Evaluation of physico-chemical changes in sub-layers of multi-layer anticorrosive marine paint systems: Plasticizer and solvent release

Increased awareness of the environmental impact of solvent-based anticorrosive marine coatings has urged to predict long-term performance of a coating in order to make dry-docking less frequent. Each coating system was composed by three layers: topcoat, \ and primer. All samples were exposed to four different standard artificial weathering tests: a neutral salt spray test (NSS ISO 9227) and three cycles (QUV ASTM G53, ASTM D5894 and ISO 20340). Besides, the same samples were exposed to a natural weathering during 4 years in three different locations: Pipady (south of France), Kure Beach (North Caroline, USA) and Bandol (south of France). This research project focused exclusively on the degradation of the basecoat and primer by FTIR spectroscopy, PyGC/MS and dynamical mechanical analysis. Basecoat and primer binders formulated with dibutylphtalate as a plasticizer were found to strongly evolve during artificial cycle tests. An extensive diffusion of plasticizer was observed with a rise in T_g of the epoxy binder as high as 40 °C. The impact of these physico-chemical changes on the corrosion protection properties of the whole system were discussed based on electrochemical impedance spectroscopy (EIS) in 3 wt% NaCl solution, SEM observations, pull-off test and measurements of delaminated areas.     

Multilayer organic–inorganic coating incorporating TiO2 nanocontainers loaded with inhibitors for corrosion protection of AA2024-T3

Organic–inorganic multilayer coating containing organically modified silicates, epoxy resins and TiO₂ nanocontainers loaded with 8-hydroxyquinoline were produced on AA2024-T3 substrates via dip coating method. The parameters of the curing temperature and time were optimized via variation in a widespread range in order to realize coatings with best anticorrosive properties. Curing temperature at 110 °C for 24 h presented the best anticorrosive behavior. The morphology of the coating was examined via scanning electron microscopy. The composition of the coatings was determined by energy dispersive X-ray analysis and Fourier transform infra-red spectroscopy. Furthermore, the coatings were exposed to corrosive environment and evaluated by electrochemical impedance spectroscopy. We demonstrate that the presence of loaded TiO₂ nanocontainers enhances the anticorrosive properties of the coatings; specifically, the total impedance values were increased about two orders of magnitude compare to the bare substrate after 400 h of exposure to aggressive environment.     

Performance of paint systems with polyurethane topcoats, proposed for atmospheres with very high corrosivity category

The EN ISO Standard 12944-5 describes the types of paint and paint systems commonly used for corrosion protection of steel structures. In this work four paint systems, applied on steel, including polyurethane topcoats, recommended for atmospheres with high corrosivity (C5 category), codified by 1–4, were studied. Systems 1 and 4 include zinc rich primers and epoxy/polyamide intermediates, system 2 has solvent free epoxy/polyamide primer and intermediate and, system 3 is a hybrid system with vinyl–acrylic water based primer and a high solids epoxy/polyamide intermediate. Systems 2–4 have acrylic–polyurethane topcoats and, the topcoat of the system 1 was identified as an aliphatic polyurethane.

According to EN ISO 12944-6, water condensation and neutral salt spray tests were performed. Three exposure times were considered taking into account the durability ranges of paint systems: low, medium and high, respectively. The paint systems were complementary submitted, during 30 days, to ultraviolet radiation with water condensation test according to ASTM G 154. At the same time, natural exposure was conducted in the marine atmosphere of Sines, with very high corrosivity (>C5).

The paint adhesion, before and after artificial ageing, was evaluated by cross-cut test and, for the systems with dry thickness greater than 250 μm, by pull-off test. Visual inspections were carried out.

For the exposure in UV radiation test chamber and at test site, gloss reduction, colour change and chalking were measured. Chemical changes on polyurethane topcoats exposed in the UV radiation test chamber were studied by Fourier transform infrared spectroscopy (FTIR).

In spite of the higher aesthetic degradation by UV radiation, of the aliphatic polyurethane topcoat of the system 1 relatively to the acrylic–polyurethane topcoats of the other systems, system 1 with ethyl silicate zinc rich primer and epoxy intermediate, was the one that presented the best corrosion protection when exposed in artificial and natural salty environments. At the test site, the worst anticorrosive behaviour seems to be presented by the system 2 with two coats of solvent free epoxy paint.     

水性环氧防腐涂料的制备与性能研究

从4种不同的体系中优选出了高性能的水性环氧乳液及固化荆作为水性防腐涂料的成膜物质.采用傅立叶变换红外光谱考察了树脂与固化剂不同配比时涂层的组成,研究了水性环氧树脂及固化剂不同配比对涂层性能的影响,确定了水性环氧树脂乳液和固化剂的最佳质量比为2:1.正交试验结果表明,当复合铁钛粉、铁红和滑石粉的质量比为1:1:1.5时,涂层具有较好的性能;在此配比下,研究了颜填料体积浓度(Pvc)对涂层性能的影响,采用扫描电镜考察了不同PVC的涂层的截面形貌.结果发现,当PVC为47.7%时,涂层具有最佳性能.     

Performance evaluation of alkyd coatings for corrosion protection in urban and industrial environments

The performance of alkyd based coatings exposed in two different sites in Ecuador, urban and industrial locations, for corrosion protection was evaluated. Atmospheric test sites and corrosion resistance of coatings were examined using mainly ISO and ASTM standards. The alkyd resin degradation was characterized by different methods such as FTIR-ATR, DSC, TGA and SEM.     

Determination of epoxy coating wet-adhesive strength using a standardized ASTM/ISO scratch test

A new approach for evaluating the wet-adhesive strength of epoxy-based coatings was carried out based on a recently standardized ASTM/ISO scratch test. A linearly increasing scratch normal load was applied during scratch to induce progressively increased delamination stress at the coating and steel substrate interface. Thus, the applied critical load to cause coating debonding can be experimentally determined. To find out the corresponding stress magnitude to incur coating debonding, finite element methods (FEM) modeling was conducted to analyze the stress fields around the scratch tip during scratching. The wet-adhesive strength is then quantitatively determined. Based on the above methodology, investigation on a set of model coating systems suggests that the critical load for coating delamination is significantly influenced by water exposure time, coating thickness, and substrate surface roughness. By combining the standardized scratch tests and FEM modeling, the proposed approach is found to be effective for quantitative assessment of epoxy coating wet-adhesive strength and for the development of high performance protective coatings for various industrial applications.     

Oxidation protection of carbon/carbon composites with SiC/indialite coating for intermediate temperatures

In order to improve the oxidation resistance of carbon/carbon composites at intermediate temperatures, a novel double-layer SiC/indialite coating was prepared by a simple and low-cost method. The internal SiC transition layer was prepared by pack cementation and the external indialite glass–ceramic coating was produced by in situ crystallization of ternary MgO–Al₂O₃–SiO₂ glass. The microstructures and morphologies of coating were determined by scanning electron microscopy (SEM), X-ray diffraction (XRD) and energy dispersive spectroscopy (EDS). Oxidation resistance of the as-coated C/C composites was evaluated in ambient air at temperature from 800 °C to 1200 °C. Nearly neglectable mass loss was measured after 100 h isothermal oxidation test, indicating that SiC/indialite coating possesses excellent oxidation protection ability. The as-coated samples have a good thermal shock resistance and no obvious damage was found in the coating even after suffered more than 11 thermal cycles between test temperature and room temperature. The oxidation protection mechanism of this coating was also discussed.     

Structure and properties of AlSi/polyester coating

Powder coatings, which are formed by plasma spray technique, are being used in industrial applications. Resistance of plastics and their based composite materials to chemicals, solvents, atmospheric conditions, and high impact strength even at low service temperature increases the importance of plastic and plastic based coating applications. In this study, aluminum silicon based polyester (AlSi/polyester) coating was applied by plasma spraying technique with and without intermediate bond layer coat (NiAl). The effect of coating thickness, intermediate bond layer coat, and plasma spraying parameters on bond strength of coating were studied experimentally. The bond strengths of the coatings were determined according to the ASTM C‐633–79. Microstructures of the coating were examined by optic microscopy and scanning electron microscopy (SEM), respectively. Obtained results indicated that plasma spraying current rate, coating thickness, and spraying distance were important factors on bond strength of coating. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2437–2444, 2004     

Self-healing anticorrosive organic coating based on an encapsulated water reactive silyl ester: Synthesis and proof of concept

In this paper a self-healing anticorrosive organic coating based on an encapsulated water reactive organic agent is presented. A reactive silyl ester is proposed as a new organic reactive healing agent and its synthesis, performance, incorporation into an organic coating and evaluation of self-healing capabilities is described. Such silyl esters are good candidates to be used in self-healing anticorrosive organic coating systems since they present the capability to react with water/humidity and metallic substrates, removing thus the need of presence of a crosslinker or catalyst in the system unlike traditional encapsulated approaches. In order to prove the self-healing ability and reactivity of the presented silyl ester encapsulated system, Fourier transform infrared spectroscopy (FTIR), electrochemical impedance spectroscopy (EIS) and scanning vibrating electrode technique (SVET) were used, showing the high capability of these techniques to be used in the development and evaluation of self-healing anticorrosive organic coatings and the good results in corrosion protection offered by the proposed silyl ester healing agent.     

老化时间对桥连聚硅氧烷涂层防腐性能的影响

为提高涂层防腐蚀性能,以环氧丙氧丙基三甲氧基硅烷(GPTMS)和N-(3-三甲氧基硅基乙基)乙二胺(NTMDA)为原料经环氧-胺基开环反应得到含羟基有机桥联硅烷前驱体GN。然后,前驱体GN在乙酸催化下制得硅烷溶胶。最后,将硅烷溶胶以浸渍-提拉方式沉积在Q235钢片上,得到含羟基桥联聚倍半硅氧烷涂层。用极化曲线和电化学阻抗谱等技术对涂层的防腐蚀性能进行评价,重点探究了胶体老化时间对涂层防腐蚀性能的影响规律。结果表明：当胶体老化时间为4 h时,涂层在低频0.01 Hz处的电化学交流阻抗相较于空白钢片高出1.5个数量级,具有优异的防腐蚀性能。另外,涂层附着力级别为1级。     

Painting method for hydroxyapatite coating on titanium substrate

Coating on prostheses and implantable devices is one of the ways to increase the osseointegration of these products. However, plasma spray techniques, that are normally used, present high complexity and high cost. In this work, a new methodology for coating with nanometric hydroxyapatite is presented, with a low cost and ease of production. The technique proposed involves the formation of a suspension of hydroxyapatite (HAp) and oil of turpentine (OT) and its application, with a paintbrush, on the titanium substrate. In order to qualify the process for medical devices, the properties of the titanium substrate, before and after the coating process, the calcium phosphate phases present and the adhesive bond of the coating were evaluated. The results indicated that thermal treatment does not affect the properties of ASTM F67 titanium in order to compromise the properties and the analyses, by X-ray diffraction and Raman spectroscopy, proved that no formation of second phases of calcium phosphate occurred. The adhesive bond assay showed that the coating behaved according to ISO 13779–2, i.e., it had adhesive bond values higher than 15 MPa. The proposed new coating method proved promising for the titanium coating and is an alternative to the complex and high cost processes normally used in metal implants.     

水性基料在超薄型钢结构防火防腐涂层体系构建中的应用

探讨了市面上不同树脂水分散体作为超薄型钢结构防火防腐涂料基料的可能性,通过长时间浸泡涂层考察各水性树脂的耐水性、涂层致密性以及填料溶失程度,结果表明:水性基料不适用于含有水溶性填料的单涂层体系。通过热重分析对比发泡填料体系和各树脂的热降解行为,选择热降解温程较为相似的乙酸乙烯酯共聚物和环氧共聚物作为优化涂层防火功能的主要基料。通过垂直燃烧实验测试被涂覆试样的背板温度,优化了防火涂层的颜基比;并通过调整基料复配比例,使得涂层在灼烧后可以得到膨胀厚实且粘附稳定、致密均匀的发泡层。以此为基础,构建了防腐—防火—封闭的多层防火防腐体系,该体系具有良好的耐腐蚀性及耐火性,尤其是长期浸泡后的可持续耐火性与溶剂型同类产品相当。     

Synthesis of electroactive tetraaniline-based acrylic polyol by atom transfer radical polymerization for anticorrosive coating application

In this work, block copolymers of butyl acrylate and glycidyl methacrylate (GMA) having molecular weights 10,000 Da were synthesized with varied GMA block lengths by 10%, 20%, and 30% using atom transfer radical polymerization. The synthesized copolymers were further reacted with tetraaniline to formulate conductive polyol and further characterized by mass spectroscopy, UV–visible spectroscopy, ¹HNMR, and FTIR. The block copolymers formed were evaluated by gel permeation chromatography, Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry, and nuclear magnetic resonance (NMR) techniques for structural elucidation. These polyols were formed with 10, 20, and 30 wt% with isocyanate (HDI N-3300) to form a polyurethane. The effect of concentration of conducting polyol on anticorrosive coating performance properties, namely mechanical and optical properties, was further studied. The anticorrosive performance was evaluated by salt spray test and electrochemical impedance spectroscopy.     

Effect of artificial weathering and temperature cycling on the performance of coating systems used for wooden windows

The effects of ultraviolet light irradiation and water spray and temperature cycling on the color stability of waterborne coating systems on spruce were investigated. The test samples were treated with three coating systems (white and brown pigmented acrylate waterborne coatings systems with different layering) from six producers. The artificial weathering was carried out based on standardized (504 h) and increased weathering parameters (504 h). Thirty cycles of temperature changes were performed. Discoloration suggesting the rate of degradation process and color stability was measured by a spectrophotometer in L*a*b* color space. The results showed greater color stability of white coating systems during both experiments. The producer of acrylate coatings with iodopropynyl butyl carbamate and permethrin as biocides and benzotriazole, silicon dioxide and methylsiloxane as additives was characterized by the best coatings performance. The most sensitive color parameter to describe the surface quality as a result of irradiation and water spray has proven to be a change of lightness. A tendency towards degradation with increasing lightness was observed during weathering. The effect of temperature itself on color change was minimal. Scanning electron microscopy and energy dispersive spectroscopy revealed microscopic changes of coatings caused by artificial weathering.     

Characterization of high performance composite coating for the northern pipeline application

High performance composite coating (HPCC) provides a potential, excellent coating alternative for integrity maintenance of pipelines in the northern area. In this work, the physical, chemical and mechanical properties of HPCC were investigated to determine the microstructure, water permeability, cathodic disbondment resistance, electrochemical impedance, adhesion and impact resistance of the coating. It is shown that the addition of polyethylene layer significantly improves the compactness of the coating and enhances its resistance to water and chemical penetration, resulting in a small water vapor transmission rate and permeance. There is a quite small cathodic disbondment of HPCC under the standard test. The impedance characteristic measured on HPCC-coated steel shows a capillary behavior, indicating an effective protection over the underlying steel from corrosion. The adhesion of HPCC to the substrate ranks top one according to both ASTM and CSA standards. The impact energy of HPCC is 9.7 J at 22 °C, and about 10.2 J around 0 °C.     

常温固化氟碳涂料防腐涂层配套体系及施工质量控制(一)

常温固化FEVE氟碳涂料以其优异的耐候性能在防腐领域获得越来越广泛的应用.为充分发挥氟碳涂料的耐候性,实现涂层体系的长效防腐,必需进行合理的涂层配套体系设计和严格的施工质量控制.综述了氟碳防腐涂层体系设计的一般原则和施工质量控制.介绍了ISO 12944、JT/T 722等标准在氟碳防腐涂层体系设计中的应用,归纳了不同腐蚀类型下,长寿命防腐氟碳涂层体系的实例及特点.     

Designing of phosphorous based highly functional dendrimeric macromolecular resin as an effective coating material for carbon steel in NaCl: Computational and experimental studies

Objective of this study is to develop a highly effective and durable phosphorus based epoxy resin as anticorrosive coating material for carbon steel in 3% NaCl medium. The hexaglycidyl N,N′,N″-tris (4,4′-ethylene dianiline) phosphoramide (HGTEDPA) was characterized using spectral methods. The anticorrosive formulation (HGTEDPA-MDA) was synthesized using HGTEDPA curing with 4,4′-methylenedianiline (MDA). The formulation (HGTEDPA-MDA) coated steel specimens were exposed to UV radiation for a specific durable (189 days) and durability of the formulation was tested along with its inhibition effectiveness. The anticorrosive property of the formulation was evaluated using electrochemical (electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization (PDP)) methods. Results showed that HGTEDPA-MDA coating improved the corrosion resistance value even after exposing 180 days to the UV radiation. PDP study suggested that HGTEDPA-MDA before and after UV radiations acted as mainly anodic and cathodic type of inhibitor, respectively. The EIS and PDP results were corroborated with density functional theory (DFT) and molecular dynamic simulations (MDS) methods and a reasonable good agreement was observed. DFT study revealed that HGTEDPA-MDA interacts with the metallic surface using donor–acceptor interactions. MDS study revealed that HGTEDPA-MDA spontaneously interacts with steel surface and adsorb using horizontal orientation.     

颜填料体积浓度对水性环氧导静电防腐蚀涂层性能的影响

考察了颜填料体积浓度（PVC）对水性环氧导静电防腐蚀涂料涂层导静电性能和防腐蚀性能的影响,运用X射线能谱（EDX）分析了导电填料的元素组成,采用电化学阻抗谱（EIS）、扫描电镜（SEM）等手段对不同颜填料体积浓度的涂层进行了性能测试及表征,根据不同颜填料体积浓度涂层的物理机械性能、盐水浸泡实验结果和电化学阻抗谱分析,确定该水性环氧导静电防腐蚀涂料的最佳颜填料体积浓度为35%。     

An investigation of the effect of pigment on the degradation of a naturally weathered polyester coating

A series of coil coatings based on a polyester/melamine resin formulation, incorporating different pigment systems, were naturally weathered after being exposed to the elements in Hainan, PRC, for 2 years. The surface chemistry and morphology, before and after weathering, was investigated using both traditional (i.e., gloss retention, color change) and novel (i.e., X-ray photoelectron spectroscopy [XPS], atomic force microscopy [AFM], and scanning electron microscopy [SEM]) methods. Chemical changes occurring in the coating bulk were investigated using step-scan photoacoustic Fourier transform infrared spectroscopy (SSPA-FTIR). It was found that the coating surface morphology, surface chemistry, and bulk chemistry, both before and after weathering, were all affected by the type and concentration of the pigments included in the coating formulation. Moreover, it was found that different types of pigment catalyze different coating degradation mechanisms.     

Electrochemical impedance studies of corrosion protected surfaces covered by epoxy polyamide coating systems

Electrochemical impedance spectroscopy (EIS) was used to study the corrosion behavior of different types of commercial quality epoxy polyamide dry coatings on mild steel, with thickness between 150 and 250 μm, which were previously weather accelerated in a wet chamber. The following data were established on the basis of impedance curves and corresponding equivalent circuits: the coating capacity that relates to the coating dimension, the pore resistance that represents conductive paths through the pores, and Warburg coefficients, which are the measure of ion diffusion through the coating. EIS data were compared with a criterion in the European standard, and samples were classified on the basis of their quality, also receiving a final ranking by summing-up all the individual rankings. Suggestions have been made, namely that the use of anticorrosive active pigments is obsolete, when the thickness of the coatings exceeds 200 μm.