Chromate replacement in coatings for corrosion protection of aerospace aluminium alloys

Mixed rare earth organophosphates have been investigated as potential corrosion inhibitors for AA2024-T3 with the aim of replacing chromate-based technologies. Cerium diphenyl phosphate (Ce(dpp) 3) and mischmetal diphenyl phosphate (Mm(dpp) 3) were added to epoxy coatings applied to AA2024-T3 panels and they were effective in reducing the amount and rate of filiform corrosion in high humidity conditions. Ce(dpp) 3 was the most effective and characterisation of the coating formulations showed approximately a factor of 5 reduction in both the number of corrosion filaments initiated as well as the length of these. Mm(dpp) 3 appeared to reduce the corrosion growth rate by a factor of 2 although it was the more effective inhibitor in solution studies. Spectroscopic characterisation of the coatings indicated that the cerium based inhibitor may disrupt network formation in the epoxy thus resulting in a coating that absorbed more water and allowed greater solubilisation of the corrosion inhibiting compound.

Microstructural development and mechanical properties in wrought Mg-Zn-RE alloys

Magnesium-zinc alloys with and without rare earth metals were examined. Particles form when rare earth metals are present and these affect the development of the internal structures in the alloys. Finer, more numerous and more uniformly distributed particles result in alloys with the best combination of high strength and ductility.

Compositional effects on the restoration behaviour in Mg-Zn-Re alloys

Additions of rare earth elements to magnesium alloys are qualitatively reported in the literature to retard recrystallisation. However, their effect in the presence of other (non-rare earth) alloy additions has not been systematically shown nor has the effect been quantified. The microstructural restoration following the hot deformation of Mg-xZn-yRE (x = 2.5 and 5 wt.%, y = 0 and 1 wt.%, and RE = Gd and Y) alloys has been studied using double hit compression testing and microscopy. It was found that, in the absence of rare earth additions, increases in zinc level had a negligible influence on the kinetics of restoration and the microstructure developed both during extrusion and throughout double hit testing. Adding rare earth elements to Mg-Zn alloys was found to retard restoration of the microstructure and maintain finer recrystallised grains. However, in the Mg-Zn-RE alloys, increasing the zinc concentration from 2.5 wt.% to 5 wt.% accelerated the restoration process, most likely due to a depletion of rare earth elements from solid solution and modification of the particles present in the matrix.

Effect of alloying and extrusion temperature on the microstructure and mechanical properties of Mg-Zn and Mg-Zn-RE alloys

Extruded Mg-Zn-RE alloys have been shown to exhibit excellent combinations of yield strength and ductility, but it is not completely clear how adding rare earth metals to Mg-Zn alters the microstructure and affects the mechanical properties. Microstructural changes and the resulting mechanical properties from changes in composition and extrusion temperature have been investigated for Mg-. x Zn-. y RE (. x=2.5 and 5. wt.%, y=0 and 1. wt. %, and RE=Gd and Y) alloys. Adding RE to Mg-Zn increased the strength and reduced the ductility, while increasing the zinc concentration in the Mg-Zn-RE alloys had the reverse effect.

Effects of alloying elements on the corrosion behavior and biocompatibility of biodegradable magnesium alloys: a review

Magnesium (Mg) based alloys have been extensively considered for their use as biodegradable implant materials. However, controlling their corrosion rate in the physiological environment of the human body is still a significant challenge. One of the most effective approaches to address this challenge is to carefully select alloying compositions with enhanced corrosion resistance and mechanical properties when designing the Mg alloys. This paper comprehensively reviews research progress on the development of Mg alloys as biodegradable implant materials, highlighting the effects of alloying elements including aluminum (Al), calcium (Ca), lithium (Li), manganese (Mn), zinc (Zn), zirconium (Zr), strontium (Sr) and rare earth elements (REEs) on the corrosion resistance and biocompatibility of Mg alloys, from the viewpoint of the design and utilization of Mg biomaterials. The REEs covered in this review include cerium (Ce), erbium (Er), lanthanum (La), gadolinium (Gd), neodymium (Nd) and yttrium (Y). The effects of alloying elements on the microstructure, corrosion behavior and biocompatibility of Mg alloys have been critically summarized based on specific aspects of the physiological environment, namely the electrochemical effect and the biological behavior. This journal is © the Partner Organisations 2014.

Mechanical properties, in vitro corrosion and biocompatibility of newly developed biodegradable Mg-Zr-Sr-Ho alloys for biomedical applications

Our previous studies have demonstrated that Mg-Zr-Sr alloys can be anticipated as excellent biodegradable implant materials for load-bearing applications. In general, rare earth elements (REEs) are widely used in magnesium (Mg) alloys with the aim of enhancing the mechanical properties of Mg-based alloys. In this study, the REE holmium (Ho) was added to an Mg-1Zr-2Sr alloy at different concentrations of Mg1Zr2SrxHo alloys (x = 0, 1, 3, 5 wt. %) and the microstructure, mechanical properties, degradation behaviour and biocompatibility of the alloys were systematically investigated. The results indicate that the addition of Ho to Mg1Zr2Sr led to the formation of the intermetallic phases MgHo3, Mg2Ho and Mg17Sr2 which resulted in enhanced mechanical strength and decreased degradation rates of the Mg-Zr-Sr-Ho alloys. Furthermore, Ho addition (≤5 wt. %) to Mg-Zr-Sr alloys led to enhancement of cell adhesion and proliferation of osteoblast cells on the Mg-Zr-Sr-Ho alloys. The in vitro biodegradation and the biocompatibility of the Mg-Zr-Sr-Ho alloys were both influenced by the Ho concentration in the Mg alloys; Mg1Zr2Sr3Ho exhibited lower degradation rates than Mg1Zr2Sr and displayed the best biocompatibility compared with the other alloys.

Potentiostatic control of ionic liquid surface film formation on ZE41 magnesium alloy

The generation of potentially corrosion-resistant films on light metal alloys of magnesium have been investigated. Magnesium alloy, ZE41 [Mg−Zn−Rare Earth (RE)-Zr, nominal composition 4 wt % Zn, 1.7 wt % RE (Ce), 0.6 wt % Zr, remaining balance, Mg], was exposed under potentiostatic control to the ionic liquid trihexyl(tetradecyl)phosphonium diphenylphosphate, denoted [P_6,6,6,14][DPP]. During exposure to this IL, a bias potential, shifted from open circuit, was applied to the ZE41 surface. Electrochemical impedance spectroscopy (EIS) and chronoamperometry (CA) were used to monitor the evolution of film formation on the metal surface during exposure. The EIS data indicate that, of the four bias potentials examined, applying a potential of −200 mV versus OCP during the exposure period resulted in surface films of greatest resistance. Both EIS measurements and scanning electron microscopy (SEM) imaging indicate that these surfaces are substantially different to those formed without potential bias. Time of flight-secondary ion mass spectrometry (ToF-SIMS) elemental mapping of the films was utilized to ascertain the distribution of the ionic liquid cationic and anionic species relative to the microstructural surface features of ZE41 and indicated a more uniform distribution compared with the surface following exposure in the absence of a bias potential. Immersion of the treated ZE41 specimens in a chloride contaminated salt solution clearly indicated that the ionic liquid generated surface films offered significant protection against pitting corrosion, although the intermetallics were still insufficiently protected by the IL and hence favored intergranular corrosion processes.

An electrochemical impedance study of ionic liquid film formation and aqueous corrosion of magnesium alloy ZE41

Ionic liquid surface treatments are proposed as a method of controlling corrosion processes on magnesium alloys. An important magnesium alloy, ZE41 (nominally 4% Zn and 1% rare earth), was treated with the ionic liquid trihexyl(tetradecyl)phosphonium diphenylphosphate (P₆₆₆₁₄DPP). Impedance spectra were acquired at intervals during the treatment, indicating the development of a film and allowing a measure of the film formation process to be obtained over time. Mechanically polished and electro-polished surfaces were prepared; these surfaces, treated and untreated, were subsequently exposed to 0.1 M NaCl aqueous solutions. The corrosion behavior of the prepared surfaces were assessed using impedance spectroscopy and optical microscopy. The results indicated a significant role for the method of surface preparation used and, in both cases, the ionic liquid treatment produced a more corrosion-resistant surface.

Solute segregation and texture modification in an extruded magnesium alloy containing gadolinium

The alloy Mg-1.5Gd has been extruded at different temperatures to produce two significantly different textures. At lower extrusion temperatures there was significant solute clustering in the matrix, coupled with segregation of solute to the grain boundaries. At higher temperatures these two phenomena were both less pronounced. It is suggested here that segregation of solute to the grain boundaries plays a significant role in the texture modification effect that rare earth elements have in magnesium alloys.

The corrosion inhibition of aluminium alloy 7075-T651 with cerium and Mischmetal di phenyl phosphate

Previous studies have shown that cerium diphenyl phosphate (Cedpp) 3 is a very effective inhibitor of corrosion of aluminium alloys in chloride solutions. This paper describes the results of further studies using electrochemical and constant immersion corrosion tests to compare the effectiveness of Ce(dpp) 3 and Mischmetal diphenyl phosphate Mm(dpp) 3 as inhibitors of corrosion pitting on AA7075-T651 aluminium alloy. The results shows that both Ce(dpp) 3 and Mm(dpp) 3 are excellent inhibitors of pitting corrosion of this alloy in very aggressive environments of continuously aerated 0.1M and 1.0M sodium chloride (NaCl) solutions. Polarisation tests indicate that these compounds act as a cathodic inhibitors by reducing the rate of the oxygen reduction reaction, which results in a decreased corrosion current density and a separation of the corrosion potential from the pitting potential. This inhibition is thought to be due to the formation of a surface film consisting of rare earth metal oxide, aluminium oxide and a cerium-aluminium organo-phosphate complex. Surface analysis data from scanning electron microscopy and X-ray Energy Dispersive Spectroscopy show the complex nature of this protective film. This work further develops our understanding about the mechanisms through which these complex films form, and how inhibition occurs in the presence of these compounds.