Cathodic Polarization Research Articles

Interaction Between Uranium Trifluoride and the Mixture of Lithium and Beryllium Fluorides

Equilibrium potentials of uranium (U3+/U0) have been measured in the LiF-BeF2-UF3 melt as a function of temperature and uranium fluoride concentration. The empirical equation of uranium potential isotherms and polytherms have been obtained. Cathode polarization of uranium in the molten mixture of beryllium and lithium fluorides has been measured using the current switch off method form the stationary state. Uranium ions were found to have primarily the-valence of three in the LiF-BeF2 electrolyte in the studied temperature and uranium fluoride concentration ranges. A conditional standard potential of uranium (U3+/U0) in the molten mixture of lithium and beryllium fluorides was calculated relative to the reference fluorine electrode according to the experimentally obtained data on the equilibrium potentials of the uranium electrode in the LiF-BeF2-UF3 melt. Standard conditional changes in the Gibbs energy, enthalpy and entropy at the formation of uranium trifluoride from the elements in the form of dilute solutions were determined. The enthalpy of mixing of liquid uranium fluoride and the 0.73LiF–0.27BeF2 melt was calculated.

Partially phosphorylated poly(vinyl alcohol) – A promising candidate in corrosion protection of magnesium for the biomedical industry?

Partially phosphorylated poly(vinyl alcohol) (PPVA) as anticorrosive coating for AZ31 magnesium alloy was investigated in Hank’s Balanced Salt Solution (HBSS). Four phosphoric acid levels were used to modify PVA, resulting in four PPVA products. They were characterized using thermogravimetric analysis (TGA), water contact angle (WCA), and swelling test. PPVA-coated Mg alloys were evaluated using hydrogen evolution, cathodic polarization, electrochemical impedance spectroscopy (EIS), and scanning electron microscopy (SEM). TGA indirectly revealed crosslinked regions in the PPVA structure that increased with acid content. WCA and hydrogen evolution tests suggested that PPVA is a promising polymer for biomedical applications. Corrosion tests showed that the PPVA with 10% acid addition significantly improved the impedance modulus and lowered the cathodic kinetics compared to uncoated samples. The findings of the study suggested that the acid addition in PVA must be at least 10 % to guarantee improved corrosion resistance in HBSS, which indicates this material has potential for biological applications.

Hydrogen embrittlement of the nickel alloy UNS N07718 for two different heat-treating schedules

The role of the nickel alloy 718 microstructure has been widely discussed and it is well established the δ phase detrimental effect on the material’s ductility and toughness when exposed to hydrogen. However, other microstructural features that might influence the embrittlement process are more elusive, which requires more in-depth studies. Having selected heat-treating schedules to mitigate δ phase precipitation, this work aims to assess the hydrogen embrittlement of two alloy 718 variants with nominal yield strengths of 120 and 150 ksi. Fundamentally, the idea is to understand the extent of the hydrogen damage caused by an increase in mechanical strength beyond the limit of 140 ksi specified in the API 6ACRA. Slow strain rate (SSR) and fracture toughness (FT) testing were applied to evaluate the mechanical behavior under cathodic polarization. The microstructure of both variants is comprised of recrystallized austenite grains and a very low content of grain boundary δ phase. Nanosized disk-shaped γ″ particles are also present for both variants, although the 150 ksi material shows a higher volume fraction and a finer distribution of this phase. Despite having the same overall fracture features, nanostructure differences between the variants and the consequent impact on hydrogen apparent solubility and slip planarity produced lower values of plastic elongation and initiation fracture toughness for the stronger material.

Boosting the Electrolysis of Monosaccharide-Based Streams in an Anion-Exchange Membrane Cell.

A systematic study on the electrochemical reforming of monosaccharides (fructose, glucose, and xylose) using Pt-based anodic electrocatalysts is here presented for the first time to completely optimize the anodic catalyst and electrolyzer operating conditions. First, the electro-oxidation of each molecule was studied using a monometallic (Pt) and two bimetallic (PtNi and PtCo) anodic electrocatalysts supported on graphene nanoplatelets (GNPs). Tests in a three-electrode cell showed superior electrochemical activity and durability of PtNi/GNPs, especially at potentials higher than 1.2 V vs RHE, with the highest electrocatalytic activity in d-xylose electro-oxidation. Then, monometallic (Pt and Ni) and bimetallic electrocatalysts with different Pt:Ni mass ratios (1:1 and 2:1) were studied for d-xylose electro-oxidation, with the 2:1 mass ratio presenting the best results. This electrocatalyst was selected as the most suitable for scale-up to an anion-exchange membrane electrolyzer, where the optimal operating potential was determined. Additionally, stable operating conditions of the electrolyzer were achieved by cyclic H2 production and cathodic regeneration polarization steps. This led to suitable and reproducible H2 production rates throughout the production cycles for renewable hydrogen production from biomass-derived streams.

Protective Properties of Calcareous Deposit Layer for Cathodically Polarized AH36 Steel in Natural Seawater

A calcareous deposit is a by-product of the cathodic polarization in seawater environments. This study presents the results of evaluating the anticorrosion and anti-macro-biofouling effectiveness of a calcareous deposit layer on the surface of the cathodically polarized AH36 structural steel in tropical seawater. The polarization is induced with initial current densities at which the calcareous deposit layer formed with both aragonite and brucite for 12 months continuously. The protective properties of the layer were compared with those of the passive layer from corrosion products under the same environmental conditions. The macro-biofouling in the tropical seawater is observed in the closed and open surfaces of the steel. The comparison of the anticorrosion property shows that, to some degree, the calcareous deposit layer contributes to surface passivation, as in the case of the corrosion product layer. In addition, the composition of the brucite and aragonite in the calcareous layer in the study plays a role as a macro-biofouling growth-limiting factor.

Degradation of iron‐nickel alloy interconnects in contact with lanthanum nickelates based double‐layer electrodes during long‐term tests

AbstractThis paper focuses on long‐term tests held during 1,000 h on different Membrane‐Electrode‐Interconnect Assemblies (MEIAs), consisting of an Fe‐Ni alloy interconnect and an electrochemical cell based on a Ce0.8Sm0.2O2–δ electrolyte, the double‐layer working electrode with a La2NiO4 + δ – Ce0.8Sm0.2O2–δ composite functional layer, and a LaNi0.6Fe0.4O3–δ current collector layer, and a platinum reference electrode (O2, LaNi0.6Fe0.4O3–δ|La2NiO4 + δ – Ce0.8Sm0.2O2–δ|Ce0.8Sm0.2O2–δ|Pt, O2). These tests were carried out on MEIAs with the Cr‐free 47ND alloy of the Fe–Ni system with and without surface modification at 850°C in air. The electrochemical performance of MEIAs was studied without polarization as well as under cathodic and anodic polarization with current density 0.5 A cm−2 by means of electrochemical impedance spectroscopy (EIS). The mechanism of the MEIA evolution during long‐term test is discussed.

Electric field inducing quick release and targeted migration of corrosion inhibitors loaded by CTAB-MMT/epoxy coatings for enhancing self-healing properties

In this work, CTAB-MMT/epoxy coatings (CMC) are prepared by modifying epoxy resin with CTAB-MMT composite through a hydrothermal method. Meanwhile, external electric field generated by the cathode polarization is further stressed on the coatings to enhance their self-healing properties. When the coatings are scratched by external force, the electric field tends to induce the corrosion inhibition group CTA+ to overcome the electrostatic interaction with MMT and detach from MMT, and then the released CTA+ migrates to the carbon steel surface targetedly and quickly to form an adsorption film to inhibit corrosion under the action of electric field.

Kinetic Evaluation on Lithium Polysulfide in Weakly Solvating Electrolyte toward Practical Lithium-Sulfur Batteries.

Lithium-sulfur (Li-S) batteries are highly considered as next-generation energy storage techniques. Weakly solvating electrolyte with low lithium polysulfide (LiPS) solvating power promises Li anode protection and improved cycling stability. However, the cathodic LiPS kinetics is inevitably deteriorated, resulting in severe cathodic polarization and limited energy density. Herein, the LiPS kinetic degradation mechanism in weakly solvating electrolytes is disclosed to construct high-energy-density Li-S batteries. Activation polarization instead of concentration or ohmic polarization is identified as the dominant kinetic limitation, which originates from higher charge-transfer activation energy and a changed rate-determining step. To solve the kinetic issue, a titanium nitride (TiN) electrocatalyst is introduced and corresponding Li-S batteries exhibit reduced polarization, prolonged cycling lifespan, and high actual energy density of 381 Wh kg-1 in 2.5 Ah-level pouch cells. This work clarifies the LiPS reaction mechanism in protective weakly solvating electrolytes and highlights the electrocatalytic regulation strategy toward high-energy-density and long-cycling Li-S batteries.

Study the Effect of “Di-dodecyl amine” as a Corrosion Inhibitor for Carbon Steel in HCl Medium

Numerous organic compounds have been investigated for their potential to reduce corrosion under various circumstances. This study investigated the effects of di-dodecyl amine, an organic chemical, on carbon steel metal corrosion at different temperatures while HCl acid was present. The examination was carried out using accepted methods for polarization, weight loss, and corrosion process testing. The obtained findings demonstrated that the corrosion rate reduces with increasing inhibitor concentration, leading to increased inhibition efficiency. Furthermore, as shown in the weight loss technique, the corrosion rate lowers with increasing surface coverage with organic inhibitor at 313 °C. In the anodic and cathodic polarization methods, as well as in the inhibition efficiency, it is observed to see the cathodic and anodic curves through which the occurrence of the potential and corrosion current is known. The current and corrosion potential decreases with increasing inhibitor concentration. The amines and methyl motiveless in this inhibitor's composition give it their efficacy since they may coat the metal surface and stop corrosion

Surface Evolution of Ni Electrode Under Cathodic Polarization in Acidic Solution

The surface morphology and structure of nickel cathode is closely related to its service performance and stability for water electrolysis applications. However, the surface evolution of nickel under cathodic polarization has not been systematically studied. In this work, we investigated the morphology evolution of the Ni electrode under cathodic polarization by altering the current density, temperature and composition of electrolyte. A corrosion rate of less than 0.0054 mm a−1 is observed under cathodic polarization at 0.2 mA cm−2. Uniform corrosion appears at low current density (0.2–2 mA cm−2) while serious pitting at high current density (20–200 mA cm−2). The corrosion preferentially takes place at the surface flaws, scratches and cavities. The cathodic corrosion is due to the uneven distribution of the surface potential between the plane and the depression part of the electrode. The mechanism is further confirmed by finite element simulation. The obtained result may provide reference for the design and application of various Ni-based cathodes.

Processes at Platinum Electrodes during the Cathode Polarization in Alcohol Erbium Nitrate Solution

Processes at Platinum Electrodes during the Cathode Polarization in Alcohol Erbium Nitrate Solution

Effect of cathodic polarizations on the failure behavior of epoxy coating/low alloy steel systems under high hydrostatic pressure

Failure behavior of epoxy coating/low alloy steel systems applied with cathodic polarization at 0.1 MPa and 15 MPa was investigated based on a deep−sea environment simulation test device. The results showed that the diffusion of water into the coating was significantly accelerated by the high hydrostatic pressure under the same polarization potential, and the time of water uptake of the coating that reached saturation was shortened; the coating's physical structure was significantly affected by the high hydrostatic pressure; the generation of highly conductive Fe3O4 was promoted in the corrosion products, which accelerated the metal corrosion process. Under the same hydrostatic pressure, with the negative shift of the polarization potential, the coating protective performance was significantly reduced and metal corrosion was mitigated to a certain extent; the water transport behavior showed a tendency to shorten the time of water uptake of the coating that reached saturation and lengthen the duration of the saturation state, which may be related to a more severe degree of cathodic delamination and the increase of water consumption for cathodic reactions under the coating. In addition, the increase of the weakly conductive α−Fe2O3 content in the corrosion products may cause a reduction in the cathodic protection current at the same polarization potential, resulting in the reduction of the protection effect on the metal.

The Effect of Sulfuric Acid Anodization on the Electrochemical Properties of Aluminum Alloy AlSi10Mg Prepared by Selective Laser Melting

Aluminum alloy, AlSi10Mg, prepared by selective laser melt (SLM) fabrication was anodized in 9.8% sulfuric acid (Type II) at 15 V for a total of 23 min. Experiments were performed to study the potentiostatic anodization process and its effects on the oxide coating morphology, thickness, and electrochemical properties of the alloy. Prior to anodization, the alloy microstructure is composed of aluminum cells encapsulated in a silicon network. Anodizing the abraded and polished AlSi10Mg surface produced a porous oxide layer with a thickness of 5 μm. The oxide coating weight was 698 ± 29 mg/ft2. The oxide coating forms in the aluminum cells that are isolated from one another by the silicon eutectic phase. In electrochemical tests, the anodic and cathodic potentiodynamic polarization currents were suppressed by factors of 15× and 215×, respectively, as compared to the unanodized controls. The data indicate the anodic oxide coating suppresses the cathodic more than the anodic reaction rate. Linear polarization resistance (R p) values increased by 279× after anodization. The corrosion current density values (j corr) decreased by 133× after anodization. Taken together, the electrochemical data indicate the anodic oxide coating (unsealed) increases the corrosion resistance of the SLM alloy by two orders of magnitude.

Electrochemical Synthesis and Performance of AgCl/Ag/Sliver Mesh Collector Composite Electrode for Seawater Batteries

High-energy-density and easy-to-implement battery storage technologies are essential for the exploitation of marine resources. AgCl is a promising cathode material for seawater batteries due to its environmental friendliness and high capacities density, but its inherent low conductivity limits its application in specific scenarios. In this paper, AgCl was electrochemically grown on a sparsely conductive Ag/Sliver mesh collector (SMC) substrate, and an excellent performance AgCl/Ag/SMC composite electrode is obtained. The cathodic polarization curves indicate that the current density of the AgCl/Ag/SMC electrode was 208.2 mA cm−2 at 0.4 V (vs RHE) potential, which is significantly higher than that of the conventional AgCl cathode material. The AgCl/Ag/SMC electrode demonstrated a very high discharge capacity of 181.7 mAh g−1 at 30 mA cm−2, and the assembled cell was found to be in good condition at 100 mA cm−2 with a power density of up to 154.7 mW cm−2, showing very excellent performance. Furthermore, investigation of the mechanism and depth of discharge experiment reveal the kinetic and microscopic reasons for the high performance of AgCl/Ag/SMC composite electrodes. Therefore, this study provides an efficient and feasible solution for the electrochemical preparation of highly active cathode materials for Mg-AgCl seawater batteries.

Facile preparation of ZIF-67 on TiO2 and enhancement photocathodic protection for 316L stainless steel

Photocathodic protection (PCP) anticorrosion using sunlight is a green and sustainable technology. However, the ease of carriers compounding and the low light utilization are still the main restraints to its development. To develop an effective photoanode, a metal-organic framework (MOF, i.e., ZIF-67) material is electrodeposited and grown in-situ on TiO2 nanorods. The morphological structure, light absorption properties, photoelectrochemical properties and cathodic protection principle of ZIF-67/TiO2 photoanode are analysed by SEM, PL, I-V and EIS. The material characterization and light absorption characteristics show that the photoanode has good light absorption performance and higher electron hole separation efficiency. Photoelectrochemical test shows that ZIF-67/TiO2 photoanode has excellent photocathodic protection for 316L stainless steel (316L SS). ZTRs-60 has the optimal protection effect. Under simulated sunlight, the OCP of 316L SS coupled ZTRs-60 is -0.41 V vs. Ag/AgCl, and the current density of the I-t curve can reach 20 μA/cm2. EIS and Tafel tests show that the photogenerated electrons transfer to the stainless steel surface, which promotes the cathode polarization process and alleviates the metal corrosion.

The inhibitor effect of migrating corrosion inhibitors on Q235 steel in high alkaline environment under cathodic polarization

PurposeThis study aims to investigate the corrosion inhibitor effect of migrating corrosion inhibitor (MCI) on Q235 steel in high alkaline environment under cathodic polarization.Design/methodology/approachThis study investigated the electrochemical characteristics of Q235 steel with and without MCI by polarization curve and electrochemical impedance spectroscopy. Besides, the surface composition of Q235 steel under different environments was analyzed by X-ray photoelectron spectroscopy. In addition, the migration characteristic of MCI and the adsorption behavior of MCI under cathodic polarization were studied using Raman spectroscopy.FindingsDiethanolamine (DEA) and N, N-dimethylethanolamine (DMEA) can inhibit the increase of Fe(II) in the oxide film of Q235 steel under cathodic polarization. The adsorption stability of DMEA film was higher under cathodic polarization potential, showing a higher corrosion inhibition ability. The corrosion inhibition mechanism of DEA and DMEA under cathodic polarization potential was proposed.Originality/valueThe MCI has a broad application prospect in the repair of damaged reinforced concrete due to its unique migratory characteristics. The interaction between MCIs, rebar and concrete with different compositions has been studied, but the passivation behavior of the steel interface in the presence of both the migrating electric field and corrosion inhibitors has been neglected. And it was investigated in this paper.

Influence of cathodic polarization on stress corrosion cracking susceptibility of 35CrMo steel for high strength bolt in simulated deep-sea environment

The effect of cathodic polarization on stress corrosion cracking (SCC) of 35CrMo steel for high strength bolt in the simulated deep-sea environment has been studied. The results show that 35CrMo steel has a higher SCC sensitivity at open circuit potential in the simulated deep-sea environment than that in the shallow seawater. With potential negatively shifted to −750 mV, 35CrMo steel presents the lowest SCC sensitivity. And the SCC susceptibility is increased significantly with the further negative shift of potential because of the intensive hydrogen evolution. When the potential is below −950 mV, hydrogen embrittlement with hydrogen-enhanced-plasticity mediated decohesion should be the dominant SCC micro-mechanism.

Analysis of the influence of local electrodeposition conditions on the accuracy of electrochemical 3D-printing

Problem. Additive manufacturing of metal parts by local electrodeposition is a new promising area with several unique features. The use of electrolysis makes it possible to manufacture metal parts at room temperature with high accuracy and low energy consumption. The accuracy and speed of electrochemical 3D printing are inversely related, and therefore it is important to find optimal electrodeposition conditions at maximum speed without degrading accuracy. The aim of the study. The purpose of this work was to analyse the influence of electrodeposition parameters (electrode distance, electrical conductivity and electrolyte polarization) on the accuracy of metal deposit formation in a computer model and to conduct experimental verification of optimal conditions for electroforming a real object from copper sulphate electrolyte. Methodology of implementation. To achieve the goals of the study, computer simulation of the electrochemical deposition process in the COMSOL Multiphysics software and electrochemical measurements of the characteristics of copper sulphate electrolytes were used. Research results. Computer simulation established optimal conditions: the distance between the edge of the capillary and the surface on which deposition occurs is not more than 0.5 mm, the electrolyte in which the inverse slope of the cathode polarization curve is not lower than 2000 mA/(V×cm2) and the electrical conductivity is not higher than 0.02 S/сm. The influence of the electrolyte composition on the inverse polarization of the cathode process and its electrical conductivity was investigated. The optimal composition of the electrolyte was selected, containing 200 g/L CuSO4, 60 g/L H2SO4, 0.2 g/L KCl and RUBIN T-200 additive. In the selected electrolyte, the value of the inverse slope of the cathode polarization curve is 2120 mA/(V×cm2). Verification of the process of local electrodeposition in the selected electrolyte during the electroformation of a cylindrical object with a diameter of 4 mm and a height of 100 μm was carried out. It was determined that no more than 5 % of metal was deposited outside the capillary of the working electrode. Conclusions. The results of the work can be used to create an electrochemical 3D printing system. Further research should be aimed at approbation of the obtained parameters of local electrodeposition in an installation that simulates the operation of a 3D printer and establish the accuracy and speed of printing of a three-dimensional object. Key words: additive manufacturing, electrical conductivity, electrolyte composition, polarization, local electrodeposition.

Carbon nitride interlayer-enhanced TiO2/WO3 nanorods with surface oxygen vacancies for durable photocathodic performance on 304 stainless steel in simulated seawater

To achieve a long-term photocathodic protective effect on metals in the marine environment, efficient charge mobility and electron storage are essential. Herein, we develop an oxygen vacancy (VO)-involved TiO2-wrapped WO3 nanorod composite by PPy-derived carbon nitride interlayer (TiO2/CNx/WO3) for the photoelectrochemical cathodic protection of 304SS in 3.5 % NaCl solution. The introduced CNx can serve not only as an electron channel to accelerate carrier migration but also as an efficient reductant to generate VO at the interfaces of TiO2 and WO3 during crystallization. The incorporated VO tunes the electronic structure and produces the mid-gap states, which lower the energy barrier for electron-hole separation. Meanwhile, WO3 nanorods as an electron self-storage pool make the photocathodic protection functional in darkness. Consequently, the as-prepared TiO2/CNx/WO3 photoanode yields a photocurrent density of 18.23 μA·cm−2 and a photoinduced cathodic polarization potential of −306 mV in simulated seawater. Even in the absence of light illustration, it can polarize 304SS to approximately −200 mV and continuously to 300 mV after 12h. This work will offer a universal strategy for the rational design and fabrication of highly efficient semiconductor composite materials in the field of photocathodic anticorrosion.

Behavior of calcium lignosulfonate under oxygen pressure acid leaching condition

The behavior of calcium lignosulfonate (CLS) in the oxygen pressure acid leaching process of ZnS concentrate was investigated using total organic carbon assessment (TOC), UV–visible spectrophotometry, Fourier transform infrared spectroscopy (FTIR), and gas chromatography-coupled mass spectrometry (GC–MS) as characterization methods. The effect of the CLS degradation products on zinc electrowinning was also discussed. The results showed that the temperature was positively correlated with the degradation of CLS, while the initial acidity had only significant effects in the range of 0–50 g/L and oxygen partial pressure range of 0–0.1 MPa. At an oxygen partial pressure of 0.2 MPa, an acidity of 160 g/L, and a reaction temperature of 150 °C, about 82.4% of CLS was degraded. In the oxygen pressure acid leaching process, CLS underwent polymerization and decomposition reactions, and its aromatic rings and side chain groups were damaged to varying degrees. At 120 °C, CLS was partially converted into sulfonic acids, phenols, and esters of higher molecular weights. At 150 °C, CLS further degraded into lower-molecular-weight aromatic ethers and sulfonic acids with shorter carbon chains. These organics were relatively stable and were the main sources of organic compounds during the oxygen pressure leaching process of zinc concentrates. The addition of CLS had a significant negative impact on zinc electrowinning, which was related to the adsorption of CLS on the cathode surface, enhancing cathodic polarization and inhibiting zinc reduction kinetics.