Effect of titania and zinc oxide particles on acrylic polyurethane coating performance

The outer environment, especially UV portion of solar radiation and water (in the form of moisture or rain) has an adverse effect on the surface appearance of heat-treated wood. Exposure to UV triggers the chain scission reactions which change the intrinsic properties of heat-treated wood and discoloration of wood surface. Repeated temperature and humidity variations cause swelling and shrinking of wood surface, which consequently create cracks and fissures exposing wood's sub superficial layers to atmospheric agents. Therefore, wood industries move towards the development of coatings in order to protect the heat-treated wood while retaining wood's natural look. Water based acrylic polyurethane coatings are highly efficient, non toxic and durable coatings with upgraded film properties. In this study, an attempt is made to improve the performance of these coatings by incorporating natural antioxidant (bark extract) and inorganic UV absorbers (nano and micro titania and nano zinc oxide) into the coatings. The main objectives of this study are to investigate the wetting and penetration characteristic of these new coatings on the wood surface and to study coating thickness variation with weathering time. The Sessile-drop method and fluorescence microscope are used for this investigation. The wettability of different coatings applied to heat-treated jack pine early wood and late wood is compared. The results show that there is a significant difference between the contact angle of early wood and late wood for acrylic polyurethane coating containing titania micro particles. The contact angle between water and coated wood surface reveals that the degree of orientation of the coating materials increases as the weathering time increases. The penetration characteristics of all the four coatings are found to be very poor. In addition, the relationship between the coating thickness and the UV exposure time is studied for four water based acrylic polyurethane coatings with different additives. It is found that the coating thickness decreases with increasing weathering time and a tissue deformation beneath the coating surface takes place during weathering.     

Surface properties of impregnated and varnished Scots pine wood after accelerated weathering

In this study, the effect of accelerated weathering on the surface properties of Scots pine specimens impregnated with wolmanit‐CB, tanalith‐E, and adolit‐KD5 and coated with synthetic and polyurethane varnishes was investigated by measuring surface hardness, glossiness, and colour. Results showed that weathering caused an increase in the hardness of impregnated and varnished specimens, while it caused a decrease in the glossiness of specimens. Surfaces became rougher and darker after weathering in comparison with the initial surfaces of wood specimens. Positive values of the chromatic coordinates indicated that the wood surfaces changed from their original colour to a reddish and yellowish colour. The highest colour change was detected in the specimens coated with polyurethane varnish alone. Both copper‐based wood preservative treatment and varnish coating improved the surface properties of specimens in comparison with the surface properties observed on specimens coated with varnish alone.     

Photocurable epoxy/cubic silsesquioxane hybrid materials for polythiourethane: Failure mechanism of adhesion under weathering

A new inorganic–organic hybrid coating containing epoxy‐functionalized cubic silsesquioxane (CSSQ) has been developed, which can be polymerized cationically by UV radiation. This solvent‐free solution can be used as hybrid coating for polythiourethane (PTU) substrate. The surface properties of the coating film were determined by adhesion and scratch resistance. The excellent adhesion of coating films on the substrate was observed at the initial stage before weathering, but deteriorated after exposure to the sunshine. The low viscosity of hybrid coating solution (～ 15 mPa s) leads to fast curing and the formation of hybrid coating film during the photopolymerization reaction. The adhesion failure was evaluated by atomic force microscopy (AFM), Fourier transform infrared spectroscopy (FTIR), and X‐ray photoelectron spectroscopy (XPS) analyses. AFM images showed that the surface is smooth at the initial stage, but a texture surface was developed after weathering. The shrinkage of the hybrid film due to the increase in crosslinking density by postpolymerization would affect the surface roughness after weathering. XPS analysis indicated that the adhesion failure occurred by photodegradation of the PTU substrate during weathering. The weathering resistance was significantly improved by adding UV absorbers, which protected the polymer substrate from the photodegradation. The advantages of the hybrid coating include fast cure speed, solvent‐free formulation, and improved surface properties of the coating film. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effect of addition of nanosized UV absorbers on the physico-mechanical and thermal properties of an exterior waterborne stain for wood

This study describes the effects of the addition of inorganic nanosized UV absorbers on physico-mechanical and thermal properties of an exterior commercial acrylic-based waterborne stain for wood. Electronic microscopy and water vapor (WV) permeability measurements were performed to characterize the free films of the acrylic stain and resulting nanocomposite coatings. An accelerated weathering method was used to evaluate aging behavior of the coatings on wood through appearance, T_g, abrasion resistance, adhesion strength, hardness and Young's modulus changes. In addition to improving the protection against UV, the doped TiO₂ and silica-coated ZnO nanoparticles in powder form have improved the abrasion resistance and barrier effect against water vapor diffusion of the acrylic stain. For most of nanocomposite coatings, the addition of ZnO hydrophilic nanoparticles in predispersed form has resulted in a decrease in WV permeability, while the adhesion strength and abrasion resistance of those coatings were negatively affected. The addition of ZnO nanoparticles has decreased the T_g of the acrylic stain. Finally, the accelerated weathering has induced an increase in T_g, hardness, Young's modulus (stiffness) and an increase in apparent adhesion strength and abrasion resistance of the coatings. The T_g values of the aged nanocomposite coatings were lower than that of unmodified acrylic stain.     

Effect of addition of nanosized UV absorbers on the physico-mechanical and thermal properties of an exterior waterborne stain for wood

This study describes the effects of the addition of inorganic nanosized UV absorbers on physico-mechanical and thermal properties of an exterior commercial acrylic-based waterborne stain for wood. Electronic microscopy and water vapor (WV) permeability measurements were performed to characterize the free films of the acrylic stain and resulting nanocomposite coatings. An accelerated weathering method was used to evaluate aging behavior of the coatings on wood through appearance, T_g, abrasion resistance, adhesion strength, hardness and Young's modulus changes. In addition to improving the protection against UV, the doped TiO₂ and silica-coated ZnO nanoparticles in powder form have improved the abrasion resistance and barrier effect against water vapor diffusion of the acrylic stain. For most of nanocomposite coatings, the addition of ZnO hydrophilic nanoparticles in predispersed form has resulted in a decrease in WV permeability, while the adhesion strength and abrasion resistance of those coatings were negatively affected. The addition of ZnO nanoparticles has decreased the T_g of the acrylic stain. Finally, the accelerated weathering has induced an increase in T_g, hardness, Young's modulus (stiffness) and an increase in apparent adhesion strength and abrasion resistance of the coatings. The T_g values of the aged nanocomposite coatings were lower than that of unmodified acrylic stain.     

Wood surface modification by in-situ sol-gel deposition of hybrid inorganic–organic thin films

Interest in the use of nanoparticles of iron, titanium, aluminum, and zinc oxides in transparent coatings for wood is increasing. Such nano-composite coatings have the potential of not only preserving the natural color of the wood, but also stabilizing the wood surface against the combined degradative effects of sunlight and moisture. The nanoparticles can be used as additives to coating formulations or deposited directly as thin films on a substrate. Thin film deposition can be accomplished by plasma-enhanced chemical vapor or by sol-gel deposition. This paper describes sol-gel deposition of a hybrid inorganic–organic thin film on wood using a mixture of metal–organic precursors and its effect on weathering properties of the wood surface. Presented at the 5th International Woodcoatings Congress: Enhancing Service Life, sponsored by the Paint Research Association (PRA), in Prague, Czech Republic, on October 17–18, 2006.     

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.     

Exterior wood coatings. Part-2: Modeling correlation between coating properties and their weathering performance

Understanding how a coating’s properties are related to its performance characteristics and how measuring its properties can be used for predicting the performance of coating in service was the main focus of this study. A number of exterior penetrating wood stains were characterized in terms of glass transition temperature (T _g), solid content, viscosity, and surface tension. The contact angles of liquid coatings were measured on wood treated with chromated copper arsenate, alkaline copper quat, and copper azole as well as untreated wood. Also, the film thicknesses of the cured coatings on wood surfaces were measured by back-scattered electron imaging of osmium-treated samples. Partial least square-regression (PLS-R) modeling was used to correlate measured coating properties with their weathering performance on the preservative-treated and untreated wood substrates, based on water repellency, color retention, and visual ratings after 3 years of natural weathering. A PLS model was developed with 77% fitting accuracy and 69% prediction ability. This model indicated that preservative treatments significantly affected coating performance, and among coating properties, film thickness, viscosity, and glass transition temperature had the greatest effects on the coatings’ performance in exterior.     

Optical and surface properties of whey protein isolate coatings on plastic films as influenced by substrate,protein concentration,and plasticizer type

Composite film structures of common plastic polymers including polypropylene (PP) or poly(vinyl chloride) (PVC) with whey protein isolate (WPI) coatings may be obtained by a casting method. Optical and surface properties of the resulting WPI‐coated plastic films, as affected by protein concentration and plasticizer type, were investigated to examine the biopolymer coating effects on surface modification with polymeric substrates of opposite polarity. The measured properties involved specular gloss, color, contact angle, and critical surface energy. Regardless of the substrates, WPI‐coated films possessed excellent gloss and no color, as well as good adhesion between the coating and the substrate when an appropriate plasticizer was added to the coating formulations. The protein concentration did not significantly affect gloss of WPI‐coated plastic films. Among five plasticizers applied, sucrose conferred the most highly reflective and homogeneous surfaces to the coated films. The WPI coatings were very transparent and the coated films with various protein concentrations and plasticizers showed no noticeable changes in color. Experimental results suggest that WPI coatings formulated with a proper plasticizer can improve the visual characteristics of the polymeric substrate and enhance water wettability of the coated plastic films. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 335–343, 2004     

蜡助剂在水性木器涂料中的应用

蜡助剂是水性木器涂料中使用的一种功能性助剂，本文研究了不同种类的蜡助剂在水性木器涂料中的使用对漆膜性能的影响。采用复配法将水性蜡助剂加入到水性木器涂料中，蜡助剂在涂料成膜时均匀地分散在整个涂层中，蜡助剂的加入能够显著提高漆膜的抗回粘性和耐刮伤性能，但是大粒径的蜡助剂会引起漆膜光泽的下降。     

Synthesis and characterization of novel hyperbranched alkyd and isocyanate trimer based high solid polyurethane coatings

In the present work, hyperbranched urethane alkyd high solid coatings were formulated by mixing hyperbranched alkyd and isocyanate trimer. Initially, a second generation hyperbranched polyol (HBP) was synthesized using dipentaerythritol (DPE) as a core material and 2,2-bis(methylol)propionic acid (BMPA) as a chain extender. This was reacted with varying concentrations of linseed oil fatty acid (LOFA) to make a series of hyperbranched alkyd (HBA) resins. Viscosity and volume solid of the HBA resins were measured. The resins were characterized by Fourier transform infrared (FTIR), and ¹³C Nuclear magnetic resonance (¹³C NMR) spectroscopic techniques. The hyperbranched alkyd resins containing varying amount unreacted hydroxyl groups were cured with hexamethylene diisocyanate (HDI) trimer (Desmodur N 3390) depending on their NCO: OH ratio to make hyperbranched urethane alkyd coatings. A series of such coatings were made by mixing HBA/isocyanate trimer (Desmodur N 3390) ratio with respect to the hydroxyl group present on the HBA. The performance of the coated specimens was evaluated by various techniques such as pull-off adhesion strength, tensile strength, abrasion resistance, scratch resistance, flexibility, and impact resistance tests. The weathering properties of the coated specimens were evaluated by UV-Weatherometer. Corrosion resistance of the coated specimens was evaluated by electrochemical impedance spectroscopy (EIS), salt spray, seawater immersion and humidity tests. It was observed that, there exists an optimum coating composition in terms of NCO: OH (HBA: Desmodur N 3390) ratio which showed excellent enhancement in terms of the mechanical, weathering and corrosion resistance properties than remaining coating compositions.     

Effects of expandable graphite on char morphology and pyrolysis of epoxy based intumescent fire-retardant coating

The current study was designed to investigate the effects of expandable graphite (EG) on fire protection properties of intumescent fire-retardant coating for steel structures. Several formulations of intumescent coating were prepared and tested according to ISO 834 for char expansion. The chars were found without cracks and bonded with the steel substrate. The results showed that the coating slowly degraded during the test and char remained in contact with vertically tested coated substrate. The coated substrates were also tested for weather resistance using humid and ultraviolet environment. The char was characterized by using FESEM, XRD, FTIR, TGA, and XPS analysis. FESEM examined char morphology of the coatings after furnace fire test. XRD and FTIR showed the presence of graphite, borophosphate; boron oxide and sassolite in the char. TGA and DTGA results disclosed that EG improved the residual mass of coating. XPS analysis showed the percentages of carbon and oxygen are 48.50 and 43.45 in char of formulation with 12.8% EG. The results of weathering test coatings showed decreased in char expansion because of a humidity and UV light. The formulation with 9.8% EG showed the maximum char expansion and high residual mass among the formulations investigated in this study. The weathering tested coated samples showed their capability of fire protection.     

Improving the mechanical resistance of waterborne wood coatings by adding cellulose nanofibres

In the present study, microfibrillated cellulose (MFC) and nanocrystalline cellulose (NCC) were applied as additives for a waterborne acrylate/polyurethane-based wood coating in order to improve the mechanical resistance of coated wood surfaces. Coating mixtures containing up to 5 wt% nanocellulose were prepared by high-shear mixing and applied to wood substrates. The optical, mechanical and chemical properties of cured coatings were characterized. Surface roughness, gloss, scratch resistance, abrasion resistance and resistance against chemicals were determined according to the relevant European standards. Additionally, nanoindentation (NI) was used to assess the micromechanical properties of modified and unmodified coatings. Owing to a higher surface roughness, cellulose-filled coatings showed significantly lower levels of gloss than the unmodified coating indicating that nanocellulose acts as a matting agent. NI experiments revealed a slightly positive effect of nanocellulose addition on the hardness and modulus of the coatings. While scratch resistance improved consistently with increasing nanocellulose addition, abrasion resistance was found to improve only sporadically. Tensile tests on free-standing coating films revealed a significantly higher tensile strength and modulus for cellulose-filled coatings. Overall, the results suggest that the addition of cellulose nanofibres primarily improves the internal cohesion of the coating layer whereby MFC was more effective than NCC.     

Organic–inorganic hybrid linseed oil‐based urethane oil wood coatings

To prepare alkoxysilane‐functionalized urethane oil (AFUO) using linseed oil, 3‐aminopropyltriethoxysilane (APTES) was first reacted with diisocyanate to obtain an NCO‐terminating oligomer. The reaction was continued by adding linseed oil glyceride to form an AFUO prepolymer. The auto‐oxidative drying coating was obtained after adding a metal dryer to the AFUO prepolymer. Urethane oil (UO) coating, as a control, was obtained by the same procedure as that for AFUO, but without containing alkoxysilane‐functional groups in the formation. Siloxane hybrid urethane oil (SHUO) wood coatings were prepared by mixing tetraethyl orthosilicate (TEOS) solutions, as an external crosslinking agent by sol–gel process, with the AFUO and UO coatings. We found that introducing of APTES into the molecular chains of the UO coating resulted in a film with superior impact and abrasion resistance, and it is the most efficient process to enhance the UO films. The addition of TEOS into AFUO coatings shortened the curing time and further improved the crosslinking density of the AFUO films; however, the physical properties like impact resistance, bending resistance, and gloss were even worse than AFUO films. Mixing of TEOS and UO coating also shorten the curing time and improved the heat resistance, lightfastness, and hardness of the UO coating. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44562.     

具有可视胶化性能的水性双组分木器漆的研制

开发了一种木器用双组分水性聚氨酯涂料,该体系在到达活化期的同时可产生液态漆可视胶化的现象,且漆膜性能在活化期内各时间段均能保持稳定。重点讨论了乳液、配套固化剂对体系性能的影响。实验发现只有特定的乳液和固化剂搭配才能保证达到活化期内出现液态漆可视胶化以及漆膜性能在活化期内保持稳定的目标,并且该产品漆膜性能与溶剂型双组分聚氨酯木器涂料的相当。该涂料产品适合零售市场对水性木器漆的需求。     

Natural weathering performance and the effect of light stabilizers in water-based coating formulations on resin-modified and dye-stained beech-wood

This study assesses the performance of untreated and resin-modified beech-wood (Fagus sylvatica L.) during outdoor weathering. Boards modified with thermosetting N-methylol melamine (NMM) and phenol–formaldehyde (PF) resins, which were partly dye stained, were coated solely with a waterborne acrylic binder and formulations containing the same binder with different types and contents of photo-protective additives. Most modifications of the wood substrate changed the original color of wood, except for sole NMM modification. Changes in mass and capillary water uptake during exposure of modified, uncoated and coated boards were less than those of respective controls. Surface defects and cracks were clearly fewer on modified wood than on the controls, but no clear difference was observed among the topcoats containing UV-protective agents (UV-PA). The color stability during outside weathering depended on the treatment and coating formulation. Untreated and NMM-modified boards became grayer, and the NMM-dye-modified boards turned to a lighter gray, while PF-modified boards adopted a darker, blackish color. The weathered coating on the modified boards, particularly with PF resin, showed less blistering, flaking, and cracking than that on the controls. UV-PA stabilized the color and adhesion on all boards compared to the sole binder formulation. We conclude that wood modification with NMM and PF resin improves the natural weathering performance of wood coated with acrylic coatings. Combination of modification with staining enables diversification of the optical appearance.     

Green metal organic coating from recycled PETs and modified natural rubber for the automobile industry

Novel elastomeric polyurethane coating precursors from renewable natural rubber and waste bottle PET were prepared for metal coating applications. The elastomeric PU was synthesized from; modified natural rubber with hydroxyl functional groups (HLNR), modified NR grafted with polysiloxane (PDMS-g-LENR) and modified PETs (P-ET-PA and P-T-PA) such as a polyol/polyacid; a commercial MDI (Millionate MR-200) as an isocyanate. The physical properties such as film-thickness, gloss, hardness, adhesion (cross-cut and scratch-adhesion), impact test, Erichsen, bending and chemical resistance of the coated film were investigated by following the industry standards for automobile coatings. The properties of the coated films were influenced by the ratio of polyol/polyacid and the polyol nature. It was found that the coated film prepared from both of modified NR presented good adhesion with the metallic substrate by absence the surface treatment. Single layer of PU elastomer film prepared from both modified PETs with HLNR35 and MDI with mole ratio of 0.1:0.3:0.75 showed good physical properties following the industry standards for automobile coatings. The presence of PDMS-g-LENR in the coatings improved the thermal stability when compared to HLNR35. Furthermore, salt spray test and electrochemical impedance spectroscopy (EIS) were used to examine the corrosion behavior of the coated steel. It could be concluded that the best anticorrosive behavior was shown by the PDMS-g-LENR and P-T-PA formulas.     

Mechanical recycling of nanocellulose containing multilayer packaging films

The aim of this study was to demonstrate mechanical recycling of low density polyethylene (LDPE) films coated with a thin layer of cellulose nanofibrils (CNFs). CNF acts as an effective barrier against oxygen and mineral oil residues. Two different CNF grades were tested, and both were applied onto plasma activated LDPE film using a pilot coating line. The coated films were shredded with the help of liquid nitrogen, compacted and compounded with virgin LDPE and compatibilizer, and processed into cast films and injection molded test specimens. The CNF coatings were completely blent as microscale agglomerates in the LDPE matrix. The effect of these agglomerates on the barrier and heat sealing properties was statistically insignificant compared to recycled uncoated LDPE. The mechanical properties were only moderately changed. CNF‐coated LDPE films can therefore be recycled back into films without sacrificing the characteristic properties of the base polymer. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46237.     

Melt versus solvent coating: Structure and properties of block–copolymer‐based pressure‐sensitive adhesives

Pressure‐sensitive adhesives (PSAs) composed of a styrene–isoprene–styrene triblock copolymer and a midblock‐associating resin were prepared via solvent and hot‐melt coating. The formulations and thermal histories up to the point of coating were identical, yet significant differences in the properties were observed as a function of the coating method. The solvent‐coated PSA showed superior shear holding power, and the hot‐melt‐coated PSA performed better in tack and peel tests. Two factors resulting from the processing conditions were responsible for these property differences. The quick cooling process occurring after hot‐melt coating led to a poorly defined microstructure and, therefore, less physical crosslinking. Rheological data for melt‐pressed and solvent‐cast PSA films confirmed these microstructural differences. The increased solubility of the tackifier in the solvent additionally created a composition gradient in the solvent coating. Annealing improved the long‐range order of both hot‐melt and solvent coatings, producing a body‐centered cubic microstructure identified by small‐angle X‐ray scattering. This microstructure improved the shear strength of both types of adhesive coatings, whereas the peel and tack properties of the solvent coatings remained inferior to those of the hot‐melt coatings because of differences in the surface compositions. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3355–3367, 2002     

TEM,XPS and thermo-mechanical properties of novel sustainable hybrid coatings

This work contributes to the development of a new generation of protective coatings composed of organic–inorganic materials. A silica based hybrid film was used in this work as high performance materials. The silica sol–gel film reveals enhanced thermo-mechanical properties in comparison with the pure polymer film. Herein, we demonstrate the possibility of employing cheap SiO₂ as prospective nano-fillers for hybrid coatings with active thermo-mechanical properties. Organic–inorganic hybrid coatings based on polyimide and silica were synthesized through a simple physical mixing technique. 3,3′,4,4′-Biphenyltetracarboxylic dianhydride (BPDA), benzene-1,3-diamine (BDA), 3,3′-oxydianiline (ODA) and SiO₂, were used as precursors for the hybrid coatings. These hybrid coatings were deposited via spin coating onto a galvanized iron, aluminum and copper in order to study the adhesive strength. The effects induced by the silica content on the mechanical properties of the coated samples were investigated. The mechanical properties of hybrid composite were found to be enhanced compared to polyimide coating. The main objective was to observe potential improvements in the mechanical and thermal properties of PI–silica hybrid films. Morphology, and structural changes in the composite films were studied as well as adhesion and impact strength and these characteristics were compared with those of unreinforced polyimide films.