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.     

Facile preparation and good performance of nano-Ag/metallocene polyethylene antibacterial coatings

Metallocene polyethylene/nano-silver coatings were prepared by a facile air-spray method on polymer films. Different from the prevailing strategy to endow polyethylene with antibacterial performance, we used metallocene polyethylene sol and nano-silver as a precursor to deposit coatings on polymers at a relatively low operating temperature. Antibacterial coatings with excellent mechanical properties, water resistance, and low silver release were achieved. The composite coatings were examined in terms of surface characteristics, mechanical properties, and antibacterial activity against two representative bacterial strains including Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus). The composite coatings exhibited favorable microstructure, good mechanical properties, and suitable crystallinity. The antimicrobial tests indicated that the fabricated composite coatings showed promising antibacterial activity against E. coli and S. aureus. Furthermore, Ag ions released by the composite coating after 30 days were under 1.2 ppb. These results indicated a promising prospect of the composite coating for wide antibacterial applications.     

Impedance sensor for the early failure diagnosis of organic coatings

A miniature impedance sensor used for field diagnosis of the early failure of coatings has been developed based on microelectronics and electrochemical impedance spectroscopy (EIS). The aging process of polyurethane-based coatings in salt spray test chamber was studied using the impedance sensor. Several critical indexes related to EIS such as phase angle (θ_10Hz, θ_15kHz), breakpoint frequency (f_b), specific capacitance (C_10Hz, C_15kHz), and impedance modulus (Z_0.1Hz) were proposed to evaluate the severity of coating degradation. The results indicated that the impedance sensor could accurately monitor the degradation process of coatings, and once Z_0.1Hz?<?10⁶ Ω cm², f_b?>?100 Hz, or θ_10Hz?<?20°, the coating may be regarded as completely degraded and fails to protect the metal substrate.     

A fluorine–silicone acrylic resin modified with UV-absorbing monomers and a free radical scavenger

A novel UV-absorbing and free-radical-catching fluorine–silicone acrylic resin with 2-(4-benzoyl-3-hydroxyphenoxy) ethyl acrylate (BHEA), 2,2,6,6-tetramethyl-4-piperidyl methacrylate (TMPM), dodecafluoroheptyl methacrylate (DFMA) and 3-methacryloxypropyltrimethoxysilane (MPS) as functional monomers was successfully synthesized by solution copolymerization. Based on various investigations, our characterization results for the resin and its coating indicated that the resin exhibits high UV-absorbing and free-radical-catching performances, and the hydrophobicity of the varnish coating was promoted by the actions of fluorine and silicone. In addition, the weatherability improved because of the enduring triple protection of the UV absorbent (BHEA), free-radical-catching agent (TMPM), fluorine (DFMA) and silicone (MPS). After a 1000-h aging test, the color difference (?E) and rate of loss of gloss (?G) of varnish coatings were 2.96% and 62%, respectively, and the impact strength and flexibility of color paint coatings were 420 N cm and 2 mm, respectively. Moreover, the chemically bonded free-radical-catching agent (TMPM) showed a more enduring performance for producing nitroxides than the simple blend.     

Influence of stabilizer additives on thermochromic coating for temperature monitoring

Compounds based on smart materials are functional structures that can be used as thermochromic sensors for temperature monitoring in equipment such as pipelines, motors, and heat exchangers. We developed thermochromic coatings based on 1,3,3-trimethylindolino-β-naphthopyrylospiran acrylic polyurethane with and without 2-(2H-benzotriazol-2-yl)-4,6-ditertpentylphenol photostabilizer additives and antioxidant butylated hydroxytoluene and applied them on stainless-steel plates by the spray lay-up method. The samples were analyzed using a weathering chamber with UVA and UVB radiation to monitor their degradation process, revealing complete degradation of the coating without antioxidant and photostabilizer, leading to loss of its thermochromic characteristic.     

Partition of <Emphasis Type="Italic">n</Emphasis>-Butanol Among Phases and Solubilization Ability of Winsor type III Microemulsions

The partition of n-butanol in Winsor type III (W-III) microemulsions was investigated in this work. Three kinds of anionic surfactants (sodium dodecyl sulfate (SDS), sodium dodecyl sulfonate (DSS), and sodium dodecyl benzene sulfonate (SDBS)) and two kinds of anionic/cationic surfactant mixtures (SDS/octadecyl trimethyl ammonium chloride (OTAC) mixtures and DSS/OTAC mixtures) were studied. Internal standard gas chromatography was employed in n-butanol content analysis. The results showed that no water exists in the excess oil (EO) phase and no oil exists in the excess water (EW) phase. For the W-III microemulsions obtained by salinity scanning, relatively constant n-butanol content in the EO (11–12 v%) and EW (1–4 v%) was found under different salinities. Accurate measurement of n-butanol content in each phase is important for those systems having low solubilization ability. For the W-III microemulsions prepared using SDS/OTAC surfactant mixture, the percentage of n-butanol distributed into the interfacial layer decreased while the fraction of n-butanol in the interfacial layer first increased sharply and then tended to be stable with the addition of n-butanol. For the different optimum W-III microemulsion systems tested, most of the surfactant-to-alcohol molar ratio data are near 1:3, but obvious deviation could be observed for some data. On the basis of the accurate measurement of n-butanol content in the EO and EW phases, the standard free energy, ΔG _o→in ^* (T = 298.15 K) of n-butanol transferring from the EO phase to the interfacial region was calculated. The results show negative ΔG _o→in ^* values. For microemulsions with the same components, n-butanol content is an important factor influencing the ΔG _o→in ^* value, and a high absolute value of ΔG _o→in ^* leads to high solubilization ability.     

Synthesis and surface analysis of self-matt coating based on waterborne polyurethane resin and study on the matt mechanism

Self-matt coating of waterborne polyurethane (WBPU) was synthesized by combining prepolymer and self-emulsification methods. The emulsion was fabricated from both hydroxy carboxylic acid and aminosulfonic acid types of hydrophilic chain-extending agents, in which the 2-[(2-aminoethyl) amino] ethane sulphonate sodium (AAS salt) was produced in laboratory. This emulsion demonstrated an excellent matt performance without the addition of extra matting agents after filming. Four different kinds of surface properties were measured on the film: the specular gloss (60° gloss meter), the contact angle (CA), the surface roughness degree (3D Surface Profilometer), and the topography of the coatings surface (SEM). The results showed that tons of spherical particles with diameter in a few micrometers were aggregated on the film surface. The effect of the roughness parameters (R _a and R _q ) and the average particle size of the emulsions on the specular gloss degree were probed. The research indicated that the emulsion with average particle size in the range of 2.5–3.0 µm and, meanwhile, the film with roughness parameters R _a and R _q both greater than 1 µm could attain the best matt effect. The WBPU emulsions showed good physical and mechanical properties, and were introduced into wood varnish for matting purpose.     

Effect of functionalized multiwalled carbon nanotubes on weather degradation and corrosion of waterborne polyurethane coatings

A series of waterborne polyurethane/functionalized multiwalled carbon nanotube (WBPU/f-MWCNT) nanocomposite dispersions was prepared using three defined concentrations of 0.5, 1.0 and 2.0 wt% carboxyl functionalized multiwalled carbon nanotubes (f-MWCNTs). All dispersions were coated on mild steel and exposed under natural weather condition for a maximum of 365 days. Both exposed and unexposed coatings were characterized by potentiodynamic polarization (PDP) and X-ray photoelectron spectroscopy (XPS) analyses. The pristine WBPU coating showed slight degradation and corrosion protection. Inclusion of a higher content of f-MWCNTs significantly improved both the degradation and corrosion protection efficiencies of the coatings. Maximal degradation and corrosion protection was observed when 2.0 wt% f-MWCNT was mixed with WBPU for all of the coatings.     

Synthesis and characterization of bio-based benzoxazine oligomer from cardanol for corrosion resistance application

The Mannich-like condensation of a cardanol, paraformaldehyde, and N,N′-bis(2-aminoethyl)ethane-1,2-diamine were carried out to synthesize the amine functional benzoxazine (Bnz) resin. The amine functionality of Bnz resin was evaluated by physiochemical methods, and the structure was characterized using Fourier transform infrared and ¹H-nuclear magnetic resonance spectroscopy. The added functionality into the Bnz resin backbone was utilized to modify the Bnz resin structure by glycidoxypropyltrimethoxysilane (GPTMS) in various proportions. The results revealed that the silane-modified Bnz coatings have improved mechanical, chemical, and solvent resistance properties as compared to the neat Bnz coating. The gel and water absorption of polyamide-cured coatings also has been evaluated. Furthermore, the cured films have been evaluated for glass transition temperature (T _g) and thermal resistance by differential scanning calorimetry and thermogravimetric analysis, respectively. The corrosion resistance properties were studied by salt spray and electrochemical analysis. It was observed that the highly crosslinked structure of the GPTMS-modified Bnz coatings enhanced the barrier protection to corrosive species.     

The effect of formulation variables on fouling-release performance of stratified siloxane–polyurethane coatings

The effects of formulation variables, such as type of polyol, solvent type and solvent content, and coating application method, on the surface properties of siloxane–polyurethane fouling-release coatings were explored. Fouling-release coatings allow the easy removal of marine organisms from a ship’s hull via the application of a shear force to the surface. Self-stratified siloxane–polyurethane coatings are a new approach to a tough fouling-release coating system. Combinatorial High Throughput Experimentation was employed to formulate and characterize 24 different siloxane–polyurethane coatings applied using drawdown and drop-casting methods. The resulting coatings were tested for surface energy using contact angle measurements. The fouling-release performance of the coatings was tested using a number of diverse marine organisms including bacteria (Halomonas pacifica and Cytophaga lytica), sporelings (young plants) of the green macroalga (Ulva linza), diatom ((microalga) Navicula incerta), and barnacle (Amphibalanus amphitrite). The performance of the majority of the coatings was found to be better than the silicone standards, Intersleek^® and Silastic^® T2. An increase in solvent content in the formulations increased the surface roughness of the coatings. Coatings made with polycaprolactone polyol appeared to be somewhat rougher compared to coatings made with the acrylic polyol. The adhesion strength of sporelings of Ulva increased with an increase in solvent content and increase in surface roughness. The adhesion strengths of Ulva sporelings, C. lytica, and N. incerta were independent of application method (cast or drawdown) in contrast to H. pacifica adhesion, which was dependent on the application method.     

Amorphous polyamide coating resins from sugar-derived monomers

In this article, the synthesis of bio-based polyamides for powder coating applications and their evaluation in a solventborne coating system are reported. The M _n values of the resins were between 3000 and 4000 g mol^?1 and the resins displayed T _g values from 60 to 80°C. Both amine and carboxylic acid functionalities (total ~0.6 mmol g^?1) were introduced for curing purposes. The resins were cured with triglycidyl isocyanurate (TGIC) or N,N,N′,N′-tetrakis(2-hydroxyethyl)adipamide (Primid XL-552). The curing reaction was followed using rheology which indicated that TGIC achieved higher reaction rates and higher gel contents. The DSC analysis of the cured disks showed that all cured samples were amorphous as is desired for the targeted coating application. The resins required a curing temperature higher than 150°C. Aluminum panels were coated using a solventborne approach and the coatings were cured at 180°C during 1 h. Dewetting was observed on all panels. Network formation was adequate for an amine-functional resin cured with TGIC as indicated by solvent resistance testing. In conclusion, the developed bio-based polyamide resins are promising materials to be used as binder resins in powder coating applications.     

Synthesis of waterborne polyurethane–silver nanoparticle antibacterial coating for synthetic leather

An antibacterial coating composed of silver nanoparticles and waterborne polyurethane was synthesized for use on synthetic leather. In this study, silver nanoparticles were prepared and used as nanofiller to impart antibacterial property. Silver nanoparticles were synthesized by using poly(vinyl pyrrolidone) as dispersant and sodium borohydride (NaBH₄) as reducing agent. Silver nanoparticles were characterized by transmission electron microscopy (TEM), Fourier-transform infrared (FTIR) spectroscopy, and X-ray diffraction (XRD) analysis. The optimum dispersant was selected according to the zeta potential of dispersions. Waterborne polyurethane was synthesized by using isophorone diisocyanate, 2-bis(hydroxymethyl)propionic acid, triethylamine, and polytetramethylene ether glycol. Waterborne polyurethane–silver antibacterial coating was obtained by ultrasonic dispersion, and then cast on the surface of synthetic leather. The antibacterial property and coating adhesion were investigated. The results showed silver nanoparticles homogeneously dispersed in waterborne polyurethane and adhesion reaching grade 4. Antibacterial testing showed bacterial reduction of 99.99% for Escherichia coli and 87.5% for Staphylococcus aureus.     

Effective incorporation of ZnO nanoparticles by miniemulsion polymerization in waterborne binders for steel corrosion protection

A nanohybrid waterborne binder was synthesized by miniemulsion polymerization with the incorporation of ZnO nanoparticles in order to increase the corrosion protection capability. This system was compared to a neat waterborne binder and to a physical blend of the binder with an aqueous ZnO nanoparticles dispersion. The hybrid dispersion was characterized by SEM and TEM, while the corrosion behavior of these latexes was investigated by electrochemical measurements (open circuit potential and electrochemical impedance spectroscopy in 3.5 wt% NaCl solution), evaluating the effect of the incorporation of these nanoparticles into the polymeric matrix. The incorporation of ZnO nanoparticles by blending showed similar behavior to the neat coating despite flash rust reduction on the metal surface. In contrast, the hybrid binder prepared by miniemulsion polymerization has shown the best performance according to the values of pore resistance (R _i ) and coating capacitance (C _c). In general, this study shows how useful can be the miniemulsion polymerization methodology to design hybrid coating formulations, obtaining homogenous distribution of ZnO nanoparticles within the film. Indeed, a heterogeneous distribution can hinder the effectiveness and the corrosion protection capabilities of promising nanoparticles.     

Influence of pH in the synthesis of ferric tannate pigment for application in antifouling coatings

Ferric tannate was synthesized at pH 4 and pH 7 (FT4 and FT7, respectively) as a new class of environmentally friendly antifouling pigments. The solubility of both pigments was evaluated by gravimetric tests, showing that FT4 is more soluble than FT7. A mixture of rosin/acrylic resin (9:1 w/w) was sufficient to form an antifouling coating due to improved matrix properties. Electrochemical impedance spectroscopy (EIS) measurements were used to determine the apparent water coefficient of diffusion (D) and coating behavior. The D in the coating formulated with FT4 exhibited better values than that obtained with FT7. EIS results showed that both coatings present Fickian behavior at the initial stages of immersion, while flat Nyquist plots revealed penetration of water in the films. The physicochemical characteristics of FT4 pigment were determined by thermogravimetry and Fourier transform infrared. Immersion tests in the Mediterranean Sea demonstrated the excellent efficacy of the FT4-containing coating against marine fouling after six months of immersion.     

Boron-containing UV-curable oligomer-based linseed oil as flame-retardant coatings: synthesis and characterization

A boron-containing UV-curable oligomer was derived from linseed oil, phenylboronic acid and glycidyl methacrylate to use in flame-retardant coating applications. The synthesized UV-curable oligomer was characterized for its structural and physicochemical properties by means of Fourier transform infrared (FTIR), ¹H and ¹¹B-nuclear magnetic resonance (NMR) spectroscopy techniques. The boron-containing UV-curable oligomer (BELO) was added to a conventional polyurethane acrylate (PUA) at varying concentrations ranging from 10 to 40 wt% in the presence of a photoinitiator and a reactive diluent. LOI and UL-94 tests were performed to understand the flame-retardancy behavior of the synthesized BELO oligomer, and the results revealed that the flame retardancy of UV-curable coatings enhanced as the percentage of BELO oligomer in the coating formulations increased. The glass transition temperature (T_g) and thermal stability of cured coatings were analyzed by differential scanning calorimetry and thermogravimetric analysis, respectively. The TGA analysis showed that char yield at 600 °C increased by increasing the BELO oligomer content. The mechanical properties, and stain, solvent, and chemical resistance and thermal behavior of the coatings were investigated. Incorporation of BELO into the PUA coating formulations and the comparison of the properties of BELO-incorporated PUA coatings with those of the conventional PUA coating exhibited interesting results.     

Nanoindentation as an alternative to mechanical abrasion for assessing wear of polymeric automotive coatings

Mechanical abrasion followed by transmission delta-haze measurement is a standard means to assess wear in polymeric silicone automotive hard coatings. However, the drawbacks of this abrasion–transmission (A–T) technique (drift, variability, sample size, and test time) make an alternative measurement method desirable. Literature reports have shown that the ratio of hardness to modulus can successfully predict wear performance in ceramic and metallic nanocomposite coatings. This work studied measures from both nanoindentation and nanoscratch testing to determine which could be a viable alternative to the historical A–T test for a specific polymeric coating system. Both nanoindentation measures of hardness (H) and the ratio of hardness to modulus (H/E _r) showed high repeatability compared with the other measures evaluated in this study and compared with the historical test. Of these two measures, the ratio H/E _r with an exponential fit showed the strongest correlation with A–T delta-haze measurements. Key formulation and process factors affecting abrasion resistance in automotive coatings were analyzed in a designed experiment with historical A–T delta-haze and nanoindentation H/E _r as responses. Analysis showed significant benefits to the use of the H/E _r measure of abrasion resistance in modeling coating performance.     

Polysiloxanes with Quaternary Ammonium and Polyether Groups for Silyl-Terminated Polypropylene Oxide Waterborne Emulsions

In this paper, polysiloxanes with pendant quaternary ammonium and polyether segments (EQAPS, nonionic–cationic silicone surfactant) were synthesized through hydrosilylation of poly(dimethylhydro)siloxane with allyl poly(ethylene glycol) acetic ester (M _n  = 540) and allyl glycidyl ether, followed by a ring-opening reaction of epoxide groups with diethyl amine and quaternization with benzyl chloride. The chemical structures of EQAPS and intermediate products were characterized by ¹H-NMR and FT-IR spectra. The surface activity and thermal properties of EQAPS were studied with surface tension measurement and differential scanning calorimetry analysis, respectively. The results showed that the EQAPS had a much smaller critical micelle concentration value (118 mg/L) and lower glass-transition temperature (T _g: ?57 °C). The silyl-terminated polypropylene oxide waterborne emulsions, which were substantially free from organic solvent, were prepared via a phase-inversion emulsification technique using EQAPS as single emulsifier and/or poly(ethylene glycol) (\(\bar{M}\) _n  = 400) as cosolvent. The electrical properties of the system indicated that the phase inversion was completely accomplished. The viscosity of the emulsions with different solid contents was measured, and the results showed that the most suitable solid content was about 50 wt%. The emulsions with smaller particle size (12 μm) had better storage stability (48 days at 50 °C) and freeze–thaw stability.     

Electrochemical impedance study for modeling the anticorrosive performance of coatings based on accelerated tests and outdoor exposures

In this study, the atmospheric corrosive protection characteristics of four organic coatings were modeled based on the evolution of low-frequency impedance (|Z| _ω→0) over time when subjected to accelerated tests and outdoor exposures. Environmental characteristics such as the time of wetness, chloride and sulfate depositions, and ultraviolet radiation were defined as explanatory variables. The results obtained helped to establish a relationship between |Z| _ω→0, acquired from electrochemical impedance spectra, and the explanatory variables. An adjustment factor was calculated for each coating against the most aggressive natural exposure, resulting in a good prediction of |Z| _ω→0 and the performance of the coatings for other outdoor tests.     

Effect of different structured POSS/GMA-containing copolymers on the morphology of porous coating by breath-figures method

Polyhedral oligomeric silsesquioxane (POSS) and glycidyl methacrylate (GMA) are used to synthesize linear L-(PGMA-b-MA-POSS), dicephalous D-(PGMA-b-MA-POSS)₂, and four-armed T-(PGMA-b-MA-POSS)₄ through atom transfer radical polymerization (ATRP). These different structured POSS/GMA-containing copolymers are applied to build the porous films through breath-figures (BF) method. L-(PGMA-b-MA-POSS) is easy to form the ordered porous BF film, and T-(PGMA-b-MA-POSS)₄ tends to form well-distributed BF film due to its high segment density which is beneficial to stabilize water drop. It is proven that solvent has a great effect on the morphologies of BF film. The perfect BF film is developed in the relatively wet atmosphere as 5–8 μm diameter of pores casted in THF and 2–4 μm diameter of pores casted in CH₂Cl₂ with regular morphology. The developed BF film has superior stability than the film developed in natural conditions due to the shorter stable balancing time. Therefore, it is believed that the obtained porous films show great potential in coating application.     

Novel amphiphilic temperature responsive graft copolymers PCL-<Emphasis Type="Italic">g</Emphasis>-P(MEO<Subscript>2</Subscript>MA-<Emphasis Type="Italic">co</Emphasis>-OEGMA) via a combination of ROP and ATRP: synthesis,characterization, and sol-gel transition

A series of well-defined novel amphiphilic temperature-responsive graft copolymers containing PCL analogues P(αClεCL-co-εCL) as the hydrophobic backbone, and the hydrophilic side-chain PEG analogues P(MEO₂MA-co-OEGMA), designated as P(αClεCL-co-εCL)-g-P(MEO₂MA-co-OEGMA) have been prepared via a combination of ring-opening polymerization (ROP) and atom transfer radical polymerization (ATRP). The composition and structure of these copolymers were characterized by ¹H NMR and GPC analyses. The self-assembly behaviors of these amphiphilic graft copolymers were investigated by UV transmittance, a fluorescence probe method, dynamic light scattering (DLS) and transmission electron microscopy (TEM) analyses. The results showed that the graft copolymers exhibited the good solubility in water, and was given the low critical temperature (LCST) at 35(±1) °C, which closed to human physiological temperature. The critical micelle concentrations (CMC) of P(αClεCL-co-εCL)-g-P(MEO₂MA-co-OEGMA) in aqueous solution were investigated to be 2.0 × 10^?3, 9.1 × 10^?4 and 1.5 × 10^?3 mg·mL^?1, respectively. The copolymer could self-assemble into sphere-like aggregates in aqueous solution with diverse sizes when changing the environmental temperature. The vial inversion test demonstrated that the graft copolymers could trigger the sol-gel transition which also depended on the temperature.