Grooving corrosion in electric resistance welded steel pipe in sea water

The mechanism of grooving corrosion in electric resistance welded (ERW) carbon steel pipe in sea water was investigated. Grooving corrosion is a selective localized corrosion of the weld. Scanning electron microscopic observation revealed that corrosion pits initiated immediately on the MnS inclusions and developed into grooving corrosion with the aid of the macro-cell formed between the anodic narrow weld and cathodic base metal of the pipe. High localized corrosion susceptibility of MnS inclusions in the weld is due to their surrounding S-enriched portions caused by the rapid heating and cooling in welding.     

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.     

Localized corrosion behaviour of reinforcement steel in simulated concrete pore solution

The correlation of localized corrosion behavior and microstructure of reinforcement steel in simulated concrete pore solutions was investigated. The SEM/EDS analysis showed that most of ferrite, minor amount of pearlite and some MnS inclusions existed on the steel surface. The SKPFM results indicated a higher corrosion tendency at the ferrite grain boundaries, pearlite grains and MnS inclusions. The EIS and electrochemical polarization measurements demonstrated the influence of pH and chloride concentration on the corrosion behavior. In situ optical observations and AFM images revealed a detail of the localized corrosion behavior, which was in good agreement with the results from the other measurements.     

Characterization and analysis about the heterogeneity of inclusions in a 500kg steel ball

The distribution and transfer mechanism of MnS inclusions are distinguished from the solute segregation in a 500 kg steel ball. The increase of MnS inclusions is obvious from the surface to the center of the steel ball, while the increase of solute content is slight. The massive MnS inclusions converge in the channel zone and in heterogeneous zones. During solidification, the interface tension drives MnS inclusions to the frontier of the dendritic zone. Some inclusions trapped may float to induce the channel zone. Solidification contraction tears such channel zone to attract more melt enriched with inclusions. Some inclusions converge in the extra-dendritic melt. At later solidification stage, solidification contraction dominates the macro-distribution of extra-dendritic melt to produce the heterogeneous zones.     

Die Entstehungs- und Ausbreitungskinetik von Sulfatnestern bei der atmosphärischen Korrosion von Stahl

Kinetics of formation and propagation of sulfate nests on steel The atmospheric corrosion of steel starts at individual sites, the number of which increases until the steel surface is covered by a rust layer. The initial distribution of corrosion sites seems to be connected with active sulfide inclusions (in particular MnS). The manganese sulfates formed are hydrolised, so that sulfuric acid is formed which initiates the formation of sulfate nests. The ferrous sulfate formed in such nests is again hydrolised and this reaction controls the rate of sulfate nests propagation. Good rust protection requires the removal of such sulfate nests which can be achieved only by removal of the rust layer (either mechanically or by pickling); mere rinsing or the use of rust stabilizers are not sufficient.     

Corrosion behaviour of an Fe3Al-type intermetallic in a chloride containing solution

The corrosion behaviour of an Fe₃Al-base intermetallic compound with different crystal structures in a chloride containing solution has been investigated. The corrosion current densities of this intermetallic were independent of the material crystal structure showing a passive state stable with time. These corrosion rates were of the same order of magnitude as for 316L stainless steel. The pitting corrosion resistance evaluated by means of cyclic anodic polarization curves was high for all different states. Amongst the different crystal structures of this intermetallic alloy, the two ordered states present the lowest pitting probability. This Fe₃Al intermetallic shows higher pitting corrosion resistance than the 316L stainless steel but its capacity for repassivation is lower. A damaging factor of influence on the pitting corrosion behaviour is the presence of non-metallic inclusions on the surface which reduce the pitting corrosion resistance by almost a half.     

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.       

锆脱氧对船板EH36夹杂物和耐蚀性能的影响

为研究脱氧方式对船板夹杂物形态和耐蚀性能的影响,采用锆脱氧和铝脱氧,对比两种脱氧条件下钢板晶粒尺寸、夹杂物形态和耐腐蚀性能。结果表明,锆脱氧试验钢夹杂物主要为钙铝酸盐夹杂、球形复合氧化物;其中,大颗粒和长条状MnS夹杂物的密度较低,夹杂物弥散细小,可以阻止晶界迁移带来的晶粒长大,有效细化钢板晶粒尺寸。锆脱氧形成的钢中细小氧化物可以作为MnS异质形核核心,降低了钢基体MnS夹杂微区电化学腐蚀敏感性与扩展速度;这种复合氧化物电化学稳定性好,与铝脱氧方式相比,可以有效提升钢板耐蚀性能。     

Mechanism of copper action on pitting phenomena observed on stainless steels in chloride media

The influence of the addition of copper on the resistance to pitting corrosion of stainless steels has been investigated using different experimental techniques--current transient analysis, polarization curves in acidic media, pitting and repassivation potential measurements, XPS and SEM observations--so that pit initiation, propagation and repassivation could be analysed separately. Copper addition is shown to act in three different ways on pitting corrosion. On the one hand, copper reduces steel dissolution rates in acidic chloride media and also pit propagation rates. On the other hand, copper addition in steel is shown to lower repassivation potentials in neutral chloride environments and also to delay pit repassivation. Lastly, when copper is injected into solution as CuCl₂ or when the steel is polarized at anodic potentials so that copper can dissolve from the steel into solution, pit initiation close to sulfide inclusions is prevented. A model is proposed for these three different actions of copper, showing that the role of this element is complex and that no relevant information can be drawn from only considering its effect on the pitting potential.     

硫质量分数对船体钢诱发点蚀行为的影响研究

采用腐蚀浸泡的方法研究了酸性氯离子环境下S质量分数对低合金船板钢耐蚀性的影响,探讨了非金属夹杂物诱发点蚀形核的机理。结果表明,杂质元素S对钢的耐蚀性具有不利影响。随着S质量分数的增加,钢的耐点蚀性能恶化。S元素损害耐蚀性主要与钢中的非金属夹杂物有关。不同种类夹杂物诱发点蚀的机理有显著差异。单一MnS夹杂物与基体间存在缝隙,其诱导点蚀形核包括缝隙腐蚀和夹杂物溶解两个过程,MnS夹杂物是最敏感的点蚀诱发源;MXS-Al2O3复合夹杂物同样能诱发低合金钢的点蚀形核,包裹在Al2O3外层的硫化物优先发生溶解,成为腐蚀介质的通道,从而引发局部腐蚀。MnS-Al2O3夹杂物的点蚀形核能力大于CaS-Al2O3夹杂物,CaS遇到水容易发生水解并在夹杂物周边形成OH-,阻碍了坑内部的酸化,有利于抑制钢的耐局部腐蚀性能。     

碳钢及低合金钢点蚀性能的研究

选择三种典型的碳钢、低合金钢,通过极化试验比较了它们之间的点蚀诱发敏感性和模拟孔蚀的“闭塞腐蚀电池”,试验研究了它们之间的孔蚀扩展行为。结果表明,B钢的点蚀诱发能力小于A钢和C钢;在同样的阴极极化电位下,B钢的阳极溶解电流也明显小于后两者。电子探针分析了不同夹杂物在诱发点蚀过程的腐蚀特征,夹杂物是钢中主要的点蚀诱发源。显微分析“闭塞腐蚀电池”腐蚀形貌,发现腐蚀形貌具有平行沟槽状。初步分析原因是沿轧向延伸的磷偏析带及夹杂物所导致的。扫描电镜和能谱仪对腐蚀产物的形貌、成分分析结果表明：B钢的锈层均匀致密,而A钢的锈层呈网状、疏松且有大量裂纹和孔洞。     

The corrosion behavior of carbon steel in CO2‐saturated NaCl crevice solution containing acetic acid

The corrosion behavior of X52 carbon steel electrodes in CO₂‐saturated NaCl crevice solution containing HAc was investigated by electrochemical measurements. Chemical environment measurements by Cl^? and pH microprobes show an enrichment of Cl^? ions and an increase of pH values inside the crevice. Moreover, both increments could accelerate with the decreasing dimension of the crevice mouth due to the high diffusive resistance. When the electrode in the crevice solution is coupled with the electrode in bulk solution, the alkalization and the enrichment of Cl^? ions in the crevice solution can result in a negative shift of potential of the electrode in crevice solution, while the potential of the electrode in bulk solution shifts positively during the corrosion process. Thus, a galvanic corrosion is established with the electrode in the crevice solution acting as anode while another in the bulk solution as cathode, i.e., the corrosion in the crevice solution was enhanced while the corrosion in the bulk solution was retarded. The anodic dissolution and the cathodic reduction processes dominate in the crevice solution and in the bulk solution, respectively.     

Effect of Fe-Zn alloy layer on the corrosion resistance of galvanized steel in chloride containing environments

In this study, the effect of Fe-Zn alloy layer that is formed during galvanizing process on the corrosion behavior of galvanized steel has been investigated. The galvanostatic dissolution of galvanized steel was carried out in 0.5 M NaCl solution to obtain the Fe-Zn alloy layer on the base steel. The alloy layer was characterized to be composed of FeZn₁₃, FeZn₇ and Fe₃Zn₁₀ intermetallic phases, which constitute the zeta, delta1 and gamma layers of galvanized steel, respectively. It was observed that the alloy layer has similar cathodic polarization behavior but different anodic polarization behavior compared to galvanized steel. The anodic current plateau of alloy layer was up to 100 times lower than that of galvanized coating. Corrosion test performed in wet-dry cyclic condition has shown that the alloy layer has lower corrosion rate as compared to galvanized steel. From the results of corrosion test of alloy layer and base steel, it was concluded that Zn²⁺ has positive effect on the protectiveness of the zinc corrosion products. The measurement of surface potential over the alloy/steel galvanic couple has confirmed the galvanic ability of alloy layer to protect both the alloy layer itself and the base iron during initial stage of atmospheric corrosion.     

Effects of Modified Inclusions and Precipitates Alloyed by Rare Earth Element on Corrosion and Impact Properties in Low Alloy Steel

This study has focused on the morphology and distribution of inclusions and precipitates modified by rare earth (RE) elements, which has a decisive influence on microstructure, corrosion properties and impact behaviors in Q355 low alloy steel. Characterized by the method of electrolytic extraction and ASPEX-scanning electron microscopy (ASPEX-SEM), small-sized spherical RE inclusions have been modified to replace elongated MnS and large-sized Al₂O₃. Q355RE steel after RE alloying has lower corrosion rate and higher value of α/γ, due to the formation of stable and dense rust layers. Q355RE steel also exhibits better resistance to fracture at low temperature, owing to the presence of RE modification to inclusions and its effects on reducing crack initiation and propagation. Nano-scale RE precipitates containing sulfur and phosphorus is observed along grain boundaries by transmission electron microscopy (TEM). The purification of grain boundaries by RE is beneficial to the improvement of corrosion and impact properties.     

A study of the effects of inhibitive and aggressive ions on oxide-coated aluminium using secondary ion mass spectrometry

A Cameca Ion Analyser has been used to examine aluminium surfaces, supporting barrier-type anodic films ca. 720Å thick, after natural immersion for 1–25 h in 1M chloride and chromate/dichromate solutions of varying pH, and neutral 1M phosphate solution. In chloride solutions, chloride is present on the film surface, but not within the film material per se, within the limits of measurement. The degree of film thinning is governed by pH, being more pronounced in alkaline than acid solutions. In chromate/dichromate solutions, chromium uptake occurs by two distinct mechanisms. The first is associated with relatively rapid chromate/dichromate reduction to Cr₂O₃, probably hydrated, within flaws in the anodic film. The second is associated with a more gradual direct chromate/dichromate anion entry into the bulk material probably through the intercrystalline regions in the film, ultimately resulting in film thinning, even in neutral solutions. In phosphate solutions, phosphate anions penetrate and thin bulk anodic alumina in a similar manner to chromate/dichromate anions. The results are interpreted on the basis of the differing surface chemical properties of the various anions in relation to bulk alumina.     

Effect of surface mechanical attrition treatment (SMAT) on zinc phosphating of steel

The effects of surface mechanical attrition treatment (SMAT) of EN8 steel on the growth of phosphate coatings, morphological features and corrosion resistance of the resultant coatings have been studied. SMAT enabled the formation of a uniform surface profile although the average surface roughness is increased after treatment. SMAT increased the extent of metal dissolution and the rate of growth of phosphate coating. In spite of the similarity in phase composition, the phosphate crystallite size is relatively high for samples treated by SMAT. Compared to the untreated one, a cathodic shift in E_corr with a corresponding decrease in i_corr is observed for SMAT treated EN8 steel after phosphating. For all tested samples, zinc phosphate coatings deposited on EN8 steel after SMAT using 8 mm Ø balls for 30 min offers the highest corrosion resistance. The increase in surface roughness by SMAT is partly compensated by the expected improvement in corrosion resistance.     

Pitting corrosion behaviour of austenitic stainless steels - combining effects of Mn and Mo additions

Mn and Mo were introduced in AISI 304 and 316 stainless steel composition to modify their pitting corrosion resistance in chloride-containing media. Corrosion behaviour was investigated using gravimetric tests in 6 wt.% FeCl₃, as well as potentiodynamic and potentiostatic polarization measurements in 3.5 wt.% NaCl. Additionally, the mechanism of the corrosion attack developed on the material surface was analysed by scanning electron microscopy (SEM), X-ray mapping and energy dispersive X-ray (EDX) analysis. The beneficial effect of Mo additions was assigned to Mo⁶⁺ presence within the passive film, rendering it more stable against breakdown caused by attack of aggressive Cl⁻ ions, and to the formation of Mo insoluble compounds in the aggressive pit environment facilitating the pit repassivation. Conversely, Mn additions exerted an opposite effect, mainly due to the presence of MnS inclusions which acted as pitting initiators.     

X80管线钢在近中性pH溶液中腐蚀行为研究

目的研究X80管线钢在近中性p H溶液中的腐蚀与应力腐蚀裂纹萌生行为。方法采用电化学实验和浸泡实验研究X80管线钢在近中性p H溶液中的腐蚀行为,采用慢应变速率拉伸实验研究X80管线钢在近中性p H溶液中,在自腐蚀电位和外加电位下的应力腐蚀裂纹萌生行为。结果 X80管线钢在近中性p H溶液中的极化曲线只有活化区,没有钝化区,其自腐蚀电位约为-750 m V,浸泡195天后,试样表面没有氧化膜出现,但是观察到点蚀坑。在自腐蚀电位下,X80管线钢试验表面有大量的应力腐蚀裂纹;在-500 m V阳极外加电位下,X80管线钢试验表面几乎没有观察到应力腐蚀裂纹;在-850 m V阴极外加电位下,X80管线钢试验表面的应力腐蚀裂纹很少,但是随着外加阴极电位负移到-1300 m V时,X80管线钢试验表面的应力腐蚀裂纹增多。结论 X80管线钢在近中性p H溶液中发生均匀腐蚀,但是夹杂物剥落能在X80管线钢表面形成点蚀坑。在近中性p H溶液中,在自腐蚀电位下,X80管线钢应力腐蚀裂纹萌生敏感性最强;外加阴极电位抑制应力腐蚀裂纹萌生,但是随着外加阴极电位的负移,应力腐蚀裂纹萌生敏感性增强;外加阳极电位下,由于均匀腐蚀的作用,应力腐蚀裂纹萌生敏感性较弱。     

Über das Korrosionsverhalten von Zink und feuerverzinktem Stahl in erwärmtem Wasser

Corrosion behaviour of zinc and hot dip galvanized steel in warm water The corrosion rate of zinc and hot dip galvanized steel in continuously flowing tap water is but little influenced by water temperature. The slight decrease of the corrosion rate which has been found at higher temperatures (60°C) can be attributed to the preferential formation of zinc oxide at these temperatures, this oxide being less soluble than the hydroxide formed at lower temperatures. The potential shift toward more noble values at higher temperatures does, however, depend from water composition and may eventually start as early as at 35 °C; in certain critical potential ranges the uniform corrosion may even be changed into pitting. Addition of phosphate to the water may reduce either the corrosion rate or it may restrict the potential shift (in this latter case the appearance pitting is prevented). The measurement of the electrode potential (not of the polarization resistance) thus yields information on the danger of pitting corrosion. The quality of the zinc surface seems to be important in those cases where the ZnFe alloy layer protrudes to the zinc surface.     

Effect of Immersion Time and Cooling Mode on the Electrochemical Behavior of Hot-Dip Galvanized Steel in Sulfuric Acid Medium

In this work, we investigated the influence of galvanizing immersion time and cooling modes environments on the electrochemical corrosion behavior of hot-dip galvanized steel, in 1 M sulfuric acid electrolyte at room temperature using potentiodynamic polarization technique. In addition, the evolution of thickness, structure and microstructure of zinc coatings for different immersion times and two cooling modes (air and water) is characterized, respectively, by using of Elcometer scan probe, x-ray diffraction and metallography analysis. The analysis of the behavior of steel and galvanized steel, vis-a-vis corrosion, by means of corrosion characteristic parameters as anodic (β _a) and cathodic (β _c) Tafel slopes, corrosion potential (E _corr), corrosion current density (i _corr), corrosion rate (CR) and polarization resistance (R _p), reveals that the galvanized steel has anticorrosion properties much better than that of steel. More the immersion time increases, more the zinc coatings thickness increases, and more these properties become better. The comparison between the two cooling modes shows that the coatings of zinc produced by hot-dip galvanization and air-cooled provides a much better protection to steel against corrosion than those cooled by quenching in water which exhibit a brittle corrosive behavior due to the presence of cracks.