耐候钢新型表面锈层稳定剂处理及其耐3.5％NaCl溶液周浸腐蚀性能

目的解决耐候钢裸露使用初期锈液流挂与飞散的问题。方法制备了新型耐候钢表面锈层稳定剂,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海洋大气环境下,锈层稳定剂对耐候钢锈层结构及耐腐蚀性能的影响。结果表面锈层稳定化处理后,耐候钢表面生成的锈层区分为致密且连续的内锈层和外锈层。室内加速腐蚀168 h后,耐候钢的失重腐蚀速率由未处理的5.71 g/(m~2×h)降低到表面处理后的3.31 g/(m~2×h),失重腐蚀速率降低了约42%。耐候钢的锈层电阻由未处理的96?·cm~2提高到表面处理后的167.7?·cm~2,锈层电阻提高了约75%。表面处理后的耐候钢锈层中,Cr元素以α-(Fe_(1-x)Cr_x)OOH的形式存在于基体与锈层的界面处,Cr元素在内锈层与基体结合处发生聚集。结论新型锈层稳定剂可以明显改善耐候钢锈层结构,细化锈层晶粒,阻碍Cl~-的渗透,有助于耐候钢表面快速生成致密、连续且稳定的保护性锈层。     

耐候钢表面锈层稳定化研究现状

耐候钢表面形成的致密保护性锈层使其具有良好的抗大气腐蚀性能,经锈层稳定化处理后再使用是耐候钢最具有现实意义的使用方式。耐候钢表面锈层的组织结构、形成机理及过程、保护机理的研究,对于锈层稳定化处理技术和处理剂的开发具有基础性作用。首先,全面综述了近年来耐候钢表面锈层的研究进展,耐候钢经过基体铁的溶解、锈的还原、锈的再氧化等过程,形成了以Fe3O4、α-FeOOH、无定形的羟基氧化物（FeOx(OH), x=0~1）为主的连续致密内锈层,以β-FeOOH、γ-FeOOH为主的疏松多孔外锈层,内外锈层构成了耐候钢表面锈层。相较于普碳钢,耐候钢表面锈层具有连续致密、阳极钝化、离子选择性等特性,使得耐候钢具有良好的抗大气腐蚀性能。然后,归纳了目前国内外主要的锈层稳定化处理方法及其优缺点,主要有氧化物涂膜处理、氧化铁-磷酸盐系处理、喷丸+高温氧化处理等方法,但存在应用范围狭窄、有污染等问题。最后,基于合金元素在耐候钢中的作用提出了锈层稳定化处理剂组分的设计思路,并从应用范围、绿色环保、缩短稳定化周期等提出了耐候钢表面锈层稳定化处理剂研究的进一步建议。     

耐候钢锈层的稳定化处理及锈层的生长机制EI北大核心CSCD

开发一种新型耐候钢表面锈层稳定化处理剂,促进锈层的快速生长和稳定。以Q420NH耐候钢为基材,水性丙烯酸树脂为成膜物,加入两类添加剂——稳定剂(钼酸钠、磷酸钾、硝酸钠)和羟基氧化铁,制备出稳定化处理剂,涂刷于耐候钢的表面,在盐雾环境中研究锈层的生成过程。结果表明,水性丙烯酸树脂具有一定的氧气和水渗透性,适合作为稳定化处理的成膜物。在90 d的盐雾试验中,锈层厚度随盐雾时间的增长而不断增加,并且稳定化处理后试样的锈层厚度大于裸钢的锈层厚度。XRD结果显示,稳定化处理不改变耐候钢锈层的成分,Q420NH裸钢和稳定化处理的耐候钢的锈层均主要由Fe_(3)O_(4)、γ-FeOOH、α-FeOOH、β-FeOOH组成。SEM和截面Raman光谱结果表明,稳定化处理的试样锈层中保护性的α-FeOOH相分布更加广泛。EDS结果证明Cr、Cu合金元素在锈层中富集,电化学阻抗谱说明稳定化处理后的试样具有更佳的耐腐蚀性能。稳定化处理技术促进了耐候钢表面保护性锈层的生长,缩短了稳定化进程,提高了锈层的保护性能。     

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。     

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。     

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。     

耐候钢锈层的稳定化处理及锈层形成

针对裸耐候钢保护性锈层生成时间较长及环境污染等问题,提出了一种含有合金元素的锈层稳定化处理剂,并采用喷淋的方式对耐候钢表面进行预处理。通过干湿交替腐蚀实验(CCT),对比了裸钢试样和预处理试样在模拟工业大气环境下的腐蚀规律。采用增重法评价了试样的耐蚀性;采用XRD分析了试样表面锈层的物相组成;采用SEM、电化学阻抗法(EIS)和吸水-脱水实验对锈层的致密性进行了表征和分析。结果表明,预处理试样的耐蚀性能优于裸钢试样;耐候钢经该处理剂处理后不改变耐候钢表面的腐蚀产物类型,但能够促进腐蚀产物中α-FeOOH相的生成;且经处理后耐候钢表面锈层的裂纹、孔洞等缺陷减少,致密性提高。     

耐候钢表面锈层稳定化处理用新型涂层研究

针对耐候钢裸露使用时出现的锈层稳定化时间过长及早期锈液流挂和飞散的问题，提出了Zn—Ca系磷化 丙烯酸树脂—SiO2复合膜新型耐候钢表面锈层稳定化处理技术．采用干湿周浸实验研究了该复合膜耐候钢试样的腐蚀行为和耐大气腐蚀性能．得出了能有效避免锈液流挂、促进耐候钢表面锈层稳定化的最佳复合膜处理工艺，即Zn—Ca磷化 B—13Si(120℃)复合膜处理．并从理论上探讨了该复合膜提高耐候钢抗大气腐蚀性能、促进表面锈层稳定化的作用机理和模型。     

耐候钢表面稳定化处理及锈层结构研究

针对免涂装耐候钢使用过程中暴露出的锈液流挂问题,设计了一种耐候钢锈层稳定化处理液,并对稳定化处理后的耐候钢进行了半年的大气暴晒实验。分析了耐候钢稳定锈层形成过程中,锈层的结构及演化行为。腐蚀动力学曲线结果表明：耐候钢表面锈层经过4个阶段逐渐达到稳定状态,每个阶段的增(失)重均呈线性变化。锈层中Cu、Cr富集提高了锈层电化学保护性能,缩短了稳定化进程。     

耐候钢的腐蚀及表面稳定化处理技术

介绍了耐大气腐蚀用钢（耐候钢）表面稳定化锈层的结构、组成和形成机理，耐候钢的使用方式及存在的问题，较全面地阐述了国内外有关加速耐候钢稳定化锈层形成过程的表面处理技术及原理。     

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。     

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.     

Q235钢在海水淡化一级反渗透产水中的腐蚀行为

采用旋转挂片和SEM, EDS及IR分析研究Q235钢在海水淡化一级反渗透产水中(RO)的腐蚀速度和腐蚀产物变化规律,并利用动电位扫描、电化学阻抗法研究腐蚀过程及腐蚀反应控制步骤。结果表明,Q235钢在海水淡化一级反渗透产水中腐蚀速度在48 h内迅速增大至1.4 mm/a,其后保持稳定。锈层初期为γ-FeOOH薄层,随时间延长逐渐转为由Fe₃O₄构成的内锈层及由γ-FeOOH和α-FeOOH构成的外锈层。腐蚀过程受阴极控制,初期腐蚀阻力达到最大,其后由于大量γ-FeOOH在酸性条件下极易转化为对腐蚀反应没有阻滞作用的Fe₃O₄,腐蚀阻力迅速减小,腐蚀速度迅速增大,当Q235钢表面γ-FeOOH生成和转化达到平衡后,腐蚀阻力保持稳定,腐蚀速度也不再发生变化。     

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 Rust Layers on the Corrosion Behavior of Ultra-High Strength Steel 300M Subjected to Wet–Dry cyclic Environment with Chloride and Low Humidity

The influence of rust layers on the corrosion behavior of ultra-high strength steel 300 M subjected to a simulated coastal atmosphere was investigated by corrosion weight loss, surface analysis techniques, and electrochemical methods.The results exhibit the presence of a large proportion of c-Fe OOH and a-Fe OOH and a small amount of Fe3O4 in the outer rust layer. During the wet–dry cyclic process, the bonding performance and the density of outer rust layer deteriorate with the thickness of outer rust. The inner rust layer plays a main role on protectiveness, which can be attributed to the formation of an ultra-dense and adherent rust film with major constituent of a-Fe OOH and a-Fe2O3 on the steel.     

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.     

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.     

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.