The influence of zinc surface pretreatment on the adhesion of epoxy coating electrodeposited on hot-dip galvanized steel

The adhesion and electrochemical properties of epoxy coatings electrodeposited on hot-dip galvanized steel with and without passive films were investigated during exposure to 3% NaCl. The passive films were formed in hot air, in boiling water and by chromating. Adhesion was measured both by a standardized pull-off method and by swelling in N-methyl pyrrolidone. Pretreatment of hot-dip galvanized steel with passive film formed in hot air increases both dry and wet adhesion strength of the epoxy coating compared to pretreatment with passive film formed in boiling water and chromate coating. The overall increase of wet adhesion for this sample was maintained throughout the whole investigated time period. It was shown that the change in adhesion of epoxy coating on a chromate coating is smallest of all investigated samples, although the initial value of adhesion on this surface had the lowest value. The corrosion stability of coated Zn samples pretreated by different methods, was investigated by electrochemical impedance spectroscopy and in the initial time of exposure to NaCl the highest values of pore resistance were also obtained for the epoxy coating on Zn pretreated in hot air, whereas the epoxy coating on a HDG steel with a chromate coating showed the smallest change in electrochemical properties (pore resistance, coating capacitance, charge-transfer resistance) during prolonged exposure time.     

Corrosion stability of polyester coatings on steel pretreated with different iron–phosphate coatings

The influence of steel surface pretreatment with different types of iron–phosphate coatings on the corrosion stability and adhesion characteristics of polyester coatings on steel was investigated. The phosphate coating was chemically deposited either from the simple novel plating bath, or with the addition of NaNO₂, as an accelerator in the plating bath. The morphology of phosphate coatings was investigated using atomic force microscopy (AFM). The corrosion stability of polyester coatings on steel pretreated by iron–phosphate coatings was investigated by electrochemical impedance spectroscopy (EIS) in 3% NaCl solution, while “dry” and “wet” adhesion were measured by a direct pull-off standardized procedure. It was shown that greater values of pore resistance, R_p, and smaller values of coating capacitance of polyester coating, C_c, on steel pretreated with iron–phosphate coating were obtained, as compared to polyester coating on steel phosphated with accelerator, and on the bare steel. The surface roughness of phosphate coating deposited on steel from the bath without accelerator is favorable in forming stronger bonds with polyester coating. Namely, the dry and wet adhesion measurements are in accordance with EIS measurements in 3% NaCl solution, i.e. lower adhesion values were obtained for polyester coating on steel phosphated with accelerator and on the bare steel, while the iron–phosphate pretreatment from the novel bath enhanced the adhesion of polyester coating on steel.     

Evaluation of the effects of surface treatments on the cathodic delamination and anticorrosion performance of an epoxy-nanocomposite on steel substrate

The St-37 type steel substrates were pretreated with Cr(VI) and Cr(III) conversion coatings where the latter was then post-treated with Co(II) and Ni(II) chemical treatments. The epoxy coatings containing 3.5 wt% nano-sized ZnO particles were applied over the chemically treated steel samples. The corrosion resistance of the samples was studied by a DC polarization technique. A scanning electron microscope (SEM) was utilized to investigate the morphology of the pretreated and post-treated samples. Electrochemical impedance spectroscopy (EIS) was utilized to investigate the corrosion resistance of the epoxy nanocomposites for different immersion times in 3.5 wt% NaCl solution. The adhesion strengths of the coatings were measured before and after 120 days of immersion in the corrosive electrolyte using a pull-off test. The cathodic delamination (CD) of the painted samples was also investigated. Results showed that conversion coatings can significantly increase the corrosion resistance and adhesion strength of the epoxy coating on the steel, and also reduce the rate of CD in comparison with an untreated sample. The adhesion strength and corrosion resistance of the epoxy coating on the Cr(III) pretreated samples were significantly greater than on the Cr(VI) sample. The increase in adhesion strength and corrosion resistance was more pronounced on the samples that were post-treated with Co(II) and Ni(II) chemical treatments. The cathodic disbonded areas of the Cr(III)–Co(II) and Cr(III)–Ni(II) post-treated samples were significantly lower than the Cr(III) and Cr(VI) pretreated samples. Results showed that Cr(III)-based conversion coatings can improve the anticorrosion performance and reduce CD compared with those with Cr(VI).     

A comprehensive study of the green hexafluorozirconic acid-based conversion coating

The effect of four practical parameters (deposition temperature, time, bath pH and concentration of Zr) on electrochemical and morphological properties of zirconium based conversion coating (ZrCC) on cold rolled steel (CRS) substrates was investigated. DC polarization and electrochemical impedance spectroscopy (EIS) measurements were used for electrochemical studies. Micro structural characterization was carried out by FE-SEM, AFM and EDS. The optimal conditions were determined as follows: solution temperature 20–30 °C, immersion time 60–120 s, pH = 4 and acid concentration of 4% vol. In such condition, corrosion resistance values were maximum and uniformity was improved. Microscopical observations revealed that ZrCC comprises a two-layered structure. The film formation mechanism of ZrCC was discussed in detail. After achieving the optimum conditions, epoxy nanocomposites were applied on ZrCC treated CRS samples and corrosion performance of fully painted system was investigated. Finally the adhesion strength of subsequently applied organic coating on ZrCC treated substrates was measured by pull-off technique which exhibited considerable high values.     

Electrochemical effects of silane pretreatments containing cerium nitrate on cathodic disbonding properties of epoxy coated steel

In the recent years, silane materials, because of their environmental friendly nature and ease of application have been attended as an alternative for chromate conversion coatings. Different materials were searched for improvement of the efficiency of silane formulation. In this research, pretreatment of carbon steel substrates was carried out using γ-glycidoxypropyl-trimethoxysilane (γ-GPS) as functionalized silane. Cerium nitrate as a corrosion inhibitor material was introduced into the silane material and epoxy resin was applied on the pretreated steel substrates. Effects of the pretreatment on electrochemical properties, cathodic disbondment, dry and wet adhesion strength, and surface morphology of resultant epoxy coating were investigated. Results showed that pretreatment of steel substrate with γ-glycidoxypropyl-trimethoxysilane (γ-GPS) doped with cerium nitrate leads to improvement of cathodic disbondment and also dry and wet adhesion of epoxy coating. Furthermore, this type of pretreatment reduced the disruption of interfacial bonds at the binder/substrate interface. Addition of 2?wt% cerium nitrate into the silane formulation led to the maximum efficiency of resultant coating.     

AFM adhesion force measurements on conversion-coated EN AW-6082-T6 aluminium

Atomic force microscopy (AFM) has been used to measure the adhesion force between functionalised AFM tips and smooth surfaces of an EN AW-6082-T6 aluminium alloy, both before and after application of different conversion coatings. In addition, the surface of a sapphire sample was studied as a model aluminium surface. The results obtained for the sapphire surface were highly reproducible, and were used as a mean to establish proper routines for the more complex industrial surfaces. The adhesion force between a chromate conversion-coated (CCC) EN AW-6082-T6 aluminium alloy and a COOH functionalised tip was significantly increased compared to the uncoated surface, probably as a result of strong hydrogen bonding. However, the adhesion force decreased with time during the first 24 h after treatment due to aging of the CCC. Chromate-free Ti–Zr-based treatment also increased the adhesion, but the adhesion force varied significantly due to non-uniform deposition and composition of the conversion coating. The measured AFM adhesion forces correlated qualitatively with macroscopic adhesion test results obtained previously for these specific conversion coatings. The AFM technique may thus provide useful information on the adhesion behaviour of heterogeneous conversion-coated aluminium surfaces.     

Adhesion of electron beam curable coatings on metal substrates

Electron beam (EB) curing is growing more and more important as a curing technique in industrial coatings, for example on substrates like wood, paper and plastics. However, commercial applications of EB curing on metal substrates are rather limited. The main technical cause for this originates from the insufficient adhesion and flexibility shown by EB cured coatings when applied on metal parts. However, adhesion and flexibility can be improved by various ways, in particular via a proper choice of the chemical pretreatment of the substrate. Adhesion of coatings, based on acrylated resins, on hot dipped galvanized steel can be improved dramatically by using a pretreatment, which is not usual in the current field of commercial coil coating. Pretreatments investigated show no relationship to surface tension, so it is highly probable that a chemical graft reaction, initiated by the electron beam, occurs at the interface of the coating and pretreatment layer. Experiments also show that cationic curing binder systems show promise with respect to adhesion and flexibility. Without optimizing the coating formulation (no wetting agents or other additives are used) relatively good adhesion and flexibility can be obtained on hot dipped galvanized steel, under both wet and dry conditions. The adhesion and flexibility are shown to be dependent on the radiation dose, and can be further improved by post-heating. In this case the polymer network gets the opportunity to relax internal stresses that are built up during the cure reaction.     

Self-healing and anticorrosive properties of Ce(III)/Ce(IV) in nanoclay–epoxy coatings

The self-healing and anticorrosion effects of cerium nitrate in epoxy–clay nanocomposite coatings systems were studied. Different amounts of cerium (III) were added to epoxy–montmorillonite clay composites and the nanocomposite coatings were prepared and applied on cold rolled steel panels. Ultrasonication was applied to disperse the nanoclay into the epoxy cerium nitrate composition. Electrochemical impedance spectroscopy (EIS) was used to study the self-healing and anticorrosion behaviors of the coatings. The structure of the dry coating and the protective mechanism of the pigments in the coating were investigated by scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX) analysis and field emission electron microscopy (FESEM). Transmission electron microscopy (TEM) illustrated the separation of clay layers which interacted with the epoxy resin. Electrochemical impedance data indicated that the epoxy cerium (III)–montmorillonite nanocomposite coatings were superior to the epoxy coatings in corrosion protection properties. The self-healing behavior of such coatings was due to the presence of cerium nitrate that could be released at the defects within the coating and hindered the corrosion reactions at the defective sites. It was shown that the best corrosion protection was achieved with nanocomposite coatings containing 4 wt% clay and 2 wt% cerium nitrate.     

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.     

不同表面处理条件下复合涂层体系失效过程的EIS特征

研究了不同表面处理条件下环氧富锌/环氧云母氧化铁/氯化橡胶涂层体系的电化学阻抗谱特征。利用Bode图、涂层吸水率、涂层电阻及特征频率的变化评价了表面处理对涂层防护性能的影响。结果表明,基材表面状态不同的复合涂层体系吸水率相对稳定阶段所持续的时间长短顺序为：手工打磨>表面锈蚀>表面未处理,与涂层的防护寿命长短、涂层/基材间的黏附力大小顺序一致。此外,不论基材表面处理程度如何,当涂层体系的特征频率增加到1400 Hz左右时,涂层电阻均发生较快降低,吸水率发生较大增长,涂层失去防护作用。     

Sol–gel incorporation of silica nanofillers for tuning the anti-corrosion protection of acrylate-based coatings

The aim of the present work is to synthesize through sol–gel approach new hybrid polymeric nanocomposites to be used as coating materials. An acrylic-based polymer was prepared by free-radical copolymerization of two monomers widely used for coatings, namely 2-ethylhexylacrylate (EHA) and glycidyl methacrylate (GMA) bearing epoxy moieties, in which silica nanoparticles were incorporated by in situ acid hydrolysis and subsequent condensation of tetraethoxysilane (TEOS). Glycidoxypropyl trimethoxysilane (GPTS) was used as coupling agent to fine-tune the compatibility between organic and inorganic phases. The morphology, mechanical properties and corrosion resistance of thin films applied on aluminum alloys were optimized by varying the content of silica nanoparticles whose properties were strongly affected by the TEOS/GPTS ratios. Performances of the obtained hybrid materials were scrutinized by atomic force microscopy (AFM), differential scanning calorimetry (DSC), thermal gravimetric analysis (TGA), and electrochemical impedance spectroscopy (EIS). Thus it was evidenced that an optimum amount of silica nanoparticles with a precise morphology and composition in term of TEOS/GPTS ratio is needed to maintain good coating barrier properties. Outstanding anti-corrosion protection was reached by using optimized hybrid films.     

Wet adhesion of low-VOC coatings on wood: A quantitative analysis

Adhesion of coatings on wood is most critical under wet conditions. However, the mechanisms controlling the adhesion are not well understood. Therefore, a quantitative analysis of coating adhesion on wood is needed. A new technique is presented to measure the wet adhesion quantitatively based on measuring the forces needed to peel the coating from the wood with a tape. Differences in peel forces corresponded to areas in the wood with a lower or a higher degree of coating penetration. Coatings with better penetration and substrate wetting showed an improved adhesion and the better adhering coatings had an increased level of cohesive failure in the coating. Chemical analysis of the air-faced and wood-faced side of the coatings showed differences in chemical composition. The stored strain energy due to hygroscopic stress could reduce the actual level of adhesion significantly. Surface energy effects did not contribute to reduced adhesion after exposure to water. The interfacial work of adhesion between coating and wood was very much lower than the measured force and lacked correlation with measured differences in adhesion. Therefore, it can be concluded that mechanical anchoring plays a dominant role in obtaining good adhesion of a coating on wood.     

Computer simulation of structure and properties of crosslinked polymers: application to epoxy resins

In this work, a methodology has been developed for construction of atomistic models of crosslinked polymer networks. The methodology has been applied to low molecular weight water soluble epoxy resins crosslinked with different curing agents that are being considered for use as a primer coating on steel. The simulations allowed the crosslink density and the amount of free crosslinking sites in the coatings to be predicted. Shrinkage of the resin upon curing was reproduced by the simulation. In addition, the barrier properties of the model coatings were estimated. The interface between an inorganic substrate and cured epoxy resin has been constructed and the strength and molecular mechanisms of adhesion have been revealed. The developed methodology has a potential to significantly impact on the design and development of new coatings with improved barrier and adhesion properties.     

Electrochemical investigations on the corrosion protection effect of poly(vinyl carbazole)‐silica hybrid sol–gel materials

A series of sol–gel derived organic–inorganic hybrid coatings consisting of organic poly (vinyl carbazole) (PVK) and inorganic silica (SiO₂), with 3‐(trimethoxysilyl)propyl methacrylate (MSMA) as coupling agent, were successfully synthesized. First of all, vinyl carbazole (VCz) monomers are copolymerized with MSMA by performing free‐radical polymerization reactions with AIBN as initiator. Subsequently, as‐prepared copolymer (i.e., sol–gel precursor) was further reacted with various feeding content of tetraethyl orthosilicate (TEOS) through organic acid (CSA)‐catalyzed sol–gel reaction to form a series of PVK‐silica hybrid (PSH) sol–gel materials. The as‐synthesized hybrid materials were subsequently characterized by Fourier‐Transformation infrared (FTIR) spectroscopy and solid‐state ²⁹Si NMR. It should be noted that the PVK‐SiO₂ hybrid (PSH) coating on cold‐rolled steel (CRS) electrode with low silica loading (e.g., 10 phr) was found to be superior in anticorrosion property over those of neat PVK based on a series of electrochemical measurements such as corrosion potential, polarization resistance, corrosion current, and electrochemical impedance spectroscopy in 3.5 wt% NaCl electrolyte. The better anticorrosion performance of PSH coatings as compared to that of neat polymer may probably be attributed to the stronger adhesion strength of PSH coatings on CRS electrode, which was further evidenced by Scotch tape test evaluation. Increase of adhesion strength of PSH coatings on CRS electrode may be associated with the formation of Fe–O–Si covalent bonds at the interface of PSH coating and CRS electrode based on the FTIR–RAS (reflection absorption spectroscopy) studies. POLYM. COMPOS., 2012. © 2011 Society of Plastics Engineers     

Effects of carbon nanotube content on adhesion strength and wear and corrosion resistance of epoxy composite coatings on AA2024-T3

The effects of multiwalled carbon nanotube (MWCNT) content on the adhesion strength and wear and corrosion resistance of the epoxy composite coatings prepared on aluminum alloy (AA) 2024-T3 substrates were evaluated using atomic force microscopy (AFM), blister test, ball-on-disk micro-tribological test and electrochemical impedance spectroscopy (EIS). The adhesion strength of the epoxy composite coatings improved with increasing MWCNT content. Increased MWCNT content also decreased the friction coefficient and increased the wear resistance of the epoxy composite coatings due to improved solid lubricating and rolling effects of the MWCNTs and the improved load bearing capacity of the composite coatings. Finally, EIS indicated that increased MWCNT content increased the coating pore resistance due to a decreased porosity density, which resulted in an increase in the total impedance of the coated samples.     

Adhesion and corrosion resistance of epoxy primers used in the automotive industry

One of the most important factors in corrosion prevention by protective coatings is the loss of adhesion of the coating under environmental influence. Thus, adhesion strength is often used when characterizing protective properties of organic coatings on a metal substrate. In this work, the adhesion of different epoxy primers (pigment-free, zinc-rich and chromate-based) was examined on steel. Both the dry and wet adhesion strengths of organic primers were measured directly by a pull-off standardized procedure, as well as indirectly by the NMP test. The corrosion stability of coated samples was investigated by electrochemical impedance spectroscopy. It was shown that under dry test conditions all the samples showed very good adhesion. However, different trends in adhesion for different primers during exposure to the corrosive agent (3% NaCl solution) were observed. The lowest adhesion values were obtained for chromate-based epoxy primer; however, the change in adhesion of this protective system during immersion in 3% NaCl solution for 25 days was the smallest of all investigated samples. Electrochemical impedance measurements in 3% NaCl solution confirmed good protective properties of pigmented epoxy primers on steel, i.e., greater values of pore resistance and charge-transfer resistance, and smaller values of coating capacitance and double-layer capacitance, were obtained for these protective systems.     

Investigating the role of key ingredients on cathodic delamination resistance of high-build pigmented epoxy coatings

Organic coatings applied on cathodically protected metallic structures must have good resistance to cathodic delamination or disbonding (CD). Both environmental conditions and coating composition influence the CD resistance. In the present study, the effect of types of epoxy resin, curing agents and their mixing ratio on cathodic delamination rate was studied in a high-build pigmented coating. Furthermore, the influence of platey fillers on CD resistance was also studied. In order to bring out correlations, if any, between adhesion and CD resistance, pull-off adhesion strengths (both dry and wet) of these coatings were also measured. Fairly good correlation was found between residual (wet) pull-off adhesion strength and CD resistance. When tested at 60 and 90°C, all the coatings under investigation showed chalking. Among the coatings under investigation, the one based on Bisphenol F epoxy and modified cycloaliphatic amine adduct exhibited excellent CD resistance.     

Imaging in evaluation of polymer coatings adhesion to glass at high humidity

Adhesion reduction occurring after polymer coated glass was immersed in water was studied in a variety of UV-cured urethane acrylate coatings containing alkyloxysilane adhesion promoting additives. It was observed that water accumulated under the coating surface in drops and formed ‘blisters’ in the glass-polymer interface. A non-destructive imaging technique was developed to measure the average size of the water blisters. The size of the water blisters within the interface was correlated with the wet adhesion force measured by coating resistance to 180° peel. The force of coating resistance to 180° peel off glass surface decreased non-linearly with the increase of the average size of the water blisters. It was concluded that the decrease in adhesion between the coating and glass was a result of stretching and breaking of the silane bridging bonds and polymer fibrils by water condensing on the glass surface within the polymer-glass interface. The mathematical model relating coating wet peel resistance force with the size of the debonding produced by water accumulation was presented.     

Formulation and performance evaluation of hydroxyl terminated hyperbranched polyesters based poly (ester–urethane–urea) coatings on mild steel

A low molecular weight, anticorrosive hyperbranched poly (ester–urethane–urea) [HB-P(EUU)] coatings were formulated using 2nd generation hydroxyl terminated hyperbranched polyesters (OH–HBPEs), isophorone di-isocyanate (IPDI) as a cross linking agent and dibutyltin dilaurate (DBTDL) as a catalyst with certain additives. First, NCO terminated prepolymers (HBPEUs) were formulated by reacting OH–HBPEs with IPDI at NCO:OH ratio of 1.1:1 for 4 h at 70–80 °C, then HBPEUs were mixed with DBTDL and various additives and finally coated on pretreated cold rolled mild steel (MS) substrates by dip coating method. Before applying on MS substrates, viscosity and volume solid of coatings were measured. The molecular structure of HBPEUs was characterized by ATR-FTIR and ¹H NMR analysis. Surface morphology of coated panels was characterized by atomic force microscopy (AFM) and found that coating components were homogeneously distributed and surface was smooth and crack free. Performance of coated substrates was evaluated by various tests such as cross hatch and pull off adhesion, abrasion resistance, scratch resistance, impact resistance, flexibility, and pencil hardness. UV stability of coated substrates was evaluated by UV-whether-o-meter and corrosion resistance property was evaluated by salt spray, humidity, polarization and electrochemical impedance (EIS) test. Results were also compared with polyurethane coating based on linear polyester. HB-P(EUU) coatings showed excellent enhancement in mechanical, durability as well as corrosion resistance properties than their linear counterpart.     

Investigation on the Mechanical and Thermal Properties of Intercalated Epoxy/Layered Silicate Nanocomposites

Epoxy resin/layered silicate nanocomposites with various clay contents were prepared. The structural studies showed the intercalation of epoxy polymer chains into the clay galleries. The adhesion analysis of nanocomposite coating films on metallic substrates showed the excellent adhesion of epoxy-based nanocomposite coatings on iron plates, especially in lower clay loadings. According to the hardness test results, the organoclay minerals caused the increasing of the hardness of epoxy nanocomposites. The thermal properties of nanocomposites were evaluated by means of DSC and TGA analysis. The tensile and compression strengths of cured epoxy/clay systems were also investigated.