Einflußeiner Verzinkung auf die Korrosion von mit Zementmörtel beschichtetem Stahl in NaCl-Lösung

Effect of galvanizing on the corrosion of steel in concrete immersed in NaCl solution Galvanized or pickled steel sheet specimens were embedded in portland cement mortar of various water cement ratios and curing conditions and then wholly or partially immersed in 0.5 M NaCl solution for 1 to 5 yrs. Free corrosion potentials and electrical resistances have been measured. Immersion conditions and the presence of zinc have a significant effect on the corrosion resistance of the embedded steel sheets. The potentials of the wholly immersed specimens are very negative. Thus, these specimens cannot act as cathodes in corrosion cells, and the steel sheets within the mortar do not corrode. The partially immersed specimens, on the other hand, show very noble potentials. Also in the case of galvanized steel sheets the potentials are shifted to the same positive values in the course of exposure time. Thus, all these specimens can act as cathodes in corrosion cells. Localized corrosion generally occurs at the water/air line. In the case of pickled specimens the mortar is cracked due to growing corrosion products. In the case of galvanized steels the corrosion is retarded significantly. The test results are discussed in detail with respect to practical problems of cell formation, internal and external protection of pipes as well as the corrosion resistance of reinforced concrete.     

Schwingungsrißkorrosion von Baustahl in Offshore-Konstruktionen bei unterschiedlichen Frequenzen und Umgebungsbedingungen

Corrosion fatigue of structural steel in offshore structures at different frequencies and environmental conditions The effect of frequency on the corrosion fatigue in seawater was investigated by use of welded and unwelded bending specimens of plate material (20 mm, StE 460) by performing mainly endurance orientated constant-amplitude tests. The test frequency was varied in a wide range (10; 1, 0,1; 0,01 s^?1). The tests were performed in air as well as in artificial seawater at free corrosion, at a cathodic protection (U_H¹ = ?650 mV) and at an extreme polarization (U_H = ?850 mV). A general grading of the endurance – given by N_fr – with respect to the frequency was evaluated in the expected sequence at free corrosion only. Thereby the frequency effect is smaller as was expected and is intensively pronounced only at the lowest frequency of 0,01 s^?1. But this frequency already results in smaller N_fr – values of welded specimens at air as well as at an extreme cathodic polarization U_H = ?850 mV and higher loading. The results of air and free seawater-corrosion show the usual small scatter whereas those of the cathodic potentials U_H = ?650 and ?850 mV are significantly larger. At U_H = ?650 mV some results mark a significantly better behaviour than in air, the other ones are inside the scatter of the results in air. At the extreme cathodic polarization (U_H = ?850 mV) some results are situated in a domain of significant shorter endurance than in air; this results from negative influence of the increased cathodically emerged hydrogen at this potential. The phase of the fatigue crack initiation is shortened by free seawater corrosion compared with an air environment; it is enhanced by a cathodic protection with U_H = ?650 mV.     

Lochkorrosion stickstofflegierter austenitischer CrNiMnMoN-Stähle in 3%iger NaCl-Lösung

Pitting corrosion of nitrogen alloyed austenitic CrNiMnMoN steels in 3% NaCl solution Nitrogen containing austenitic CrNiMnMoN steels investigated electrochemically in chloride containing aqueous solutions exhibit pitting corrosion susceptibility which may be attributed to the materials conditions after solution annealing and work hardening. The range of passivity of high chromium steels goes up to a potential of E ≈? 1300 mV_{H H}, but beyond the limiting potential E_L for stable pitting there may be pitting phenomena on the rolled surfaces of the specimens. At potentials between E ≈? 300 mV_H and E_N various current density peaks appear and indicate the range of repassivable pitting in terms of pit formation on the cutting edges of the specimens. After cold rolling of the sheet the current density is increased in the entire potential range, since the pit density cutting edges and rolled surfaces increases as deformation is increased. Such cold working, however, does not result in a shift of the limiting potential E_L for stable pitting. Investigations concerning the place of formation of the pits indicate that nuclei are preferentially formed at the sites of sulfide inclusions the different shapes of which produce pits of corresponding appearance on the different faces of the specimen. The growth of the pit is influenced by the depth of the pores resulting from the dissolution of the inclusion, and by lattice defects in the metal.     

The corrosion and protection of steel in saturated Ca(OH)2 contaminated with NaCl

The corrosion of steel in saturated Ca(OH)₂ containing different concentrations of NaCl has been investigated at different potentials, oxygen contents and temperatures. The initiation of pits takes place only above the pitting potential. Repassivation of developed pits is shown to follow the threshold concentration for the initial corrosion step. Above the threshold concentration, existing pits can continue to grow at potentials below the pitting potential, and partial cathodic protection with a potential change of 50 mV is needed to arrest the corrosion. An explanation of the corrosion process is proposed. The corrosion rate is shown to be under anodic control. The growth of pits below the pitting potential is caused by the change in pH of the pit solution, which reaches a steady state regulated by the hydrolysis of the solution within the pit, and by the diffusion rate of hydroxyl ions into the pit from the bulk solution.     

Strömungsabhängigkeit der Lochkorrosion eines Cr-Ni-Stahles in NaCl-Lösung. Teil II: Versuche mit Ultraschall

Flow dependence of the pitting corrosion of CrNi steel in NaCl solution Test (with CrNi steel 19 9 in 1 N NaCl) with supersonic agitation have confirmed the results obtained with the rotating disc electrode. Supersonic treatment increases the pitting potential for stable pitting and reduces maximum corrosion current density. The treatment has but little effect, however, on the pitting potential for repassivating pitting corrosion. Cycling tests under galvanostatic conditions show that the effect supersonic action comes to bear almost immediately. Switching on or off the supersonic source results in immediate repassivation or loss thereof. Similar to experiments on rotating discs the pits are very small and, consequently, constitute practically no corrosion risk.     

Chloride-induced steel corrosion in alkali-activated fly ash mortar: Increased propensity for corrosion initiation at defects

Chloride contents at the steel–mortar interface that initiate steel corrosion were determined for carbon steel in alkali-activated fly ash mortar for three different exposure conditions: exposure to 1 M NaCl solution; leaching in deionized water and then exposure to 1 M NaCl solution; and leaching in deionized water, aging in air at 20°C and natural CO₂ concentration, and then exposure to 1 M NaCl solution. For comparison, a Portland cement mortar, exposed to 1 M NaCl solution, was studied. The median values of the corrosion-initiating chloride contents (average over the full length of the rebar) in the alkali-activated fly ash mortar varied between 0.35 and 1.05 wt% Cl with respect to binder, consistently lower than what was obtained for the Portland cement mortar, but with no clear trend regarding the exposure conditions. For most of the alkali-activated fly ash mortar specimens, preferential corrosion at the connection between the working electrode and the external measurement setup was observed, while preferential corrosion did not occur for the Portland cement mortar. Scanning electron microscopy and auxiliary experiments in synthetic solutions indicated that this behavior was caused by inhomogeneities at the steel–mortar interface in the alkali-activated mortar, likely due to its peculiar rheological properties in the fresh state.     

Loch- und Spaltkorrosion von Chrom- und Chromnickelstählen in chloridhaltigen Lösungen

Pitting and crevice corrosion of stainless steels in chloride solutions In practice stainless steels in chloride containing waters are found to be susceptible to crevice corrosion and pitting. Corrosion tests were carried out on AISI 304 L stainless using a simulated crevice and the compositions of the electrolyte in the crevice determined. Long term potentiostatic tests were used to determine the critical potentials for crevice corrosion (U_S), for various steels in sodium chloride solutions at different concentrations and temperatures. The steels studied were 22 CrMo V 121, X 22 CrNi 17 and AISI 304 L. Like the critical pitting potential (U_L), U_S was found to have a strong dependence on the chloride content of the external solution. At higher concentrations the two potentials were similar. At lower concentrations the U_S was lower than U_L. The knowledge of these critical potentials together with well known rest potentials for a steel in an electrolyte of known concentration, allows conclusions to be drawn about its susceptibility to pitting and crevice corrosion. The method is suitable also for other passive metals.     

Schnelle Lochkorrosion durch ungewöhnliche Anodenstabilisierung in einem Stahl/Wasser-System

Fast pitting corrosion in a steel/water system as a result of unusual stabilization of anodes Corrosion damage as a result of fast pitting was observed in industrial equipment made of unalloyed steel. The rate of formation and the manifestation of the pits are similar to pitting corrosion of stainless steels. Estimation of the kinetics of the localized corrosion in terms of differential aeration cells led to a model which indicates the stabilization of small anodic regions. The stabilization was caused by precipitation of the products of reaction between ferrous ions and polymeric silicate. The high rate of pitting also suggests that the oxygen entering the system during service periods involving the exposure of the system to air has enhanced the corrosion. These ideas could be substantiated by experiments, which also revealed particularly the effect of the concentration of NaCl. Anodic passivation by the addition of Na₂CO₃ or perhaps inhibition may be considered as candidate protective measures.     

Pit-to-crack transition in pre-corroded 7075-T6 aluminum alloy under cyclic loading

Pit-to-crack transition experiments were conducted on 1.600 mm and 4.064 mm 7075-T6 aluminum alloy. Specimens were corroded using a 15:1 ratio of 3.5% NaCl solution and H₂O₂ prior to fatigue loading. Cracks originating from corrosion pits were visually investigated in order to understand how pit-to-crack transitions occur.All prior corroded specimens in the study fractured from cracks associated with pitting. Pit-to-crack transition was successfully acquired visually. Corroded 7075-T6-4.064 mm specimens experienced more of an overall fatigue life reduction than 7075-T6-1.600 mm specimens. Results indicated that quantities such as pit surface area and surrounding pit proximity are as important as pit depth in determining when and where a crack will form.     

海水飞溅区Ni-Cu-P钢的锈层和耐点蚀性能研究

在海水飞溅区对实验室冶炼的Ni-Cu-P钢、含Cu低合金钢和碳钢进行660 d的挂片实验,评价Ni-Cu-P钢的耐蚀性能;采用Fourier变换红外(FTIR)光谱、电感耦合等离子体原子发射光谱(ICP-AES)、电子探针(EPMA)、SEM和EDAX等技术,分析3种钢表面的锈层特征.结果表明,Ni-Cu-P钢表现出比...     

Einfluß sulfatreduzierender Bakterien auf den kathodischen Korrosionsschutz

Influence of sulfate-reducing bacteria on cathodic protection Sulfate-reducing bacteria (SRB) are frequently encountered at coating defects of cathodically protected pipes buried in soil. In laboratory experiments the corrosion behaviour of steel St 37 was studied at potentials in the range of ?0.5 V > U_Cu/CuSo4 > ?1.27 V and at the open circuit potential in the presence of a mixed culture containing SRB. For simulation of real conditions the experiments were performed on steel samples in sand columns through which a glucose-containing mineral salts solution was continuously pumped. On the basis of the corrosion rates determined an immediate corrosion risk was not evident for a homogeneous mixed electrode even at the open circuit potential. There was only an increase in protective current demand compared to sterile conditions. Hydrogen permeation through the low-alloy steel was slightly higher in the presence of SRB-containing mixed cultures than under sterile and H₂S-free conditions. The observed permeation current densities indicated that at potentials of U_Cu/CuSo4 < ?0.85 V hydrogen-induced corrosion damage was not to be expected under sulfate-reducing conditions.     

Korrosionsverhalten feuerverzinkter Baustähle in überwiegend sandhaltigen Böden

Corrosion behaviour of galvanized steel in mainly sandy grounds In mainly sandy grounds with different portions of fine parts < 0,06 mm (2,5–20,4%) specimens of ungalvanized and galvanized steel were stored outside and in the laboratory. Besides the composition of the ground, the salinity and the temperature of the ground were varied too. The corrosion rate and, for ungalvanized specimens, the behaviour to pitting corrosion were determined. Furthermore the factors characterising the corrosion behaviour such as specific resistance of soil and corrosion potential were investigated continuously. The loss in weight of metal was much greater for ungalvanized than for galvanized specimens and increased for ungalvanized specimens with an increasing portion of fine parts in the ground. Additions of salt at the beginning of the tests produced an increased amount of metal wastage, but for galvanized specimens they only had an influence upon initial corrosion. The increased removals of material started since contents of 3 · 10^?3 MolCl^? + SO/kg. If salts were added to the ground after 2 years (after the formation of a surface layer), they increased the wastage of material for ungalvanized but not for galvanized specimens. Apart from ungalvanized bars in the soil with a fineness portion of 20,4%, corrosion, after an acceleration at the beginning, slowed down owing to the formation of a surface layer. Ungalvanized specimens were attacked by a strong pitting corrosion and that more in aerated than in dense and, thus, water-containing grounds. The additions of salt accelerate more an uniform corrosion of material than a pitting corrosion. As for galvanized specimens after a local removal of zinc under extreme conditions the steel base had been hardly corroded away. The parts free of zinc were protected cathodically by the still existing zinc. The corrosion of steel depends upon the temperature: by increasing the temperature from 4 to 20°C increases of corrosion up to 100% were stated. As for galvanized surfaces temperature has only a small influence upon corrosion.     

Al-Zn-Sn-Ga阳极合金的孔蚀活化钝化机理

采用SEM观察Al-Zn-Sn-Ga合金微观下孔蚀的发展过程。结合电化学相关理论,模拟计算由组织中第二相优先溶解而形成的点蚀孔内pH值与蚀孔深度之间的函数关系;探讨在中性NaCl溶液的腐蚀条件下,自催化效应对该合金蚀孔发展的影响。结果表明,合金的腐蚀孔内pH值随着腐蚀坑深度的增加而急速变大,但在孔蚀深度为0~10^-4 cm数量级时pH值变化却极小,此时合金蚀孔由于Ga汞齐等因素的作用导致阴极反应较快,从而使蚀孔钝化。通过三维形貌仪测得该合金点蚀孔钝化深度约10^-5 cm数量级,表明理论计算与实验现象吻合较好     

Die Lochkorrosionsanfälligkeit des Vergütungsstahles X20Cr13 in Natriumchloridlösungen

Pitting corrosion susceptibility of the heat treatable steel X20Cr13 in sodium chloride solutions For blades in steam trubines it is common to use the heat-treatable steels with 13% Cr (X20Cr13). Cracking of blades in the region of the turbine, where the steam starts to get wet, have often been referred to be caused by corrosion fatigue. The fatigue cracks sometimes start at inclusions in the material, but more often at pits caused by pitting corrosion. Pitting is brought about by chloride containing blade deposits. To examine the pitting behaviour of the steel in NaCl-solutions we measured the mixed-potential, the potentiostatic piting potential, the mass-loss and the pits per area as depending on temperature (20–80°C), pH (5–7–9), oxygen content (20 μg/kg up to saturation with oxygen) and chloride content (8×10^?5 mole/l up to saturation with NaCl 5,4 mole/l). The results show that steel X20Cr13 suffers pitting corrosion because of it's low Cr content in all technical possible NaCl solutions down to a Cl content of 10^?5 mole/l at the mixed potential.     

The influence of Mn compared to that of Cr,Mo and S on the resistance to initiation of pitting and crevice corrosion in austenitic stainless steels

A large number of production and laboratory heats in grades AISI 304 and 316 with normal and extremely low managanese and sulphur contents and a number of production heats in more highly alloyed austenitic stainless steels have been studied with regard to their resistance to initiation of pitting and crevice corrosion at various temperatures. The criteria for resistance to initiation was the potentiodynamic pitting potential in 0.1 M NaCl and synthetic seawater and the time to attack initiation for crevice corrosion in 0.5 and 5% NaCl solutions. A large number of production and laboratory heats in grades AISI 304 and 316 with normal and extremely low managanese and sulphur contents and a number of production heats in more highly alloyed austenitic stainless steels have been studied with regard to their resistance to initiation of pitting and crevice corrosion at various temperatures. The critieria for resistance to initiation was the potentiodynamic pitting potential in 0.1 M NaCl and synthetic seawater and the time to attack initiation for crevice corrosion in 0.5 and 5% NaCl solutions. The main aims of the study were to examine both the effect of manganese relative to that of chromium, molybdenum and sulphur and the effect of heat treatment and sulphide composition on steels with low manganese contents. Mathematical models for calculation of the pitting potentials have been constructed and multiple linear regression analysis gave the equations and their reliabilities. Lowering of the Mn content in austenitic stainless steels to 0.2% gives rise to a material of interest for constructions where pitting or crevice corrosion are judged to be the only potential types of attack, where operational disturbances leading to greatly increased corrosivity do not occur, where attack can not be tolerated, and where steel with normal managanese content has not exhibited fully satisfactory corrosion resistance. If the above conditions are fulfilled the low manganese content can be said to correspond to the same positive effect as is obtained by an addition of the least 1.5% Mo.     

Untersuchung über die Auswirkung der Elementbildung zwischen Stahl in Beton und Stahl in Erdboden

Investigation of the effect of galvanic corrosion between steel in concrete and steel in soil The investigation of cathodic polarization of steel in concrete on samples of portland cement and blast furnace cement revealed that oxygen reduction on steel in portland cement is less hindered than on steel in blast furnace cement. As to the magnitude of the cathodic current the aeration of the samples is important. Dry stored samples before measuring case a higher current density than wet stored ones. A significant relationship of the cathodic current depending on the water/cement value and the storage time of concrete could not be ascertained. The polarization resistances for portland cement samples lie within 86 and 3000 kΩ · cm² and for blast furnace cement samples between 430 and 5100 kΩ · cm². The measurements of the anodic current densities on corrosion cells of steel in concrete/steel in solution and steel in wet sand respectively rendered, by varying the cathode/anode aspect ratio from 1000: 1 to 1: 1, values for portland cement samples between 560 and 1,2 μAJcm² (corresponding to an annual corrosion of 6,5 and 0,014 mm respectively), and for blast furnace cement samples values between 730 and 0,28 μA/cm² (corresponding to an annual corrosion rate of 8,5 and 0,003 mm respectively). A decrease of the anodic current density variable with time could not be observed during the 28 days of measurements. On account of the investigations the following conclusions can be made: A formation of a corrosion cell with steel in concrete/steel in soil is particularly then to be expected if the concrete is dry on one side, e.g. the foundation of a building where oxygen diffuses by way of the gas pores in the concrete from the inner side to the cathode. This is less serious if the concrete is fully embedded in soil and thoroughly moistened. In this case the transport of oxygen has to be carried via waterfilled pores.     

Einfluß der Kationenzusammensetzung von Chloridlösungen beim Modellieren von Korrosionseinflüssen der Küstenatmosphären

Influence of the cation composition of chloride solutions in modelling corrosion effects due to caoastal atmospheres Pure sodium chloride solutions cannto be used for accelerated weathering tests in artificial sea atmosphere. A spray liquid suitable for such tests is artificial seawater containing (grams/litre) 27 NaCl, 6 Mg chloride, 1 Ca chloride and 1 KCl. The corrosion behaviour of the two metals studied – iron and zinc – is characterized by typical differences, in particular variations depending on the salt quantity applied. While the corrosion of iron at first increases with the salt concentration applied and achieves a maximum at about 1000 mg/m²d, the losses of zinc increase just to a salt quantity of 200 mg/m² d and are then practically constant up to about 1000 mg/m²d; at higher concentrations there is again a slight diminuation of corrosion. The corrosion in artificial seawater is more pronounced than in sodium chloride solutions; this fact can be attributed to the hydrolysis of the chlorides in seawater, which gives rise to the formation of anodic and cathodic regions on the metal surface; as a consequence, pH differences are created and corrosion is enhanced. In order to simulate natural conditions as closely as possible the application of the salt spray should be interrupted by extended dry periods.     

Zum Spannungsrißkorrosionsverhalten rekristallisierter Bleche der AlLi-Legierung 8090-T81

On the stress corrosion cracking behaviour of recrystallized 8090-T81 Sheets The stress corrosion cracking behaviour of a recrystallized sheet of the Al-Li-Cu-Mg-Zr alloy 8090-T81 was studied performing accelerated tests under constant deformation, constant load, and slow strain rate conditions. The used electrolytes were an aqueous 3.5% NaCl solution, an aqueous solution of 2% NaCl + 0.5% Na₂CrO₄ at pH = 3, and synthetic seawater according to ASTM D1141. Alternately immersed in 3.5% NaCl solution according to ASTM G44 the investigated alloy was found to be susceptible to stress corrosion cracking was not promoted by continuous immersion in aerated 3.5% NaCl solution, 3.5% NaCl solution saturated with carbon dioxide, and in acid chromate inhibited 2% NaCl solution. Using the slow strain rate technique with continuously immersed flat tensile specimens stress corrosion cracking was only observed in synthetic seawater. Under specific environmental conditions hydrogen embrittlement can occur in the investigated material.     

Cu-Ti合金在模拟S2-污染海水中的腐蚀行为研究

通过浸泡实验与电化学测试,研究了固溶态Cu-4wt.%Ti合金在模拟污染海水(含S2-的3.5wt.% NaCl溶液)的腐蚀行为。借助扫描电子显微镜(SEM)、X射线衍射(XRD)以及X射线光电子能谱仪(XPS)对铜钛合金表面腐蚀产物进行测试分析。结果表明：含Cl-溶液中铜钛合金的腐蚀形式为点蚀,点蚀坑尺寸较小,分布均匀。添加S2-后点蚀更容易被诱发,点蚀坑尺寸较大。当NaCl溶液中的S2-浓度达到60ppm时,点蚀坑在合金表面相互连接,呈现出均匀腐蚀的形态;S2-<和Cl-对铜钛合金的腐蚀存在竞争吸附,S2-吸附性强对铜钛合金的腐蚀剧烈;在含S2-的NaCl溶液中腐蚀产物主要为CuS、Cu2S、Cu2O以及Cu2(OH)3Cl。S2-浓度较大时会导致溶液中OH-浓度增加,使腐蚀产物膜层厚度与致密度增加,因此当S2-浓度达到100ppm时铜钛合金能够发生钝化从而减缓腐蚀。     

Characteristics of the random transients caused by clustered pitting corrosion for Al–Mg microelectrode

The clustered pitting corrosion process has been investigated by electrochemical noise measurement using two nominally identical Al–Mg microelectrodes in aerated 3.5 wt% NaCl solution (pH 3.5). Current transients associated with the metastable pitting were detected and the pits were examined by scanning electron microscopy (SEM) observation. The results show that two types of clustered pits can be characterized by current transients separately. Pit interaction is confirmed by one transient with multiple peaks. Considering the nonFaradic current and cathodic current of H₂ evolution inside the pit, the average volume determined from an integrated charge associated with individual single peak current transient is lower than that of actual pits, while the single peak transient count is more than that from SEM observation. It thus implies that reactivation of one metastable pit occurs and the relevant millisecond transient demonstrates only a single peak associated with nanopit for each reactivation. The results from this work shed insight into the use of statistical analysis of current transients to forecast the corresponding pit morphology.