Mg-Mn-Ce镁合金表面超疏水复合膜层的制备及耐腐蚀性能

采用微弧氧化技术和有机镀膜技术相结合的复合处理方法实现Mg-Mn-Ce镁合金表面改性,获得超疏水复合膜层,研究微弧氧化膜的表面特征、有机镀膜电化学反应过程、复合膜层的润湿特性和耐腐蚀性能。结果表明:镁合金经微弧氧化处理后由于微弧氧化膜表面呈微纳多孔结构,表现为超亲水特性,其蒸馏水的静态接触角接近0°;在微弧氧化膜上经有机镀膜后,其形成的有机薄膜的静态接触角高达173.3°,表现出优良的超疏水特性。镁合金经微弧氧化处理后具有良好的耐腐蚀性能,经有机镀膜超疏水复合处理后,耐腐蚀性能得到进一步提高。复合膜层在3.5%NaCl溶液中,与基体相比动电位极化腐蚀电流密度减小了3个数量级、而电化学阻抗提高了3个数量级,耐腐蚀性能明显改善。微弧氧化与有机镀膜相结合的复合处理使镁合金表面在实现超亲水-超疏水功能转换的同时显著提高镁合金的耐腐蚀性能。     

Mg-Li合金表面浅绿色超疏水复合膜层的制备及耐蚀性能研究

通过微弧氧化着色技术在Mg-Li合金表面生成浅绿色类陶瓷膜层,并在着色膜表面有机镀膜复合改性。用蒸馏水在镀膜表面的静态接触角以及动电位极化曲线和电化学阻抗谱测试,分别研究复合改性前后润湿性及耐蚀性。结果表明,微弧氧化着色表面通过有机镀膜生长了一层有机薄膜,接触角由近0°变为169.2°,实现了超亲水到超疏水的功能转化。Mg-Li合金基体经微弧氧化着色改性后,耐蚀性能明显提高,经复合改性后耐蚀性能进一步提高;与基体相比,超疏水复合膜在0.1 mol/L NaCl溶液中的动电位极化腐蚀电流密度减小3个数量级,电化学阻抗提高3个数量级。     

基于微/纳二元结构镁合金超疏水膜层的制备

利用微弧氧化技术在镁合金表面制备微米级粗糙结构,采用环氧树脂溶液和纳米二氧化硅分散液对该表面进行涂覆处理,再利用全氟硅烷改性,制备得到具有超疏水性的复合膜层。采用扫描电镜、X射线衍射仪、接触角测量仪、高速摄影系统和电化学工作站评价膜层的形貌结构、润湿性和耐蚀性。结果表明:微弧氧化层所具有的微米级结构和纳米二氧化硅颗粒组成的微/纳二元粗糙结构对疏水性的提高具有重要作用;复合膜层表面的接触角随二氧化硅分散液浓度的提高呈现先增加后减小的趋势,并最终逐渐稳定在150°左右;当二氧化硅分散液溶度为10 g/L时,复合表面的接触角最大可达161°。同时该表面对水滴呈现低黏附特性。动电位极化曲线表明:与镁合金基底相比,微弧氧化层和复合膜层的耐蚀性提高2~3个数量级。     

AZ31B镁合金表面改性微弧氧化膜的结构及耐蚀性能（英文）

利用十四烷酸溶液化学浸泡的方法改性微弧氧化AZ31B镁合金,获得了具有疏水特性的微弧氧化膜。采用接触角测量仪检测膜层的润湿性能;利用SEM、XRD和FT-IR等方法表征膜层的形貌和结构;通过极化曲线和浸泡实验考察样品在3.5%NaCl溶液中的耐蚀性能。结果表明:改性时间从0 h增至5 h时,膜层的静态接触角从0°增加到了138°,膜层的微孔尺寸减小,微孔数量减少;化学改性未改变微弧氧化膜的晶体结构,但改性样品的自腐蚀电位正移,自腐蚀电流密度降低,耐蚀性能得到提高,且疏水性和耐蚀性随着烷基链的增长而增强。氧化膜表面微观多孔的结构促进低表面能烷基羧酸的润湿铺展,烷基链通过双配位键合作用形成单分子层,封闭或缩小微孔,致密微弧氧化膜,并赋予其疏水特性,进一步提高微弧氧化膜对镁合金的腐蚀防护能力。     

镁合金表面功能纳米薄膜的制备

通过有机镀膜技术，对镁合金表面进行改性。对有机镀膜处理后的镁合金表面的接触角，表面自由能进行了测定。研究了不同有机镀液，在恒电流作用下，有机镀膜时间对镁合金表面性能的影响。结果表明，经过TTN溶液有机镀膜后，镁合金板表现出亲水性，其表面能比未处理镁合金板的表面自由能要高；而经过DHN和DAN溶液有机镀膜后，镁合金板表现出良好的疏水性，其表面能比未处理镁合金板的表面自由能要低，在二者中DHN处理后的疏水效果最好。实现了对镁合金表面疏水、亲水表面改性，能够很好的扩大镁合金在工业中的应用领域。     

镁合金表面微弧氧化/自组装复合膜的耐蚀性能

目的 提高镁合金基体的耐蚀性能.方法 采用微弧氧化工艺对镁合金进行预处理,再通过自组装技术处理,在镁合金表面制备微弧氧化/十六烷基三甲氧基硅烷自组装复合膜层.通过SEM、EDS对复合膜的微观组织结构进行分析,并通过XPS、拉曼光谱分析了复合膜的表面成分,利用电化学阻抗谱、极化曲线、盐雾实验和浸泡实验检测了复合膜层的耐腐蚀性能.结果 复合膜均匀覆盖在镁合金表面,且复合膜较为光滑,主要含有C、O、F、Si等元素.经过自组装处理后,膜层从亲水性转为疏水性,接触角达到145.07°.经电化学性能测试,复合膜的Rct值能达到2.242×106?·cm2,与微弧氧化膜相比,增大了2个数量级;此外,复合膜的腐蚀电流密度为1.314×10-8 A/cm2,与微弧氧化膜相比也降低了2个数量级,具有较好的耐腐蚀性.浸泡120 h后,复合膜的腐蚀电流密度仍有1.061×10-5 A/cm2,盐雾实验进行120 h也没有出现明显的腐蚀现象.结论 自组装技术明显提高了镁合金基体的耐蚀性能,微弧氧化膜在一定程度上增强了自组装膜层对基材的粘附力.由于复合膜的疏水性使得水滴在膜层表面停留的时间减少,所以膜层的耐蚀性会随着疏水性增大而大大提高.     

MB8镁合金表面超疏水复合膜层的制备与表征

利用微弧氧化技术在镁合金表面制备微米级粗糙结构,采用环氧树脂溶液和纳米二氧化硅分散液对该表面进行涂覆处理,得到二氧化硅纳米颗粒均匀分布的粗糙表面,再利用全氟硅烷改性,制备得到具有超疏水性的复合膜层。采用扫描电镜、X射线衍射仪、接触角测量仪、高速摄影系统评价膜层的形貌结构和润湿性。结果表明,微弧氧化层所具有的微米级结构和纳米二氧化硅颗粒组成的微/纳二元粗糙结构对疏水性的提高具有重要作用;复合膜层表面的接触角随二氧化硅分散液浓度的提高呈现先增加后减小趋势,并最终逐渐稳定在150o左右;在二氧化硅分散液浓度为10.0g/L时,复合表面的接触角最大,可达161o,在此条件下获取的复合表面对不同pH值的液滴均具有超疏水性。同时该表面对水滴呈现低黏附特性。     

疏水性三嗪硫醇类分子膜的制备与表征

采用有机镀膜方法在低碳钢表面成功制备了疏水性三嗪硫醇类分子膜。通过循环伏安曲线分析了低碳钢表面有机镀膜的成膜过程,利用蒸馏水接触角和动电位极化曲线对所镀膜层的润湿性和耐腐蚀性能进行了表征。结果表明:低碳钢表面有机镀膜成膜过程同时存在3个反应,即基体与有机单体之间的电化学反应、金属有机化合物和有机单体之间的聚合反应及有机单体之间的聚合反应;有机镀膜后低碳钢表面蒸馏水静态接触角由基体的65.5°增大到96.3°,实现了由亲水到疏水特性转变;腐蚀电流从14.80μA/cm2降低到0.53μA/cm2,耐腐蚀性能得到显著提高。     

镁合金材料表面处理技术研究新动态

对镁合金材料近年来在表面微弧氧化、表面超疏水膜层、激光表面改性以及溶胶-凝胶涂层四个方面的研究动态进行了简要综述。镁合金材料采用双极性和混合(单极和双极的组合)电流模式微弧氧化处理的膜层生长速率较快,膜层更致密且硬度更高,膜层的耐磨性和耐腐蚀性能更好。在高浓度苛性碱为主的强碱性溶液中添加适量的添加剂,经短时间(~3 min)微弧氧化处理,即可获得中性盐雾试验达200 h以上的致密耐腐蚀膜层。采用水热法、电化学刻蚀、微弧氧化和电沉积等方法,可在镁合金材料表面形成具有微纳米多级结构的粗糙表面,再用低表面能物质对粗糙表面进行修饰,可在镁合金表面获得超疏水膜层,从而提高镁合金的耐腐蚀性能。镁合金材料激光表面改性处理可改善其表面成分,细化晶粒,使组成相分布更均匀以及提高表层的固溶度极限,从而提高镁合金材料的耐腐性能、摩擦磨损抗力和疲劳强度。溶胶-凝胶有机/无机杂化涂层与镁合金基材良好的附着力,不仅可提高镁合金的耐腐蚀性能,还可以使镁合金具有抗氧化、耐磨损、防水性以及其他性能。     

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。     

镁合金微弧氧化复合膜研究进展

微弧氧化（MAO）表面处理技术常用于改善镁合金的特定性能,但MAO膜容易产生微孔和微裂纹从而降低镁合金的耐蚀性。为了提高镁合金微弧氧化膜的使用寿命,主要综述了国内外MAO工艺过程调节措施和MAO膜后处理技术的最新研究进展,重点介绍了近年来国内外镁合金MAO复合膜的研究热点。着重介绍了通过工艺过程调节提高镁合金MAO膜长期保护性能的几项措施：通过电参数和电源类型调节协同电解液成分调整提高MAO膜耐蚀性;通过加入电解液添加剂提高MAO电解液稳定性和电导率;利用具有自封孔作用的添加剂可以参与成膜的特点提高MAO膜致密性;通过复合工艺在MAO膜传统封孔后进一步封闭孔隙。此外,详细介绍了包括疏水涂层、化学镀、类金刚石涂层、生物膜涂层等复合膜工艺的研究进展,强调了复合膜不仅耐蚀性高而且具有功能化应用前景：超疏水复合膜对镁基底具有主动的腐蚀保护作用,超疏水膜协同MAO膜可以提高表面的疏水性;镀镍层致密无微孔且与MAO膜交错咬合能够改善镁MAO膜的导电性和耐蚀性;MAO涂层代替金属缓冲层能够提高类金刚石涂层和基体界面结合强度;生物复合涂层不仅耐蚀性高还具有促进细胞增殖和分化生物活性的作用。最后,基于镁...     

Polymer plating on AZ31 magnesium alloy surface and film evaluation of corrosion property

The polymeric thin film was prepared on the surface of AZ31 magnesium alloy by polymer plating of 6-dihexylamino-1,3,5-triazine-2,4-dithiol monosodium (DHN) in order to modify its surface feature and to improve its anti-corrosive property. Cyclic voltammetry was used to study the electrochemical reaction and film growth process of poly(6-dihexylamino-1,3,5-triazine-2,4-dithiol) (PDH) film, and the reaction peaks for film formation and growth were affirmed. The polymeric film weight was determined by electronic balance and its insoluble fraction in tetrahydrofuran was also measured. Contact angle meter was applied to test the surface wettability with distilled water drops at ambient temperature. It was found that the polymer-plated AZ31 alloy showed hydrophobic property with its distilled water contact angle up to 117.2°. The performance property of polymeric thin film formed on AZ31 surface was studied by potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) in the corrosion solution of 3.5% NaCl. The electrochemical experiment results showed that polymer-plated thin film with hydrophobic and insulative characteristics could provide surface modification and an effective anti-corrosive protection to magnesium alloy substrate compared to the blank one.     

微弧氧化膜层表面化学镀Ni-P合金工艺研究

研究了镁合金微弧氧化后化学镀Ni-P合金层的工艺、镀层的结构,结果表明：化学镀得到的镍层具有很强的化学活性,对微弧氧化膜层可以起到封孔作用,镀液所及的地方都能被镍层覆盖。微弧氧化膜的耐酸蚀能力得到很大提高。     

锆微弧氧化表面处理技术研究进展

锆及锆合金是重要的核结构材料和有潜力的生物医用材料,但在实际应用中,腐蚀、磨损易造成其失效,而适当的表面改性是提高它们服役性能的有效手段。重点介绍了锆及锆合金微弧氧化（MAO）表面处理技术的研究现状,讨论微弧氧化过程中电压电流特征及微弧放电机理,总结电解液体系及电参数对锆微弧氧化膜生长及膜层性能的影响规律,最后指出目前存在的问题和后续的研究方向。锆微弧氧化膜硬度高,致密性好,能大幅度提升基材的抗磨损和抗腐蚀性能。因此,锆微弧氧化技术在核电及生物医学领域有着很好的应用前景。此外,电解液中铝、硅元素进入微弧氧化膜后可以稳定膜层中高温氧化锆相（t-ZrO2）,避免膜层中应力集中和微裂纹的产生。用P和Ca元素修饰后的锆微弧氧化膜具有较好的生物活性、抗体液腐蚀和抗菌性能。     

Electroless plating of palladium and copper on polypyrrole films

A novel process for the metallization of polypyrrole (PPY) film surface through consecutive electroless plating of palladium and copper in the complete absence of the SnCl₂ sensitization step was demonstrated. X-ray photoelectron spectroscopy (XPS) technique was used to characterize the polymer surface at each stage of the metallization process. It was found that only the fully reduced PPY film could reduce palladium ions to palladium metal (Pd(0)) in substantial amounts from either the Pd(NO₃)₂ or PdCl₂ acid solution. The palladium metal was necessary for catalyzing the subsequent electroless plating of copper. The reduction of Pd(II) ions in acid solution to Pd(0) on the film surface was accompanied by a simultaneous increase in intrinsic oxidation state and doping level of the film. The copper plating process after the palladium uptake step was highly dependent on the [Pd]/[N] ratio on the film. Through XPS and Auger photoeletron spectroscopy measurements, it was postulated that during the electroless copper plating process, the Cu(II) ions were first reduced to Cu(I) on the PPY film surface before complete reduction to copper metal.     

Nanoscale smooth interface maintained metallisation of polyimide using low concentration ozone micro–nano bubbles dispersed in water

In order to induce adhesion of electroless CuNiP deposition to polyimide (PI) film substrate, surface modification of PI film with an aqueous dispersion of ozone micro–nano bubbles was investigated. The treatment resulted in maximum adhesion strength of 1·14 kN m^?1 for a treatment time of 5 min. Structure of the modified PI surface, the PI/plating interface, mechanism for adhesion and laminate properties were analysed. Despite increased adhesion, surface roughness of PI was not notably changed by the ozone induced surface modification. Contact of PI surface with high ozone concentration micro–nano bubbles with sufficient frequency was found to modify the surface with a low total ozone concentration of the aqueous dispersion. Cross-sectional observation of the interface suggested that formation of a thin nanoporous anchor layer on the PI surface was responsible for plating adhesion. This method provides an environment friendly and improved process for plating on PI using low concentration ozone treatment.     

Fabrication of super-hydrophobic surface on copper surface by polymer plating

The 6-(N-allyl-1,1,2,2-tetrahydroperfluorodecyl)amino-1,3,5-triazine-2,4-dithiol monosodium) (ATP) was used to fabricate polymeric thin film on pure copper plate to achieve super-hydrophobic surface. The copper plates were pretreated to gain rough surfaces by chemical etching before polymer plating. The polymer plating process of ATP on copper in Na₂CO₃ aqueous solution and the growth mechanism of poly(6-(N-allyl-1,1,2,2-tetrahydro-perfluorodecyl) amino-1,3,5-triazine-2,4-dithiol) (PAT) thin film was studied by means of cyclic voltammetry. The polymeric film was investigated by using X-ray photoelectron spectroscopy (XPS), and the etched surfaces were observed by atomic force microscopy (AFM). A contact angle meter was applied to measure the contact angles with distilled water drops at ambient temperature. The experimental results indicated that the polymeric film formed on rough copper surface exhibits super-hydrophobic property with a distilled water contact angle of 155°. The wettability of copper surfaces was discussed on the basis of both Wenzel and Cassie theories. The etching and polymer plating processes are time-saving, inexpensive, environmental and fairly convenient to carry out. It is expected that this technique will advance the production of super-hydrophobic materials with new applications in large scale. Moreover, this kind of thin film can be used as a dielectric material due to its insulated feature.     

Preparation of Sn4+-Doped Titanium Dioxide Photocatalytic Films on 304 Stainless Steel by Duplex Treatment

Sn⁴⁺-doped titanium dioxide photocatalytic films were synthesized on 304 stainless steel (SS) by a duplex treatment. The SS substrates were alloyed with titanium (Ti) through cathodic-arc ion plating followed by a microarc oxidation (MAO) treatment in different electrolytes. Field-emission scanning electron microscopy, x-ray diffraction, and energy dispersive spectroscopy were used to characterize the films surface morphology, crystalline phase, and composition, respectively. Photocatalytic activity was measured using an UV-Vis spectrophotometer. It was found that the films with a porous structure are mainly composed of TiO₂, which exists in an anatase and rutile state. Furthermore, small quantities of SnO₂ have been found in the Sn⁴⁺-doped titanium dioxide films. The fraction of anatase varies with the MAO time and electrolytes, whereas the pore size remains the similar with the same MAO current intensity and density and the surface roughness increases slightly with increasing MAO time. It was also found that the photocatalytic activity of the Sn⁴⁺-doped porous film improved, and the film synthesized with a shorter MAO time in a lower Na₂SnO₃-containing electrolyte is superior to the films with longer MAO times and higher Na₂SnO₃ concentrations.