AZ31B镁合金表面微弧电泳复合膜层微观结构及耐蚀性表征

采用微弧氧化技术在AZ31B镁合金表面制备陶瓷层,利用其表面多孔结构借助电泳技术沉积有机膜层,对比研究陶瓷层和复合膜层表面粗糙度、表面及截面形貌、电化学性能及划伤腐蚀特性。结果表明:陶瓷层表面放电微孔被电泳层完全填充并形成均匀膜层,复合膜层表面粗糙度明显降低;微弧电泳复合膜层腐蚀电流密度与陶瓷层和基体相比分别降低2个和4个数量级,极化电阻分别增大2个和4个数量级,腐蚀倾向降低;微弧电泳复合膜层电化学阻值与陶瓷层相比增加4个数量级,同时电容值降低4个数量级,耐蚀性显著提高;由于陶瓷层与电泳层的机械嵌合作用,复合膜层划伤腐蚀过程表现为基体腐蚀及陶瓷层与基体界面的破坏,复合膜层界面处结合完好。     

热镀锌层在饱和Ca(OH)2溶液中的腐蚀行为

热浸镀锌是保护混凝土钢筋的有效措施之一。用饱和Ca(OH)2溶液模拟混凝土孔隙液,研究热镀锌层在该模拟液中的腐蚀行为。采用电化学测试、SEM、EDS和XRD手段分别分析了试样在不同浸泡阶段的电化学参数、表面微观形貌以及腐蚀产物的化学成分和相组成,结果表明:在浸泡腐蚀过程中,锌晶粒的晶界处优先出现腐蚀小孔,然后在小孔附近开始生成锌酸钙晶体Ca[Zn(OH)3]2.2H2O,随着锌酸钙晶体不断生长,逐渐覆盖锌层表面,形成耐蚀性逐渐增强的保护层。当锌基底被锌酸钙晶体完全覆盖后,腐蚀电流密度Jcorr降至临界钝化值附近,锌层处于钝化状态。     

Zn-Al-Mg-RE涂层自封闭特性在复合涂层中的作用机制

通过铜加速醋酸盐雾腐蚀试验,研究了自封闭特性在Zn-Al-Mg-RE高速电弧喷涂层与舰船涂料结合成防腐复合涂层中的作用.经过480h的试验,在基体上直接涂装涂料的试样表面的划痕里充满了铁锈,而中间喷有高速电弧喷涂层的试样表面划痕里只有少量的白锈.这说明在腐蚀环境中,Zn-Al-Mg-RE高速电弧喷涂层表面的微观孔隙能够被自身的腐蚀产物堵塞,生成的腐蚀产物非常致密,能够阻止缺陷处继续被腐蚀.从试验结果可知在复合涂层体系中,高速电弧喷涂层的自封闭特性起到了积极的作用.     

热浸锌铝合金镀层表面纳米晶腐蚀产物共沉积机理

采用XRD和TEM对热浸锌铝合金镀层在动态充气海水全浸试验时所形成的白色腐蚀产物进行了研究,结果表明：腐蚀产物主要由典型的纳米级Zn4CO3(OH)6.H2O,Zn5(OH)8Cl2和Zn6Al2CO3(OH)16.4H2O微晶组成,而这种纳米晶的形成与由吸附引起的Zn^2 和Al^3 离子的共沉积有关,镀层表面腐蚀后首先生成Al(OH)3凝胶,当凝胶吸附的锌离子超过异相核的临界过饱和度时,发生锌、铝氢氧化物的共沉淀,生成双氢氧化物,由于晶体长大速度较慢不能与沉淀形核同步进行,导致镀层表面形成了微晶状态的腐蚀产物。     

镀锌板上丙烯酸树脂复合膜的制备和表征

在镀锌钢板表面制备了丙烯酸树脂复合膜,用扫描电子显微镜观察膜层的微观形貌.用傅里叶变换红外光谱表征膜层的分子结构,用中性盐雾试验和电化学方法测试其耐蚀性,并用划痕浸泡实验测试膜层的自修复性能.结果表明:丙烯酸树脂复合膜表面致密平整;耐中性盐雾腐蚀达72 h;阻抗值和极化电阻值均较大,说明丙烯酸树脂复合膜能有效抑制腐蚀电化学反应;划痕浸泡试验证明丙烯酸树脂复合膜具有自修复功能.成膜过程中碳酸锆铵能够和丙烯酸树脂分子上的羟基和羧基发生交联反应,形成互穿网络结构,提高膜层内部的交联密度,有效地阻挡外界环境的侵蚀,当膜层破损时钼酸盐和磷酸盐与锌反应形成难溶盐吸附在破损处,起到自修复作用.     

钢桥面沥青混凝土铺装层下热喷锌涂层的腐蚀行为

研究了钢桥面沥青混凝土铺装层下热喷锌防腐蚀涂层的腐蚀特征,并在此基础上提出锌涂层腐蚀导致沥青混凝土铺装层性能下降的理论假设模型。采用IM6ex电化学工作站研究了热喷锌涂层的腐蚀电位、腐蚀电流与时间的关系,涂层的极化特性,采用XRD分析了锌涂层的腐蚀产物。结果表明锌涂层腐蚀产物中存在大量ZnO和Zn5(CO3)2(OH)6,破坏了粘结层与锌涂层之间的粘结,起到裂纹源的破坏作用,使铺装层在载荷的作用下提前失效。     

Zn在模拟酸雨大气环境中的腐蚀行为

利用自制的降雨喷淋装置模拟Zn在酸雨条件下的大气腐蚀行为,采用扫描电镜(SEM)、X射线能谱(EDS)、X射线衍射(XRD)和电化学测试技术分别研究Zn腐蚀48、96、144、192和240 h后的腐蚀产物成分、锈层截面形貌以及表面锈层的电化学特性,分析了锈层对Zn腐蚀行为的影响。结果表明:主要的腐蚀产物为Zn(OH)2、Zn SO4、Zn4SO4(OH)6·3H2O和Zn5(OH)8Cl2·H2O;腐蚀过程中,Zn的表面形成了具有较好保护性的锈层,随着腐蚀时间的延长,锈层对Zn的保护作用先增强后减弱。     

电弧喷涂Zn和Al涂层在含SRB海水中的腐蚀行为与机理

利用电弧喷涂技术在Q235钢基体上分别制备了Zn、Al涂层,研究涂层在含硫酸盐还原菌(SRB)海水中的腐蚀行为与机理。采用EIS、PC等电化学方法研究Zn、Al涂层在SRB一个生长周期内的腐蚀电化学行为,采用SEM和EDS对浸泡15 d后的涂层表面微观形貌和化学成分进行分析。EIS和PC结果表明,Zn、Al涂层在含SRB海水中的腐蚀速率均表现出先增大后减小的趋势,在整个实验过程中,Zn涂层的腐蚀速率一直大于Al涂层;SEM分析表明,浸泡结束后,Zn涂层表面覆盖了一层由微生物(SRB)和腐蚀产物共同组成的混合膜层,而铝涂层表面的覆盖层主要为生物膜,腐蚀产物较少。EDS结果显示,Zn涂层表面的S元素含量远高于Al涂层,说明SRB的代谢活动对Zn涂层的影响相对较大。     

镀锌钢在红沿河大气环境中的腐蚀行为

目的研究镀锌钢在红沿河地区SO2和Cl-含量较高的大气环境中的腐蚀行为与机理。方法根据GB/T 6464—1997将制备好的试样在红沿河核电厂进行现场暴晒试验,分别暴晒4、12、18、24个月后取回试样。利用失重分析、X射线衍射(XRD)和扫描电镜(SEM)等技术,观察与分析试样暴晒后的腐蚀产物。结果镀锌钢腐蚀失重随暴晒时间的延长而线性增加;随着暴晒时间的延长,锌镀层表面形成的腐蚀产物成分变化不大,以Zn12(SO4)3Cl3(OH)15·5H2O和6Zn(OH)2·Zn SO4·4H2O为主;腐蚀产物随暴晒时间的延长逐渐增加,产物形貌略有变化,以球状和针状为主。暴晒18个月后,腐蚀产物分为双两层,内层致密,外层疏松;暴晒24个月后,腐蚀产物厚度稍有增加,疏松层向致密层转变。结论 SO2与Cl-是镀锌钢在红沿河地区的大气腐蚀过程的主要影响因子。镀锌钢表面形成的腐蚀产物对锌镀层的保护作用较差。     

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。     

Self-healing protective films prepared on zinc by treatments with cerium(III) nitrate and sodium phosphate

Chromate-free, self-healing protective films were prepared on a surface of zinc electrode previously treated in a solution of cerium(III) nitrate Ce(NO₃)₃ by coverage of the surface with a layer of sodium phosphate Na₃PO₄. The self-healing ability of the film was examined by polarization measurements of the electrode after scratching the surface with a knife-edge crosswise and immersed in an aerated 0.5 M NaCl solution for many hours and by observation of pit formation at the scratches. A thin film containing 0.0552 mg/cm² of Na₃PO₄·12H₂O prepared on the electrode previously treated in 1×10⁻³ M Ce(NO₃)₃ at 30 °C for 30 min and dried at 90 °C for 23 h was highly self-healing and protective against corrosion of zinc in 0.5 M NaCl at the scratches. No pit was detected at the scratches on the electrode coated with this film after immersion for 72 h.     

Self-healing mechanism of a protective film prepared on a Ce(NO3)3-pretreated zinc electrode by modification with Zn(NO3)2 and Na3PO4

Self-healing mechanism of a protective film against corrosion of zinc at scratches in an aerated 0.5 M NaCl solution was investigated by polarization measurements, X-ray photoelectron spectroscopy (XPS) and electron-probe microanalysis (EPMA). The film was prepared on a zinc electrode by treatment in a Ce(NO₃)₃ solution and addition of aqueous solutions containing 9.98 or 19.9 μg/cm² of Zn(NO₃)₂ · 6H₂O and 55.2 μg/cm² of Na₃PO₄ · 12H₂O. After the coated electrode was scratched with a knife-edge crosswise and immersed in the NaCl solution for many hours, polarization measurements, observation of pit formation at the scratches, XPS and EPMA were carried out. This film was remarkably protective and self-healing against zinc corrosion on the scratched electrode. The cathodic and anodic processes of zinc corrosion were markedly suppressed by coverage of the surface except for scratches with a thin Ce₂O₃ layer containing a small amount of Ce⁴⁺ and the surface of scratches with a layer composed of Zn₃(PO₄)₂ · 4H₂O, Zn(OH)₂ and ZnO mostly.     

Corrosion behavior of a cerium-based conversion coating on alumina borate whisker-reinforced AA6061 composite pre-treated by hydrogen fluoride

Cerium-based conversion coatings have been made on alumina borate whisker-reinforced AA6061 composite pre-treated with hydrogen fluoride. The pre-treatment prior to coating significantly affects the microstructure and the corrosion behavior of the ultimate coated composites. The coating deposited on composite pre-treated for 20 s provides better corrosion protection than that pre-treated for 180 s. A self-healing effect is observed on the coated composite with pre-treatment for 20 s in the early stage of immersion, while no self-healing effect appears with pre-treatment for 180 s. It is largely because the morphologies of the coatings are remarkably different under the two pre-treatment conditions.     

Mechanistic changes in cut-edge corrosion induced by variation of organic coating porosity

The scanning vibrating electrode technique (SVET) has been used to investigate the mechanism of corrosion occurring at exposed metallic cut edges of galvanised steel materials coated with identical thickness organic polymeric layers. Organically coated galvanised steel samples have been prepared by application of a 30 μm polyester coating to both sides of a pre-treated hot dip zinc (99.85%) aluminium (0.15%) galvanised steel substrate. In separate samples the coatings were applied to both sides simultaneously and then cured or applied sequentially to each side curing after each application. Electrical impedance spectroscopy (EIS) was used to probe the porosity of the resulting organic coatings. This revealed that simultaneous coating application and curing resulted in both polymer layers showing EIS pore resistance of 0.6 MΩ whereas sequential coating resulted in one side showing a pore resistance of 0.6 MΩ and the other showing a capacitive EIS response with no measurable porosity. When the metallic cut edges of organically coated steel materials, coated with symmetric thicknesses of organic layers of identical pore resistance, are exposed to 5% NaCl the SVET iso-current contour maps show that both zinc layers behaving as local anodes. In addition, there is significant sample passivation in the 24 h exposure period. In the samples coated with materials of identical thicknesses but different porosity, the SVET iso-current contour maps show anodic activity focussed beneath the organic coating with the capacitive EIS signature. The greater porosity of the coating on the opposite side of the exposed cut edge enables oxygen transport to the delaminating surface and this forces anodic activity onto the other zinc layer.     

Effect of chromate on the electrochemical behavior of sintered Zn-Al coating in seawater

To improve the anticorrosion resistance of chromium-free Zn-Al sintered coating, characteristics of chromate on zinc-aluminum-chromium were studied by electrochemical methods. Depth profiles of elements were obtained by glow discharge spectrum (GDS) and X-ray photoelectron spectroscopy (XPS) was used to analyse the chemical states of main elements in Zn-Al coatings. Corrosion behaviors of steel samples coated with chromium-free Zn-Al and zinc-aluminum-chromium exposed to seawater were investigated by using electrochemical impedance spectroscopy (EIS) measurement. Both in open circuit potential and EIS monitoring self-healing phenomena of chromate were obviously observed. The self-healing function endows zinc-aluminum-chromium coating with better anticorrosion performance. Electrochemical analysis show that self-healing action of coatings is missing when replace chromate with molybdate and silane.     

A self-healing protective film prepared on zinc by treatment in a Ce(NO3)3 solution and modification with Ce(NO3)3

A self-healing protective film was prepared on a zinc electrode by treatment in 1 × 10⁻³ M Ce(NO₃)₃ at 30 °C for 30 min to form a thin layer of hydrated Ce₂O₃ and by modification with 114 μg/cm² of Ce(NO₃)₃ · 6H₂O. The film was dried at 30 °C under a dry atmosphere. After the electrode surface was scratched with a knife-edge crosswise and immersed in an aerated 0.5 M NaCl solution at 30 °C for many hours, polarization measurement of the electrode was carried out in the NaCl solution. The protective efficiency of the film was markedly high, 97.7% at the immersion time, t_i=24 h. Neither pit-like anodic dissolution feature nor pit was observed within the scratches at t_i=72 h. X-ray photoelectron spectroscopy and electron-probe microanalysis revealed that Ce³⁺ migrating into the scratches from the film was adsorbed on the hydrated or hydroxylated zinc surface to form a new layer of hydrated Ce₂O₃ within the scratches, resulting in the self-healing activity of the film for preventing zinc corrosion at the scratched surface.     

Combination of zinc alloy coating with thin plasma polymer films for novel corrosion protective systems on coated steel

Steel sheet used in automotive applications has to be corrosion protected effectively, which is usually realized by zinc or zinc alloy coatings with a thickness range of 5–10 μm. Steel sheet for areas of a car body which are exceptionally stressed by corrosion, e.g. cavity flanges or joints, may be protected additionally by a thin weldable organic coating with a thickness of 2–4 μm. A very promising approach to a significantly reduced use of resources is the combination of zinc alloy coatings with thin plasma polymer films deposited by means of plasma-enhanced chemical vapour deposition (PECVD). Such plasma polymer films of just a few 100 nm thickness show excellent barrier and adhesion properties as well as a high mechanical stability.Within this work thin plasma polymer films were deposited on zinc alloy coated steel substrates using the strip hollow cathode (SHC) method, which was modified for application on grounded substrates. A pulsed DC glow discharge in a mixture of argon and an organosilane precursor was used for the deposition of films with a thickness of 100–500 nm.The chemical compositions of the coatings were determined by means of X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy. The morphologies of the coating systems were studied by means of scanning electron microscopy. The performance of the coating systems has been studied in different specific tests of corrosion and processing behaviour. The investigated coating systems show a corrosion resistance comparable to reference samples of electro-galvanised steel sheet with additional organic coating even with a coating thickness less of half of the reference samples.     

Porous ceramic coating formed on 316L by laser cladding combined plasma electrolytic oxidation for biomedical application

In order to improve the bioactivity of 316L stainless steel, a titanium layer was prepared on the surface of 316L by laser cladding (LC), followed by plasma electrolytic oxidation (PEO) to form a porous ceramic coating on titanium layer. The morphologies, microstructure and compositions of the coated samples were characterized by 3D surface profiler, SEM, EDS, XRD and XPS. The corrosion resistance and bioactivity of the coatings were evaluated by potentiodynamic polarization and immersion test in simulated body fluid (SBF), respectively. The results showed that the porous ceramic coating mainly consisted of anatase and rutile, and highly crystalline HA was also detected. The main elements of the PEO coating are Ca, P, Ti and O. The LC+PEO composite bio-coating has more excellent corrosion resistance than the 316L substrate in simulated body fluid. Furthermore, the composite coating could effectively improve the bioactivity of 316L stainless steel.     

钼酸盐后处理提高热镀锌上磷化膜耐蚀性的探讨

将磷化后的热镀锌钢板用钼酸盐后处理,以提高磷化膜的耐蚀性。用SEM、EDS、电化学极化测量和盐雾试验研究了钼酸盐后处理对磷化膜组成和耐蚀性的影响。结果表明,经钼酸盐处理后,磷化膜上磷酸锌晶体间的孔隙被钼酸盐膜填补,从而在锌层表面形成了由磷化膜和钼酸盐膜构成的连续完整致密的复合膜;复合膜的极化电阻Rp显著增大,腐蚀电流密度显著减小,耐蚀性大大增强。磷化300s、后处理50s时复合膜的耐蚀性最优,Rp比单磷化膜的增加了一个数量级。     

光热自修复涂层的研究进展

综述了光热触发自修复涂层的结构设计与修复机制、填料的种类及其特点、涂层的修复效率与防腐应用,重点阐述了基于碳基填料、等离激元纳米材料、有机填料、四氧化三铁纳米颗粒等光热响应物质自修复涂层的国内外最新研究进展,详细分析了填料含量、光照波长、光照强度、基体类型等对涂层的自修复性能和耐蚀性能的影响规律。最后,提出了光热自修复涂层目前存在的问题以及发展前景,未来应进一步优化涂层的制备工艺,提升光热转换效率,降低制备成本,并将涂层的多重修复机制相结合,共同提升涂层的长效防护能力,使之早日实现工业应用。