Effect of rare earth on inclusion evolution and corrosion resistance of HRB400E steel

The effect of rare earth elements Ce and La on the evolution behavior of inclusions in HRB400E steel was studied through experimental observations and thermodynamic calculations. Neutral salt spray corrosion experiments were also conducted to investigate the effect of Ce–La on the corrosion resistance of steel. The results showed that the typical inclusions in steel without rare earth were MnS and MnO–SiO₂. A small amount of Mn–Si–O–S inclusions was also observed. After adding rare earth, the typical inclusions were transformed into isolated (Ce,La)₂O₂S, (Ce,La)₂O₃ + MnS, and (Ce,La)₂O₂S + MnS complex inclusions. The thermodynamic calculations indicated that the rare earth elements in molten steel preferentially reacted with MnO–SiO₂ inclusions and dissolved oxygen and sulfur to form (Ce,La)₂O₃ and (Ce,La)₂O₂S. Small amounts of [S] and [Mn] adhered to the surface of the nucleated rare earth inclusions to form complex inclusions. After Ce–La treatment, the corrosion rate of the steel decreased from 3.491 to 1.992 mm year⁻¹, and the corrosion resistance was improved. The change in corrosion behavior is due to the modification of the inclusions into rare earth inclusions with good compatibility with the steel matrix.     

Effects of sulfur addition on pitting corrosion and machinability behavior of super duplex stainless steel containing rare earth metals: Part 2

To elucidate the effects of sulfur addition on pitting corrosion and machinability behavior of alloys containing rare earth metals, a potentiostatic polarization test, a critical pitting temperature test, a SEM-EDS analysis of inclusions, and a tool life test were conducted. As sulfur content increased, the resistance to pitting corrosion decreased due to the formation of numerous manganese sulfides deteriorating the corrosion resistance and an increase in the preferential interface areas for the initiation of the pitting corrosion. With an increase in sulfur content, the tool life increased due to the lubricating films of manganese sulfides adhering to tool surface.     

Ce 盐封孔对 SiCp/ Al 复合材料表面 Ni-P 镀层的影响

为提高SiCp/Al复合材料的耐腐蚀性能,先化学镀镍,再沉积稀土封孔,讨论了稀土溶液主盐Ce(NO3)3浓度和沉积时间对镍-稀土多层膜耐蚀性能的影响。结果表明:化学镀镍的SiCp/Al复合材料在室温下沉积稀土时,采用Ce(NO3)3含量1 g/L、成膜时间2 h的条件获得的多层膜耐蚀性最好,其腐蚀电位为-0.48mV,腐蚀电流密度为3.54×10-8A/cm2;稀土在膜层中以Ce的氧化物颗粒堆积状态存在,起到了封孔的作用;膜层中的镍磷合金呈多晶态,而稀土含量少,未能测出;稀土溶液浓度越高,沉积速度越快,而在相同浓度下,膜层厚度随着时间的延长而增加,越厚则膜层结合力越差。     

Mikrobiell induzierte Korrosion (MIC) in marinem Milieu

Microbial induced corrosion (MIC) in marine environment Steel box‐piles immersed in brackish water of the Baltic Sea show a perforation of the wall (10 mm of thickness) after a service life of 35 years. The calculated corrosion rate by that is 290 μm/a and is much higher than usual corrosion rates in marine environments. Investigations of material have shown, that the steel corresponds well with a common mild steel used for sheet piles. At the outer plain the structure shows normal surface corrosion, while inside, according to microscopic studies, pitting corrosion occurs. Beneath the oxidative corrosion product (e.g. γ‐Fe₂O₃, maghemite) there are sulfur enriched phases as well as elementary sulfur detectable (by means of different methods like X‐ray Diffraction, REM‐EDX and IR‐Spectroscopy). The corrosion products are covered with a calcitic layer and have to be removed prior to investigation. By means of microbiological techniques, “sulfate reducing bacteria” (SRB) could be detected in high concentrations between the corrosion products inside the steel structures. These bacteria are deriving from the marine sediment and earn their energy using electrons from the steel accompanied by chemical reduction of the sulfate from the sea water. By that the anodic process of iron dissolution is accelerated. The anaerobic environment inside the closed structures promotes the metabolic activity of the bacteria. As a first and cost saving repair it is proposed, to force the oxidation by opening the structures. Of course preventative corrosion protection – coating (inside and outside) or filling (inside) – would have been the best prevention of corrosion.     

Influence of Sulfur Content on the Corrosion Resistance of 17-4PH Stainless Steel

According to specification standards, the basic chemical composition of steel 17-4PH for special and critical applications is 15-17% Cr, 3.0-5.0% Ni, 3.0-5.0% Cu, 0.07% C (max) and 0.15-0.45% (Nb + Ta) (wt.%). The maximum sulfur content is 0.030%. However, as it will be shown in this work, this maximum limit for sulfur is too high for services where high corrosion resistance is necessary. Two samples of 17-4PH steel with similar base compositions, but quite different sulfur contents (0.027% and 0.001%S), were compared with respect to pitting corrosion and sensitization. Both materials were heat treated according to commercial treatments A, H900, H1100, H1150 and H1150D (ASTM A-1082). Two corrosion tests were applied to compare the steels. The first one was the double-loop electrochemical potentiodynamic reactivation (DL-EPR) test in 0.25 M H₂SO₄ + 0.01 KSCN solution, which is used to measure the degree of sensitization. The second test was the anodic polarization in 3.5%NaCl solution, commonly used to evaluate the pitting corrosion resistance. Detailed microstructural characterization by magnetic measurements, light optical and scanning electron microscopy was performed. As main conclusion, despite that both steels have chemical compositions in accordance with the standards, the steel with higher sulfur was much more susceptible to pitting and sensitization.     

The preparation and characteristics of a rare earth/nano-TiO2 composite coating on aluminum alloy by brush plating

Nano-TiO₂ modified rare earth composite coatings are prepared on 2024 aluminum alloy by brush plating. The composite coating is composed of mainly Ce(OH)₃, Ce(OH)₄, CeO₂ and TiO₂, with less cracks and lower porosity. The addition of nano-TiO₂ enhances the adhesive strength of the rare earth coating to Al substrate, results in refined coating grains and increases the micro-hardness of the coating. The nano-TiO₂ modification obviously improves the corrosion resistance of the rare earth coating. For the composite coating containing 2% TiO₂, both the corrosion current density and the impedance are reduced by more than one order of magnitude in contrast to the values for the pure rare earth coating. The higher barrier ability and increased Ce³⁺ content in the Ce oxides may explain the increase of the corrosion resistance.     

Effect of pre-oxidation on the hot corrosion of CoNiCrAlYRe alloy

The effect of pre-oxidation on the resistance to hot corrosion was examined by corroding the CoNiCrAlYRe alloy at 900 °C in molten Na₂SO₄. Preoxidized specimens featured strong adhesion of oxide scale with uniform multi-layered structure. The time of pre-oxidation was crucial for controlling Al content sufficient for subsequent hot corrosion. However, direct corrosion yielded a defective and non-protective oxide scale, which allowed detrimental penetration of sulfur into substrate. Sulfur migrating along phase boundary was trapped by yttrium to diminish slightly sulphidation. Thus, two advantages of proper pre-oxidation treatment were presented, as keeping repairing for Al₂O₃ scale and inhibiting sulfur penetration.     

Hot corrosion of materials: Fundamental studies

Hot corrosion is the accelerated oxidation of materials at elevated temperatures induced by a thin film of fused salt deposit. Because of its high thermodynamic stability in the mutual presence of sodium and sulfur impurities in an oxidizing gas, Na₂SO₄ is often found to be the dominant salt in the deposit. The corrosive oxyanion-fused salts are usually ionically conducting electrolytes that exhibit an acid/base chemistry, so that hot corrosion must occur by an electrochemical mechanism that may involve fluxing of the protective oxides. With the aid of high-temperature reference electrodes to quantify an acid/base scale, the solubilities for various metal oxides in fused Na₂SO₄ have been measured, and these show remarkable agreement with the theoretical expectations from the thermodynamic phase stability diagrams for the relevant Na-Metal-S-O systems. The solubilities of several oxides infused Na₂SO₄-NaVO₃ salt solutions have also been measured and modeled. Such information is important both in evaluating the corrosion resistance of materials and in interpreting any oxide fluxing/reprecipitation mechanisms. Various electrochemical measurements have identified the S₂O₇ ^2? anion (dissolved SO₃) as the oxidant that is reduced in the hot corrosion process. Electrochemical polarization studies have elucidated the corrosion reactions and clarified the corrosion kinetics of alloys. Mechanistic models for Type I and Type II hot corrosion are discussed briefly.     

Review of the development and breakdown of protective oxide scales on alloys exposed to coal-derived atmospheres

Metal components in coal utilization and conversion systems are subject to severe corrosion by sulfur and other impurities in coal-derived environments. Most of the alloys and metallic coatings designed to withstand high-temperature aggressive environments rely on the formation of protective Cr ₂O₃ and Al ₂O₃ scales. However, in mixed-gas environments containing sulfur, either the protective oxide scales do not form or they rapidly break down. In order to understand corrosion behavior in mixed-gas environments, previous work on corrosion of high-temperature materials in coal-related applications is summarized. Current ideas for the development of protective oxide scales on alloys in mixed-gas environments by preoxidation and by the addition of reactive elements to the alloys are reviewed. Finally, future studies are recommended as being important to the development of alloys with better corrosion resistance in mixed-gas environments.     

Hot corrosion studies of a salt-coated Ni-based superalloy under flowing wet air and sulfur vapor ambient

Corrosion of a salt-coated Ni-superalloy has been studied at 900°C under a wet air and sulfur vapor ambient. The corrosion thickness, after an incubation of ~60 hr, linearly increases with the corrosion time t and the onset of surface spallation occurred at t ≈ 60 hr. The corroded layer consists of a corrosion front dominated by Cr₃S₄ scales and linear precipitate structures, an inner corrosion layer dominated by Ni₃S₂ and NiO, and an outer corrosion layer dominated by Al₂O₃ networks surrounding the Ni₃S₂ and/or NiO scale structures. The corrosion mechanism is discussed based on the coexistence of H₂O, sulfur, and oxygen.     

On the “coke” growth in carburizing and sulfidizing atmospheres upon High temperature corrosion of iron and nickel base alloys

The graphite deposition from carbonaceous atmospheres can initiate a catastrophic deterioration of alloys in high temperature corrosion. The graphite nucleation and growth is catalyzed by metal surfaces and affected by the presence of sulfur. Gravimetric studies have been performed on the carbon transfer from CH₄? H₂ or CH₄? H₂? H₂S atmospheres to iron, nickel or ironnickel alloys at 1000°C. The carbon activities were a_c = 1 (equilibrium with graphite), a_c = 5 or a_c = 10; the sulfur pressure was in a range where the metal surfaces are nearly saturated with adsorbed sulfur. The carburization, i.e. the transfer of C into solid solution is retarded in the presence of sulfur since surface sites are blocked for the methane decomposition. In the sulfur-free environment graphite layers grow with their basal planes parallel to the metal surface – for nickel an epitaxial growth occurs which is extremely slow. In the presence of sulfur the graphite can only nucleate in small islets which grow to irregular nodules. This results in a retardation by sulfur of the graphitisation on iron, whereas the growth of graphite on nickel is accelerated by sulfur. The transition between these ways of graphitisation behaviour was studied for Fe? Ni.     

Physicochemical studies of mild steel corrosion and atmospheric corrosivity mapping of Karachi: An important harbor city of modern Maritime Silk Route

This paper has reported physicochemical features of mild steel's corrosion products and provided atmospheric corrosivity maps of Karachi harbor city, drafted on the basis of spatial distribution of corrosion data from July 2018 to June 2019 at 10 different urban, industrial, and marine test sites. Exposure tests have been performed to study atmospheric corrosivity, corrosion products, and corrodants including chloride, sulfur dioxide, time of wetness (TOW), and corrosion rate as per ISO and ASTM standards. Scanning electron microscope, Fourier-transform infrared spectroscopy, and X-ray diffraction have corroborated the presence of lepidocrocite, goethite, magnetite, and quartz phases at almost all the test sites, with slight variations in their morphologies and quantities. The data analysis has revealed that TOW is a major detrimental factor to accelerate corrosion of mild steel at Karachi city. The corrosivity category of all urban and marine test sites is found in C₄–C₅ range, whereas for industrial test sites, it is found in C₃–C₅ range. Resultant corrosivity maps have shown that the prevailing atmosphere is significantly corrosive at Karachi harbor city. This study has furnished a novel product of atmospheric corrosivity map, which is the first-ever corrosivity map for Pakistan.     

Rare earth chloride and nitrate salts as individual and mixed inhibitors for aluminium alloy 7075-T6 in chloride solution

The aim of the study was to investigate various rare earth salts as corrosion inhibitors of aluminium alloy 7075-T6. Rare earth salts, CeCl₃, LaCl₃, Ce(NO₃)₃ and La(NO₃)₃, were studied, first as individual inhibitors in the concentration range between 0.001 and 0.05?M. Second, the inhibitory effect of mixtures of chloride or nitrate salts was studied at an overall inhibitor concentration of 0.01?M. The corrosion properties of AA7075-T6 in the absence and presence of individual and mixed rare earth salts were investigated using electrochemical potentiodynamic technique in 0.1?M NaCl. The topography, morphology and composition of the inhibited surfaces were recorded. The highest inhibitory effectiveness was exhibited by CeCl₃, followed by mixtures of CeCl₃ and LaCl₃. During immersion for 12?h the corrosion protection remained high. Nitrate rare earth salts showed less protection, both as individual or as mixed inhibitors. Deposits containing both cerium and lanthanum were formed primarily on Cu-based intermetallics.     

The corrosion of iron and of three commercial steels in H2?H2S and in H2?H2S-CO2 gas mixtures at 400–700 °C

The corrosion behavior of three commercial steels including a carbon, a low-chromium (2.25Cr-1Mo) and a medium-chromium (9Cr-1Mo) steel in H₂? H₂S and in H₂? H₂S-CO₂ mixtures has been investigated at 400–700 C under two sulfur pressures at each temperature. The ternary mixtures had the same sulfur pressure as the binary gases, but also a small partial pressure of oxygen. The corrosion of pure iron in the same H₂? H₂S mixtures was also studied for comparison. The scales formed on the steels were always composed of sulfides only: they showed a typical duplex structure as well as a strong tendency to crack and spall off during cooling. The corrosion kinetics of the steels were generally irregular, presenting an initial period of decreasing rate and a second approximately linear stage. On the other hand, the scales formed on iron were compact and well adherent to the metal, while the corrosion kinetics appeared to be generally controlled by a surface reaction step, leading to a transition from linear to parabolic behavior. The kinetics and mechanisms of scale growth for both iron and the steels are examined and discussed.     

磷偏析对低碳钢孔蚀扩展的影响

    选择6种冶金因素各有特点的低碳钢,通过模拟“闭塞腐蚀电池”试验和室内挂片试验,结合金相组织、硫印、磷偏析和腐蚀形貌分析,研究磷偏析对孔蚀扩展的影响.结果表明,腐蚀形貌上呈现出凹凸状的平行腐蚀沟槽,这种平行腐蚀沟槽与磷偏析相关,而不是与沿轧制延伸的夹杂物(硫偏析)或平行的带状组织(碳偏析)相关.凹凸状的平行腐蚀沟槽形成原因是磷在溶液中离解为磷酸根离子,产生微溶的金属盐,在蚀坑的阳极活化区沉淀,从而抑制了阳极溶解.       

Morphological Development of Subscale Formation in Fe–Cr–(Ni) Alloys with Chloride and Sulfates Coating

Three types of stainless steel (430, 304, and 310) with a coating of NaCl, NaCl/AlCl₃, or NaCl/Al₂(SO₄)₃ are exposed at 750 and 850°C. Results show that NaCl has a major effect on corrosion and sulfur plays an important role in intergranular corrosion. After high-temperature exposure with a 100% NaCl coating, the morphologies of alloys 304 and 310 show typical uniform subscale attack the depths of attack increasing with temperature, while alloy 430 showed a planar attack. Alloy 310 has the highest chromium content and has the least metal loss. After high-temperature exposure with a NaCl/AlCl₃ coating, the corrosion morphologies and depths of attack are similar to those associated with an NaCl coating, but only voids are larger in the subscale. When coated with NaCl/Al₂(SO₄)₃, the alloys are attacked simultaneously by sulfur and chlorine at 750°C, resulting in a typical sulfur-attack intergranular corrosion. However, as the temperature increases to 850°C, the corrosion morphology changes to a uniform subscale attack.     

Electrochemische Untersuchungen zur Hochtemperaturkorrosion von Chromstählen in Alkalisulfatschmelzen

Electrochemical investigation into the high temperature corrosion of chromium steels in alkali sulfate melts Electrochemical and corrosion-chemical investigations have been carried out with scaling resistant chromium steels, iron, chromium and platinum in a eutectic (Li, Na, K)₂-SO₄. It has turned out that sufficiently exact data concerning corrosion reactions can be obtained only from mass losses, not, however, from current density. The corrosion behaviour depends from potential. Comparable to the conditions in aqueous solutions potential ranges exist with passive and transpassive corrosion and with a rupture potential which depends from the chromium content of a steel. Protective oxide layers exist in the passive range where the mass loss becomes almost constant after a certain in cubation period. In the transpassive range corrosion follows an almost parabolic law with formation of an inner sulfide layer and a thicker external oxide layer where chromium is enriched. These layers are largely formed by oxidizing media carried to the metal surface via sulfur oxides; during this reaction inert marks in the steel remain unchanged. Sulfur oxides may be formed as secondary consecutive products by reactions between metal ions and sulfates. The solubility of metal ions in the sulfate melt is an important parameter for corrosion rates. Oxide ions (as reduction products of O₂) act as inhibitor on the anodic partial reaction, while SO₃ and ferric ions have a large lating effect, so that the anodic dissolution is autocatalyzed. Chlorides, too, act as stimulators in the transpassive range. Corrosion at the free corrosion potential is largely controlled by ferric ions which act as anodic and cathodic stimulators in acid melts. In neutral melts under oxygen an 18% chromium steel is passive.     

Chromate replacement in coatings for corrosion protection of aerospace aluminium alloys

Mixed rare earth organophosphates have been investigated as potential corrosion inhibitors for AA2024‐T3 with the aim of replacing chromate‐based technologies. Cerium diphenyl phosphate (Ce(dpp)₃) and mischmetal diphenyl phosphate (Mm(dpp)₃) were added to epoxy coatings applied to AA2024‐T3 panels and they were effective in reducing the amount and rate of filiform corrosion in high humidity conditions. Ce(dpp)₃ was the most effective and characterisation of the coating formulations showed approximately a factor of 5 reduction in both the number of corrosion filaments initiated as well as the length of these. Mm(dpp)₃ appeared to reduce the corrosion growth rate by a factor of 2 although it was the more effective inhibitor in solution studies. Spectroscopic characterisation of the coatings indicated that the cerium based inhibitor may disrupt network formation in the epoxy thus resulting in a coating that absorbed more water and allowed greater solubilisation of the corrosion inhibiting compound.     

Investigations of the degradation of high-temperature alloys in a potentially oxidizing-chloridizing gas mixture

The degradation of high-temperature alloys in argon-5.5% oxygen-0.96% hydrogen chloride-0.86% sulfur dioxide at 900°C under isothermal and thermal cycling conditions has been investigated. All the alloys showed reasonable resistance under isothermal conditions, although the Al₂O₂ ***-forming material, alloy 214, gave the lowest amount of corrosion, consistent with Al₂O₃ being a more effective barrier than Cr₂O₃ to inward penetration of chlorine or sulfur-containing species from the environment. Significant internal corrosion was observed for some alloys. Degradation of all the alloys was much more severe under thermal cycling conditions because of the failure of the protective scales. In all cases, formation of volatile chlorine-containing compounds was observed. Degradation of the alloys resulted from the penetration of chlorine-containing species through the initially formed oxide scale and formation of chlorides or, possibly, oxychlorides at the alloy-scale interface or in the subjacent alloy. The sulfur dioxide did not play any obvious role in the process.     

Effects of mode-I stresses on the oxidation and failure mechanisms of Ni-20Cr and Ni-15Cr-8Fe alloys in sulfur dioxide

Two alloys, Ni-20Cr and Ni-15Cr-8Fe, as wire specimens, were exposed to sulfur dioxide between 325 and 800°C, with applied external stresses (mode I). Their mechanical properties have been investigated, and the variation of their radius has been precised by conductivity measurements. For the Ni-20Cr alloy, below 550°C, the failure process combines cracking and corrosion: Cr₂S₃ crystals formed at the tip of the cracks facilitate their propagation. Above 550°C, no barrier effect is observed, and intergranular corrosion takes place. For the Ni-15Cr-8Fe alloy, mode-I stresses bolster intergranular corrosion.