添加剂作用下制备环境友好型铈基镁合金稀土转化膜

采用Ce（SO4）2-H2O2溶液体系在AZ91D镁合金表面制备环境友好型稀土转化膜,并在处理液中添加Ni（NO3）2和十二烷基苯磺酸钠以提高室温下的成膜效果。采用SEM、EDS、XRD、GIXD等方法研究镁合金表面稀土转化膜的微观形貌与元素组成以及微观结构,采用自腐蚀电位跟踪法对镁合金在稀土溶液中的成膜过程进行研究。添加剂十二烷基苯磺酸钠比Ni（NO3）2能更有效地提高转化膜的致密性与耐腐蚀性能。与从不含添加剂处理液中得到的转化膜相比较,添加十二烷基苯磺酸钠得到的转化膜的自腐蚀电流密度从7.41×10-5A/cm2降低到2.20×10-5A/cm2,电位？时间曲线第二阶段的成膜时间从5min缩短到2min。稀土转化膜的主要成分为Mg、Al、O和Ce。添加剂Ni（NO3）2和十二烷基苯磺酸钠可分别将转化膜中Ce元素的含量从18.92%增加到22.32%和25.08%。RXD与GIXD研究表明在所有溶液中得到的转化膜均为非晶态结构。     

添加剂对镁合金表面Ce-Mn转化膜组织和耐蚀性能的影响

以Ce(NO3)3-KMn O4为主要成膜剂,向体系中分别加入NH4HF2、Na F、Sr Cl2、Na BF4、十二烷基苯磺酸钠(C18H29-Na O3S)、Na B4O7添加剂,室温下在镁合金表面制备了Ce-Mn转化膜。用扫描电镜(SEM)及能谱仪(EDS)对转化膜的微观形貌和成分进行分析,并用极化曲线研究转化膜的耐腐蚀性能。结果表明,添加剂不改变膜层成分,但对膜层组织结构及耐腐蚀性能有较大影响,较佳的添加剂为十二烷基苯磺酸钠,添加十二烷基苯磺酸钠生成的转化膜,膜层裂纹细小,耐蚀性更好。     

AZ91D镁合金无铬铈盐转化膜的正交试验研究

为了代替剧毒Cr^6＋化学转化膜处理工艺,采用硝酸铈以及高锰酸钾为无铬化学转化处理液的主要成膜成分,通过正交试验优化了以Ce（NO3）3,为主盐的镁合金铈盐化学转化膜工艺,并对成膜规律进行了研究。试验表明,本工艺所获得的铈盐化学转化膜具有优良的外观和良好的耐腐蚀性。此外,借助扫描电镜分析手段对转化膜的微观形貌进行了分析,还对氧化膜成膜机制进行了探讨。     

水轮机用6063铝型材的表面转化膜制备与表征

采用化学浸泡法在水轮机用6063铝型材表面制备化学转化膜,研究了Ce(NO_3)_3浓度、KMn O_4浓度、成膜时间和p H值对表面转化膜层耐点滴腐蚀时间和膜厚的影响,并研究了转化膜层的耐腐蚀性能和形貌,得到了适宜的转化膜制备工艺。结果表明,水轮机用6063铝型材表面转化膜的最佳成膜时间为30 min,Ce(NO_3)_3和KMn O_4浓度分别为10 g/L和2 g/L,p H值为2。最佳成膜工艺下的转化膜的耐腐蚀性能相对6063合金基材有明显提高。     

Preparation and Corrosion resistance of Cerium-based Chemical Conversion Coating on AZ91 Magnesium alloy

采用Ce(NO3)3为主盐的稀土盐处理溶液,在AZ91镁合金表面形成无毒,无污染的铈盐化学转化膜,并研究成膜规律及其耐蚀行为。利用对膜层的外加扰动小,更易得到重复性高结果的电化学阻抗谱技术评价膜层耐蚀性能。初步优化了处理时间、温度、Ce(NO3)3液浓度和促进剂等因素对膜层结构和膜层耐蚀性能的影响,并获得了最好的成膜条件：温度35℃,时间为30min,处理液主盐Ce(NO3)3的浓度为0.02mol/l和4ml/l成膜促进剂。结果表明：优化后的工艺能够在AZ91镁合金表面获得宏观黄色致密,微观具有微小裂纹并分层的膜层,内层膜Ce含量较外层的低但致密。工艺优化制备的稀土化学转化膜能有效提高镁合金的耐蚀性能,有效抑制阴阳极反应,自腐蚀电位提高240mV,自腐蚀电流密度降低达到2个数量级。     

建筑铝型材表面转化膜的制备及膜层组成分析

以钼酸钠和十二烷基苯磺酸钠混合溶液为成膜试剂,在建筑用6061铝型材表面制备了无Cr复合转化膜,对复合转化膜层的成膜过程和组织结构进行了观察,并探讨了转化膜的形成机理。结果表明,随着成膜时间的延长,转化膜表面的显微小孔逐渐被均匀分布的微裂纹所覆盖,微裂纹宽度逐渐增加;复合转化膜层由非晶态氧化物和氢氧化物组成,主要为MoO3、MoO(OH)2、CeO2、Ce(OH)4、Ce(OH)3、MnO2、Al(OH)3、Al2O3以及可能存在的MoO2。     

AZ91镁合金表面铈基稀土转化膜的制备及腐蚀电化学行为

考察了铈盐溶液中的AZ91镁合金电化学行为,包括开路电位,阴、阳极极化行为等,并据此开展了Ce(NO3)3为主盐的稀土盐转化膜研究,在AZ91镁合金表面形成无毒、无污染的铈盐化学转化膜,并研究成膜规律及其耐蚀行为.采用电化学阻抗谱技术优化了处理时间、温度、Ce(NO3)3液浓度和促进剂等因素对膜层结构和膜层耐蚀性能的影响,并获得了最好的成膜条件:处理温度为35℃,时间为30 min,主盐Ce(NO3)3的浓度为0.02 mol/L和促进剂H2O2浓度为4 mL/L.结果表明:采用优化后的工艺能够在AZ91镁合金表面获得宏观黄色致密、微观具有微小裂纹并分层的膜层,表层Ce含量较高.工艺优化制备的稀土化学转化膜能有效提高镁合金的耐蚀性能,有效抑制阴、阳极反应,自腐蚀电位提高250 mV,自腐蚀电流密度降低2个数量级.长期全浸实验结果表明,转化膜能有效提高镁合金的耐腐蚀性能,浸泡60 h后,保护性大大降低.     

热镀锌层柠檬酸改进型铈盐转化膜的生长机理

将热镀锌钢板浸入含有25 g/L Ce(NO3)3·6H2O、4~6 g/L H2O2(30%)、15~20 g/L H3Cit的处理液中,在70℃下处理10 s~240 min,从而在其表面获得铈盐转化膜。采用中性盐雾试验(NSS)和电化学极化曲线来分析膜层耐蚀性能,确定最佳成膜时间范围。采用扫描电镜(SEM)观察膜层的微观形貌,利用能谱仪(EDS)、X射线光电子能谱仪(XPS)、红外吸收光谱仪(IR)分析膜层的化学组成。结果表明:处理时间为10 min左右的铈盐转化膜耐腐蚀性能最优,最佳工艺条件下得到的铈盐转化膜的耐蚀性能与铬酸盐转化膜的相当;随着处理时间的延长,膜的厚度增加,膜层的裂纹变宽;处理时间超过10 min后膜层逐步产生脱落,耐腐蚀性能也随之降低;转化膜的生长过程中,前期以柠檬酸铈吸附膜的沉积为主,后期以Ce(OH)3/Ce2O3及Ce(OH)4/CeO2的沉积占主导。     

镧铈双稀土耐蚀转化膜的制备及性能研究

采采用浸渍法在AZ91镁合金表面制备镧铈双稀土转化膜,优化了侵蚀转化处理工艺,并研究了双稀土转化膜的微观形貌、膜层成分及耐蚀性。利用正交试验确定成膜的最佳工艺为:处理温度30℃,Ce3+:La3+=2∶1(摩尔比),V双氧水=5 ml,p H=4~5.腐蚀性能测试结果表明,成功的在AZ91镁合金表面沉积出黄色致密、有微小裂纹的耐腐蚀转化膜。     

钢铁工件复合稀土成膜及其耐蚀性能

利用Ce(NO3)3溶液在钢铁工件表面制得一种金黄色的稀土转化膜.通过正交优化实验确定稀土转化膜的最佳成膜工艺条件，并且对该膜进行3.5%的NaCl浸泡实验测定其耐蚀性能.利用Ce(NO3)3和Na2MoO4复合稀土成膜的钢铁试片在3.5%的NaCl中的腐蚀速率为0.0143 mg/h·cm2；复合稀土成膜实验表明：复合处理的钢铁试片，其膜层的结合力有明显的改善，所制备稀土转化膜具有良好的耐蚀性能.      

AZ91 镁合金表面Ce-Mn 转化膜组织及性能表征

室温下,在AZ91 镁合金表面制备Ce-Mn 复合转化膜,通过单因素实验研究了Ce(NO3 )3 浓度和KMnO4 浓度对转化膜耐腐蚀性能的影响,确定了较佳的浓度配比。分析了转化膜的结构及组成,通过交流阻抗谱,研究了Ce-Mn 对基体镁合金的防护机制。结果表明:Ce-Mn 转化膜为非晶态物相结构,膜层主要由铈、锰和少量镁的氧化物或氢氧化物组成,Ce-Mn 转化膜可对镁合金起到较好的防护作用。     

铝合金Ce-Mn转化膜溶液中HF2-离子作用机理研究

利用电子探针显微分析（EPMA）、X射线衍射（XRD）、能谱仪（EDS）、X射线光电子能谱分析（XPS）对Ce-Mn转化膜膜层进行表面和截面元素分布、相组成分析及沉淀物粉末的物相分析。结果表明,HF₂^-盐作为Ce-Mn转化膜溶液的促进剂,主元素F不是Ce-Mn复合膜层的组成成分,并不参与膜层的生长过程。通过对铝合金基体的腐蚀及其表面氧化膜(Al₂O₃)的溶解,使铝合金阴极区快速暴露,形成的[AlFe₆]^3-总量小于1.8mmol/L,完全溶于溶液。     

氟处理对AZ31B镁合金生物耐蚀降解行为的影响

采用低温化学方法在AZ31B镁合金表面制备出氟涂层,并研究了涂层的表面特征,氟处理后AZ31B镁合金在模拟体液中的腐蚀行为。结果表明,氟涂层均匀致密,与基体结合良好。经氟处理后的AZ31B镁合金的耐蚀性能有较大提高,其在模拟体液中的降解缓慢,合金浸泡后溶液的pH值保持在7.5~8.8之间,有效降低了合金降解而引起的碱性增强趋势。氟涂层在模拟体液中会逐渐转化为Ca3(PO4)2,新生成的表面膜会继续起到保护合金基体的作用。     

Process Optimization for Cerium Oxide Based Conversion Coating of AZ91D Magnesium Alloy at Room Temperature

The Ce2SO4/H2O2 containing solution is used to prepare a chrome-free cerium oxide based chemical conversion coating on AZ91D magnesium alloy at room temperature,and an orthogonal experiment was carried out to optimize the treating process.The effect of preparing parameters on the coating growth and the corrosion resistance were studied.It was found that H2O2 is the dominant influence factor on the coating weight gain in the orthogonal experiment,with Ce(SO4)2 coming next and immersion time having the least impact,while the most dominant influence factor on the corrosion resistance is Ce(SO4)2,with H2O2 coming next and immersion time having the least impact.The coating has the best corrosion resistance,treated in the solution of 10 g/l Ce(SO4)2 and 12 ml/l H2O2 for 4 min.SEM was adopted to study the micro-morphology of the conversion coating on magnesium alloy surface The prolonged immersion time duration or the increased concentration of Ce(SO4)2 and H2O2 will increase the coating thickness,but tiny cracks appears resulted from the fast coating deposition.     

Microstructure and formation mechanism of Ce-based chemical conversion coating on 6063 Al alloy

In order to accelerate the conversion coating formation on 6063 Al alloy in the Ce(NO3)3 solution, accelerants of chloride and ammonium salt were used. The coating morphology, composition and structure were analyzed with SEM/EDS, EPMA, XPS and XRD. The coating morphology is influenced by the composition, pH value and temperature of the treating solution. The coating composed of metal oxide, metal hydroxide and hydrate appears to be amorphous. The elements in the coating are Al, Ce, O, Mn and Mg, while the Ce element exists in the forms of Ce3+ and Ce4+. The accelerant of chloride can increase the compactness and Ce content of the coating, so the coating corrosion resistance is remarkably improved. A scheme for the electrochemical reaction in the coating formation was proposed, and the potential change in the coating formation was also studied. It is found that chloride can shorten the time period of the first and the second stages in coating formation.     

Characteristics of Ce-Mn film on 6061 alloys and its improved performance

HF_2~- was applied to accelerate the Ce-Mn film formation on 6061A1 alloy in the Ce~(3+)-MnO_4~-solution.The process of film formation,the composition and structure of the film were analyzed by scanning electron microscopy(SEM) equipped with energy-dispersive spectroscopy(EDS),X-ray photoelectron spectroscopy(XPS)and X-ray diffractometer(XRD).The film formation process includes three stages.At the initial stage,a threedimensional(3D) skeleton was formed quickly,and then the skeleton was fully filled with cerium oxide and manganese oxide,resulting in a dense structure.Subsequently,a new skeleton was formed and also filled.Al,Ce,O and Mn were detected in the film.Ce existed mainly in the form of Ce~(4+)(89%).The film existed in an amorphous form and was composed of ceria(cerium hydroxide),manganese dioxide and aluminum oxide.After electrostatically spraying fluorocarbon powder,the resultant products satisfied the required mechanical performance and exhibited almost non-filament corrosion compared with commercially available chromium-free conversion film.Its corrosion resistant time to acetate spray can reach 2000 h,which is consistent with that of fluorocarbon paint.The results showed that Ce-Mn film can offer an attractive prospect to eliminate volatile organic compounds(VOC) problem arisen by using fluorocarbon paint in the process of industrial production.     

Phytic acid conversion coatings on magnesium surface treatment with cerium chloride solution

A chromium-free composite conversion treatment for magnesium by phytic acid and CeCl₃ solutions was studied. The composite coatings on the surface of magnesium presented network-like cracks, which was consisted of Mg, O, C, P and Ce elements. The distribution of Ce on the surface layer was non-uniform. The crack sizes of the composite coating were smaller than that of the phytic acid conversion coating. The corrosion process of the coatings was evaluated through electrochemical impedance spectroscopy in 3.5% NaCl solution, and the equivalent circuit of RL(Q(R(QR))) model was obtained through the characteristics of EIS. The average corrosion rate of the composite coating was reduced at least 50% compared with that of pure phytic acid conversion coating.     

AZ91 D 镁合金表面铈转化膜及环氧 / 氟碳涂层附着性研究

利用化学浸泡法在AZ91D镁合金表面制备铈盐转化膜,优化了铈盐转化处理工艺,研究了铈盐转化膜的微观形貌、组织结构及耐蚀性能。在转化膜表面分别涂覆环氧树脂和氟碳树脂涂层,测试了两种复合涂层的力学性能。结果表明:铈盐转化膜由双层膜组成,在优化的工艺条件下进行转化处理能够提高镁合金的耐腐蚀能力;铈盐转化膜对环氧树脂的适应性要优于氟碳树脂。     

Surface treatment of Cf/Al composites with immersion in aqueous solution containing Ce ions for corrosion barrier

In this study, Ce‐rich coating is investigated as corrosion inhibitor of carbon fibers reinforcement aluminum matrix (Cf/Al) composites. The coatings are obtained by immersion in aqueous solution containing Ce(NO₃)₃ onto composite surface, whereas the Ce‐rich coating process produces a coating with highly heterogeneous nature of the surface, but micro‐cracked layer with “dry‐mud” morphology. The coatings were composed of Ce‐rich nano‐particles, Ce‐rich particles with a sphere‐like morphology, which are agglomerated particles with diameter 4 ～ 8 nm and piled up for this coating. TEM observation for Ce conversion coating of the corresponding ring‐like SAED patterns could not be matched to any of the previously reported structures of cerium compounds. Results of high‐resolution XPS spectra of Ce3d obtained for Ce conversion coating show that the Ce3d spectra has several components with binding energies characteristic of Ce³⁺ and Ce⁴⁺. The Ce‐rich coating process produces effective corrosion protecting of Cf/Al composites, which is verified by electrochemical measurement results. The R_t values of coated sample are higher than those of uncoated sample, this confirms the better corrosion resistance of coating obtained after immersion treatment for Cf/Al composites.     

Improving corrosion resistance of aluminium metal matrix composites using cerium sealed electroless Ni–P coatings

Abstract

A conversion coating treatment using cerium salts was developed for the surface sealing of electroless nickel–phosphorus (Ni–P) coatings on carbon fibre reinforced aluminium (Cf/Al) composites. The corrosion resistances of uncoated and coated materials (i.e. the Ni–P coating, the Ce conversion coating and Ce sealed Ni–P coatings) were evaluated in 3·5 wt-%NaCl solution using potentiodynamic polarisation and electrochemical impedance spectroscopy. Ce sealed Ni–P coating showed the highest corrosion resistance and clearly improved the overall corrosion resistance of Cf/Al composites. Thus, the Ce sealed Ni–P coating had no obvious microcracks that were generally evident in the more conventional Ce conversion coatings. This is presumed to occur because the electroless nickel surface is relatively homogeneous, compared with the Cf/Al composite surface on which different local coating thicknesses would encourage increased microcrack formation. X-ray photoelectron spectroscopy analysis showed that the Ce conversion coating mainly contained both Ce³⁺ and Ce⁴⁺ species; however, Ce⁴⁺ species were the dominant oxidation state on Ce sealed Ni–P coatings.