloyed molten steel. Also, the interaction of the penetrated glaze with alumina in the SEN base refractory materials leads to the formation of a high-viscous alumina-rich glaze during the SEN preheating process. This, in turn, creates a very uneven surface at the SEN internal surface. Furthermore, these uneven areas react with dissolved REM in molten steel to form REM aluminates, REM silicates and REM alumina-silicates. The formation of the large “in-situ” REM oxides and the reaction of the REM alloying elements with the previously mentioned SEN´s uneven areas may provide a large REM-rich surface in contact with the primary inclusions in molten steel. This may facilitate the attraction and agglomeration of the primary REM oxide inclusions on the SEN internal surface and thereafter the clogging. The study revealed the disadvantages of the glass/silicon powder coating applications and the SEN decarburization. The decarburization behaviors of Al2O3-C, ZrO2-C and MgO-C refractory materials from a commercial Submerged Entry Nozzle (SEN), were also investigated for different gas atmospheres consisting of CO2, O2 and Ar. The gas ratio values were kept the same as it is in a propane combustion flue gas at different Air-Fuel-Ratio (AFR) values for both Air-Fuel and Oxygen-Fuel combustion systems. Laboratory experiments were carried out under nonisothermal conditions followed by isothermal heating. The decarburization ratio (α) values of all three refractory types were determined by measuring the real time weight losses of the samples. The results showed the higher decarburization ratio (α) values increasing for MgO-C refractory when changing the Air-Fuel combustion to Oxygen-Fuel combustion at the same AFR value. It substantiates the SEN preheating advantage at higher temperatures for shorter holding times compared to heating at lower temperatures during longer holding times for Al2O3-C samples. Diffusion models were proposed for estimation of the decarburization rate of an Al2O3-C refractory in the SEN. Two different methods were studied to prevent the SEN decarburization during preheating: The effect of an ZrSi2 antioxidant and the coexistence of an antioxidant additive and a (4B2O3 ·BaO) glass powder on carbon oxidation for non-isothermal and isothermal heating conditions in a controlled atmosphere. The coexistence of 8 wt% ZrSi2 and 15 wt% (4B2O3 ·BaO) glass powder of the total alumina-graphite refractory base materials, presented the most effective resistance to carbon oxidation. The 121% volume expansion due to the Zircon formation during heating and filling up the open pores by a (4B2O3 ·BaO) glaze during the green body sintering led to an excellent carbon oxidation resistance. The effects of the plasma spray-PVD coating of the Yttria Stabilized Zirconia (YSZ) powder on the carbon oxidation of the Al2O3-C coated samples were investigated. Trials were performed at non-isothermal heating conditions in a controlled atmosphere. Also, the applied temperature profile for the laboratory trials were defined based on the industrial preheating trials. The controlled atmospheres consisted of CO2, O2 and Ar. The thicknesses of the decarburized layers were measured and examined using light optic microscopy, FEG-SEM and EDS. A 250-290 μm YSZ coating is suggested to be an appropriate coating, as it provides both an even surface as well as prevention of the decarburization even during heating in air. In addition, the interactions between the YSZ coated alumina-graphite refractory base materials in contact with a cerium alloyed molten stainless steel were surveyed. The YSZ coating provided a total prevention of the alumina reduction by cerium. Therefore, the prevention of the first clogging product formed on the surface of the SEN refractory base materials. Therefore, the YSZ plasma-PVD coating can be recommended for coating of the hot surface of the commercial SENs. / <p>QC 20111014</p>

The submerged entry nozzle (SEN) is used to transport the molten steel from a tundish to a mould. The main purpose of its usage is to prevent oxygen and nitrogen pick-up by molten steel from the gas. Furthermore, to achieve the desired flow conditions in the mould. Therefore, the SEN can be considered as a vital factor for a stable casting process and the steel quality. In addition, the steelmaking processes occur at high temperatures around 1873 K, so the interaction between the refractory materials of the SEN and molten steel is unavoidable. Therefore, the knowledge of the SEN behaviors during preheating and casting processes is necessary for the design of the steelmaking processes  The internal surfaces of modern SENs are coated with a glass/silicon powder layer to prevent the SEN graphite oxidation during preheating. The effects of the interaction between the coating layer and the SEN base refractory materials on clogging were studied. A large number of accretion samples formed inside alumina-graphite clogged SENs were examined using FEG-SEM-EDS and Feature analysis. The internal coated SENs were used for continuous casting of stainless steel grades alloyed with Rare Earth Metals (REM). The post-mortem study results clearly revealed the formation of a multi-layer accretion. A harmful effect of the SENs decarburization on the accretion thickness was also indicated. In addition, the results indicated a penetration of the formed alkaline-rich glaze into the alumina-graphite base refractory. More specifically, the alkaline-rich glaze reacts with graphite to form a carbon monoxide gas. Thereafter, dissociation of CO at the interface between SEN and molten metal takes place. This leads to reoxidation of dissolved alloying elements such as REM (Rare Earth Metal). This reoxidation forms the “In Situ” REM oxides at the interface between the SEN and the REM alloyed molten steel. Also, the interaction of the penetrated glaze with alumina in the SEN base refractory materials leads to the formation of a high-viscous alumina-rich glaze during the SEN preheating process. This, in turn, creates a very uneven surface at the SEN internal surface. Furthermore, these uneven areas react with dissolved REM in molten steel to form REM aluminates, REM silicates and REM alumina-silicates. The formation of the large “in-situ” REM oxides and the reaction of the REM alloying elements with the previously mentioned SEN´s uneven areas may provide a large REM-rich surface in contact with the primary inclusions in molten steel. This may facilitate the attraction and agglomeration of the primary REM oxide inclusions on the SEN internal surface and thereafter the clogging. The study revealed the disadvantages of the glass/silicon powder coating applications and the SEN decarburization. The decarburization behaviors of Al2O3-C, ZrO2-C and MgO-C refractory materials from a commercial Submerged Entry Nozzle (SEN), were also investigated for different gas atmospheres consisting of CO2, O2 and Ar. The gas ratio values were kept the same as it is in a propane combustion flue gas at different Air-Fuel-Ratio (AFR) values for both Air-Fuel and Oxygen-Fuel combustion systems. Laboratory experiments were carried out under nonisothermal conditions followed by isothermal heating. The decarburization ratio (α) values of all three refractory types were determined by measuring the real time weight losses of the samples. The results showed the higher decarburization ratio (α) values increasing for MgO-C refractory when changing the Air-Fuel combustion to Oxygen-Fuel combustion at the same AFR value. It substantiates the SEN preheating advantage at higher temperatures for shorter holding times compared to heating at lower temperatures during longer holding times for Al2O3-C samples. Diffusion models were proposed for estimation of the decarburization rate of an Al2O3-C refractory in the SEN. Two different methods were studied to prevent the SEN decarburization during preheating: The effect of an ZrSi2 antioxidant and the coexistence of an antioxidant additive and a (4B2O3 ·BaO) glass powder on carbon oxidation for non-isothermal and isothermal heating conditions in a controlled atmosphere. The coexistence of 8 wt% ZrSi2 and 15 wt% (4B2O3 ·BaO) glass powder of the total alumina-graphite refractory base materials, presented the most effective resistance to carbon oxidation. The 121% volume expansion due to the Zircon formation during heating and filling up the open pores by a (4B2O3 ·BaO) glaze during the green body sintering led to an excellent carbon oxidation resistance. The effects of the plasma spray-PVD coating of the Yttria Stabilized Zirconia (YSZ) powder on the carbon oxidation of the Al2O3-C coated samples were investigated. Trials were performed at non-isothermal heating conditions in a controlled atmosphere. Also, the applied temperature profile for the laboratory trials were defined based on the industrial preheating trials. The controlled atmospheres consisted of CO2, O2 and Ar. The thicknesses of the decarburized layers were measured and examined using light optic microscopy, FEG-SEM and EDS. A 250-290 μm YSZ coating is suggested to be an appropriate coating, as it provides both an even surface as well as prevention of the decarburization even during heating in air. In addition, the interactions between the YSZ coated alumina-graphite refractory base materials in contact with a cerium alloyed molten stainless steel were surveyed. The YSZ coating provided a total prevention of the alumina reduction by cerium. Therefore, the prevention of the first clogging product formed on the surface of the SEN refractory base materials. Therefore, the YSZ plasma-PVD coating can be recommended for coating of the hot surface of the commercial SENs.

Quenching and partitioning (Q&P) steels show a good balance between strength and ductility due to a special heat treatment that allows to adjust a microstructure of martensite with a fraction of stabilized retained austenite. The final heat treatment step is performed at low temperatures. Therefore, joining of Q&P steels is a big challenge. On the one hand, a low joining temperature is necessary in order not to influence the adjusted microstructure; on the other hand, high joint strengths are required. In this study, joining of Q&P steels with Ag nanoparticles is investigated. Due to the nano-effect, high-strength and temperature-resistant joints can be produced at low temperatures with nanoparticles, which meets the contradictory requirements for joining of Q&P steels. In addition to the Ag nanoparticles, activating materials (SnAg and Sn) are used at the interface to achieve an improved bonding to the steel substrate. The results show that the activating materials play an important role in the successful formation of joints. Only with the activating materials, can joints be produced. Due to the low joining temperature (max. 237 °C), the microstructure of the Q&P steel is hardly influenced.