低碳钢在海水中的阴极电化学行为

采用电化学技术结合XRD分析, 研究了A3碳钢在海水中的阴极电化学行为, 探讨了锈层在阴极过程中的作用. 碳钢表面生成的锈层由内锈层和外锈层组成, 内锈层主要组成相为γ-FeOOH, α-FeOOH, β-FeOOH以及Fe₃O₄与γ-Fe₂O₃的混合物. 浸泡126 d时, 外锈层主要由γ-FeOOH组成; 浸泡364 d由γ-FeOOH, α-FeOOH, Fe₃O₄和 γ-Fe₂O₃组成. 不同锈层在阴极过程中所起的作用不同. 外锈层主要作用是阻碍溶解氧到达金属表面, 内锈层除此之外还可以参与还原反应, 加速阴极反应. 提出了一个评价锈层参与还原反应程度的参数α, 在浸泡不同时期锈层参与还原反应的比例不同, 浸泡前7 d, α值上升比较明显, 随后增加比较缓慢, 浸泡168 d后基本稳定. 探讨了内、外锈层组分的变化以及锈层各组分间的相互作用.     

桥梁耐候钢在含Cl~-离子环境中的腐蚀行为

选择3种Ni含量为3.5%的桥梁钢,采用干湿周浸加速腐蚀实验模拟海洋大气环境下桥梁钢的耐腐蚀性能变化,并利用金相显微镜、XRD和SEM等分析了不同Mn和Cu含量桥梁耐候钢组织以及其腐蚀不同时间的腐蚀形貌和锈层特征.结果表明:桥梁耐候钢的组织由准多边形铁素体、针状铁素体和粒状贝氏体组成;随着Mn含量的增加,钢的耐蚀性能增加;Ni和Mn在锈层中均匀分布,Cu在锈层的缝隙或孔洞等缺陷处富集.锈层主要由Fe_3O_4,γFeOOH和α-FeOOH组成,腐蚀不同时间后的试样锈层组成相有所不同;γ-FeOOH和α-FeOOH与钢的腐蚀速率密切相关;增加Mn含量可以促进γ-FeOOH和α-FeOOH的生成,同时抑制γFeOOH和αFeOOH的晶粒长大.     

Cu、Ni元素对耐蚀高锰阻尼钢在大气环境中腐蚀行为的影响

高锰阻尼钢因其高强度、超低屈强比、阻尼性能良好和经济性能优异等特性,在承受较大振动和冲击的桥梁、轨道交通和军工等领域展现出广阔的应用前景。而高锰钢耐蚀性能欠佳一直是限制其快速发展的关键性因素,高锰钢耐蚀性设计及其大气腐蚀行为研究均鲜有报道。为解决高锰钢耐蚀性能欠佳问题,采用真空感应熔炼和两阶段轧制工艺制备 3 种添加不同 Cu、Ni 元素含量的耐蚀高锰阻尼钢,通过大气曝晒试验、电化学测试、SEM、XRD 和 XPS 等方法对试验材料的电化学性能、 腐蚀速率、腐蚀形貌、腐蚀产物物相及结构进行表征及分析。结果表明：相较于单独添加 Cu 元素的高锰阻尼钢,钢中添加 1.2 wt.% Cu 和 1.0 wt.% Ni 元素腐蚀电位正移近 200 mV,腐蚀电流密度降低近 50%;曝晒试验后,较高含量的 Cu 和 Ni 元素协同添加使腐蚀产物中 α-FeOOH 含量明显提高,活性较高的 MnFe₂O₄和 Mn₂O₃含量降低,耐蚀产物 NiOOH 及 CuO 含量增加。腐蚀产物颗粒均匀细小,产物层整体致密光滑,保护性能提高,其腐蚀速率相较于单独添加 Cu 元素的高锰阻尼钢降低 70%,表现出优异的耐蚀性能。所提出的高锰阻尼钢耐蚀性的成分设计方案及耐蚀机理可为未来高锰阻尼钢在桥梁中的应用提供数据支持。     

一种耐候钢耐蚀性能的分析

对耐候钢和Q235B开展了周期浸润腐蚀试验,并对试样进行了检测分析。金相、扫描电镜(SEM)检测结果显示耐候钢的锈层较薄,与基体结合紧密。X射线衍射分析结果表明,耐候钢锈层中主要是α-FeOOH,这是耐大气腐蚀性能更好的主要原因。EPMA成分扫描分析显示,对耐候性有益的元素Cu、Cr、P、Si在锈层中富集,促进了结构较致密的α-FeOOH的生成,成为保护层;同时,提高了锈层和基体的结合和粘附性,防止在长时间的腐蚀中锈层剥落,提高了耐大气腐蚀性。     

在Q235钢表面原位生长的氧化铁膜对其在含Cl-溶液中腐蚀行为的影响Ⅰ-原位生长的γ-FeOOH膜的防护性能

    利用动电位极化曲线和交流阻抗谱等电化学测量技术,研究了Q235钢表面原位生长的γ- FeOOH膜在0.25 mol/L Na₂SO₄+10^-4mol/L NaCl、0.25 mol/L Na₂SO₄+10-3mol/L NaCl、0.25 mol/L Na₂SO₄+10^-2 mol/L NaCl水溶液中的电化学行为及在不同浓度的Cl^-水溶液中γ-FeOOH膜对Q235钢的保护作用.结果表明,Cl^-含量较低时,γ-FeOOH膜的存在明显地促进了Q235钢的阴极反应,该膜对基材无保护作用;随Cl-浓度的增加,阴极电流密度大幅减小,当Cl^-浓度达到10^-2 mol/L时,γ-FeOOH 膜能在一定程度上抑制基材的腐蚀,此时γ-FeOOH膜表现出对基材有保护作用.     

耐候锈层的耐腐蚀机理研究

通过模拟工业大气环境的周期浸润实验室加速试验,研究耐候钢和碳钢的锈层腐蚀初期生长规律以及耐候钢锈层的耐腐蚀机理;对试验钢样进行了腐蚀失重分析,通过扫描电镜、X射线衍射等手段对锈层形貌和结构进行分析.结果发现,腐蚀初期耐候钢的锈层组织成分主要以α-FeOOH为主;碳钢的锈层组织成分主要以Fe2O3为主.α-FeOOH晶体枝晶尺寸纤细,锈层致密具有保护性;Fe2O3枝晶粗大,锈层疏松和多孔不具有保护性.     

模拟工业大气条件下高锰耐候钢的腐蚀行为

应用电化学阻抗谱研究了在模拟工业大气的腐蚀溶液中Mn对耐候钢耐腐蚀性能的影响,并通过锈层电子探针面扫描验证了实验结果。电化学阻抗谱结果显示,在腐蚀初期高锰耐候钢表现出较强的点蚀反应特征,腐蚀后期则显示和比对钢相同的耐腐蚀能力。在模拟工业大气腐蚀条件下,Mn在耐候钢的内锈层中没有产生富集,Cr 和Cu在内锈层和钢基体界面中形成了富集带,这是保护性锈层生成的主要原因。     

表面涂层改性技术在提高耐候钢抗海洋性大气腐蚀中的应用

表面涂层改性处理的耐候钢挂片在2年的海洋性大气环境下暴晒,其腐蚀率是原耐候钢挂片腐蚀率的1／6。采用偏光、红外吸收、X射线衍射及EPAM对挂片锈层结构和组成进行了分析,发现碳钢、耐候钢表面锈层主要由γ-FeOOH、α-FeOOH及Fe3O4组成。α-FeOOH趋向在钢铁表面分布。改性涂层处理可以加速耐候钢表面生成保护性致密锈层,该锈层中富集有大量Cr,而碳钢挂片、裸露耐候钢挂片、涂层耐候钢挂片表面疏松锈层中没有Cr的富集。     

不同NaCl浓度对耐候钢腐蚀产物的影响

对Q450耐候钢在不同浓度NaCl溶液中模拟海洋大气环境进行了周期浸润试验.采用光学显微镜、扫描哇镜和X射线衍射仪对钢的腐蚀形貌、锈层截面和腐蚀产物进行了观察和分析.结果表明:随着NaCl浓度的提高,锈层变得疏松多孔;不同浓度NaCl溶液中主要腐蚀产物相同,均为γ-FeOOH及少量Fe3O4.     

建筑用耐候钢在含Cl-环境中的腐蚀行为研究

研究了桥梁建筑用耐候钢在含Cl-环境下表面锈层的腐蚀行为。结果表明,耐候钢组织由粒状贝氏体、针状铁素体以及准多边形铁素体组成。材料中的微量合金元素Mn可以降低腐蚀后期晶粒尺寸,促进α-FeOOH和γ-FeOOH相形成,提高材料表面锈层致密度。而Cu主要富集在锈层孔洞和缝隙处,能够改善表面锈层质量,提高耐候钢的抗腐蚀性。     

In-depth distribution of rusts on a plain carbon steel and weathering steels exposed to coastal-industrial atmosphere for 17 years

In-depth distribution of rusts on two weathering steels and a plain carbon steel exposed to atmosphere for 17 years under a bridge at a coastal + industrial region in Japan were studied. In the rust layer on all specimens, α-FeOOH, β-FeOOH, γ-FeOOH, Fe₃O₄ and so-called amorphous rust were found. Within rust layers, there were thick parts and thin parts, which were finely and complicatedly distributed on steels. Among these rust species, α-FeOOH was dominant on all specimens. α-FeOOH appeared almost homogeneously through the rust layer. Its concentration was higher on weathering steels than on plain carbon steel. β-FeOOH was found mainly at thick parts and was scarce at thin parts of rust layers. Concentration of α-FeOOH was higher and that of γ-FeOOH was lower on weathering steels than on plain carbon steel. Amorphous rust was located at the bottom of the rust layer irrespective of steel types. Concentration of magnetite was negatively correlated with concentration of β-FeOOH.     

A study of the evolution of rust on Mo–Cu-bearing fire-resistant steel submitted to simulated atmospheric corrosion

The corrosion evolution of a Mo–Cu-bearing fire-resistant steel in a simulated industrial atmosphere was investigated by corrosion weight gain, XRD, EPMA, XPS, and polarization curves. The results indicate that the corrosion kinetics is closely related to the rust composition and electrochemical properties. As the corrosion proceeds, the relative content of γ-FeOOH and Fe₃O₄ decreases and α-FeOOH increases, and the rust layer becomes compact and adherent to steel substrate. Molybdenum and copper enrich in the inner rust layer, especially at the bottom of the corrosion nest, forming non-soluble molybdate and Cu(I)-bearing compounds responsible for enhanced corrosion resistance of the rust layer.     

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...     

Characterization of the rust formed on weathering steel exposed to Qinghai salt lake atmosphere

The product formed on weathering steel exposed to salt lake atmosphere for 12 months was investigated by X-ray diffraction (XRD), infrared transmission spectroscopy (IRS), scanning electron microscopy (SEM), electron probe micro analyzer (EPMA) and electrochemical techniques. The rust was mainly composed of β-FeOOH, Fe₈(O,OH)₁₆Cl_1.3 and a little γ-FeOOH. Amorphous δ-FeOOH was only on skyward surface. The rust layer suppressed anodic reaction and facilitated the cathodic reaction. The very small value of rust resistance R_r in this work indicated that the rust had poor protective ability. Cl element was rich in the whole rust layer and played an important role in accelerating the corrosion of weathering steel in salt lake atmosphere.     

Influences of metal ions on the formation of γ-FeOOH and magnetite rusts

To elucidate the role of anti-corroding alloying metals in weathering steels, the γ-FeOOH and Fe₃O₄ particles were prepared by air-oxidation of FeSO₄ solutions containing different amount of Ti(IV), Cr(III), Cu(II) and Ni(II). The crystallinity and particle size of γ-FeOOH were lowered by adding Cr(III), Cu(II) and Ni(II) but not influenced by Ti(IV). All the metal ions impeded the crystallization and particle growth of Fe₃O₄ in a similar manner. The results on γ-FeOOH and Fe₃O₄ were compared with those on α- and β-FeOOHs previously reported to know the comprehensive effects of metal ions on the formation of rusts.     

低碳贝氏体钢在青岛曝晒一年的锈层力学性能和抗热震性能研究

研究了低碳贝氏体钢在青岛曝晒一年后表面锈层的相组成、形貌、力学性能以及抗热震性能.结果表明:锈层由α-FeOOH、β-FeOOH、γ-FeOOH、Fe3O4以及非晶相组成;锈层的表面和截面形貌显示锈层较为致密,合金元素Cr和Cu在锈层中接近钢基体处有明显的富集现象;锈层的弹性模量和硬度随距锈层/钢基体界面的距离增大而降低;锈层/钢基体的结合强度和抗热震能力均高于锈层本身.     

Structure of titanium-doped goethite rust

To investigate the influence of titanium addition on the formation and structure of goethite (α-FeOOH) rust which is one of main corrosion products of weathering steel, the artificially synthesized α-FeOOH rusts were prepared by hydrolysis of aqueous solutions of Fe(III) containing Ti(IV) at different atomic ratios (Ti/Fe) in the range 0-0.1. The obtained rusts particles were observed by TEM. Characterization by XRD, N₂ absorption, Mössbauer spectroscopy was also done. TEM observation revealed that the α-FeOOH rust particle size increased with the increase of Ti/Fe, and that Ti-enriched poorly crystalline particles were formed around the rust particles. XRD confirmed that the crystallite size increased with the increase of Ti/Fe, while the XRD peaks decreased in intensity. Specific surface area obtained by N₂ absorption increased with the increase of Ti/Fe. It is deduced from the obtained results that the addition of Ti(IV) increases the crystallite size of α-FeOOH, and produces double domain particles consisting of the particle core and a porous poorly crystalline shell. It is thought that such unique rust structure produced by titanium addition contributes to the protective properties of rust layer of the weathering steel.     

Composition and protective ability of rust layer formed on weathering steel exposed to various environments

The compositional change of rust (corrosion products) layer formed on weathering steel exposed to atmosphere with different amount of air-borne sea salt particles in Japan have been investigated by the X-ray diffraction method. The mass ratio (α/γ) of crystalline α-FeOOH to γ-FeOOH, in the rust layer formed on the weathering steel exposed in an industrial environment, increases with an increase in exposure duration. The α/γ is closely related to the corrosion rate in environments when the amount of air-borne salt is less than 0.2 mg NaCl/dm²/day (2.31 × 10⁻⁷ g NaCl/m²/s). However this is not the case in seaside environments with a higher amount of air-borne salts. The mass ratio (α/γ^∗) of crystalline α-FeOOH to the total mass of γ-FeOOH, β-FeOOH and Fe₃O₄, in the rust layer formed on the weathering steel is related to the corrosion rate even in seaside environments certainly more than 0.2 mg/dm²/day (2.31 × 10⁻⁷ g/m²/s) of air-borne salt particles. When the α/γ^∗ is more than 1, a higher corrosion rate more than 0.01 mm/year (3.17 × 10⁻¹³ m/s) is not observed. The α/γ^∗ is a protective ability index of rust formed on weathering steel.     

Corrosion resistance and mechanical properties of low-alloy steels under atmospheric conditions

The corrosion resistance and mechanical strength of four newly developed low-alloy steels (LAS) were compared with a carbon steel (SS400) and a weathering steel (Acr-Ten A) using a laboratory-accelerated test that involved cyclic wet/dry conditions in a chloride environment (5 wt.% NaCl). The new LAS were designated 1605A, 1605B, 1604A, and 1604B. After 72 cycles of cyclic corrosion tests, the susceptibility of the steels to corrosion could be listed in the following order based on their weight loss (from high to low): SS400 > Acr-Ten A > 1604B ? 1604A > 1605B ? 1605A. The change in mechanical properties by corrosion was the least for SS400, Acr-Ten A was second, and effects of corrosion on the mechanical properties of the other four low-alloy steels were similar. Finally, the characteristics of the rust layers on each LAS sample were observed by SEM, and analyzed by FTIR and EPMA. The results indicated that most of the rust layers on the test steels were composed of a loose outer rust layer and a dense inner rust layer. The outer rust layer of each steel was composed of α-FeOOH, γ-FeOOH, magnetite (Fe₃O₄), H₂O, and amorphous ferric oxyhydroxide (FeO_x(OH)_3−2x, x=0-1), while the inner rust layer was composed mainly of Fe₃O₄ with a little α-FeOOH. In addition, it was apparent that the copper and chromium alloying additions were enriched, respectively, at the rust-layer/substrate interface and in the rust layers. Finally, combining the results of the accelerated tests and the rust layer analysis showed that low-alloy steels, such as 1605A and 1605B, have better weathering steel properties than Acr-Ten A for use in the humid and salty weather.