Effects of pigmentation on siloxane–polyurethane coatings and their performance as fouling-release marine coatings

Siloxane–polyurethane paints were formulated and characterized for coating properties and performance as fouling-release (FR) marine coatings. Paints were formulated at 20 and 30 pigment volume concentrations with titanium dioxide, and aminopropyl-terminated poly(dimethylsiloxane) (APT-PDMS) loadings were varied from 0 to 30% based on binder mass. The coatings were characterized for water contact angle, surface energy (SE), gloss, and pseudobarnacle (PB) adhesion. The assessment of the FR performance compared with polyurethane (PU) and silicone standards through the use of laboratory biological assays was also performed. Biofilm retention and adhesion were conducted with the marine bacterium Cellulophaga lytica, and the microalgae diatom Navicula incerta. Live adult barnacle reattachment using Amphibalanus amphitrite was also performed. The pigmented coatings were found to have properties and FR performance similar to those prepared without pigment. However, a higher loading of PDMS was required, in some cases, to obtain the same properties as coatings prepared without pigment. These coatings rely on a self-stratification mechanism to bring the PDMS to the coating surface. The slight reduction in water contact angle (WCA) and increase in pseudobarnacle release force with pigmentation suggests that pigmentation slowed or interfered with the self-stratification mechanism. However, increasing the PDMS loading is an apparent method for overcoming this issue, allowing for coatings having similar properties as those of clear coatings and FR performance similar to those of silicone standard coatings.     

Simulations of nanoscale and macroscopic property changes on coatings with weathering

Coatings are designed for and applied on a surface for both aesthetics and protection of the substrate. Many properties are measured to indicate performance, and eventual failure, of a coating under these two broad categories. Monte Carlo simulations have shown success in predicting trends in macroscopic properties during exposure. The Central Limit Theorem (CLT) is applicable because damage made to a coating can come from the accumulation of a vast number of very small damage events. Application of the CLT to property equations has generated additional equations for the prediction of properties of a coating with exposure, including measurable properties such as gloss, color, fracture toughness, and contact angle. These equations, when fitted to measured data, provide in sight into the mechanisms of degradation processes, since the fitting parameters are physically based. They also offer a means to scale accelerated testing measurements to early field measurements of the property of interest for predicting lifetime in varied environments. Presented at the 82nd Annual Meeting of the Federation of Societies for Coatings Technology, October 27–29, 2004, in Chicago, IL.     

Monte carlo approach to estimating the photodegradation of polymer coatings

The degradation of a polymer coating and predicting the coating lifetime based on physical properties and distribution within the coating of the polymer binder, pigments, and fillers are economically very important. As technologies advance and allow for control of coatings at the nanoscale level, methods such as Monte Carlo can be used not only to predict the behavior of a nanodesigned coating with time but also to design coatings, such as optimizing pigment particle distributions or optimum hard and soft phase distributions of the binders in multiphase systems for maintaining the desired property with time. Erosion of the coating surface was simulated using Monte Carlo techniques where terrestrial solar flux is the initiator for polymer segment cleavage and removal. The impact on the sensitivity of the polymer adjacent to the detached polymer segment can be increased or decreased in the model based on the chemistry and surface energy of the remaining polymer matrix. Multiple phases with varying sensitivity to degradation can be modeled. The Monte Carlo generates a statistically similar surface topography and chemistry of the coating. The results of the Monte Carlo model are compared to measurable properties such as gloss, fracture toughness, and wetting contact angle, using various published correlations of the property to the surface topology. The simulated properties change through the life-time of the coating in ways that are consistent with observed behavior. Apparently, complicated changes in many properties can be described by the repeated application of simple, random processes. Presented at the 79th Annual Meeting of the Federation of Societies for Coatings Technology, October 28–November 1, 2002, in New Orleans, LA.     

Specular gloss versus surface topography for oil‐filled nanoparticle coatings on paper

The appearance or printing quality of paper surfaces is mostly characterized by their glossiness, measured with a glossmeter as specular reflectance. The gloss properties of a base paper substrate can be improved after application of a poly(styrene‐co‐maleimide) nanoparticle coating under pure conditions or in the presence of different vegetable oils. The specular gloss properties of 11 different nanoparticle paper coatings have been determined under 75° and 85° incident light angles, with good relation between values along parallel (machine) and perpendicular (transverse) direction. The gloss properties for the different coatings have been further related to the surface topography. Therefore, the statistical and spatial surface roughness parameters have been studied in detail at two length scales including non‐contact profilometry (1 × 1 mm²) and atomic force microscopy (2 × 2 μm²). Based on values of the Rayleigh parameter for non‐contact profilometry, the surfaces can be considered as optically rough. The gloss values cannot be directly related to statistical surface roughness parameters. Otherwise, an experimental power‐law model for gloss has been proposed as a function of (β/Sq) with correlation length β and root‐mean‐square roughness Sq. A best‐fit model illustrates that gloss properties of various nanoparticle paper coatings mainly relate to the spatial surface roughness parameters determined from non‐contact profilometry. © 2015 Wiley Periodicals, Inc. Col Res Appl, 41, 596–610, 2016     

Estimating service lifetimes in weathering: an optimistic view

Directly correlating lifetime to coating composition by using standardized, artificial exposures, or even natural exposure, is often very difficult. However, significant progress can be made by breaking down the problem into smaller questions, which can be separately addressed. If one understands the physical parameters that affect end-use properties, then one can also group, and thus correlate, properties according to whether they depend on processes at the surface or in the bulk of a coating, or whether they depend on defects. A scheme is presented that shows how one can use knowledge from analytical physical or chemical materials science in a statistical model related to the “chemical paradigm.” Simple physical models that use this information, about the initial state of the coating and its rate of degradation, can be used to compare the performance of coatings and estimate, simply, service lifetime depending on the property of interest, in the environment of interest. One can see that different properties are sensitive in different ways to the degradation process and decay with a different rate. Thus, although properties may be determined by the same degradation process, and location within a coating, they do not correlate directly. These approaches show how to organize our knowledge of degradation processes, and environments, and be able to make some testable predictions on how coating properties deteriorate. Presented at the 2006 FutureCoat! conference, sponsored by the Federation of Societies for Coatings Technology, in New Orleans, LA, on November 1–3, 2006     

Synthesis of UV-curable polysiloxanes containing methacryloxy/fluorinated side groups and the performances of their cured composite coatings

Three novel UV-curable polysiloxanes consisting of polysiloxane backbone with methacryloxy/fluorinated side groups were synthesized, and their structures were characterized by FT-IR, ¹H NMR and ¹³C NMR. A series of UV-cured composite coatings based on the synthesized polysiloxanes and an epoxy methacrylate were obtained through photopolymerization. Their gel content, flexibility, hardness, gloss, contact angle, thermal behavior as well as water absorption ratio were investigated. Results found that the siloxane component could enhance the flexibility and gloss of coatings, while the presence of fluorinated groups could improve the hardness. The combination of silicon and fluorine in the same polymer could increase thermal stability and water resistance of the coatings and decrease their surface energy simultaneously. The observation of the fractured-surface morphology showed that the polysiloxanes could be well dispersed in the epoxy methacrylate to some extent. A suitable addition of such polysiloxane in photocurable coating matrixes may provide excellent properties for the cured coatings and widen their applications.     

Gloss and degradation of hydroxyl polyacrylic resin/hexamethylene‐1,6‐diisocyanate coatings under ultraviolet and natural‐exposure aging

Reactive coatings of hydroxyl polyacrylic resin (HPAR) with hexamethylene‐1,6‐diisocyanate were carried out under accelerated 313‐nm ultraviolet (UV) aging for 2000 h and under natural exposure in Lhasa, Tibet, for 24 months. With UV irradiation and exposure time, the gloss changes in coatings with HPAR containing 3.0% or less hydroxyl groups decreased exponentially, whereas the gloss decay of coatings with HPAR containing over 4.5% hydroxyl groups decreased linearly. During 254‐nm UV aging, the gloss changes in coatings with HPAR containing 1.4% or less hydroxyl groups decreased as a Gaussian function. The weather resistance of a coating was correlated to the HPAR, UV irradiation, temperature, and humidity. Scanning electron microscopy indicated that there were degradation reactions and that some substance was lost in the matrix polymer during accelerated UV aging; then, uneven surfaces appeared and caused decreased gloss. Accelerated UV aging was faster than natural‐exposure aging, and the aging velocity of 254‐nm UV was 3–5 times faster than that of 313‐nm UV. Through the changes in the gloss, the aging tolerance of a coating could be monitored, and its aging resistance could also be predicted. The dynamic mechanical thermal analysis results showed that the coatings had good properties. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1271–1278, 2007     

A macroscopically nondestructive method for characterizing surface mechanical properties of polymeric coatings under accelerated weathering

The surface of coatings and plastics is the first target in any degradation process initiated by ultraviolet (UV) radiation or mechanical stress (via scratch and abrasion). Surface damage can lead to changes in optical, morphological, and mechanical properties and can result in pathways for ingress of moisture and corrosive agents. Current test methods for monitoring performance of protective coatings focus on chemical properties and optical properties, such as color and gloss measurements, or invasive tests such as abrasion and cross-cut adhesion. In this study, a macroscopically nondestructive performance protocol using nanoindentation metrology via a well-controlled scratch test was applied to evaluate the scratch resistance and monitor the surface mechanical property changes in a protective coating under accelerated weathering. Polyurethane (PU) coatings with different polyol compositions were chosen for this study. Coating specimens were exposed to high-intensity UV radiation at 55°C and 75% RH conditions. Exposed specimens were removed at specified UV exposure times for surface modulus/hardness and scratch resistance characterization via nanoindentation and scratch test. The effect of polyol type and UV radiation dose on the scratch damage (scratch morphology) was investigated and correlated with the surface hardness and modulus of the materials.     

Silicone-acrylic hybrid aqueous dispersions of core–shell particle structure and corresponding silicone-acrylic nanopowders designed for modification of powder coatings and plastics. Part III: Effect of modification with selected silicone-acrylic nanopowders on properties of polyurethane powder coatings

Polyurethane powder coating systems consisting of polyester resin, blocked polyisocyanate and two types of “nanopowders” containing core–shell nanoparticles where the core was silicone resin of very low glass transition temperature and the shell was poly(methyl methacrylate) were examined. The blocked polyisocyanate was synthesized using biuretpolyisocyanate obtained from ureapolyisocyanate as starting material capable for blocking and ɛ-caprolactam as blocking agent. The surface properties of cured powder coatings were investigated using scanning electron microscopy (SEM) combined with energy dispersive spectrometry (EDS), X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). The surface structure was correlated with the chemical structure of the coatings and macroscopic surface behavior: contact angle, surface free energy, gloss, abrasion resistance, hardness and adhesion to the steel surface.     

Novel high‐solids pigmented coatings prepared from a new‐synthesized isophthalate‐based oligoester,a melamine resin,and various fillers

A new‐synthesized hydroxyl‐terminated isophthalate‐based liquid oligoester (L‐311), an hexakis(methoxymethylol)melamine resin, and various inert pigments (fillers) such as either kaolins (Al₂O₃ · 2SiO₂ · 2H₂O) of different particle sizes (1.50 and 4.80 μm) or calcium metalsilicate (CaSiO₃) were used to prepare high‐solids pigmented coatings (PA and PW series, respectively). The physical, chemical, and mechanical properties (pencil hardness, Knoop hardness, flexibility, impact resistance, adhesion, gloss, solvent, and mar resistance) of the new‐formulated pigmented coatings were correlated to the chemical species of the filler, the filler's load and particle size, the quantity of the crosslinker, and the introduction of large particle size colloidal silica into the coating. For measuring the mar resistance of the pigmented coatings, the Taber abrasion method was applied and the inverse wear index, F [=I^?1, cycles/cg (wear index l, weight loss (cg) per number of cycles)], was directly related to the mar resistance. Either when kaolins or calcium metalsilicates were used as fillers, the Knoop hardness, the impact, and mar resistance of the films were affected from the filler's load, whereas the quantity of melamine resin (crosslinker) affected the knoop hardness, the gloss, and the mar resistance. The fillers' particle size and the introduction of large particle colloidal silica affected mainly the mar resistance and the gloss, respectively. The pencil hardness of the PW‐pigmented coatings series (F‐2H) was higher than that of the PA‐series (B‐HB). The chemical composition of the inert pigment proved to be a very important parameter in the preparation of pigmented coatings with specific properties that aim to meet modern and particular demands for various end‐up uses. All the new‐formulated high‐solids (nonvolatiles by weight ～ 70%) pigmented coatings (PA and PW series) presented excellent adhesion (5B), flexibility (> 32%), methyl ethyl ketone (MEK) resistance (>200 rubs), high pencil hardness, good knoop hardness, and very good impact resistance (from 100 up to 160 in.‐lb), independently of the species of the filler (kaolins or calcium metalsilicate). © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 576–590, 2002; DOI 10.1002/app.10309     

Effects of UV degradation on surface hydrophobicity, crack, and thickness of MWCNT-based nanocomposite coatings

Surface degradation is a common problem in polymeric coatings when they are exposed to sunlight, moisture, and oxygen. In order to reduce their surface degradation, thus keeping the coatings’ original properties, multi-wall carbon nanotubes (MWCNTs) were added, and the coatings were exposed to UV light and salt fog for various lengths of time. At 0 days of UV exposure, contact angle values of 0%, 0.25%, 0.5%, 1%, and 2% MWCNT-based nanocomposite coatings of 75 μm (∼3 mil) thickness were between 85° and 89°. However, after 16 days of UV exposure, contact angle values of the same samples were reduced to 11°, 13°, 34°, 50°, and 54°, respectively. Longer UV exposures resulted in several microcracks on the surface of the coated samples in the absence of nanoscale inclusions, while very minimal cracks or degradation appeared on the MWCNT-loaded samples. Test results also showed that UV exposure along with salt fogging reduced the coating thickness up to 24% at 0% CNTs; in contrast, this reduction was only 7% with a 2% MWCNT coating. These results clearly indicate that MWCNTs added to polymeric coatings reduce UV degradation, lessen surface cracks, protect the film thickness, and hence increase the lifetime of the polymeric coatings.     

Relating gloss loss to topographical features of a PVDF coating

Semi-gloss commerical poly(vinylidene fluoride) (PVDF) coatings typically have 60° gloss values between 20 and 50. Gloss is affected by PVDF crystallite structures and by the pigmentation. In this article, we have demonstrated that for some pigmented PVDF coatings, after 10 years of Florida exposure, the principal proximal cause of gloss changes is the formation of micron-scale pits, rather than the emergence of pigment particles at the coating surface. We have used laser scanning confocal microscopy (LSCM) and light scattering to characterize the surface topography and near-surface structure of weathered and unweathered PVDF coatings. Florida-weathered PVDF coatings show only a modest increase in the root mean square (RMS) roughness of the surface, even when oticeable gloss loss has occurred. Changes in gloss can be correlated with surface roughness and other topographical, features, including the formation of pits and the emergence of pigments. Presented at the 82nd Annual Meeting of the Federation of Societies for Coatings Technology, October 25–27, 2004, in Chicago, IL.     

Modifications of paper and paperboard surfaces with a nanostructured polymer coating

Organic nanoparticles synthesized by imidization of styrene-maleic anhydride copolymers are deposited as a top-coating onto paper and paperboard substrates from a stable aqueous dispersion with maximum solid content of 35 wt.%. The morphology, physical characteristics and chemical surface properties of the coatings are discussed in this paper, using scanning electron microscopy, atomic force microscopy, contact angle measurements and Raman spectroscopy. Due to the high glass transition temperature of the polymer nanoparticles, a unique micro- to nanoscale structured coating is formed that favourably improves the gloss, printing properties (ink-jet printing test and off-set printing test), surface hydrophobicity (maximum water contact angle 140°) and water repellence (reduction of Cobb-values). The interaction of the nanoparticle coatings with the cellulosic paper web results in improvement of the mechanical paper strength and is attributed to hydrogen-bonding between the nanoparticles and the cellulosic fibers.     

Effect of functional groups (methyl,phenyl) on organic–inorganic hybrid sol–gel silica coatings on surface modified SS 316

Organic–inorganic hybrid sol–gel based silica coatings derived from hydrolysis and condensation of organically modified silane precursors like phenyltrimethoxysilane and methyltriethoxysilane along with tetraethoxysilane were deposited on different surface pre-treated (as-cleaned, plasma-treated, shot-blasted) SS 316 grade stainless steel substrate, using dip coating technique. The coatings were heat treated at 150 °C for 2 h in air. The pre-treated surfaces were characterized using X-ray Photoelectron Spectroscopy and Scanning Electron Microscopy. The water content of the sols was determined by Karl Fischer titration to evaluate the degree of completion of hydrolysis and condensation reactions. Cured coatings were characterized to evaluate thickness, water contact angle, pencil scratch hardness, gloss, and shrinkage in coating thickness. Impact test was carried out on pigmented coatings derived from sols synthesized using the two silane precursors. The corrosion resistance and water durability tests were carried out to compare the coatings derived from using different precursors and different surface pre-treatments. The corrosion tests were carried out for 1 h and 24 h exposure to a 3.5% NaCl solution by electrochemical polarization measurements. It was found that coatings from methyl substituted organically modified alkoxysilane exhibited better hydrophobicity, scratch hardness, impact resistance and barrier properties with respect to corrosion, when compared to those derived from phenyl substituted trialkoxysilane. The difference in performance of coatings was explained on the basis of difference in hydrolysis and condensation rates between the two organically modified silane precursors used for the sol synthesis.     

Modifications of paper and paperboard surfaces with a nanostructured polymer coating

Organic nanoparticles synthesized by imidization of styrene-maleic anhydride copolymers are deposited as a top-coating onto paper and paperboard substrates from a stable aqueous dispersion with maximum solid content of 35 wt.%. The morphology, physical characteristics and chemical surface properties of the coatings are discussed in this paper, using scanning electron microscopy, atomic force microscopy, contact angle measurements and Raman spectroscopy. Due to the high glass transition temperature of the polymer nanoparticles, a unique micro- to nanoscale structured coating is formed that favourably improves the gloss, printing properties (ink-jet printing test and off-set printing test), surface hydrophobicity (maximum water contact angle 140°) and water repellence (reduction of Cobb-values). The interaction of the nanoparticle coatings with the cellulosic paper web results in improvement of the mechanical paper strength and is attributed to hydrogen-bonding between the nanoparticles and the cellulosic fibers.     

粉末涂料用含硅聚酯树脂的合成及性能研究

通过采用二取代有机硅氧烷、二取代硅油和二氯硅烷等含硅单体,制备了粉末涂料用含硅聚酯树脂,并研究了含硅树脂及其粉末涂料的性能.结果 表明:有机硅的引入会造成涂层光泽升高、机械性能和流平性下降,涂层的耐热性显著增加,在黏度相差不大的前提下,涂层的耐候性显著降低.硅原子会通过重排的形式在涂层表面富集,增加涂层的静态水接触角,...     

Polyurethane powder coatings containing polysiloxane

In this study, blocked polyisocyanate crosslinkers (PIC) for powder coatings were synthesized using isophorone diisocyanates (IPDI), formic acid, poly(dimethylsiloxane), ?-caprolactam, dibutyltin dilaurate as well as triethylamine as catalysts. The chemical structures of these compounds were confirmed by means of IR and NMR spectroscopy and the molecular weight distributions were investigated using gel permeation chromatography (GPC). Polyurethane powder coating systems consisting of polyester resin and synthesized polyisocyanate were examined. The surface structure of powder coatings was investigated with confocal laser scanning microscopy (CLSM), scanning electron microscopy (SEM) equipped with energy dispersive spectrometer (EDS) and X-ray photoelectron spectroscopy (XPS). The surface structure was correlated with the chemical structure of the coatings and macroscopic surface behavior: contact angle, surface free energy, gloss, abrasion and scratch resistance, hardness as well as adhesion to steel surface.     

Prediction of service lifetime and performance of a prosthetic thermoplastic

The service lifetime and performance for a prosthetic and orthotic thermoplastic, Subortholen^TM, was measured using correlations between artificial and natural weathering degradation data of (1) the accumulated carbonyl compound concentration at the polymer surface, (2) changes in thickness of the surface reaction zone, and (3) changes in hardness and tensile properties. An empirical, mathematical relationship between artificial and natural weathering exposures is presented. Results show that the hardness degradation is a useful parameter to estimate the different stages in clinical performance of Subortholen. Corroborating hardness, tensile properties, and weathering exposure time, the service lifetime for Subortholen was determined to be 4–6 years. This finding indicates that the correlation between artificial and natural weathering degradation may provide an effective way to calculate the most appropriate time to replace a worn prosthetic or orthotic device before the device passes into a dangerous stage. © 1995 John Wiley & Sons, Inc.     

Advanced techniques for nanocharacterization of polymeric coating surfaces

Surface properties of a polymeric coating system have a strong influence on its performance and service life. However, the surface of a polymer coating may have different chemical, physical, and mechanical properties from the bulk. In order to monitor the coating property changes with environmental exposures from the early stages of degradation, nondestructive techniques with the ability to characterize surface properties with micro- to nanoscale spatial resolution are required. In this article, atomic force microscopy has been applied to study surface microstructure and morphological changes during degradation in polymer coatings. Additionally, the use of AFM with a controlled tip-sample environment to study nanochemical heterogeneity and the application of nanoindentation to characterize mechanical properties of coatings surfaces are demonstrated. The results obtained from these nanometer characterization techniques will provide a better understanding of the degradation mechanisms and a fundamental basis for predicting the service life of polymer coatings. Presented at the 81st Annual Meeting of the Federation of Societies for Coatings Technology on November 12–14, 2003, in Philadelphia, PA.     

Evaluation of the ASTM D7869-13 test method to predict the gloss and color retention of premium architectural finishes-I

A recently developed xenon arc-based accelerated weathering cycle, ASTM D7869-13, has been validated for automotive and aerospace coatings, but its ability to predict the gloss and color retention of premium architectural finishes has not yet been evaluated. We review new weathering data comparing the performance of poly(vinylidene fluoride) (PVDF) architectural finishes in south Florida exposure as well as several accelerated exposure methods including ASTM D7869-13. ASTM D7869 accurately reproduced Florida rank order gloss and color retention trends for coatings made with PVDF-acrylic blends and inorganic pigments, as well as the gloss and color changes seen in Florida for 70% PVDF masstone coatings made with a number of single organic pigments. However, the D7869 cycle has difficulty predicting the rank order of rutile TiO₂ grades for the gloss retention of PVDF coatings in Florida, as well as the magnitude and direction of color fade from organic pigment degradation in organic pigment/inorganic pigment blends. One open question that remains is whether the ASTM D7869 cycle might have some utility for industry standard or specification purposes, if the test is limited to specific reference colors or more ideally to specific reference pigments.