Zero resistance ammeter of metallic alloys in aqueous solutions

In the present work, the corrosion current density of a low carbon steel, a pure aluminum, a stainless steel, a copper–nickel alloy were obtained in 1 M NaOH, 1 M KCl, 1 M NaCl, 1 M H₂SO₄ solutions, respectively. The obtained corrosion data from the optical interferometry technique, as a zero resistance Ammeter were compared with corrosion data obtained on the same alloys, in the specified solutions, from an electronic zero resistance-Ammeter as well as from the linear polarization method. The comparison among the three techniques indicates that there is a contrast in the results among the investigated alloys. In general, the results of the optical interferometry were found to fall in between the corrosion values of the zero resistance ammeter and the linear polarization method, because the technique works based on the electromagnetic principle, in the absence of electronic noise. As a result, the optical interferometry can be considered as a useful zero resistance-Ammeter for measuring the corrosion current density of metallic electrodes in aqueous solutions, at the open circuit potential of the electrodes in the aqueous solutions.     

Interferometric Sensor for Electrochemical Studies of Metallic Alloys in Aqueuos Solution

In a previous study a mathematical model relating surface and bulk behaviors of metals in aqueous solution was developed. The model was established based on principles of holographic interferometry for measuring microsurface dissolution, i.e., mass loss, and on those of electrochemistry for measuring the bulk electronic current, i.e., corrosion current. In the present work, an interferometric sensor was built based on the above model, and the corrosion current density of coated copper and brass in seawater were obtained using this sensor. The interferometric sensor was also utilized for the first time to measure the initial stage of the anodization process (oxidation) of aluminium samples in aqueous solution. This was carried out chemically in different acid concentrations (3.125–25% H₂SO₄) at room temperature. The sensor was further used for observation of catalytic activities, i.e., pitting corrosion, which occurred subsequent to the anodization of the aluminium samples in aqueous solutions, after an oxide film had been formed.     

Measurement of the a.c. impedance of aluminium samples by holographic interferometry

In the present investigation, holographic interferometry was utilized for the first time to measure the alternating current (a.c.) impedance of aluminium samples during the initial stage of anodization processes in aqueous solution without any physical contact. The anodization process (oxidation) of the aluminium samples was carried out chemically in different sulphuric acid concentrations (0.5–3.125% H₂SO₄) at room temperature. In the mean time, a method of holographic interferometric was used to measure the thickness of anodization (oxide film) of the aluminium samples in aqueous solutions. Along with the holographic measurement, a mathematical model was derived in order to correlate the a.c. impedance of the aluminium samples in solutions to the thickness of the oxide film of the aluminium samples which forms due to the chemical oxidation. The thickness of the oxide film of the aluminium samples was measured by the real-time holographic interferometry. Consequently, holographic interferometry is found very useful for surface finish industries especially for monitoring the early stage of anodization processes of metals, in which the thickness of the anodized film as well as the a.c. impedance of the aluminium samples can be determined in situ. In addition, a comparison was made between the a.c. impedance values obtained from the holographic interferometry measurements and from measurements of electrochemical impedance spectroscopy. The comparison indicates that there is good agreement between the data from both techniques.     

Measurement of surface resistivity/conductivity of metallic alloys in aqueous solutions by optical interferometry techniques

Optical interferometry techniques were used for the first time to measure the surface resistivity/conductivity of the pure aluminium (in seawater at room temperature), UNS No.304 stainless steel (in seawater at room temperature), and pure copper (in tap water at room temperature) without any physical contact. This was achieved by applying an electrical potential across the alloys and measuring the current density flow across the alloys, during the cyclic polarization test of the alloys in different solutions. In the mean time, optical interferometry techniques such as holographic interferometry were used in situ to measure the orthogonal surface displacement of the alloys, as a result of the applied electrical potential. In addition, a mathematical model was derived in order to correlate the ratio of the electrical potential to the current density flow (electrical potential/electronic current flow = resistance) and to the surface (orthogonal) displacement of the metallic samples. In other words, a proportionality constant (surface resistivity or conductivity = 1/surface resistivity) between the measured electrical resistance and the surface displacement (by the optical interferometry techniques) was obtained. Consequently the surface resistivity (ρ) and conductivity (σ) of the pure aluminium (in seawater at room temperature), UNS No.304 stainless steel (in seawater at room temperature), and pure copper (in tap water at room temperature) were obtained. Also, electrical resistivity values (ρ) from other source were used for comparison sake with the calculated values of this investigation. This study revealed that the measured value of the resistivity for the pure aluminium (7.7 × 10¹⁰ Ω cm in seawater at room temperature) is in good agreement with the one found in literature for the aluminium oxide, 85% Al₂O₃ (5 × 10¹⁰ Ω cm in air at temperature 30 °C). Unfortunately, there is no measured value for the resistivity of cupric oxide (CuO), cuprous oxide (Cu₂O), or even the oxide of the UNS No.304 stainless steel in literature comparing those values with the measured values in this study.     

Effect of substrate bias voltage on corrosion of TiN/Ti multilayers deposited by magnetron sputtering

Austenitic stainless steel can be attack by localized corrosion in saline environments, such as seawater. TiN/Ti multilayers can improve the corrosion resistance of the stainless steel better than TiN monolayers, because the titanium layers improve the impermeability of TiN/Ti multilayers. In this work, 1.75-4.55 μm thick layers were deposited on to grounded or −100 V biased substrates of 304 stainless steel substrates by reactive magnetron sputtering. The corrosion resistance of the layers was studied by means of potentiodynamic polarization in 0.5 M NaCl solutions. It was found that the pitting corrosion resistance was dependent on the bias and period number of the multilayers.     

Investigation of the characteristics and corrosion resistance of Al2O3/TiN coatings

Al₂O₃ /TiN double and Al₂O₃/Cr/TiN triple coatings were produced on stainless steel substrates using plasma-detonation techniques. Investigation of the microstructure and characteristics of the coatings after the preparation was performed by X-ray diffraction (XRD), transmission electron microscopy (TEM) and Auger electron spectroscopy (AES). The corrosion resistance of the coatings was studied in several electrolytic solutions (0.5 M H₂SO₄, 1 M HCl, 0.75 M NaCl) using electrochemical techniques (open circuit potential, cyclovoltammetry and potentiodynamic polarization). The obtained results showed, in most of the cases, an improvement of the corrosion resistance, except in NaCl solutions. The effect of the controlled thickness of TiN and Cr layers as well as the additional treatment with a high-current electron beam was also investigated. Nuclear reaction analysis (NRA), Rutherford backscattering spectroscopy (RBS) and scanning electron microscopy (SEM) were applied for the characterization of the samples before and after the corrosion experiments.     

Identification of Green Rust Compounds in the Aqueous Corrosion Processes of Steels; the Case of Microbially Induced Corrosion and Use of 78 K CEMS

Fe(II)-Fe(III) hydroxy-sulphate Green Rust 2, GR2(SO₄ ^–), is obtained by microbially induced corrosion of steel. Transmission Mössbauer spectroscopy (TMS) was used to characterise the corrosion products of steel sheet piles under the biofilm at low sea-water level in a harbour. To understand the process, iron coupons maintained in aqueous solutions of 4 M NaCl and 0.1 M NaHCO₃ of pH 7.4 were studied by X ray diffraction and conversion electron Mössbauer spectroscopy (CEMS) at 78 K. The Fe(II)-Fe(III) hydroxy-carbonate, GR1(CO₃ ^–), covers the surface, as predicted by the E_h-pH diagram.     

Composition and corrosion resistance of coatings on the basis of nitrides of titanium and chromium

Ti-Cr-N coatings were deposited on a low-carbon steel St3 substrate by overlapping of Ti and Cr plasma flows in residual nitrogen atmosphere using ion bombardment. Auger electron spectroscopy and X-ray diffraction were used to analyze the element and phase composition of the deposited coatings. It was established that, under constant deposition conditions (the arc current, gas pressure, bias voltage), coatings possess the fcc structure of a (Ti,Cr)N solid solution with uniform distribution of elements along the depth. The growth of the substrate bias voltage leads to an increase of titanium concentration in the coating due to changes in the interaction processes (condensation and sputtering) of the deposited materials with the substrate. Corrosion tests of the coatings and steel St3 were performed in acid (1 M H₂SO₄) and salt (3% NaCl) media. It was found that the corrosion processes progress less intensely in salt solution than in acid medium.     

Electrochemical impedence spectroscopy versus optical interferometry techniques during anodization of aluminium

In the present investigation, holographic interferometry was utilized for the first time to measure in situ the thickness of the oxide film, alternating current (AC) impedance, and double layer capacitance of aluminium samples during anodization processes in aqueous solution without any physical contact. The anodization process (oxidation) of the aluminium samples was carried out by the electrochemical impedance spectroscopy (EIS), in different concentrations of sulphuric acid (1.0–2.5% H₂SO₄) at room temperature. In the mean time, the real-time holographic interferometric was used to measure the thickness of anodized (oxide) film of the aluminium samples in aqueous solutions. Also, mathematical models were applied to measure the AC impedance, and double layer capacitance of aluminium samples by holographic interferometry, during anodization processes in aqueous solution. Consequently, holographic interferometric is found very useful for surface finish industries especially for monitoring the early stage of anodization processes of metals, in which the thickness of the anodized film, the AC impedance, and the double layer capacitance of the aluminium samples can be determined in situ. In addition, a comparison was made between the electrochemical values obtained from the holographic interferometry measurements and from measurements of EIS. The comparison indicates that there is good agreement between the data from both techniques.     

Exceptionally high cavitation erosion and corrosion resistance of a high entropy alloy

Cavitation erosion and corrosion of structural materials are serious concerns for marine and offshore industries. Durability and performance of marine components are severely impaired due to degradation from erosion and corrosion. Utilization of advanced structural materials can play a vital role in limiting such degradation. High entropy alloys (HEAs) are a relatively new class of advanced structural materials with exceptional properties. In the present work, we report on the cavitation erosion behavior of Al_0.1CoCrFeNi HEA in two different media: distilled water with and without 3.5 wt% NaCl. For comparison, conventionally used stainless steel SS316L was also evaluated in identical test conditions. Despite lower hardness and yield strength, the HEA showed significantly longer incubation period and lower erosion-corrosion rate (nearly 1/4th) compared to SS316L steel. Enhanced erosion resistance of HEA was attributed to its high work-hardening behavior and stable passivation film on the surface. The Al_0.1CoCrFeNi HEA showed lower corrosion current density, high pitting resistance and protection potential compared to SS316L steel. Further, HEA showed no evidence of intergranular corrosion likely due to the absence of secondary precipitates. Although, the degradation mechanisms (formation of pits and fatigue cracks) were similar for both the materials, the damage severity was found to be much higher for SS316L steel compared to HEA.     

Crevice corrosion of copper alloys by optical interferometry

In the present investigation, an optical corrosion-meter has been developed for testing of materials and evaluation of different corrosion phenomena. The idea of the optical corrosion-meter was established based on principles of 3D-holographic interferometry for measuring microsurface dissolution, i.e. mass loss, and on those of electrochemistry for measuring the bulk electronic current, i.e. corrosion current of metallic samples in aqueous solutions. In the present work, an early stage of crevice corrosion of an aluminium brass and a pure copper sample in seawater and tap water, respectively, was monitored in situ by the optical corrosion-meter during the cyclic polarization test. The observations of crevice corrosion were basically interferometric perturbations detected on the surface of both alloys underneath a crevice assembly, made of a Teflon bolt, a Teflon nut, and a Teflon washer. The crevice assembly was used on all tested samples to create a differential aeration cell between the surface of the sample and areas underneath the crevice assembly in seawater. Each Teflon washer contained radial grooves and had 20 plateaus which formed crevices (shield areas) when pressed against the surface of the sample. The interferometric perturbations were interpreted as a localized corrosion in the form of an early crevice corrosion of depth ranging between 0.3 μm and several micrometers. Consequently, results of the present work indicate that holographic interferometry is a very usefull technique as a 3D-interferometric microscope for monitoring crevice corrosion at the initiation stage of the phenomenon for different metallic samples in aqueous solutions.     

Development and evaluation of electroless Ag-PTFE composite coatings with anti-microbial and anti-corrosion properties

Electroless Ag-polytetrafluoroethylene (PTFE) composite coatings were prepared on stainless steel sheets. The existence and distribution of PTFE in the coatings were analysed with an energy dispersive X-ray microanalysis (EDX). The contact angle values and surface energies of the Ag-PTFE coatings, silver coating, stainless steel, titanium and E. coli Rosetta were measured. The experimental results showed that stainless steel surfaces coated with Ag-PTFE reduced E. coli attachment by 94-98%, compared with silver coating, stainless steel or titanium surfaces. The anti-bacterial mechanism of the Ag-PTFE composite coatings was explained with the extended Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. The anticorrosion properties of the Ag-PTFE composite coatings in 0.9% NaCl solution were studied. The results showed that the corrosion resistance of the Ag-PTFE composite coatings was superior to that of stainless steel 316L.     

Electrochemical recycling of cell phone Li-ion batteries: application as corrosion protector of AISI 430 stainless steel in artificial seawater

This article aims to present a new alternative to waste management of spent Li-ion batteries from cell phones. In this sense, the proposed is recycling the cobalt from Li-ion cathode by electrodeposition and apply it as corrosion protector of AISI 430 stainless steel. Thus, two greatest environmental problems can be solved, producing a low-cost and high-corrosion-resistant stainless steel. The cobalt electrodeposition bath came from acid dissolution of spent Li-ion cathode with chemical formula LiCoO₂. The charge efficiency for cobalt electrodeposition in ?1.0 V and pH = 3 reaches 95 %. A protective layer of Co₃O₄ was successfully obtained by treatment of AISI 430 stainless steel with cobalt electrodeposited at 800 °C for 200 h in air atmosphere. The corrosion current of AISI 430 stainless steel in artificial seawater was reduced from 30 to 0.76 μA cm^?2. The treatment proposed produces a AISI 430 stainless steel with double of corrosion resistance and half of cost if compared with AISI 304 stainless steel.     

Influence of treating frequency on microstructure and properties of Al2O3 coating on 304 stainless steel by cathodic plasma electrolytic deposition

Alumina ceramic coatings were fabricated on 304 stainless steel by cathodic plasma electrolytic deposition (CPED). Influence of treating frequency of the power supply on the microstructure and properties of the coatings were studied. The results indicated that coatings obtained at various frequencies on 304 stainless steels were all composed of α-Al₂O₃ and γ-Al₂O₃, and α-Al₂O₃ was the dominant phase. The contents of α-Al₂O₃ decreased gradually in a very small rate with increasing the frequency and γ-Al₂O₃ gradually increased. The surface of alumina ceramic coating was porous. With increasing the frequency, the coating surface gradually became less rough and more compact, resulting in low surface roughness. The bonding strength of Al₂O₃ coating was higher than 22 MPa and was not strongly affected by treating frequency. With increasing the frequency, the alumina coated steels showed better and gradually increasing corrosion resistance than the uncoated one in 3.5% NaCl solution. The coating steel with desirable corrosion resistance was obtained at 800 Hz whose corrosion current potential and corrosion density were −0.237 V and 7.367 × 10⁻⁸ A/cm², respectively.     

Effect of surface nanocrystallization induced by fast multiple rotation rolling on hardness and corrosion behavior of 316L stainless steel

A nanostructured layer was fabricated by using fast multiple rotation rolling (FMRR) on the surface of 316L stainless steel. The microstructure in the surface was characterized by transmission electron microscopy and X-ray diffraction. The effects of FMRR on the microhardness, surface roughness and corrosion behavior of the stainless steel were investigated by microhardness measurements, surface roughness measurements, potentiodynamic polarization curves and pitting corrosion tests. The surface morphologies of pitting corrosion specimens were characterized by scanning electron microscopy. The results show that FMRR can cause surface nanocrystallization with the grain size ranges from 6 to 24 nm in the top surface layer of the sample. The microhardness of FMRR specimen in the top surface layer remarkably increases from 190 to 530 HV. However, the surface roughness slightly rises after FMRR treatment. The potentiodynamic polarization curves and pitting corrosion tests indicated that the FMRR treated 316L stainless steel with a surface nanocrystallized layer reduced the corrosion resistance in a 3.5% NaCl solution and enhanced the pitting corrosion rate in a FeCl₃ solution. Possible reasons leading to the decrease in corrosion resistance were discussed.     

Evaluation of corrosion in electrochemical systems using Michelson interferometry

This work presents the performance of a simple Michelson interferometric configuration, allowing monitoring and evaluation of corrosion and oxide layer growth in aluminium during aqueous corrosion processes in a distilled water solution, without any physical contact with the sample. This alternative experimental arrangement introduces a simpler alignment compared with a preliminary proposal [Habib K. In situ measurement of oxide film growth on aluminium samples by holographic interferometry. Corrosion Sci 2001; 43, 449–55], and the obtained interferograms offer a qualitative and possibly quantitative evaluation of an important physical parameter related to the corrosion process kinetics. Interferograms were obtained as a function of time to register changes related to the corrosion dynamics and oxide growth process. Experimental results correlate with the well-known corrosion process taking place over the aluminium sample under these experimental conditions.     

Modified electrochemical emission spectroscopy (MEES) As technique of NDT for detection localized corrosion of copper alloys in seawater

An early stage of localized corrosion, i.e., pitting and crevice corrosion, of a pure copper and a brass in uncoated and coated conditions in seawater was investigated in situ by a new non-destructive testing (NDT) method. The new method of localized corrosion detection is based on the optical corrosion-meter for measuring the corrosion current density (J) and on a modified electrochemical noise technique for determining the corrosion admittance (A_c) at the open-circuit potential of the alloys in solutions. The observations of localized corrosion were basically interferometric perturbations detected by the optical corrosion-meter only on the uncoated copper and the coated brass at the beginning of the tests. The interferometic perturbations interpreted as a localized corrosion in the form of an early pitting and crevice corrosion, of a depth ranging from 0.3 μm to several micrometers, of the uncoated copper and the coated brass, respectively. Also, the early stage of localized corrosion of the same alloys in the same conditions was determined in situ by a modified electrochemical noise (EN) technique, called the modified electrochemical emission spectroscopy (MEES) technique, simultaneously during the optical interferometry measurements. Determinations of localized corrosion by the MEES technique were electrochemical noise spectra detected on corrosion admittance (A_c)-time plots of the alloys in solutions. The corrosion admittance parameter, A_c=(dJ/dV), which defined the MEES technique, is capable of indicating localized corrosion and uniform corrosion activities. In this investigation, the parameter A_c was modified in which the change of the corrosion current density (dJ) was measured by the optical corrosion-meter rather than by the zero resistance ammeter, which is usually used for measuring the dJ in electrochemical noise technique. Consequently, results of the present work indicate that optical corrosion-meter as an electromagnetic method of measuring the corrosion current density, and MEES technique, as an electronic method for determining the A_c, are very useful techniques as non-destructive methods for the detection of localized corrosion at the initiation stage of the phenomenon.     

Electrochemical synthesis and characterization of polyaniline-coated PEMFC metal bipolar plates with improved corrosion resistance

This article reported the electrochemical deposition of polyaniline (PANI) on 316-L stainless steel (316LSS) to improve the anti-corrosion performance as PEMFC metal bipolar plates. The results indicate that PANI can increase the corrosion potential of 316LSS by more than 410.57 mV and effectively decrease the corrosion current density by four orders of magnitude in comparison with the uncoated 316LSS. The experimental results showed that the PANI increased the open-circuit potential of the steel by about 140 mV. The polarization current value of PANI-coated 316LSS reduced to 2.3 × 10^?7 A/cm² under the PEMFC cathode working condition. During exposure for 12 h, Nyquist plots of PANI-coated 316LSS did not change substantially. This indicates that the PANI coating was an effective barrier against the inward penetration of corrosive species.     

Study of La0.8Sr0.2Co0.2Cr0.8O3 − δ as a candidate coating material for the positive current collector in Na/S battery

Perovskite La_0.8Sr_0.2Co_0.2Cr_0.8O_3 − δ (LSCC) ceramic synthesized by the conventional ceramic processing technique was studied as a novel coating material for the cathode current collector in Na/S battery. Its structure, electrical conductivity, density and thermal expansion coefficient (TEC) were investigated. The corrosion performance of LSCC was in particular evaluated by electrochemical techniques in combination with long-term dip-immersion tests. The results indicated that LSCC exhibited excellent corrosion resistance in molten sodium tetrasulfide at 350 °C. The corrosion current density i_corr (0.081 mA cm^− 2) was much lower than that of 316 L stainless steel by approximately two orders of magnitude. The corrosion rate of LSCC deduced from immersion test was as low as about 12 μm year^− 1.     

Studies on stability of PEC cells formed with CdS:Al films

Aluminum doped and undoped CdS films are deposited on stainless steel substrates by chemical bath deposition technique and are employed in PEC cells. The effects of heat treatment to photoanode and addition of salts like KCl and NaCl in an electrolyte on the stability of the PEC cells are studied. It is found that though the PEC cells formed with CdS films are stable in NaOH-Na₂S-S electrolyte, the stability of PEC cells formed with Al doped CdS films is achieved only after the addition of saturated salts in the electrolyte.