Taxonomy for protective ability of rust layer using its composition formed on weathering steel bridge

For a quantitative evaluation of the protectiveness of a rust layer formed on a weathering steel bridge, the relationship between the corrosion rate of the bridge and the composition of the rust layers formed on the girders was first investigated. These corrosion rates were clearly classified by the protective ability index (PAI) of α/γ^∗ and (β + s)/γ^∗, where α, γ^∗, β and s are the mass ratio of crystalline α-FeOOH, the total of γ-FeOOH, β-FeOOH and the spinel-type iron oxide (mainly Fe₃O₄), β-FeOOH and spinel-type iron oxide, analyzed by XRD, respectively. The inequality of the former index α/γ^∗ > 1 expressed the protectiveness criterion of the rust layer, while that of the latter index, (β + s)/γ^∗< 0.5 or > 0.5, classified the corrosion rate of the non-protective rust layer. The PAI is useful for a quantitative evaluation of the protectiveness of a rust layer formed on a weathering steel bridge and is an important item for the corrosion assessment of the bridge.     

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.     

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.     

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.     

Influence of carbon content and microstructure on corrosion behaviour of low alloy steels in a Cl containing environment

Corrosion behaviour of low alloy steels (A and B) with different carbon content was studied by a salt fog test and an outdoor test. A commercial weathering steel 09CuPCrNi was used for comparison. The corrosion resistance of steels A and B with homogeneous microstructures was better than that of the commercial weathering steel 09CuPCrNi in the salt fog test. Steel A with an ultra-low-carbon content had far less weathering resistance than the other steels in the outdoor test. Selective corrosion of large pearlite produces stress in initial corrosion product films. Uniform corrosion product films with few cracks tend to form on homogeneous microstructures such as ferrite and bainite, and this is advantageous for the formation of a compact rust layer in the initial stage of atmospheric corrosion. However, uniform microstructures will result in over even interfaces between rust layers and bases, which will lead to frequent peeling of rust layers from bases because stress is induced by large temperature fluctuations and wet-dry alternations. Protection of the rust layer on a low alloy steel is dependent on the rust density and the bonding performance of the rust-base rather than the proportion of the rust phase in the initial stage of atmospheric corrosion. These results indicate that homogenous microstructures, proper amounts of carbon content and fine carbon-rich phases that are produced by appropriate processes are beneficial for the corrosion resistance of steels.     

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...     

耐大气腐蚀钢及其腐蚀产物的研究概况

本文介绍了耐候钢的发展,国内外使用及研究的情况,概述了合金元素对耐候钢耐蚀性能的影响及作用机理,并对腐蚀产物的组成及腐蚀产物锈层转化及演变的过程、机制进行了分析,对今后耐候钢的发展趋势提出了展望。     

Morphology of rust phases formed on weathering steels in various laboratory corrosion tests

The morphology and growth characteristics of rust phases formed on ASTM A-588 weathering steel in three different types of laboratory tests—accelerated atmospheric exposure simulation tests (AAEST), salt fog test, and continuous immersion test in plain as well as salt water—are analyzed using microstructural information obtained from representative exposed specimens studied in a scanning electron microscope (SEM). The ultimate and most dominant phase in the AAEST was α-FeOOH whereas an amorphous phase designated as amorphous bulk (AB) appeared as “cotton bolls” in the adherent, sedimentary layer formed on the steel surface during continuous immersion. Crystalline phases α-, δ-, and γ-FeOOH as well as γ-Fe₂O₃.H₂O were found developed on top of the first-formed sedimentary amorphous layer, containing another amorphous phase designated as amorphous mix (AM). Magnetite was the dominant phase obtained in the salt fog test. It forms in layers and seems to transform to α-FeOOH through formation of whiskers and rods on its surface. Sandy grains of γ-Fe₂O₃.H₂O were also seen in the rusts obtained in this test.     

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 通过周期性浸润腐蚀试验,研究了组织结构对贝氏体高强钢的耐腐蚀性能的影响。贝氏体高强钢和其退火试样的失重数据表明,贝氏体组织的耐腐蚀性能略优于铁素体和珠光体组织。运用扫描电镜和X射线衍射仪等分析测试手段对耐蚀机制进行了研究,发现两种试样均存在较致密的内锈层和疏松外锈层。两种试样的锈层成分主要是稳定的α-FeOOH和少量的γ-FeOOH组成。贝氏体组织的高强钢的锈层晶体更细小,均匀的组织结构有利于增强钢的耐腐蚀性能。     

Corrosion resistance and corrosion behavior of high-copper-bearing steel in marine environments

Thus far, research on the corrosion resistance of copper-containing steel has been limited to Cu content of less than 1%, and the corrosion resistance of antibacterial Cu-containing steel with Cu content above 3% has not been reported. In this study, 0Cu3 carbon steel (CS), 0Cr15Cu3 stainless steel (SS), and Q345 CS were investigated. The corrosion resistance and corrosive behavior of high-copper (high-Cu)-bearing steel in a marine environment were examined by scanning electron microscopy, energy dispersive spectrometry, X-ray diffraction, electrochemical impedance spectroscopy, and potentiodynamic polarization. Coupon test results showed that the Cu in the 0Cr15Cu3 SS and 0Cu3 CS can promote the formation of stable α-FeOOH from γ-FeOOH in the outer rust layers, and make the rust layers more thick and dense. In the electrochemical experiment, the impedance loop diameters and R_ct values of the 0Cr15Cu3 SS and 0Cu3 CS were higher than those of Q345, while the I_corr was less than that of Q345, which indicates that the anticorrosion property of these two types of high-Cu-bearing steel was higher than that of Q345. The aim of this study was to define the properties of corrosion resistance and corrosive behavior in high-Cu-bearing steels to promote their application in marine engineering.     

Nano-scale chemical analysis of rust on a 2% Si-bearing low alloy steel exposed in a coastal environment

Corrosion products of the rust layer formed on a 2% Si-bearing low alloy steel during atmospheric exposure at a coastal area in Japan for three years were characterized. The inner layer of the rust, i.e., near oxide/metal interface, has a layer structure and the average grain size of corrosion products is finer than that in the upper region that is few micro meter above the interface. A series of nano probe energy disperse X-ray spectroscopy (EDS) and selected area electron diffraction (SAED) analyses performed using a field emission gun (FEG) transmission electron microscope (TEM) revealed that the inner layer consists of an iron rich, coarse grained β-FeOOH matrix and the silicon enriched narrow band composed a mixture of α-FeOOH and nano-meter size silicon oxide. On the other hand, the α-FeOOH single phase area exists where the layer structure did not develop. The result of detailed microstructural analyses indicated that the silicon plays an important role in modifying the rust layer structure.     

The Suppression of transformation of γ-FeOOH to α-FeOOH accelerating the steel corrosion in simulated industrial atmospheric environment with a DC electric field interference

ABSTRACT

The initial corrosion of steels exposed to the simulated industrial atmospheric environment with a direct current (DC) electric field for 30 days was investigated using weight loss, electrochemical and characterisation methods. The results show that the steel weight loss increased with the increase in DC electric field intensity. The steels exposed to the DC electric field interference exhibited a higher corrosion rate than the blank samples during the exposure. The microstructural studies reveal that the existence of the DC electric field favours the growth of the γ-FeOOH, while suppresses the transformation of γ-FeOOH into α-FeOOH during the 30 days’ exposure, as a result of decreasing the protective ability and stable property of the rust layer. The amount of porous γ-FeOOH enhances the transmission of oxygen and conductivity of the whole rust layer. All these induce an accelerated effect of DC electric field on the initial steel corrosion in simulated industrial environment.     

The corrosion resistance of ultra-low carbon bainitic steel

The corrosion resistance of ultra-low carbon bainitic (ULCB) steel was compared with a weathering steel 09CuPCrNi through accelerated corrosion tests. The results indicated that the corrosion resistance was almost the same for ULCB and 09CuPCrNi based on the weight loss. It can be seen that the grain refinement did not deteriorate corrosion resistance property. The homogeneous microstructure, lower carbon content and random distributing ∑3 boundary could effectively increase the corrosion resistance of the ULCB steel. The characteristics of the rust layers indicated that the inner rust layer contained nanocrystalline Fe_3−xO₄ particles, while copper and chromium alloying additions were enriched at the rust layer and substrate interface in ULCB steel. These factors played important roles in forming a compact protective rust layer.     

Cu、Mn的协同作用对低合金钢在模拟海洋大气环境中腐蚀的影响

    用增重法、扫描电镜、X射线衍射、电子探针和X射线光电子能谱等手段研究了在模拟海洋大气干湿交替环境下16Mn钢和Cu-Mn耐候钢的腐蚀行为及Cu、Mn共添加对低合金钢腐蚀行为的影响.结果表明：Cu-Mn耐候钢的腐蚀速率低于16Mn钢,其锈层更致密;两种钢的铁锈均由Fe₃O₄,α-FeOOH,β-FeOOH,γ-FeOOH和大量无定形相组成;添加Cu使Fe₃O₄含量增加,添加Mn使γ-FeOOH含量减少;Cu在Cu-Mn耐候钢锈层中以CuFeO₂存在;Mn在两种钢锈蚀初期以MnO存在,后期为Mn₃O₄.Cu、Mn的协同作用使Cu-Mn耐候钢抗大气腐蚀性能优于16Mn钢.     

Influence of outer rust layers on corrosion of carbon steel and weathering steel during wet–dry cycles

The influence of the rust layers of carbon steel and weathering steel on the corrosion were investigated. It was found that corrosion of carbon steel slows down when its outer rust layer is removed. This phenomenon might be attributed to the shortening of the wetting time in wet–dry cycles when the outer rust layers are removed. What is more, growth time of the corrosion products is shortened as well, which results in the formation of the fine corrosion products. However, the behavior of corrosion of weathering steel is not obviously influenced by the outer rust layer and the wetting time.     

Corrosion behavior of steel under wet and dry cycles containing Cr ion

The corrosion behavior of mild steel has been investigated during the wet and dry cyclic transitions containing Cr³⁺ ion added as sulfate in order to gain a better understanding of the influence of Cr on the atmospheric corrosion of steels. The corrosion rate during drying is greatly suppressed by the existence of Cr³⁺ ion in the electrolyte covered with the surface. Lower corrosion rates are observed during drying even if the surface have been polarized to negative potentials below −200 mV_SHE during the wet corrosion conditions in which the surface-covered electrolyte contains Cr³⁺ ion. This corrosion behavior is identical to the case of Cr-containing steel for the wet and dry cyclic transitions without the addition of Cr³⁺ ion. The composition of rust layer after the wet and dry cyclic transitions is composed of α-FeOOH, γ-FeOOH and Fe_3−δO₄ for both cases of non-Cr³⁺ and Cr³⁺-containing condition, and no significant difference in the mass fraction of the above rust substances between two conditions is observed by means of Mössbauer spectroscopy. The only difference in the rust layer is that the rust formed under the wet and dry cyclic transitions containing Cr³⁺ ion contains a certain amount of Cr near the steel/rust interface. Those results suggest that the role of Cr during the wet and dry cyclic transitions is the inhibition of the rust reduction and the formation of Fe²⁺-state intermediate by the existence of Cr in the rust layer. This can lead to the inhibition of the oxygen reduction during drying.     

Effects of DBU, morpholine, and DMA on corrosion of low carbon steel exposed to steam

Effects of morpholine, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), and dimethylamine (DMA) on oxidation kinetics and oxide phase formation/transformation of AISI 1018 steel at 120 °C were evaluated. Low carbon steel samples were exposed to steam in an autoclave containing amine added aqueous solution at pH of 9.5 for 1, 2, 4, 6, 8, and 12 h. Control samples exposed to plain steam and amines showed the highest and lowest weight loss respectively. Fourier Transform Infrared Spectrophotometry (FTIR) showed that DBU containing steam favored formation of magnetite (Fe₃O₄) while steam with DMA formed more α and γ-FeOOH. Transformation of magnetite to hematite (α-Fe₂O₃) was fastest for morpholine. Analysis of oxides morphology was done utilizing Scanning Electron Microscopy (SEM). Oxides formed in plain or DMA containing steam exhibited acicular particles of goethite/hematite (α-FeOOH/α-Fe₂O₃) compared to DBU containing steam that showed equiaxed particles of magnetite/maghemite (Fe₃O₄/γ-Fe₂O₃). Morpholine containing steam promoted agglomeration of thin sharp platelets into coarse flakes of hematite.     

Magnetic property based characterization of rust on weathering steels

The characterization of rusts on weathering steels is important in understanding the origin of their corrosion resistance. Rust consists of several phases, e.g. α-, β- and γ-FeOOH, which are anti-ferromagnetic with different Neél temperatures. Rust on so-called advanced weathering steel containing 3 wt.% Ni [H. Kihira, A. Usami, K. Tanabe, M. Ito, G. Shigesato, Y. Tomita, T. Kusunoki, T. Tsuzuki, S. Ito, T. Murata, in: Proc. Symp. on Corrosion and Corrosion Control in Saltwater Environments, Honolulu, 1999, The Electrochemical Soc., pp. 127-136] contains in addition a ferrimagnetic spinel phase [M. Kimura, H. Kihira, Y. Ishii, T. Mizoguchi, in: Proc. 13th Asian-Pacific Corrosion Control Conference, Osaka, 2003; M. Kimura, H. Kihira, N. Ohta, M. Hashimoto, T. Senuma, Corros. Sci., this volume; M. Kimura, N. Ohta, H. Kihira, Mater. Trans. JIM, in press]. The nanostructure of real rust cannot be elucidated satisfactorily only with conventional analytical methods such as X-ray diffraction, because of the complex mixture of phases with fine and imperfect crystallites. Because of the short range of the super-exchange coupling between Fe ions in a solid, the magnetic properties can give information on local configurations even in the absence of perfect crystalline coherence. Therefore, the magnetic properties of rust samples were investigated in detail using a Superconducting Quantum Interference Device (SQUID) magnetometer and Mössbauer spectroscopy. SQUID magnetometry is effective to determine the quantity of the ferrimagnetic phase. The temperature dependence of the Mössbauer spectrum gives information about not only the fractions of the phases but also the distribution of grain volume, V, in each phase according to the super-paramagnetic relaxation effect. This approach has been applied to rust of conventional [T. Okada, Y. Ishii, T. Mizoguchi, I. Tamura, Y. Kobayashi, Y. Takagi, S. Suzuki, H. Kihira, M. Ito, A. Usami, K. Tanabe, K. Masuda, Jpn. J. Appl. Phys. 39 (2003) 3382] and advanced weathering [H. Kihira, A. Usami, K. Tanabe, M. Ito, G. Shigesato, Y. Tomita, T. Kusunoki, T. Tsuzuki, S. Ito, T. Murata, in: Proc. Symp. on Corrosion and Corrosion Control in Saltwater Environments, Honolulu, 1999, The Electrochemical Soc., pp. 127-136] steels.The grains of the rust formed on advanced weathering steel have clearly bimodal Gaussian distributions of volume with peaks at V ≈ 5 × 10⁻²⁴ m³ and V ≈ 16 × 10⁻²⁴ m³ in α-FeOOH and β-FeOOH phases. The outer layer has grains of γ-FeOOH which are an order of magnitude smaller. The inner layer, in contrast, has a continuous distribution of grain volume, consistent with the formation of a continuous densely packed thin protective rust layer which prevents further corrosion.     

耐候钢表面稳定锈层形成机理的研究

研究了耐候钢在青岛近海大气中曝晒3a的腐蚀行为, 观察测定了锈层与基体的界面形貌、相组成及锈层中合金元素的分布.结果表明,腐蚀3a的 耐候钢表面锈层有明显的分层现象;内锈层组织致密,主要有各向同性的α-FeOOH构成,在 偏光下检测消光;外锈层有γ—FeOOH和Fe2O3构成,在偏光下检测炫光;在内锈层中有 合金元素的富集.     

Electrochemical techniques for determining corrosion rate of rusted steel in seawater

Corrosion rates of mild steel for long-term immersion were estimated by electrochemical and weight-loss methods. The results showed that application of electrochemical methods yielded erroneous values. The main reason was that, β-FeOOH, produced after long-term immersion with high electrochemical activity in the inner rust layer, exerted significant influence. In electrochemical tests, even small polarization can make β-FeOOH participate in cathodic reaction, which leads to overestimating corrosion rate. In order to confirm it, electrochemical behaviour was studied in aerated and deaerated conditions to investigate the effect of rust layers on reduction reaction. After calibration, the electrochemical measurement result was coincided with the weight loss.