Mg-V and Mg-Zr alloys with nominal compositions 1, 6, 17.5, 27 wt% V and 2, 8.6 and 10.6 wt% Zr respectively were produced by PVD. All deposits exhibited compositional inhomogeneity, columnar microstructures and a strong basal texture. The solid solubilities of V and Zr in Mg were extended approximately to 17 wt% V and 10 wt% respectively. Grain refinement occurred with increasing solute content. The solid solution break up temperature decreased as the V and Zr content in the alloys increased. Pure V precipitated when the extended solid solubility of was exceeded. Both c and a lattice parameters, as well as the c/a ratio decreased with increasing V content in the Mg-V alloys. The slight increase of the a-lattice parameter and the decrease of the c one led to a decrease of the c/a ratio with increasing Zr additions in the Mg-Zr alloys. The air-formed oxide on the surfaces of the Mg-V alloys consisted predominantly of hydromagnesite at the outermost surface with Mg(OH)2 in excess of MgO underneath. No evidence of V oxide in the surface film was found. Magnesium oxide was also found between the grains of the deposits. The air-formed oxide on the surfaces of the Mg-Zr alloys consisted of ZrO2, MgO and possibly Zr sub-oxide. The presence of the oxides beween the columnar grains gave rise to graded metal/oxide interfaces. The outermost surfaces of the Mg-Zr alloys were similar to the Mg-V ones. Analysis of changes of the Auger parameters of the Mg-V and Mg-Zr alloys was also undertaken in order to investigate the electronic changes that take place upon alloying Mg with V and Zr. Charge transfer between 0.09 and 0.11 electrons/atom from Mg to V as well as changes in the V d charge were calculated by measuring the Mg and V Auger parameters and using the charge transfer model of Thomas and Weightman. Electron transfer between 0.02 and 0.03 electrons/atom from Mg to Zr was also found to occur upon alloying Mg with Zr. The electron transfer has been related to changes in crystal structure. The Mg-V and Mg-Zr alloys were examined after immersion in 3 wt% NaCl solution for 5 and 15 minutes, 9 hours and 7 days. The dramatic increase in the corrosion rate of the Mg-V alloys was attributed to the precipitation of pure V. The unsatisfactory corrosion performance of the Mg-V alloys was attributed to the absence of compositional uniformity through the thickness of the Mg-V deposits and the low thermodynamic stability of the corrosion products in the saline environment. Hydromagnesite at the outermost surface and Mg(OH)2, MgO and V2O4 in the bulk of the corrosion layer were the corrosion products. MgH2 and areas enriched in metallic V within the bulk of the corrosion products were also detected. The low corrosion rates of the Mg-Zr alloys, the lowest ever reported for Mg alloys, were attributed to the nature of the corrosion products and particularly the Zr contribution. The corrosion products were enriched in Zr, and were non-porous and in many cases well adherent. X-ray and electron diffraction suggested the existence of only Mg(OH)2 and MgO in the corrosion products, indirectly implying the participation of zirconium oxide/hydroxide in an amorphous/nanocrystalline state. Surface analysis indicated that a Zr oxide coexisted with Mg(OH)2 and MgO below a magnesium carbonate overlayer and also suggested the existence of Zr hydrous oxide (hydroxide). The repetition of the substrate pattern, as well as the fact that Zr hydroxide was replaced with ZrO2 and Zr sub-oxide as the metal-oxide interface was approached, implied a corrosion mechanism involving inwards diffusion of the anionic species.

Thesis (Ph.D.) - University of Queensland, 2005. / Includes bibliography.

Aim of this study is to improve corrosion resistance of magnesium alloy AZ91 by conversion coatings. Influence of alloy microstructure on conversion coating growth and corrosion resistance was evaluated. Properties of pure magnesium and magnesium alloy AZ91 as well as the influence of alloying elements on properties of this alloy are described in theoretical part. Recent results of corrosion protection by conversion coatings on AZ type magnesium alloys are summarised in recherché part. Practical part focuses on preparation of hexavalent chromium based conversion coating and phosphate-permanganate based conversion coating on as cast AZ91 magnesium alloy, these coatings were subsequently applied on annealed AZ91 magnesium alloy. Corrosion protection of the coatings prepared on as cast and annealed alloy was evaluated by potentiodynamic measurements and testing in neutral salt spray. Furthermore the influence of plasma activation on phosphate-permanganate coating surface was studied.

This thesis describes magnesium alloys, their properties and methods of their production. However, experimental part is focused on AZ91 magnesium alloy. Conversion coatings were prepared on the AZ91 surface – chromate coating, phosphate permanganate coating and fluoride coating. Corrosion resistance of the prepared coatings were compared by immersion tests and by potentiodynamic methods. Evaluation of corrosion resistance by immersion tests was successful only for phosphate permanganate coating. Only this coating was removed during cleaning of the samples. For comparison of corrosion resistance was important to find the correct procedures and optimize the measurements methods. For these purposes have been chosen galvanic zinc coating on steel sheets. Thickness of the zinc coating were 8 and 30 microns. This coatings provide uniform zinc surface without heterogenities which was important for the potentiodynamic measurements. After optimization methods for potentiodynamic measurements by galvanic zinc coatings have been measured magnesium alloy AZ91 uncoated and coated by conversion coatings. For uncoated AZ91 magnesium alloy was determined suitable method so called virgin cathodic curve. On the other hand, for the coated AZ91 magnesium alloys was determined suitable method so called combined curve, within which we measured cyclic voltammetry curve (± 5 mV) and then virgin anodic curve.

Magnesium and its alloys are considered as the potential biomaterials due to their biocompatibility and biodegradable characteristics but suffer from poor corrosion performance. Various surface modification techniques are employed to improve their corrosion resistance. In present case, laser surface melting was carried out on AZ31B Mg alloy with various laser energy densities using a continuous wave ytterbium laser. Effect of laser treatment on phase and microstructure evolution was evaluated by X ray diffraction and scanning electron microscopy. Multi-physics thermal model predicted time temperature evolution along the depth of the laser treatment zone. Additionally, electrochemical method and bio-immersion test were employed to evaluate the corrosion behavior in simulated body fluid medium. Microstructure revealed grain refinement and even distribution of Mg17Al12 phase along the grain boundary for laser treated samples leading to substantial enhancement in the corrosion resistance of the laser treated samples compared to the untreated alloy. The laser processed samples also possessed a superior wettability in SBF solution than the untreated sample. This was further reflected in enhanced bio-integration behavior of laser processed samples. By changing the parameters of laser processing such as power, scanning speed, and fill spacing, a controllable corrosion resistance and bioactivity/biocompatibility of the implant material was achieved.

In the present investigation, MMCs have been fabricated using the creep-resistant AE42 magnesium alloy as matrix and reinforcing it with saffil short fibres (essentially δ-Al2O2) and SiC particles in various combinations. These MMCs have been investigated for their creep, wear and corrosion behaviour. The above properties of the matrix AE42 alloy have also been investigated for comparison. Further, laser surface melting has been carried out on a creep-resistant MRI 230D Mg alloy and the corrosion and wear behaviour of this alloy before and after laser surface melting has been investigated. The creep tests on the AE42 alloy were carried out in the temperature range of 1500 to 2400C at the stress levels ranging from 40 to 120 MPa and the composites were tested in the temperature range of 1750C to 3000 at the stress levels ranging from 60 to 140 MPa both in the longitudinal direction (LD) and in the transverse direction (TD). Wear tests were conducted on a pin-on-disc set-up under dry sliding condition at a constant sliding velocity of 0.837 m/s for a constant sliding distance of 2.5 km in the load range of 10 to 40 N for the AE42 alloy and the composites, which were tested both in LD and TD, and for a constant sliding distance of 1km in the load range of 5 to 20 N for the MRI 230D alloy before and after laser melting. All the materials were subjected to electrochemical corrosion tests in a 5 wt.% NaCl solution having ph value 11 for 22 hours. All the composites in both LD and TD exhibit lower creep rate as compared to the AE42 alloy and it is higher in TD than in LD. The creep resistance of the hybrid composites, in which saffil short fibres are partially replaced by SiC particles, is observed to be comparable , i.e., of the same order of magnitude , to that of the composite reinforced with Saffil short fibres alone at all the temperatures and stresses employed in both LD and TD. Wear rate of all the composites in both LD and Td is found to be lower than the alloy at all the loads employed and it is higher in TD than LD, Wear rate progressively decreases with the partial replacement of Saffil short fibres by Sic Particles, and is lowest for the composites reinforced with 10 vol.% Saffil short fibres and 15 vol.% Sic particles in both LD and TD. It is 34% and 35% lower than the 20% Saffil composite at 40 N load in LD and TD, respectively. The Ae42 alloy exhibits the best corrosion resistance and the addition of the Saffil short fibres and/or Sic particles in the AE42 alloy deteriorates its corrosion resitance. The composite reinforced with Saffil short fibres alone exhibits slightly better corrosion resitance than the hybrid composites. However, there is no systematic trend of corrosion resistance with SiC particles content. The laser surface melting is found to improve the corrosion, hardness and wear resistance of the MRI 230D alloy. High temperature climb of dislocation is found to be the dominant creep mechanism in the AE42 alloy in the stress and temperature range employed. Various glide and climb of dislocation are found to be the dominant creep mechanisms for all the composites in both LD and TD in the stress and temperature range employed. The presence of SiC particles in the hybrid composites improves the wear resistance in both LD and TD since these particles remain intact and retain their load bearing capacity even at the highest load employed in the present investigation. They promote the formation of iron-rich transfer layer and they also delay the fracture of Saffil short fibres to higher loads in case of the composites in LD. Under the experimental conditions used in the present investigation, the dominant wear mechanism is found to be abrasion for the AE42 alloy and its composites in both LD and TD. It is accompanied by severe plastic deformation of surface layers in case of the alloy, the fracture of Saffil short fibres as well as the formation of iron-rich transfer layer in case of the composites in Ld, and the fracture and pull-out of the Saffil short fibres in case of the composites in TD. The lower corrosion resistance of all the composites is not caused by the galvanic coupling between reinforcements and matrix, and is related to the microstructural changes, such as, distribution of precipitates and the nature of the film formed at the surface. The improved corrosion resistance following laser surface melting is due to the absence of the Al2Ca phase at the grain boundary, microstructural refinement and increased solid solubility, particularly of Al, owing to rapid solidification; the improved hardness and wear resistance is due to grain refinement and solid solution strengthening. To conclude, the creep resistance of the hybrid composites is comparable, wear resistance is better and corrosion resistance is slightly inferior to the composite reinforced with Saffil short fibres alone. Therefore, from the commercial point of view, the use of the hybrid composites, replacing a part of the expensive Saffil short fibres by cheap SiC particles, is beneficial. The laser surface melting is beneficial for the corrosion and wear resistance of the MRI 230D alloy.

Aim of the present work was to explore the possibility of improving strength of cast Mg by alloying additions, viz., Si and Zn+Al. All the alloys were produced by squeeze casting technique using squeeze pressure of 12MPa and their microstructure, tensile and corrosion properties were studied. Mg-Si system was chosen because the intermetallic compound Mg2Si possesses many desirable properties, such as, low density, high hardness, high melting point. Hence, there is scope for improving the strength of Mg by dispersion of primary Mg2Si particles. Addition of Si to Mg resulted in the formation of �-Mg, particles of primary Mg2Si and eutectic as microstructural constituents. The morphology of primary Mg2Si changed from polyhedral shaped particles to dendrites as Si content was increased from 3.57 to 5.5 wt%. Volume fraction of primary Mg2Si increased with increase in Si content. Particle size of primary Mg2Si also increased with increase in silicon content but at the same time it was found to be dependent on melt temperature, i.e., a lower particle size was obtained at higher melt temperatures. Addition of Al and Sr was made to Mg-2Si alloy in order to further increase the strength by solid solution strengthening and refinement/modification of primary Mg2Si particles/eutectic. Addition of 1.2 wt% Al to Mg-2Si alloy resulted in irregular type of morphology of Mg2Si particles and increased particle size. Addition of 0.2 wt% SrtoMg-2Si-1.2Al alloy resulted in slight refinement of primary Mg2Si particles and modification of eutectic. Addition of 0.4 wt% Sr resulted in both refinement and restoration of morphology of Mg2Si particles from irregular to polyhedral shape. This was accompanied by destruction of eutectic, and rods containing Mg, Si, Al and Sr were observed. The addition of 1.33 wt%Si to Mg resulted in improvement in 0.2%PS by about 80 MPa,UTS by about 40MPa and these values did not change much till the addition of 3.57 wt% Si. A drop in the strength values was observed at Si content of 5.5 wt%,where transition in morphology of primary Mg2Si occurred from polyhedral to dendrite. Addition of Si resulted in reduction in % elongation by about 2%. The addition of Al and Sr did not change the tensile properties of binary Mg-2Si alloy much. It was concluded that the volume fraction and size of primary Mg2Siparticles obtained with Si addition up to 3.57 wt% did not contribute much to strength and the strengthening mainly came from the eutectic present in the matrix. As Si content was increased to 5.5 wt% in order to increase the volume fraction of primary Mg2Si particles, the morphology of Mg2Si changed to dendritic type resulting in reduction in strength. Thus, the maximum increase in strength is achieved at near eutectic composition,i.e.,intheMg-1.33Sialloy,andfurtherincreaseinstrengthdoesnotseem to be feasible with this alloy system. The ductility of all the Mg-Si based alloys was also low, i.e, 0.5% elongation to fracture or less. Regarding the corrosion behaviour, the addition of Si to Mg deteriorated the corrosion resistance and the addition of Al and Sr further worsened it. Since further improvement in tensile properties did not seem feasible with Mg-Si alloy system, the focus was shifted to Mg-Zn-Al alloy system. There is scope for improvement in strength in Mg-Zn-Al alloy system by solid solution strengthening, grain refinement and precipitation hardening. It was observed that the addition of Zn and Al resulted in microstructure containing α-Mg grains and secondary phase at the grain boundary. XRD analysis showed the secondary phase to be Al5Mg11Zn4 but EDS analysis did not match with this composition. Therefore, the nature of this phase remains uncertain. Addition of 6 wt% Zn and 1 wt% Al resulted in improvement in strength as well as ductility: 0.2%PS improved by about 70 MPa, UTS by about 100 MPa and % elongation by about 7%. Addition of small amounts of Caresultedinrefinementofmicrostructurecausingimprovementinstrengthwithout much decrease in % elongation. Increase in Al content from 1 to 4 wt% resulted in increase in 0.2%PS but UTS slightly decreased, as % elongation reduced. Alloys subjected to T6 heat treatment showed improvement in strength but slight reduction in % elongation. ZA64 alloy in T6 condition gave 130 MPa 0.2%PS, 225 MPa UTS and 4.9% elongation, which are much higher tensile properties as compared Mg-Si alloys. All the three mechanisms mentioned above contribute to the strengthening. There is scope for further improvement in strength by employing a more suitable heat treatment. Regarding corrosion behaviour, addition of 6 wt% Zn and 1 wt% of Al to Mg did not deteriorate its corrosion resistance much. Addition of small amounts of Ca was found to be beneficial for corrosion resistance, whereas an increase in Al content lowered the corrosion resistance. Heat treatment also reduced the corrosion resistance.

Indiana University-Purdue University Indianapolis (IUPUI) / In recent years, magnesium alloys, due to their high strength and biocompatibility, have attracted significant interest in medical applications, such as cardiovascular stents, orthopedic implants, and devices. To overcome the high corrosion rate of magnesium alloys, coatings have been developed on the alloy surface. Most coating methods, such as anodic oxidation, polymer coating and chemical conversion coating, cannot produce satisfactory coating to be used in human body environment. Recent studies demonstrate that micro-arc oxidation (MAO) technique can produce hard, dense, wear-resistant and well-adherent oxide coatings for light metals such as aluminum, magnesium, and titanium. Though there are many previous studies, the understanding of processing conditions on coating performance remains elusive. Moreover, previous tests were done in simulated body fluid. No test has been done in a cell culture medium, which is much closer to human body environment than simulated body fluid. In this study, the effect of MAO processing time (1 minute, 5 minutes, 15 minutes, and 20 minutes) on the electrochemical behaviors of the coating in both conventional simulated body fluid and a cell culture medium has been investigated. Additionally a new electrolyte (12 g/L Na2SiO3, 4 g/L NaF and 4 ml/L C3H8O3) has been used in the MAO coating process. Electrochemical behaviors were measured by performing potentiodynamic polarization and electrochemical impedance spectroscopy tests. In addition to the tests in simulated body fluid, the MAO-coated and uncoated samples were immersed in a cell culture medium to investigate the corrosion behaviors and compare the difference in these two kinds of media. The results show that in the immersion tests in conventional simulated body fluid, the 20-minute MAO coated sample has the best resistance to corrosion due to the largest coating thickness. In contrast, in the cell culture medium, all MAO coated samples demonstrate a similar high corrosion resistance behavior, independent of MAO processing time. This is probably due to the organic passive layers formed on the coating surfaces. Additionally, a preliminary finite element model has been developed to simulate the immersion test of magnesium alloy in simulated body fluid. Comparison between the predicted corrosion current density and experimental data is discussed.