The corrosion behaviour of cast Al-Mg alloy A535 and its composites containing 10 wt.% and 15 wt.% fly ash, and 10 wt.% hybrid reinforcement (5 wt.% fly ash + 5 wt.% SiC) was investigated using weight-loss and electrochemical corrosion tests, optical microscopy, Scanning Electron Microscopy (SEM) and Energy Dispersive X-ray Spectroscopy (EDS). The tests were conducted in fresh water collected from the South Saskatchewan River and 3.5 wt.% NaCl solution at room temperature. The pH of the salt solution varied from 3 to 9. For comparison, two other aluminum alloys, AA2618 and AA5083-H116, were tested in the same electrolytes. The results of the weight-loss corrosion test showed that unreinforced A535 alloy had a lower corrosion rate in fresh water and seawater environments than the composites at all the tested pH values. The corrosion rate of the composites increased with increasing fly ash content. As expected, the corrosion rates of A535 alloy and the composites tested in fresh water were lower than those in salt solution. The results of the potentiodynamic and cyclic polarization electrochemical tests showed that the corrosion potential (Ecorr) and pitting potential (Epit) of the alloy were more positive than those of the composites. The corrosion and pitting potentials of the composites became more negative (active) with increasing fly ash content. The composites showed more positive (noble) repassivation or protection potential (Erp) than the matrix alloy, with the positivity increasing with fly ash content. Analysis of the electrochemical noise data showed that pitting corrosion was the dominant mode of corrosion for the alloy in 3.5 wt.% NaCl solution. Optical microscopy and SEM revealed that Mg2Si phase and Al-Mg intermetallics corroded preferentially to the matrix. The EDS data indicated that the protective oxide film formed on A535 contained Al2O3 and MgO.

Magnesium and its alloys are extensively used for various industries such as aerospace, automobile and electronics due to their excellent properties such as low density, high strength and stiffness and electromagnetic shielding. However, the wide spread applications of these alloys are limited due to the undesirable properties such as poor corrosion, wear and creep resistance and high chemical reactivity. These alloys are highly susceptible to galvanic corrosion in sea water environment due to their high negative potential (-2.37 V vs SHE). The effective way of preventing corrosion is through the formation of a protective coating, which acts as a barrier between the corrosive medium and the substrate. Many surface modification methods such as electro/ electroless plating, conversion coating, physical and chemical vapour depositions, thermal spray coating etc., are available currently to improve the corrosion resistance of Mg alloys. Of these methods, the electroless nickel plating has gained considerable importance because of its excellent properties such as high hardness, good wear and corrosion resistance. The properties of binary electroless nickel coating have been further improved by the addition of a third element such as cobalt, tungsten, tin and copper etc. It has been reported that the addition of tungsten as the third element in the Ni-P improves the properties such as hardness, wear and corrosion resistance, thermal stability and electrical resistance. Magnesium alloys are categorized as a “difficult to plate metal”, because of their high reactivity in the aqueous solution. They react vigorously with atmospheric oxygen and water, resulting in the formation of the porous oxide/ hydroxide film which does not provide any protection in the corrosive environment. Further, the presence of this oxide film prevents the formation of a good adhesive bond between the coating and the substrate. The surface treatment process for removal of the oxide layer is very much essential before plating the Mg alloy. Currently two processes such as zinc immersion and direct electroless nickel plating are adopted to plate Mg alloys. Etching in a solution of chromate and nitric acid followed by immersion in HF solution to form a conversion film is necessary for direct electroless nickel (EN) plating of Mg alloy. However, strict environmental regulations restrict their usage because of hazardous nature. Expensive palladous activation treatment is a well-known process as a replacement for chromate-HF pretreatments for Mg alloys. It has been reported that EN plating has been carried out over Mg alloys by using conversion coating followed by HF treatment. Formation of an intermediate oxide layer by electrolytic methods is also one of the ways these toxic pretreatments can be avoided. Microarc oxidation (MAO) is an environment friendly surface treatment technique which provides high hardness, better corrosion and wear resistance properties for the Mg alloys. EN coating has been prepared on MAO layer for improving the corrosion resistance. These MAO/EN composite coatings have been prepared using chromic acid and HF pretreatment process. As the replacement for the chromate-HF pretreatment, SnCl2 and PdCl2 sensitization and activation procedures respectively were adopted over MAO layer for the deposition of Ni-P coating. From the above reported literature, it can be inferred that for the activation of inert MAO layer to deposit electroless nickel coating, the hazardous chromate/HF and highly expensive PdCl2 activation processes were followed. Therefore, there is a need for identifying an alternative simple and cost effective pretreatment process for the deposition of electroless nickel. It is well known that borohydride is a strong reducing agent that has been used for the deposition of Ni-B coatings. In the present study, an attempt has been made to utilize borohydride in the pretreatment process for the reduction of Ni2+ ions over the MAO interlayer, which provides the nucleation sites for the deposition of Ni-P coating. Ni-P and Ni-P/Ni-W-P duplex coatings were deposited from stabilizer free carbonate bath on AZ31B Mg alloy to improve the corrosion resistance of the base substrate. The conventional chromate and HF pretreatment processes were followed for the deposition of electroless nickel coating. In order to improve the corrosion resistance of the duplex coating, post treatments such as heat treatment (4 h at 150°C) and chromate passivation were adopted. EDX analysis of AZ31B Mg alloy showed the presence of 2.8 wt.% of Al and 1.2 wt. % Zn with the balance of Mg for AZ31B Mg alloy. After the chromic acid and HF treatment, the magnesium content was reduced from 90.0 wt % to 54.9 wt%, which could be due to the incorporation of chromium on the surface layer. The surface showed about 17.8 wt. % of F. The alloy exhibited the roughness of about 0.29± 0.01µm after mechanical polishing. The roughness value was significantly changed after the chromic acid treatment processes. The maximum roughness of about 1.28±0.06 µm was obtained after the HF activation. XPS analysis confirmed the existence of chromium in +3 oxidation state after the chromic acid treatment. The Ni-P coating thickness of about 25 microns was obtained in 1 h and 15 min. In the case of duplex coatings, Ni-P plating was done for 45 min. to obtain approx. 17 microns thickness and Ni-W-P plating was done for 1.15 h to obtain a thickness of approx. 10 microns, resulting in a total thickness of 25 ± 5 microns. Ni–P coating exhibited nodular morphology with porosity. The size of these cluster nodules were of about 10 µm in diameter. On the other hand, the duplex coating exhibited a less nodular, dense and smooth appearance. From the compositional analysis it was found that Ni–P coating contained about 6 wt. % P. In the case of duplex coating, the P content was reduced to 3 wt % due to the incorporation of about 2 wt% of tungsten. In corrosion studies, the potentiodynamic polarization data obtained for bare Ni-P coating in 0.15 M NaCl solution exhibited a higher current of about 218 μA/cm2 as compared to the substrate due to the porosity of the coating. However, the Ni-P/Ni-W-P duplex showed 55 times improvement in corrosion resistance, vis-a-vis Ni-P due to the dense nature of the coating. The corrosion resistance of the coatings increased in the following order: Ni-P < bare alloy < duplex < duplex-passivated < duplex-heat treated passivated. In EIS study, the Nyquist plot obtained for the bare substrate and Ni–P coating showed the presence of inductance behavior at the lower frequency region due to the adsorption of electroactive species over the substrate through the porous oxide layer. However, the passivated and duplex passivated coatings exhibited only capacitive behavior due to their compact nature. From the above, it can be concluded that, direct deposition of Ni-P coating over the chosen Mg alloy using chromic acid and HF pretreatment process resulted in porous morphology, which affected the corrosion resistance of the coating. As an alternative strategy, the microarc oxidation conversion coating was developed on Mg alloy and characterized. The MAO coating was developed using silicate electrolyte at three different current densities (0.026, 0.046 and 0.067 A/cm2) for about 15 min. With respect to the MAO coating, an increase in the current density increased the pore diameter and decreased the pore density. The surface of the coating became coarser and rough. The cross-sectional morphology of the coating showed two district layers namely the dense and thin inner layer and a porous thick outer layer. The thickness of the coating increased with increase in current density. MAO coating prepared at an intermediate current density of 0.046 A/cm2 exhibited a higher thickness of about 12 µm and a further increase in current density showed a decrease in thickness, due to the greater rate of dissolution of Mg, relative to the rate of deposition. The surface roughness of the MAO coatings also increased with increase in current density. The Ra value increased from 1.39±0.06 to 3.52±0.17 µm with increase in current density. XRD peaks obtained for the Mg substrates corresponded predominately to magnesium. However, the coated specimens showed the presence of peaks corresponding to Mg2SiO4 along with Mg and MgO. The corrosion measurements for the bare substrate and MAO coatings were carried out in 3.5% NaCl medium (0.6 M). Based on potentiodynamic polarization studies, the MAO coating prepared at 0.046 A/cm2 exhibited a lower corrosion current density with a higher Rp value, which was about five orders of magnitude higher than the bare substrate, due to the dense nature of the coating. In EIS study, MAO coatings were fitted with the two time constants equivalent circuit containing outer porous layer and inner barrier layer. The barrier layer resistance values were higher than that of porous layer resistance, which indicated that the resistance offered by barrier layer was higher than the porous layer. The total resistance value obtained for the coating prepared at 0.046 A/cm2 were higher compared to the other coatings, which attested to its better corrosion resistance. The electrochemical noise measurement was carried out for longer immersion durations upto 336 h in 3.5% NaCl solution. The noise resistance value obtained for the base Mg alloy was about 100 Ω at 1h immersion, whereas for the MAO coating prepared at 0.04 A/cm2 a maximum value of about 34.8 MΩ was achieved and it was retained even after 96 h of immersion. Mott–Schottky analysis showed that the oxide layer on magnesium substrate acted as a n-type semiconductor, whereas the MAO coatings exhibited p-type semiconductor behavior. The MAO coating obtained at an intermediate current density showed a higher acceptor density and the flat band potential, which resulted in the better performance of the coating in corrosive environment. In another set of investigations, the Ni-P and Ni-P/Ni-W-P coatings were deposited on AZ31B Mg alloy with MAO coating as an interlayer. The MAO layer was activated by a simple borohydride pretreatment process. During the pretreatment process, the MAO coating was subjected to mild alkali treatment, immersion in the Ni-P plating solution and finally immersion in borohydride solution. During each pretreatment step, the sample was characterized for their surface morphology and composition. The surface morphology showed the distribution of spherical particles over the surface of MAO coating after immersion in the Ni-P plating solution. EDX analysis showed the presence of 2.4 wt. % of Ni, which confirmed that Ni ions were adsorbed over the surface of the MAO coating during the pretreatment process. XPS analysis carried out after immersion in the Ni-P plating solution indicated that Ni existed in +2 oxidation state. The surface became smooth and uniform with flake- like morphology after the borohydride treatment, which indicated that the surface was etched by the borohydride solution. EDX analysis showed the presence of 1.8 wt.% of Ni after borohydride reduction. XPS analysis confirmed the reduction of nickel to the zero oxidation state. Additionally, MAO/Ni-P and MAO/Ni-P/Ni-W-P duplex coatings were developed on MAO coating after a simple borohydride pretreatment. Ni-P and duplex coatings showed uniform and dense nodular morphology without any defects, which clearly indicated that the borohydride treatment provided a uniform and homogeneous active surface for the deposition of electroless nickel based coatings. Borohydride pretreatment process resulted in excellent bonding between MAO/Ni-P layers in the cross section. Based on potentiodynamic polarization studies, the corrosion current values obtained for MAO/ Ni-P and MAO/Ni-P/Ni-W-P duplex coatings were about 1.44 and 1.42 µA/cm2, respectively. The coating showed about 97 times improvement in corrosion resistance compared to the bare substrate, attesting to the dense nature of the coating. In EIS study, the single time constant equivalent circuit was used for fitting the spectra, which pertained to the coating /electrolyte interface. The single time constant could be attributed to the pore-free dense, uniform coatings developed over the MAO interlayer. For the MAO/Ni-P and MAO/Ni-P-Ni-W-P duplex coatings, the charge transfer resistance of about 15 and 11 kΩcm2 were obtained for duplex and Ni-P coatings, which reinforce the better corrosion protective ability of the coating. The above investigation confirms that MAO coatings have good corrosion resistance in the aggressive chloride medium. Consequently, they can serve as an ideal interlayer for the deposition of the electroless nickel coating. Even if the electroless nickel coating is found to fail in harsh environments, the MAO interlayer can protect the base substrate due to its higher corrosion resistance. It is also noteworthy that the borohydride treatment provides better adhesion between the MAO/Ni-P interlayer.

Mg-alloys, despite being the lightest structural metallic materials, find limited applications due to their poor workability, which is due to the hcp structure that does not provide sufficient number of independent slip systems for compatible deformation. Workability improves with the increase in the deformation temperature, when non-basal slip starts playing a larger role in deformation. Efforts were made to improve the workability through control of texture, grain refinement and alloying. Alloying activates non-basal slip by decreasing the critical resolved shear stress (CRSS) on non-basal planes or by promoting cross slip through an increase in the stacking fault energy (SFE) on basal planes. In this thesis, the effect of Li addition to the most widely used wrought Mg-alloy AZ31 on its workability is examined. Plastic deformation behaviour of a series of AZ31-Li alloys with temperature, T, and strain rates, ε , as variables was studied, so as to identify the optimum Li content that results in highly workable alloy. The T and ε combinations that are best suited for hot deformation of these alloys were also identified through processing maps and microstructural analysis. First, deformation behaviour of the base AZ31 is examined in detail. Compression tests were carried out, with T ranging between 150 and 400 °C and at ranging from 10-3 to 102 s-1, covering entire hot working range of the alloy. The results suggest that the deformation behaviour of AZ31 could be partitioned into three temperature regimes. In low T regime, twinning played an important role. It changes the orientation and increases hardening rate, θ (given by dσ/dε where σ and ε are true stress and strain respectively); material exhibits macroscopic flow localization and cracking along twin boundaries. The onset of twinning was examined in detail by examining the local maxima before ϵpeak strain in plot between d2σ/dε2 vs. ε. Twinning was found to occur at all the deformation conditions. Dynamic recrystallization (DRX) was observed at temperatures above 250 °C whereas deformation at low T (< 250 °C) led to extensive twinning at all . ε . At intermediate T of 250-300 °C, plastic strains tend to localize near grain/twin boundaries, confining DRX only to these regions. Increase in T promotes non-basal slip, which, in turn, leads to uniform deformation; DRX too becomes uniform. The dependence of critical stress (σc) for the onset of DRX and peak flow stress (σp) on Zener-Hollomon parameter (Z) indicates that these stresses increase with Z. Activation energy (Q) for the deformation of AZ31 was estimated at peak stress and steady state conditions. High values of Q (150-200 kJ/mol) indicate cross slip as the rate controlling mechanism, at the peak, in the stress-strain responses. For steady state, Q corresponds to lattice/grain boundary diffusion (90-150 kJ/mol). Next, the effect of Li on deformation behaviour of AZ31 was examined. In addition to AZ31 without any Li (0Li), three alloys 1 (1Li), 3 (3Li) and 5 (5Li) wt% Li were prepared with the aid of a specially designed set-up for melting and casting of Li containing alloys. Experimental results on homogenized alloys show that 1Li alloy’s overall response is similar to that of 0Li alloy, but 3Li and 5Li alloys exhibit distinctly different deformation behaviour. Li addition facilitates cross slip by increasing SFE on basal planes, thus leading to change in the deformation mechanism of the alloy. Increased softening due to cross slip decreases θ and also the twin density at low ϵ (<10-2 s-1). During deformation at low ϵ and low T, high Li alloys reveal cavities along the grain boundaries in contrast to cracking along twin boundaries that was observed in AZ31. In the intermediate T range, high Li alloys reveal the presence of a small mantle, which can be attributed to the increased cross slip with increasing Li. In fact, Li addition was found to restrict DRX and promote dynamic recovery (DRY). As ϵ increases in this T regime deformation becomes more homogeneous and twinning occurs extensively in high Li alloys. This results in remarkable increase in dσ/dε (θ) in these alloys and DRX was predominantly seen at twinned regions. At high ϵ -T regime, where non-basal slip and twinning occur uniformly, DRX is observed throughout the samples. On the basis of d2σ/dε2 – ε plots, it was found that twinning occurs at almost all -T combinations examined in present study for 0Li and 1Li alloys. In high Li alloys, twinning activity was found to be insignificant at low ε , resulting in low twin density than low Li alloys. Twinning occurs at very early stages of deformation. In the low T and high ε regime, extensive twinning in high Li alloys is noted. In high T regime, presence of twins was not prominent due to the preferential occurrence of DRX at twin boundaries. Estimated values of Q in high Li alloys were found to be very low and correspond to lattice/grain boundary diffusion of Li in Mg, indicating that cross slip is no longer the rate controlling mechanism. Instead, unpinning of kinks from Li atoms appears to control the deformation. Cross slip is promoted by Li through increase in SFE at basal planes. Onset of the DRX was predicted and it was observed that high Li alloys posses lower σc at low ε , but at high ε , σc was either comparable to or higher than low Li alloys. Processing maps were generated for all the alloys using Prasad's as well as Murty's models. Instability predictions of Prasad’s and Murty’s models are similar, except that isoefficiency contours in the latter are slightly shifted to higher ε . These maps indicate to an increase in the workability with the addition of Li to AZ31. Instability predicted by processing maps in the low ε regime in high Li alloys is attributed to underestimation of stress values due to spline interpolation. High sensitivity observed for high Li alloy at intermediate ε (10-1 – 100 s-1) is attributed to the change in the deformation mode i.e. from slip to twinning. Deformation at high T leads to dissolution of Li containing precipitates, which in turn increases the solid solution strengthening in the alloy. Hence, increase in flow stress is observed with increase in T in high Li alloys. This structural change too causes instability predictions in the high -T regime. The 0 Li alloy exhibits peak efficiency of 45% in T = 250-400 °C and ε = 10-1.25 - 100.25 s-1 regime. DRX is observed in this regime and optimum conditions for deformation predicted for this alloys are T = 350 °C and ε = 10-1 s-1. These alloys can be worked at low ε regime too (T = 250-400 °C and ε = 10-2.5 – 10-1 s-1) where the softening mechanism is DRY. Accordingly, it is concluded that the intrinsic workability of AZ31Mg-alloy increases with the addition of 3% and 5% Li.

Coronary artery disease (CAD) affects every fifth person in the world. The gold-standard treatment for CAD is stent implantation, however, the existing therapy is not sufficient due to many reasons. For instance, in-stent restenosis, biocompatibility, controlled degradation rate, protein adsorption, and adequate endothelialization are still the main concerns. In the last two decades, the field of stent technology has been grown rapidly and many new stent types and in vitro testing methods for stent characterization have been developed to minimize the aforementioned issues. In this vicinity, there are still many unaddressed issues: i) the quantitative analysis of corrosion is conducted with simpler samples made of stent material instead of stents, in most cases due to the absence of a mathematical model to calculate the entire stent surface area (ESSA); ii) in vitro stent testing in environments that are very far from actual physiological environments; iii) Evaluation of the influence of in-vitro test conditions on coated metallic stents; iv) absence of flow-induced shear stress (FISS) corrosion model, to mention a few. This thesis presents the novel ESSA model, the fluid dynamic experimental setup with the integration of various sensors and pH control, the influence of in vitro degradation behavior of the titanium oxynitride (TiOxNy) coated stainless steel stents and anodized AZ31 samples, and the FISS corrosion model. The results show some important contributions in this field, however, there is still a huge potential for the development of promising stent characterization solutions. / Die koronare Herzkrankheit (KHK) betrifft jeden fünften Menschen auf der Welt. Der Goldstandard bei der Behandlung von KHK ist die Stent-Implantation, doch die bestehende Therapie ist aus vielen Gründen nicht ausreichend. So sind beispielsweise die Restenose im Stent, die Biokompatibilität, die kontrollierte Abbaugeschwindigkeit, die Proteinadsorption und die angemessene Endothelialisierung nach wie vor die Hauptprobleme. In den letzten zwei Jahrzehnten hat sich die Stenttechnologie rasant weiterentwickelt, und es wurden viele neue Stenttypen und In-vitro-Testmethoden zur Stentcharakterisierung entwickelt, um die oben genannten Probleme zu minimieren. In dieser Umgebung gibt es noch viele ungelöste Probleme: i) die quantitative Analyse der Korrosion wird mit einfacheren Proben aus Stentmaterial anstelle von Stents durchgeführt, in den meisten Fällen aufgrund des Fehlens eines mathematischen Modells zur Berechnung der gesamten Stentoberfläche (ESSA); ii) In-vitro-Stent-Tests in Umgebungen, die sehr weit von der tatsächlichen physiologischen Umgebung entfernt sind; iii) Bewertung des Einflusses von In-vitro-Testbedingungen auf beschichtete metallische Stents; iv) Fehlen eines FISS-Korrosionsmodells (flow-induced shear stress), um nur einige zu nennen. In dieser Arbeit werden das neuartige ESSA-Modell, der strömungsdynamische Versuchsaufbau mit der Integration verschiedener Sensoren und pH-Kontrolle, der Einfluss des In-vitro-Degradationsverhaltens der mit Titanoxynitrid (TiOxNy) beschichteten Edelstahlstents und anodisierten AZ31-Proben sowie das FISS-Korrosionsmodell vorgestellt. Die Ergebnisse zeigen einige wichtige Beiträge in diesem Bereich, jedoch gibt es noch ein großes Potenzial für die Entwicklung von vielversprechenden Lösungen zur Charakterisierung von Stents.