A comprehensive review on anticorrosive/antifouling superhydrophobic coatings: Fabrication, assessment, applications, challenges and future perspectives.

Superhydrophobicity (SHP) is an incredible phenomenon of extreme water repellency of surfaces ubiquitous in nature (E.g. lotus leaves, butterfly wings, taro leaves, mosquito eyes, water-strider legs, etc). Historically, surface exhibiting water contact angle (WCA) > 150° and contact angle hysteresis <10° is considered as SHP. The SHP surfaces garnered considerable attention in recent years due to their applications in anti-corrosion, anti-fouling, self-cleaning, oil-water separation, viscous drag reduction, anti-icing, etc. As corrosion and marine biofouling are global problems, there has been focused efforts in combating these issues using innovative environmentally friendly coatings designs taking cues from natural SHP surfaces. Over the last two decades, though significant progress has been made on the fabrication of various SHP surfaces, the practical adaptation of these surfaces for various applications is hampered, mainly because of the high cost, non-scalability, lack of simplicity, non-adaptability for a wide range of substrates, poor mechanical robustness and chemical inertness. Despite the extensive research, the exact mechanism of corrosion/anti-fouling of such coatings also remains elusive. The current focus of research in recent years has been on the development of facile, eco-friendly, cost-effective, mechanically robust chemically inert, and scalable methods to prepare durable SHP coating on a variety of surfaces. Although there are some general reviews on SHP surfaces, there is no comprehensive review focusing on SHP on metallic and alloy surfaces with corrosion-resistant and antifouling properties. This review is aimed at filling this gap. This review provides a pedagogical description with the necessary background, key concepts, genesis, classical models of superhydrophobicity, rational design of SHP, coatings characterization, testing approaches, mechanisms, and novel fabrication approaches currently being explored for anticorrosion and antifouling, both from a fundamental and practical perspective. The review also provides a summary of important experimental studies with key findings, and detailed descriptions of the evaluation of surface morphologies, chemical properties, mechanical, chemical, corrosion, and antifouling properties. The recent developments in the fabrication of SHP -Cr-Mo steel, Ti, and Al are presented, along with the latest understanding of the mechanism of anticorrosion and antifouling properties of the coating also discussed. In addition, different promising applications of SHP surfaces in diverse disciplines are discussed. The last part of the review highlights the challenges and future directions. The review is an ideal material for researchers practicing in the field of coatings and also serves as an excellent reference for freshers who intend to begin research on this topic.

Efficacy of imidazolium and piperidinium based ionic liquids on inhibiting biofilm formation on titanium and carbon steel surfaces.

In the present study, the efficacies of three different cationic and anionic ionic liquids (ILs) on biofilm formation on materials used in cooling water systems were evaluated. Two imidazolium based ILs; 1-Ethyl 3-Methylimidazolium tetrafluoroborate - (IL-E) and 1-Butyl-3-methylimidazolium chloride - (IL-I) with anionic fluoride and chloride groups and one piperidinium based IL, N-methyl-N-propylpiperidinium bis(trifluoromethylsulfonyl)imide - (IL-M) with fluoromethyl group as anion were used. The efficacy of these ILs were evaluated on planktonic and sessile cells of major biofilm formers in cooling water systems using Gram negative bacterium Pseudomonas sp. and Gram positive bacterium Bacillus sp. Further their effect on inhibiting biofilm formation on titanium and carbon steel surfaces were also evaluated. Results showed that planktonic cells of Pseudomonas sp. and Bacillus sp. were effectively inhibited by 25 ppm of IL-M and IL-E, respectively. For both bacteria, 50 ppm of IL-I was enough to inhibit and eradicate the sessile cell formation. Among the three ILs, IL-E was the best in inhibiting the adhesion of bacterial cells on Ti and CS surfaces. These results suggest that Imidazolium based ILs are effective in controlling sessile cell formation and eradicating mature biofilm as compared to piperidinium based IL. Further, Imidazolium based IL with fluoride anion (IL-E) was the best in inhibiting adhesion of these bacterial cells and thereby biofilm formation on material surfaces. This study establishes the feasibility of using ILs in cooling water system for bacterial biofilm control along with other conventional biofouling control methods.

Antibacterial and cytotoxic assessment of poly (methyl methacrylate) based hybrid nanocomposites.

Poly (methyl methacrylate) (PMMA) is an extensively used implant material in biomedical devices. Biofilm formation creates issues in PMMA-based biomedical implants, while emergence of drug resistant pathogens poses an additional complication. Hence development of surfaces that resist bacterial colonisation is extremely desirable. In this context, nanomaterials are among the potential choices. In the present work, nanocomposites (NCs) were developed by incorporation of chemically synthesized nanoparticles of CuO, cetyl trimethyl ammonium bromide (CTAB) capped CuO and ZnO (singly and in combination) in PMMA. The efficacy of these NCs was assessed against Staphylococcus aureus (S. aureus) and Escherichia coli (E. coli) bacteria which are prevalent in many implant-associated infections. Results revealed species-specific response of the bacteria towards nanomaterials. CuO NC (0.1% (w/v)) was more effective against E. coli, while CTAB capped CuO NC and ZnO NC were very effective against S. aureus. Furthermore, combination of nanoparticles improved efficacy of nanocomposites against both the bacterial species. In vitro cytotoxicity assay using L6 myoblast cell line showed that all NCs at 0.1% (w/v) were biocompatible, showing >85% cell viability. The present study suggests that combination of NPs is a promising option to combat implant infection by multiple organisms.

A silver nanoparticle loaded TiO2 nanoporous layer for visible light induced antimicrobial applications.

A nanoporous TiO2 layer was formed on commercially pure titanium by a simple anodization method in aqueous hydrofluoric acid (HF) medium. Silver nanoparticles (AgNP) were loaded into the nanoporous TiO2 layer by UV light irradiation. The morphology, chemical composition and photocatalytic activity of the modified titanium surfaces were characterized by scanning electron microscopy, Raman spectroscopy, X-ray photoelectron spectroscopy and UV-vis absorption spectroscopy techniques. The redox behavior of the AgNP loaded TiO2 layer was analyzed by cyclic voltammetry (CV) studies. The impedance behavior of the nanoporous TiO2 layer with and without AgNP was investigated by electrochemical impedance spectroscopy (EIS). The antibacterial effect of the AgNP loaded TiO2 layer was evaluated using Pseudomonas sp. and Bacillus sp. cultures. The efficacy of this modified layer to act as an antibacterial agent to minimize biofouling of titanium is demonstrated in this investigation.

Studies of detailed biofilm characterization on fly ash concrete in comparison with normal and superplasticizer concrete in seawater environments.

In cooling water systems, many concrete structures in the form of tanks, pillars and reservoirs that come in contact with aggressive seawater are being deteriorated by chemical and biological factors. The nuclear industry has decided to partially replace the Portland cement with appropriate pozzolans such as fly ash, which could densify the matrix and make the concrete impermeable. Three types of concrete mixes, viz., normal concrete (NC), concrete with fly ash and superplasticizer (FA) and concrete with only superplasticizer (SP) were fabricated for short- and long-term exposure studies and for screening out the better concrete in seawater environments. Biofilm characterization studies and microscopic studies showed excellent performance of FA concrete compared to the other two. Laboratory exposure studies in pure cultures of Thiobacillus thiooxidans and Fusarium oxysporum were demonstrated for the inhibition of microbial growth on fly ash. Epifluorescence and scanning electron microscopic studies supported the better performance of the FA specimen. Thus, the present study clearly showed that FA concrete is less prone to biofilm formation and biodeterioration.

Studies to control biofilm formation by coupling ultrasonication of natural waters and anodization of titanium.

The main objective of this study was to investigate the combined effect of ultrasonication of natural waters and anodization of titanium on microbial density and biofilm formation tendency on titanium surfaces. Application of 24 kHz, 400 W high power ultrasound through a 14 mm horn type SS (stainless steel) Sonicator with medium amplitude of 60% for 30 min brought about three order decrease in total bacterial density of laboratory tap water, cooling tower water and reservoir water and two order decrease in seawater. Studies on the effect of ultrasonication on dilute pure cultures of Gram-negative and Gram-positive bacteria showed five order and three order decrease for Pseudomonas sp. and Flavobacterium sp. respectively and two order and less than one order decrease for Bacillus sp. and Micrococcus sp. respectively. Ultrasonication increased lag phase and reduced logarithmic population increase and specific growth rate of Gram-negative bacteria whereas for Gram-positive bacteria specific growth rate increased. Studies on the biofilm formation tendency of these ultrasonicated mediums on titanium surface showed one order reduction under all conditions. Detailed biofilm imaging by advanced microscopic techniques like AFM, SEM and epifluorescence microscopy clearly visualized the lysed/damaged cells and membrane perforations due to ultrasonication. Combination of ultrasonication and anodization brought about maximum decrease in bacterial density and biofilm formation with greater than two order decrease in seawater, two order decrease in Bacillus sp. culture and more than four order decrease in Flavobacterium sp. culture establishing the synergistic effect of anodization and ultrasonication in this study.

Studies on the distribution of bacterial isolates in rare earth environment.

Rare earth soil is precious, but very common across Arabian coast especially in Chavara, (Quilon district, Kerala) south west coast of India. They are widely distributed but usually occur in small amounts and enhance the soil properties. In the present study, 18 different bacterial isolates were identified from three different samples such as soil and biofilm formed on metal surfaces from the rare earth environment of Chavara using 16S rDNA gene sequencing. The accumulation of rare earth elements (REE) by microbes was studied using FT-IR analysis. In the FTIR spectrum of the test system, a peak at 1548 and 1449 cm(-1) indicates the presence of aromatic nuclei (carboxylic acid), while C=C stretch for C-O-C group was noticed at 1237 cm(-1). Thus significant variations in the peak position confirm the presence of carboxyl group and thus it was confirmed that rare earth elements induce the bacteria to produce carboxylic acid and thereby accumulate rare earth elements.

Accumulation of rare earth elements by siderophore-forming Arthrobacter luteolus isolated from rare earth environment of Chavara, India.

In this study, Arthrobacter luteolus, isolated from rare earth environment of Chavara (Quilon district, Kerala, India), were found to produce catechol-type siderophores. The bacterial strain accumulated rare earth elements such as samarium and scandium. The siderophores may play a role in the accumulation of rare earth elements. Catecholate siderophore and low-molecular-weight organic acids were found to be present in experiments with Arthrobacter luteolus. The influence of siderophore on the accumulation of rare earth elements by bacteria has been extensively discussed.

Studies on microbiologically influenced corrosion of SS304 by a novel manganese oxidizer, Bacillus flexus.

A manganese oxidizing bacterium was isolated from the surface of steel scraps and biochemical tests and 16S rRNA sequencing analysis confirmed the isolate as Bacillus flexus. Potentiodynamic polarization curves showed ennoblement of open circuit potential, increased passive current, a lowering of breakdown potential, active re-passivation potential and enhanced cathodic current in the presence of B. flexus. Adhesion studies with B. flexus on SS304 specimens with different surface treatments demonstrated decreased adhesion on passivated and FeCl(3) treated specimens due to the removal of MnS inclusions. The present study provides evidence that surface treatment of stainless steels can reduce adhesion of this manganese oxidizing bacterium and decrease the probability of microbiologically influenced corrosion.

Bioaccumulation of cerium and neodymium by Bacillus cereus isolated from rare earth environments of Chavara and Manavalakurichi, India.

Rare earth elements (REEs) are among the common minerals in the Rare earth environment that are very precious and also enhance soil properties. The aim of this present study is to evaluate the accumulation of REEs by bacterial isolates of rare earth environment. Morphological and biochemical characterization were done for 37 bacterial isolates and also molecular studies were carried out using 16S rRNA sequencing method. The assessment of REEs composition in soil samples of Chavara and Manavalakurichi analyzed using Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) showed the abundance of Cerium and Neodymium among lanthanides. The bioaccumulation study of rare earth elements by Bacillus cereus were accomplished employing FT-IR spectrum and ICP-OES analysis. The significant accumulation of rare earth elements especially Cerium and Neodymium was noticed in Bacillus cereus isolated from rare earth environment.