Performance of zinc phosphate coatings obtained by cathodic electrochemical treatment in accelerated corrosion tests

The formation of zinc phosphate coating by cathodic electrochemical treatment and evaluation of its corrosion resistance is addressed. The corrosion behaviour of cathodically phosphated mild steel substrate in 3.5% sodium chloride solution exhibits the stability of these coatings, which lasts for a week's time with no red rust formation. Salt spray test convincingly proves the white rust formation in the scribed region on the painted substrates and in most part of the surface on unpainted surface. The protective ability of the zinc corrosion product formed on the surface of the coated steel is evidenced by the decrease in the loss in weight due to corrosion of the uncoated mild steel, when it is galvanically coupled with cathodically phosphated mild steel. Potentiodynamic polarization curves reveal that E_corr shifts towards higher cathodic values (in the range of −1000 to −1100 mV versus SCE) compared to that of uncoated mild steel and conventionally phosphated mild steel substrates. The i_corr value is also very high for these coatings. EIS studies reveal that zinc dissolution is the predominant reaction during the initial stages of immersion. Subsequently, the non-metallic nature of the coating is progressively increased due to the formation of zinc corrosion products, which in turn enables an increase in corrosion resistance with increase in immersion time. The zinc corrosion products formed may consist of zinc oxide and zinc hydroxychloride.     

Phenol electropolymerization on phosphated mild steel via zinc electrodeposition

Phenol electropolymerization to polyoxyphenylene coatings on phosphated steel and phosphated galvanized steel, normally impossible under the conditions allowing effective coating formation on either steel or zinc, is activated by cathodic deposition of zinc. A critical zinc amount has been found to be necessary to suppress electrochemical processes competitive with electropolymerization and induce coating formation with nearly 100% efficiency. SEM analysis showed that this critical amount of zinc corresponded to the formation of a low number of zinc nuclei emerging at the surface of the phosphate layer, on which, however, polyoxyphenylene was formed as a continuous coating. A.c. impedance tests showed that initial barrier properties are worse for coatings grown on zinc-plated phosphated samples than for those grown on steel from the same solutions. However, the long term corrosion resistance is much better in the former case, the improvement being largely associated with zinc cathodic protection     

Influence of substrate on the cathodic electrodeposition behavior of waterborne epoxy resins

A modified epoxy–amine adduct was prepared and was then emulsified in water, and was subsequently deposited on a cathode substrate at constant voltage (200 V) or constant current (1 mA/cm²) by the aid of a DC power supply. The cathode was made of different substrates such as bare steel, phosphated steel and aluminum. The results show that the film conductance was greatest on the aluminum substrate which was followed by bare steel and phosphated steel.     

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.     

Surface Composition and Topography of Electrodeposited Polypyrrole Coatings on Steel Substrates

Polypyrrole coatings were successfully electrodeposited on low-carbon steel substrates from aqueous oxalate solutions. The surface composition and topography of the polypyrrole coatings formed under different conditions were investigated by X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). The results show that the surface composition of the electrodeposited polypyrrole coatings basically reflects their bulk composition. Deposition of polypyrrole coatings on steel substrates also increased the surface roughness of the steel substrates.     

Surface Composition and Topography of Electrodeposited Polypyrrole Coatings on Steel Substrates

Polypyrrole coatings were successfully electrodeposited on low-carbon steel substrates from aqueous oxalate solutions. The surface composition and topography of the polypyrrole coatings formed under different conditions were investigated by X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). The results show that the surface composition of the electrodeposited polypyrrole coatings basically reflects their bulk composition. Deposition of polypyrrole coatings on steel substrates also increased the surface roughness of the steel substrates.     

Adhesion and tribological properties of TiTaBN coatings with a graded interlayer deposited by pulsed DC biased and continuous dc biased magnetron sputtering

The properties of TiBN-based coatings are significantly affected by adding alloying elements and coating parameters. Therefore, in this study, TiTaBN coatings with graded interlayer (CWGIL) were deposited on D2 steel substrates by pulsed DC biased (PDCB) and continuously DC biased (CDCB) closed field unbalanced magnetron sputtering (CFUBMS). The structural, mechanical, adhesion and tribological properties of the coatings were analysed with EDS, SEM, XRD, microhardness, scratch testing and a pin-on-disc tribo-tester (under various atmospheric conditions). TiTaBN CWGIL deposited by PDCB magnetron sputtering (MS) had a very dense microstructure, high hardness and a high critical load value. TiTaBN CWGIL deposited by PDCB MS had a lower friction coefficient, the wear rate and the penetration depth in all atmospheric conditions. In conclusion, the application of a PDCB substrate instead of a CDCB one dramatically increases the performance of CFUBMS-deposited TiTaBN coatings.     

Behaviour of intact and scratched phosphate coatings on zinc, zinc–nickel and mild steel in dilute sodium phosphate solution

Impedance measurements were performed at room temperature in a 0.005 M Na₂HPO₄ solution on steel and on electrodeposited Zn and Zn–12%Ni before and after phosphating. It was found that potential and impedance parameters (R _ct and C _d) for phosphated materials attained nearly steady values within about 20 min, indicating that this solution did not cause meaningful changes in phosphate coatings and that it could therefore be used for the quality evaluation of these coatings. On scratches in phosphate coatings on Zn or Zn–12%Ni phosphate deposits rapidly formed, probably owing to enhanced dissolution of the locally exposed substrates at the nobler potentials of the coated materials. This demonstrates that damaged coatings can easily recover on Zn substrates in a non-aggressive phosphate solution. It is suggested that the formation of phosphate deposits on bare metal amidst phosphate coatings should be taken into account in the porosity determination by chemical or electrochemical methods.     

Corrosion behavior of nanohybrid titania–silica composite coating on phosphated steel sheet

Corrosion resistance behavior of sol–gel-derived organic–inorganic nanotitania–silica composite coatings was studied. Hybrid sol was prepared from Ti-isopropoxide and N-phenyl-3-aminopropyl triethoxy silane. The structure, morphology, and properties of the coating were characterized by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and thermo gravimetric analysis. The corrosion performances of the sol–gel-coated samples were investigated by electrochemical impedance spectroscopy (EIS) and standard salt spray tests. The hybrid coatings were found to be dense, more uniform, and defect free. In addition, the coatings also proved its excellent corrosion protection on phosphated steel sheet.     

Adhesion characteristics and corrosion stability of epoxy coatings electrodeposited on phosphated hot-dip galvanized steel

The influence of hot-dip galvanized steel (HDG) surface pretreatment with phosphate coatings on the corrosion stability and adhesion characteristics of epoxy coatings electrodeposited on HDG steel was investigated. Phosphate coatings were deposited on hot-dip galvanized steel from baths with different concentrations of NaF (0.1, 0.5 and 1.0 g dm⁻³) and at different temperatures (50, 65 and 80 °C). The influence of fluoride ion concentration in the phosphating bath, as well as the deposition temperature of the bath, on the adhesion characteristics and corrosion stability of epoxy coatings on phosphated HDG steel was investigated. The dry and wet adhesions were measured by a direct pull-off standardized procedure, as well as indirectly by NMP test, while corrosion stability was investigated by electrochemical impedance spectroscopy (EIS).     

Phenol electropolymerization: a straight route from monomers to polymer coatings

Recent results on phenol electropolymerization aimed at the simultaneous production and deposition of protective coatings are described. Discussion is especially focused on the electrochemical growth mechanism of the non-conducting polymer films (previously unpublished chronoamperometric and chronopotentiometric results are provided and compared with a simple model), incorporation of corrosion inhibitors, the selected inhibitor being 2-benzothiazolylthiosuccinic acid, coating of phosphated mild steel and phosphated galvanized steel via the cathodic deposition of minor Zn amounts in the phosphate layer pores and protective performance of the coated samples, studied by a.c. impedance. It is shown that significant advances have been achieved since 1987, when a comprehensive review was published, in both the fundamental understanding of the process and the protective capabilities of the coatings.     

附着力促进剂对光固化金属涂层附着力提升的研究

为了探究附着力促进剂对光固化金属基涂层附着力的影响，本文通过划格法、拉拔法及搭接剪切实验，系统研究了磷酸酯类附着力促进剂、硅烷偶联剂对光固化金属基（低碳钢、铝板）涂层附着力的促进作用。结果表明：磷酸类附着力促进剂能够显著提高光固化金属基（低碳钢、铝板）涂层的附着力，而硅烷偶联剂对光固化金属基（低碳钢、铝板）涂层的附着力无明显提升作用。     

In-situ phosphatizing coatings III: A water-reducible alkyd baking enamel

We report the successful formulation of stable and compatible in-situ phosphatizing coatings (ISPCs) for a waterborne alkyd-amino baking enamel applied on bare cold-rolled steel (CRS), iron phosphated Bonderite 1000 (BD), and iron phosphated plus Parcolene 60 chromated (BD+P60) coupons. The enhanced coating adhesion of water-based ISPCs is confirmed by the cathodic delamination measurements. After 100 hr of salt spray (fog) test, the corrosion resistance performance (measured by the corrosion disbondment across the “X” scribe, d in mm) of the water-based ISPC on CRS panel (d=4.0−7.0 mm) outperformed that of the control alkyd paint on B-1000 (d=26 mm) and also on BD+P60 (d=14 mm) coupons. The superior coating performance of water-based ISPCs is believed to result from the in-situ metal surface phosphatization as detected by the reflectance FTIR technique. Department of Chemistry and Biochemistry, DeKalb, IL 60115-2862.     

Inhibition of nickel coated mild steel corrosion by electrosynthesized polyaniline coatings

Polyaniline (PANI) coatings were electrochemically synthesized on nickel (Ni) coated mild steel (MS) and their corrosion protection properties were investigated. In this work, the Ni layer (∼1 μm thick) was electrodeposited on MS under galvanostatic condition. Thereafter, the PANI coating was deposited over the Ni layer from aqueous salicylate medium by using cyclic voltammetry. These bi-layered composite coatings were characterized by cyclic voltammetry, UV–vis absorption spectroscopy and Fourier transform infrared (FTIR) spectroscopy. The corrosion protection properties of Ni coated MS (Ni/MS) and PANI coated Ni/MS (PANI/Ni/MS) were investigated in aqueous 3% NaCl by using open circuit potential (OCP) measurements, potentiodynamic polarization technique and electrochemical impedance spectroscopy (EIS). It was shown that the top layer of PANI exhibits a lower porosity behavior with respect to Ni coating and reduces the corrosion rate of Ni/MS almost by a factor of 3500 and increases the lifetime of Ni coating.     

纳米SiO2改性阴极电泳漆的制备及耐蚀性研究

以获得纳米二氧化硅改性阴极电泳漆为目的,用硅烷偶联剂在水介质中分散纳米SiO2粉体,通过分散液的吸光度来评价分散效果.然后将分散后的纳米粉体添加到阴极电泳漆中得到纳米改性电泳漆.试片经磷化-电泳涂装后得到复合涂层,并对复合涂层的耐蚀性能进行评价.金相显微观测表明,纳米改性电泳漆膜表面有较均匀的小突起,而未改性复合膜层表面比较光滑.吸水性测试表明,与未改性复合漆膜相比,改性后的复合涂层漆膜疏水性能有一定提高.耐酸、碱性试验表明,改性复合膜层的耐酸性明显优于未改性复合膜层,两种复合膜层的耐碱性都较好.     

Novel isocyanate-free self-curable cathodically depositable epoxy coatings: Influence of epoxy groups on coating properties

Novel self-curable cathodically depositable coatings were developed from glycidyl functional epoxy ester-acrylic graft co-polymer (EEAG) without using any external crosslinking agents. The EEAG-amine adducts (EEAGAs) were prepared by reacting EEAG with varying amount of diethanolamine (DEoA) which are neutralized with acid and dispersed in deionised water to give stable dispersion for cathodic electrodeposition (CED) coatings. The dispersions were cathodically electrodeposited on phosphated steel panels and thermally cured to give uniform coating. The coatings were evaluated for different mechanical, chemical and corrosion resistance properties. The coatings were evaluated for their thermal properties using thermo gravimetric analysis (TGA). The final properties of the coatings were found to be affected by the amount of amine reacted with epoxy. The coating films showed good overall performance properties for their use in coating industry.     

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.     

Effect of conducting composite carbon nanotube‐poly(o‐toluidine) coatings on the corrosion resistance of stainless steel material

This study examines the use of poly(o‐toluidine) (POT) coatings and poly(o‐toluidine)/oxidized multi‐walled carbon nanotubes (POT‐MWCNT) composite on 304 stainless steel for corrosion protection. The POT coatings and its composite were synthesized on steel substrates under cyclic voltammetric conditions. These coatings were characterized by cyclic voltammetry (CV), Fourier transform infrared (FTIR) spectroscopy, and scanning electron microscopy (SEM). The ability of POT and its composite to serve as a corrosion protective coating was examined by potentiodynamic polarization, CV, and potential‐time measurements. The nanocomposite layers as well as the pure POT layer keeps the stainless steel in a passive state. POLYM. COMPOS., 34:1180–1185, 2013. © 2013 Society of Plastics Engineers     

Adhesion of poly(m-, p-phenylene isophtalamide) coatings to metal substrates

The adhesive properties of wear-resistant poly(m-, p-phenylene isophtalamide) coatings to substrates of ferrous and non-ferrous metal materials which are the most common in mechanical engineering were investigated experimentally. The results of measurements of adhesive characteristics taken with the help of such methods as a cross cutting test, a quantitative peel test, a lap shear strength test, a contact angle test and a spreading radius test are discussed in terms of the three most common mechanisms of adhesion: mechanical coupling, molecular bonding, and thermodynamic adhesion. It was established that the adhesive properties of poly(m-, p-phenylene isophtalamide) coatings depend on the content of a ferrite component in the structure of carbon steel substrates.     

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.