Corrosion of an Additively Manufactured Ti6Al4V Alloy in Saline and Acidic Media.

The present work aims to provide corrosion performance data for an additively manufactured Ti6Al4V alloy in saline and polluted environments. The as-received additively manufactured material underwent heat treatment at 850 °C for 3 h to transform the acicular α' microstructure into a lamellar α microstructure. Comparative corrosion assessments were conducted between the heat-treated substrates, the as-received condition, and a conventionally mill-annealed alloy. Potentiodynamic polarization experiments were carried out in saline (3.5 wt.% NaCl) and acid aqueous media ((NH4)2SO4 containing Harrison's solution). The corrosion performance of additively manufactured substrates matched or surpassed that of the conventional alloy in Harrison's solutions while remaining inferior in saline medium, despite forming a thicker passive film. Overall, the XY plane showed better corrosion performance, particularly after the elimination of the acicular α' martensite by the applied heat treatment. The results also suggested that the presence of the coarse ß phase was beneficial in 3.5 wt.% NaCl solution and detrimental in Harrison's solutions, more so in acidified and fluorinated conditions.

Biological Performance of Duplex PEO + CNT/PCL Coating on AZ31B Mg Alloy for Orthopedic and Dental Applications.

To regulate the degradation rate and improve the surface biocompatibility of the AZ31B magnesium alloy, three different coating systems were produced via plasma electrolytic oxidation (PEO): simple PEO, PEO incorporating multi-walled carbon nanotubes (PEO + CNT), and a duplex coating that included a polycaprolactone top layer (PEO + CNT/PCL). Surfaces were characterized by chemical content, roughness, topography, and wettability. Biological properties analysis included cell metabolism and adhesion. PEO ± CNT resulted in an augmented surface roughness compared with the base material (BM), while PCL deposition produced the smoothest surface. All surfaces had a contact angle below 90°. The exposure of gFib-TERT and bmMSC to culture media collected after 3 or 24 h did not affect their metabolism. A decrease in metabolic activity of 9% and 14% for bmMSC and of 14% and 29% for gFib-TERT was observed after 3 and 7 days, respectively. All cells died after 7 days of exposure to BM and after 15 days of exposure to coated surfaces. Saos-2 and gFib-TERT adhered poorly to BM, in contrast to bmMSC. All cells on PEO anchored into the pores with filopodia, exhibited tiny adhesion protrusions on PEO + CNT, and presented a web-like spreading with lamellipodia on PEO + CNT/PCL. The smooth and homogenous surface of the duplex PEO + CNT/PCL coating decreased magnesium corrosion and led to better biological functionality.

Ciprofloxacin Release and Corrosion Behaviour of a Hybrid PEO/PCL Coating on Mg3Zn0.4Ca Alloy.

In the present work, a hybrid hierarchical coating (HHC) system comprising a plasma electrolytic oxidation (PEO) coating and a homogeneously porous structured polycaprolactone (PCL) top-coat layer, loaded with ciprofloxacin (CIP), was developed on Mg3Zn0.4Ca alloy. According to the findings, the HHC system avoided burst release and ensured gradual drug elution (64% over 240 h). The multi-level protection of the magnesium alloy is achieved through sealing of the PEO coating pores by the polymer layer and the inhibiting effect of CIP (up to 74%). The corrosion inhibition effect of HHC and the eluted drug is associated with the formation of insoluble CIP-Me (Mg/Ca) chelates that repair the defects in the HHC and impede the access of corrosive species as corroborated by FTIR spectra, EIS and SEM images after 24 h of immersion. Therefore, CIP participates in an active protection mechanism by interacting with cations coming through the damaged coating.

Chromate-Free Corrosion Protection Strategies for Magnesium Alloys-A Review: Part III-Corrosion Inhibitors and Combining Them with Other Protection Strategies.

Owing to the unique active corrosion protection characteristic of hexavalent chromium-based systems, they have been projected to be highly effective solutions against the corrosion of many engineering metals. However, hexavalent chromium, rendered a highly toxic and carcinogenic substance, is being phased out of industrial applications. Thus, over the past few years, extensive and concerted efforts have been made to develop environmentally friendly alternative technologies with comparable or better corrosion protection performance to that of hexavalent chromium-based technologies. The introduction of corrosion inhibitors to a coating system on magnesium surface is a cost-effective approach not only for improving the overall corrosion protection performance, but also for imparting active inhibition during the service life of the magnesium part. Therefore, in an attempt to resemble the unique active corrosion protection characteristic of the hexavalent chromium-based systems, the incorporation of inhibitors to barrier coatings on magnesium alloys has been extensively investigated. In Part III of the Review, several types of corrosion inhibitors for magnesium and its alloys are reviewed. A discussion of the state-of-the-art inhibitor systems, such as iron-binding inhibitors and inhibitor mixtures, is presented, and perspective directions of research are outlined, including in silico or computational screening of corrosion inhibitors. Finally, the combination of corrosion inhibitors with other corrosion protection strategies is reviewed. Several reported highly protective coatings with active inhibition capabilities stemming from the on-demand activation of incorporated inhibitors can be considered a promising replacement for hexavalent chromium-based technologies, as long as their deployment is adequately addressed.

Chromate-Free Corrosion Protection Strategies for Magnesium Alloys-A Review: Part II-PEO and Anodizing.

Although hexavalent chromium-based protection systems are effective and their long-term performance is well understood, they can no longer be used due to their proven Cr(VI) toxicity and carcinogenic effect. The search for alternative protection technologies for Mg alloys has been going on for at least a couple of decades. However, surface treatment systems with equivalent efficacies to that of Cr(VI)-based ones have only begun to emerge much more recently. It is still proving challenging to find sufficiently protective replacements for Cr(VI) that do not give rise to safety concerns related to corrosion, especially in terms of fulfilling the requirements of the transportation industry. Additionally, in overcoming these obstacles, the advantages of newly introduced technologies have to include not only health safety but also need to be balanced against their added cost, as well as being environmentally friendly and simple to implement and maintain. Anodizing, especially when carried out above the breakdown potential (technology known as Plasma Electrolytic Oxidation (PEO)) is an electrochemical oxidation process which has been recognized as one of the most effective methods to significantly improve the corrosion resistance of Mg and its alloys by forming a protective ceramic-like layer on their surface that isolates the base material from aggressive environmental agents. Part II of this review summarizes developments in and future outlooks for Mg anodizing, including traditional chromium-based processes and newly developed chromium-free alternatives, such as PEO technology and the use of organic electrolytes. This work provides an overview of processing parameters such as electrolyte composition and additives, voltage/current regimes, and post-treatment sealing strategies that influence the corrosion performance of the coatings. This large variability of the fabrication conditions makes it possible to obtain Cr-free products that meet the industrial requirements for performance, as expected from traditional Cr-based technologies.

Chromate-Free Corrosion Protection Strategies for Magnesium Alloys-A Review: PART I-Pre-Treatment and Conversion Coating.

Corrosion protection systems based on hexavalent chromium are traditionally perceived to be a panacea for many engineering metals including magnesium alloys. However, bans and strict application regulations attributed to environmental concerns and the carcinogenic nature of hexavalent chromium have driven a considerable amount of effort into developing safer and more environmentally friendly alternative techniques that provide the desired corrosion protection performance for magnesium and its alloys. Part I of this review series considers the various pre-treatment methods as the earliest step involved in the preparation of Mg surfaces for the purpose of further anti-corrosion treatments. The decisive effect of pre-treatment on the corrosion properties of both bare and coated magnesium is discussed. The second section of this review covers the fundamentals and performance of conventional and state-of-the-art conversion coating formulations including phosphate-based, rare-earth-based, vanadate, fluoride-based, and LDH. In addition, the advantages and challenges of each conversion coating formulation are discussed to accommodate the perspectives on their application and future development. Several auspicious corrosion protection performances have been reported as the outcome of extensive ongoing research dedicated to the development of conversion coatings, which can potentially replace hazardous chromium(VI)-based technologies in industries.

Corrosion of Steel Rebars in Anoxic Environments. Part I: Electrochemical Measurements.

The number of reinforced concrete structures subject to anoxic conditions such as offshore platforms and geological storage facilities is growing steadily. This study explored the behaviour of embedded steel reinforcement corrosion under anoxic conditions in the presence of different chloride concentrations. Corrosion rate values were obtained by three electrochemical techniques: Linear polarization resistance, electrochemical impedance spectroscopy, and chronopotenciometry. The corrosion rate ceiling observed was 0.98 µA/cm2, irrespective of the chloride content in the concrete. By means of an Evans diagram, it was possible to estimate the value of the cathodic Tafel constant (bc) to be 180 mV dec-1, and the current limit yielded an ilim value of 0.98 µA/cm2. On the other hand, the corrosion potential would lie most likely in the -900 mVAg/AgCl to -1000 mVAg/AgCl range, whilst the bounds for the most probable corrosion rate were 0.61 µA/cm2 to 0.22 µA/cm2. The experiments conducted revealed clear evidence of corrosion-induced pitting that will be assessed in subsequent research.

Corrosion of Steel Rebars in Anoxic Environments. Part II: Pit Growth Rate and Mechanical Strength.

Reinforced concrete may corrode in anoxic environments such as offshore structures. Under such conditions the reinforcement fails to passivate completely, irrespective of chloride content, and the corrosion taking place locally induces the growth of discrete pits. This study characterised such pits and simulated their growth from experimentally determined electrochemical parameters. Pit morphology was assessed with an optical profilometer. A finite element model was developed to simulate pit growth based on electrochemical parameters for different cathode areas. The model was able to predict long-term pit growth by deformed geometry set up. Simulations showed that pit growth-related corrosion tends to maximise as cathode area declines, which lower the pitting factor. The mechanical strength developed by the passive and prestressed rebar throughout its service life was also estimated. Passive rebar strength may drop by nearly 20% over 100 years, whilst in the presence of cracking from the base of the pit steel strength may decline by over 40%.

Hierarchical Functionalized Polymeric-Ceramic Coatings on Mg-Ca Alloys for Biodegradable Implant Applications.

Magnesium-based implants present several advantages for clinical applications, in particular due to their biocompatibility and degradability. However, degradation products can affect negatively the cell activity. In this work, a combined coating strategy to control the implant degradation and cell regulation processes is evaluated, including plasma electrolytic oxidation (PEO) that produces a 13 µm-thick Ca, P, and Si containing ceramic coating with surface porosity, and breath figures (BF) approach that produces a porous polymeric poly(ε-caprolactone) surface. The degradation of PCL-PEO-coated Mg hierarchical scaffold can be tailored to promote cell adhesion and proliferation into the porous structure. As a result, cell culture can colonize the inner PEO-ceramic coating structure where higher amount of bioelements are present. The Mg/PEO/PCL/BF scaffolds exhibit equally good or better premyoblast cell adhesion and proliferation compared with Ti CP control. The biological behavior of this new hierarchical functionalized scaffold can improve the implantation success in bone and cardiovascular clinical applications.