SiO2纳米粒子对溶胶凝胶涂层性能的影响

在高强钢表面制备了防护性溶胶凝胶涂层,并研究了不同浓度二氧化硅纳米粒子的加入对于涂层形貌、耐蚀性和硬度的影响。采用扫描电子显微镜(SEM)和电子能谱(EDS)观察了涂层的微观结构和成分;采用显微硬度计测试了涂层的硬度;采用电化学方法研究了二氧化硅纳米粒子的浓度对于涂层耐蚀性能的影响;采用傅里叶红外光谱研究涂层的化学结构,进而探讨了二氧化硅纳米粒子对于涂层的强化机理。结果显示涂层加入二氧化硅纳米粒子的最佳浓度为500 mg.L-1,此条件下的涂层表面均匀致密,有较高的硬度并且在3.5%NaCl溶液中体现出较好的耐蚀作用。纳米粒子在溶胶中反应形成活性羟基基团并与硅烷发生反应生成空间网状结构,从而强化涂层。     

添加氧化铈对AZ91D镁合金表面富镁涂层的保护作用

通过Machu测试、电化学交流阻抗(EIS)和扫描电子显微镜(SEM)等方法研究了添加氧化铈对AZ91D镁合金表面富镁涂层防护性能的影响.氧化铈添加量较少(0.1%,w)时,对涂层耐蚀性无影响;添加量过多(3%)时,涂层耐蚀性降低;添加氧化铈颗粒为0.5%时,涂层的阻抗增大,涂层电容降低,对AZ91D镁合金基体的保护性能明显提高.尽管添加氧化铈不改变富镁涂层对AZ91D镁合金的保护机制,但可显著延长涂层的服役寿命.氧化铈能够降低纯镁颗粒的电化学反应活性,使镁粉腐蚀速率降低,阴极保护时间延长.添加一定量氧化铈后,也有利于涂层屏蔽性能提高,氧化铈能降低AZ91D镁合金表面阳极腐蚀电流密度,提高镁合金腐蚀电位,从而有利于富镁涂层发挥对镁合金基体的阴极保护作用.     

溶胶凝胶法制备超疏水二氧化硅涂膜及其表面润湿行为

采用溶胶-凝胶法以正硅酸乙酯(TEOS)和甲基三乙氧基硅烷(MTES)为前驱体制备超疏水SiO2涂层。红外光谱(FTIR)和热重分析(TGA)表征合成SiO2的化学组成,通过透射电镜(TEM)和扫描电镜(TEM)观察制备SiO2的结构形貌,扫描电镜(SEM)和原子力显微镜(AFM)观察SiO2涂膜的表面形貌,通过测试水接触角(WCA)讨论SiO2涂层的表面微观结构与其表面疏水性能的关系。结果表明以TEOS和MTES为共前驱体可以制备得到表面带-CH3基团的SiO2溶胶,SiO2溶胶在老化过程中纳米SiO2粒子由于自组装作用形成草莓状微米-纳米双微观结构,这种结构赋予SiO2涂膜表面不同等级的粗糙度,使得水滴与涂膜表面接触时能够形成高的空气捕捉率和较小的粗糙度因子,与SiO2表面疏水性的-CH3基团共同作用形成类荷叶超疏水结构。     

核壳式氯霉素分子印迹聚合物碳纳米管复合材料的制备及应用

本文以多壁碳纳米管(MWCNTs)为载体,采用溶胶-凝胶法先在MWCNTs表面包覆硅层,得到MWCNTs@SiO2,再以氯霉素(Chloramphenicol,CAP)为模板,无水乙醇为溶剂,氨丙基三乙氧基硅烷(APTES)和苯基三甲氧基硅烷(PTMOS)为双功能单体,四乙氧基硅烷(TEOS)为交联剂,采用表面分子印迹技术合成具有核壳结构的CAP分子印迹聚合物包覆的碳纳米管复合材料。采用透射电镜(TEM)、红外(IR)光谱和热重(TG)分析技术对CAP分子印迹聚合物复合材料的结构、形貌进行了表征,并对其吸附性能进行了详细研究。结果表明,制备的分子印迹聚合物吸附动力学快,吸附容量大,选择性好,印迹因子达到4.2,并且可循环使用。将制备的分子印迹聚合物材料应用于实际样品鸡蛋中CAP含量的测定,回收率可达72.3%~84.1%。     

表面活性剂辅助酸催化溶胶-凝胶法制备高强度超亲水二氧化硅减反增透纳米粒子涂层

以正硅酸乙酯(TEOS)、十六烷基三甲基溴化氨(CTAB)、盐酸(HCl)、乙醇和水为原料,通过溶胶-凝胶法提拉涂膜,再经700 ℃快速淬火200 s,制备了二氧化硅（SiO2）纳米粒子涂层。 研究了CTAB浓度、提拉速度、停留时间和提拉涂膜次数对透射率的影响,结果表明,当CTAB质量分数为2.5%,提拉速度为100 mm/min,停留时间为60 s,提拉涂膜1次得到的SiO2纳米粒子涂层透射率最高,可达95.9%。 该涂层具备超亲水性并能耐受6H铅笔刮痕测试。 实验还表明,在SiO2溶胶液中加入CTAB,通过其与TEOS部分水解生成的物种的相互作用,可以改善酸性催化条件下形成的SiO2溶胶的微观结构,从而提高了涂层的透射率和亲水性。     

Janus纳米材料的制备及结构调控

用3-(甲基丙烯酰氧)丙基三甲氧基硅烷(MPS)、 氨丙基三乙氧硅烷(APTES)和正硅酸乙酯(TEOS)溶胀聚苯乙烯中空微球的壳层, 在壳层表面通过溶胶-凝胶过程, 使亲油和亲水基团通过自组装作用分别朝向聚苯乙烯基体和水相, 形成Janus结构. 用良溶剂N,N-二甲基甲酰胺(DMF)溶解除去聚苯乙烯, 得到二氧化硅基复合Janus纳米材料. 改变反应体系pH值和单体用量等可以调控Janus纳米材料微结构, 得到Janus中空球和纳米片.     

LC4铝合金表面电泳沉积硅锆有机-无机杂化涂层的制备及性能

采用阴极电泳沉积的方法在LC4铝合金表面制备硅锆有机-无机杂化涂层, 并探讨了电泳沉积条件对涂层形貌、结构以及耐蚀性的影响. 采用纳米粒度仪检测了不同硅锆杂化溶胶的zeta电位; 采用扫描电子显微镜(SEM)和原子力显微镜(AFM)观察了涂层的表面微观形貌和粗糙程度; 采用傅里叶红外光谱(FTIR)研究了涂层的化学结构; 采用电化学方法研究了沉积电压对涂层耐蚀性能的影响, 进而探讨了电泳沉积增强杂化涂层耐蚀性的机理. 结果显示沉积体系的pH为1.6、沉积电压为5 V时为最佳的沉积条件, 所获得的硅锆有机-无机杂化涂层表面均匀致密性最好, 粗糙程度和耐蚀性都得到了明显的改善, 在3.5% NaCl溶液中体现出较好的耐蚀作用.     

含PEG的双亲性氟硅改性丙烯酸树脂防污涂层的制备及性能

以烯丙基聚乙二醇(APEG)、甲基丙烯酸甲酯(MMA)和丙烯酸丁酯(BA)为共聚物单体合成了含聚乙二醇(PEG)的羟基丙烯酸预聚物(BOH),该预聚物再与α,ω-三乙氧基硅烷封端的聚二甲基硅烷低聚物(TSU)和α,ω-三乙氧基硅烷封端的全氟聚醚低聚物(PFU)通过缩合反应制得含有PEG的氟硅改性丙烯酸交联网络防污涂层.通过核磁共振氢谱(~1H-NMR)、红外光谱(FTIR)对聚合物的结构进行了表征.通过原位纳米测试系统、接触角测试和生物评价等表征方法,探讨了树脂中TSU,PFU和BOH配比对表面能、弹性模量及其生物防污性能的影响.结果表明兼具氟硅低表面能性和PEG抗蛋白吸附性能的交联网络涂层TFS-BOH-B具有好的防污性能,且随着TSU和PFU含量增加,防污性能提高.     

单分散PS/SiO_2纳米复合微球的制备与表征

采用一种简单和低成本的方法制备单分散SiO2包覆聚苯乙烯(PS)(PS/SiO2)核-壳型纳米复合微球.首先在聚乙烯吡咯烷酮(PVP)存在下制备了PS纳米微球,然后在NH4OH/乙醇溶液中通过溶胶-凝胶过程在PS微球表面包覆SiO2.PS纳米微球的制备在水介质中进行,无需使用共单体,使用的是常用的过硫酸钾自由基引发剂;包覆处理前不用进行溶剂交换或离心处理.研究了PVP,NH4OH和原硅酸乙酯(TEOS)的用量对PS/SiO2纳米复合微球尺寸和形态的影响.随着PVP用量增加,PS微球变小,因此得到较小的PS/SiO2纳米复合微球;NH4OH用量对SiO2包覆层的厚度没有影响,但对SiO2包覆层的表面形态有影响,随着NH4OH用量增加包覆层表面变得粗糙;随着TEOS溶液用量增加,生成的SiO2增加,其包覆层的厚度增加.     

染料敏化太阳能电池用琼脂糖基磁性聚合物电解质的电化学性能

以琼脂糖为聚合物基质,N-甲基吡咯烷酮为溶剂,磁性纳米粒子四氧化三铁为无机纳米颗粒添加剂制备了用于染料敏化太阳能电池(DSSC)的磁性聚合物电解质.通过研究不同小分子表面活性剂,聚乙二醇(PEG200)、曲拉通(TritonX-100)、乙酰丙酮和三者混合的表面活性剂对掺杂有1%(w)Fe3O4的磁性聚合物电解质离子电导率的影响,发现PEG200的加入可有效提高琼脂糖基磁性聚合物电解质的离子电导率.同时,对不同PEG200浓度添加下的电解质进行离子电导率测试研究发现:当PEG200加入量为61.8%(w)时,电解质具有最佳的离子电导率(2.88×10-3S·cm-1);对染料敏化太阳能电池进行电化学交流阻抗谱(EIS)测试的结果表明:染料敏化太阳能电池的电子寿命和复合电阻随着PEG200浓度的增加是先增大后减小,最大的电子寿命和复合电阻出现在PEG200浓度为68.3%(w)处.     

Two layered silica protective film made by a spray-and-dip coating method on 304 stainless steel

The silica coating has attracted much attention because of its superior corrosion resistance with almost no harm to human health and to the environment. In this study, a two layered silica film was tried to get an enhanced corrosion resistance. The silica film was prepared on the hairline finish 304 stainless steel surfaces by-a-spray- and subsequent-dip-coating process. The spray coating solution was prepared by mixing sodium silicate solution, silica colloid, tetraethyl orthosilicate (TEOS), methyltriethoxysilane (MTES), ethanol, and distilled water. Then the solution was sprayed onto the stainless steel surface, and was dried and heat treated. The dip coating solution was prepared by a simple mixing of TEOS and acidic water into ethanol, and the prior spray coated sample was dipped into the solution. The outer dip coated layer was intended to cover spray coated rough and porous layer and hence to enhance the corrosion resistance. A homogeneous and crack free surface was successfully obtained after the dip coating. The prepared silica film was characterized using scanning electron microscopy, potentiodynamic polarization scan, and electrochemical impedance spectroscopy. The two layered film showed an enhanced corrosion resistance. The enhancement was attributed to a protecting effect of the dip coated layer where the diffusion of ionic species was successfully impeded.     

钼酸盐封闭后处理的热镀锌钢板硅烷膜的耐蚀性

为进一步增强硅烷膜的耐蚀性, 将硅烷化热镀锌钢板用钼酸盐溶液进行封闭后处理, 并采用扫描电子显微镜(SEM)、中性盐雾(NSS)实验、盐水全浸实验和电化学技术研究了所得复合膜层的表面形貌和耐蚀性能. 结果表明: 经钼酸盐溶液封闭处理后, 硅烷膜的孔隙被填充, 在锌层表面形成了由硅烷膜和钼酸盐转化膜构成的连续完整致密的复合膜; 复合膜的耐蚀性能明显提高, 且与钼酸盐溶液的封闭时间有关, 封闭60 s时所形成的复合膜的耐蚀性最佳. 在5%(w, 质量分数)NaCl溶液中的电化学测量结果表明: 硅烷化热镀锌钢板经钼酸盐溶液封闭处理后, 同时抑制了腐蚀过程中的阳极和阴极反应, 但主要是抑制阴极反应, 导致腐蚀电流密度明显减小, 发挥了单一硅烷膜和单一钼酸盐转化膜腐蚀防护的协同效应, 腐蚀防护效率高达99.1%; 随浸泡时间延长, 试样低频扩散阻抗先增大后减小, 表明膜层具有一定的“自愈”能力, 其耐蚀性优于常规铬酸盐钝化膜.     

Corrosion behavior of AA2024-T3 alloy treated with phosphonate-containing TEOS

Protection from corrosion of the aluminum alloy AA2024-T3 coated with a tetraethoxysilicate (TEOS)/aminotrimethyllenephosphonic acid (ATMP) film in a 0.05-mol L⁻¹ NaCl solution was evaluated using electrochemical impedance spectroscopy, scanning electron microscopy, energy disperse spectroscopy, and atomic force microscopy. The present work investigates the influence of different pretreatment procedures of the alloy surface and the ATMP concentration on the corrosion resistance of the coated samples. The undoped sol–gel coatings did not provide adequate corrosion protection. The best corrosion protection was achieved using acetic acid pretreatment and subsequent deposition of an ATMP-modified TEOS film with an optimal concentration of 5.00 × 10⁻⁴ mol L⁻¹ in the deposition bath. The acetic acid pretreatment promotes a decrease in galvanic corrosion and the surface enrichment of aluminum favoring the metalosiloxane and the metal–phosphonic bonds with increasing likely reaction sites, thus promoting the formation of a more homogeneous and compact coating with improved resistance.     

Utilization of biowaste as an eco-friendly biodegradable corrosion inhibitor for mild steel in 1 mol/L HCl solution

This report focuses on the application of a biodegradable biowaste [human hair-(HHR)], to produce a mild steel corrosion inhibitor. The performance of HHR extract in inhibiting metallic corrosion in 1 mol/L HCl was investigated. The analysis of the metal corrosion behavior using electrochemical and weight loss techniques revealed that HHR exhibits an efficient corrosion-mitigating effect via adsorption on the metal surface following a Langmuir isotherm. Tafel-plot results revealed the mixed-mode corrosion protection behavior of HHR. Surface analysis using scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), atomic force microscopy (AFM), and Fourier transform infrared (FT-IR) spectroscopy provided evidence for the precipitation of a protective HHR film on the metal surface.     

Preparation and characterization of anticorrosion Ormosil sol–gel coatings for aluminum alloy

Organically modified silicate (Ormosil) coatings have been synthesized through the sol–gel method for corrosion protection of aluminum alloy. Silica-based unmodified coatings were also designed to investigate the effect of tetraethoxysilane (TEOS) content on the properties of the coatings. The surface morphology of the coatings was characterized by scanning electron microscopy. The corrosion resistance was evaluated by immersion test, electrochemical impedance spectroscopy and potentiodynamic polarization measurements. In addition, the surface potential differences of the coated samples were determined by scanning Kelvin probe. The results showed that a better corrosion resistance of unmodified coating was prepared by controlling the TEOS/EtOH/H₂O molar ratio of 0.109/1/1.52. Ormosil coatings provided excellent barrier properties and corrosion resistance in comparison with the unmodified sol–gel coatings. The Ormosil coating modified with triethoxyoctylsilane exhibited corrosion resistance properties superior to the other Ormosil coatings after exposure to 3.5 wt% NaCl solution for 10 days.     

Cathodic etching for fabrication of super-hydrophobic aluminum coating with micro/nano-hierarchical structure

A facile method for fabricating super-hydrophobic surfaces on the magnetron sputtering aluminum film by cathodic electrochemical etching followed by the modification of myristic acid was presented in this article. The morphologies and the compositions of the films were characterized by means of scanning electron microscopy (SEM), Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS), respectively. The corrosion behavior of the super-hydrophobic film was evaluated by potentiodynamic polarization measurement, linear polarization measurement, and electrochemical impedance spectroscopy. After the treatment with cathodic electrochemical etching, the thin aluminum film remained unbroken and the bulk structure of the aluminum coating maintained a microcrystalline morphology while the surface of the coating presented a petal-shaped microstructure dotted with nano-sized floccules. Aluminum myristate was formed on the nano/microstructural surface of the coating when the sample was modified in melting myristic acid. The static water contact angle on the surface was larger than 165°, which demonstrated that a super-hydrophobic film was prepared on the magnetron sputtering aluminum coating. The corrosion resistance of the aluminum coating was enhanced remarkably because of the super-hydrophobic modification.     

690合金在300 ℃含硫模拟碱性水化学中的腐蚀行为

690 合金作为压水堆核电站蒸汽发生器传热管的一种关键材料, 其在碱性环境下还原态硫导致的钝化膜的腐蚀退化是引发应力腐蚀开裂的关键原因之一. 本文采用动电位极化曲线, 结合扫描电镜(SEM)、俄歇能谱(AES)、二次离子飞行时间质谱(ToF-SIMS)研究了690合金在300 ℃模拟碱性水化学中的腐蚀行为, 并分析了硫代硫酸根与硫酸根对钝化膜特性的影响. 实验结果表明: 300 ℃碱性溶液中690合金表面钝化膜为外层的多孔层与内层的紧密层组成的双层结构, 所加入的硫酸盐种类对690合金的耐蚀性有较大影响; 硫代硫酸根使690合金钝化电流密度增加, 过钝化电位降低, 即钝化膜的耐蚀性降低; 此外, 硫代硫酸根使钝化膜中的Cr含量降低而Ni 含量提高, 硫代硫酸根会在合金表面电化学还原成为更低价态的硫进入钝化膜, 使钝化膜中的硫化物增多也是导致钝化膜防护性能变差的原因; 而硫酸根与钝化膜的作用较弱, 对钝化膜的影响较小.     

Corrosion of Nickel-based Alloy G30 in the Stratum Water Containing H2S/CO2

The influences of temperature and CO2 pressure on the corrosion of nickel-based alloy G30 in the stratum water containing H2S/CO2 were investigated with the aid Mott-Schottky analysis and scanning electron microscopy（SEM） of electrochemical impedance spectroscopy（EIS）, The results indicate that alloy G30 is in the passive state in the stratum water, which is related to the formation of the passive film on its surface. This passive film can significantly protect the substrate from further corrosion. And the film protection is enhanced with decreasing temperature and CO2 pressure. Auger electron spectrometry（AES） and X-ray photoelectron spectrometry（XPS） results reveal that the passive film shows the double-layer structure, i.e. the inner chromium oxide and the outer iron/nickel spinel oxides or hydroxides with Mo oxides dispersing throughout the inner and outer scale.     

硅烷改性含氟丙烯酸酯共聚物乳液

利用正硅酸乙酯(TEOS)水解和长链烷基三甲氧基硅烷(WD-10)的硅烷偶联剂作用,以甲基丙烯酸甲酯(MMA)、丙烯酸丁酯(BA)和甲基丙烯酸十二氟庚酯(DFMA)为原料的核壳型含氟丙烯酸酯聚合物乳液进行原位复合改性。通过XRD、FTIR、SEM-EDX、TEM、RGD、DSC、NMR等测试技术分析和讨论了合成的聚合物乳液的乳胶粒子结构和形态,以及TEOS和WD-10含量对改性的聚合物乳液稳定性和对聚合物成膜性的影响。结果表明,TEOS水解产生了S iO2,核壳型结构粒子基本呈现圆形分布,粒径为40~50 nm。TEOS的最佳质量分数为3.1%~3.8%,WD-10含量宜控制在TEOS质量分数为0.9%~0.95%之间。     

Construction and corrosion behaviors of a bilayer superhydrophobic film on copper substrate

A novel bilayer superhydrophobic film was constructed on Cu substrate by a simple multi‐step process. First, (3‐mercaptopropyl) trimethoxysilane (MPTMS) molecules were self‐assembled onto the pre‐etched Cu surface via covalent bonding followed by hydrolysis and condensation, then 1H, 1H, 2H, 2H‐perfluorodecyltrichlorosilane (PFDTS) were grafted onto the resultant hydroxyl terminated surface via the Si‐O‐Si bonding. The so‐prepared sample was defined as Cu‐MPTMS‐PFDTS. The structure and morphology of the samples were characterized by means of contact angle measurement, X‐ray photoelectron spectroscopy and scanning electron microscopy. The corrosion behaviors of the films were evaluated by Tafel plot and electrochemical impedance spectroscopy on an electrochemical work station. The results indicated that the bilayer superhydrophobic film possessed better corrosion protection as compared with the control samples. The superiority of the corrosion protection was mainly ascribed to the following two aspects: the superhydrophobicity and polysiloxane micro‐structures of the Cu‐MPTMS‐PFDTS. Copyright © 2012 John Wiley & Sons, Ltd.