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.     

Die Lochkorrosion austenitischer Chrom-Nickel- und Chrom-Nickel-Molybdän-Stähle in schwefelsaurer Bromidlösung und ihre Inhibition durch Nitrationen

Pitting corrosion of austenitic chromium nickel and chromium nickel molybdenum steels in sulfuric acid containing bromides, and its inhibition nitrate ions In acidified bromide solution CrNi steels are attacked under pitting when a certain critical potential has been exceeded; this potential is higher than in the case of chloride containing solutions. Bromides are, consequently, less active than chlorides, but the pit density is considerably higher under idential corrosion conditions. While the pitting corrosion in chloride solutions can be considerably reduced by molybdenum addition to the steel, this effect is but little pronounced in the case of bromide solutions (with Mo additions up to 4% the potential is displaced by 0.2 V toward positive values). Mo additions around 2% are even dangerous since the pitting density is considerably increased in that range. Similar to the conditions in chloride solutions corrosion in bromide solutions is inhibited by nitrate additions; the potential limit is considerably higher in the bromide solution; this phenomenon points to stronger adsorption of bromide ions at the metal surface.     

Über den Zusammenhang zwischen Lochkorrosion und Festigkeitsverhalten austenitischer Chrom-Nickel-Stähle

Relations between pitting corrosion and mechanical strength of austenitic chromium nickel steels The shape, depth and size as well as the frequency of pits formed under potentiostatic conditions on the surfaces of chromium-nickel steels (German designations X 5 CrNi 18 9 and X 5 CrNiMo 18 10) in 3% NaCl are studied with reference to stress mechanical effects of pitting corrosion. Comparative studies of pitting corrosion and strength behaviour of specimens at- tacked under pitting enable the residual tensile strength to be represented as a function of potential, and the tensile strength as such to be plotted as a function of a corrosion index containing pit depth and number. External effects like thermal treatment, alloy composition and cold deformation can be interpreted uniformly on the basis of all these graphical representations.     

Elektrochemische Untersuchung der Lochkorrosion chemisch beständiger Stähle

Electrochemical investigation into the pitting corrosion of corrosion resistant steels In view of the fact that the characteristics termed pitting potential depend from the measuring methods and nonstationary defects and hysteresis phenomena produced thereby these condition have been investigated on three different systems. In sulphate inhibited chloride solution an actual hysteresis is found with two critical boundary potentials for pit formation and pit passivation. The first of these potentials may be found either by potentiocinetic or by potentiostatic methods, the second only galvanostatically. In the case of 35% Cr steel no hysteresis is found; in this case there is no connection between pitting potential and the current and potential variations found during the investigation. With this material pitting corrosion may occur below the pitting potential while the pit passivation potential is a function of the properties of the measuring circuit. The pitting behaviour of austenitic CrNi steels containing various amounts of molybdenum may be characterized potentiostatically or potentiocinetically, but at low voltage feed rates only.     

Beeinträchtigung der Lochkorrosionsbeständigkeit von CrNi-Stählen durch dünne Oxidschichten

Influence of thin oxide films on pitting corrosion of CrNi steels Chloride-induced pitting corrosion of stainless steel (Materials No. 1.4301 and 1.4571) was investigated with the aid of chronopotentiostatic tests. Oxide films upon the surface (temper colours), addition of inhibitors (sulphate and nitrate) and temperature were the testing variables. Two different critical pitting potentials have been found, which give information on the potential ranges for stable passivity, latent and stable pitting corrosion. The results only indicate a small effect of Mo content of the material and test temperature. The inhibitors (sulphate and nitrate) have a marked effect. Specimens with a clean surface produced by pickling are markedly more resistant against pitting corrosion than specimens with a yellow temper colour, whereas the difference in corrosion resistance between yellow and blue films is relatively small. The width of the critical potential range for pitting corrosion generally increases with increasing oxide film thickness.     

Mikrobielle Werkstoffzerstörung – Simulation,Schadensfälle und Gegenmaßnahmen für metallische Werkstoffe: Manganoxidierende Bakterien und Lochkorrosion an Turbinenteilen aus CrNi-Stahl in einem Laufkraftwerk

Microbial deterioration of materials – simulation, case histories and countermeasures for metallic materials: Manganese oxidizing bacteria and pitting of turbine components made of CrNi steel in a hydroelectric power plant In a hydroelectric power plant pitting corrosion of the turbine runner blades (material G-X 5 CrNi 13 4) and the discharge ring (X 3 CrNi 13 4) ocurred at chloride levels of 170 mg/l maximum. Both, potentiostatic stepwise experiments and immersion tests gave no indication for susceptibility to pitting or crevice corrosion of this material in such water. Analysis of calcareous deposits found on the metal surface revealed high amounts of manganese dioxide. It is shown experimentally, that the CrNi-steel can undergo chloride induced pitting corrosion if polarized by manganese dioxide. Manganese oxidizing bacteria and possibly fungi were found to form the deposits. This case may be considered as microbiologically influenced corrosion (MIC) under aerobic conditions.     

Oberflächenpotentialprofile von metallen

Surface potential profiles of metals Using a microcapillary method in connection with simultaneous metallographic observation surface potential profiles have been determined with the potential probe in alcoholic acid solutions on cast iron, CrNi aciers steels 188, Cr steel with 17% Cr (welded) and an AlCu alloy. It was possible to distinguish cementite from ledeburite, not however, from austenite. The potential of 188 steel under pitting conditions decreases as a linear function of pit depth. The appearance of potential minima in a weld of ferrite steels is evidence of a intercrystalline corrosion in that particular medium. The precipitation of CuAl₂ in AlCu alloys at 150 °C at the grain boundaries forms an element with the grain boundary as the anode giving rise to intercrystalline corrosion.     

南海大气环境下304不锈钢的点蚀特性研究

目的 研究南海大气环境中服役的304不锈钢的点蚀原因与机理。方法 以不同暴露周期的304不锈钢试样为研究对象,采用动电位极化、电化学交流阻抗谱、扫描电镜和Kelvin 探针技术对其进行分析研究。结果 随着暴露时间的延长,304不锈钢表面的点蚀坑数量和深度均逐渐增加,其极化曲线中,钝化区间缩短,点蚀电位负移,阳极极化曲线斜率明显减小,并出现反复再钝化现象,钝化曲线逐渐消失,同时阻抗测试中的膜层电阻越来越小。SEM分析表明,304不锈钢暴露初期出现不连续的点蚀,点蚀坑向纵深发展,暴露后期出现点蚀群,局部有多个点蚀坑连成一片形成溃疡状的腐蚀表面,同时随暴露时间的延长,扫描试样微区的Kelvin表面电位不均匀性逐渐增强。结论 304不锈钢试样的耐蚀能力随暴露时间的增加而不断下降,点蚀现象不断增加。暴露初期,点蚀坑主要向纵深发展;暴露后期,点蚀坑的宽度达到一定程度后,本体溶液向坑内迁移,稀释了坑内溶液的酸度,点蚀坑向纵深和横向同时发展。     

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.     

Der Einfluß von Schwefeldioxid,Schwefelwasserstoff und Kohlenmonoxid auf die Lochkorrosion von austenitischen Chrom-Nickel-Stählen mit bis zu 4 Massen-% Molybdän in 1 M Natriumchlorid-Lösung

The Influence of SO₂, H₂S and CO on Pitting Corrosion of Austenitic Chromium-Nickel Stainless Steels with up to 4 wt. % Molybdenum in 1 M NaCl Active corrosion of chromium-nickel stainless steel X 5 CrNi 189 (AISI 304) in H₂SO₄ is stimulated by H₂S as well as by SO₂ (extension of the potential range of active corrosion, increase of the maximum corrosion rate in the active state and of the passivation current density), but is inhibited by CO (decrease of both maximum active corrosion rate and passivation current density). It is investigated whether likewise stimulating and inhibiting effects are valid also in case of pitting corrosion of austenitic stainless steels with molybdenum contents ranging from about zero (material no. 1.4301) to 4 wt. % (material no. 1.4449), tested in 1 M NaCl (ambient temperature) saturated with the gases mentioned above. The pitting corrosion behaviour of the materials investigated is judged by their pitting potentials measured by potentiostatically controlled experiments (testing time 24 hrs). The pitting potentials are compared with those measured in 1 M NaCl, N₂-bubbled. Pitting corrosion is stimulated by SO₂, CO and H₂S, with the stimulating efficacy increasing in the sequence given before. No stimulation is found only in 1 M NaCl, SO₂-bubbled,-with the highest Mocontent. In all other cases, stimulation of pitting corrosion increases with increasing Mo-content of the stainless steels. In coarse approximation, the critical limiting potentials of stable pitting in 1 M NaCl, bubbled with H₂S, SO₂ CO, correspond to the critical potentials of repassivating pitting corrosion found in N₂-bubbled 1 M NaCl. The chemical reactions and reaction products of SO₂ in aqueous solution are discussed. The nature of the stimulating component of the corrosive medium is not quite clear. The stimulating effects of SO₂ or one of its reaction products and of H₂S on pitting are in keeping with their stimulating effect on active corrosion of the steels investigated. The stimulating effect of CO, however, is in contradiction to the results expected and cannot be explained.     

孔蚀发展过程动力学分析

根据物质守恒、电荷守恒关系和电化学动力学,对球形、柱形蚀孔且其孔内存在和不存在沉积层,共四种典型状态下蚀孔的发展过程进行动力学分析,得到孔蚀电流、蚀孔深度和孔径随时间的变化关系。结果表明:孔蚀电流随时间发展共有四种特征函数,t~(1/2)、t、t~2和t~*ln(t),每一函数均对应特定的蚀孔发展状态.此四种函数构成一般蚀孔电流随时间关系的基集合,线性组合后得到普遍性孔蚀发展动力学方程。详细讨论了孔蚀发展与诸影响因素的关系,孔内沉积层存在与否及性能如何对蚀孔发展有显著影响,对球形孔的影响大于对柱形蚀孔。进而分析缓蚀剂抑制孔蚀发展的可能途径和效果,确定了孔蚀发展缓蚀剂须具备的条件;模型的正确性得到三方面结果的证实:实测304不锈钢在NaCl介质中孔蚀发展过程的电流关系,由建立的动力学方程给予了很好的解释。模型得到的孔蚀电流增长的最大方式是时间二次方,最小方式是平方根,与大量的文献结果吻合。孔蚀深度随时间仅有两种变化关系,幂函数和指数函数,与孔蚀深度的统计研究结果一致。     

Selektive Korrosion von Duplexstahl. Teil 2: Lokale Korrosionserscheinungen an Duplexstahl X2CrNiMoN22‐5‐3 unter Einwirkung von Chloriden und mechanisches Verhalten in Abhängigkeit vom Gefügezustand

Selective corrosion of duplex stainless steel. Part 2: Localized corrosion manifestations under exposure of chlorides on duplex stainless steel X2CrNiMoN22‐5‐3 and mechanical behavior in dependence of the microstructure In completion to part 1 of this paper this part deals with interrelations between localized corrosion manifestations, mechanical properties and the microstructure of duplex stainless steel X2CrNiMoN22‐5‐3. The pit formation on duplex stainless steels is substantially determined by the distribution of the alloying elements within single phases and by defects in the oxide layer. The positive properties of molybdenum become ineffective at thicker oxide layers due to the fact, that molybdate, which is responsible for inhibition of pitting, can not be formed. Depletion areas caused by precipitations are preferential attack places for corrosion. The influence of chlorides for duplex stainless steels in rolled and welded conditions is characterized by a logarithmic dependence.     

Pitting Kinetics of 304 Stainless Steel Using ESPI Detection Technique

The electronic speckle pattern interferometer was used to in situ monitor the pitting corrosion of 304 stainless steel at anodic polarization.The pitting current and pitting current density of a single pit were obtained.The pit growth was controlled by the corrosion products diffusion.The pit morphology was observed by a scanning electron microscope.The results showed that the pit was dish shaped,and the geometric parameters and pit growth time conformed to the function of Y = A+B1t+B2t2+B3t3.     

Beitrag zum Mechanismus der Lochfraßkorrosion des Nickels

A contribution to the mechanism of the pitting corrosion of nickel The pitting corrosion of nickel has been studied as a function of time, pH, potential and concentration in various salt solutions. It has been revealed that the number of pits as a function of time depends from the salt concentration and this dependence may be linear or parabolic. The potential dependence of the number of pits, on the other hand, follows an exponential law. From the salts included in the present study the chlorides in particular give rise to pitting; their effect is in part rather stimulated by nitrates. Sulfates, too, affect the action of chlorides, but their effect is different, depending on their concentration On the basis of the experimental results the author discusses possible mechanisms of pit formation and pit growth.     

Elektrochemische Prüfung der Wirksamkeit von Heizöl-Inhibitoren

Electrochemical testing of the effectiveness of fuel oil inhibitors The potential/time and current density/potential curves for unalloyed steel were obtained in NaCl solutions with different concentrations of a certain type of inhibitor. The results show that the inhibitor acts as a passivator. A comparison with the results of conventional static tests shows that even a 99 pC inhibiting effect against uniform corrosion does not constitute an effective protection against pit corrosion. An effective protection is only obtained if the steel specimen can, like a platinum electrode, be polarized up to oxygen formation without any penetration of the Cl^?-ions.     

Effect of Surface Finish on the Pitting Corrosion Behavior of Sensitized AISI 304 Austenitic Stainless Steel Alloys in 3.5% NaCl Solutions

The effect of surface condition down to 120 and 1000-grit finish, corresponding to 1.47 and 0.06 microns RMS (Root Mean Square), respectively, on the pitting corrosion behavior of sensitized and mill-annealed AISI (American iron and steel institute) 304 stainless steel was studied in 3.5% NaCl solutions at 23 and 50°C by electrochemical methods. The polarization curves have revealed a clear dependence of pitting corrosion on the surface finish, on the degree of sensitization, as well as on the test temperature. Surface condition has made a significant contribution to pit initiation in that the pitting potential was lowered as the surface roughness increased. The deleterious effect of surface roughness on the pitting potential of the AISI 304 stainless steel alloy in 3.5% NaCl is more pronounced on sensitized samples and becomes more evident with increasing sensitization time and test temperature.     

Beitrag zur Wachstumskinetik der interkristallinen Korrosion von ausgehärteten Al-Cu-Legierungen – Teil I: Ergebnisse der Folien-Durchbruchsmethode

Contribution to the growth kinetics of the intergranular corrosion of age-hardened Al-Cu alloys – Part I: Results of the foil penetration technique The growth kinetics of the intergranular corrosion (IC) of age-hardened Al-Cu-alloys in aqueous chloride solutions under potentiostatic conditions have been investigated using the foil penetration technique originally developed for pit growth measurements. The two tested systems were a pure binary Al-4% Cu-alloy (sheet thicknesses 0.2 and 0.5 mm) in 0.01 m NaCl, pH 11, and a commercial AA 2024 type alloy (various sheet thicknesses ranging from 0.2 to 1.0 mm) in 0.1 m NaCl, pH 7, respectively. Both alloys were tempered to maximum IC susceptibility and have been tested at potentials where selective anodic dissolution of the grain boundary regions occurs. As a reference system, the pit growth kinetics in commercial pure aluminum (sheet thicknesses ranging from 0.2 to 1.0 mm) in 0.01 m NaCl + 0.01 m Na₂SO₄ (as pit initiation inhibitor), pH 11, have been investigated at an applied potential considerably higher than the pitting potential. The experimental results have shown that, for the IC in the finegrained commercial alloy, a uniform growth kinetic valid for the whole range of sheet thicknesses, as for the case of pitting, cannot be formulated. The correlation of the current-time-curves and the attack morphologies (after penetration) for different sheet thicknesses with the penetration times leads to the conclusion that the growth kinetics of intergranular attacks are related to the number of sites of active attack (cracks) per metal volume. This specific number of actively growing cracks depends on the grain size and on the electrochemical conditions and, for given parameters, on the exposure time and therefore on the sheet thickness. For the commercial alloy examined, the following three stages of attack with decreasing penetration velocity of the IC could be distinguished:

• activation stage
• transition stage
• stable, macroscopic grain boundary dissolution.

The coarse-grained pure binary alloy showed a markedly higher penetration velocity of the IC under milder electrochemical conditions. This alloy is suitable for a model investigation of the first stage of attack but no quantitative kinetic information could be obtained from the only two disposable sheet thicknesses. The pit growth measurements in pure aluminum showed that the square root-of-time growth law previously found for thin foils and sheets is valid for deep pits too. The discussion explains that the electrochemical mechanisms of pitting of aluminum and of the IC in Al-Cu-based alloys are identical and that the basic difference lies in the geometry of the sites of attack. The ohmic control of the aluminum dissolution and therefore of the growth kinetics of pits and intergranular cracks is governed by the total anodic area and its different time dependence during the growth of the sites of local attack.     

Eine Charakterisierung Der Lochfraßkorrosion Des Nickels-II. Wachstumskinetik Und Lochmorphologie In Neutralen Sulfat- Und Perchloratlösungen

Potentiostatic current-time-measurements in sulphate and perchlorate solutions result in a quadratic time dependence for the growth of single pits on high purity nickel. In connection with studies of the pit morphology a new model for the propagation of pits is suggested. According to this model the development of a pit depends on the formation of a hydroxide or oxide layer at the opening of the pit or within the pit area. The model permits a new interpretation of the critical pitting potential and its observed pH-dependence. Furthermore, it gives a qualitative explanation of the influence of solution agitation on pitting corrosion.     

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。     

Einfluß des Kriechens auf die Spannungsrißkorrosion austenitischer Chrom-Nickel-Stähle in heißer 35%iger Magnesiumchloridlösung

Creep effect on stress corrosion cracking of austenitic CrNi steels in boiling 35% magnesium chloride solution Potentiostatic and potentiodynamic polarization curves of steel X 5 CrNi 18 9 in 35% MgCl₂-solution at 120° C do not show significant differences. Important for SCC tests is a narrow potential region before the onset of the potential of pit nucleation. SCC-experiments were carried out using two different techniques:

• (a) loading in the electrolyte
• (b) prestraining in air at 120° C; after transient creep the SCC test was initated.

Applying the technique described under (b) a decrease of SCC-susceptibility according to the crack nucleation expected in the slip dissolution model does not take place. Accordingly the dependence of time to failure on potential as well as on stress is found to be almost similar. Only in the absence of pitting a SCC threshold stress exists with its value in the range of yield strength. On the other hand SCC failure in the elastic region (< 0.1 σ_y) is observed when crack nucleation starts in corrosions pits.