α-ZrP/PANI电控离子交换膜对Pb~(2+)的选择性分离

采用电化学方法在水相中合成了一种新型的电活性α-磷酸锆(α-Zr P)/聚苯胺(PANI)阳离子交换材料,考察该膜在含Pb~(2+)溶液中的电控离子交换性能。分别在碳纳米管(CNTs)和PANI纳米纤维修饰的Au基体上制备了不同结构的α-ZrP/PANI杂化膜,并结合电化学石英晶体微天平(EQCM)技术,原位检测杂化膜的生长过程,分析其成膜机理。研究结果表明,在PANI纤维上制备的杂化膜因其三维多孔结构具有更高的离子交换容量;α-Zr P上的P-OH不仅能够为聚苯胺氧化还原提供氢质子,而且对Pb~(2+)表现出良好的吸附选择性,使该膜在中性含Pb~(2+)溶液中表现出良好的电活性。通过控制该杂化膜的氧化还原状态可以实现对重金属Pb~(2+)离子的选择性分离和回收。     

聚苯胺膜/不锈钢复合双极板的耐蚀性和导电性

目的在316L不锈钢(SS)表面沉积聚苯胺(PANI)薄膜,制备PANI/316L SS复合材料双极板,提高316LSS在质子交换膜燃料电池工作环境下的耐腐蚀性能和导电性能。方法采用循环伏安法,在0.1 mol/L苯胺单体与0.2 mol/L H2SO4组成的水溶液中,在316L SS基体上电化学聚合PANI薄膜。采用SEM观察表面形貌,采用FTIR和Raman分析PANI官能团结构,采用XPS分析PANI膜中元素组成和化学键合状态。采用开路电位(OCP)、极化曲线和电化学阻抗谱(EIS)研究PANI/316L SS腐蚀性能。采用四探针技术研究PANI膜的导电性。结果 SEM观察显示PANI膜为纤维状堆积物。红外光谱发现苯环、醌环和S==O伸缩振动,拉曼光谱发现掺杂态的半醌自由基C—N+·,确定合成的PANI具有中间氧化态结构。XPS分析表明,聚合过程发生了质子酸掺杂,"对阴离子"(SO42-)进入PANI分子链中,掺杂度为3%～4%。电化学测试表明,PANI/316L SS的OCP为0.15～0.25 V,PANI使316L SS腐蚀倾向降低,随着Cl-浓度的升高,腐蚀电流密度增大。结论在酸性含Cl-介质中,PANI/316L SS体系耐蚀性好,膜/基界面处保护性氧化膜Fe2O3和Cr2O3的形成,使PANI/316L SS体系耐腐蚀性能提高。在制备条件下,PANI膜厚度介于146～315μm之间,电导率范围为1.33～8.91 S/cm。     

聚苯胺/改性石墨复合材料的电化学制备及其防腐蚀性能研究

采用恒电流法、恒电流阶跃电流法、循环伏安法及自聚合法等4种方法将聚苯胺(PANI)原位沉积在自制的改性石墨(MGE)上,制备出聚苯胺/改性石墨复合材料(PANI/MGE)。利用扫描电镜和红外光谱对PANI/MGE的微观形貌和分子结构进行了表征,利用电化学阻抗谱研究了不同聚合方法所得复合材料的防腐蚀性能。结果表明,4种聚合方法所得复合材料微观形貌与聚合前的改性石墨相似,都呈现平面的片层结构,没有聚合物团簇聚集现象产生。4种聚合方法均能成功实现聚苯胺的原位沉积,聚苯胺与改性石墨之间存在较强的相互作用,且以恒电流阶跃所得复合材料中两者的相互作用最强。5种不同涂层中,恒电流阶跃聚合所得涂层的防腐蚀性能最好,稳定的自腐蚀电位及涂层阻抗最高;循环伏安聚合及恒电流聚合所得两种复合涂层的阻抗及自腐蚀电位均随时间的延长而逐渐下降,涂层很快失效。     

聚苯胺/环氧涂层对AZ91D镁合金耐蚀性能的影响

通过化学氧化法合成本征态及氢氟酸掺杂态聚苯胺(PANI),用红外光谱对其结构进行表征。以环氧树脂为成膜物质,在AZ91D镁合金基体上制备了本征态及氢氟酸掺杂的 PANI/环氧涂层,用EIS方法研究涂层在3.5%NaCl溶液中的耐蚀性,并用SEM对浸泡后基体表面形貌进行观察。实验结果表明,与环氧清漆相比,本征态PANI的加入明显改善了环氧涂层的耐蚀性,而氢氟酸掺杂后进一步提高了PANI/环氧涂层的性能。用XPS对基体表面分析,发现添加聚苯胺的涂层在镁合金表面形成了具有保护作用的产物膜。     

聚苯胺/不锈钢双极板在H2SO4中腐蚀性能的变化规律

目的提高质子交换膜燃料电池(PEMFC)双极板的耐蚀性。方法采用循环伏安法,在316L不锈钢(SS)表面电合成导电聚苯胺(PANI)膜,制备PANI/316L SS复合双极板。用红外光谱确定PANI官能团结构,用扫描电镜观察表面形貌,用X射线光电子能谱研究PANI膜成分和键合状态。用0.2 mol/L H2SO4模拟PEMFC腐蚀环境,采用极化曲线研究PANI/316LSS耐腐蚀性能,采用开路电位(OCP)和电化学阻抗谱(EIS),研究PANI/316L SS在长期浸泡过程中的腐蚀行为的变化规律。结果 PANI膜具有中间氧化态结构,呈现纤维堆积形貌。XPS结果表明,PANI膜中含有C、N、S和O等元素,聚合过程中"对阴离子"SO42-通过"掺杂"进入PANI分子链。涂覆PANI薄膜的316L SS腐蚀电位提高了0.17 V,长期浸泡过程中,OCP介于0.19～0.32 V之间,说明PANI/316L SS的腐蚀倾向降低。浸泡初期,OCP增大对应于膜/基界面处钝化膜的形成;浸泡中期,OCP下降/上升与钝化膜的溶解/修复有关;浸泡后期,OCP持续下降源于钝化膜的溶解。EIS的Nyquist图由高频端容抗弧和低频端扩散尾构成。结论随着浸泡时间延长,PANI膜被氧化,导致"对阴离子"SO_4~(2-)从PANI中发生"脱掺杂",使膜电阻增加,容抗弧半径增大。浸泡82天,PANI/316L SS体系仍具有良好的耐腐蚀性能。     

钢板电镀锌表面聚苯胺膜硅烷改性的研究

在加入硅烷偶联剂γ-APS的苯胺中性溶液中采用恒电流法在电镀锌钢板上制备聚苯胺膜,采用SEM观测其表面形貌,测试不同条件下聚合膜的厚度.交流阻抗和盐雾实验表明,加入γ-APS后,聚苯胺膜层的致密性和防护性明显提高,接近铬酸盐钝化膜.通过XPS分析,得到γ-APS改性聚苯胺膜掺杂度为11%、氧化度为64%;与改性前聚苯胺膜相比较,掺杂度降低、氧化度增高.结合红外光谱和XPS分析,发现聚苯胺膜中存在4种化学环境:C-Si-O-Si,C-Si-OH,C-Si-O-C,C-Si-O-Zn.     

基于聚苯胺的光固化防腐蚀涂层

利用十二烷基苯磺酸 (DBSA) 对本征态的聚苯胺 (PANI) 进行掺杂,将不同含量的掺杂后的聚苯胺分别加入到光固化树脂聚氨酯丙烯酸酯 (6071) 中,制备了一种低VOC排放的光固化聚苯胺防腐蚀涂层。通过实时红外以及漆膜性能的测试选择了合适的光引发剂,通过电化学阻抗谱、盐雾实验以及极化曲线对涂层的防腐蚀性能进行了测试。结果表明,加入0.4%DBSA-PANI的光固化涂层具有最佳的防腐蚀性能。     

SSA 掺杂的苯胺 / 吡咯导电共聚物的制备及结构表征和防腐蚀性能

在磺基水杨酸(SSA)的酸体系中,以过硫酸铵为氧化剂,采用化学氧化聚合法,调整聚合单体配比,制备了SSA掺杂的苯胺/吡咯导电共聚物(PANI/PY-SSA),通过FT-IR,SEM和XRD等测试手段对其分子结构、微观结构和有序化程度进行了表征。同时,将该导电共聚物加入到环氧树脂涂料中,通过Tafel极化曲线和EIS阻抗谱研究了PANI/PY-SSA对低碳钢材料的防腐蚀性能。结果表明,PY共聚改性明显提高了聚苯胺对金属的保护能力,且当聚合单体配比n(AN)∶n(PY)=3∶7时,制备的PANI/PY-SSA防腐蚀性能最好,涂层的Ecorr为-0.335 V,Jcorr为7.972×10-8 A/cm,RC为2.103×105Ω·cm2,CC为1.646×10-8 F/cm2。     

阴极气体O2对石墨烯/聚苯胺/不锈钢双极板耐蚀性的影响

目的 提高质子交换膜燃料电池(PEMFC)双极板的耐腐蚀性能。方法 采用循环伏安法(CV)在316L不锈钢(SS)基材上制备还原氧化石墨烯(rGO)/聚苯胺(PANI)层-层复合双极板。用透射电镜(TEM)和扫描电镜(SEM)进行形貌观察,用红外光谱(FTIR)和拉曼光谱(Raman)确定官能团结构,用紫外可见光谱(UV-vis)确定分子共轭状态,用X射线光电子能谱(XPS)确定化学成分和键合状态。在模拟PEMFC阴极工作环境下研究rGO/PANI/316L SS层-层复合双极板的耐腐蚀性能,向体系中通入氧气(O₂),测量开路电位(OCP)、电化学阻抗谱(EIS)和极化曲线评价双极板的抗腐蚀性能。结果 在离子液体1-乙基-3-甲基咪唑硫酸甲酯中,通过电聚合能够获得厚度为53μm的PANI膜层,在pH=4的0.03 mol/L K₂SO₄溶液中还原氧化石墨烯(GO),在PANI上获得厚度为10μm的rGO膜层。PANI呈中间氧化态,sp2杂化的r GO和PANI之间的相互作用使得共轭效应增强。连续致密的rGO覆盖在多孔的P...     

聚苯胺在防腐方面的研究及应用现状

聚苯胺(PANI)具有良好的热稳定性和环境稳定性,经掺杂后,具有导电性及电化学性,可作为填料应用于金属防腐领域。但其分子链骨架刚性强、分子间作用力大,不易加工成型,不溶于常规的有机溶剂,当其作为填料应用到防腐涂料中存在溶解性、分散性差且与金属基底附着力不强等缺点,如能对其进行合理有效的改性,则可解决上述问题。简要探讨了溶液聚合法、反相微乳液聚合法、模板聚合法以及电化学聚合法等PANI的制备方法,并针对PANI在防腐涂料应用中存在的问题,重点阐述了PANI的质子酸掺杂改性及复合改性等不同改性方法,通过掺杂不同的质子酸对PANI进行化学改性,可降低PANI分子链之间的相互作用,从而提高其溶解性、导电性和防腐性能。将不同性能的材料与PANI进行复合改性,改善分子间作用力,能提高其加工性,从而更好的应用于金属的腐蚀防护工作。最后介绍了PANI在腐蚀防护过程中的作用、在防腐蚀涂料中的应用及相关理论的研究现状,并指出PANI防腐涂层的研究重点和发展方向。     

Corrosion protection of aluminum alloy by epoxy coatings containing polyaniline modified graphene additives

In the study, polyaniline/reduced‐graphene oxide (PANI‐RGO) composites, fabricated by loading 2, 5, and 8wt% graphene oxide, was prepared by in‐situ emulsion polymerization and reduction. They are characterized by Fourier transform infrared spectroscopy, X‐ray diffraction, and scanning electron microscopy. Epoxy coatings adding PANI and PANI‐RGO composites were coated on the surface of AA5083 Al alloy. The anticorrosion performance of the coatings is measured by electrochemical impedance spectroscopy and potentiodynamic polarization curve in 3.5wt% NaCl solution. The results demonstrate that the epoxy/PANI‐RGO coating exhibits a better protection against AA5083 alloy corrosion compared with the epoxy/PANI coating. Enhancement of the passivation performance of PANI was obtained by the addition of RGO into epoxy/PANI coating system.     

Electro-Synthesis of Nano-Colloidal PANI/ND Composite for Enhancement of Corrosion-Protection Effect of PANI Coatings

The polyaniline/nanodiamond (PANI/ND) nanocomposite coating was prepared on mild steel via electrochemical polymerization using cyclic voltammetry technique. The ultrasonic irradiation was used for effectively dispersing ND particles in electropolymerization solution. The prepared nanocomposite films were found to be nano-colloidal, and very adherent with low porosity. The corrosion performance of the coatings was investigated in 0.5 M H₂SO₄ solution by electrochemical impedance spectroscopy and polarization methods. The obtained results showed that the presence of ND particles significantly enhanced the corrosion protection performance of the PANI films in 0.5 M H₂SO₄ corrosive medium. X-ray diffraction and FT-IR techniques confirmed the intercalation of the nanoparticles in PANI matrix.     

Influence of tungstate ion dopants in corrosion protection behavior of polyaniline coating on mild steel

Electropolymerization of polyaniline (PANI) and polyaniline‐tungstate (PANIW) coatings on mild steel were successfully performed using cyclic voltammetry technique. Processes were carried out in aqueous electrolyte solutions of 0.3 M oxalic acid + 0.1 M aniline and 0.3 M oxalic acid + 0.1 M aniline + 0.001 M sodium tungstate dehydrate. Corrosion protection of PANI and PANIW coatings was evaluated with the help of open circuit potential (E_ocp) monitoring and electrochemical impedance spectroscopy (EIS) methods. All the results reveal the influence of additional doping agent (i.e., tungstate) in corrosion protection behavior of PANI coating.     

汽车活塞环表面Ni60A-Cr2O3复合涂层的制备与性能

采用超声速等离子喷涂法在汽车活塞环用45钢表面制备了Ni60A-Cr2O3复合涂层,通过X射线衍射(XRD),扫描电镜(SEM),摩擦磨损试验,电化学试验和浸泡腐蚀试验研究了Cr2O3含量对Ni60A-Cr2O3复合涂层物相组成、显微组织、耐磨性能和耐腐蚀性能的影响。结果表明:Ni60A-Cr2O3复合涂层中除有增强相Cr2O3外,还含有FeNi3、Fe(C,B)6和Cr23C6等含Cr析出相;随着复合涂层中Cr2O3含量的增加,复合涂层的磨损量呈现先减小而后增加的趋势,在Cr2O3质量分数为35%时磨损量最小,Ni60A-Cr2O3复合涂层中适宜的Cr2O3添加量为35%;Ni60A涂层和35%Cr2O3+65%Ni60A复合涂层的磨损机制分别为黏着磨损和磨粒磨损;极化曲线测试结果和浸泡腐蚀试验结果都表明,在1.5mol/L H2SO4和3.5%NaCl溶液中,35%Cr2O3+65%Ni60A复合涂层的耐腐蚀性能都要优于Ni60A涂层的。     

Effect of Aspergillus niger Tiegh. L-10 on the physical and chemical properties of a polyaniline coating in the growth substrate

The influence of the growth of Aspergillus niger Tiegh. fungi on the morphological, chemical and electrochemical properties of the polyaniline (PANI) modified Ni surface has been investigated. The strain of Aspergillus niger Tiegh. L-10 was cultivated on the malt extract agar (DIFCO OXOID). A PANI film was synthesized by potentiodynamic polymerization in an aqueous 0.3 M H₂C₂O₄ solution containing 0.1 M aniline on the Ni electrode. The electrochemical behaviour of polymer films was determined in a 0.05 M H₂SO₄ solution by the cyclic voltammetry method. The composition of PANI and Aspergillus niger Tiegh. treated PANI surfaces have been characterized using X-ray photoelectron spectroscopy (XPS). The morphology has been studied using scanning electron microscopy (SEM). The attachment of a polymer film via the metabolic product resulted in oxidation of the surface. It was estimated that at the PANI/microorganism interface, a Ca-complexed carboxylate interfacial reaction product was formed.     

Comparison study on anticorrosion performances of the epoxy coatings with two different nano‐polyanilines for Q235 steel

Sulfuric acid doped nano‐polyaniline was prepared by direct mixed oxidation in two different systems. A novel approach for preparing polyaniline (PANI) in FeCl₂/H₂O₂ system was developed. The PANI possessed an excellent dispensability. Corrosion protection of epoxy coatings containing two kinds of polyaniline (PANI) on Q235 steel was studied by electrochemical impendance spectroscopy (EIS) technique and Tafel polarization test in 3.5 wt% sodium chloride (NaCl) aqueous solution. The results indicated that the epoxy coating containing PANI obtained in FeCl₂/H₂O₂ system had the best performance of the corrosion protection among three systems under investigation. The possible protective mechanism of PANI was discussed.     

Corrosion study of Ni/Zn compositionally modulated multilayer coatings using electrochemical impedance spectroscopy

Ni/Zn compositionally modulated multilayer (CMM) coatings were deposited using dual bath technique. Coatings corrosion performance was evaluated using electrochemical impedance spectroscopy (EIS) during extended immersion times up to 48 h. The results of electrochemical impedance spectroscopy showed that Ni/Zn CMM coatings had better corrosion resistance compared to that of the zinc single layer coating. The modified corrosion product which is formed on the Ni/Zn CMM coatings during extended exposure times and also a good barrier effect of the nickel layer against aggressive species in these coatings can be two important reasons for high corrosion performance and so protection performance of the Ni/Zn CMM coatings.     

Corrosion inhibition performance of polymer-alloy bilayer coatings: electropolymerised polyaniline and electrodeposited ZnNi with different layer orders

Polyaniline (PANI) conducting polymer coatings have been obtained galvanostatically with various current densities (from 0·1 to 0·4 mA cm^?2) and ZnNi alloy coatings have been obtained galvanostatically at 30 mA cm^?2 current density. Corrosion protection performances of monolayered PANI and ZnNi alloy coatings and multi-layered ZnNi/PANI and PANI/ZnNi coatings on st-37 low carbon mild steel (MS) have been investigated by an open circuit potential method, Tafel extrapolation method and electrochemical impedance method in 3·5 wt-% NaCl solution. In addition, the surface morphology of the coatings has been characterised by using scanning electron microscopy (SEM). Synthesising PANI films between two metal layers provided better corrosion protection to the steel. MS/PANI/ZnNi layer formation exhibited the biggest corrosion protection performance among all layer formations of the films and protected MS for up to 72 h.     

Synthesis and properties of electrodeposited Ni-CeO_2 nano-composite coatings

Current machinery requires metallic materials to have better surface properties. Based on an orthogonal experimental design and analysis method, the CeO_2-reinforced nickel nano-composite coatings were prepared by direct current electrodeposition in a nickel sulfate bath containing CeO_2 nanoparticles. Statistical results indicate that current density is the most significant variable in the electrodeposition processing, while temperature is the least important factor. The microstructure of Ni and Ni-CeO_2 nano-composite coatings was characterized by scanning electron microscopy(SEM) equipped with energy-dispersive spectroscopy(EDS), and X-ray diffraction(XRD).The microhardness of the Ni coating is enhanced by the incorporation of CeO_2 nanoparticles. Potentiodynamic polarization and electrochemical impedance spectroscopy(EIS) were used to characterize the corrosion behavior of Ni and Ni-CeO_2 coatings. These studies show that NiCeO_2 coating has better corrosion resistance compared to Ni coating.