The role of basecoat pigmentation on the biological resistance of an automotive clearcoat

This work aims to study the effect of various natural and artificial biological compounds on an automotive acrylic/melamine clearcoat applied over silver and black basecoats containing pigments. The visual performance of the coating system was evaluated at different aging conditions. To this end, analytical techniques including optical microscopy, scanning electron microscopy, gonio-spectrophotometery, gloss measurement, ATR-FTIR spectroscopy, and DMTA analysis were utilized to investigate the optical and mechanical response of the system upon exposure to the biological materials. Results indicated different effects produced by gums and bird droppings on both silver and black systems at all aging processes. In addition, a more severe effect of biological attacks was observed on the clearcoat samples applied on the black basecoat which had experienced postaging conditions. However, it was found that pancreatin and bird droppings influence the coating systems more severely compared to the natural and synthetic Arabic gums.     

An evaluation of an automotive clear coat performance exposed to bird droppings under different testing approaches

In this study, the effects of two types of biological materials, i.e. natural bird droppings and pancreatin, on properties of an automotive acrylic melamine clear coat were studied. In addition, two different testing approaches including pre-aging and post-aging were utilized to investigate the biological resistance. To this end, effects of these biological materials on clear coat surface properties and appearance were investigated by different techniques including digital camera, SEM, AFM, optical microscopy and a gloss meter. In addition the mechanical properties of clear coats were evaluated by micro Vickers measurement and DMTA analysis. For further investigation FTIR analysis was utilized to have a more understanding of the failure mechanism.Results showed that the biological materials have an extremely vital effect on the appearance of the coatings. Decreasing of t_g and hardness of the films made by pancreatin and bird droppings were observed and were attributed to the chemical alterations as proved by FTIR analysis. It was also found that the biological degradation occurred on the samples experienced the post-aged testing method was more severe than the samples exposed to pre-aged testing. On the other hands, although bird droppings and pancreatin revealed a same failure mechanism, the effect of the former was more severe. In addition, it has been shown that the enzymatic structure of biological materials is responsible for the catalyzing the hydrolytic degradation of clear coat at neutral pH. Therefore, the biological degradation mechanism may be regarded as an enzymatically induced hydrolytic cleavage.     

A mechanistic study of degradation of a typical automotive clearcoat caused by bird droppings

This study aims at investigating the degradation mechanism of an automotive clearcoat caused by bird droppings. Natural bird droppings and their synthetic equivalent (pancreatin) were utilized for this purpose. The presence of highly-etched areas on the surface of coatings and structural variations of clearcoat after being attacked by these materials corresponded to a catalyzed hydrolytic degradation. This finding was obtained using different analytical techniques. Based on these studies, three possible hypotheses were presented, including acid catalysis, metal ion catalysis, and enzymatic catalysis. The conditions required for the occurrence of each hypothesis were discussed. It was found that acid and metal ions have a weak contribution to catalyze the hydrolysis reaction of clearcoat, whereas enzymes existing in bird droppings were mainly responsible for this hydrolytic degradation.     

Electrochemical impedance spectroscopy; a tool for organic coatings optimizations

Electrochemical impedance spectroscopy (EIS) was applied to the optimization of automotive electrodeposited coatings, container interior coatings and industrial maintenance coatings. The electrochemical impedance data were used to predict corrosion protection, film porosity, solution absorption into the coatings and film delamination properties. Variables such as resin contents, crosslink densities, cure temperatures, and solvent types and contents were evaluated for these various types of coatings. In general the electrochemical impedance data correlated well with conventional exposure tests results such as salt fog, cyclic scab corrosion and delamination tests. The impedance spectra permits a rather rapid (15–75 min per sample) assessment of the film's characteristics even when no visually observable changes have occurred. Electrochemical impedance spectroscopy provides a technique to optimize coatings while reducing the time of coating evaluations and gives insight into the chemical and physical properties of the coatings.     

Investigation on corrosion and wear resistance of MgO-Al2O3 composite coating prepared by plasma electrolytic oxidation

Ceramic coatings were prepared on 6061 Al alloy in a mixed electrolyte with/without MgO powders at different treatment durations. The results of energy dispersive spectroscopy (EDS) and X-ray diffraction (XRD) showed that MgO powder was incorporated into the coatings, and Mg species gradually aggregated into coating inside as prolonging the oxidation time. Scanning electron microscopy (SEM) showed that MgO additive had a certain effect on the microstructures and coating thickness. The corrosion behavior tests evaluated by potentiodynamic polarization tests and electrochemical impedance spectroscopy (EIS) in 3.5 wt% NaCl solution suggested that at the same treatment time, the addition of MgO powders can improve the corrosion resistance of the coating, and the Mg-rich layer can affect the corrosion resistance of the coating. The tests of mechanical properties showed that the addition of MgO powders improved the stability and hardness of the coating.     

Investigating the degradation resistance of silicone-acrylate containing automotive clearcoats exposed to bird droppings

This work reports preparation of acrylic/melamine based clearcoats containing various loads of a reactive polysiloxane additive. The additive was incorporated into the clearcoat formulations up to 8 wt% to enhance its resistance against bird droppings. Contact angle measurements, ATR spectroscopy, energy dispersive X-ray analysis, appearance measurements together with different microscopic techniques were utilized to reveal the effects of additive on the properties of the coating prior and after exposure to pancreatin, the synthetic equivalent of natural bird droppings. Appearance measurements, as well as optical microscope images obviously indicated that the additive improved the clearcoats resistance against pancreatin. Results revealed that surface free energy of the films was reduced in the presence of additive. It was also found that at high concentrations of additive, a significant part of it remained in the bulk, forming a second phase. This resulted in a lack of sufficient reactive groups and lead to an under-cure state at the clearcoat surface.     

Polyurethane coatings: a perfect product class for the design of modern automotive clearcoats

This paper gives a brief background of 2 K polyurethane coatings for automotive exterior application. Basic properties that make this class of raw materials such an important and successful one are described. Additionally, a helpful method for characterization of basic mechanical parameters is given and chemical strategies for improving the mechanical strength of this type of coating are reviewed. © 2018 Society of Chemical Industry     

Composite coatings of lanthanum-doped fluor-hydroxyapatite and a layer of strontium titanate nanotubes: fabrication,bio-corrosion resistance,cytocompatibility and osteogenic differentiation

Poor bio-corrosion resistance and undesirable incomplete osseointegration restrict the application of hydroxyapatite (HA) as an implant coating material. In this study, a novel F-and-La co-substituted hydroxyapatite (FLaHA) coating, which was reinforced with strontium titanate nanotubes (STNTs), was applied on Ti substrates using a combination method of anodization, electrochemical deposition and hydrothermal treatment. To the best of our knowledge, this is the first report on the development of FLaHA/STNT coatings for improving the chemical stability and the mechanical and biological properties of Ti substrates. The STNT exhibits an evenly-distributed porous and latticed structure on Ti substrates that favours the infiltration of FLaHA crystals. Different characterisation techniques, such as x-ray photoemission spectroscopy, x-ray diffraction, field-emission scanning electron microscopy and energy-dispersive spectroscopy, have clearly confirmed the successful synthesis of STNT-FLaHA coatings that constitute oriented nanorod arrays. Isolated hexagonal nanorod grains, with diameters of 200–300?nm, that stand on a substrate provide a uniform morphology to the surface of electrodeposited thin films at micro-scales. The survival of the coatings was prolonged because of their good degradation resistance. Owing to the anchoring effect of the STNT layer, the adhesion strength of the FLaHA/STNT coating was 15.9?±?5.4?MPa, which was two times higher than that of STNT-free HA coatings. The potentiodynamic polarisation curves and the Nyquist plot confirmed that the conversion coating significantly improved the bio-corrosion resistance of the Ti substrates in the SBF solution. Roughness and hydrophilicity of the control HA layer were even greater than those of the FLaHA/STNT coating. However, it provided better cell adhesion, spreading, proliferation and osteogenic differentiation for mouse pre-osteoblasts cells. That is, the FLaHA/STNT coating could enhance osteoconductivity by improving the cell-adhesion, proliferation and differentiation of osteoblast. Therefore, FLaHA/STNT nanocomposite coatings can be used as implant materials with multi-functional properties, such as good biocompatibility and high mechanical and corrosion-inhibiting properties.     

Electrochemical characterisation of protective organic coatings for food packaging

A very common material for food packaging is steel, in the form of metallic containers (cans), in particular for beverage packaging. The corrosion degradation of the packaging must be carefully controlled, not only because the packaging integrity must be preserved, but also in order to avoid any significant contamination of the food or drink, compromising the flavour. In order to increase the coating performance and the food compatibility, new organic coatings are under development with very high protective properties, with the final aim to increase the shelf life of the product. An electrochemical characterisation is often used to study the protective performance of organic coatings on metal substrate for various applications. Some different coatings for food packaging were considered in the present study, including materials with different chemical composition and different pigments content. The protective properties were quantified using electrochemical impedance spectroscopy (EIS) measurements, comparing the electrochemical substrate activity with electrochemical noise (EN) and scanning Kelvin probe (SKP) measurements. The influence of mechanical deformations on the protective properties was also investigated. The results obtained on the studied coatings confirmed the validity of the electrochemical approach and showed that, in general, the coatings containing pigments (TiO₂) have better performance than clearcoats, while comparing the different polymers, epoxy–phenolic coatings have a better corrosion protection than epoxy–melamine coatings.     

Organic‐Inorganic Hybrid Coatings Based on Polyfunctional Silanols as New Monomers in Sol‐Gel Processing

Organic‐inorganic hybrid materials offer the opportunity to combine the desirable properties of organic polymers (toughness, elasticity) with those of inorganic solids (hardness, chemical resistance). Since improved mechanical and chemical resistance is an increasing demand for various coating applications, hybrid materials were developed based on polyfunctional silanols as new monomers in sol‐gel processing. After hydrolysis and condensation with different co‐reactants, coatings with superior optical and mechanical properties are obtained at ambient temperature. Such hybrid coatings show excellent chemical resistance and high UV stability. Although the adhesion to many substrates is good without additional pretreatment, the hybrid coatings exhibit a very anti‐adhesive surface. Due to these properties potential applications include automotive clear coats, hard coats for plastics, anti‐graffiti coatings and biocide‐free fouling‐release coatings.     

The effects of weathering on the mechanical performance of automotive paint systems

The durability of automotive paint systems continues to be a great concern to both auto companies and their coating suppliers. Recent advances in assessing the durability of coatings by measuring weathering-induced chemical composition changes have greatly increased our ability to discern superior from inferior coatings. However, different coatings will likely tolerate different amounts of weathering-induced chemical composition changes while still maintaining their mechanical integrity. Thus, a means of linking chemical composition changes to changes in relevant mechanical properties would be highly desirable. The fracture energy, the amount of mechanical energy required to propagate a crack in a material, is a sensitive measure of the brittleness of a material and is relevant to a number of potential failure mechanisms in automotive paint systems. The fracture energy of clearcoats can vary widely depending on the formulation of the clearcoat (initial chemical composition and additive package) and on the amount of weathering. Weathering embrittles most coatings. Weathering-induced changes in the fracture energy are related to chemical composition changes occurring in the clearcoat. Because the brittlest materials will not crack without an applied stress, the stress distribution in complete paint systems as a function of weathering must also be known to accurately anticipate mechanical failures. Measuring thermoelastic constants of individual layers allows for computation of the stresses in complete paint systems. Stresses tend to increase with weathering. The presence of flaws in the clearcoat changes the stress distribution dramatically. Coupled with fracture energy measurements, the stress measurements provide additional insight into paint system failure mechanisms.     

Studying the effects of the chemical structure of an automotive clearcoat on its biological degradation caused by tree gums

The effects of artificial and natural tree gums on the mechanical, chemical, and aesthetic performances of two automotive acrylic/melamine clearcoats were studied. To this end, two clearcoats with different acrylic/melamine ratios were investigated. Biological experiments were performed under post-aging conditions using an accelerated weathering test. Analytical techniques including optical microscopy, scanning electron microscopy (SEM), gloss measurement, FTIR, and DMTA analyses were utilized to reveal the responses of the coating system upon exposure to the aforementioned biological materials. Contact angle measurements were also conducted to estimate the surface energy of the coatings. Greater crosslinking density, together with a higher T _g and damping behavior of the clearcoat, indicative of a greater degree of cure, were obtained as the ratio of melamine crosslinker increased. It was shown that both Arabic and natural tree gums could strongly attach to the clearcoats’ surface, imposing a significant stress during the drying process, thereby leading to a physical failure. In addition, the acidic nature of these biological materials leads to a chemical alteration in the clearcoats’ structure. The greater crosslinking density and lower hydrophilicity of the clearcoats containing higher melamine crosslinker were responsible for the weaker interaction of gums with the surface. This showed a greater capability for stress damping. Small surface cracks with fracture morphology on the coatings exposed to biological materials at higher exposure times (in the xenon test) were also observed. This is discussed based on the adhesion of the coatings to gums at longer exposure times, because of significant stress.     

In Vitro Corrosion and Cytocompatibility of ZK60 Magnesium Alloy Coated with Hydroxyapatite by a Simple Chemical Conversion Process for Orthopedic Applications

Magnesium and its alloys—a new class of degradable metallic biomaterials—are being increasingly investigated as a promising alternative for medical implant and device applications due to their advantageous mechanical and biological properties. However, the high corrosion rate in physiological environments prevents the clinical application of Mg-based materials. Therefore, the objective of this study was to develop a hydroxyapatite (HA) coating on ZK60 magnesium alloy substrates to mediate the rapid degradation of Mg while improving its cytocompatibility for orthopedic applications. A simple chemical conversion process was applied to prepare HA coating on ZK60 magnesium alloy. Surface morphology, elemental compositions, and crystal structures were characterized using scanning electron microscopy, energy dispersive spectroscopy, and X-ray diffraction, respectively. The corrosion properties of samples were investigated by immersion test and electrochemical test. Murine fibroblast L-929 cells were harvested and cultured with coated and non-coated ZK60 samples to determine cytocompatibility. The degradation results suggested that the HA coatings decreased the degradation of ZK60 alloy. No significant deterioration in compression strength was observed for all the uncoated and coated samples after 2 and 4 weeks’ immersion in simulated body fluid (SBF). Cytotoxicity test indicated that the coatings, especially HA coating, improved cytocompatibility of ZK60 alloy for L929 cells.     

Preparation and physicochemical characterization of hydroxyapatite coatings on zinc surfaces

This work presents a study on an alternative coating method based on electrochemical techniques which are designed to form a crystalline hydroxyapatite layer very similar to the process corresponding to the formation of natural bone. In this study, a sample electrochemical method of coating the solid surfaces of zinc, with a film of apatite, was developed. The hydroxyapatite deposit was investigated by means of scanning electron microscopy, X-ray diffraction, infrared spectroscopy, and chemical analysis. The data suggest that the method utilized in this work can be successfully applied to obtain deposition of uniform coatings of crystalline hydroxyapatite on zinc substrates. As a result, both the lattice parameters a and c of the apatite layer decreased with increasing Zn fraction.     

An improved accelerated weathering protocol to anticipate Florida exposure behavior of coatings

A new accelerated weathering protocol has been developed which closely replicates the performance of automotive and aerospace coating systems exposed in South Florida. IR spectroscopy was used to verify that the chemical composition changes that occurred during accelerated weathering in devices with a glass filter that produced a high fidelity reproduction of sunlight’s UV spectrum matched those that occurred during natural weathering. Gravimetric water absorption measurements were used to tune the volume of water absorption during accelerated weathering to match that which occurred during natural weathering in South Florida. The frequency of water exposure was then scaled to the appropriate UV dose. A variety of coating systems were used to verify the correlation between the physical failures observed in the accelerated weathering protocol and natural weathering in South Florida. The new accelerated weathering protocol correctly reproduced gloss loss, delamination, cracking, blistering, and good performance in a variety of diverse coating systems. For automotive basecoat/clearcoat paint systems, the new weathering protocol shows significant acceleration over both Florida and previous accelerated weathering tests. For monocoat aerospace systems, the new weathering protocol showed less acceleration than for automotive coatings, but was still an improvement over previous accelerated tests and was faster than Florida exposure.     

Electrochemical study of corrosion behavior of graphene coatings on copper and aluminum in a chloride solution

Electrochemical characteristics and corrosion behavior of graphene coatings on Cu and Al in a 0.1 M NaCl solution were investigated. The graphene coatings were deposited on a Cu surface by chemical vapor deposition. Multiple graphene layers were then mechanically transferred from the growth substrate, Cu, onto Al surface by a transfer technique. The corrosion stability of graphene coatings was determined by electrochemical impedance spectroscopy and open circuit potential, while the corrosion rate was evaluated using potentiodynamic sweep measurements. Surface morphologies of the graphene coatings were analyzed by scanning electron microscopy and energy dispersive spectroscopy. Obtained results indicate that Cu coated with graphene grown using chemical vapor deposition shows corrosion-inhibiting properties in 0.1 M NaCl. On the other hand, Al coated with a multilayer graphene film mechanically transferred from the Cu surface exhibits electrochemical characteristics similar to an Al oxide on bare Al. Better protective properties of graphene coating on Cu compared to the graphene coating on Al were observed, probably due to the breakage of Al oxide film, causing the corrosion of Al to proceed rapidly in the presence of chloride electrolyte.     

Hydroxyapatite-carboxymethyl cellulose-graphene composite coating development on AZ31 magnesium alloy: Corrosion behavior and mechanical properties

In this study, hydroxyapatite (HA) coatings containing carboxymethyl cellulose (CMC) and graphene (Gr) were developed on AZ31 magnesium alloy through two-step electrophoretic deposition method. The morphology and chemical bonding of coatings were characterized and also the phase identification was done using scanning electron microscopy, Fourier transform infrared spectroscopy, and X-ray diffraction, respectively. Moreover, the corrosion behavior of the applied coatings was compared with the bare AZ31 Mg alloy substrate in the simulated body fluid by the means of potentiodynamic polarization test and electrochemical impedance spectroscopy. Obtained results revealed that the novel HA-CMC-Gr coating possesses the highest corrosion resistance compared to the HA, HA-CMC, and HA-Gr coatings due to its uniform and compact structure. To investigate the mechanical properties and to elucidate the effect of CMC on the adhesion of coating-alloy interface, pull-off test was employed, where results demonstrated that the addition of CMC increases the adhesion force from 1.06 MPa to 1.62 MPa. Besides, the modulus of elasticity and the hardness of HA and HA-Gr composite coatings were compared by applying nanoindentation test. Interestingly, it is detected that the presence of Gr has considerably increased the elastic modulus of the coating by approximately 30% in comparison to the pure HA coating.     

A novel composite protective coating with UV and corrosion resistance: Load floating and self-cleaning performance

The research in functional materials has been the focus in studying industrial applications, particularly in the field of superhydrophobic functional bionic material. Although many studies of superhydrophobic surfaces have been published at this stage, the performance remain unsatisfactory, especially in a variety of harsh environments in practical applications, such as extremely cold weather, acidic or alkaline environment, prolonged exposure to light, high temperature, or oily wastewater, etc. The mechanical strength and corrosion resistance of coatings in such environments are all mighty challenges. In this study, we propose a fluoro silane-modified zinc oxide (FAS-ZnO) as a nano-filler. A superhydrophobic and oleophobic composite coating was successfully prepared through a single step by spraying suspensions containing attapulgite (ATP), FAS-ZnO, and carboxylated polyphenylene sulfide (PPS–COOH) onto desired substrates. In addition, stearic acid was added as a binder and used to enhance the bonding strength between the filler and the substrate. The composite coatings were characterized by FE-SEM, XRD and FT-IR on substrates, and the corrosion resistance of the coatings was evaluated by electrochemical impedance spectroscopy (EIS) and salt spray chamber experiments. The composite coatings showed excellent corrosion resistance due to the synergistic effect of FAS-ZnO and ATP. It was found that the composite coating had good hydrophobic and oleophobic contact angles of 161 ± 1.5° and 159 ± 1°, respectively, which were mainly attributed to the construction of nano-scale structures. It is worth noting that the composite coating performed excellently in chemical stability, self-cleaning performance, UV resistance, anti-fouling function, mechanical strength, and load-bearing floating ability. The coating maintained its highly hydrophobic surface after being stretched through a universal testing machine. Based on the multiple key properties in the composite coating, it can be expected to be applied to large equipment and instrument surfaces in extreme outdoor environments.     

The investigation of the tribocorrosion properties of DLC coatings deposited on Ti6Al4V alloys by CFUBMS

Various machine components produced from titanium alloys used in various industries are subject to a combination of electrochemical and mechanical effects. The science of surface transformations resulting from the interaction of mechanical loading and chemical reactions that occur between elements of a tribosystem exposed to corrosive environments is described as tribocorrosion. This research focuses on the tribocorrosion behaviour of Ti6Al4V alloys after coated by using closed field unbalance magnetron sputtering (CFUBMS). The structural analyses of the coatings were performed using Raman spectroscopy and scanning electron microscopy (SEM). Tribocorrosion experiments were performed in a pin-on-disc tribotester under electrochemical polarisation in NaCl 1 wt.% solution. This study shows that the Ti-DLC coating is protecting the Ti6Al4V alloy and having good performance in corrosion and tribocorrosion conditions. The OCP values for Ti6Al4V substrate and Ti-DLC protective coatings during tribocorrosion tests were measured as −560 V and −330 V, respectively. These results showed that Ti-DLC protective coating on Ti6Al4V substrates increased the tribocorrosion resistance by acting as a barrier layer.     

Comparison of electrochemical behavior of CrN single-layer coating and Cr/CrN nanolayered coating produced by cathodic arc evaporation physical vapor deposition

The aim of the present work is to study the CrN single-layer coating and the Cr/CrN nanolayered coating by cathodic arc evaporation physical vapor deposition (CAE-PVD) on AISI 304 stainless steel and to assess the electrochemical behavior of the coatings. Field emission scanning electron microscopy (FE-SEM) and X-ray diffraction (XRD) were utilized to study the morphology and microstructure of the coatings. The mechanical behavior of the coatings was studied by the nanoindentation technique. The electrochemical behavior of the formed coatings in 3.5 wt.% NaCl solution was investigated via electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization (PDP) tests. Based on the microscopic images, it was realized that both CrN and Cr/CrN coatings were formed having a dense structure on the substrate. The results of EIS measurements showed gradual changes in the polarization resistance of the Cr/CrN nanolayered coating during the immersion time. However, significant changes in the polarization resistance of the CrN single-layer coating were seen by increasing immersion time comparing with the Cr/CrN coating. The higher polarization resistance of the Cr/CrN coating can be attributed to the effects of the interface between the layers in comparison to the CrN coating.