外加电位下X80双相管线钢在模拟沿海土壤环境中的应力腐蚀行为

采用交流阻抗谱、极化试验、慢应变拉伸试验研究了不同外加电位下在模拟沿海土壤环境中X80双相管线钢的应力腐蚀行为,对拉伸断口和极化后试样进行SEM表面形貌及能谱分析。结果表明,与慢扫极化(模拟的非裂尖区域)相比,X80双相管线钢快扫极化模拟的裂尖腐蚀电位较负且腐蚀电流较大。-750 mV外加阴极电位处于裂尖自腐蚀电位范围,不足以起到阴极保护的作用,对应力腐蚀仍十分敏感。外加电位为-1050 mV时,阴极反应速率显著大于阳极反应,阴极反应产生的氢被金属吸收且扩散,慢应变拉伸未经颈缩即发生断裂,为准解理断裂。外加阴极电位为-900 mV,阴极电流有效抑制了阳极溶解反应,因此管线钢在模拟沿海土壤溶液中慢应变拉伸抗拉强度和断面收缩率都最高,断口表现为韧性断裂,侧面裂纹细小,阻抗模值最大,应力腐蚀敏感性最小。     

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。     

Predicting the mechanisms and crack growth rates of pipelines undergoing stress corrosion cracking at high pH

A fundamentally based mathematical model was developed with the goal to predict, as a first step, the crack growth rate (CGR) of high pH stress corrosion cracking (SCC) of buried steel pipelines. Two methods were used to predict CGRs and for both methods the model has included the film rupture and repassivation mechanism. The two methods are distinguished by the expression used to determine the active anodic current density at the crack tip. In the first method, this current density is expressed by the anodic polarization curve with a large peak current density and the prediction tends to yield a larger CGR and a lower pH at the crack tip. By contrast, when the Butler–Volmer equation is used to express the crack tip anodic current density, with a predicted low CGR the chemistry at the tip does not appear to have any significant change due to the high buffer of the solution.The predicted mechanism responsible for the steady-state crack growth is shown to be the balance between the increasing stress intensity factor as the crack grows, which tends to increase the crack tip strain rate and thus the CGR, and the change of the crack tip condition, which, for large CGRs, is the significant shift in the more negative direction of the crack tip potential, and for low CGRs, the increase of ferrous ion concentration, and either tends to decrease CGR.Limitations currently existing in the model and proposal for further development of the model are discussed.     

真空度对2205双相钢在热浓缩海水中点蚀行为的影响

目的研究真空度对2205双相不锈钢在海水淡化环境中耐点蚀性能的影响。方法在1.5倍人工浓缩海水中,采用循环阳极极化曲线与电化学阻抗谱等电化学方法,研究了2205双相不锈钢的点蚀和再钝化行为,并通过扫描电子显微镜对极化后试样的腐蚀形貌进行分析。结果测试了七种不同真空状态下2205双相不锈钢的循环阳极极化曲线和电化学阻抗谱,发现随着真空度的升高,试样的自腐蚀电位和点蚀电位均不断降低,分别约从-256 m V和605 m V下降到-485 m V和363 m V(均vs.SCE),点蚀倾向明显增大。同时,Nyquist曲线中的半圆弧逐渐变得扁平,Bode图中的相位角约从80°下降到77°,但是点蚀电位与再钝化电位之差逐渐升高。不同真空度下循环阳极极化后,试样表面的点蚀坑形貌不完全相同,蚀坑数量随着真空度的升高而明显减少,当真空度升高为0.72时,点蚀坑尺寸明显减小。结论随着真空度的逐渐升高,不锈钢钝化膜的致密性和保护性降低,电化学阻抗值逐渐减小,耐点蚀性能变差,但是再钝化性能却有所增强。循环阳极极化后试样的腐蚀程度减小。     

Effects of Cathodic Potential, Bicarbonate, and Chloride Ions on SCC of X70 Pipeline Steel

This is an investigation on the stress corrosion cracking (SCC) behavior of X70 pipeline steel in high pH carbonate-bicarbonate solutions with different concentrations of bicarbonate and chloride ions and at cathodic potential of ?1100 mV versus saturated calomel electrode (SCE) using slow strain rate testing. Electrochemical techniques such as potentiodynamic polarization and electrochemical impedance spectroscopy were used to investigate the electrochemical behavior of X70 pipeline steel in solutions with different concentrations. X70 pipeline steel fracture surface morphology in these different solutions was also studied by scanning electron microscopy (SEM). The results suggested that the susceptibility to SCC for X70 pipeline steel decreased in the most dilute carbonate-bicarbonate solution in the absence of the chloride ion. Also, at potential of ?1100 mV versus SCE, all fracture surfaces showed semi-brittle behavior with transgranular cracks.     

氮对00Cr18Ni5Mo3Si2双相不锈钢应力腐蚀破裂性能的影响

用慢应变速率方法(SSRT)评价了合金元素氮对00Cr18Ni5Mo3Si2(18-5Mo)钢SCC 性能的影响.发现适宜的含氮量为0.11%,此含氮量的钢最耐30%MgCl_2(沸)溶夜中的应力腐蚀破裂(SCC)。由恒电位 SSRT 实验,得出三种不同含氮量的钢的 SCC电位范围和临界破裂电位。结果表明,氮提高了应力腐蚀临界破裂电位,阳极极化降低了氮的作用,当阳极极化至-350mV(SCE)以上时,氮几乎不起作用。氮改变了相比例,从而影响双相钢性能。扫描电镜(SEM)、能谱仪(EDAX)配合金相分析发现:阳极极化削弱了氮通过两相比例对双相钢 SCC 性能的影响。在开路电位下,α、γ相均对裂纹的发展起阻止作用;在较低的阳极极化电位下.α、γ相均对裂纹起一定阻止作用,在较高阳极极化电位下,它们对裂纹的阻止作用消失。由此认为较高的阳极极化电位使α相γ相的电化学保护作用消失。     

En24钢在海水中的应力腐蚀

用恒位移弯曲试验,慢应变速率试验、动电位扫描和浸蚀试验研究了En24钢在海水中的应力腐蚀特性。结果表明,En24钢的环境敏感断裂倾向随强度降低而降低;强度低于临界值,则不出现应力腐蚀裂缝。外加电位对En24钢的环境敏感特性有重要影响,裂缝扩展平台速度于-900mV处出现极小值。依据裂缝扩展动力学、断口形貌、物理冶金参数和电化学等方面的判据,认为En24钢在海水中的应力腐蚀与电位密切相关。低于-900mV,属氢致开裂;高于-900mV,则由阳极溶解过程所制约;在一定电位范围内,不排除两种机理共同作用的可能性。     

阴极极化下X80钢在鹰潭土壤模拟溶液中应力腐蚀行为研究

采用电化学阻抗和慢应变速率方法,结合扫描电子显微镜,研究了不同阴极极化电位下X80钢在鹰潭土壤模拟溶液中的应力腐蚀行为。结果表明：鹰潭土壤模拟溶液中,X80钢/溶液界面处电荷转移电阻随阴极极化程度增加先升后降。在自腐蚀电位条件下开裂机理为阳极溶解,当外加电位为-1000 mV (vs SCE),应力腐蚀敏感性最低,此电位为最佳保护电位;继续增大阴极极化程度,应力腐蚀敏感性增加,此时开裂机制为氢和应力协同作用下的氢致开裂。     

Stress corrosion cracking of steam turbine disc steel--measurement of the crack-tip potential

In situ measurements have been made of the crack-tip potential in a fatigue-precracked compact tension specimen of a 3% NiCrMoV steam turbine disc steel immersed in simulated steam condensate environments at 90 °C. Despite high corrosion potentials of 0.1 V saturated calomel electrode (SCE) the extent of crack-tip anodic polarisation was very constrained, a limiting potential of about −0.61 V SCE being attained. Surprisingly, adding chloride up to 1500 ppb, or separately sulphate at 406 ppb, had no impact on the tip potential and its variation with corrosion potential, compared with pure water. Increasing the pH of initially neutral pure water also had no significant effect.     

不同外加电位下 X80 管线钢在近中性 pH 溶液环境中的裂纹扩展行为研究

目的研究不同外加电位下,X80管线钢在近中性p H溶液环境中的裂纹扩展行为。方法对X80管线钢紧凑拉伸试样进行近中性p H溶液环境中的循环加载试验,利用拍摄装置记录不同循环次数下的裂纹长度,并利用扫描电镜(SEM)观察裂纹扩展面上的微观形貌。研究不同外加电位下,X80钢在近中性p H溶液环境中的裂纹扩展速率,分析其裂纹扩展规律。结果在开路条件下,循环加载755次时,裂纹扩展4.6 mm后失稳断裂;在外加电位为-775 m V(vs.SCE)的条件下,循环加载671次时,裂纹扩展3.677 mm后失稳断裂;在外加电位为-1125 m V(vs.SCE)的条件下,循环加载625次时,裂纹扩展3.882 mm后失稳断裂。结论在开路电位和弱阴极电位下,裂纹扩展受到阳极溶解机制和氢脆机制的混合控制,以阳极溶解机制为主,裂纹扩展速率均较低;随着外加电位降低,裂纹扩展机制逐渐过渡为主要受氢致开裂作用控制,裂纹扩展速率显著增加。     

Corrosion behavior of Cu–Al–Be shape memory alloys with different compositions and microstructures

The corrosion behavior of Cu–Al–Be shape memory alloys with different microstructures and Be content in a 3.5% NaCl solution was studied by weight loss, cyclic anodic polarization and chronoamperometric measurements. The beryllium has a beneficial effect in β alloys. A pitting potential of −100 mV/SCE was found by anodic polarization tests for all the studied alloys, corresponding to the formation of pits produced by severe dealuminization. Samples with precipitates were more susceptible to pit formation. The corrosion behavior is strongly affected by the alloy microstructural conditions, and the β samples present higher pitting resistance and repassivation ability.     

维尼纶醛化机腐蚀监控技术的研究

本文研究SUS36不锈钢,在醛化液中的腐蚀行为及电化学条件、介质中的杂质离子浓度等因素的影响。提出了醛化机不锈钢腐蚀监控的参数。结果表明,在Cl~-浓度小于600pm的醛化液中,采用恒电位(300mV左右)阳极保护,能有效地控制腐蚀。本文还给出维尼纶醛化机不锈钢设备恒电位阳极保护装置的工艺设计及工业应用试验结果。     

锰铜合金腐蚀裂缝在3.5%NaCl中的电化学行为

<正> 锰铜系高阻尼合金在铸态下具有优良的机械性能与阻尼性能,是一种新的舰艇螺旋浆材料。该合金的主要成份是:35～36%Cu,4～4.5%Al,2.5～3.5%Fe,1～2%Ni,余量 Mn,实艇试验表明,采用这种合金对降低螺旋浆的振动和噪声有明显的效果。但是,锰铜合金在海水介质中有 SCC 敏感性。实验室试验得出,该合金在3.5%NaCl 中的 K_(?)cc 约等于26kgf/mm~3 /2。现场试验也发现,经焊补的锰铜合金螺旋浆很快在焊缝周围出现开裂。本工作沿用前人的方法,采用闭塞电池模拟腐蚀裂缝,初步探讨了锰铜合金在海水介质中发生 SCC 的原因及可能防止的方法。     

Crack tip chemistry and electrochemistry of environmental cracks in AA 7050

The role of the crack environment in establishing environment-assisted crack (EAC) propagation in AA 7050 alloys is elucidated. A suite of mini-electrodes provided real-time in situ measurements of the crack potential, pH, and chloride concentration during stage II cracking in a chromate-chloride electrolyte under electrochemical control. For material aged to an EAC-susceptible condition, crack growth during an incubation period is characterized by tip polarization to near the applied electrode potential (E_App) and bulk-like chemistry near the crack tip. In contrast, establishment of high-rate crack growth coincided with the development of an acidic, high chloride concentration tip environment and tip depolarization. During steady state high rate crack growth, the tip potential was ∼−0.85V_SCE; near-tip potential gradients were ∼1 V/cm. Large ohmic potential drop within fast-growing cracks is indicative of net anodic current in the near tip region and increased mass transport resistance within the crack due to solid corrosion products and/or hydrogen bubble formation. Microinjection of a corrosion-inhibiting or corrosion-promoting solution at the tip suppresses or prompts, respectively, the transition from incubation to high-rate cracking, highlighting the intimate dependence of the crack growth kinetics on the local chemistry. The exceptional EAC resistance of over-aged AA 7050 is intrinsic; injection of an acidic aluminum chloride solution at the tip of a crack of this material while polarized to a high E_App failed to induce brittle crack advance.     

Untersuchungen zur interkristallinen Spannungsrißkorrosion unlegierter Stähle in Ammoniumcarbonatlösungen

Investigation into the intercrystalline stress corrosion cracking of unalloyed steels in sodium carbonate solutions The steel St 36 is characterized by a very pronounced susceptibility to intercrystalline corrision, even under constant load. This sensitivity is limited to a potential zone of about 100 mV situated at the beginning of the passivity range (between ?600 and ?500 (SCE)). While a plastic deformation is not necessary for the initiation and propagation of cracks the propagation is accelerated at high loads. There is, however, no critical elongation rate which would give rise to preferential stress corrosion cracking. It is not possible to maintain the hypothesis according to which the stress corrosion cracking susceptibility would decrease at sufficiently low elongation rates. On the base of the results obtained one may assume the existence of disturbed zones in the oxide layer and the nucleation of cracks at such sites (possibility of “pre-existing-paths” according to parkins). The crack propagation would then be a function of the ratio of rate of advancement of the crack tip (which is assumed to be active) and the rate of repassivation of the crack walls, this repassivation being due to the formation of magnetite.     

The effect of temperature on the behaviour of a zinc-mild steel couple in a solution containing chloride ions

The time and temperature dependence of a zinc-mild steel galvanic cell has been examined in a sodium borate-hydrochloric acid buffer solution (pH 7·60) within the temperature range 30–90°C. In each cell the zinc electrode passivated either spontaneously or under the influence of the galvanic action with a corresponding increase in potential. However, the widely reported potential reversal was not observed. This latter is attributed to the fact that in this particular solution the breakdown (pitting) potential of the zinc is always less noble than the corrosion potential of the steel whether in deaerated or oxygen saturated solution. Potential reversal would therefore require the zinc to exceed its breakdown potential which the polarization curves show will require considerable and maintained anodic polarization; but potential reversal and anodic polarization of zinc are mutually exclusive. In all the cells investigated the mild steel was cathodically protected, although at 90°C the polarization was insufficient to prevent corrosion entirely. At 30°C, in a deaerated solution, the passive film on zinc remained intact producing very effective cathodic protection of the steel without extreme loss of zinc. However, under all other conditions examined the zinc became pitted resulting in unacceptable penetration of the metal.     

X100管线钢在酸性土壤模拟溶液中的应力腐蚀行为

采用慢拉伸(SSRT)、动电位极化和SEM观察等方法,研究了在不同的阴极保护电位条件下X100钢在酸性土壤模拟溶液中的应力腐蚀行为.结果表明,X100钢发生穿晶裂纹的应力腐蚀,裂纹的萌生和发展与阴极保护电位有关.完全阳极过程控制时,X100钢无裂纹出现,但出现晶间腐蚀;在混合过程控制时,应力腐蚀敏感性较低,裂纹发展缓慢;在完全阴极过程控制时,氢脆机制起主要作用,裂纹扩展迅速.     

Electrochemical behavior of corroded and protected construction steel in cement extract

The corrosion behavior of corroded, cathodically protected and control (reference) construction steel, previously embedded in concrete, was studied in cement extract (pH 12.6, considered as concrete pore water), using cyclic voltammetry (CVA) and potentiodynamic polarization (PDP). The necessity for this investigation occurred from the previously observed and commented discrepancies in the recorded corrosion parameters for corroded and protected steel in embedded conditions 1 . Therefore this study aimed to evaluate how the “naturally” formed in concrete product layers (after 460 days) will influence the electrochemical behavior of the steel in cement extract. The PDP measurements reveal the lowest corrosion resistance to be for the previously corroded steel samples, for which the most active corrosion potential (?0.7 V SCE) and the highest anodic current in the potential region 0 to 0.6 V (SCE) were recorded. The CVA tests support the results from PDP and correlate the properties of the naturally formed layers with the recorded peak current densities and peak potentials with cycling. For all specimens, except the corroded ones, the peak potential initially shifts anodically, which denotes for a high corrosion resistance in the former and low corrosion resistance in the latter case. For the control and protected specimens, the passive current in the potential region of 0 to 0.6 V (SCE) remains almost unchanged with cycling, i.e. the protective properties of the initial layers remain unchanged. Thickening of the film with cycling does not influence the corrosion resistance of the previously formed layers. For the protected specimens, however, a tendency to reach a steady state and change of peak currents' height only were observed, without a pronounced shift to more anodic values. An increase in the peak current only, not accompanied by anodic shift of the peak potential, suggests that the layers in the cathodically protected specimens are more homogeneous and compact. Overall it can be stated that in cement extract, the product layer with lowest corrosion resistance is the one on the surface of the corroded steel reinforcement. The product layers in the protected specimens (although similar to control conditions) are with the highest corrosion resistance.     

A537钢及工业纯铁在3.5%NaCl水溶液中腐蚀疲劳裂纹扩展机理的识别

本文根据外加电位对腐蚀疲劳裂纹扩展速率的影响,断口微观形貌特征及声发射活动性分析三种判别方法,研究了A537钢及工业纯铁在3.5%NaCl中性水溶液中腐蚀疲劳裂纹扩展机理。结果表明,扩展机理取决于外加电位值。对A537钢,外加电位在-800mV(SCE)以上时,裂纹扩展以阳极溶解控制为主,以下时以氢脆控制为主。对工业纯铁,对应的转换电位为-1000mV(SCE)。