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.     

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.     

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.     

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.     

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.     

耐候钢表面锈层稳定化处理技术研究

目的解决耐候钢裸露使用初期锈液流失导致污染环境的问题。方法制备了耐候钢表面锈层稳定化处理溶液。通过周期浸润循环腐蚀试验、锈层微观分析和电化学测试等方法,研究了在模拟工业大气环境下,表面处理溶液对耐候钢锈层结构及耐腐蚀性能的影响。结果表面处理后,耐候钢的开路电位由处理前的-0.395 V降低到-0.475 V,表面快速生成一层连续致密的氧化层。加速腐蚀16 d后,耐候钢的腐蚀速率由未处理时的0.209 mg/(cm^2·d)降低到表面处理后的0.106 mg/(cm^2·d),降低了约49%;锈层的自腐蚀电位由未处理的-0.216 V提高到处理后的-0.073 V,提高了约66%,自腐蚀电流密度由未处理时的7.41μA/cm^2降低到1.58μA/cm^2,降低了约79%。随着腐蚀时间从1 d延长至16 d,处理后的耐候钢锈层中α-FeOOH的质量分数由2.96%增加到4.46%,增加了51%,γ-FeOOH的质量分数由2.06%降低到1.65%。表面处理后的耐候钢锈层中,Cu和Cr元素在锈层与基体结合处和锈层内部发生富集。结论处理溶液降低了耐候钢表面的开路电位,可使耐候钢快速生成致密且连续的锈层,锈层中Cu、Cr元素富集促进了γ-FeOOH向α-FeOOH的转化,提高了锈层电化学保护性能,降低了后期腐蚀速率,缩短了稳定化进程。     

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.     

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。     

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.     

Atmospheric corrosion of hot and cold rolled carbon steel under field exposure in Saudi Arabia

Carbon steel (hot and cold rolled) specimens have been exposed to the action of different atmospheres at 20 test sites distributed in Saudi Arabia and was investigated in terms of environmental factors such as average temperature, average relative humidity and deposition rates of atmospheric pollutants (Cl⁻ and SO₂). Applying the standard ISO 9223 norm aggressiveness of the atmospheres corresponding to 0the different test sites has been determined. Calculations of corrosion rates were made via loss of weight and characterization of the corrosion products formed on samples has been carried out by means of X-ray diffraction (XRD). The major constituent of the rust formed in marine and marine-industrial environment is goethite (α-FeOOH). These samples also show the presence of a large proportion of lepidocrocite (γ-FeOOH) and small amounts of ferrihydrite and maghemite (γ-Fe₂O₃). In the case of urban and rural samples goethite is the major constituent of corrosion layers. The rust formed under the urban environment also contains large amounts of ferrihydrite and in a lesser proportion, of goethite and maghemite.     

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.     

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...     

Enhancement of electric conductivity of the rust layer by adsorption of water

The rust layers on the weathering steels exposed for 17 or 18 y at seven different sites in Japan were studied by electrochemical impedance under wet condition and measurement of amount of water vapor adsorbed. The transient of amount of adsorbed water vapor into the rust layer during humidity jump from 0% to 80% RH indicated that saturation of adsorbed water vapor took place within 1 h. From the semi-infinite model of diffusion, apparent diffusion coefficients of H₂O in the rust were calculated. It was found the apparent diffusion coefficient was higher when the amount of air-borne salt of exposure sites was higher. The impedance diagram of the rusted steels was analyzed with an equivalent circuit consisting of a series connection between an ohmic resistance and a parallel circuit of charge transfer resistance-redox capacitance. The double layer capacitance on the gold electrodes pressed onto the rust layer was further added on the circuit. The impedance showed that the rust layer behaved as a dielectric layer under dry condition, while the conductance was greatly enhanced with wet condition. The charge transfer resistance evaluated from the simulation under wet condition was largely dependent on the amount of air-borne salt in environment. It was concluded that the rust layer formed in the site with relatively large amount of air-borne salt revealed high conductivity under wet condition. For the rust formation followed by the Evans model during wet-dry cycles, the higher conductivity induced the more facilitative reduction of the rust layer under wet condition and the larger growth of the rust layer in a wet-dry cycle.     

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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。     

Electrochemical impedance of thin rust film of low-alloy steels

The quality of the rust film formed on the steel is a significant factor in atmospheric corrosion. In the present paper, ion-exchange membranes were adopted to simulate the anion and cation selective permeability of the rust film. The i-E curve and the electrochemical impedance of a carbon steel covered with the ion-exchange membrane were measured to discuss the effect of the ion transfer inside the rust film on the anodic dissolution. The electrochemical impedance of the rust film membrane was measured. The electrochemical impedance of the rust film membrane shows the apparent capacitive behavior. It was found that the film had huge capacitance of order 10 mF cm⁻². The resistance of the rust films of Fe-3%Ni, Fe-1%W and Fe-0.6%Mo was large value, indicating that the low ion permeability rate inside the rust film contributed to decreasing the corrosion rate of low-alloy steel.     

Electrochemical characterisation of the porosity and corrosion resistance of electrochemically deposited metal coatings

Electrochemical techniques for the assessment of porosity in electrodeposited metal coatings are reviewed. The determination of porosity and corrosion, resistance is illustrated by electrochemical data from three coating/substrate systems namely: electroless nickel on aluminium and steel and immersed gold coatings on an electroless copper-plated ABS polymer. Nickel coatings were up to 24 μm thick while gold deposits had thickness between 75 and 190 nm. Tafel extrapolation and linear polarisation resistance methods were used to determine the corrosion rate of the coated substrates. The aluminium samples were tested in 5% w/v (0.85 mol dm^− 3) NaCl, while coated steel and ABS samples were immersed in 0.125 mol dm^− 3 H₂SO₄ and 0.1 mol dm^− 3 NaBH₄, respectively, at 295 K. Current vs. time curves and anodic polarisation behaviour have also been considered.     

A Mössbauer spectroscopic study of rust formed during simulated atmospheric corrosion

Steel coupons were subjected to 100% relative humidity and were inoculated every day with 100 μl of 0.01 N solutions of NaCl, Na₂SO₄, LiCl or CsCl. The first solid rust constituent that formed contained significant amounts of both γ-FeOOH and ferrihydrite. In contrast, only γ-FeOOH was observed in the rust formed during atmospheric corrosion and during wet-dry cycling with distilled water in the laboratory. The ferrihydrite in time was converted to γ-FeOOH, α-FeOOH, and γ-Fe₂O₃. The fractions of ferrihydrite + γ-FeOOH in the rust formed as a function of time during atmospheric exposure and during rusting in the laboratory environment were the same in the two cases.     

EFFECT OF DAMNIFICATION IN RUST LAYER ON CORROSION BEHAVIORS OF LOWCARBON BAINITIC STEEL IN THE ENVIRONMENT CONTAINING Cl−

利用电化学、金相、能谱等方法, 研究了低碳贝氏体钢在表面锈层受到不同程度的损伤后, 在含Cl^-环境中的继续腐蚀行为. 实验发现, 低碳贝氏体钢和作为对比材料的低碳钢试样的表面锈层受损伤后, 在继续腐蚀过程中均能很快得到修复. 在损伤程度与继续腐蚀时间相同的条件下, 低碳贝氏体钢的锈层电阻与损伤修复率均高于低碳钢. 低碳贝氏体钢基体/锈层界面的断裂韧性高于锈层本身.在受外界作用时, 锈层不会沿基体/锈层界面彻底脱落从而在基体表面保存残留锈层. 残留锈层能明显促进新锈层在损伤部位的形成. 原有锈层与损伤部位新形成的锈层中Cu和Cr含量接近, 并与钢基体的含量相当.     

Corrosion resistance of the Dhar iron pillar

The corrosion resistance of the 950-year old Dhar iron pillar has been addressed. The microstructure of a Dhar pillar iron sample exhibited characteristics typical of ancient Indian iron. Intergranular cracking indicated P segregation to the grain boundaries. The potentiodynamic polarization behaviour of the Dhar pillar iron and mild steel, evaluated in solutions of pH 1 and 7.6, indicate that the pillar iron is inferior to mild steel under complete immersion conditions. However, the excellent atmospheric corrosion resistance of the phosphoric Dhar pillar iron is due to the formation of a protective passive film on the surface. Rust analysis revealed the presence of crystalline magnetite (Fe_3−xO₄), α-Fe₂O₃ (hematite), goethite (α-FeOOH), lepidocrocite (γ-FeOOH), akaganeite (β-FeOOH) and phosphates, and amorphous δ-FeOOH phases. The rust cross-section revealed a layered structure at some locations.     

Corrosion behaviour of low-carbon bainitic steel under a constant elastic load

The corrosion behaviour of low-carbon bainitic weathering steel in an environment containing chlorine ions (Cl⁻) was studied by applying different constant elastic loads. The results showed that the applied elastic load reduces the resistance of the rust layer to Cl⁻ diffusion because of the porous structure as well as the enhanced anion selectivity in the rust: this leads to more severe corrosion of the steel compared with load-free conditions. The corrosion rate increased with increasing loads. Corrosion enhancement can be attributed to mechanical-chemical interactions at the steel surface.