Growth of Anodic Layers on 304L Stainless Steel Using Fluoride Free Electrolytes and Their Electrochemical Behavior in Chloride Solution.

Anodic layers have been grown on 304L stainless steel (304L SS) using two kinds of fluoride-free organic electrolytes. The replacement of NH4F for NaAlO2 or Na2SiO3 in the glycerol solution and the influence of the H2O concentration have been examined. The obtained anodic layers were characterized by scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and potentiodynamic polarization tests. Here, it was found that, although the anodic layers fabricated within the NaAlO2-electrolyte and high H2O concentrations presented limited adherence to the substrate, the anodizing in the Na2SiO3-electrolyte and low H2O concentrations allowed the growth oxide layers, and even a type of ordered morphology was observed. Furthermore, the electrochemical tests in chloride solution determined low chemical stability and active behavior of oxide layers grown in NaAlO2-electrolyte. In contrast, the corrosion resistance was improved approximately one order of magnitude compared to the non-anodized 304L SS substrate for the anodizing treatment in glycerol, 0.05 M Na2SiO3, and 1.7 vol% H2O at 20 mA/cm2 for 6 min. Thus, this anodizing condition offers insight into the sustainable growth of oxide layers with potential anti-corrosion properties.

Degradation of primary nanoplastics by photocatalysis using different anodized TiO2 structures.

In recent years, plastic pollution has become an environmental problem requiring urgent attention. Recently, the release of nano-sized plastics (<1 µm) into the environment has raised concern due to the possible adverse effects that their small size can have on the trophic web. Advanced oxidation processes are efficient at removing organic pollutants such as dyes and pharmaceuticals, making them a viable approach for treating these hazardous materials. This study proposes the use of photocatalysis as an alternative for removing polystyrene nanoparticles (PS-NPs) from aqueous media. A comparative study was carried out to determine the photocatalytic activity of three different TiO2 photocatalysts synthesized by anodization. Elimination and degradation were monitored by turbidimetry, TOC, FTIR, and GC/MS, and the presence of carbonyl groups and intermediate products was recorded to confirm PS-NP degradation. Statistical analysis revealed that PS-NP elimination using TiO2/T and TiO2/M as photocatalysts was more efficient than with photolysis. The results indicate that the mixed structure (nanotubes/nanograss) reduces the concentration of PS-NPs in dispersion 2 times more efficiently than photolysis with UV light does. Despite the challenges posed by nanoplastic contamination, this study provides a useful remediation approach; a technique that, to date, has received little attention.

The Role of the Reactive Species Involved in the Photocatalytic Degradation of HDPE Microplastics Using C,N-TiO2 Powders.

Microplastics (MPs) are distributed in a wide range of aquatic and terrestrial ecosystems throughout the planet. They are known to adsorb hazardous substances and can transfer them across the trophic web. To eliminate MPs pollution in an environmentally friendly process, we propose using a photocatalytic process that can easily be implemented in wastewater treatment plants (WWTPs). As photocatalysis involves the formation of reactive species such as holes (h+), electrons (e-), hydroxyl (OH●), and superoxide ion (O2●-) radicals, it is imperative to determine the role of those species in the degradation process to design an effective photocatalytic system. However, for MPs, this information is limited in the literature. Therefore, we present such reactive species' role in the degradation of high-density polyethylene (HDPE) MPs using C,N-TiO2. Tert-butanol, isopropyl alcohol (IPA), Tiron, and Cu(NO3)2 were confirmed as adequate OH●, h+, O2●- and e- scavengers. These results revealed for the first time that the formation of free OH● through the pathways involving the photogenerated e- plays an essential role in the MPs' degradation. Furthermore, the degradation behaviors observed when h+ and O2●- were removed from the reaction system suggest that these species can also perform the initiating step of degradation.

Microplastic pollution reduction by a carbon and nitrogen-doped TiO2: Effect of pH and temperature in the photocatalytic degradation process.

Microplastics (MPs) are pollutants formed by plastics ≤ 5 mm and are present in marine and terrestrial environments. Due to their large surface to volume ratio and chemical surface properties, MPs adsorb hazardous chemicals from their surrounding environment. When MPs are consumed by fauna, they transfer those substances through the trophic chain. An essential issue of MPs is their disposal. Due to their size, the disposal methods commonly used for plastic items are not suited for MPs. Here, photocatalysis in an aqueous medium is proposed as an alternative to fight MPs pollution. Although the photocatalysis of MPs has been reported, the effect of operating variables in the process has not been investigated. To fill this gap, the impact of pH and temperature on the degradation process of HDPE MPs was investigated using C,N-TiO2 and visible light. Degradation was followed by mass loss, carbonyl index calculation and microscopy. It was found that photocatalysis at low temperature (0 °C) increases MPs' surface area by fragmentation, and low pH value (pH 3) favours hydroperoxide formation during photooxidation. By using the design of experiments tool, it was demonstrated that there is a combined effect of pH and temperature in the photocatalysis of HDPE MPs.

Bacterial and fungal biofilm formation on anodized titanium alloys with fluorine.

Orthopaedic device-related infections are closely linked to biofilm formation on the surfaces of these devices. Several modified titanium (Ti-6Al-4V) surfaces doped with fluorine were studied in order to evaluate the influence of these modifications on biofilm formation by Gram-positive and Gram-negative bacteria as well as a yeast. The biofilm studies were performed according to the standard test method approved by ASTM (Designation: E2196-12) using the Rotating Disk Reactor. Four types of Ti-6Al-4V samples were tested; chemically polished (CP), two types of nanostructures containing fluorine, nanoporous (NP) and nanotubular (NT), and non-nanostructured fluorine containing samples (fluoride barrier layers, FBL). Different species of Gram-positive cocci, (Staphylococcus aureus and epidermidis), Gram-negative rods (Escherichia coli, Pseudomonas aeruginosa), and a yeast (Candida albicans) were studied. For one of the Gram-positive (S. epidermidis) and one of the Gram-negative (E. coli) species a statistically-significant decrease in biofilm accumulation for NP and NT samples was found when compared with the biofilm accumulation on CP samples. The results suggest an effect of the modified materials on the biofilm formation.