The beginning of this thesis is dedicated to polymeric materials, which include plastics an composites. Plastics are shortly divided into two groups, thermoplastics and thermosets. The following part is the use of plastics and composites in traffic industry and briefly this work focuses on techniques of recycling of this materials. This work also focuses on the techniques of thin film deposition, electroless plating, electrodeposition as well and plating in the vacuum environment. special techniques of thin film deposition are also mentioned shortly. The coatings of polymer including cleaning and surface activation is introduced using various techniques including plasma treatment. The surface treatment of polyetheretherketone (PEEK) is included too. The final part describes performed experiments and discussion of results.

Magnesiumwerkstoffe sind aufgrund ihrer geringen Dichte und hohen spezifischen Festigkeit für den Leichtbau prädestiniert. Ziel der vorgelegten Arbeit ist es, durch die gleichzeitige Verbesserung des Korrosions- und Verschleißverhaltens neue Anwendungsfelder für Magnesiumlegierungen zu erschließen. Anhand der Magnesiumlegierung AZ91D wurden die Möglichkeiten einer lokalen beanspruchungsgerechten Modifikation von Struktur und Gefüge im oberflächennahen Bereich durch eine Elektronenstrahl(EB)-Flüssigphasen-Randschichtbehandlung ohne Zusatzstoff (EB-Umschmelzen) und unter Verwendung von Al-Si-Zusatzstoffen (EB-Umschmelzlegieren) aufgezeigt. Die mittels verschiedener hochfrequenter Strahlablenktechniken erzeugten Schichten weisen eine deutliche Gefügefeinung, neue Gefügemorphologien sowie eine veränderte Phasenverteilung und/oder -neubildung auf, sind riss- und porenfrei und haben eine ausgezeichnete schmelzmetallurgische Anbindung an den Grundwerkstoff. Anhand von Tauchversuchen und potentiodynamischen Polarisationsmessungen in verschieden konzentrierten NaCl-Lösungen konnte eine signifikante Verbesserung des Korrosionsverhaltens der generierten Schichten im Vergleich zum Ausgangszustand nachgewiesen werden. EB-umschmelzlegierte Schichten weisen im Ergebnis von Trockenverschleißtests (Stift-Scheibe) eine deutliche Reduzierung des spezifischen Verschleißkoeffizienten auf.

In this study, several types of modified methods were tried for improving natural fiber reinforced composites and also three kind of natural fibers were used for reinforced composite. Plasma polymerization increased fiber tensile and composites mechanical properties. It is higher effect than alkali treatment. Resin impregnation was expected cheaper method than plasma polymerization. Polyvinyl Alcohol resin impregnation method can increase fiber tensile strength, interfacial shear strength between fiber and composites mechanical properties. And with Bamboo/polypropylene/maleic anhydride polypropylene water absorption ratio also can decrease. / 博士(工学) / Doctor of Philosophy in Engineering / 同志社大学 / Doshisha University

Indiana University-Purdue University Indianapolis (IUPUI) / Repair is an alternative treatment option in many cases to replacement of resin matrix composite restoration. However, aged resin matrix composites have a limited number of carbon-carbon double bonds to adhere to a new layer of rein. Therefore, surface treatments of the aged resin matrix composite surface prior to repairing could improve the repair bond strength. The objectives of this study were to: 1) To evaluate various surface treatments on shear bond strength of repair between aged and new microhybrid resin matrix composite, and 2) To assess the influence of applying a silane coupling agent after surface treatments. Eighty disk-shaped resin matrix composite specimens were fabricated and thermocycled 5000 times prior to surface treatment. Specimens were randomly assigned to one of the three surface treatments (n = 20): 1) Airborne abrasion with 50 μm aluminum oxide, 2) Tribochemical silica coating (CoJet), or 3) Er,Cr:YSGG laser and control group (n = 20). Specimens were cleaned with 35-percent phosphoric acid, rinsed, and dried. Each group was assigned into two subgroups (n =10): a) no silanization, and b) with silanization. Adhesive agent was applied and new resin matrix composite was bonded to each conditioned surface. Bond strength was evaluated by shear test. Data were analyzed with a two-way ANOVA model. The interaction between conditioning and silanization was significant(p = 0.0163), indicating that comparisons of silanization must be evaluated for each conditioning method, and that comparisons of conditioning methods must be evaluated separately with and without silanization. Airborne particle abrasion showed significantly higher repair bond strength than Er,Cr:YSGG laser without silanization (p < 0.0001) and with silanization(p = 0.0002), and higher repair bond strength than the control without silanization (p < 0.00001) and with silanization (p < 0.00001). Airborne particle abrasion did not have significantly different in repair bond strength than Tribosilica coating without silanization (p = 0.70) or with silanization (p = 0.33). Tribosilica coating had significantly higher repair bond strength than Er,CR:YSGG laser without silanization (p < 0.0001) and with silanization (p < 0.0001), and significantly higher repair bond strength than control without silanization (p < 0.0001), but not with silanization (p =0.16). Er,CR:YSGG laser and control did not have significantly different repair bond strength without silanization (p = 1.00) or with silanization (p = 0.11). There was no effect of silanization on repair bond strength overall (p = 0.34) for any of the surface conditioning methods (p = 0.76 for airborne particle abrasion; p = 0.39 for tribosilica coating; p = 1.00 for Er,Cr:YSGG laser, or p = 0.39 for control). Airborne particle abrasion with 50-μm aluminum oxide particle and tribochemical silica coating followed by the application of bonding agent provided the highest shear bond strength values, suggesting that they might be adequate methods to improve the quality of the repairs of resin-matrix composites.

The project aims to develop a methodology to study the variation in properties of wood polymer composites (WPC’s) with/without surface treatment at different humidity conditions. The project aims to investigate the behavior of biocomposites at 50%, 80%and 100% relative humidity (RH). Also to clarify if the hydrophilization effect helps to preserve the structural integrity of the materials for longer periods at these conditions. The comparison between biocomposites comprising polypropylene (PP) with both untreated wood fibers (WF) or FibraQ (hydrophobic surface-treated wood fibers from Biofiber Tech) was made. The focus was on the mechanical properties, water absorption, macro- and microstructures. The results show that PP comprising FibraQ exhibits lower moisture uptake than the PP comprising untreated WF at high relative humidity conditions. The mechanical properties did not seem significantly affected by the surface treatment at high relative humidity conditions. It is also concluded that since the study only ran for four weeks, there was not enough time to fully understand the influence of moisture uptake over the materials’ properties.

Corrosion can cause devastating damage to materials, and to protect materials from corrosion is crucial, especially in the aeronautical industry. An electroplated Zinc-Nickel coating provides excellent corrosion protection of steel. Electroplating of ZnNi is a sensitive process which needs frequent and fast feedback controls and adjustments of the process electrolyte. A common process control for electroplating processes is the Hull cell test, which is investigated in this study. The Hull cell test is a lab scaled electroplating unit, which spans a wide range of current densities. It is crucial to establish the relation between process parameters in the Hull cell and the resulting coating characteristics in order to implement it as a process control. The purpose of this study is to establish these relations for the ZnNi electroplating process, and evaluate if the Hull cell test is a suitable process control for this process. How the process parameters; current density, temperature, metal ion concentration, and carbonate contaminations affect the coating characteristics; visual appearance, thickness, composition, surface structure, and phase content has been established. Influence on the coatings were mainly seen at current densities higher and lower than the ones used in production. This demonstrates the strength of the Hull cell test for early detection of process deviations. Coating thickness and composition was measured with X-ray fluorescence. However, the composition values for thin coatings were discovered to be inaccurate, which was avoided by increasing the plating time. Once addressed, the Hull cell test is suitable as a process control for the electroplating process of ZnNi.

Des travaux scientifiques récents ont ouvert de nouveaux champs d’application aux traitements mécaniques tels que le grenaillage. Il a été montré que de tels traitements, réalisés avant un traitement de nitruration à la surface d’alliage ferreux, permettaient d’abaisser les températures de traitement et d’augmenter significativement les cinétiques de diffusion. Nous avons entrepris de tester les performances de cette combinaison de traitements mécanique et thermochimique sur des aciers inoxydables et des alliages à base nickel austénitiques. Des essais ont été réalisés à partir d’une technique de grenaillage mécanique appelée « Surface Mechanical Attrition Treatment » (SMAT). Des billes en métal ou en céramique sont introduites dans l’enceinte et mises en mouvement par la sonotrode. Les billes percutent et introduisent donc une déformation plastique à la surface des échantillons. Après cette étape, les échantillons subissent un traitement thermochimique de nitruration assisté plasma. La comparaison des résultats obtenus après nitruration sur des échantillons traités mécaniquement avec ceux n’ayant pas été pré-traités mécaniquement a permis de quantifier les effets des traitements combinés. Les analyses par diffraction des rayons X, les mesures de microdureté, les observations au microscope optique/électronique à balayage/électronique en transmission, les analyses de texture par EBSD (Electron BackScatered Diffraction) et la mesure des profils de concentration en azote par SIMS (Secondary Ion Mass Spectrometry) et SDL (Spectroscopie à Décharge Luminescente) ont montré l’importance de la nature de la couche transformée mécaniquement sur la diffusion de l’azote / Recent scientific work has opened new fields of application to mechanical treatments such as shot blasting or peening. Indeed, it has been shown that this treatment, performed before a nitriding treatment on the surface of ferrous alloy, lowers processing temperatures and significantly increases the diffusion kinetics. We undertook to test this combination of mechanical and thermochemical treatments on stainless steels and nickel-based alloys. The mechanical treatments were done by Surface Mechanical Attrition Treatment (SMAT). This method is implemented in a box where metal or ceramic balls were introduced and set in motion by an ultrasound system in order to impact the surface of the pieces. The treated samples were then nitrided at low temperature by using a remote plasma. The comparison of the results obtained after nitriding treatments on mechanically treated samples and those not mechanically treated allows quantifying the effects of the combined treatments. Analyses by X-ray diffraction, microhardness measurement, observations by optical and scanning and transmission electron microscopy, texture analysis by EBSD (Electron Diffraction BackScatered) and measurement of nitrogen concentration profiles by SIMS (Secondary Ion Mass Spectrometry) show the importance of the nature of the deformed layer

Les matériaux métalliques sont utilisés dans des conditions de plus en plus sévères et doivent présenter une parfaite intégrité sur des périodes de plus en plus longues. L’objectif de ce travail de thèse est d’évaluer le potentiel d'un traitement de refusion laser pour améliorer la résistance à la corrosion d'un acier inoxydable de type 304L ; l’utilisation du laser dans le domaine des traitements de surface constituant un procédé en pleine évolution à cause des changements récents dans la technologie des lasers. Dans le cadre de ce travail, le choix du laser s’est porté sur un laser nano-impulsionnel à fibre dopée ytterbium dont les caractéristiques permettent la fusion quasi-instantanée sur quelques microns de la surface traitée, immédiatement suivie d'une solidification ultra-rapide avec des vitesses de refroidissement pouvant atteindre 1011 K/s. La combinaison de ces processus favorise l'élimination des défauts surfaciques, la formation de phases hors équilibre, la ségrégation d’éléments chimiques et la formation d’une nouvelle couche d’oxyde dont les propriétés sont gouvernées par les paramètres laser. Afin de les corréler avec la réactivité électrochimique de la surface, l’influence de deux paramètres laser sur les propriétés physico-chimiques de la surface a été étudiée : la puissance du laser et le taux de recouvrement des impacts laser. Pour clarifier ces relations, la résistance à la corrosion par piqûration des surfaces traitées a été déterminée par des tests électrochimiques. Pour des paramètres laser spécifiques, le potentiel de piqûration d'un acier inoxydable de type 304L augmente de plus de 500 mV traduisant ainsi une meilleure tenue à la corrosion localisée en milieu chloruré. L’interdépendance des différents phénomènes résultant du traitement laser a rendu complexe la hiérarchisation de leur effet sur la sensibilité de l’alliage testé. Cependant, il a été montré que la nature de l’oxyde thermique formé au cours de la refusion laser et ses défauts sont du premier ordre pour l’amorçage des piqûres. / Metallic materials are more and more used in severe conditions with particularly strong request for improving their behavior in aggressive environment and especially over long periods. The objective of this PhD work is to estimate the potentiality of a laser surface melting treatment on the improvement of the stainless steel 304L corrosion resistance, surface treatments by laser can be revisited on the basis of a recent change in the laser technology. In the frame of this work, a nano-pulsed laser fiber was chosen : it allows the treated surface to be melted for few microns in depth, followed by an ultra-fast solidification occuring with cooling rates up to 1011 K/s. The combination of these processes leads to the elimination of the surface defects, the formation (trapping) of metastable phases, the segregation of chemical elements and the growth of a new oxide layer which properties are governed by the laser parameters. To correlate these latter to the electrochemical reactivity of the surface, the influence of two laser parameters on the physico-chemical properties of the surface was studied : the laser power and the overlap of the laser impacts. To support this approach, the pitting corrosion resistance of the samples was determined by standard electrochemical tests. For specific laser parameters, the pitting potential of a 304L stainless steel was increased by more than 500 mV corresponding to an important enhancement in localized corrosion resistance in chloride environment. The interdependence of the different phenomena resulting from the laser treatment lead to a quite complex prioritization of their role on the sensibility of the 304L. However, it was demonstrated that the nature of the thermal oxide formed during the laser surface melting and the induced defects are first-order parameters for the initiation of pits.

Le secteur industriel du traitement de surface (TS), secteur d’excellence en Bourgogne Franche-Comté, est contraint de recourir à de nouvelles méthodes d’épuration des eaux du fait d’une règlementation européenne de plus en plus stricte. En effet, notamment dans le cadre de la Directive Cadre sur l’Eau, les industriels doivent sans cesse améliorer la qualité de leurs rejets et diminuer les impacts générés par ceux-ci. Ce travail de thèse s’inscrit dans cet objectif. Ainsi, trois grands types d’investigations ont été menés : le premier a permis de définir la composition qualitative et quantitative en substances dangereuses (SD) des rejets de TS et d’étudier leur variabilité temporelle ; le second a validé des modifications d’une station physico-chimique de traitement des eaux franc-comtoise pour diminuer le flux de SD ; le dernier a proposé des solutions innovantes par bioadsorption sur des matériaux de cyclodextrine et par procédé d’oxydation avancée (POA) soit par ozone/UV, soit par l’utilisation de catalyseurs Pd-Cu pour atteindre le même objectif.[...] / The industrial sector of surface treatment (ST), sector of excellence in Bourgogne Franche-Comté, is forced to resort to new methods for water treatment due to European regulations increasingly strict. Indeed, particularly in the context of the Water Framework Directive, industries must continually improve the quality of their discharge waters and reduce the impacts generated by them. This work is part of this. Thus, three types of investigations were conducted: the first has defined qualitative and quantitative composition of hazardous substances (HS) in ST discharge waters and study their temporal variability; the second has approved changes in a physicochemical wastewater decontamination station to decrease HS water flow; the last proposed innovative solutions by biosorption on cyclodextrin materials and advanced oxidation process (AOP) by ozone / UV, or by the use of Pd-Cu catalysts to achieve the same objective.[...]

The theoretical part of the thesis focuses on the description of particulate materials and their mechanical behaviors with a focus on flow properties. Great emphasis is placed on measuring the shear properties using a Jenike shear machine, on the correct procedure for standardized measurement and evaluation using Mohr's circles. The theoretical part focuses on the characterization of particulate matter using a variety of methods available, such as visual, separation, sedimentation, surface methods and methods of scanning field and flow. The practical part is focused on the determination of flow characteristics and surface finishing of finely ground limestone Omyacarb VA with various grain sizes. The surface was modified using stearic acid and calcium stearate. Attention was paid to the influence of the concentration of surface-regulating substances on the flowability of the material. The flowability of commercially supplied material was compared with lab modified materials and the determination of the theoretical content of stearic acid or calcium stearate was accomplished. Shear properties were measured using the Jenike shear machine. The material was further tested by laser diffraction and SEM with EDS particle surface analysis and elemental surface mapping.