耐候钢表面锈层及其稳定化处理现状与发展趋势

综述了耐候钢表面稳定化锈层的形成、组成及其结构,并讨论了影响耐候钢表面锈层稳定化的因素;介绍了主要的锈层稳定化处理技术;同时,指出了耐候钢表面锈层稳定化技术的研究出发点,并对该技术的发展趋势进行了展望。     

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。     

耐候钢锈层稳定化处理技术及其评价方法

概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其评价方法,着重阐述了耐候钢锈层稳定化处理技术的有机-无机复合膜技术,并展望了这一方面国内外的发展趋势。     

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。     

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。     

耐候钢表面预处理对其腐蚀行为的影响

通过向带锈耐候钢表面喷淋锈层稳定化剂进行预处理,使锈层表面形成了一层化学转化层,并进而研究了其对耐候钢继续腐蚀行为的影响。利用干湿循环交替腐蚀(CCT)、增重实验、场发射扫描电镜(SEM)及能谱仪(EDS)、X射线衍射分析仪(XRD)和电化学工作站等实验手段对经过预处理及未处理样品进行对比测试。结果表明:该转化层对腐蚀性离子Cl-有显著的拦截效应,并导致样品在腐蚀过程中增重减缓;预处理不改变腐蚀产物的类型,但会造成锈层内非晶相比例上升并使锈层颗粒更加细小;转化层的短期效应与长期影响不同,转化层的存在总体上有利于加速锈层稳定化。     

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。     

耐候钢表面锈层稳定化过程研究

通过大气暴露腐蚀试验对比分析了碳钢和耐候钢的腐蚀情况 ,并对试片表面腐蚀产物进行了XRD和EPMA分析 ,研究了耐候钢表面锈层的稳定化过程。     

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。     

耐大气腐蚀钢的研究概况

综述了国内外耐大气腐蚀钢(即耐候钢)的发展概况及 合金元素对其耐大气腐蚀性能的影响和作用机理，介绍了目前较先进的Ca-Ni、Ca-Si改性的合金化作用原理和各种耐候钢表面稳定化处理技术和解决措施；并展望了我国耐候钢的发展趋势.     

Atmospheric corrosion of ASTM A-242 and ASTM A-588 weathering steels in different types of atmosphere

The work analyses the atmospheric corrosion resistance of two widely used weathering steels: ASTM A-242 and ASTM A-588. The steels were exposed for up to 5 years in different types of atmosphere: rural, urban, industrial and marine. The atmospheric corrosion resistance of the steels was evaluated and the rust layers formed on them were characterised by X-ray diffraction, optical microscopy and scanning electron microscopy. The most relevant conclusions reached include the following: (a) the visual appearance (colouring) of the rust, rust texture, nature of the corrosion products and compactness of the rust layers formed are similar in both types of weathering steel. (b) No great differences are observed in the corrosion resistance. Slight differences occur in the industrial atmosphere, where ASTM A-242 presents 10–13% less corrosion than ASTM A-588. (c) In the C2-C3 ISO corrosivity atmosphere both types of weathering steels are adequate for unpainted use. However are not suitable in higher ISO corrosivity atmosphere.     

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.     

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.     

Ni对耐候钢在模拟海洋大气环境下耐蚀性的影响

通过周期浸润加速腐蚀实验,研究了不同Ni含量的耐候钢在模拟海洋大气环境下的腐蚀规律.采用失重法评价耐候钢的耐蚀性,并利用扫描电镜 (SEM),X射线衍射(XRD) 和电化学方法对耐候钢表面生成的锈层进行了分析.结果表明,随着Ni含量的增加实验钢的耐蚀性逐渐增加,当Ni含量超过3%(质量分数) 其耐蚀性较对比钢提高了两倍;Ni的存在能够提高实验钢的自腐蚀电位,并促进保护性腐蚀产物α-FeOOH的形成;电化学阻抗测试结果表明,实验钢中Ni含量越多,实验钢的电阻越大,锈层的保护性越好.     

部分钢铁材料在北京地区腐蚀规律研究

对17种黑色金属在北京地区自然环境暴露16年的大气腐蚀数据进行了回归分析,研究发现,碳钢、低合金钢和耐候钢的腐蚀规律符合双对数曲线方程的数学模型,腐蚀过程是阻滞过程。在北京地区,低碳钢、低合金钢和耐候钢的耐腐蚀性能差异不大,严格控制硫含量的低碳钢具有相当好的耐候性。     

耐候钢及其腐蚀产物的研究概况

介绍了耐候钢的发展、国内外使用及研究状况，概述了合金元素对耐候钢耐大气腐蚀性能的影响及其作用机制的研究进展，并对腐蚀产物的组成、锈层形成及其演变的电化学过程方面的研究进行了介绍，对今后耐候钢的研究与发展前景提出了展望。     

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.     

New contributions to the understanding of rust layer formation in steels exposed to a total immersion test

Adherent (AR), differentiated as scraped and hit, and non-adherent (NAR) rusts formed on carbon and weathering steels exposed to chloride solutions in total immersion tests were examined by means of different techniques. The NAR for both steels is composed of lepidocrocite, the most abundant, akaganeite, and goethite, whereas the AR in both steels contains additionally a spinel phase (magnetite/maghemite), which is the most abundant. Differences in crystallographic, relative amount, physical and chemical properties of the compounds in the different rust layers on both steels are reported. For both steels around 21% of the corroded iron converts completely into adherent rust.