Corrosion Rate and Mechanism of Degradation of Chitosan/TiO2 Coatings Deposited on MgZnCa Alloy in Hank's Solution.

Overly fast corrosion degradation of biodegradable magnesium alloys has been a major problem over the last several years. The development of protective coatings by using biocompatible, biodegradable, and non-toxic material such as chitosan ensures a reduction in the rate of corrosion of Mg alloys in simulated body fluids. In this study, chitosan/TiO2 nanocomposite coating was used for the first time to hinder the corrosion rate of Mg19Zn1Ca alloy in Hank's solution. The main goal of this research is to investigate and explain the corrosion degradation mechanism of Mg19Zn1Ca alloy coated by nanocomposite chitosan-based coating. The chemical composition, structural analyses, and corrosion tests were used to evaluate the protective properties of the chitosan/TiO2 coating deposited on the Mg19Zn1Ca substrate. The chitosan/TiO2 coating slows down the corrosion rate of the magnesium alloy by more than threefold (3.6 times). The interaction of TiO2 (NPs) with the hydroxy and amine groups present in the chitosan molecule cause their uniform distribution in the chitosan matrix. The chitosan/TiO2 coating limits the contact of the substrate with Hank's solution.

Morphological and Surface Potential Characterization of Protein Nanobiofilm Formation on Magnesium Alloy Oxide: Their Role in Biodegradation.

The formation of a protein nanobiofilm on the surface of degradable biomaterials such as magnesium (Mg) and its alloys influences metal ion release, cell adhesion/spreading, and biocompatibility. During the early stage of human body implantation, competition and interaction between inorganic species and protein molecules result in a complex film containing Mg oxide and a protein layer. This film affects the electrochemical properties of the metal surface, the protein conformational arrangement, and the electronic properties of the protein/Mg oxide interface. In this study, we discuss the impact of various simulated body fluids, including sodium chloride (NaCl), phosphate-buffered saline (PBS), and Hanks' solutions on protein adsorption, electrochemical interactions, and electrical surface potential (ESP) distribution at the adsorbed protein/Mg oxide interface. After 10 min of immersion in NaCl, atomic force microscopy (AFM) and scanning Kelvin probe force microscopy (SKPFM) showed a higher surface roughness related to enhanced degradation and lower ESP distribution on a Mg-based alloy than those in other solutions. Furthermore, adding bovine serum albumin (BSA) to all solutions caused a decline in the total surface roughness and ESP magnitude on the Mg alloy surface, particularly in the NaCl electrolyte. Using SKPFM surface analysis, we detected a protein nanobiofilm (∼10-20 nm) with an aggregated and/or fibrillary morphology only on the Mg surface exposed in Hanks' and PBS solutions; these surfaces had a lower ESP value than the oxide layer.

Study of the Failure Mechanism of a High-Density Polyethylene Liner in a Type IV High-Pressure Storage Tank.

The use of Type IV cylinders for gas storage is becoming more widespread in various sectors, especially in transportation, owing to the lightweight nature of this type of cylinder, which is composed of a polymeric liner that exerts a barrier effect and an outer composite material shell that primarily imparts mechanical strength. In this work, the failure analysis of an HDPE liner in a Type IV cylinder for high-pressure storage was carried out. The breakdown occurred during a cyclic pressure test at room temperature and manifested in the hemispherical head area, as cracks perpendicular to the liner pinch-off line. The failed sample was thoroughly investigated and its characteristics were compared with those of other liners at different stages of production of a Type IV cylinder (blow molding, curing of the composite material). An examination of the liner showed that no significant chemical and morphological changes occurred during the production cycle of a Type IV cylinder that could justify the liner rupture, and that the most likely cause of failure was a design-related fatigue phenomenon.

Albumin Protein Impact on Early-Stage In Vitro Biodegradation of Magnesium Alloy (WE43).

Mg and its alloys are promising biodegradable materials for orthopedic implants and cardiovascular stents. The first interactions of protein molecules with Mg alloy surfaces have a substantial impact on their biocompatibility and biodegradation. We investigate the early-stage electrochemical, chemical, morphological, and electrical surface potential changes of alloy WE43 in either 154 mM NaCl or Hanks' simulated physiological solutions in the absence or presence of bovine serum albumin (BSA) protein. WE43 had the lowest electrochemical current noise (ECN) fluctuations, the highest noise resistance (Zn = 1774 Ω·cm2), and the highest total impedance (|Z| = 332 Ω·cm2) when immersed for 30 min in Hanks' solution. The highest ECN, lowest Zn (1430 Ω·cm2), and |Z| (49 Ω·cm2) were observed in the NaCl solution. In the solutions containing BSA, a unique dual-mode biodegradation was observed. Adding BSA to a NaCl solution increased |Z| from 49 to 97 Ω·cm2 and decreased the ECN signal of the alloy, i.e., the BSA inhibited corrosion. On the other hand, the presence of BSA in Hanks' solution increased the rate of biodegradation by decreasing both Zn and |Z| while increasing ECN. Finally, using scanning Kelvin probe force microscopy (SKPFM), we observed an adsorbed nanolayer of BSA with aggregated and fibrillar morphology only in Hanks' solution, where the electrical surface potential was 52 mV lower than that of the Mg oxide layer.

Corrosion Stiction in Automotive Braking Systems.

This review paper targets the corrosion-stiction phenomenon that can occur in automotive braking systems under static conditions in aggressive environments. The corrosion of gray cast iron discs can lead to a strong adhesion of the brake pad at the pad/disc interface that can impair the reliability and performance of the braking system. The main constituents of friction materials are initially reviewed in order to highlight the complexity of a brake pad. Corrosion-related phenomena, including stiction and stick-slip, are considered in detail to discuss the complex effect of the chemical and physical properties of friction materials on these phenomena. In addition, testing methods to evaluate the susceptibility to corrosion stiction are reviewed in this work. Electrochemical methods, including potentiodynamic polarization and electrochemical impedance spectroscopy, are useful tools for a better understanding of corrosion stiction. The development of friction materials with low susceptibility to stiction should follow a complementary approach targeting an accurate selection of the constituents, control of local conditions at the pad-disc interface, and the use of specific additives or surface treatments to reduce the corrosion susceptibility of gray cast-iron rotors.

Electronic properties and surface potential evaluations at the protein nano-biofilm/oxide interface: Impact on corrosion and biodegradation.

The formation of a protein nano-biofilm, which exhibits a special electronic behavior, on the surface of metals or oxide biomaterials considerably influences the crucial subsequent interactions, particularly the corrosion and biodegradation processes. This study discusses the impact of electrical surface potential (ESP) of a single or nano-biofilm of albumin protein on the electrochemical interactions and electronic property evolutions (e.g., charge carriers, space charge capacitance (SCC), and band bending) occurring on the surface oxide of CoCrMo implants. Scanning Kelvin probe force microscopy (SKPFM) results indicated that ESP or surface charge distribution on a single or nano-biofilm of the albumin protein is lower than that of a CoCrMo complex oxide layer, which hinders the charge transfer at the protein/electrolyte interface. Using a complementary approach, which involved performing Mott-Schottky analysis at the electrolyte/protein/oxide interface, it was revealed that the albumin protein significantly increases the SCC magnitude and number of n-type charge carrier owing to increased band bending at the SCC/protein interface; this facilitated the acceleration of metal ion release and metal-protein complex formation. The nanoscale SKPFM and electrochemical analyses performed in this study provide a better understanding of the role of protein molecules in corrosion/biodegradation of metallic biomaterials at the protein nano-biofilm/oxide interface.

Early failure of cement with loosening and dislocation of the femoral component in a unicompartmental knee replacement: a case report with microscopic assessment.

Background Medial unicompartimental knee artrhoplasty (UKA) is a valuable and well-known option in the treatment of medial osteoarthritis (OA). Early recovery and good results are usually reported. Failure mechanism include septic and mechanical loosening, bearing dislocation and lateral or patello-femoral joint OA evolution. The rare case of an atraumatic dislocation of the cemented femoral component of a UKA is presented together with a literature review and a microscopic analysis of the loosened component. Methods The case of a 60-years old man who suffered a UKA failure due to a complete loosening and migration of the cemented femoral component 5 months after its implantation is reported. A review of the literature pertaining early similar catastrophic failures is discussed. Furthermore a stereo-microscopic and scanning electronic microscopic evaluation of the femoral component was performed. Results A UKA-to-TKA revision was performed. Septic loosening was ruled out and one-year follow up showed patient satisfaction with good clinical and radiographic results. Few cases of complete dislocation of the UKA femoral component are reported in the literature. Macro- and microscopic evaluation showed an almost completely smooth surface at the cemented surface of the posterior condyle of the femoral component.   Conclusions Whilst mobile bearing dislocation is a well-known complication of UKA, few cases of this potentially catastrophic complication are reported in the literature. Early UKA failure with complete implant loosening may be determined by a suboptimal cementing technique with inadequate cement penetration into the trabecular bone. In the present case, the absence of cement penetration into the posterior condyle may be one of the reason of the component dislocation after standing up starting with the knee in a highly flexed position.

On Growth and Morphology of TiO2 Nanotubes on CP-Ti by Anodic Oxidation in Ethylene Glycol Electrolyte: Influence of Electrolyte Aging and Anodization Parameters.

Anodic oxidation of CP-Ti, for production of TiO2 nanotubes, has been extensively described in terms of the electrochemical mechanism of tubular growth or the effect of the parameters on the final tube morphology. Recently, a kinetic growth model was proposed to describe the distinct morphologies of the anodic oxide layer as phases of the nanotubular development process, offering a new perspective for the tuning of nanotube production. In this work, the anodizing behavior of a CP-Ti alloy in an ethylene glycol electrolyte was investigated in light of this new model. The final morphology of the nanotubes was characterized by SEM, considering the effects of electrolyte aging, the microstructure, the applied potential difference and time on the morphological development of nanotubes. Electrolyte aging was shown to lead to a decreased dissolution effect on the oxide. The applied potential difference was shown to lead to an increased dissolution effect and more rapid nanotube growth kinetics, while time resulted in extended dissolution. Moreover, the obtained results were analyzed considering a previous study focused on the anodizing behavior of the α- and ß-phases of Ti6Al4V alloy. Overall, the tube morphology resembled that obtained for the Al-containing α-phase of the Ti6Al4V alloy, but the growth kinetics were considerably slower on CP-Ti.

Effect of Thermal Treatment on Corrosion Behavior of AISI 316L Stainless Steel Manufactured by Laser Powder Bed Fusion.

The effect of post-processing heat treatment on the corrosion behavior of AISI 316L stainless steel manufactured by laser powder bed fusion (L-PBF) is investigated in this work. Produced stainless steel was heat treated in a broad temperature range (from 200 °C to 1100 °C) in order to evaluate the electrochemical behavior and morphology of corrosion. The electrochemical behavior was investigated by potentiodynamic and galvanostatic polarization in a neutral and acidic (pH 1.8) 3.5% NaCl solution. The microstructure modification after heat treatment and the morphology of attack of corroded samples were evaluated by optical and scanning electron microscopy. The fine cellular/columnar microstructure typically observed for additive-manufactured stainless steel evolves into a fine equiaxed austenitic structure after thermal treatment at high temperatures (above 800 °C). The post-processing thermal treatment does not negatively affect the electrochemical behavior of additive-manufactured stainless steel even after prolonged heat treatment at 1100 °C for 8 h and 24 h. This indicates that the excellent barrier properties of the native oxide film are retained after heat treatment.

On Growth and Morphology of TiO2 Nanotubes on Ti6Al4V by Anodic Oxidation in Ethylene Glycol Electrolyte: Influence of Microstructure and Anodization Parameters.

Different studies demonstrated the possibility to produce TiO2 nanotubes (TNTs) on Ti6Al4V alloy by electrochemical anodization. However, the anodizing behavior of α and ß-phases in organic electrolytes is not yet clarified. This study reports on the anodizing behavior of the two phases in an ethylene glycol electrolyte using different applied potentials and anodizing times. Atomic force and scanning electron microscopies were used to highlight the anodic oxides differences in morphology. It was demonstrated that the initial compact oxide grew faster over the ß-phase as the higher Al content of the α-phase caused its re-passivation, and the higher solubility of the V-rich oxide led to earlier pores formation over the ß-phase. The trend was inverted once the pores formed over the compact oxide of the α-phase. The growth rate of the α-phase TNTs was higher than that of the ß-phase ones, leading to the formation of long and well defined nanotubes with thin walls and a honeycomb tubular structure, while the ones grown over the ß-phase were individual, shorter, and with thicker walls.

Effect of Heat Treatment on Microstructure and Selective Corrosion of LPBF-AlSi10Mg by Means of SKPFM and Exo-Electron Emission.

The paper deals with the evolution of the microstructure of AlSi10Mg alloy obtained by laser powder bed fusion (LPBF), as a function of the post-processing heat treatment temperature. This was approached by complementary methods including FE-scanning electron microscopy, scanning Kelvin probe force microscopy and exo-electron emission techniques. The fast cooling rate of the LPBF process as compared to traditional casting produces a very fine microstructure with high mechanical properties and corrosion resistance. However, the LPBF-AlSi10Mg alloy can be susceptible to selective corrosion at the edge of the melt pools generated by the laser scan tracks. Post-process thermal treatments of the Al alloy induce a marked modification of the silicon network at melt pool edges, in particular at high temperature such as 400 °C. It was found that this is associated to a more homogeneous distribution of Volta potential. Analysis of exo-electron emission confirms the silicon diffusion during thermal treatment. The modification of the silicon network structure of the LPBF-AlSi10Mg during thermal treatment reduces the susceptibility to selective corrosion.

Single tracks data obtained by selective laser melting of Ti6Al4V with a small laser spot diameter.

Nowadays, advanced metal components with high geometrical complexity can be 3D printed by using the Selective Laser Melting (SLM) technology. Despite SLM resolution and accuracy are generally limited to some tenths of mm, it should be possible to produce finer and more precise details by applying lasers with a small spot diameter. However, to present date the data collected with small laser spot diameters are poor. In this work, experimental data describing the effects of laser power and scan speed on single track formation when applying a small laser spot diameter of 50 µm on Ti6Al4V powder are reported. SEM images and the extracted geometrical data characterizing the obtained single tracks are provided here, as well as their microstructural analysis and microhardness measurements.

Sealing porous anodic layers on AA2024-T3 with a low viscosity benzoxazine resin for corrosion protection in aeronautical applications.

In this paper, a 4-ethylphenol-para-phenylenediamine (4EP-pPDA) benzoxazine has been applied and cured on previously anodized AA2024-T3 substrates. The porous surface oxide layers obtained from sulfo-tartaric anodizing appeared to be highly impregnated by the benzoxazine resin, sealing the anodic films. Through rheological, morphological and chemical characterization, the curing process has been identified to be the key step for the impregnation to occur, related to the low viscosity of the 4EP-pPDA benzoxazine attained during thermal curing. Moreover, the typical surface porosity of the anodic layer reappeared after curing, offering a good anchoring to possible top coats. Finally, high and enduring barrier properties of this hybrid organic-inorganic layer have been highlighted through Electrochemical Impedance Spectroscopy (EIS) and correlated with recent results obtained by Molecular Dynamics Simulations (MDS). These barrier properties appeared to be strongly influenced by the curing process parameters, as has been assessed using alternative curing cycles limiting their duration and lowering the curing temperature. Consequently, adapting the curing process enables the optimization of the barrier properties of the system while respecting the dependence of the mechanical properties of the AA2024-T3 substrate on thermal treatment at high temperatures.

Possible production of ceramic tiles from marine dredging spoils alone and mixed with other waste materials.

Dredging spoils, due to their composition could be considered a new potential source for the production of monolithic ceramics. Nevertheless, abundance of coloured oxides in these materials preclude the possibility of obtaining white products, but not that of producing ceramics with a good mechanical behaviour. As goal of the present research we have produced and studied samples using not only dredging spoils alone, but also mixtures with other waste materials such as bottom ashes from an incinerator of municipal solid waste, incinerated seawage sludge from a municipal seawage treatment plant and steelworks slag. Blending of different components was done by attrition milling. Powders were pressed into specimens which were air sintered in a muffle furnace and their shrinkage on firing was determined. Water absorption, density, strength, hardness, fracture toughness, thermal expansion coefficient of the fired bodies were measured; XRD and SEM images were also examined. The fired samples were finally tested in acidic environment in order to evaluate their elution behaviour and consequently their environmental compatibility. It is observed that, although the shrinkage on firing is too high for the production of tiles, in all the compositions studied the sintering procedure leads to fine microstructures, good mechanical properties and to a limitation of the release of many of the most hazardous metals contained in the starting powders.