Polymeric coatings represent a well-established protection system that provides a barrier between a metallic substrate and the environment. The development of a smart organic coating for the protection of metallic structures in marine and offshore applications is a challenge. In the present study, we investigated the use of self-healing epoxy as an organic coating suitable for metallic substrates. The self-healing epoxy was obtained by mixing Diels-Alder (D-A) adducts with a commercial diglycidyl ether of bisphenol-A (DGEBA) monomer. The resin recovery feature was assessed through morphological observation, spectroscopic analysis, and mechanical and nanoindentation tests. Barrier properties and anti-corrosion performance were evaluated through electrochemical impedance spectroscopy (EIS). The film on a metallic substrate was scratched and subsequently repaired using proper thermal treatment. The morphological and structural analysis confirmed that the coating restored its pristine properties. In the EIS analysis, the repaired coating exhibited diffusive properties similar to the pristine material, with a diffusivity coefficient of 1.6 x 10(-6) cm(2)/s (undamaged system 3.1 x 10(-6) cm(2)/s), confirming the restoration of the polymeric structure. These results reveal that a good morphological and mechanical recovery was achieved, suggesting very promising applications in the field of corrosion-resistant protective coatings and adhesives.

Magnesium alloys are an exciting challenge for the biomaterials field given their well-established biodegradability and biocompatibility. However, when exposed to biological fluids, their rapid degradation and hydrogen release are the main drawbacks for clinical applications. This work aimed to investigate the influence of the current density applied during the plasma electrolytic oxidation (PEO) treatment on the durability of an AZ31 magnesium alloy. In particular, specific interest was directed to the degradation rate undergone by the PEO coating, obtained under two different current density conditions, when exposed to Hank's solution at 37 degrees C to simulate the physiological environment, employing the techniques of potentiodynamic polarization and electrochemical impedance spectroscopy. Experimental results highlighted that the plasma electrolytic oxidation technique resulted in an improvement in the corrosion resistance of the magnesium alloy in the test solution. The current density affected the morphology of the coating. In particular, the anodic oxide coating obtained by applying the highest current density showed a higher thickness and fewer but larger pores, while the lowest current density generated a thinner PEO coating characterized by several but smaller pores. Surprisingly, the best corrosion resistance has been exhibited by the anodic oxide coating grown at the highest current density.

Internal prosthesis and grafts are currently made of Ti alloys, stainless steels and Co-Cr alloys. In spite of excellent biocompatibility, they show some drawbacks that concern their mechanical properties (e.g. elastic modulus) and the need of secondary surgery for removing the implant. For this reason, a growing attention has been focused on biodegradable materials that can be absorbed into the body after tissue remodelling. In particular, Mg alloys are promising candidates for temporary implants thanks to their high biocompatibility, biodegradability and good mechanical properties that match those of human bone. In this work, the surface modifications of biodegradable AZ31 alloy were analysed after immersion for 15 days in a physiological solution (NaCl 0.09%) by using X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and scanning electron microscopy (SEM) techniques. XPS analysis of the surface of as-supplied AZ31 alloy showed the presence of MgO, whereas after immersion in the physiological solution, only Mg (OH)(2) was detected. The result has been discussed with reference to literature data. From the photoemission spectra and quantitative analysis, a small amount of Ca (about 2 wt%) was also detected.

An efficient yet accurate procedure was developed for the seismic assessment of reinforced concrete (RC) bridges subject to chloride-induced corrosion. The procedure involves using incremental modal pushover analysis to assess corroded bridges as an alternative and less computationally demanding approach to non-linear dynamic analysis. A multi-physics finite-element analysis is performed to evaluate the effects of chloride-induced corrosion on bridge columns. In doing so, chloride ingress in concrete is numerically simulated as a diffusion process by considering the effects of temperature, humidity, corrosion-induced cover cracking and concrete aging. The estimated chloride concentration is then employed to evaluate the corrosion current density, from which the effects of corrosion on reinforcement, cracked cover concrete, confinement and plastic hinge length can be determined for subsequent non-linear static analysis. A case study of a typical bridge structure is presented. The proposed procedure can be used to assess the seismic performance of irregular RC bridges exposed to severe corrosive environments.

Fluoride-based mouthwashes and gels are preventive measures in countering demineralization and caries but, modifying environmental acidity, can reduce the wet corrosion resistance of orthodontic alloys. To evaluate chemical stability, in vitro experiments were conducted on stainless steel and nickel-titanium wires, weighed before and after immersion in household fluorinated mouthwashes and gels, measuring weight variations and elution of metal ions from acid corrosion phenomena. Elution samples were analyzed by inductively coupled plasma mass spectrometry, detecting residual ion concentration, while surface changes were analyzed under scanning electron microscopy. Results showed stainless steel wires do not undergo significant erosion when exposed to most fluorinated mouthwashes but, at prolonged exposure, alloys elute gradually greater amounts of metals and Ni-Ti wires become more sensitive to some mouthwashes. Ions' elution varies considerably, especially for Ni-Ti wires, if exposed to household fluorinated gels, for which significant negative values were obtained. Changes, affecting wires' outer layer, negatively act on shiny appearance and luster, reducing corrosion resistance. Although examined orthodontic wires showed good chemical stability and low toxicity, surface corrosion from exposure to fluorinated agents was observed. Home use must be accompanied by clinician prescription and, for household dental gels, must follow manufacturers' recommendations, ensuring prophylactic action without damaging alloys surfaces.

The need for greater efficiency in the field of shallow closed-loop geothermal systems has led to the proposal for groutless coaxial geothermal heat exchangers made of steel. In terms of heat transfer performance, they are superior to traditional grouted U-shaped or double-U plastic ones, but they are still not well accepted by the market because there are doubts about their safety in terms of reliability. This work aims to explore the detectability of defects that can lead to external pipe failures such as corrosion or leakages, using active infrared thermography, in order to contribute to the proposal of possible on-site inspection procedures. The experimental work was carried out in the laboratory on a pipe sample that was made of threaded-jointed sections of steel. Defects of various entities have been artificially introduced to simulate internal corrosion, generally related to the presence of chemicals in the heat transfer fluid. Different failures in threaded joints were also simulated and detected after the processing of thermal data.

A preliminary assessment for the Divertor Tokamak Test facility Vacuum Vessel (VV) water chemistry was performed using both experiments and simulations. The requirement to use 8000 ppm B in water enriched with 95% 10B as a neutron shield implies that water has a pH60C=3.6. Materials in contact with the borated water are stainless steel type, 316LN, resistant to general corrosion from borated water. Corrosion, however, is a complex phenomenon affected both by water chemistry and material characteristics. No water chemistry guidelines exist for nuclear fusion cooling circuits so the assessment was based on nuclear fission power plants operational experience. The need to add additives to minimize corrosion was assessed using metal release experiments and simulations with the use of computer codes devoted to the estimation of activated corrosion products (ACPs) production and transport. The release of ions induced by general corrosion was found to be more influenced by water chemistry (more releases were measured in the borated water environment than UPW) than microstructure (base metal vs welds). The possible addition of hydrogen in the DTT VV cooling circuit was also assessed, but without considering water radiolysis at this stage. It was found that at these low temperature (60-80°C) the addition of hydrogen seem not beneficial if the oxygen content can be maintained low.

Source for production of ion of deuterium extracted from rf plasma (SPIDER) is the 100 keV negative ion source prototype of the ITER neutral beam injector. The cooling plant is one of the SPIDER auxiliary systems where ultrapure water (UPW) is used as the cooling media, thanks to its advantageous properties such as good cooling performance and high resistivity. Water resistivity needs to be maintained above certain values during SPIDER operation to enable the electrical insulation of in-vessel components that operate at different voltages. Nonetheless, degradation of water resistivity was observed in some circuits during operation. Water resistivity degradation had a negative impact on the SPIDER experimental campaign since it limits cooling plant availability. To understand the cause for the observed water degradation, sampling points were installed to sample water during operation. Ad hoc experiments have been performed on the worst affected circuit, and water samples were analyzed by inductively coupled plasma mass spectrometry (ICP-MS). Circulation experiments were conducted at constant temperature, pressure, and flow rate to assess water degradation by monitoring water conductivity increase. ICP-MS analyses on water from the worst affected circuit revealed the presence of Cu in relevant quantities and Zn. Corrosion induced by the presence of a non-compatible component with SPIDER requirements was found. The identified component was made of a galvanized steel plate, carbon steel, and brass. This was found responsible for the contamination of the cooling loop and its water properties' degradation.

The Divertor Tokamak Test (DTT) vacuum vessel (VV) is a toroidal chamber that ensures an enclosed vacuum environment for the plasma, a confinement barrier, and temperature control. Water flows in the double-shell D-shaped VV cross-sectional structure made from stainless steel to operate at a set temperature. Beyond temperature control, the water cooling circuit needs to act as a neutron shielding media to protect the structures installed outside of the VV, namely, the superconducting coils. The shielding function is achieved due to the addition of boric acid in the water. The requirement on the borated water for the DTT VV is to have 8000-ppm B solution highly enriched in ¹⁰B (95% ¹⁰B). Given the lack of water chemistry guidelines for fusion power plants, the water chemistry requirements from fission power plants were investigated. In this work, general corrosion of stainless steel, 316L type family, in concentrated borated water solutions was investigated experimentally using metal release test. Samples were exposed to ultrapure water (UPW) and 8000-ppm B borated water at 80 °C for one week to quantify the amount of ions released in solution. 316L general corrosion was studied considering the different water chemistries, UPW versus borated water, and steels microstructures. DTT VV presents many welded joints, so general corrosion of welding-induced microstructure was here investigated compared to 316L base microstructure. The release of ions from general corrosion was found to be more influenced by water chemistry than microstructure.

In this work, engineered stimuli-responsive mesoporous silica nanoparticles (MSNs) were developed and exploited in polymer coatings as multifunctional carriers of a typical corrosion inhibitor, benzotriazole (BTA). In detail, a new capping system based on a BTA-silver coordination complex, able to dissolve in acid and alkaline conditions and to simultaneously tailor the BTA release and the capture of chloride ions, was properly designed and realized. Acrylic coatings embedding the engineered MSNs were deposited onto iron rebar samples and tested for their protective capability in acid and alkaline environments. Results highlighted the high potential of the proposed system for the protection of metals, due to the synergistic effect of the mesoporous structure and the capping system, which guaranteed both the sequestration of chloride ions and the ondemand release of the effective amount of anticorrosive agents able to ensure the enhanced protection of the substrate.

When a free nucleus absorbs or emits a gamma ray, it recoils to conserve energy, just like a gun recoils after shooting a bullet. Nuclei bound to a crystal lattice conserve energy when they absorb or emit gamma rays from a nuclear transition as they are fixed so their movement is restricted. This restriction is recoilless nuclear resonance fluorescence--the Mössbauer effect. The energy transmitted through a sample reveals its electronic and molecular structure and magnetic properties but only when the atoms in the source and sample are the same isotope--Co/Fe is the most common couple. So, many of its applications are to identify iron species or how they change as a function of environmental conditions, like corrosion. A bibliometric map identified six major clusters centred around: nanoparticles and magnetite (FeO), crystal structure and spectroscopy, oxidation and catalysis, X-ray diffraction (XRD) and Raman spectroscopy, Fe and cathodes, and Co and thin films. In the last 30 years, the number of articles per year that mention the technique has hovered around 1250. More recently, Mössbauer spectroscopy has experienced a great rediscovery, particularly in the industrial sector for the solution of some problems, but also in space exploration.

A generalized cyclic steel model characterized by isotropic and kinematic hardening, inelastic buckling in compression and corrosion of rebars in reinforced concrete (RC) structures is presented. The model has been implemented in a fiber code, to perform seismic analyses of RC sections. The model is particularly accurate with respect to experimental cyclic behavior of rebars with buckling in compression when the strain does not exceed 1.5%. Twelve configurations of RC cross sections were selected as case studies for three geometries and different steel arrangements, assumed representative of RC columns or bridge piers (in a suitable scale). Each section was subjected to two groups of cyclic curvature histories representative of severe seismic loads, not far from collapse. Different axial loads and corrosion percentages (no corrosion, moderate, or high) have been selected to perform cyclic parametric analyses. One of the cases was taken from an experimental test on columns, deriving also steel characteristics used in all numerical cases. The results of the comparison among RC sections have been discussed. Numerical results show that the maximum compressive strain for steel rebars is always smaller than 1.5%, therefore the proposed steel model is accurate and represents a valid tool for structural assessment. Corrosion reduces RC section capacity, affecting various rebar mechanical characteristics, in particular buckling behavior.

In this paper, Nb, NbN, and Nb/NbN thin films were successfully deposited on AISI 304 stainless steel (304 SS) as the bipolar plate (BPP) for proton-exchange membrane fuel cell (PEMFC) by employing a radio-frequency (RF) magnetron sputtering system. Corrosion assessments in simulated PEMFC operating conditions (1 M H2SO4+ 2 mg/kg HF, 70 degrees C) revealed that the Nb and NbN coatings significantly improved the corrosion resistance of the 304 SS substrates. The Nb and NbN deposited samples at 350 degrees C exhibited superior corrosion resistance compared to those coated at 25 degrees C. Potentiostatic tests were also performed at the constant potentials of +0.644 and -0.056 V vs. Ag/AgCl to simulate the cathodic and anodic PEMFC conditions, respectively. The minimum current densities were recorded for the Nb coating in both anodic and cathodic conditions. Compared with the 304 SS substrate, all coatings showed lower interfacial contact resistance (ICR) and higher hydrophobicity. Among the tested coatings, the Nb coating exhibited the smallest ICR (9 m omega center dot cm(2)at 140 N/cm(2)). The results of this investigation revealed that the Nb and NbN coatings deposited by RF magnetron sputtering on 304 SS can be regarded as promising candidates for BPPs in PEMFCs.

This study evaluates mechanisms of biogenic mineral formation induced by bacterial iron reduction for the stabilization of corroded iron. As an example, the Desulfitobacterium hafniense strain TCE1 was employed to treat corroded coupons presenting urban natural atmospheric corrosion, and spectroscopic investigations were performed on the samples' cross-sections to evaluate the corrosion stratigraphy. The treated samples presented a protective continuous layer of iron phosphates (vivianite Fe(PO)8H2Oand barbosalite FeFe(PO)(OH)), which covered 92% of the surface and was associated with a decrease in the thickness of the original corrosion layer. The results allow us to better understand the conversion of reactive corrosion products into stable biogenic minerals, as well as to identify important criteria for the design of a green alternative treatment for the stabilization of corroded iron.

Three-dimensional chemical mapping was adopted to investigate an ancient fire-gilded buckle found in Rome. Time-of-flight secondary ion mass spectrometry (ToF-SIMS) and scanning electron microscopy with energy dispersive spectroscopy (SEM-EDS) were used to detect and locate degradation products aiming to identify the alteration processes. Inorganic and organic compounds present in the outermost part of such a class of cultural heritage objects can be considered the result of long-term interaction with the burial environment. ToF-SIMS depth profiling experiments can provide chemical information at the molecular level and high resolved spatial information (about 1 ?m laterally, and 1 nm in depth). In this work, the attention was focused on the identification and localization of the ionic and molecular species involved in the degradation process. Results showed the presence of copper oxides, chlorides, and sulfides as common corrosion products but also the presence of species related to copper and bronze corrosion process, such as atacamite and its polymorphs. 3D maps for all the relevant molecular species allowed to visualize at the same time the eruption of copper chlorides throughout the micro/nanochannels present on the gold surface, the recrystallization of compounds of minor elements from the substrate, a pathway followed by silico-aluminates from the surface toward the internal corrosion layers, but mostly the evidence of biological activity of Sulfur Reducing Bacteria (SRB) living in anaerobic conditions.

The aim of this study was to develop smart materials with stimuli-responsive properties for the long-term protection of steel. The idea was to obtain a tailored and controlled release of protective agents in response to the environment stimuli. First, the protective efficacy of three inhibitors containing a carboxylic moiety, such asp-aminobenzoic (pAB), succinic (SA), and caffeic (CA) acids, was investigated in alkaline chloride solutions. The results revealed that pAB is the most effective protective agent, significantly better than SA and CA. It is surprising that the steel surface in the pAB solution remains unchanged even after 5 months of corrosion treatment, whereas the formation of degradation products in the SA and CA solutions was observed after only 6 days. Based on these findings, pAB was selected and used for the functionalization of silica nanoparticles and layered double hydroxides (LDHs) that can act as delivery vehicles and as an inhibitor reservoir. Specifically, pAB was chemisorbed on silica amino groupsviaan amide bond, and this makes possible a gradual inhibitor release induced by an alkaline environment. The intercalation of pAB in its anionic form into the LDHs structure is responsible for a completely different behavior since the release is induced by chloride ions and occurs by an anionic exchange reaction. Thus, these materials play a dual role by acting as an inhibitor reservoir and by capturing chlorides. These findings reveal that it is possible to create a reservoir of corrosion inhibitors gradually released on demand based on the chemical environment. The stimuli-responsive properties and the complementary protective action of inhibitor-loaded silica and LDHs make them attractive for the long-term protection of steel and open the way for innovative solutions in the preservation of concrete cultural heritage.

The long-term interaction between Cu-based alloys and environmental species gives rise to the formation of different and sometimes unusual compounds (i.e., the patina) with distinctive chemical and structural features as a function of the peculiar characteristics of the context. In this paper, we describe some representative case studies concerning degraded bronze Roman valuable or common use objects, and we show that an attentive study at a microscale level, as for forensic analysis, allows one to understand the chemical processes that underlie the formation of the surface alteration products. The achieved information describe fragments of chemical life and disclose the complex chemical changes suffered by the artifacts, allowing one to write their chemical biography. This challenging approach expands the panorama of available information and demonstrates that it is possible to reconstruct the different modes through which the bronze surfaces and interfaces have interacted with environmental species, organic matter, and microorganisms, opening up a new possibility to describe complex environmental chemical stories, in certain cases interrelated.

Neutron scattering in combination with scanning electron and atomic force microscopy were employed to quantitatively resolve elemental composition, nano- through meso- to metallurgical structures and surface characteristics of two commercial stainless steel orthodontic archwires--G&H and Azdent. The obtained bulk composition confirmed that both samples are made of metastable austenitic stainless steel type AISI 304. The neutron technique's higher detection sensitivity to alloying elements facilitated the quantitative determination of the composition factor (CF), and the pitting resistance equivalent number (PREN) for predicting austenite stability and pitting-corrosion resistance, respectively. Simultaneous neutron diffraction analyses revealed that both samples contained additional martensite phase due to strain-induced martensite transformation. The unexpectedly high martensite content (46.20 vol%) in G&H was caused by combination of lower austenite stability (CF = 17.37, p = .03), excessive cold working and inadequate thermal treatment during material processing. Together, those results assist in revealing alloying recipes and processing history, and relating these with corrosion resistance and mechanical properties. The present methodology has allowed access to unprecedented length-scale (µm to sub-nm) resolution, accessing nano- through meso-scopic properties. It is envisaged that such an approach can be extended to the study and design of other metallic (bio)materials used in medical sciences, dentistry and beyond.

Aluminum alloys are considered one of the best choices as structural material for aerospace applications, guaranteeing lightweight and strength at the same time. In this work Al-Li alloys with 6% (wt %) of Li are used. To increase further the strength of the material, new alloys are produced by adding different quantities (0.01, 0.05, 0.1, and 0.5 wt %) of rare earths (Nd, Y, Ce, Pr). The microstructure of the samples is examined using scanning electron microscope (SEM). The improvement of the mechanical properties is measured by means of Vickers hardness tests. Also the corrosion resistance of the alloys is evaluated with open circuit voltage (OCV) measurements. At the same time, the thermophysical properties are measured as well, at various temperatures, from 80 to 500 degrees C. The results show that an increase in the Rare Earth (RE) content causes an increase in the mechanical properties and a reduction in the thermal conductivity. Regarding the corrosion resistance, a maximum in the corrosion properties can be found for 0.05% of RE.

The use of polymeric coatings with self-healing ability is a viable approach for a new smart corrosion protection strategy. Polymer systems are usually applied on a metal surface to provide an effective barrier against the corrosive species. The protective coatings have to delay the inexorable water uptake, blister or crack formation and delamination. Among self-repairing polymers, in this area of interest, Diels-Alder epoxy resins arc particularly appealing for coating application, because the products and intermediates obtained during the healing treatment are stable to aggressive environments. such as the major oxidation agents, air and water. In addition, the chemical stability and crosslinked structure of epoxies are preserved and ensure the coating functionality. An intrinsic mendable epoxy system, containing bifunctional adducts, has been prepared by Diels-Alder reaction. Optical microscopy and nanoindention tests validated the morphological and structural recovery of the coating. Immersion test in saline solution revealed the complete restoration of the corrosion protection for a healed sample.