Characterization of ceramic sol-gel coatings as an alternative chemical conversion treatment on commercial carbon steel

Sol-gel yttria-stabilized zirconia (YSZ) thin films were prepared on commercial carbon steel sheets by dip-coating technique followed by a low temperature heat treatment (473, 573, and 673 K for 1 h) in order to improve both corrosion properties and adhesion. For comparison, zirconia (ZrO₂) coatings have been also analyzed. Electrochemical techniques, Fourier Transform Infrared (FT-IR), X-ray diffraction (XRD) and scanning electron microscopy (SEM) were used to characterize the anticorrosion behavior of the coatings in a 3.5 wt% NaCl solution. The adhesion with a polyester organic coating was evaluated by the pull-off technique. The typical thickness of the deposited layers ranged from 1 to 1.3 μm depending on process parameters. The obtained results indicated that sol-gel ZrO₂ and YSZ coatings without an organic coating can act as protective barriers against wet corrosion during the first hours, but they fail when the time exposure is longer than 1 day. However, when synthesized films were used as a pre-treatment and an organic coating was added (top-coated), the anticorrosive and adhesion properties were strongly affected by the temperature of the treatment, and an increase in both properties was observed at higher temperatures. The structural and morphological characteristics of the coating provide an explanation of the role of each film in the electrochemical behavior in this aggressive medium. Comparing both systems, YSZ displayed greater protective and adhesion values than exhibited for ZrO₂ which can be correlated with the stabilization of the cubic phase.     

Electrochemical corrosion and materials properties of reactively sputtered TiN/TiAlN multilayer coatings

TiN/TiAlN multilayers of 2 μm thickness were successfully prepared by reactive DC magnetron sputtering method. XRD pattern showed the (1 1 1) preferential orientation for both TiN and TiAlN layers. XPS characterization showed the presence of different phases like TiN, TiO₂, TiON, AlN and Al₂O₃. Cross sectional TEM indicated the columnar growth of the coatings. The average RMS roughness value of 4.8 nm was observed from AFM analysis. TiN/TiAlN coating showed lower friction coefficient and lower wear rate than single layer coatings. The results of electrochemical experiments indicated that a TiN/TiAlN multilayer coating has superior corrosion resistance in 3.5% NaCl solution.     

Effect of arc current on microstructure,texturing and wear behavior of plasma sprayed CaZrO3 coatings

In order to enhance the biocompatibility of metallic implants, various ceramic coatings are currently in vogue. CaZrO₃, a promising candidate material, was deposited through plasma spraying on stainless steel (316L) substrates at arc currents of 400, 500 and 600 A. The coatings were characterized using a SEM, XRD, surface profilometers and a tribometer. It was found that the arc current had profound effects on the thickness, microstructure, phase evolution, crystallinity and wear behavior of the coatings. The cross-sectional images and fractographic analysis showed that a denser coating with better inter-splat fusion was produced at arc current of 600 A. The average roughness (Ra) of the coatings increased from 3.62 to 6.68 μm as the arc current was increased from 400 to 600 A. The feedstock (powder) and the coatings were predominantly composed of CaZrO₃ along with a minor amount of CaZr₄O₉ phase. The rise in the arc current resulted in a slight increase in the relative proportion of the CaZrO₃ phase. Also, the coating produced at arc current of 600 A exhibited highest crystallinity. The detailed XRD analysis of (002) and (200) reflections of the ferroelectric CaZrO₃ revealed the preferred orientation of crystals in the coatings. The presence of this texture is explained on the basis of shifting the unstable Zr⁴⁺ ion in oxygen octahedral cage preferably in one direction. The increase in the arc current decreased the coefficient of friction and, as a result, relatively better wear resistance was observed for the coating produced using higher arc current. Moreover, the coating fabricated using arc current of 600 A reduced the volumetric weight loss by 13 times during the wear test as compared to the substrate. Plasma sprayed CaZrO₃ coating not only enhanced the wear resistance of the stainless steel but also showed the potential to furnish a bioactive surface.     

Microstructure and performance of block copolymer modified epoxy coatings

The effects of two diblock copolymers, poly(ethylene-alt-propylene)-b-poly(ethylene oxide) (PEP–PEO) and poly(1,2-butadiene)-b-poly(2-vinyl pyridine) (PB–P2VP) on the mechanical properties of epoxy coatings were studied. Both modifiers self-assembled into spherical micelles of 10–20 nm diameter in cured bulk epoxy. This morphology was preserved in 15 μm thick coatings; however, micelle segregation to the coating/substrate interface was also observed. The critical strain energy release rate, G_1c, of bulk thermosets was enhanced by up to fivefold with the addition of block copolymers. Likewise, the abrasive wear resistance of thin coatings increased with modifier inclusion. The results showed that at 5 wt.% of loading, block copolymers were able to impart a 40% increase in abrasive wear resistance to modified coatings over neat ones. Block copolymer modifiers did not sacrifice the modulus and glass transition temperature of bulk thermosets and coatings, or the hardness and transparency of coatings.     

SiC coating toughened by SiC nanowires to protect C/C composites against oxidation

A dense SiC coating toughened by SiC nanowires was prepared on carbon/carbon (C/C) composites using a two-step technique of chemical vapor deposition (CVD) to protect them against oxidation. The morphologies and crystalline structures of the coatings were characterized by scanning electron microscopy, transmission electron microscopy and X-ray diffraction. SiC nanowires played a role in decreasing the size of the cracks and improving the thermal shock resistance of the coating. The result of thermal shock between 1773 K and room temperature for 21 times indicates that, compared with the SiC coating without SiC nanowires, the average size of the cracks in the SiC coating toughened with SiC nanowires reduced from 5 ± 0.5 to 3 ± 0.5 μm. The weight loss of the SiC coated C/C composites decreased from 9.32 to 4.45% by the introduction of SiC nanowires.     

The influence of Ce-based coatings as pretreatments on corrosion stability of top powder polyester coating on AA6060

Cerium-based conversion coatings (CeCCs) are one of the most prospective alternatives to the widely used chromate conversion coatings (CCCs) due to their anticorrosion efficiency, environmentally friendly nature and low cost. In this work, the CeCCs on AA6060 were prepared by immersion into aqueous cerium salt solutions at room temperature, and subsequently post-treated in heated phosphate solution. The effect of counter ion (nitrate and chloride) on the coating properties was studied testing CeCCs as sole or conversion layers for the top polyester coating. Since the 60 μm thick polyester coating was applied, an artificial defect of 0.8 mm hole was introduced to faster assess the differences between pretreatments. The system with CCC pretreatment was used as reference. Corrosion properties were investigated in 0.5 M NaCl solution by electrochemical impedance spectroscopy while the adhesion strength was measured by NMPR (N-methyl-2-pyrrolidone) and pull-off tests. As shown, the post-treated chloride-based CeCC offered better protection than crack-free thin nitrate-based CeCC, when used as sole coatings. On the other hand, it was brought to evidence that in combination with top powder polyester coating, the CeCC deposited from nitrate solution exhibited better protection compared to protective system pretreated with chloride-based one. Excellent polyester coating adhesion was found independently on aluminium surface pretreatment.     

A comparative investigation of the tribological behavior and scratch response of polyester powder coatings filled with different solid lubricants

Employing coatings is one of the most effective methods to reduce friction and protect contacting surfaces from wear. The deposition of protective coatings from thermosetting polymer powders has witnessed a rapid growth as an ecological, economic and energy efficient technology. During the last few decades, many new deposition techniques have been developed, and more and more tribological coatings have been made available. In this context, our present investigation tried, firstly to analyze the friction and wear behavior of electrostatically sprayed polyester powder coatings deposited on an aluminum substrate and secondly to focus on the response of these thermosetting coatings to micromechanical deformation under scratch test loading. The effect of graphite and hexagonal boron nitride (hBN) solid lubricant fillers on the friction and wear behavior of polyester composite coatings was evaluated using a reciprocating tribometer under dry friction condition. The experimental findings show that the additions of graphite or hBN are effective in enhancing the wear life of polyester powder coatings. Meanwhile, under the same sliding conditions, the wear results revealed that the polyester coating filled with only 10 wt.% of graphite has a higher anti-wear ability compared to the polyester coating filled with the same weight fraction of hBN. Thus, the two reinforcing polyester matrix fillers play an important role in reducing the plastic deformation of the coatings and enhance the formation of thick third body between the sliding parts as the fraction of solid lubricant increases from 0 wt.% to 10 wt.%. From the scratch analyses, we deduced that coatings scratch behavior is severely affected by the kind and amount of fillers inside the polyester matrix. In fact, the best friction characteristic and scratch resistance are observed in the case of polyester coatings filled with very low amount of hBN (5 wt.%).     

Anticorrosion performance of eco-friendly silane primer for coil coating applications

In this paper, corrosion resistance and adhesion of environmental friendly silane primer on coil substrate was studied. Primer was formulated by using methyltrimethoxysilane and 3-glycidoxypropyltrimethoxysilane via acid hydrolysis and condensation reaction. Three different formulations (5%, 15% and 30%) were developed on the basis of sol/water ratio. Aluminium coils was dipped into primer and cured at 120 °C for 20 min. Fourier Transform Infrared Spectroscopy and Scanning Electron Microscope was used to analyse the structural and morphological behaviour of the coating. Corrosion resistance of the coating was evaluated by salt-spray test and potentiodynamic polarization measurement. The adhesion behaviour of the coating was investigated by cross hatch test, before and after salt-spray immersion. Results showed that 15 wt% sol content showed significant improvement in the corrosion resistance, adhesion of the coating and its UV resistance. Silane primers have excellent adhesion with substrate and commercial grade polyester, polyurethane and polyvinyldiene fluoride top coats.     

Attrition strength of water-soluble cellulose derivatives coatings

The aim of this paper was to compare the attrition strength of microparticles coated with various water-soluble cellulose derivatives coatings using the repeated impact tester (RIT). As a core material glass beads of diameter 650-850 μm were used. Four water-soluble cellulose derivatives have been investigated as coating materials: methylcellulose (MC), two types of carboxymethylcellulose (CMC — low and high viscous type) and hydroxypropylcellulose (HPC). Within the research coatings of 5 μm and 20 μm thickness were attrition tested. For all tested cellulose derivatives coatings, attrition occurred according to the layer fatigue sub-mechanism. Overall, HPC coatings were found to be the strongest since they did hardly show any coating mass loss during attrition testing. Most of the low viscous CMC coatings were resistant to fatigue for a low number of impacts, only, and they have shown the lowest strength against attrition. Attrition data showed the relationship between coating uniformity and coating strength in that uneven and irregular surfaces resulted in a lower strength against attrition. Coating thickness also influenced the results of the repeated impact tests: thicker coatings generally presented a higher attrition strength compared to 5 μm coatings. Testing two different carboxymethylcellulose types showed the influence of molecular weight on the coating strength. High viscous CMC, having a higher molecular weight, also presented a higher strength against attrition.     

Soy-based,high biorenewable content UV curable coatings

Utilization of biorenewable materials in UV curing coatings technology is a “green + green” solution to sustainable development. In this work, acrylated epoxidized soybean oil based UV curable coating performance was significantly enhanced by incorporating synthesized acrylated sucrose and hyperbranched acrylates. Acrylated sucrose monomers were synthesized using solventless bulk reactions and characterized by mass spectroscopy and infra-red spectroscopy. Synthesized acrylated sucrose comprised of acrylated monomers with varying degree of acrylation, and the degree of acrylation of the acrylated sucrose increased with reaction time. Acrylated sucrose monomers obtained after 6 and 12 h reactions were formulated into acrylated soybean oil based UV curable coatings with commercial hyperbranched acrylates to produce biorenewable materials based UV curable coatings. Acrylated sucrose monomers increased the toughness but reduced the water resistivity and thermal stability of the coatings, the toughening effect was explained by the soft and hard micro phase separation in the cured coating films. Hyperbranched acrylates increased the coating hardness, adhesion, modulus, solvent resistance and glass transition temperature. Coating formulations containing both the acrylated sucrose monomers and the hyperbranched acrylates exhibited balanced coating performance with reasonably high biorenewable content.     

Hard polyurethane coatings on compliant polycarbonate: An application of the 3D deformation response model to scratch visibility

The present investigation deals with the design of a transparent protective coating and its application on flat substrates in polycarbonate. The experimental analyses looked into the formulation of the coating material, the best strategy to deposit it as well as the characterization of the coated substrates. Visual appearance and morphological features of the coatings were studied by combined scanning electron microscope and contact gauge surface profiler. Their scratch and wear endurance were assessed by progressive and constant load scratching procedure and dry sliding linear reciprocating tribological tests. Imaging analyses were also used to evaluate the deformation response of the coating material to scratch and wear. Analytical modeling was developed accordingly, thus allowing to establish a strict relation between the design criteria of the coatings, the overall (coating + substrate) material performance and the loading conditions. The experimental findings showed the organic coatings were able to significantly improve the micro-mechanical and tribological response of the bare polycarbonate, thus making it available for a large share of applications where high performant, scratch and wear resistant materials are an ineluctable pre-requisite.     

Electrochemical preparation and characterization of Ni/SiC compositionally graded multilayered coatings

In our study, Ni/SiC functionally graded coatings have been obtained by electrochemical deposition of silicon carbide microparticles (mean diameter 2 μm) from nickel Watts baths with different concentrations of SiC particles in solution. The SiC particles were characterized by electroacustics technique in order to determine zeta potential and particle size. Moreover, the effect of the concentration of SiC particles in solution on the amount of SiC deposited in the nickel layer was investigated. Further experiments showed that the degree of particle incorporation provoked changes in the texture of the nickel matrix. The characterization of the coatings proved that the Ni/SiC graded composite coatings were bright and compact, presented good adhesion and improved the hardness and wear resistance of pure nickel electrodeposits.     

Extreme wet adhesion of a novel epoxy-amine coating on aluminum alloy 2024-T3

Amine-epoxy polymer systems are widely used, for example as matrix materials for structural composites employed in aerospace industry and in industrial coatings on metal substrates for corrosion protection. This work focuses on the investigation of different epoxy-amine coatings on the adhesion performance on aluminum AA-2024 substrates. Two different epoxies (Epikote 828 (aromatic) and Eponex 1510 (aliphatic)) and four different amines (1,8-diaminooctane, Dytek A, Jeffamine EDR148 and Jeffamine D230) as curing agent were used in different stoichiometric ratios. These different epoxy-amine coatings were characterized using differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), tensile tests (pull-off) and water-uptake measurements. Pull-off tests in dry conditions showed comparable adhesion of the coatings. Surprisingly, pull-off results showed after water soaking a higher wet adhesion of the coatings prepared with Eponex 1510 as compared to coatings prepared with Epikote 828. Moreover, the combination of Eponex 1510-Jeffamine EDR148 coatings resulted in high adhesion values (∼7 MPa) with pull-off tests and these values did not change after immersion for two weeks in water. This combination shows extreme good wet adhesion performance as compared to any other epoxy-amine coating. Complete recovery was demonstrated of the adhesion of Eponex 1510-Jeffamine D230 coating after being immersed for two weeks in water and dried for two weeks. Furthermore, in contrast with Epikote 828 water uptake measurements showed almost nil water uptake for all coatings prepared with Eponex 1510. Optical microscopy investigations on the residues of the coatings after pull-off tests revealed adhesive failure in wet condition for Epikote 828, while coatings prepared with Eponex 1510 showed cohesive failure.     

Effects of phase separation on stress development in polymeric coatings

A cantilever deflection technique was used to monitor stress in situ during drying of cellulose acetate coatings. Porosity was introduced in some coatings using dry-cast phase separation. Stress and weight loss profiles for dense coatings, a coating that contained small (∼1 μm) pores, and a coating that contained small (∼1 μm) pores and macrovoids (∼200 μm) are compared. In-plane tensile stress after drying ranged from 30 MPa (dense coatings) to 5 MPa (macrovoid-containing coating). The stress profiles for dense coatings feature a period of rapidly and then slowly increasing stress due to constrained shrinkage. For a coating that formed small pores, drying and stress development are delayed, stress rises and then drops a small amount due to capillary pressure relief. The stress profiles for the small pore and macrovoid-containing coatings are similar, except for a stress plateau at early stages of drying, which may be caused by macrovoid growth.     

Effect of electroless nickel interlayer on the electrochemical behavior of single layer CrN, TiN, TiAlN coatings and nanolayered TiAlN/CrN multilayer coatings prepared by reactive dc magnetron sputtering

The electrochemical behavior of single layer TiN, CrN, TiAlN and multilayer TiAlN/CrN coatings, deposited on steel substrates using a multi-target reactive direct current (dc) magnetron sputtering process, was studied in 3.5% NaCl solution. The total thickness of the coatings was about 1.5 μm. About 0.5 μm thick chromium interlayer was used to improve adhesion of the coatings. With an aim to improve the corrosion resistance, an additional interlayer of approximately 5 μm thick electroless nickel (EN) was deposited on the substrate. Potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) were used to study the corrosion behavior of the coatings. Scanning electron microscopy and energy dispersive X-ray analysis were used to characterize the corroded samples. The potentiodynamic polarization tests showed lower corrosion current density and higher polarization resistance (R_p) for the coatings with EN interlayer. For example, the corrosion current density of TiN coated steel was decreased by a factor of 10 by incorporating 5 μm thick EN interlayer. Similarly, multilayer coatings of TiAlN/CrN with EN interlayer showed about 30 times improved corrosion resistance as compared to the multilayers without EN interlayer. The porosity values were calculated from the potentiodynamic polarization data. The Nyquist and the Bode plots obtained from the EIS data were fitted by appropriate equivalent circuits. The pore resistance (R_pore), the charge transfer resistance (R_ct), the coating capacitance (Q_coat) and the double layer capacitance (Q_dl) of the coatings were obtained from the equivalent circuit. Multilayer coatings showed higher R_pore and R_ct values as compared to the single layer coatings. Similarly, the Q_coat and Q_dl values decreased from uncoated substrate to the multilayer coatings, indicating a decrease in the defect density by the addition of EN interlayer. These studies were confirmed by examining the corroded samples under scanning electron microscopy.     

Anticorrosive polyurethane paints with nano- and microsized phosphates

Two types of phosphate fillers (nanosized aluminum phosphate and microsized aluminum–zinc phosphate) were tested as anticorrosive fillers in 2 K solvent-borne polyurethane paints based on commercial acrylic resin with OH groups and an isophorone diisocyanate-type hardener. Three coating compositions containing commercial fillers (mica/quartz, TiO₂, wollastonite, talc) and also mentioned nanosized aluminum phosphate or microsized aluminum–zinc phosphate were prepared using a pearl-mill as well as a laboratory dissolver, applied onto a steel substrate and cured at room temperature for 14 days. An influence of the type and content of a phosphate filler on properties of polyurethane paints and coatings has been investigated. Incorporation of nanosized aluminum phosphate into coating compositions increases their viscosity while cured paints exhibit reduced adhesion to steel substrates. The results of corrosion tests in a salts spray chamber as well as immersion in an aqueous NaCl solution indicated that the paint system with 9.8 wt.% of applied nanofiller had similar protective properties to a polyurethane coat containing a higher dose (i.e. 15.6 wt.%) of commercial microsized aluminum–zinc phosphate.     

Frictional wear in high temperature thermotropic liquid crystalline polymers: correlation with glass transitions

Wholly aromatic thermotropic main chain liquid crystalline copolymers (LCPs) with varying glass transitions (T_g) were tested for wear resistance, particularly under high friction conditions, where surface temperatures can rise. Dynamic mechanical spectroscopy and DSC were used to characterize molecular relaxations. Three copolyester LCPs which all contain a substantial fraction of main chain 1,4-phenyl groups were chosen for this study. These included semi-crystalline Vectra^® A900, a semi-crystalline LCP containing phenyl hydroquinone (phHQ-LCP), and a low crystallinity LCP containing t-butyl substituted hydroquinone (t-butylLCP). These have glass transitions of 100, 160 and 175 °C, respectively, and heat deflection temperatures (HDTs) of 170, 260 and 174 °C, respectively. HDT is dependent in part on crystallinity. The wear performance was found to depend mainly on T_g and not HDT, suggesting a microscopic failure mechanism related to the amorphous phase. This is supported by the relatively poor elevated temperature wear performance of Vectra^® compared to the higher T_g LCPs. Shear strength measurements on the neat LCP resins did not correlate with wear properties of the blends, most likely because the measurements were made at room temperature and not elevated temperatures.     

Coatings prepared from waterborne polyurethane dispersions obtained with polycarbonates of 1,6-hexanediol of different molecular weights

Waterborne polyurethane dispersions (PUDs) were synthesized with polycarbonates of 1,6-hexanediol of different molecular weight (500–3000 Da) and their properties, adhesion (Hatch adhesion) and coatings on stainless steel properties (Pencil hardness, Persoz hardness, gloss at 60°, chemical resistance, yellowness index) were characterized. The hatch adhesion of the polyurethane coatings to stainless steel was very good and decreased slightly by increasing the molecular weight of the polycarbonate of 1,6-hexanediol. Both the Pencil and Persoz hardness values of the coatings increased by increasing the hard segments content in the polyurethane, i.e. by decreasing the molecular weight of the polycarbonate of 1,6-hexanediol, whereas the gloss and the yellowness index were lower for the coatings obtained with the polycarbonate of 1,6-hexanediol of molecular weight of 500 Da. Very good chemical resistance against ethanol for all polyurethane coatings on stainless steel plates was obtained but for long time of ethanol in contact with the coating surface the chemical resistance decreased, more markedly for the polyurethane coating obtained with the polycarbonate of 1,6-hexanediol of higher molecular weight. In summary, the segmented structure of the waterborne polyurethane dispersion determined the properties of the polyurethane coatings obtained from them.     

Mining tailings as a raw material for glass-bonded thermally sprayed ceramic coatings: Microstructure and properties

Magnesium aluminate, MgAl₂O₄, spinel powders for thermal spraying, were synthesized from secondary raw materials by spray drying and subsequent reaction sintering. Talc ore mining tailings and aluminium hydroxide precipitate from aluminium anodizing process were studied. A stoichiometric MgAl₂O₄ spinel coating was prepared as a reference using pure raw materials. Atmospheric plasma spraying resulted in the formation of ceramic coatings. Microstructural investigations revealed that the reference coatings exhibited crystalline lamellar microstructure of MgAl₂O₄ but secondary coatings contained amorphous areas between the crystalline MgAl₂O₄ clusters. Abrasive wear test results revealed considerably lower wear rate for secondary coatings. It is suggested that the different structure of coatings, particularly the high degree of amorphous phase between the isolated crystalline MgAl₂O₄ clusters caused the higher abrasive wear resistance by changing the wear mechanism. The dielectric breakdown strength of the secondary coatings were at the same level, 24 V/μm, as compared to reference coating, 23 V/μm.     

Application of EIS and salt spray tests for investigation of the anticorrosion properties of polyurethane-based nanocomposites containing Cr2O3 nanoparticles modified with 3-amino propyl trimethoxy silane

The Cr₂O₃ nanoparticles were modified with 3-amino propyl trimethoxy silane in order to obtain proper dispersion and increment compatibility with the polyurethane coating matrix. The nanocomposites prepared were applied on the St-37 steel substrates. The existence of 3-amino propyl trimethoxy silane on the surface of the nanoparticles was investigated by Fourier transform infrared (FTIR) spectroscopy and thermal gravimetric analysis (TGA). Dispersion of the surface modified particles in the polyurethane coating matrix was studied by a field emission-scanning electron microscope (FE-SEM). The electrochemical impedance spectroscopy (EIS) and salt spray tests were employed in order to evaluate the corrosion resistance of the polyurethane coatings. Polarization test was done in order to investigate the corrosion inhibition properties of the Cr₂O₃ nanoparticle on the steel surface in 3.5 wt.% NaCl solution. The adhesion strengths of the coatings were evaluated by pull-off adhesion tester before and after 120 days immersion in 3.5 wt.% NaCl solution. FT-IR and TGA analyses revealed that surface modification of the nanoparticles with 0.43 silane/5 g pigment resulted in the greatest amount of silane grafting on the surface of particles. Results obtained from FE-SEM analysis showed that the surface modified nanoparticles dispersed in the coating matrix properly. Results obtained from EIS and salt spray analyses revealed that the surface modified particles enhanced the corrosion protection performance of the polyurethane coating considerably. The improvement was more pronounced for the coating reinforced with 0.43 g silane/5 g pigment. Moreover, the adhesion loss decreased in the presence of surface modified nanoparticles with 0.43 silane/5 g pigment.