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.     

聚己内酯在有机/无机杂化体系中的受限结晶行为

通过Sol Gel技术合成了聚己内酯 (PCL) /二氧化硅 (SiO2 )杂化材料 ,并对杂化样品进行了DSC和WAXD测试 .实验结果表明杂化样品中PCL的结晶度随二氧化硅含量增加而减小 ,当样品中二氧化硅含量达到 60 %时 ,PCL为非晶态 ;含有PCL结晶的杂化样品中PCL熔融温度基本相同 ,但是比纯PCL的熔融温度低 .杂化样品中结晶PCL的结晶结构和微晶尺寸和纯PCL的一致 .这说明杂化材料中PCL的结晶行为和结晶度受到了限制 ,含PCL结晶的样品中PCL的结晶结构和微晶尺寸并没有受到影响 .     

二氧化硅-聚苯胺(SiO2-PANI)杂化透明导电薄膜的制备和表征

本文采用溶胶-凝胶法,以3-巯丙基三甲氧基硅烷(MPTMS)和聚苯胺为主要原料,制备得到有机-无机杂化透明导电薄膜.着重研究制备过程中醋酸、间甲酚和聚苯胺含量对薄膜结构、导电性和可见光透过率的影响.通过红外光谱可知,采用溶胶-凝胶法可制得结构稳定的杂化导电材料.醋酸作为水解缩聚反应的反应剂和催化剂,当其与3-巯丙基三甲氧基硅烷的物质的量比为0.4时.MPIMS的水解缩聚速率和聚苯胺掺杂入无机前驱体的掺杂速率达到平衡.此外,透明杂化导电薄膜的方块电阻随间甲酚和聚苯胺含量的增加而降低,当间甲酚和3-巯丙基三甲氧基硅烷的物质的量比为5,聚苯胺和二氧化硅的质量比为3/7时,薄膜的方块电阻为3.23 kΩ/□,可见光透过率为80%.     

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。     

石墨烯-聚苯胺杂化超级电容器电极材料

聚苯胺是一类具有超高比电容的导电高分子材料, 利用其与石墨烯的协同效应, 改善各自的固有缺点, 可以制得高性能的超级电容器. 本文综述了石墨烯-聚苯胺杂化电极材料的制备方法和石墨烯表面性质对电极材料电化学性能的影响, 讨论了优化杂化电极的结构与性能.     

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。     

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。     

二氧化硅-聚苯胺(SiO2-PANI)杂化透明导电薄膜的制备和表征

本文采用溶胶-凝胶法,以3-巯丙基三甲氧基硅烷(MPTMS)和聚苯胺为主要原料,制备得到有机-无机杂化透明导电薄膜。着重研究制备过程中醋酸、间甲酚和聚苯胺含量对薄膜结构、导电性和可见光透过率的影响。通过红外光谱可知,采用溶胶-凝胶法可制得结构稳定的杂化导电材料。醋酸作为水解缩聚反应的反应剂和催化剂,当其与3-巯丙基三甲氧基硅烷的物质的量比为0.4时,MPTMS的水解缩聚速率和聚苯胺掺杂入无机前驱体的掺杂速率达到平衡。此外,透明杂化导电薄膜的方块电阻随间甲酚和聚苯胺含量的增加而降低,当间甲酚和3-巯丙基三甲氧基硅烷的物质的量比为5,聚苯胺和二氧化硅的质量比为3/7时,薄膜的方块电阻为3.23 kΩ/□,可见光透过率为80%。     

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。     

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。     

Water‐resistant conducting hybrids from electrostatic interactions

Conductive hybrids were prepared in a water/ethanol solution via the sol–gel process from an inorganic sol containing carboxyl groups and water‐borne conductive polyaniline (cPANI). The inorganic sol was prepared by the hydrolysis and condensation of methyltriethoxysilane with the condensed product of maleic anhydride and aminopropyltriethoxysilane as a catalyst, for which the carboxyl counterion along the cPANI backbone acted as an electrostatic‐interaction moiety. The existence of this electrostatic interaction could improve the compatibility of the two components and contribute to the homogeneous dispersion of cPANI in the silica phase. The electrostatic‐interaction hybrids displayed a conductivity percolation threshold as low as 1.1 wt % polyaniline in an emeraldine base, showing 2 orders of magnitude higher electrical conductivity than that without electrostatic interactions. The electrostatic‐interaction hybrids also showed good water resistance; the electrical conductivity with a cPANI loading of 16 wt % underwent a slight change after 14 days of soaking in water. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1424–1431, 2007     

ELECTROSTATIC INTERACTION HYBRIDS FROM WATER-BORNE CONDUCTIVE POLYANILINE AND INORGANIC PRECURSOR CONTAINING CARBOXYL GROUP

Electrostatic interaction conductive hybrids were prepared in water/ethanol solution by the sol-gel process from inorganic sol containing carboxyl group and water-borne conductive polyaniline （cPANI）. The electrostatic interaction hybrids film displayed 1-2 orders of magnitude higher electrical conductivity in comparison with common hybrids film, showing remarkable conductivity stability against water soaking. Most strikingly, it displayed ideal electrochemical activity even in a solution with pH = 14, which enlarged the conducting polyaniline application window to strong alkaline media.     

Synthesis, infrared stealth and corrosion resistance of organically modified silicate-polyaniline/carbon black hybrid coatings

Hybrid coatings based on organically modified silicate-polyaniline/carbon black (Ormosil-PANI/CB) were synthesized through a sol-gel technique with different carbon black (10-30 wt%) and PANI/CB (10-30 wt%) contents. These hybrid films were deposited via spin coating onto an aluminum alloy in order to improve the corrosion protection and to act as infrared stealth coatings. The effects induced by the PANI/CB composites on the chain dynamic, thermal properties, infrared stealth, and anticorrosion performances of the coated samples were investigated. The rotating-frame spin-lattice relaxation times and scale of the spin-diffusion path length indicated that the configuration of the hybrid films was highly cross-linked and dense. Thermal properties of these Ormosil-PANI/CB hybrids have been improved over the pure Ormosil analyzed by thermal gravimetric analysis (TGA). The thermal extinction of the hybrid coatings increased with the increase in the carbon black and PANI/CB content. Potentio-dynamic and salt-spray analysis revealed that the hybrid films provided an exceptional barrier and corrosion protection in comparison with untreated aluminum alloy substrates.     

Incorporation of Reactive Corrosion Inhibitor in Waterborne Acrylic Polyurethane Coatings and Evaluation of its Corrosion Performance

Hydroxyl-epoxy phosphate (HEP) as a reactive corrosion inhibitor was innovatively synthesized by the reaction of bisphenol A epoxy resin with phosphoric acid. HEP was mixed with hydroxyl acrylate resin, and crosslinked with waterborne isocyanate curing agent, which was used to form waterborne HEP/acrylic polyurethane composite (HEP-APU) coatings on Q235 steel surfaces. Electrochemical impedance spectroscopy and polarization curves were applied to analyze the corrosion behavior of the HEP-APU coatings in 3.5wt% NaCl solutions. The results indicated that the HEP-APU coatings show a superior passivation property and efficient corrosion protection of Q235 steel. The waterborne acrylic polyurethane coating containing 0.5wt% HEP exhibited the best corrosion performance among all the coating specimens. The improved flash-rust resistance can be attributed to the introduction of the phosphate group which could form phosphate film on the steel substrate.     

Corrosion behavior of tantalum alloying on γ‐TiAl by double‐glow plasma surface metallurgy technique

The Ta coating with corrosion resistance is grown on the γ‐TiAl substrate by double‐glow plasma surface metallurgy technique, followed by the electrochemical test in 10 wt%, 20 wt% HCl and 10 wt%, 40 wt% H₂SO₄ solution. The data of nanohardness and elastic modulus are collected by the nanoindention test. The adhesion strength of Ta coating is investigated by means of the scratch test. The study of corrosion resistance is performed using potentiodynamic polarization and electrochemical impedance spectroscopy and measured by SEM and X‐ray diffraction. Results highlight that the Ta coating is tightly bonded to the γ‐TiAl substrate, consisting of the deposition layer and diffusion layer. Experimental data indicate that the Ta coating presents excellent corrosion resistance, which is confirmed by the high values of polarization resistance (R_p) and the low values of corrosion current density (i_corr). The surface nanohardness of the Ta coating is improved from 3.41 to 7.29 GPa, nearly twice of that of the substrate. The Ta₂O₅ formed on the coating is able to hold back the penetration of adverse ions inwardly, owing to its dense structure and adhesion effect. Copyright © 2017 John Wiley & Sons, Ltd.     

Modification of proton conductive polymer membranes with phosphonated polysilsesquioxanes

New hybrid membranes for fuel cell applications based on sulfonated poly(ether ether ketone) (SPEEK) and phosphonated polysilsesquioxanes were synthesized. The impedance spectroscopy measurements show an increase of the proton conductivity for all studied composites, in comparison to plain SPEEK. For hybrid membranes containing 20 wt% of polysilsesquioxane with 80 mol% of phosphonated units the conductivities can reach values that are similar to Nafion 117^® at 100% RH. The best results of proton conductivity (142 mS/cm) were obtained for composites with 40 wt% of the same polysilsesquioxane at 120 °C also at 100% RH.     

大分子植酸-聚有机硅倍半氧烷的合成及性能

采用溶胶-凝胶方法, 无需小分子酸催化剂, 利用硅烷化植酸的反应活性和酸催化活性, 与硅烷单体共水解缩聚, 在聚有机硅倍半氧烷分子链上原位接枝植酸, 合成了分子量大于50000的大分子植酸-聚有机硅倍半氧烷. 用GPC, 13C NMR, 29Si NMR, XPS, Raman光谱, SEM及电化学测试等分析手段进行表征, 对比不同酸催化植酸-聚有机硅倍半氧烷(PAP), 单宁酸-聚有机硅半氧烷(TAP), 盐酸-聚有机硅半氧烷(HCP)的结构和性能, 发现植酸-聚有机硅倍半氧烷上的螯合基团与金属表面的活性基团反应而键合, 在金属表面形成致密的保护膜, PAP与TAP和HCP比较具有优异的防腐性能.     

Coordination bonding construction, characterization and photoluminescence of ternary lanthanide (Eu(3+), Tb(3+)) hybrids with phenylphenacyl-sulfoxide modified bridge and polymer units

A novel polysilsesquioxane bridge (PPSSi) is synthesized with methylene group modification of phenylphenacyl sulfoxide by isocyanate group from 3-(triethoxysilyl)propyl isocyanate (TEPIC). Then ternary lanthanide (Eu, Tb) hybrids of polysilsesquioxane bridge (PPSSi) and four kinds of polymer chain (polyacrylamide (PAM), polyvinylpyrrolidone (PVP), polymethyl methacrylate (PMMA) and polyethyl methacrylate (PEMA) were assembled wth coordination bonding. To explore the influence of the different polymeric chains on the properties of lanthanide hybrids, the microstructure and photoluminescent properties of these lanthanide coordination polymer hybrids (PPSSi-Ln-PAM (PVP, PMMA, PEMA)) are compared in detail. Four organic polymer chains with different structures not only can coordinate to the lanthanide ions by their own carbonyl groups, but also can form a polymeric matrix together with the inorganic Si-O network. The results show that all the obtained hybrids could show efficient intramolecular energy transfer and lead to excellent characteristic emission of lanthanide ions. Moreover, the different structures of the polymers induce different microstructures and different photoluminescent behavior (lifetime and quantum efficiency) for these hybrid systems. The PPSSi-Ln-PMMA hybrid leads to the longest lifetime and highest quantum efficiency.     

Anticorrosive and Microbial Inhibition Performance of a Coating Loaded with Andrographis paniculata on Stainless Steel in Seawater

With the trend for green technology, the study focused on utilizing a forgotten herb to produce an eco-friendly coating. Andrographis paniculata or the kalmegh leaves extract (KLE) has been investigated for its abilities in retarding the corrosion process due to its excellent anti-oxidative and antimicrobial properties. Here, KLE was employed as a novel additive in coatings and formulations were made by varying its wt%: 0, 3, 6, 9, and 12. These were applied to stainless steel 316L immersed in seawater for up to 50 days. The samples were characterized and analyzed to measure effectiveness of inhibition of corrosion and microbial growth. The best concentration was revealed to be 6 wt% KLE; it exhibited the highest performance in improving the ionic resistance of the coating and reducing the growth of bacteria.     

硫酸盐体系三价铬沉积机理及镀层表征

在新研发的硫酸盐三价铬镀厚铬的镀液体系中, 运用线性扫描伏安法(LSV)和循环伏安法(CV)对三价铬在铜电极表面的电沉积过程进行研究, 并运用X射线荧光测厚仪、扫描电子显微镜(SEM)、X射线能量色散谱(EDS)、X射线衍射仪(XRD)、显微硬度计和Tafel曲线表征铬镀层厚度、形貌、组成、结构、显微硬度及在3.5wt% NaCl溶液中的耐蚀性. 结果表明, 在该体系中三价铬的沉积过程分两步进行(Cr³⁺ + e →Cr²⁺ , Cr²⁺ + 2e → Cr), 第一步得到1个电子, 受电化学过程和扩散过程共同控制, 第二步得到2个电子, 为扩散控制下的不可逆过程; 该镀层为瘤状纳米晶结构, 镀层中含有少量的铁元素(1.10 wt%), 显微硬度达到789.2 Hv, 镀层在3.5wt% NaCl溶液中的腐蚀电位(E_corr)为-0.29 V, 腐蚀电流密度(j_corr)为9.26×10^-5 A·dm^-2.