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     

Preparation of Polyetheramine‐Grafted Lignin and Its Application in UV‐Resistant Polyurea Coatings

Lignin‐containing polyurea coating with good ultraviolet (UV) resistance is prepared by partially substituting polyetheramine with enzymatic hydrolysis lignin. Lignin is first grafted by polyetheramine chains via Mannich reaction, which improves its interfacial compatibility with polyurea matrix. The influences of the modified lignin on the chemical and corrosion resistance, UV‐aging property, and thermal stability of the polyurea coatings are studied. It is demonstrated that lignin‐containing polyurea coatings exhibit excellent UV‐aging properties. Aminating lignin with polyetheramine improves its dispersion in the polymer matrix. This work offers a novel method for the high‐value utilization of biomass lignin in anti‐UV polyurea coatings.     

Strain-induced multiscale structural changes in lamellar thermal barrier coatings

The thermal mismatch stress, as well as residual stress, in coating/substrate systems often leads to structural changes and subsequent coating debonding in the systems. This study focused on the changes induced in the microstructure and properties of lamellar yttria-stabilized zirconia coatings upon heating, with the aim of elucidating their starting microstructure prior to sintering. The results showed that the combined effect of the residual stress and the thermal mismatch stress results in scale-sensitive changes in the properties of the coatings. The macroscale properties changed significantly, while the microscale properties changed only slightly. Structural characterization revealed that a certain degree of expansion at the tips of both the intersplat pores and the intrasplat cracks occurs, contributing to the microscale structural changes observed in most regions. Moreover, a few mesoscale cracks covering several layers were also observed. A lamellar structural model was developed to correlate the multiscale structural changes observed with those in the properties. Finally, this study revealed that the actual starting structure of plasma-sprayed thermal barrier coatings prior to sintering is different from that in the as-deposited state. This should aid in obtaining an in-depth understanding on the microstructural and properties evolution of the constrained coatings under actual service conditions.     

Polysilazane‐based heat‐ and oxidation‐resistant coatings on carbon fibers

Carbon fibers must be protected from a high‐temperature oxidizing environment because, at approximately 500°C and above, the fibers exhibit reduced mass and strength stability. The fibers can be protected by the application of thermal coatings, which simultaneously improve the adhesive properties of the carbon fibers in the composite materials. Polysilazanes are a new family of heat‐resistant polymer coatings that are converted into silicone carbide or silicone nitride ceramic structures at high temperatures. The converted ceramics are resistant to the effects of high temperatures. In this research work, polysilazane‐based coatings were applied to carbon filament (CF) rovings with the dip‐coating method. Tensile testing at room temperature and under thermal stress was carried out to assess the mechanical and thermomechanical properties of both coated and uncoated rovings. Scanning electron microscopy and energy‐dispersive X‐ray analysis were performed to evaluate the surface topographical properties of the coated and uncoated rovings. Thermogravimetric analysis was executed to determine the thermal stability of the polymer coatings. The coating performance on the CF rovings was determined by assessment of the test results obtained. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

UV‐curable coatings with nano‐TiO2

Nano‐TiO₂ particles were first milled into butyl acetate or trimethylolpropane triacrylate (TMPTA) to obtain TSB and TST slurries, then embedded into epoxy acrylate to obtain UV‐curable coating. The influence of nano‐TiO₂ particles on the photopolymerization kinetics, tack free time, thermal and optical properties of UV‐curable coatings was investigated. It was found that TST‐based coating had a decreasing but TSB‐based coating had an increasing UV cured rate in comparison with the pristine epoxy acrylate. Nevertheless, the TST‐based coating occupied shorter tack free time, good thermal property and UV absorbance than their corresponding TSB‐based coating. POLYM. ENG. SCI. 46:1402–1410, 2006. © 2006 Society of Plastics Engineers.     

Understanding the Formation of Vertical Cracks in Solution Precursor Plasma Sprayed Yttria‐Stabilized Zirconia Coatings

Yttria‐stabilized zirconia (YSZ) deposition by the solution precursor plasma spraying (SPPS) route has been of interest for potential thermal barrier coating (TBC) applications. It has been surmised that realization of unique microstructural features like vertical cracks, nanosized pores and fine splats in the TBCs can significantly enhance coating durability and performance. However, satisfactory control over the YSZ coating microstructure has been elusive in the absence of an adequate understanding of the mechanism responsible for coating deposition in SPPS. This study demonstrates the ability to tailor microstructure of deposited YSZ coatings over a wide range, from nano‐porous coatings to a vertically cracked microstructure. Varying of precursor flow rate has been shown to dictate the pyrolysis events occurring in situ and, adopting this approach, YSZ coatings with widely varying microstructural features have been developed. The coatings have been characterized in detail and the observations correlated with in‐flight particle generation and splat formation. These studies also provide useful insights into the possible origin of vertical cracks in the coating for which a mechanism is proposed.     

Microstructure evolution and thermomechanical properties of plasma‐sprayed Yb2SiO5 coating during thermal aging

Rare‐earth monosilicates (RE₂SiO₅, RE: rare‐earth elements), such as Yb₂SiO₅, have been developed for potential application as environmental barrier coating (EBC) materials. Yb₂SiO₅ coating would experience microstructure evolution under high‐temperature environment and accordingly its thermomechanical properties would be altered. In this study, Yb₂SiO₅ coating was fabricated by atmospheric plasma spray technique. The phase stability and microstructure change before and after thermal aging at 1300°C, 1400°C, and 1500°C were investigated. The changes in mechanical and thermal properties were characterized. The results showed that the as‐sprayed coating was mainly composed of Yb₂SiO₅ with a small amount of Yb₂O₃ and amorphous phase. Defects in the coating, including interfaces, pores, and microcracks, were greatly reduced with grain growth after thermal treatment. Thermal aging significantly modified the thermal and mechanical properties of the coating. The average CTE was increased by 13.1%, and the hardness and elastic modulus was increased by 42.4% and 49.4%, respectively, after thermal aging at 1500°C for 50 hour. The thermal conductivity of thermal‐aged coating was much higher than that of the as‐sprayed coating, which was still less than 2 W/(m·K). The influence of coating microstructure on the properties was analyzed and related to the failure mechanism of EBCs.     

Preparation of novel CNSL‐based urethane polyol via nonisocyanate route: Curing with melamine‐formaldehyde resin and structure–property relationship

In this study, we report preparation of a novel cashew nut shell liquid (CNSL)‐based polyol bearing urethane groups. The urethane group in the polyol was induced via isocyanate free route from the reaction of cyclic carbonate with primary amine. The polyol was characterized by determination of hydroxyl number, Fourier transform infrared spectroscopy, nuclear magnetic resonance spectroscopy, and so forth. The polyol was then used as coating component and cured with hexamethoxy methylene melamine (HMMM). Another CNSL‐based polyol without urethane moiety from our earlier reported work was used for preparation of coating for comparative study to determine the effect of urethane group on the coating properties. The coating formulations based on these two polyols were cured with variable amounts of HMMM hardener to optimize coating properties. All the coatings were evaluated for mechanical properties such as adhesion, flexibility, pencil and scratch hardness, impact resistance, pull‐off, and adhesion. The optimized coatings were also evaluated for chemical and thermal properties. It was observed that the urethane containing polyol resulted in better adhesion to the metal substrate at higher quantity of HMMM hardener compared to the other polyol providing significant improvement in various coating properties. The final coating properties were also compared with the acrylic polyurethane coatings. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41391.     

Heat‐resistant hydrophobic–oleophobic coatings

Thermally and chemically durable hydrophobic oleophobic coatings, containing different ceramic particles such as SiO₂, SiC, Al₂O₃, which can be alternative instead of Teflon, have been developed and applied on the aluminum substrates by spin‐coating method. Polyimides, which are high‐thermal resistant heteroaromatic polymers, were synthesized, and fluor oligomers were added to these polymers to obtain hydrophobic–oleophobic properties. After coating, Al surface was subjected to Taber‐abrasion, adhesion, corrosion, and thermal tests. The effects of the particle size of ceramic powders, organic matrix, and heat on the coating material were investigated. Coating material was characterized by FTIR spectrophotometer. Surface properties and thermal resistance of the coating materials were investigated by SEM and TGA analyses. After thermal curing, contact angles of these coatings with H₂O and n‐hexadecane were measured. It was observed that coatings like ceramic particles are more resistant against scratch and abrasion than the other coatings. Also, they are harder than coatings, which do not include ceramic particles. It was seen that coatings, containing Fluorolink D10H, have high‐contact angles with water and n‐hexadecane. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2386–2392, 2006     

Microstructure and wear properties of plasma‐sprayed aluminum–silicon–polyester coatings

Powder coatings, which are made by plasma‐spraying processes, are being used in industrial applications because of their wear resistance, chemical resistance, and high impact strength even at low service temperatures. These factors increase the importance of plastic and plastic‐based coatings in industrial applications. In this study, an aluminum–silicon–polyester‐based composite coating was applied by plasma‐spraying processes with and without an intermediate bond coat (Ni–Al). The effects of the coating thickness, intermediate bond coat, and processes parameters on the microstructure and wear properties of the coating were studied experimentally. The wear properties of the coatings were determined according to ball‐on‐disk procedure. The microstructures of the coating were examined by optical microscopy and scanning electron microscopy. The results indicated that the plasma‐spraying current and thickness had a strong influence on the wear resistance and microstructural properties of the aluminum–silicon–polyester coating. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3609–3614, 2006     

A comprehensive sintering mechanism for TBCs‐Part I: An overall evolution with two‐stage kinetics

A comprehensive sintering mechanism for lamellar thermal barrier coatings was reported experimentally and theoretically in this study. To begin with, an overall property evolution with two‐stage kinetics was presented during thermal exposure. The increase in mechanical property at initial thermal exposure duration (stage‐I) was much faster with respect to that in the following longer duration (stage‐II). At the stage‐I, the in situ pore healing behavior revealed that the significant faster sintering kinetics was attributed to the rapid healing induced by multipoint connection at the intersplat pore tips, as well as a small quantity of the narrow intrasplat cracks. At the following stage‐II, the residual wide intersplat pore parts and the wide intrasplat cracks decreased the possibility of multiconnection at their counter‐surfaces, resulting in a much lower sintering kinetic. Moreover, a structural model based on the microstructure of plasma sprayed YSZ coatings was developed to correlate the microstructural evolution with mechanical property. Consequently, the model predicted a two‐stage evolutionary trend of mechanical property, which is well consistent with experiments. In brief, by revealing the pore healing behavior, this comprehensive sintering mechanism shed light to the structure tailoring toward the advanced TBCs with both higher thermal‐insulating effect and longer life time.     

Effect of hyperbranched acrylates on UV‐curable soy‐based biorenewable coatings

Utilization of biorenewable components in UV‐curable coating formulations is both economically and environmentally beneficial, particularly when compared to their petrochemical‐based counterparts. To produce UV‐curable coatings of high biorenewable content with enhanced performance, acrylated epoxidized soybean oil (ASBO) was combined with biorenewable reactive diluent tetrahydrofufuryl acrylate, adhesion promoters, photoinitiator and hyperbranched acrylates (HBAs) as synthetic tougheners. The HBAs were found to impart high functionality and low viscosity, thus increasing crosslinking in the coating network and improving mechanical and thermal properties such as film hardness, adhesion, solvent resistance, impact resistance, tensile modulus and toughness, glass transition temperature and thermal stability. Real‐time Fourier transform infrared spectroscopy showed decreased acrylate conversion when compared with a reference formulation without HBAs, which was attributed to earlier coating network vitrification during UV irradiation. ASBO‐based coatings were also thermally annealed to allow further reaction of unreacted components in the vitrified network. As a result, coating properties were further improved. Overall, the addition of HBAs as synthetic tougheners to UV‐curable ASBO‐based biorenewable coating systems was shown to greatly improve the corresponding coating properties. Copyright © 2010 Society of Chemical Industry     

Peel‐strength behavior of bilayer thermal‐sprayed polymer coatings

We prepared various bilayer polymer coatings of ethylene methacrylic acid (EMAA) copolymer and ionomer by the thermal‐spray process under a range of preheat temperatures (PTs) to investigate their ability to be repaired. The thermal properties, crystallinity, microstructure, and interface strength of the coatings were investigated with differential scanning calorimetry, X‐ray diffraction, scanning electron microscopy, and mechanical testing. Processing parameters influenced the final morphological structure of the coatings. The crystallinity of the coatings increased with a higher final temperature, whereas the coating density decreased. The decrease in density was attributed to the appearance of bubbles, 250 μm in size, formed in the coatings during the spray process. For the monolayer coating of polymer on a metal substrate, a higher PT produced a greater contact area of the coating to the substrate. The adhesion of EMAA ionomer to steel was always lower than that of EMAA copolymer to steel. This may have been largely due to the interfacial adhesion between the polymer and steel being dominated by strong secondary bond interactions. Experimental results also indicate that the peel strength between polymers was at least twofold stronger than that between the polymer and the steel substrate for PTs greater than 100°C. The mixed bilayer coating of ionomer on copolymer produced the highest peel strength. The interface between the plastic layers was clearly visible under the scanning electron microscope at lower PTs, becoming more diffuse with an increase in PT. On the basis of these observations, the adhesion mechanism between polymers was explained by the formation of welding points. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 214–226, 2003     

3D characterization of porosity in an air plasma‐sprayed thermal barrier coating and its effect on thermal conductivity

Air plasma spray (APS) thermal barrier coatings (TBCs) contain pores, cracks and splat interfaces that are preferentially aligned normal to the heat flux direction. These significantly reduce (by as much as 50%) the thermal conductivity over a fully dense coating. Here the microstructures of APS thermal barrier coatings (TBCs) have been characterized in 3D using X‐ray microcomputed tomography (μ‐CT). Pores larger than 2.8 μm³ are resolved and their contribution to thermal conductivity reduction is evaluated using image‐based microstructurally realistic numerical models. However, the models overestimate (by almost 50%) the measured thermal conductivity of the as‐deposited TBC sample. It is shown that this discrepancy is due to very fine (micrometer and submicrometer) cracks which readily sinter after short‐term exposure to temperatures representative of TBC operating conditions causing the measured thermal conductivity to rise to within 15% of that predicted. This suggests that under the realistic service conditions, the 3D image‐based models based on CT images provide a good indicator of the likely long‐term TBC performance. Virtual experiments showed that for the retained pores, the larger pores which are flatter and more oriented in the plane of the APS splats, contribute disproportionately to the beneficial reduction in thermal conductivity. Our results demonstrate that X‐ray imaging is a useful tool in establishing APS process conditions that give rise to a beneficial distribution of such pores.     

Water‐borne melamine–formaldehyde‐cured epoxy–acrylate corrosion resistant coatings

Organic protective coatings are widely used in corrosion control. However, environmental standards establish that the volatile organic compounds either must be removed or controlled at the lowest possible levels. The carcinogenic environmental impact of volatile organic compounds has led to the substitution of solvent‐borne coatings by water‐borne coating systems. Among recently developed water‐borne coatings, epoxy‐ and acrylic‐based coatings have a special significance over other reported water‐borne systems. Keeping in mind, the importance of water‐borne coatings in the present work, we report the synthesis of water‐borne epoxy–acrylate (EpAc) and melamine–formaldehyde (MF) as well as formulation of their anticorrosive coatings. The structural elucidation of MF‐cured EpAc was carried out by FTIR, ¹H NMR, and ¹³C NMR spectroscopic techniques. The coatings of EpAc‐MF were applied on mild steel strips and were evaluated for physicochemical, physicomechanical characterization, and the anticorrosive performance under different environmental conditions. The present coating system EpAc coatings exhibited superior performance as compared to the reported water‐borne epoxy–acrylatecoatings. The presence of melamine–formaldehyde in the resin increases the scratch hardness, impact resistance, alkali resistance, and thermal stability of these coatings. EpAc‐MF‐1 was found to cure at ambient temperature and exhibit good physicomechanical properties. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effect of splat-interface discontinuity on effective thermal conductivity of plasma sprayed thermal barrier coating

The thermal barrier coating obtained by atmospheric plasma spraying (APS TBCs) has a distinct lamellar microstructure, in which the splats discontinuous interfaces running parallel to the metal/ceramic interface contribute largely to the reduction in the effective thermal conductivity of APS TBCs. The dependency of such contribution on the topological structure of the interface discontinuity is investigated in the present work. Firstly, the concept of discontinuity of splats interfaces was defined to quantify the splats discontinuous interfaces revealed by microscopic observations. Then, the microstructure model with a random distribution of discontinuous interfaces was established by utilizing the finite element simulation method to investigate the effect of interlayer discontinuity on thermal conductivity of the APS TBCs. Finally, an optimal topological structure of the interface discontinuity was found to be responsible for the lowest effective thermal conductivity of the APS TBCs and typical parametrical tendencies demonstrated.     

Ambient‐cured polyesteramide‐based anticorrosive coatings from linseed oil—A sustainable resource

Ambient‐cured polyesteramide (APEA) coating resin synthesized from dihydroxy fatty amide obtained from linseed oil, a sustainable resource, and poly(styrene‐co‐maleic anhydride), a bifunctional acid component, was found to exhibit improved physicomechanical and anticorrosive properties. The structural elucidation of APEA resin has been carried out by FTIR, ¹H‐NMR, and ¹³C‐NMR spectroscopies. The physicomechanical and chemical resistance properties were investigated by standard methods. The corrosion resistance performance was evaluated in acid, alkali, and organic solvent. The thermal behavior was studied by TGA technique. A comparative study of these properties of APEA with reported baked polyesteramide (PEA) coatings was carried out. A remarkable improvement in the drying property of APEA was observed. The APEA coatings also showed improved physicomechanical and anticorrosive properties as compared to the baked PEA coatings. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1818–1824, 2005     

Vegetable oil based polyurethanamide/organo‐montmorillonite bio‐nanocomposite

The present work describes the synthesis and characterization of polyurethanamide/organo‐montmorillonite bio‐nanocomposites (OBNC) from Linseed oil‐a renewable resource. The aim of the work is (i) to widen the scope of application and improve the performance of vegetable oil based polymers, and (ii) to investigate the effect of introduction of modified clay on their structure, morphology, thermal stability, and coating properties. OBNC has been prepared by in situ polymerization of Linseed oil derived diol fattyamide and tolulylene‐2,4‐diisocyanate in the presence of different contents of OMMT (0.5–2.5 mass % in minimum amount of dimethylformamide) at room temperature. OBNC has been characterized by optical microscopy, FTIR, XRD, TEM, and TGA, which confirm the formation of OBNC. OBNC produced tough, scratch‐resistant, impact resistant, flexibility retentive coatings, which cure at room temperature with improved coating performance and thermal stability than virgin polymer. Amongst all the compositions, OMMT‐1.5 showed the best coating properties, with good scratch hardness (3.5 kg), impact (passes 200 lb/inch.) and bent test values (passes 1/8 inch). It can be commercially used as effective green coating material in future. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40278.     

A comprehensive sintering mechanism for thermal barrier coatings‐Part III: Substrate constraint effect on healing of 2D pores

During thermal exposure, the sintering of the plasma‐sprayed thermal barrier coatings (PS‐TBCs) is highly dependent on the healing of the two‐dimensional (2D) pores (including the inter‐splat pores and the intra‐splat cracks), as reported in the previous Part‐I and Part‐II based on free‐standing coatings. As a further study, this part aims to reveal the effect of substrate constraint on healing behavior of the 2D pores, since the coatings are actually bonded to superalloy substrate during real service. The healing of the 2D pores was quantitatively examined, and the multiscale mechanical properties were determined during the overall thermal exposure. In addition, a structure model was used to quantitatively correlate the evolution of 2D pores with mechanical property. The results of experiments and model prediction show that, different from the two‐stage evolutionary trends in free‐standing coatings, the overall evolution trends of microstructure and property can be divided into 3 stages affected by the substrate constraint. Moreover, the anisotropic healing of the 2D pores reported in free‐standing coatings was enhanced significantly due to the additional stress in coatings resulting from constraint of substrate. This means that the healing of inter‐splat pores became faster and severer. Given that, an outlook on structural tailoring to retard the performance degradation of TBCs was proposed.     

Potassium sodium niobate (KNN)‐based lead‐free piezoelectric ceramic coatings on steel structure by thermal spray method

For the first time, potassium sodium niobate (KNN)‐based lead‐free piezoelectric ceramic coating with strong piezoelectric response was fabricated on stainless steel substrates by thermal spray process, after introducing NiCrAlY and yttria‐stabilized zirconia (YSZ) intermediate layers. A large effective piezoelectric coefficient (d₃₃) of 125 pm/V was obtained with the thermal‐sprayed KNN‐based ceramic coating on the steel substrates. The mechanisms of improving the structure and enhancing the properties of the KNN‐based piezoelectric ceramic coatings by introducing the intermediate layers were analyzed. Ultrasonic transducers were designed and fabricated from the KNN‐based coatings directly formed on a steel plate structure, and the feasibility for generation and detection of ultrasonic waves for structural health monitoring using the thermal‐sprayed lead‐free piezoelectric ceramic coating was demonstrated.