镁合金表面铈盐掺杂硅烷膜的腐蚀电化学行为

目的为进一步提升镁合金表面常规硅烷膜的耐蚀性能。方法在γ-氨丙基三乙氧基硅烷溶液中掺杂0.50 g/L硝酸铈,采用简单化学浸渍处理,在AZ91D镁合金基体表面制备了铈盐掺杂硅烷膜。借助扫描电子显微镜(SEM)观察了铈盐掺杂前后硅烷膜的表面微观形貌,通过开路电位-时间曲线、电化学交流阻抗谱(EIS)和中性盐雾试验(NSS)研究了铈盐掺杂对5%Na Cl溶液中硅烷膜耐蚀性能的影响。结果铈盐掺杂硅烷膜比普通硅烷膜更厚且平整,其致密性、均匀一致性较好,完全覆盖了镁合金基体,已看不到磨痕。铈盐掺杂硅烷膜的稳定电位约为-1.31 V,且需要的稳定时间最长。铈盐掺杂硅烷膜具有更大的低频阻抗数值,有效遏制了侵蚀性粒子向镁合金基体的迁移和扩散,避免了镁合金基体发生阳极溶解反应。结论采用向硅烷溶液中添加硝酸铈的方法,能够在AZ91D镁合金表面制备出铈盐掺杂硅烷膜。由于铈离子在某种程度上修复了硅烷膜层中的微裂纹和缺陷,显著提升了硅烷膜的耐蚀能力。     

2A12铝合金表面铈盐掺杂硅烷杂化膜在3.5%NaCl溶液中耐蚀性能的电化学研究

采用溶胶-凝胶法,以γ-环氧丙氧丙基三甲氧基硅烷(γ-GPTMS)和正硅酸乙酯(TEOS)为前驱体,在2A12铝合金表面制备了稀土铈盐(Ce(NO3)3)掺杂的有机-无机杂化膜,研究了铈盐掺杂浓度和涂层固化温度等工艺条件.通过极化曲线和电化学阻抗谱(EIS),比较了掺杂与未掺杂有机-无机硅烷杂化膜、铬酸盐转化膜和RE转化膜在3.5%NaCl(质量分数)溶液中的耐腐蚀性能.测试结果均表明,铈盐掺杂硅烷杂化膜的极化电阻比掺杂前增大了约13倍,并显著高于铬酸盐转化膜和RE转化膜.     

The electrochemical study of corrosion resistance of silane-based hybrid films doped with rare earth salt on aluminum alloy

采用溶胶-凝胶法, 以γ-环氧丙氧丙基三甲氧基硅烷(γ-GPTMS)和正硅酸乙酯 (TEOS)为前驱体, 在2A12铝合金表面制备了稀土铈盐(Ce(NO3)3)掺杂的有机－无机杂化膜, 研究了铈盐掺杂浓度和涂层固化温度等工艺条件. 通过极化曲线和电化学阻抗谱(EIS), 比较了掺杂与未掺杂有机－无机硅烷杂化膜、铬酸盐转化膜和RE转化膜在3.5%NaCl (质量分数)溶液中的耐腐蚀性能. 测试结果均表明, 铈盐掺杂硅烷杂化膜的极化电阻比掺杂前增大了约13倍,并显著高于铬酸盐转化膜和RE转化膜.     

铈盐掺杂GPTMS/TEOS硅烷杂化膜腐蚀电化学行为随时间的变化

以γ-环氧丙氧丙基三甲氧基硅烷(GPTMS)和正硅酸乙酯(TEOS)为前躯体,采用溶胶-凝胶法在LY12铝合金基体表面制备了铈盐Ce(NO3)3掺杂有机-无机杂化膜。通过极化曲线与电化学阻抗谱(EIS)研究铈盐掺杂硅烷杂化膜在3.5%(质量分数)NaCl溶液中耐蚀性能随浸泡时间的变化。结果表明,硅烷杂化膜的极化阻抗值随浸泡时间延长而缓慢降低,但浸泡183 h后仍显著高于金属基体;铝合金点蚀电位在浸泡期间呈现先降低后升高再降低的变化。在浸泡初期,EIS曲线的高频容抗行为显著。从69 h至260 h浸泡试验结束,低频阻抗值保持基本稳定。上述变化与膜中掺杂的铈盐具有自修复性质密切相关。     

热镀锌钢表面乙烯基三乙氧基硅烷膜的腐蚀电化学行为

采用开路电位(OCP)、交流阻抗(EIS)和动电位极化法对热镀锌钢表面乙烯基三乙氧基硅烷膜腐蚀电化学行为进行了研究。结果表明,在3.5%NaCl溶液中,涂覆硅烷膜层的热镀锌钢与空白热镀锌钢相比,其低频阻抗值提高至少2个数量级,同时腐蚀电流密度减小1个数量级以上,乙烯基三乙氧基硅烷膜防腐蚀效果良好。     

Ce3+对Zn-Ni合金镀层耐蚀性能的影响

在电镀液中添加铈盐,于Q235钢表面电镀Zn-Ni合金,考察了Ce3+添加量对Zn-Ni合金镀层耐蚀性能的影响.通过稳态阳极极化曲线、塔菲尔极化曲线和交流阻抗谱,研究了镀层在30℃3.5％NaCl溶液中的腐蚀行为;同时对比了Zn-Ni合金镀层在腐蚀前后的微观结构和表观形貌.结果表明:加入铈盐,不改变Zn-Ni合金镀层的晶面择优取向,但会改变各晶面的织构系数;添加铈盐后,Zn-Ni合金镀层的致钝电流密度和维钝电流密度明显降低,极化阻抗明显增大;当镀液中添加0.80 g/L铈盐时,镀层结晶粒度明显变小且致密,使得耐蚀性能显著增加.     

盐碱土环境中涂覆导电混凝土Q235钢的腐蚀机理

通过极化曲线和电化学阻抗谱(EIS),研究了水饱和盐碱土环境中涂覆导电混凝土Q235钢的腐蚀机理,探讨了Na_2MoO_4与Na_3PO_4复配缓蚀剂的协同缓蚀作用机理。结果表明:在盐碱土环境中加速腐蚀45 d后,试样表面出现大量的孔洞以及少量的裂纹,腐蚀过程经历混凝土劣化、钝化膜的形成与破裂以及腐蚀稳定三个阶段。当Q235钢表面形成膜层结构后,其电化学阻抗谱具有三个时间常数,其中有无添加缓蚀剂的试样分别在腐蚀20 d和45 d后出现Warburg阻抗,腐蚀反应受扩散和电荷转移联合控制。在导电混凝土中添加3 g/L Na_2MoO_4与3 g/L Na_3PO_4复配缓蚀剂后,Q235钢表面形成一层致密的吸附膜,阻碍腐蚀反应的进行,其缓蚀率为89.88%。     

镀锌钢板钛盐/硅烷复合膜的耐蚀性研究

研究了镀锌钢板上钛盐钝化膜、硅烷转化膜、钛盐/硅烷复合转化膜的表面形貌和化学成分,并对比了这3种转化膜与普通铬酸盐转化膜的电化学行为和耐盐雾腐蚀性能。结果表明:镀锌钢板钝化后,腐蚀电流密度降低,极化电阻及交流阻抗得到极大提高;钛盐/硅烷复合膜的耐蚀性已经接近普通铬酸盐钝化。SEM和EIS分析表明,硅烷膜是一层物理遮盖膜。     

温度对Q235钢在大港模拟溶液中腐蚀行为的影响

主要利用极化曲线、线性极化和电化学阻抗谱(EIS)等电化学方法研究了Q235钢在不同温度下的大港模拟溶液中的腐蚀行为。试验表明:在20~50℃的范围内,其腐蚀电位比较接近阳极反应的平衡电位,其腐蚀过程受阴极反应氧的传输过程控制,随温度升高,Q235钢的腐蚀电位逐渐降低,腐蚀电流密度逐渐增大,线性极化电阻Rp以及电荷转移电阻Rt逐渐减小,在较高温下主要是通过促进阴极反应的传质过程增加了Q235钢的腐蚀速度。     

缓蚀剂在PVC热稳定剂生产废水作为冷却水用过程中的应用研究

目的通过在生产废水中加入缓蚀剂,减少废水中氯离子的腐蚀性能,使其成为生产中的冷却水,实现节能环保。方法采用失重法,研究废水温度对Q235钢腐蚀速率的影响,确定废水的腐蚀温度。研究L-抗坏血酸和L-半胱氨酸在废水中的最佳用量,制备成复配缓蚀剂,研究复配缓蚀剂膜形成的最佳时间。用塔菲尔曲线、阳极极化曲线及交流阻抗法,研究存在与不存在复配缓蚀剂膜的Q235钢的自腐蚀电流密度、极化腐蚀电流密度和极化阻抗。用SEM研究复配缓蚀剂膜腐蚀前后的形貌变化。结果在60℃的生产废水中,L-抗坏血酸的最佳用量为165 mg/L,L-半胱氨酸的最佳用量为18 mg/L,复配缓蚀剂膜的形成时间为24h。无缓蚀剂膜时,Q235钢的自腐蚀电流密度为4.918×10-5 A/cm~2;在500 m V过电位下,极化腐蚀电流密度为1.667×10-2 A/cm~2,极化阻抗为529?×cm~2。形成复配缓蚀剂膜的Q235钢片的自腐蚀电流密度为3.433×10-7 A/cm~2,极化腐蚀电流密度为4.132×10-6 A/cm~2,极化阻抗很大。复配缓蚀剂的缓蚀率为80.15%,明显高于单一缓蚀剂。SEM测试表明,在过电位为500 m V时,无缓蚀剂膜的Q235钢腐蚀十分严重,有复配缓蚀剂膜的Q235钢几乎不腐蚀。结论在PVC热稳定剂生产废水中加入适量的缓蚀剂,具有较好的缓蚀性能,基本满足作为冷却水的要求。     

烟道气氨法脱硫液对Q235碳钢腐蚀研究

采用静态挂片、极化曲线和长期点蚀实验，研究了氨法脱硫浆液中F^-和Cl^-以及 (NH₄)₂SO₄对Q235碳钢腐蚀的影响。结果表明，Q235碳钢在含卤硫铵溶液中的均匀腐蚀速率随F^-浓度和Cl^-浓度增大均呈现先降低后增高的趋势，随着 (NH₄)₂SO₄质量分数增加，均匀腐蚀速率降低；随着F^-浓度的增大，自腐蚀倾向增加；随着Cl^-浓度以及 (NH₄)₂SO₄质量分数的增大，自腐蚀倾向均降低；Q235碳钢在氨法脱硫模拟浆液中点蚀较严重，需采取重防腐措施。     

Characterization of anodic films formed on AZ91D magnesium alloy

Anodization of die-casted AZ91D magnesium alloy was performed in 3 M KOH+0.21 M Na₃PO₄+0.6 M KF base electrolyte with and without Al(NO₃)₃ addition. The anodic film was characterized by using X-ray diffraction (XRD), scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS). The corrosion resistance of the various anodized alloys was then evaluated in 3.5 wt % NaCl solution using electrochemical impedance spectroscopy (EIS) and immersion testing. The results showed that the anodic film was mainly composed of MgO. The addition of Al(NO₃)₃ into the base electrolyte results in the formation of Al₂O₃ and Al(OH)₃ in the anodic film. The maximum amount of Al₂O₃ was found in the anodic film when the alloy was anodized in the electrolyte containing 0.15 M Al(NO₃)₃. The results of EIS analysis and morphological examination showed that the MgO anodic film modified with Al₂O₃ exhibited the superior corrosiom resistance for AZ91D Mg alloy.     

O3/Cl-复合大气环境中Q235B钢的腐蚀演化特性

采用干/湿交替的实验方法模拟大气腐蚀过程。运用X射线衍射、电化学阻抗谱以及极化曲线等手段，研究了O₃/Cl^-复合大气环境中Q235B钢的腐蚀演化特性。结果表明，O₃和Cl^-的协同作用对Q235B钢的腐蚀有明显的促进作用，其腐蚀速率随着模拟环境中Cl^-含量的增加而增大。腐蚀演化特性方面，Q235B钢在腐蚀的初期阶段腐蚀速率最大，中期阶段腐蚀速率迅速下降，而到后期阶段腐蚀速率又有所提高。相比于不含O₃的大气环境，当Cl^-浓度较低时，O₃和Cl^-对Q235B钢腐蚀产物组份的影响并不明显。而当Cl^-浓度较高时，O₃和Cl^-能明显促进β-FeOOH的生成而抑制α-FeOOH和γ-FeOOH的生成。这说明O₃/Cl^-复合大气环境能促进Q235B钢的大气腐蚀与锈层相组分变化密切相关。     

The corrosion resistance of hot dip galvanised steel and AA2024-T3 pre-treated with bis-[triethoxysilylpropyl] tetrasulfide solutions doped with Ce(NO3)3

The present work aims at evaluating the anti-corrosion behaviour of a novel pre-treatment based on bis-[triethoxysilylpropyl] tetrasulfide (BTESPT) doped with cerium nitrate for application on hot dip galvanised steel and AA2024-T3 substrates. The corrosion resistance was evaluated by electrochemical impedance spectroscopy (EIS) and by the scanning vibrating electrode technique (SVET), during immersion in NaCl solutions. The electrochemical results showed that the pre-treatment provides excellent corrosion protection to the substrates. Furthermore, the results evidenced improved protection comparatively to the use of undoped BTESPT pre-treatments, both for galvanised steel and AA2024-T3. This improvement is most likely due to enhanced barrier properties of the film and additional active corrosion protection originated from the inhibiting action of the cerium-based inhibitor impregnated in the silane matrix.     

钼酸钠和三乙醇胺对Q235碳钢小孔腐蚀的抑制作用

通过动电位扫描,微区电位扫描,电化学阻抗谱及XPS等技术,考察了Na₂MoO₄和三乙醇胺 (TEA) 复配缓蚀剂对Q235碳钢孔蚀的抑制作用。结果表明：Q235碳钢在0.02 mol/L NaCl+0.1 mol/L NaHCO₃溶液中,适量的Na₂MoO₄与TEA复配对其孔蚀的抑制作用要优于单独使用Na₂MoO₄对孔蚀的抑制效果。在外加恒电位为0.3 V时,在实验溶液中碳钢表面有活性点被激活,Na₂MoO₄+TEA复配缓蚀剂能够明显抑制表面活性点的生成,并且能使形成的活性点的电位峰值迅速降低,抑制其向腐蚀小孔的转化。在加有Na₂MoO₄+TEA复配缓蚀剂的实验溶液中形成的缓蚀膜主要成分为Fe₂(MoO₄)₃,Fe₂O₃和TEA,三乙醇胺的吸附可以改善钼酸盐缓蚀膜的致密性,进一步提高缓蚀性能。     

接地极Q235碳钢材料在上海土壤环境中的腐蚀行为

通过电化学阻抗 (EIS)、极化曲线、扫描电镜 (SEM)、能谱分析 (EDS) 和X射线衍射 (XRD) 等技术对接地极Q235碳钢材料在含不同盐分的上海地区土壤中的腐蚀行为进行了研究。结果表明,在不同盐分土壤条件下,Q235碳钢的阻抗均随着浸泡时间的延长出现先升高后平稳的趋势,腐蚀速率随盐分含量增大而增大。由于沿海土壤的侵蚀性阴离子含量较高,使得所产生的锈层失去保护性。Q235碳钢腐蚀主要以全面腐蚀为主,还伴有微生物腐蚀现象,腐蚀产物膜主要由Fe₂O₃组成。根据耐腐蚀性能评价标准,接地极碳钢材料在上海土壤环境中的耐腐蚀性能为良。     

Electrodeposition of cerium (III)-modified bis-[triethoxysilypropyl]tetra-sulphide films on AA2024-T3 (aluminum alloy) for corrosion protection

The doping of rare earth salts, like Ce(III), has shown to enhance the corrosion performance of silane films due to their self-healing behaviors. In the present paper, the Ce(III)-doped bis-[triethoxysilypropyl]tetrasulphide (BTESPT) films with higher corrosion resistance were prepared by electro-assisted technique. The films were investigated using electrochemical impedance spectroscopy (EIS), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), water contact angle measurements and Fourier transform reflection absorption IR (FTRA-IR). The results showed that both the cathodic deposition and cerium-doping can promote the formation of thicker and compacter silane films and enhance their protectiveness in the early stage of immersion in the corrosive media. However, it seems that the Ce(III)-doped BTESPT films prepared by electrodeposition lose their self-healing abilities after long-term immersion. The reason is still unclear, but might be attributed to the precipitation of Ce(III) oxides or hydroxides during the electrodeposition of doped silane films.     

稀土添加剂对Ni-Fe合金镀层制备及耐蚀性能的影响

采用稀土盐CeCl₃为添加剂,通过调整镀液中CeCl₃浓度在20#钢基体上电沉积制备Ni-Fe合金镀层.采用SEM,EDS和XRD等表征镀层的结构,采用电化学极化曲线和阻抗谱研究合金镀层在3.5%(质量分数)NaCl溶液中的耐蚀行为.结果表明:稀土添加剂在低pH值酸性体系中极易生成Ce(OH)₃溶胶,抑制 (FeOH) 和Fe(OH)₂等化合物的生成,其阴极吸附特性与 (FeOH) 的吸附形成竞争,优先吸附于材料表面,从而抑制了Fe的析出;另一方面CeCl₃的加入大大提高了电流效率,使镀速增大.当CeCl₃的浓度为3 g/L时,镀层中Fe的含量控制在16%左右,获得较好的镀层质量及较好的耐蚀性能.     

Corrosion electrochemical behaviors of silane coating coated magnesium alloy in NaCl solution containing cerium nitrate

Sol–gel coatings cannot provide adequate corrosion protection for metal/alloys in the corrosive environments due to their high crack‐forming potential. This paper demonstrates the possibility to employ cerium nitrate as inhibitor to decrease the corrosion development of sol–gel‐based silane coating on the magnesium alloy in NaCl solution. Cerium nitrate was added into the NaCl solution where the silane coating coated magnesium alloy was immersed. Scanning electron microcopy (SEM) was used to examine surface morphology of the silane coating coated magnesium alloy immersed in NaCl solutions doped and undoped with cerium nitrate. The corrosion electrochemical behaviors were investigated using potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) tests. The results showed that the introduction of cerium nitrate into NaCl solution could effectively inhibit the corrosion of the silane coating coated magnesium alloy. Moreover, the influence of concentration of cerium nitrate on the corrosion inhibition and the possible inhibiting mechanism were also discussed in detail.