日本铝材复合氧化膜涂层技术的现状

日本四周环海，必须考虑海盐微粒或者混有海沙的灰泥引起铝材的腐蚀问题，因此铝窗架的防腐性非常重要。复合涂层(阳极氧化膜层上加一层有机涂层)是日本建筑铝材表面处理的最普遍的处理方式。最初，阳极氧化膜的有机涂层是使用亮漆进行喷涂处理获得的。在这以后有两种处理方式，即TFS涂层和电泳涂层。这两种涂层方法都适于大规模生产，而且涂层均匀。由于电泳涂层工艺无需有机溶剂而保护了环境，从而成了主要的工艺。电泳涂层采用的主要树脂为溶于水的丙烯酸阴离子树脂，电泳涂层表面包括光面、白色表面以及无光表面。对于无光表面，目前主要采用一种分离式树脂法。现在开发的其他方法还包括在着色的氰化膜上采用着色树脂的有机复合涂层、含氟化物树脂的电泳涂层和高耐久性涂层。     

静电喷涂高附着力疏水涂层及其性能

目的提高静电喷涂疏水涂层的附着力。方法采用硅烷偶联剂和聚二甲基硅氧烷制备了表面改性疏水二氧化硅粉末。将一定比例的聚偏氟乙烯粉末、超高分子量聚乙烯粉末与疏水二氧化硅粉末混合,制备了复合型疏水粉末。使用环氧树脂、固化剂、活性剂等配制了导电环氧树脂。通过静电喷涂工艺将复合疏水粉末喷涂到已用导电环氧树脂覆盖的铝基板表面,经过中温固化,制得了铝合金疏水复合涂层。采用扫描电子显微镜(SEM)、傅里叶变换红外光谱仪(FTIR)、接触角测量仪(CA)、百格刀附着力测试仪等,对疏水复合涂层进行测试表征。结果 SEM结果表明涂层表面构建了微米-纳米的阶层粗糙结构,经CA测试,该表面具有较好的疏水性。当混合粉末中聚二甲基硅氧烷改性二氧化硅的比例占到20%时,环氧基疏水涂层的接触角最高可达到140°,滚动角最低可达5°,附着力的等级为0级,同时疏水涂层的耐磨性和耐腐蚀性良好。结论采用简单、易于工业化的静电喷涂工艺制备了高附着力的疏水涂层,具有广泛的应用前景。     

铝合金表面电弧喷涂铝涂层工艺与性能

采用电弧喷涂工艺在6061铝合金基体表面喷涂高纯铝涂层,利用金相显微镜对涂层的组织进行观察,分析了基体与涂层的结合方式,测量了涂层的孔隙率.并采用质量分数为5%的NaCl溶液浸泡试验、盐雾试验和电化学试验,检验了涂层的耐腐蚀性.结果表明,利用电弧喷涂技术可以在6061铝合金基体表面形成均匀、致密、孔隙率低、结合良好的高纯铝涂层;高纯铝涂层耐腐蚀性较好,对铝合金基体起到了保护作用,涂层经过封孔工艺处理后保护作用更好.     

预化学镀镍时间对铝基化学镀镍层性能的影响

目的揭示试样的显微形貌随预化学镀镍时间的变化规律,并探讨试样的显微形貌、镀层的结合强度及耐蚀性能的相关性。方法以预化学镀镍时间为变量,通过化学沉积方法制得化学镀镍层。采用扫描电镜观察预镀层及化学镀镍层的表面形貌,采用热震试验、弯曲试验和划格试验测试镀层的结合力,并对化学镀镍层与铝基体之间的结合力进行评价。采用电化学方法对镀层在模拟燃料电池腐蚀介质中的耐蚀性进行评价。结果随着预化学镀镍时间的延长,颗粒尺寸不断增大,预化学镀镍层形貌先逐渐变得均匀、致密,之后又变得粗糙不均匀。化学镀镍层的耐蚀性以及与基体的结合力呈现出先增加后降低的趋势。结论预化学镀镍时间在5 min时,所得化学镀镍层的表面形貌最平整,结合力最好,耐蚀性最佳。     

2024铝合金表面无铬钛锆转化膜的制备与性能

采用钛酸盐和锆酸盐为主盐,开发了一种应用于2024铝合金表面的无铬钛锆转化膜。通过扫描电镜 (SEM)、能谱分析 (EDS)、中性盐雾实验、动电位极化曲线和电化学阻抗谱对转化膜的表面形貌、成分及耐蚀性能进行了表征和分析。结果表明：制备的无铬钛锆转化膜由微米级的微小颗粒组成,膜层均匀平整,无明显缺陷;无铬钛锆转化处理后的2024铝合金,经中性盐雾168 h,无明显腐蚀产物产生;钛锆转化膜具有较低的腐蚀电流和一定的钝化能力,可有效的提高铝合金的耐蚀性能。     

等离子喷涂Cr2O3-8TiO2涂层的封孔处理

等离子喷涂技术在工业上得到越来越广泛的应用,但涂层的高孔隙率阻碍了该技术在耐腐蚀产品中的应用。采用环氧树脂和有机硅透明树脂剂两种封孔剂对等离子喷涂Cr_2O_3-8TiO_2涂层进行封孔试验,对环氧树脂采用常规和真空两种封孔工艺。用电化学和盐雾腐蚀试验比较了封孔和未封孔涂层的耐腐蚀性能,用扫描电镜(SEM)光学显微镜(OM)观察了腐蚀前后涂层的截面形貌。结果表明,封孔涂层的耐腐蚀性明显优于未封孔涂层。未封孔涂层在盐雾腐蚀240h后出现裂纹并发生剥落。     

2A12 铝合金硬质阳 极氧化及膜层性能研究

目的对混合酸电解液体系中2A12铝合金硬质阳极氧化膜层的制备及性能进行研究。方法采用以硫酸为主的混合酸电解液体系,对2A12铝合金进行硬质阳极氧化,研究混合酸电解液主要成分对2A12硬质阳极氧化膜层性能的作用和影响。结果在硫酸的溶解、有机酸吸附以及添加剂的耦合作用下,混和酸电解液避免了2A12铝合金硬质阳极氧化膜制备过程中存在的烧蚀现象,膜层平均硬度达到400HV0.05以上。WX添加剂能够明显改善2A12铝合金硬氧化膜层的耐蚀性能,经过168 h的中性盐雾试验,仅出现了5%的白霜,但与相同厚度的7A04铝合金硬质阳极氧化膜层相比,耐蚀性较差。结论建议制备有耐蚀性要求的硬质阳极氧化膜层时选用铜含量较低的铝合金材料。     

6061铝合金表面新型黄色微弧氧化陶瓷层的制备与表征

目的 研究6061铝合金表面新型微弧氧化黄色陶瓷层的制备工艺,并对其微观结构、成分、硬度、耐蚀性能等进行表征。方法 在以Na2SiO3为基础的电解液中加入Na2SnO3进行微弧氧化处理,制备出黄色微弧氧化陶瓷层,并与传统白色、黄色、黑色微弧氧化陶瓷层作对比。采用SEM和EDS分析膜层表面形貌和元素分布,借用XPS对膜层进行成分表征,使用硬度计测试其表面硬度,采用电化学工作站和人造海水腐蚀实验评价陶瓷层的抗腐蚀性能。结果 随着电解液中Na2SnO3浓度的增加,陶瓷层中Sn元素含量增加,Si元素含量减少,陶瓷层黄色饱和度不断增强。黄色含Sn陶瓷层制备过程中,电解液中的SnO32-在高温高压下转化为SnO2,导致陶瓷层硬度达到365HV,高于白色与黑色陶瓷层。在3.5% NaCl溶液中进行电化学测试,黄色含Sn陶瓷层的腐蚀电流密度与腐蚀电位分别为9.34×10-9 A/cm2和-0.34 V,耐蚀性优于白色和黄色含Mn陶瓷层。结论 在电解液中添加Na2SnO3可在铝合金表面生成具有较高硬度和耐蚀性能良好的类似沙漠黄色的陶瓷层,为铝及其合金在多领域的应用奠定了一定的实验基础。     

Corrosion resistance of hot‐dipped zinc and zinc alloy coated sheet steels under offshore atmospheric environment

The application of hot‐dipped zinc and zinc‐aluminum alloy coatings were introduced. Exposure tests of the steels with these coatings were conducted in the offshore atmosphere in Qingdao and Xiamen for 12 years separately. Effects of the coating thickness, alloy composition and atmospheric environment on the corrosion performance were studied. Results of the onsite exposure tests were compared with the results of a previous indoor salt spray accelerated corrosion tests. The study supports that zinc‐aluminum alloy coatings are useful in providing better corrosion resistance and can be further developed for future applications.     

核工业放射性固体废物包装容器防护涂料性能研究

针对用于中、低水平放射性固体废物包装容器,研究了以双酚A型环氧树脂为基料、以改性芳香胺为固化剂的防护涂层体系的性能.辐照实验、老化实验等测试结果表明,该涂料已完全达到了我国核行业有关标准中的技术要求.     

不含铜类防污剂海洋防污涂料研制及性能

目的合成具有可控水解性能的丙烯酸锌基体树脂,用该树脂制备不含任何铜类防污剂的海洋防污涂料。方法两步法合成具有可控水解性能的丙烯酸锌基体树脂,用该基体树脂配以有机防污剂Econea、吡啶硫酮锌、吡啶三苯基硼烷等以及颜填料、助剂等制备不含任何铜类防污剂的自抛光海洋防污涂料。通过实海挂板试验、电化学阻抗性能测试、动态模拟试验对涂层进行表征。结果丙烯酸预聚物的数均分子量控制在30 000左右较为合适,即聚合反应温度控制在100℃、引发剂用量为8份时较为合适。采用自制的氢氧化锌、环烷酸以及丙烯酸预聚物制备的丙烯酸锌基体树脂具有良好的水解性能,制备的无铜自抛光防污涂料经36个月实海挂板试验验证,具有优异的防污期效。由于不含任何铜类防污剂,不会引起铝制基材表面电化学腐蚀,特别适用于铝制基材表面的防污。结论该不含任何铜类防污剂的环保型丙烯酸锌自抛光海洋防污涂料具有优异的防污性能,能够防止海洋附着生物对船底和其他海洋设施的污损,同时不会对海洋生态环境产生危害,特别是可以满足铝合金基材表面等对涂料有特殊要求的一些场合的防污需求。     

LY12铝合金三价铈盐溶液中成膜工艺

利用浸渍法在LY12铝合金表面获得了金黄色的铈转化膜, 确定了常温稀土(铈)化学转化膜成膜工艺. 应用电化学方法和浸泡试验研究了铝合金铈化学转化膜的成膜动力学及转化膜在3.5%NaCl溶液中的耐蚀性能, 并与传统的Alodine处理工艺进行了比较. 采用表面分析技术分析了膜的成分并观察了膜的微观形貌. 结果表明, 本稀土处理工艺成膜工艺简单, 成膜速度快, 耐蚀性能略优于Alodine转化膜, 能有效地抑制铝合金的点腐蚀. SEM表明铝合金铈转化膜由许多球形颗粒和块状膜构成. EDAX能谱表明, 铈转化膜主要含有铈、氧和铝3种元素, 球形颗粒含有较高浓度的氧和铈.     

海洋环境中铝合金表面改性涂层的电化学性能

目的对换热管用6061铝合金表面进行改性防护,研究一种在其表面具有牺牲性阳极保护效果且腐蚀速率小的涂层材料。方法采用线材火焰喷涂工艺在6061铝合金表面制备不同成分的锌铝涂层,分别为纯Zn、Zn50、Al95、Al、Al-RE共5种涂层,使用SEM、EDS、XRD分析测试方法对涂层形貌及成分进行分析,并测定涂层在3.5%NaCl溶液中的Tafel曲线。结果相同参数下在铝合金表面制备的涂层表观质量良好,无明显缺陷,符合热喷涂对于涂层质量的要求。常温环境下,Zn、Zn50、Al95、Al、Al-RE涂层的电位比6061铝合金的电位更负,5种涂层对6061铝合金都具有阳极性保护层的作用。结论从腐蚀电流和腐蚀电位考虑,Al95、Al-RE作为牺牲性阳极保护涂层的作用会更好。     

The electrochemical corrosion behavior of TiN and (Ti,Al)N coatings in acid and salt solution

In this study, the corrosion properties of TiN and (Ti,Al)N coatings fabricated by Hollow Cathode Ionic Plating (HCIP) were studied by electrochemical techniques such as electrochemical impedance spectroscopy (EIS) measurement and potentiodynamic measurement in acid and salt solution. It was found that both coatings showed an excellent corrosion resistance in acid and salt solutions at the beginning of long-term immersing test. The corrosion resistance of TiN coating deteriorated rapidly after nearly 100 h immersion in both acid and salt solutions. In the contrast, the corrosion rate of (Ti,Al)N coating decreased a little and then kept at a stable value. For the TiN coating, the corrosion initiated from pinholes and the underlying corrosion was very similar to pitting corrosion. With the addition of aluminum to the TiN coating, the corrosion resistance was improved, especially in salt solution. The test results demonstrated that the (Ti,Al)N coating seemed to posses certain self-repairing function. The corrosion mechanism took the form of denudation corrosion, owing to deterioration of the adhesion of the coating.     

LY12铝合金钼酸盐转化膜研究

利用浸渍法在LY12铝合金表面获得了深黄色的钼酸盐耐蚀转化膜。结果表明，本处理工艺简单，成膜速率快，铝合金的耐蚀性大为提高，具有较好的抗点腐蚀性能。扫描电镜（SEM）分析表明，膜的微观形态由大小不一的球形颗粒构成。X射线光电子能谱（XPS）实验表明，转化膜表层中钼主要以MoO2形式存在，并含有少量的MoO3，在膜的内层钼以正4价形式存在。并讨论了钼酸盐转化膜的成膜机理及耐蚀机理。     

Corrosion characteristics of electroless Ni–P coating in sulfur‐bearing solution

The corrosion behaviors of electroless Ni–P coatings deposited on carbon steel in sulfur‐bearing solutions were investigated by weight gain test and scanning electron microscopy. The results indicate that the corrosion rate of electroless Ni–P coating was directly related to the sulfur content, immersion time, and test temperature. The corrosion rate increased with the prolonged immersion time. Increasing the temperature can markedly increase the corrosion rate of electroless Ni–P coating. The electroless Ni–P coating had a better corrosion resistance than 316L stainless steel against Cl^? corrosion in sulfur‐bearing solution.     

Study on corrosive electrochemical behaviors of zinc‐rich and graphite‐filled epoxy coatings in 3.5 wt% NaCl solution

Environment behaviors and degradation mechanisms of two organic epoxy coatings coated on carbon steel sheets in 3.5 wt% NaCl neutral solution were studied by electrochemical impedance measurements and atomic force microscopy (AFM). The results showed that the coating resistance (R_p) of the graphite‐filled epoxy coating tested, which presents the film barrier performance, is higher than those of 6101 epoxy resin for initial seawater immersion, but the coating resistance of the zinc‐rich epoxy coating was lower than that of 6101 epoxy resin. After salt spray tests, zinc‐rich epoxy coating coated on the metal still has good anti‐corrosion performances due to the existence of protection effects called “electrochemical” and “chemical” protection. Those behaviors and degradation mechanisms of two coatings can be explained by a series of measured electrochemical impedance spectroscopy measurements, and two equivalent circuit models were proposed to explain the degradation processes of the two organic coatings.     

Corrosion performance of Zn–Mg–Al coated steel in accelerated corrosion tests used in the automotive industry and field exposures

The corrosion performance of Zn–Mg(1–2%)–Al(1–2%) (ZMA) coatings has been compared to zinc–iron alloy (galvannealed, GA) and zinc–aluminum coating (Zn–5Al, Galfan) as well as to conventional zinc coatings produced by hot‐dip galvanization (HDG) and electrogalvanization (EG). For this purpose, cosmetic samples (painted and uncoated) and hem‐flange panels were produced. Their corrosion performance was compared in three different accelerated corrosion tests, as regularly used by the automotive industry, e.g., VDA621‐415, N‐VDA (VDA233‐102), and Volvo STD 423‐0014. As can be concluded from our results, the behavior of ZMA coatings was strongly dependent on the testing conditions as well as on the configuration of the samples. The advantageous effect of ZMA coating was more pronounced in open situations than in confined ones, irrespective of the testing conditions. ZMA coatings provided a significant improvement in comparison to conventional coatings in tests involving a significant salt load such as VDA621‐415 or neutral salt spray especially on cosmetic configurations. By contrast, the beneficial effect of ZMA coatings was less obvious in tests with lower salt load (VDA233‐102, Volvo STD423‐0014), particularly when considering cosmetic corrosion on painted samples and corrosion in confinement. Interestingly, no significant differences were observed between samples with varying Al and Mg content in the metallic coating (1–2% each). The results were compared to data from field exposure at stationary sites.     

悬浮液等离子喷涂制备氟代羟基磷灰石生物涂层

主要以氟代羟基磷灰石(FHA)悬浮液为原料,采用悬浮液等离子喷涂技术,在钛基体表面制备了FHA涂层。通过XRD,SEM,FT-IR以及XPS等测试手段,对不同喷涂功率制备的FHA涂层进行表征,并测试其性能。结果表明,粉体及制备的涂层主要晶相为HA,但是粉体进入等离子火焰形成涂层的过程中发生分解,生成α-磷酸钙(α-TCP),β-磷酸钙(β-TCP),以及磷酸四钙(TTCP)等分解产物。XPS结果证明F离子成功取代了OH基团进入HA晶格中,导致FHA涂层的抗溶解性明显提高。电化学实验结果表明,随着喷涂功率的增加,涂层的抗腐蚀性能提高。     

Effect of Sealing Treatment on Corrosion Resistance of Plasma-Sprayed NiCrAl/Cr<Subscript>2</Subscript>O<Subscript>3</Subscript>-8 wt.%TiO<Subscript>2</Subscript> Coating

Plasma-sprayed ceramic coatings inherently contain pores and micro-cracks which is deleterious when performed in aggressive environment. Various methods were applied to the as-sprayed coatings in order to improve the corrosion resistance. In the investigation of this study, plasma-sprayed NiCrAl/Cr₂O₃-8 wt.%TiO₂ coatings were sealed by epoxy resin and silicone resin, respectively. Coatings were characterized by scanning electron microscopy/energy dispersive spectroscopy (SEM/EDS), optical microscopy (OM) and x-ray diffraction (XRD). The possible corrosion mechanism was discussed. The results of salt spray test and electrochemical measurements indicated that after the sealing treatment, the porosity of coatings decreased obviously and a compact layer was formed to protect the coating from corrosion. The silicone resin proved to be more effective than epoxy resin in enhancing the corrosion resistance of the coatings used in this research.