氧化石墨烯-水性环氧树脂固化剂的制备及性能

首先，将三乙烯四胺(TETA)和氧化石墨烯(GO)球磨，得到TETA改性GO分散液TGO；然后向其中依次滴加双酚A型环氧树脂E44、三羟甲基丙烷三缩水甘油醚(TPEG)、甲氧基聚氧乙烯-2,3-环氧丙烷(MEH)和γ-(2,3-环氧丙氧基)丙基三甲氧基硅烷(KH560)，采用原位聚合法合成了氧化石墨烯-水性环氧树脂固化剂(TGO-WPEA)；采用上述工艺，不添加GO的条件下制得水性环氧树脂固化剂(WPEA)。将WPEA和TGO-WPEA分别与环氧树脂乳液(Epikote-6520)复合制得水性环氧树脂(EP)和氧化石墨烯改性水性环氧树脂(TGO-EP)防腐涂料。通过FTIR、XPS和XRD对材料进行了结构表征，采用电化学测试和盐雾实验对TGO-EP的防腐性能进行了评价。结果表明，水性环氧树脂固化剂(WPEA)分子通过共价键连接到GO表面，改善了GO在EP中的分散稳定性和接枝率，提高了TGO-EP复合涂料对腐蚀介质的屏蔽性能。与纯EP涂层相比，TGO-EP涂层腐蚀电位从–0.267 V提高到–0.125 V，腐蚀电流密度从5.44×10^–8 A/cm²     

改性石墨烯对环氧树脂涂层耐腐蚀性能的影响

将改性后石墨烯粉末通过球磨机均匀分散于环氧树脂涂料中以提高7A52铝合金表面有机涂层的耐腐蚀性能。通过接触角、吸水率、红外光谱、开路电位及交流阻抗测试,分别评价改性石墨烯环氧树脂涂层的表面润湿性、耐水性能、耐蚀性,并通过扫描电子显微镜对石墨烯粉末及环氧树脂涂层断面形貌进行分析。结果表明:环氧树脂涂料中添加0.8%改性石墨烯粉体后,接触角由86.77°增加至101.43°,提高16%,表面由亲水性变为疏水性,涂层的耐水性提高,吸水率降低0.21%。0.8%改性石墨烯涂层在3.5%NaCl溶液中稳定后的开路电位较未添加石墨烯涂层增加0.14 V,阻抗值高出未添加改性石墨烯涂层半个数量级,且电荷转移电阻R_ct比未添加改性石墨烯涂层R_ct高出1.78×10 ⁷ Ω/cm ²,涂层的耐腐蚀性大大提高。红外光谱表明,改性石墨烯并未改变环氧树脂结构,涂层中的改性石墨烯是影响涂层性能发生变化的重要因素。研究表明改性石墨烯的加入可以有效提高涂层的耐蚀性,并且当改性石墨烯添加量为0.8%时,涂层具有优异的耐腐蚀性能。     

氧化石墨烯-水性环氧树脂固化剂的制备及性能

以三乙烯四胺（TETA）,氧化石墨烯（GO）,环氧树脂E44、三羟甲基丙烷三缩水甘油醚（TPEG）、甲基聚氧乙烯环氧基醚（MEH）和γ-(2,3-环氧丙氧)丙基三甲氧基硅烷（KH560）为原料,采用原位聚合法首先将TETA与GO球磨分散,使TETA与GO通过共价键相连,然后依次滴加E44、TPEG、MEH和KH560合成氧化石墨烯-水性环氧树脂固化剂（TGO-WPEA）,再与环氧树脂乳液（Epikote-6520）复合制得氧化石墨烯改性水性环氧树脂防腐涂料（TGO-EP）。通过FTIR、XPS和XRD对纳米材料进行结构表征,采用电化学测试和盐雾实验对复合涂层TGO-EP的防腐性能进行了研究。结果表明,固化剂分子通过共价键连接到GO表面,改善了GO在环氧树脂中的分散稳定性和接枝率,提高了TGO-EP复合涂料对腐蚀介质的屏蔽性能。与EP涂层相比,其腐蚀电位从-0.267mV提高到-0.125mV,腐蚀电流密度从5.44×10-8减小到1.09×10-8 A/cm2;EIS测试表明,浸泡20d后,TGO-EP仍具有最高的低频阻抗。     

功能化石墨烯掺杂环氧树脂船舶防腐涂料的制备及其性能的研究

采用改进的Hummers法制备了氧化石墨烯(GO),用1-萘磺酸钠(NA)和水合肼对GO进行功能化改性和化学还原,制得功能化石墨烯(NA-r GO),采用溶液共混法制备了NA-r GO掺杂环氧树脂涂料,用扫描电子显微镜观测了NA-r GO和涂料的形貌,研究了涂料的防腐性能,并初步探讨了NA-r GO在涂料中的耐腐蚀机理。结果表明,NA-r GO呈层片状结构,表面比较平整,在涂料中分散比较均匀;当NA-r GO掺杂量为1.0%~2.5%时,涂料涂层厚度保持在95±5μm,当NA-r GO掺杂量为1.5%~2.0%时,涂层硬度可达3H,当NA-r GO掺杂量为1.5%时,涂层自腐蚀电位为-410m V,自腐蚀电流密度为0.049μA/cm2;NA-r GO的掺入在初期会引起加速腐蚀,而涂料在后期则表现出良好的耐腐蚀性能。     

新型石墨烯/聚吡咯水性防腐涂料的制备及性能

传统的石墨烯防腐涂料存在填料成分不均一、防腐性能低、涂层不稳定等问题。为了提高石墨烯防腐涂料的分散性能和防腐性能,本文采用改进原位聚合法合成的石墨烯(rGO)/聚吡咯(PPy)复合物为填料,水性环氧树脂(EP)为成膜物质,制备新型石墨烯/聚吡咯水性防腐涂料(rGO/PPy/EP)。采用X射线衍射(XRD)、傅里叶红外光谱(FTIR)、拉曼光谱(Raman)、扫描电子显微镜(SEM)和透射电子显微镜(TEM)对涂料进行结构分析,通过塔菲尔极化曲线(Tafel)、交流阻抗谱图(EIS)和腐蚀形貌分析测试rGO/PPy/EP对Q235碳钢的防腐性能。结果表明:采用改进原位聚合法制备的rGO/PPy/EP涂料分散性好,结构致密。质量分数为1%rGO/PPy/EP涂料的腐蚀电位E_(corr)=–613m V,腐蚀电流密度I_(corr)=46.42μA/cm~2,对裸钢的保护度P_i=91.02%。与rGO/EP涂料相比,rGO/PPy/EP涂料的腐蚀电流密度降低了38.62μA/cm~2,对O_2和H_2O腐蚀介质具有较高的屏蔽性能。因此,原位聚合法制备的rGO/PPy水性涂料具有环境友好、分散性能强、结构稳定和防腐性能优异等优点,具有广阔的应用前景。     

石墨烯的氧化程度和含量对水性锌粉涂料防腐性能的影响

制备了 3种不同氧化程度的氧化石墨烯,利用氧化石墨烯对水性环氧富锌涂料进行改性。采用盐雾试验、电化学测试、耐冲击性及附着力测试等对改性涂层的性能进行研究,研究发现氧化程度较低的氧化石墨烯改性环氧富锌涂料性能最佳。然后探究了氧化石墨烯含量和锌粉含量对该涂层的耐腐蚀性和力学性能的影响。结果表明：氧化石墨烯（ GO）的添加可以有效延缓钢材的腐蚀,当 GO-1添加量为 0.36%（质量分数,下同）,锌粉含量为 44%时,制备所得的 GO-1/水性环氧富锌涂料的综合性能最佳。当制得的氧化石墨烯的氧化程度较小,含氧基团较少且没有出现羧基时,涂料的耐腐蚀性能得到改进。     

氧化石墨烯/聚氨酯复合涂料的制备及其性能

采用改进的Hummers法制得氧化石墨烯(GO),采用乳液聚合法制得GO/聚氨酯(PU)复合涂料。对产物的形貌和结构进行了表征,考察了GO添加量对复合涂料性能的影响。结果表明,GO呈片状多孔结构,GO/PU涂层致密性优于PU涂层;氧化反应在引入含氧基团的同时,破坏了天然石墨的晶型;GO在水中分散性较好;当GO质量分数为1%时,涂层吸水性大幅降低,硬度可达3H,自腐蚀电位为-540m V,自腐蚀电流密度为0.12μA/cm~2,防腐性能达到最佳。     

石墨烯-Al2O3复合材料的制备及其防腐性能研究

为研制具有高防腐性能的环氧树脂涂层，采用溶胶 .凝胶法制备一种石墨烯 /三氧化二铝复合材料（GA）并用硅烷偶联剂 Z.6173对其改性后（GAZ）作为填料加入到环氧树脂（EP）涂料中。结果表明：三氧化二铝主要以 α-Al₂O₃的晶型均匀包覆在石墨烯的周围；红外分析证明 Z-6173成功对GA粉体进行了改性； EIS结果表明 GAZ/EP涂层具有最佳的防腐性能，浸泡 30 d后其低频区阻抗值为 14. 5 GΩ·cm²；盐雾测试结果表明 GAZ复合材料的加入可以有效防止由石墨烯优良导电性造成的金属基底加速腐蚀的现象发生。     

聚苯胺/纳米碳酸钙复合物的制备及其防腐性能

以苯胺单体为原料、过硫酸铵为氧化剂,采用化学氧化法制备了本征态聚苯胺,将其与纳米CaCO3通过溶液共混法制备了聚苯胺/CaCO3复合物。采用扫描电镜(SEM)、X射线衍射(XRD)、紫外–可见光谱(UV–Vis)和红外光谱(IR)对聚苯胺/CaCO3复合物进行了形貌观察和结构表征。分别以聚苯胺、聚苯胺/CaCO3复合物为填料,加入到环氧树脂(EP)/聚酰胺固化剂体系中,在碳钢表面制备了EP/聚苯胺和EP/聚苯胺/CaCO3复合涂层,通过开路电位、极化曲线和交流阻抗谱等电化学方法对比研究了裸钢以及含EP涂层、EP/聚苯胺涂层、EP/聚苯胺/CaCO3复合涂层的碳钢试片在3.5%NaCl溶液中浸泡不同时间的腐蚀行为。结果表明,聚苯胺膜较好地包覆在CaCO3纳米粒子表面;CaCO3的加入增强了涂层的致密性,提高了聚苯胺分子对金属基体的粘附力。含有聚苯胺/纳米CaCO3复合物的环氧涂层具有最强的抗腐蚀能力,其次为环氧/聚苯胺涂层;两者相比,EP/聚苯胺/CaCO3复合涂层的腐蚀电位正移了59 mV,腐蚀电流密度降低了63%。     

ATO/GO纳米复合材料的制备及性能

以氧化石墨烯(GO)为前体,通过氨丙基三乙氧基硅烷(KH550)将氧化锡锑(ATO)锚定到氧化石墨烯片层上,制备得到氧化锡锑-氧化石墨烯纳米复合材料(ATO/GO)。通过高速分散法与水性环氧树脂乳液(AE)共混,制备得到氧化锡锑-氧化石墨烯/水性环氧树脂复合乳液(ATO/GO-AE)。通过XRD,XPS和SEM对其结构进行了表征。考察了ATO/GO含量对水性环氧涂料防腐及抗静电性能的影响。结果表明:随ATO/GO含量的增加,复合涂料表面电阻降低,ATO/GO质量分数等于3.0%时,表面电阻降低至1.0×10~9?以下,达到了抗静电的使用要求,漆膜水蒸汽透过率降低至62.13 g/(m~2·h),具有最低的腐蚀电流(Icorr=3.73×10~(-9) A/cm~2)和最高的腐蚀电压(Ecorr=–0.1993 V),ATO/GO的防腐效率与AE相比提高了99.95%。     

Preparation of polyvinylpyrrolidone/graphene oxide/epoxy resin composite coatings and the study on their anticorrosion performance

Waterborne epoxy resin (EP) is often used as anticorrosive coating in the industrial field. However, small holes and gaps can be formed during the curing process. The corrosive medium easily penetrates the anticorrosive coating and corrodes the metal matrix. Herein, polyvinylpyrrolidone (PVP) and graphene oxide (GO) were doped into EP to improve the shielding and resistance to corrosive media. The composite coatings were prepared successfully by solution blending method. In the PVP/GO composite materials, original spatial structure of GO was changed and the composite was mainly combined by covalent bonding. The surface morphology of hybrid filler was flat and uniform, and the structural defects of GO was reduced. Compared with single-layer anticorrosive coating, the corrosion potential of PVP/GO/EP coating moved forward and the corrosion current density decreased. The ideal corrosion resistance of PVP/GO/EP composite coatings was mainly because agglomeration of GO sheet was obviously avoided after it was modified by PVP. Furthermore, the hybrid filler can be uniformly dispersed in the aqueous EP. It blocked the gaps and holes inside the coatings, which could contribute to form anticorrosive coatings.     

水性环氧树脂/纳米SiO2复合疏水涂层的制备及性能研究

用氨基硅油（ APDMS）改性水性环氧树脂（ EP）得到疏水性的环氧树脂乳液（ APDMS-EP）;用 1H,1H,2H,2H-全氟辛基三乙氧基硅烷（ FAS）与纳米 SiO₂反应得到氟改性纳米 SiO₂（F-SiO₂）。采用不同比例的 F-SiO₂与 APDMS-EP进行复配,室温固化制备疏水涂层,并对 F-SiO₂的结构进行了表征,研究了 F-SiO₂用量对涂层的接触角、铅笔硬度、附着力、热稳定性及耐腐蚀性能的影响。结果表明： APDMS的引入使水性环氧树脂涂层的水接触角从 47.3°提高到 97.7°;加入 F-SiO₂后涂层疏水性进一步提高,当加入 15%的 F-SiO₂时,涂层对水和丙三醇的接触角分别为 120.3°和 104.5°,F-SiO₂的加入也增强了涂层的防腐性能。     

Tribological and corrosion performance of epoxy resin composite coatings reinforced with graphene oxide and fly ash cenospheres

In this work, a novel graphene oxide (GO)-fly ash cenospheres (FACs) hybrid fillers was introduced to improve the wear and corrosive resistance of epoxy resin (ER) composite coatings. The tribological behavior and the corrosion performance of three kinds of coatings (pure ER, GO/ER and GO-FACs/ER coatings) were studied and the reinforced mechanisms of coatings filled by different fillers were analyzed. The friction coefficient and wear rate of the ER coatings were decreased with the addition of GO-FACs hybrids. The scanning electron microscope images showed that the dispersibility and compatibility of GO-FACs hybrids were effectively improved compared with that of GO sheet. The water contact angle examination indicated that the hydrophobicity of the GO-FACs/ER coatings increased. The electrochemical impedance spectroscopy (EIS) results demonstrated that the GO-FACs/ER coatings have better anticorrosion performance compared with the pure ER coatings and the GO/ER coatings. The hydrophobic surface and the well dispersed fillers constitute the dual barrier to resist the corrosion medium.     

防腐环氧树脂粘接涂层的研究进展

简要介绍了粘接涂层防腐的几种机制。从填料的发展、缓蚀剂的发展、EP(环氧树脂)基体的发展和导电EP粘接涂层的发展等方面,介绍了国内外防腐EP粘接涂层的研究进展。最后基于环保性趋势对防腐EP粘接涂层的发展方向作了展望。     

Incorporation of silica network and modified graphene oxide into epoxy resin for improving thermal and anticorrosion properties

In this study, the silica network and functionalized graphene oxide (GO) were incorporated into the epoxy coating systems, which was aimed to improve the thermal property and corrosion resistance of epoxy coatings. First, tetraethyl orthosilicate (TEOS) oligomers and epoxy hybrid was fabricated through sol–gel method. Then the (3-aminopropyl) triethoxysilane (APTES) modified graphene oxide (FGO) was added into the epoxy hybrid composite to obtain anticorrosion coatings. Fourier transform infrared spectroscopy, thermogravimetric analysis (TGA), Raman spectrum, and X-ray photoelectron spectrum were conducted to evaluate the structural information of GO and APTES modified GO nanosheets. The results indicated that the APTES successfully grafted onto the surface of GO sheets. Besides, TGA curves, electrochemical measurements and salt spray test were also carried out to characterize the thermal performance and corrosion resistance of GO based epoxy coatings. The TGA results revealed that the thermal performance of epoxy coating containing silica network and FGO nanofiller (ES/FGO) was significantly strengthened compared to pure epoxy. The initial degradation temperature of epoxy coating was increased from 300 to 343.7°C after incorporation of silica component and FGO. The EIS measurements demonstrated that the impedance modulus of ES/FGO was significantly higher than neat epoxy, which indicated that the corrosion resistance of epoxy was substantially strengthened after introduction of silica component and FGO. The corrosion rate and inhibition efficiency of epoxy composite coatings were also shifted from 1.237 × 10⁻⁷ mm/year and 76.6% (for neat epoxy) to 1.870 × 10⁻⁹ mm/year and 99.6% (for ES/FGO), respectively. The salt spray test also revealed that the silica and FGO can improve the corrosion resistance of epoxy coating. Additionally, the dispersion of GO sheets was also enhanced after the modification of APTES siloxane.     

环氧豆油树脂涂层的防腐性能研究

以环氧大豆油（ESO）为主要原料,四亚乙基五胺为固化剂,在碳钢基底表面制备了环氧豆油树脂（ESOR）涂层。利用场发射扫描电镜、傅里叶红外变化光谱仪、纳米压痕仪、热重分析仪、接触角测量仪、电化学阻抗谱等技术对ESOR涂层的性能进行了表征。结果发现,原料中ESO的含量有助于提高ESOR涂层的耐水性;而当原料中ESO的含量逐渐增加时,ESOR涂层的硬度、弹性模量和耐蚀性都会随之增强;根据拟合的等效电路,ESO与四亚乙基五胺的摩尔比为2的ESOR涂层的涂层电阻R_c能达到8.22×10¹¹ Ω·cm²,电荷转移电阻R_ct能达到1.32\times10¹⁰ Ω·cm²,表现出了优异的防腐性能。     

功能型环氧树脂基防腐涂层的研究进展

环氧树脂涂层因其优异的耐蚀性能、对金属表面良好的附着力而在金属防腐领域得到广泛应用。但涂层固化过程中会形成缺陷和孔洞，腐蚀介质可以直接接触到金属表面。为了开发出具有优良耐久性的防腐涂层，研究人员使用不同的方法和材料制备了多种环氧树脂防腐涂层。该文综述了纳米粒子改性环氧防腐涂层、超疏水型环氧防腐涂层、自修复型环氧防腐涂层、导电聚合物改性环氧防腐涂层及生物基材料改性环氧防腐涂层的制备及性能。但这5种防腐涂层各有局限性，未来应该探究出新的环氧防腐涂层，在提升涂层防腐性能的同时，兼顾其他性能，使环氧树脂基防腐涂层朝着功能化、智能化的方向发展。     

Synthesis and characterization of hybrid materials based on graphene oxide and silica nanoparticles and their effect on the corrosion protection properties of epoxy resin coatings

This study focuses on the use of tetraethyl orthosilicate (TEOS) as a silica source to decorate the surface of graphene oxide (GO) nanosheets and the use of N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane (Z-6020) as a coupling agent through a one-step in-situ sol-gel process. The results of the Fourier transform infrared spectroscopy (FT-IR), UV-visible, X-ray diffraction analysis (XRD), scanning electron microscopy (SEM), and thermogravimetric analysis (TGA) revealed that fine SiO₂ nanoparticles have successfully been synthesized on the basal plane of GO by covalent bonding. The dispersion of GO sheets and GO–SiO₂ nanohybrids within the epoxy matrix was studied using XRD and SEM techniques. Then, the effect of incorporating 0.1?wt% GO sheets and GO–SiO₂ nanohybrids on the corrosion protection and barrier performance of the epoxy coating was also investigated. The results showed that the incorporation of GO–SiO₂ into the epoxy matrix improved its thermal stability. The electrochemical impedance spectroscopy (EIS) test, potentiodynamic polarization and cathodic disbonding test showed that the corrosion protection performance was significantly enhanced by the incorporation of GO–SiO₂ hybrids into the epoxy resin compared to epoxy/GO and neat epoxy resin, respectively. The water contact angle (CA) results confirmed the reduction of the hydrophobic nature of the surface after the incorporation of GO–SiO₂ hybrids.     

溴代环氧/环氧复合涂层防腐性能研究

针对金属腐蚀问题,制备了以环氧涂层为底漆,溴代环氧涂层为面漆的溴代环氧/环氧复合涂层.研究结果表明:环氧树脂的极性为涂层提供良好的附着力,溴代环氧树脂的疏水性有效提高涂层的抗渗透性能.复合涂层具有低润湿性(吸水率:0.217％,接触角:93.6° )、高附着力(干:5.28 MPa,湿:2.52 MPa)和优异的耐盐水...