我国导电聚苯胺材料研发获系列创新成果

中科院长春应化所和吉林正基科技开发有限责任公司的科技人员经过4年努力，在导电聚苯胺材料的研发方面获得了系列创新成果：在国内建立了第1条年产百吨的导电聚苯胺原料生产线、第1条年产千吨的导电聚苯胺涂料生产线；率先在国内研发出具有我国自主知识产权的聚苯胺防腐涂料、聚苯胺防腐油脂、聚苯胺防腐密封胶、聚苯胺防冻液防腐添加剂等系列高附加值聚苯胺下游产品。     

改性聚苯胺及其衍生物涂层的防腐性能

导电聚合物作为一种新型高分子材料,由于具有可逆的氧化还原特性,在金属腐蚀防护领域具有潜在的应用前景。在众多的导电聚合物中,聚苯胺因其具有独特的抗点蚀、抗划伤和防止海洋生物附着等特殊性能,被广泛应用于金属材料、化学工业和航海航天等领域, 逐渐成为防腐涂料领域的研究热点。本文通过对单一聚苯胺涂层防腐性能不足的分析,系统总结了近年来改性聚苯胺涂层在金属腐蚀防护领域的研究进展,包括单一环取代聚苯胺涂层和N取代聚苯胺涂层、改性聚苯胺复合涂层和改性聚苯胺复合材料/树脂共混复合涂层;通过各种腐蚀测试手段比较了改性聚苯胺涂层与未改性聚苯胺涂层之间防腐性能的优劣,进一步证明了供电子取代基（如烷基、烷氧基和氨基等）能够提高聚苯胺涂层的防腐性能,复合改性或与树脂共混也能够提高聚苯胺及其衍生物涂层的防腐性能;同时展望了聚苯胺及其衍生物涂料未来发展的新趋势。     

聚苯胺水性涂料的制备及其防腐性能

将有机磷酸(乙二醇单甲醚磷酸酯和乙二醇单甲醚磷酸二酯混合物)（OP）掺杂得到的导电聚苯胺（PANI-OP）加入到水性环氧树脂（WER）中,制备了聚苯胺水性防腐涂料,并且研究了其防腐蚀性能和防腐蚀机理。 透射电子显微镜观察表明,导电聚苯胺质量分数为0.1%时,其粒径分布范围为50~100 nm。 电化学阻抗谱以及开路电压的变化表明,聚苯胺的存在显著提高了涂层的防腐效果。 金属基底光电子能谱结果表明,聚苯胺水性涂料良好的防腐性能缘于在金属表面生成了致密的氧化物膜以及掺杂剂离子与溶解金属生成了不溶性的盐。     

聚苯胺在不同防腐应用体系中的应用研究进展

聚苯胺是一种具有导电性能的新型高分子材料,将其应用于防腐涂层中可以通过屏蔽和钝化成膜等作用有效延缓金属的腐蚀。本文分析了聚苯胺的性质及防腐机理,并重点介绍了聚苯胺在不同应用体系中防腐性能的表现。     

掺杂态聚苯胺的性能及其防腐应用研究进展

聚苯胺具有良好的导电性和独特的掺杂-解掺杂特性,成为近年来备受关注的导电高分子材料,其特有的抗划伤、抗点蚀和钝化性能使其在金属防腐领域拥有巨大的应用前景。聚苯胺结构中苯环的存在,使得其分子链具有较大刚性,而分子间氢键又导致其难溶、难熔、可加工性能较差,严重制约了聚苯胺的应用。掺杂过程能有效改善聚苯胺的某些性能,或赋予其新的功能,扩展聚苯胺的应用。本文综述了聚苯胺的掺杂方式、掺杂机理、聚苯胺防腐材料的制备方法,以及其在金属防腐领域的应用,展望了聚苯胺的研究和应用前景。     

基于聚苯胺微胶囊的双重自修复防腐涂层

将乳液模板法、光聚合法以及苯胺的界面聚合相结合制备了负载亚麻籽油的聚苯胺微胶囊,并将微胶囊与水性环氧树脂涂层相结合来构筑了具有优异光热转化能力的双重自修复防腐涂层.当涂层受损后,微胶囊中的自修复剂亚麻籽油释放出来,对涂层进行修复;在近红外光(NIR)的照射下,聚苯胺可以有效地吸收光能并将其转化为热能,使涂层的温度高于其玻璃化转变温度,涂层破损处实现愈合.聚苯胺微胶囊的加入不仅赋予涂层优异的自修复能力,而且大大增强了其防腐能力.涂层的表面形貌、电化学与盐雾测试结果表明,聚苯胺微胶囊添加量为10%的涂层在NIR照射3 s内,可以实现快速闭合,恢复了其阻隔性能.此外,在300 h的盐雾测试后,涂层未产生任何的腐蚀产物,而纯涂层可以明显看到腐蚀现象.这种双重自修复防腐涂层的超快响应时间和高愈合效率以及优异的防腐性能具有潜在的应用价值.     

紫外光-热双固化聚苯胺防腐涂料

以酸性磷酸酯为掺杂剂对本征态聚苯胺(EB)进行掺杂,制备了可在聚氨酯和聚氨酯丙烯酸酯中进行纳米分散的导电聚苯胺(ES),其粒径分布在80~750 nm之间可控。 在此基础上,制备了不含重金属的紫外光-热双固化聚苯胺防腐涂料。 该防腐涂料先后经过3~5 s紫外光固化和80 ℃下1~3 min的热固化,即可完成紫外光-热双固化过程。 由于ES与聚氨酯或聚氨酯丙烯酸酯之间是不相容体系,因此随着ES质量分数的增大,会导致ES的团聚,分散粒径增大。 当ES质量分数从1.0%增大到5.0%时,ES的粒径从80~119 nm增加到500~750 nm。 ES的分散粒径增大会导致防腐涂层的致密性变差,降低防腐效果。 与普通紫外光固化聚苯胺防腐涂层相比,当ES为1.0%时,紫外光-热双固化防腐涂层在质量分数为3.5%的NaCl水溶液中浸泡2160 h后,其0.1 Hz下的绝对阻抗值(|Z|_{0.1 Hz})仍高于1.0×10⁸ Ω·cm²,优于普通紫外光固化聚苯胺防腐涂层的|Z|_{0.1 Hz}(1.0×10⁷ Ω·cm²),表明紫外光-热双固化涂层的防腐效果有了显著改善。 经过500 h划叉中性盐雾试验后,普通紫外光固化防腐涂层的板面出现了锈蚀宽度小于1 mm的锈蚀,而紫外光-热双固化防腐涂层经过500 h划叉中性盐雾试验,板面没有出现生锈、起泡的现象,表明紫外光-热双固化路线对提高涂层的防腐性能具有较大的价值。     

基于可分散聚苯胺的紫外光固化防腐涂料的研究

采用酸性磷酸酯作为掺杂剂对本征态聚苯胺(EB)进行掺杂,制备了可在聚氨酯丙烯酸酯中进行纳米分散的导电聚苯胺(ES),其分散粒径分布为60~765 nm之间,进而制备了不含重金属的紫外光固化聚苯胺防腐涂料.随着体系中导电聚苯胺含量从0.5 wt%增大5.0 wt%,粒径从60~100 nm增加到190~765 nm.导电聚苯胺含量增大,导致了ES发生团聚,从而粒径增大,进而降低防腐涂层的致密性.当ES含量为1.0wt%时,粒径在110~180 nm之间,防腐涂层在3.5 wt%的Na Cl水溶液中浸泡2400 h后,其0.1 Hz下的绝对阻抗值(|Z|_(0.1 Hz))仍高于1.0×10~8Ωcm~2,同时45~50μm的防腐涂层在划叉中性盐雾试验中,500 h内没有出现起泡现象,且锈蚀宽度小于1 mm,表现出优异的防腐性能.     

水基导电聚苯胺/二氧化硅杂化材料的防腐性能研究(英文)

利用羧基同导电聚苯胺(cPANI)主链上的氮原子的相互作用,制备了静电作用型水基导电聚苯胺/二氧化硅杂化材料,研究了杂化材料涂层对冷轧钢板的防腐性能.在3.5%NaCl中,含11 wt%cPANI的杂化材料涂层的腐蚀电位比纯二氧化硅涂层正移了200 mV,腐蚀电流从13.4μA降到2.4μA,下降了5倍,表明含cPANI的静电作用型杂化涂料使冷轧钢板表面变得更惰性.阻抗分析结果表明,cPANI含量为11 wt%的静电作用型杂化材料的阻抗比纯无机二氧化硅涂层大一个数量级,而且在碱性介质中浸泡10天后,杂化材料涂层的阻抗仍然保持稳定,而纯无机二氧化硅涂层的阻抗比初始值下降了一个数量级.杂化材料的形态分析结果表明,cPANI在静电作用型cPANI/二氧化硅杂化材料中的分布比在普通cPANI/二氧化硅杂化材料中更加均匀一致,从而使得它比普通的cPANI/二氧化硅杂化材料具有更好的防腐效果.     

苯胺齐聚物对聚苯胺微纳米形貌形成的影响

聚苯胺是一种具有优异性能的导电高分子材料,在传感器、防腐、电容器、生物等领域有着广泛的应用前景。化学氧化聚合法是制备聚苯胺的常用方法。苯胺齐聚化是苯胺化学氧化聚合过程中的重要一步,不同条件下生成的齐聚物化学结构及其自组装方式的差异会导致最终聚苯胺的形貌迥异。本文结合目前人们较为认同的聚苯胺微纳米结构形成机理,基于产物形貌分类,综述了在化学氧化过程中的苯胺齐聚化反应和苯胺齐聚物自组装引导聚苯胺微纳米结构的形成,讨论了目前研究中的存在的问题并对今后研究方向进行了展望。     

聚苯胺/金属纳米粒子复合物的制备及性能

基于国内外最新研究文献及本课题组研究工作,从发展历史、制备方法、多功能性方面系统综述了近年来发展起来的聚苯胺/金属纳米粒子复合物。在聚苯胺基体中引入金属纳米粒子的方法可归纳为3大类：原位复合法、直接共混法和层层自组装法。所形成的有机聚苯胺和无机金属杂化复合物不仅能保留各自原有的特异性能,而且二组分之间还存在着相互协同作用,能够极大地提升基体聚苯胺材料的性能,电导率最高可提高100倍,电氧化催化电流最高可提高10倍。分散在聚苯胺膜中的极少量铂微粒就能使不锈钢板的腐蚀电位稳定在钝化区域。聚苯胺/金属纳米粒子复合物所表现出的突出的固有电导性、优异的反应催化性和极强的金属防腐性,使其跻身于为数不多的新型高性能复合材料之列,显示出了诱人的应用前景。     

Efficiency of anticorrosive pigments based on modified phosphates

The paper deals with the study of modified phosphate compounds from their anticorrosion action point of view. The pigments start with zinc orthophosphate, the modification of which can give phosphosilicates, phosphomolybdates, or basic phosphates. In the region of cations the combination of zinc with calcium, strontium, barium, or aluminum are possible. The modified anticorrosive pigments differ in water solubility, inhibition efficiency of the aqueous extracts and anticorrosion actions in organic coatings. The various types of modified phosphates were studied. The effect of organic inhibitor in presence of anticorrosive inorganic pigments in coatings was determined.     

Synthesis and Characterization of Polyaniline/Zeolite X Composites as Anticorrosion Coating Materials

The main target of this work is to choose the best preparation conditions to have a perfect yield of the new composites prepared from mixing Zeolite X with polyaniline. The preparation of polyaniline and polyaniline/Zeolite X composites as anticorrosion coat was studied. The composites were synthesized and characterized by X-ray diffraction, Fourier transform infrared spectroscopy and UV–visible spectroscopy techniques, which showed the successful synthesis.     

Zinc basic benzoate as eco-friendly steel corrosion inhibitor pigment for anticorrosive epoxy-coatings

The inhibitive properties of benzoate anion were known from many years ago but the employment of soluble compounds in anticorrosive paints is limited because their lixiviation would greatly increase coating permeability. However, it is possible to prepare insoluble metallic benzoates with certain cations. This paper describes the experimental procedure to prepare zinc basic benzoate to be employed in anticorrosive paints. The anticorrosive properties of zinc basic benzoate were assessed by electrochemical techniques (corrosion potential and linear polarization measurements). The nature of the compounds forming the protective layer was determined by different techniques, including spectroscopic ones. In a second stage, the anticorrosive properties of the pigment were evaluated by incorporating it in epoxy anticorrosive paints which, in turn, were evaluated by accelerated (salt spray and humidity tests) and electrochemical measurements (electrochemical impedance spectroscopy). The morphology and the nature of the protective layer grown under the paint film in the salt spray chamber was assessed by scanning electron microscopy (SEM) and UV–vis diffuse reflectance spectroscopy.

Experimental results showed that basic zinc benzoate was adequate to formulate epoxy anticorrosive paints with improved anticorrosive performance, especially with the water-borne binder.     

Behaviour of surface-treated mica and other pigments with lamellar particles in anticorrosive coatings

The paper deals with using lamellar pigments for anticorrosive barrier coatings. By depositing a ferric oxide layer on a muscovite particle a pigment is obtained, which being applied to coatings improves the mechanical properties thereof, resistance to UV radiation and acts as an anticorrosion barrier. The optimum concentration of lamellar surface-treated muscovite in the coatings amounts to 20 vol. %.     

聚苯胺复合材料的制备方法及应用进展

复合材料是由两种或多种性质不同的物质组成的多元材料,具有比各组分材料更优异的或原来不具备的性能。聚苯胺(PANI)作为最具应用前景的导电高分子材料,国内外对基于PANI的复合材料的研究也愈加关注。本文对PANI复合材料制备方法的研究成果进行了综述,主要包括原位化学法、共混法、电化学法、层层自组装法等。探讨了PANI复合材料在电极、导电、防腐、传感、分离、催化等方面的应用性能,并展望了PANI复合材料今后研究与应用的发展方向。     

Synthesis of polyaniline‐modified mesoporous‐silica containers for anticorrosion coatings via in‐situ polymerization and surface‐protected etching

An efficient type of container for anticorrosion coating based on polyaniline (PANI) modified mesoporous silica (pS) sphere has been first prepared via in‐situ polymerization and surface‐protected etching. The PANI‐modified containers not only show higher concentration of loaded inhibitor than pS, but also protect steel well because of the PANI. The coating with 1H‐benzotriazole (BTA) loaded containers shows significant anticorrosion property because of the release of BTA from containers. The structure and morphology of container are characterized by FTIR, XRD, SEM and TEM. The release of BTA from pS and PANI‐modified containers is determined by UV in water. The possible self‐healing anticorrosion performances are evaluated by EIS and polarization curves which indicate that the coating including BTA‐loaded containers performs best. The strategy of modifying pS by PANI is effective and successful. Copyright © 2016 John Wiley & Sons, Ltd.     

超疏水性聚苯胺微/纳米结构的合成及防腐蚀性能

以苯胺为单体, 过硫酸铵为氧化剂, 通过改变不同的掺杂剂, 采用"无模板"法合成了具有不同浸润性的聚苯胺微/纳米结构, 并得到超疏水聚苯胺微/纳米结构. 采用红外吸收光谱、 紫外-可见吸收光谱、 X射线衍射及扫描电镜对聚苯胺微/纳米结构及形貌进行了表征, 测定了聚苯胺微/纳米结构的接触角, 并通过Tafel极化曲线和电化学交流阻抗研究了不同疏水性的聚苯胺微/纳米结构在0.1 mol/L H₂SO₄溶液中对碳钢的腐蚀防护作用, 探讨了聚苯胺微/纳米结构的表面浸润性对腐蚀防护性能的影响. 研究结果表明, 随着聚苯胺微/纳米结构疏水性的增强, 对碳钢的腐蚀防护作用增强, 当掺杂剂为全氟辛酸时所制备的超水聚苯胺微/纳米结构表现出最佳的防腐蚀性能(η= 94.70%).     

Electropolymerized coatings of polyaniline on copper by using the galvanostatic method and their corrosion protection performance in HCl medium

The synthesis of polyaniline coatings on the copper (Cu) surface has been investigated by using the galvanostatic method. The synthesized coatings were characterized by Fourier transform infrared spectroscopy, UV–visible absorption spectrometry and scanning electron microscopy. The anticorrosion performances of polyaniline coatings were investigated in 0.5 M HCl medium by the potentiodynamic polarization technique and electrochemical impedance spectroscopy. The corrosion rate of polyaniline‐coated Cu was found to be ～27 times lower than bare Cu, and potential corrosion increased from ?0.21 V versus Ag/AgCl for uncoated Cu to ?0.19 V versus Ag/AgCl for polyaniline‐coated Cu electrodes. Electrochemical measurements indicate that polyaniline coating has good inhibiting properties with a mean efficiency of ~96% at 10 mAcm^?2 current density applied on Cu corrosion in acid media. The results of this study clearly ascertain that the polyaniline has an outstanding potential to protect Cu against corrosion in an acidic environment. Copyright © 2014 John Wiley & Sons, Ltd.     

Utilisation of industrial waste for ferrite pigments production

Preliminary results of research focused on the utilisation of specific waste from metallurgical and mining activities to obtain ferrite pigments are presented. As a source of iron in the spinel-type ferrites with the general structure MFe₂O₄ (where M is a bivalent metal such as Ca and Zn), three types of industrial wastes were used: metallurgical slag from the production of non-ferrous metals and two types of AMD (acid mine drainage) sludge: one of natural origin (Fe-sediment) and the second one synthetically prepared from AMD (Fe-precipitate). This waste was homogenised by ZnO and CaCO₃ in various stoichiometric ratios n(Ca): n(Zn): n(Fe) and calcined at the temperature of 1000–1095°C. Mineralogical (XRD) analysis of the metallurgical slag pigments confirmed the formation of zinc ferrite and hematite only (Ca from reaction components entered into other phases). The ferric component of the AMD sludge (Fe-precipitate and Fe-sediment) formed a mixture of zinc ferrite, calcium ferrite, and hematite while increased calcination temperature supported the ferritic structure formation. Prepared pigments have no considerable colour differences; they were in brown colour tones. Pigments from the AMD sludge were more dark brown coloured than those from slag. Pigments were applied in an alkyd-resin paint and consequently basic anticorrosive tests were performed. Pigments obtained from metallurgical slag showed better anticorrosive properties than those from AMD. However, because of high Pb content in pigments from the slag (0.67–1.10 mass % Pb in pigments), utilisation of these pigments in coatings is problematic. Ferrite pigments from the AMD sludge, mainly that with zinc ferrite, have promising application in anticorrosive paints but optimisation of the preparation process is required.