Effect of TiO2 pigment type on the UV degradation of filled coatings

The objective of this study was to investigate the effect of the photoreactivity of titanium dioxide (TiO₂) pigments on the photodegradation of polymeric coatings used in exterior applications. Two polymer matrices, an amine-cured epoxy (EP) and an acrylic urethane (AU), containing three types of TiO₂ pigments, classified by different levels of photoreactivity, were studied. Specimens were exposed on an ultraviolet (UV) weathering chamber, the Simulated Photodegradation by High Energy Radiant Exposure device at the National Institute of Standards and Technology. Two exposure conditions were used: ambient, dry condition [25°C and 0% relative humidity (RH)] and high temperature, wet condition (55°C and 75% RH), which is similar to more severe outdoor exposures. The physical and chemical degradations of the filled coatings were monitored at periodic intervals using a combination of laser scanning confocal microscopy (LSCM) and attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR). Progression of degradation on the coating surfaces was characterized by LSCM in terms of changes in surface roughness and morphology, pigment agglomerate size, and the occurrence of pits or holes in the coatings. The observed physical changes were correlated to the chemical changes measured by ATR-FTIR as a function of UV exposure time. Both EP and AU systems showed less degradation in terms of surface roughness and morphological changes under the dry conditions compared to the wet exposure conditions. It was observed that both the pigment type (and hence photoreactivity) and particle dispersion strongly affected the degradation of both EP and AU systems.     

Relationship between chemical degradation and thickness loss of an amine-cured epoxy coating exposed to different UV environments

The relationship between chemical degradation and thickness loss of an unpigmented, non UV-stabilized, crosslinked amine-cured epoxy coating exposed to three UV conditions was investigated. Spin-coated samples having a thickness of approximately 7 μm on an Si substrate were prepared from a stochiometric mixture of a bisphenol A epoxy resin and a tetra-functional amine curing agent. Samples were exposed outdoors and to two accelerated laboratory UV environments. Chemical degradation and thickness loss were measured by transmission Fourier transform infrared spectroscopy (FTIRS) and laser scanning confocal microscopy (LSCM), respectively. In addition, surface roughness and morphological changes were measured by atomic forcemicrosocopy (AFM) and LSCM. Substantial chemical degradation, thickness loss, and morpholocal changes occurred in the exposed films, and the rate of chemical degradation was greater than that due to the thickness loss. This additional chemical loss was attributed to an inhomogeneous degradation process in which nanoscale localized depressions initiate at certain sites on the surface, which then enlarge and deepen with exposure time. The results of this study provide a better understanding of the degradation mechanism and should lead to the development of scientific-based models for predicting the service life of crosslinked amine-cured epoxy coatings. Presented at the 82nd Annual Meeting of the Federation of Societies for Coatings Technology, October 27–29, 2004, in Chicago, IL     

Surface degradation process affected by heterogeneity in nano-titanium dioxide filled acrylic urethane coatings under accelerated UV exposure

The objective of this study was to investigate the effect of nanoparticle dispersion on surface morphological changes and degradation process in polymeric coatings during exposure to ultraviolet (UV) radiation. Three types of nano-titanium dioxide (nano-TiO₂) were selected and dispersed into acrylic urethane (AU) coating to generate degrees of nanoparticle dispersion states. Two accelerated exposure conditions: wet (30 °C and 75% relative humidity (RH)) and dry (30 °C and 0% RH), were selected. Attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR) was used to monitor surface chemical degradation. Laser scanning confocal microscopy (LSCM) was used to characterize nanoparticle dispersion and surface/subsurface morphological changes in the AU coatings during UV exposure. For a given nanoparticle, similar surface morphological changes of the coatings indicated the similar degradation processes under the wet and dry conditions, but the degradation was faster under the wet condition. Surface morphological changes were closely related to the nanoparticle dispersion in three coatings, and the heterogeneity in nanoparticle dispersion significantly affects the degradation process and dominates the degradation patterns.     

Degradation of polyester film in alkali solution

In recent years there has been a remarkable growth in coatings technology, yet polymer‐coated metals still corrode when they are exposed to severe environments. If the effectiveness of polymer coatings is to be increased, it is essential to understand the microstructure of polymer coating film and the changes that occur to the film upon environmental exposure, and relate the changes to the protective performance of coatings. The degradation of a polyester immersed in alkali solution has been investigated using a number of analytical techniques including atomic force microscopy (AFM), liquid chromatography/mass spectrometry (LC/MS), and Fourier transform infrared spectroscopy (FTIR). AFM was used to characterize the heterogeneous phase in the unexposed films and films exposed to alkali solution. Film roughness was found to increase with aging of the film in alkali medium. Total organic carbon analysis of the leached aqueous medium showed the presence of organic compounds, suggesting a chemical degradation of the film in alkali medium. FTIR analysis of the leached medium showed evidence for the formation of carboxylate species upon degradation of polyester film in alkali solution, while LC/MS analysis of the leached medium confirmed the presence of isophthalic acid and sodium isophthalate. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 2454–2463, 2000     

溶解型防污涂料动态性能研究

利用海水动态模拟实验装置模拟船舶航行时船舶水下船体防污涂料的实际服役工况,对3类船舶溶解型防污涂层进行动态模拟实验,定期测量防污涂料铜离子释放率、表面粗糙度、涂层厚度等各项性能,研究各项性能的动态变化规律,并对3类溶解型防污涂料达到一年防污期效的涂层厚度进行了计算。研究结果表明,溶解型防污涂层铜离子释放率在实验初始有大幅下降,随后逐渐稳定,表面粗糙度随时间缓慢下降;模拟航速的上升会提高涂层防污剂的释放率,增加各种涂层表面粗糙度的变化程度,加快涂层厚度减薄。     

Investigation of morphological and electrical properties of the PMMA coating upon exposure to UV irradiation based on AFM studies

The objective of study was to investigate the influence of UV irradiation on morphological changes of a polymeric surface and its electrical properties. In the presented investigation thin poly(methyl methacrylate) (PMMA) film was applied onto iron substrate by solution casting method. UV-C irradiation in range of 200–280 nm was used as a deteriorative factor to induce polymer degradation. Atomic force microscopy (AFM) method was employed to study surface topography of the PMMA coatings before and after exposure to UV-illumination. Photo-induced changes in the polymer surface taking form of microcracks were illustrated by AFM images. In order to support results obtained with AFM method, electrochemical impedance spectroscopy (EIS) measurements were conducted. The authors chose this technique to confirm whether the changes on UV-exposed PMMA surface observed on AFM images could indicate potential sites of the polymer coating long before serious damage could occur. Both methods EIS and AFM were used in order to provide information about durability of PMMA film.     

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.     

无锡自抛光防污涂料动态性能研究

利用海水动态模拟试验装置模拟船舶航行时船舶水下船体防污涂料的实际服役工况,对两类船舶无锡自抛光防污涂层进行动态模拟试验,定期测量防污涂料铜离子释放率、表面粗糙度、涂层厚度等各项性能,研究各项性能的动态变化规律,并对两类无锡自抛光防污涂料达到一年防污期效的涂层厚度进行了计算。     

Multiscale physical characterization of an outdoor-exposed polymeric coating system

Surface topography and gloss are two related properties affecting the appearance of a polymeric coating system. Upon exposure to ultraviolet (UV) radiation, the surface topography of a coating becomes more pronounced and, correspondingly, its gloss generally decreases. However, the surface factors affecting gloss and appearance are difficult to ascertain. In this article, atomic force microscopy (AFM) and laser scanning confocal microscopy (LSCM) measurements have been performed on an amine-cured epoxy coating system exposed to outdoor environments in Gaithersburg, Maryland. The formation of the protuberances is observed at the early degradation stages, followed by the appearance of circular pits as exposure continues. At long exposure times, the circular features enlarge and deepen, resulting in a rough surface topography and crack formation. Fourier Transform Infrared Spectroscopy (FTIR) study indicates that the oxidation and chain scission reactions are likely the origins of the surface morphological changes. The relationship between changes in surface roughness and gloss has been analyzed. The root mean square (RMS) roughness of the coating is related to nanoscale and microscale morphological changes in the surface of the coating as well as to the gloss retention. A near-linear dependence of RMS roughness with the measurement length scale (L) is found on a double logarithmic scale, i.e., RMS ∼ L ^f. The scaling factor, f, decreases with exposure time. The relationship between surface topography, on nano- to microscales, and the macroscale optical properties such as gloss retention is discussed. Moreover, a recent development in using an angle-resolved light scattering technique for the measurement of the specular and off-specular reflectance of the UV-exposed specimens is also demonstrated, and the optical scattering data are compared to the gloss and the roughness results.

新型防污涂料动态性能模拟研究

利用海水动态模拟实验装置模拟船舶航行时船舶水下船体防污涂料的实际服役工况,对无锡自抛光和低表面能两类环保型防污涂料进行动态性能模拟实验,定期测量防污涂料铜离子释放率、表面接触角、表面粗糙度、涂层厚度等各项性能,研究各项性能的动态变化规律,并对两类防污涂料达到一年防污期效的涂层厚度进行了计算。     

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.     

Probing photodegradation beneath the surface: a depth profiling study of UV-degraded polymeric coatings with microchemical imaging and nanoindentation

Photodegradation of polymer coatings generally involves photooxidation, resulting in the formation of oxidized products, chain scission, and crosslinking. On severe exposure to ultraviolet (UV) light in the presence of air, chemical degradation transforms into substantial changes in the physical and mechanical properties, leading to failures of the coatings. Systematic research by NIST on service life prediction of polymeric coatings indicates that the degradation of polymer coatings starts from the sub-micrometer degradation-susceptible regions at the surface and then grows in width and depth. Additionally, due to the oxygen diffusion effect and the attenuation of the UV light passing through the polymer, the degradation can be spatially heterogeneous. In this study, the changes with depth of the mechanical and chemical properties of a UV-exposed epoxy/polyurethane system were measured by nanoindentation and Fourier transform infrared spectroscopy (FTIR) microscopy using cross-sectioned specimens. Multilayers of epoxy/polyurethane samples were prepared by a draw-down technique. After curing, samples were exposed to the outdoors in Gaithersburg, MD, for four months. Cross-sectioned slices of the exposed and unexposed samples, approximately 500 nm thick as-prepared by microtoming, were used for micro-FTIR imaging. Samples for nanoindentation were prepared by embedding the epoxy/polyurethane multilayers (both exposed and unexposed) in a molding compound, followed by microtoming and polishing the embedded films in the thickness direction. Micro-FTIR images clearly show that, for the outdoor exposed samples, substantial amounts of oxidation products are distributed in the 60 μm deep region from the surface to the epoxy bulk, decreasing in the center of epoxy region and increasing again toward the epoxy/urethane interface. Nanoindentation results also show that the modulus significantly increases in the first 60 μm region after UV degradation, and then decreases gradually with depth until a value slightly higher than the modulus of the undegraded epoxy is reached. The modulus rises again in the region near the epoxy/urethane interface. These similarities in the depth profiles of the properties indicate the linkage between the chemical degradation and the mechanical degradation. The study clearly shows that the spatial distribution of chemical species and mechanical properties is heterogeneous in the thickness direction for polymer coatings after UV degradation. It also demonstrates that cross-sectional analysis using nanoindentation and micro-FTIR imaging techniques is a useful method to characterize the mechanical and chemical depth profiles of polymer coating degradation.

UV degradation of clay‐reinforced polypropylene nanocomposites

The aim of this work is to experimentally characterize the UV‐degradation process at both the surface and at different layers across the thickness of injection‐molded polypropylene (PP) matrix containing different amounts of nanosized montmorillonite (MMT) clay particles. These nanocomposite materials have been exposed to UV irradiations (λ = 320 nm) at different preset temperatures (25, 45, and 65°C) in the presence of oxygen and during different exposure times. The extent of such process at these layers was determined using both the FTIR spectroscopy and the wide‐angle X‐ray diffraction analyses. The micromechanical properties across the thickness have been characterized using the nanoindentation technique. The obtained results have indicated that the UV‐degradation process for the nanocomposite materials is much more intense than the one observed for the neat PP. Moreover, it has been noted that such degradation process is not uniform across the thickness of the exposed materials. Results obtained from the X‐ray analysis have shown an increase of the crystallinity of the polymer molecules at only the external surface of the exposed materials. This was confirmed using the nanoindentation test as an increase of the Young's modulus at this layer was noted. POLYM. ENG. SCI., 56:469–478, 2016. © 2016 Society of Plastics Engineers     

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.     

Recovery of surface defects on epoxy coatings and implications for the use of accelerated weathering

Surface roughness, arising from photodegradation, increases overall during weathering but may relax and diminish during episodes when exposure is limited. Different ambient temperatures will change the balance between photodegradation defect size and recovery, depending on the value of the glass transition temperature of the polymer. Epoxy coatings were exposed to periods of ultraviolet irradiation, after which the recovery of the surface roughness was monitored at several temperatures, above and below their glass transition temperatures. Atomic force microscopy, as well as following the increase in roughness with exposure, showed that increased exposure made phase separated domains more distinct. Recovery of nanoindentation on un-damaged coatings produced a similar value of the glass transition temperature to that deduced from the degradation roughness recovery. This was significantly lower at the surface of the epoxy coatings than was measured for the bulk. Confocal Raman spectroscopy was unable to detect any chemical difference between the surface of any films and deeper in their bulk. This evidence suggests that the low glass transition temperature is not due to different curing chemistry at the surface of the coating, but hints that the surface of these crosslinked coatings may relax differently to the bulk or have a different physical structure. These results lead to questions about how to change accelerated testing to better serve the needs of coatings’ technology and how to make progress in the overall goal of service lifetime prediction.     

Ultraviolet light treatment of thin high‐density polyethylene films monitored with a quartz crystal microbalance

Ultraviolet (UV) treatment is an effective method for modification of the surface properties of polymeric materials. In this study, the effects of the ozone‐generating UV light treatment of thin high‐density polyethylene (HDPE) films were monitored with the quartz crystal microbalance (QCM) technique both in the presence of ozone and without it. The films were further characterized by X‐ray photoelectron spectroscopy, optical microscopy, and atomic force microscopy. We found that the ozone not only modified the surface properties of the HDPE films but also etched away the polymer layer. An average etching rate of 0.48 nm/min was determined. UV light exposure of the polymer film in an argon atmosphere resulted only in minor degradation of the films; the presence of ozone was needed to cause the destruction and loss of material. The QCM technique was a straightforward method for the monitoring of the kinetics of the ablation induced by the UV–ozone treatment process. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2833–2839, 2004     

Tribomechanical and microstructural properties of cathodic arc-deposited ternary nitride coatings

Sintered carbides are promising materials for surfaces that are exposed to extreme wear. Owing to their high service load, ceramic-based thin films are coated on carbides using different techniques. In this study, non-toxic and cobalt-free powder metallurgy-sintered carbide samples were coated with TiN, TiAlN, CrAlN, and TiSiN ceramic-based thin film coatings by cathodic arc physical vapor deposition. The microstructure (phase formation, coating thickness, surface roughness, and topography), mechanical properties (hardness, modulus of elasticity, and plasticity indices), and tribological properties (nanoscratch and wear behavior) of the thin film coatings were investigated. No cracks or defects were detected in these layers. The ceramic-based ternary nitride thin film coatings exhibited better mechanical performance than the TiN coating. The TiN thin film coating had the highest average surface roughness, which deteriorated its tribological performance. The ternary nitride thin film coatings exhibited high toughness, while the TiN thin film coating exhibited brittle behavior under applied loads when subjected to nanoscratch tests. The wear resistance of the ternary nitride coatings increased by nearly 9–17 times as compared to that of the TiN coating and substrate. Among all the samples investigated, the substrate showed the highest coefficient of friction (COF), while the TiSiN coating exhibited the lowest COF. The TiSiN thin film coating showed improved mechanical and tribological properties as compared to other binary and ternary nitride thin film coatings.     

Effects of atomic oxygen and ultraviolet in low earth orbit on low surface energy polymer film

Effects of atomic oxygen (AO) and ultraviolet (UV) on a polymer film with surface energy of 8.0 mJ m⁻² derived from poly(1H,1H‐perfluorooctyl methylacrylate) were investigated by contact angle measurements, X‐ray photoelectron spectroscopy, and atomic force microscope. The film was exposed to AO with a flux of 6.73 × 10¹⁵ atoms cm⁻² s⁻¹ and UV with intensity of 15.8 mW cm⁻² at wavelength of 200–450 nm, respectively. It is found that AO and UV irradiation resulted in the reduction of film thickness, change of wettability, and increase of surface energy, and AO exhibited more serious effects than UV on the fluorinated polymer film. Reduced rate of thickness of the film was almost proportional to the AO exposure time. After exposed to AO and UV irradiation, the surface energy of the film increased to 17.3 mJ m⁻² and 11.0 mJ m⁻², respectively. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

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.