Concurrent physical aging and degradation of crosslinked coating systems in accelerated weathering

Coating degradation is a combination of both chemical and physical processes; however, physical processes have not received much attention. Physical aging has a non-negligible effect on coatings’ mechanical properties and permeability etc. through the densification that continues as a polymer approaches its thermodynamic equilibrium below the glass transition temperature, T _g. Observations in recent work showed that physical aging affects coatings’ mechanical property response during accelerated weathering and is, itself, affected by the associated chemical degradation. Two crosslinked coating systems were studied in order to compare different chemical compositions, their T _g, and their thermal response in accelerated weathering. During thermal cycling, physical aging measured by enthalpy recovery exhibited different trends in the two coatings. A “rejuvenation” mechanism was observed in the coating with a T _g between the top and bottom limits of the exposure cycle; continued aging was observed for the coating with a high T _g. Stress relaxation tests detected aging and “memory” behavior over periods comparable with accelerated weathering cycles. Both thermal and mechanical responses changed in complicated and different ways as the coatings degraded. Different degrees of coating thickness reduction were observed in both isothermal relaxation and degradation. When various coatings are evaluated, simply judging their performance under the same weathering environment is not reliable since polymer relaxation behavior depends on the relationship between the exposure temperatures and the T _g of each polymer. This paper was awarded First Place in the 2007 Gordon Awards technical paper competition, held as part of the FutureCoat! conference, sponsored by the Federation of Societies for Coatings Technology, in Toronto, ON, Canada, on October 3–5, 2007.     

Molecular relaxation phenomena during accelerated weathering of a polyurethane coating

Results from a polyester-urethane (PU) coating system under accelerated weathering showed that crosslink density, obtained from high-temperature modulus data, diminished due to chain scission. However, T _g and room-temperature tensile modulus both increased with weathering. Molecular relaxation phenomena in polymers have long been investigated to explore changes occurring in a polymer at temperatures below its glass transition and were explored for an explanation to supplement chemical degradation for these observations. Relaxation was quantified using “enthalpy recovery” which first increased with exposure, then diminished. The concurrent physical and chemical aging effects were characterized by tracking nonexponentiality in the spectrum of relaxation times, and the size of “co-operatively relaxing regions” deduced from relaxation around the glass transition. Mechanical relaxation in this coating extended longer than cycle periods typical of accelerated weathering, suggesting that frequency effects might be important when comparing accelerated to natural weathering. This paper was awarded Third Place in the John A. Gordon Best Paper competition, presented as part of 2006 FutureCoat! Conference, sponsored by Federation of Societies for Coatings Technology, November 1–3, 2006, in New Orleans, LA.     

Mechanical property changes and degradation during accelerated weathering of polyester-urethane coatings

Chemical changes, measured using spectrocopy, and crosslink density, measured by mechanical thermal analysis, were determined during accelerated weathering on a model polyester-urethane coating of known composition. The tensile modulus, measured above the glass transition temperature, and thus the crosslink density, decreased with exposure, as expected from the chemical changes. However, the tensile modulus, measured at room temperature, increased with exposure. Physical aging of the polymer network was found to occur concurrently with photodegradation and accounts for much of the increase in room temperature modulus. Increased hydrogen bonding in the increasingly oxidized polyester-urethane may also contribute to the increase in modulus at room temperature. Both physical and chemical changes must be determined if changes, and rates of change, in performance due to weathering are to be understood. Presented at the 82nd Annual Meeting of the Federation of Societies for Coatings Technology, October 27–29, 2004, in Chicago, IL     

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.     

ABS材料人工加速老化与户外自然老化的相关性

通过红外光谱、色差和力学性能等研究了丙烯腈–丁二烯–苯乙烯塑料(ABS)在人工加速老化试验(UVA,UVB和氙灯)及户外自然老化试验过程中老化行为的相关性。红外分析结果表明,不同ABS材料在人工加速老化和自然老化过程中遵循相同的光氧老化动力学,但不同光源对ABS材料的加速老化作用有明显差别;色差分析结果表明,人工加速老化试验对色差变化的加速倍率由大到小顺序为:UVBUVA氙灯。通过分析ABS材料的色差及力学性能在人工加速老化与户外自然老化过程中变化的相关性,拟合了人工加速老化与户外自然老化的时间换算方程。     

Characterization of surface phenomena: probing early stage degradation of low‐density polyethylene films

Photo‐oxidative degradation of polyethylene triggers significant deterioration in the polymer properties. Much interest is aimed at characterizing and possibly predicting photo‐oxidative damages, at early stages, prior to the occurrence of profound changes in mechanical properties. Herein, we study the degradation of low‐density polyethylene (LDPE) films, focusing on surface deterioration processes. Thin films of various molecular weights are exposed to accelerated weathering while their chemical, mechanical and morphological characteristics are monitored throughout by apparent contact angle (CA) measurements, Fourier‐transform infrared spectroscopy (FTIR), tensile test, and electron microscopy. A significant decrease in the films' CA during degradation is observed. CA is highly sensitive to two simultaneous phenomena with opposing effect: nanoscale surface roughening and composition changes. We found the latter (specifically the evolution of polar groups) to be the dominant parameter affecting the CA behavior. Consequently, simple CA measurements coincide well with conventional FTIR analysis, and are more sensitive to changes occurring at early stages of degradation. The deterioration in the mechanical properties is also characterized and is found to present poor sensitivity and high variability at these early aging stages. Thus, simple CA measurements could potentially be used as a qualitative indicator for evaluating the aging impact on LDPE. POLYM. ENG. SCI., 59:E129–E137, 2019. © 2018 Society of Plastics Engineers     

Behavior of UV‐cured print inks on LDPE and PBAT/TPS blend substrates during curing,postcuring, and accelerated degradation

During radiation curing, a reactive formulation is converted into a highly crosslinked coating film by means of polymerization reactions. This three‐dimensional (3D) network is resistant to external degrading factors as it cannot be undone by any physical–chemical means. In this study, various ultraviolet (UV)‐curable ink formulations with different pigments were developed. The behavior of the UV‐curable inks was evaluated during UV curing in a photocalorimeter or in a UV tunnel. Inks were exposed to accelerated aging in an accelerated weathering chamber and their physical–chemical properties were investigated. The presence of residual fractions of unreacted species trapped in the 3D network formed during UV curing interferes with the degradation of the main structure during exposure in the weathering chamber. The ink formulations that did not easily absorb UV light increased in gloss and hardness, indicating that residual crosslinking is taking place at the same time that degradation is occurring. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41116.     

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     

Environmental and time dependence of moisture transportation in an epoxy coating and its significance for accelerated weathering

It is increasingly appreciated that water is one of the most important factors in the durability behavior of coatings. The rate of water transportation and the degree of saturation of polymeric coatings depends on exposure history, exposure environment, and the nature of a coating. The focus here is on the time taken for transport of water and the variation it causes in thermal and mechanical properties, which have also been shown previously to have time-dependence that leads to discrepancies between different weathering regimes. This paper studied the effect of moisture on coatings’ mechanical properties and the effect of moisture and temperature on recovery of surface indentation. The reduction of mechanical properties and the increasing rate of surface defect relaxation can be explained in terms of plasticization by water. Recovery of surface defects is related to the appearance and diffusion activity of coatings during exposure. Thermogravimetric analysis showed that the content of moisture in the sample is determined by the ambient humidity, temperature, and the rate of change in these environmental parameters. Diffusion coefficients were determined from the weight change data and an activation energy was obtained via Arrhenius equation. Changes in yellowness, as an example, and signature of chemical degradation, indicated that the cycling period in accelerated weathering may affect the degradation via the amount and distribution of moisture in coatings. Diffusion of moisture is typically slow and limits the possibility of complete drying or saturation in an exposure cycle. Results from the cumulative effect of many cycles will be different depending on the conditions.     

老化试验中PE-HD的结构与力学性能研究

研究了高密度聚乙烯在海南自然曝露和氙灯人工老化后的结构和力学性能变化。结果表明：相比于自然曝露，高密度聚乙烯主要力学性能的氙灯人工老化加速倍率大约为4；老化期间，高密度聚乙烯分子间存在着交联和降解二种竞争反应，老化早期以交联为主，后期以降解为主；氙灯老化试验相比于自然曝露，老化主要集中在材料表层。     

Effect of weathering on physical properties of clearcoats

Aim of the investigations was to explore the weatherability performance of selected polymer films. The results were correlated with each other, so that measurable changes can be attributed to chemical and/or physical effects. Therefore, polyols with different aromatic content were produced. The resins were crosslinked with melamine-formaldehyde resin (1K system) and polyisocyanurate (2K system), respectively. The analyses resulted after each 100 h accelerated weathering in a period of total 1000 h. Chemical degradation processes were analysed by means of FT-IR spectroscopy. For the physical investigations were used: dynamic mechanical analysis (DMA), differential scanning calorimetry (DSC), investigation of the surface topography, contact angle measurements to determine the surface tension, and gloss measurements. The mechanical investigations proved remarkably suited for tracing the changes in properties. Already after a short exposure time these methods yielded information about the weathering behaviour of the investigated clearcoat systems.     

Accelerated clearcoat weathering studied by dynamic mechanical analysis

Automotive basecoat/clearcoat (BC/CC) systems of the acrylic polyol/melamine formaldehyde (ACR/MF) type were analyzed by dynamic mechanical analysis (DMA) before and after exposure to QUV. DMA changes after 500 h exposure were compared to gloss retention after five year Florida exposure or 2500 h QUV exposure. DMA readily distinguished between ‘poorer’ and ‘better’ BC/CC films received in a blind study. Crosslink density and T_g both increased during QUV. DMA changes depended strongly on the presence or absence of hindered amine light stabilizer (HALS). Variations in the basecoats had only minor effects on DMA results. Poly(urethane) clearcoats (without basecoats) were also studied. Differences in weathering behavior of films prepared with three widely used poly(isocyanates) are reported. Crosslink density decreased and T_g increased during QUV exposure. Stabilizers were very effective in the poly(urethane) clearcoats. DMA results are discussed in relation to FT-IR spectra obtained before and after QUV.     

Lifetime prediction of polymers

Natural and artificially accelerated weathering trials were carried out on low-density polyethylene samples used for agricultural and disposable purposes. Modifications in polymer characteristics were studied using Fourier transform infrared (FTIR) spectroscopy, different scanning calorimetry (DSC), gel permeation chromatography (GPC), scanning electron microscopy (SEM), and mechanical properties testing. The natural exposure trials were conducted at five geographical locations representing varying ambient temperature and humidity conditions and receiving different doses of solar radiation. The artificially accelerated exposure trials were carried out in an Atlas weatherometer for 5,000 hours, whereas the natural exposure was for 24 months. Rates of photo-oxidative and thermal degradation have been determined by measuring the formation of non-volatile carbonyl oxidation products which absorb in the infrared region with a maximum absorbance level at 1710cm^?1. Thermal characteristics were noticed to vary in terms of the shape and size of melting peak for both the natural and artificial weathering. This implies a change in crystallinity, which has indicated an increasing trend with exposure time. The crystalline melting temperature (T_m) remains almost steady for both exposure tests. The drop in mechanical properties and the modification in polymer chain length were also monitored. The GPC analysis indicated the change in molecular weight distribution (MWD), which shows the formation of lower molecular-weight species. Surface modifications were revealed in terms of abrasion effects apparent from SEM micrographs. A correlation between natural and artificial weathering was considered for lifetime prediction in a short exposure time. It was found that the confidence level of predicting lifetime on the basis of artificially accelerated exposure trials is dependent on many parameters, which include time, material, equipment, etc. © 1995 John Wiley & Sons, Inc.     

Rapid,reliable tests of clearcoat weatherability: a proposed protocol

In this paper, a protocol is proposed for the rapid prediction of durability of automotive enamel clearcoats. The protocol is designed to minimize test time while maximizing test reliability. The protocol is based primarily on chemical measurements of degradation rates rather than observation of physical failure.There are two key aspects to the protocol. The first is the use of electron spin resonance spectroscopy (ESR) to measure the rate of formation of free radicals in the coating under near-ambient exposure conditions (photo-initiation rate). This measure is used to rapidly screen coatings under development and to monitor the weatherability of previously qualified materials. Extensive, conventional accelerated exposure tests are performed only on new materials with low photo-initiation rates.The second key aspect is the use of spectroscopic measurements of chemical degradation both to select an appropriate accelerated exposure and to determine the ratio of the rate of chemical change during accelerated exposure to that during natural exposure (i.e. the acceleration factor). Knowing the acceleration factor and the time to failure in a valid accelerated exposure, it is possible to estimate the service life. The service life is then related to the photo-initiation rate and photo-initiation rate measurements are used in coating quality control.This report describes in detail the steps in the protocol, the kind of chemical measurements which may be required, and provides examples of its application.     

Efficacy of hindered amines in woodflour‐polypropylene composites compatibilized with vinyltrimethoxysilane after accelerated weathering and moisture absorption

In this work, the aim was to analyze the efficacy of hindered amine light stabilizers (HALS) in woodflour‐polypropylene composites compatibilized with vinyltrimethoxysilane after moisture absorption and accelerated weathering. Moisture uptake of materials decreased with incorporation of silane due to diminished accessibility of water molecules to reactive regions. In dynamic mechanical experiments performed on wet samples, a marked reduction in the storage modulus in the glassy and rubbery zone was observed, since water has a plasticizing effect. After sample weathering, in a xenon‐arc apparatus, the changes in chemical structure and physical properties after exposure were analyzed by attenuated total reflectance Fourier transform infrared (ATR‐FTIR) spectroscopy, color measurement, flexural properties, and morphological analysis by scanning electron microscopy (SEM). The data showed that HALS maintain the brightness of the materials after aging and prevent sample whitening. They also reduced color loss after aging and the SEM micrographs revealed that they inhibit surface cracking during weathering. Although a slight decline in the mechanical properties was not completely avoided, the combination of the additives studied (UV absorbers and HALS) successfully prevented the deterioration of surface materials by UV radiation. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Surface oxidation of low‐density polyethylene films to improve their susceptibility toward environmental degradation

Polyethylene wastes, particularly as films, have accumulated over the last several decades resulting in a major visual litter problem. The aim of this study was to investigate the ability of chemical reagents to oxidize the low‐density polyethylene (LDPE) film surface to increase their susceptibility toward photodegradation and thermal degradation. Three chemical agents, namely, potassium permanganate, potassium persulfate, and benzoyl peroxide, were used to oxidize the film surface to generate chromophoric groups, such as carbonyl groups, which are the main reason for the enhanced environmental degradation of photolytic polymers, such as ethylene–carbon monoxide and ethylene–vinyl ketone copolymers. For the chemical treatment, LDPE films of 70 ± 5 μm thickness were prepared by a film‐blowing technique and subsequently reacted with the aforementioned oxidizing agents. To aid the oxidation process, the reaction with potassium persulfate and potassium permanganate was performed under microwave irradiation heating. In the case of benzoyl peroxide aided oxidation, the films were subjected to repeated coating–heating treatments up to a maximum of 10 cycles. The treated films were subjected to accelerated aging, that is, xenon‐arc weathering and air‐oven aging (at 70°C), for extended time periods. The chemical and physical changes induced as a result of aging were followed by the monitoring of changes in the mechanical, structural, and thermal properties. The results indicate that the surface‐oxidized LDPE films exhibited enhanced susceptibility toward degradation; however, the extent was reduced as compared to photolytic or other degradable compositions. The ability of the chemicals to initiate degradation followed the order potassium persulfate < potassium permanganate < benzoyl peroxide. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Durability of the flame retardance of ethylene-vinyl acetate copolymer cables: Comparing different flame retardants exposed to different weathering conditions

Scientific publications addressing the durability of the flame retardance of cables during their long-term application are rare and our understanding lacks. Three commercial flame retardants, aluminum hydroxide, aluminum diethyl phosphinate (AlPi-Et), and intumescent flame retardant based on ammonium polyphosphate, applied in ethylene-vinyl acetate copolymer (EVA) model cables, are investigated. Different artificial aging scenarios were applied: accelerated weathering (UV-irradiation/temperature/rain phases), humidity exposure (elevated temperature/humidity), and salt spray exposure. The deterioration of cables' surface and flame retardancy were monitored through imaging, color measurements, attenuated total reflectance Fourier transform infrared spectroscopy, and cone calorimeter investigations. Significant degradation of the materials' surface occurred. The flame retardant EVA cables are most sensitive to humidity exposure; the cable with AlPi-Et is the most sensitive to the artificial aging scenarios. Nevertheless, substantial flame retardance persisted after being subjected for 2000 h, which indicates that the equivalent influence of natural exposure is limited for several years, but less so for long-term use. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 47548.     

Environmental degradation of some polymer blends. Blends of polystyrene with acrylonitrile butadiene styrene,poly(vinyl chloride), and polybutadiene and blends of polybutadiene with poly(vinyl chloride)

One class of polymer/additive which has become increasingly important is polymer blends. In this study the ultimate tensile strength, elongation at break, and the modulus of acrylonitrile–butadiene–styrene, poly(vinyl chloride), polybutadiene and polystyrene and their blends have been studied over an entire binary composition range. We have correlated these mechanical properties to their degradation behavior under natural and accelerated weathering by measurement of various indices during thermal and natural weathering. It was found that during natural weathering the presence of polystyrene in acrylonitrile–butadiene–styrene (ABS) improved the weatherability of ABS; the converse was true when the blends were heated in an air oven at 100°C. It was also found that the weatherability of PB was improved in the presence of polystyrene and large improvement in the rigidity was observed. Similarly, from a measurement of carbonyl index, it was found that PVC has a stabilizing effect on PB. In many cases, the 50:50 composition of the polymers gave the best compromise of good mechanical properties, heat stability, and outdoor weathering. The mechanisms of possible interactions between the degrading polymers are discussed.     

Novel Hybrid Polymer Composites Based on Anthraquinone and Eco-Friendly Dyes with Potential for Use in Intelligent Packaging Materials

This study aimed to present the influence of bio-based and anthraquinone dyes and their combinations on the optical properties of ethylene-propylene (EPM) composites after thermo-oxidative and climatic aging. Therefore, the chosen polymer was filled with a natural, plant-origin flavonoid—quercetin, and with two commercial anthraquinone dyes (C.I. Solvent Yellow 163 and C.I. Solvent Red 207). The manufactured polymer composites were subjected to accelerated aging tests: weathering and thermo-oxidation, respectively. Examination of the materials’ properties indicated that the combination of synthetic and natural dyes can result in better resistance to oxidizing agents and higher thermal stability of ethylene-propylene products. Moreover, color change of quercetin-containing samples due to exposure to simulated atmospheric conditions could be a promising solution for use as aging indicators in intelligent packaging materials that will inform about the ongoing degradation process. Another interesting finding is that these samples exhibited good fungistatic activity against Candida albicans yeast and Aspergillus niger mold. Overall, this novel solution based on hybrid polymer composites containing natural and commercial dyes is a more environmentally friendly alternative to traditional materials used in the plastic packaging industry with better and more desirable properties.     

Waterborne acrylic varnishes durability on wood surfaces for exterior exposure

The protection performance of varnishes applied to two different wooden substrates (maritime pine and iroko) for outdoor exposure was investigated for eight different varnish systems (with and without colorants and two different light stabilizers). All were subjected to accelerated artificial weathering and natural weathering. Several test methods were used to evaluate the appearance and physical–chemical properties of the coatings during the degradation. The results obtained lead to the selection of the best varnish formulation for the protection of wood for exterior use and provide useful evaluation of the test methods employed.