Towards improving wet‐adhesion in a metal oxide‐polymer coating system

An investigation using a variable radius roll adhesion test (VaRRAT) revealed an irreversible increase in the wet‐adhesion in a metal–oxide–polymer system, under specific experimental conditions. This observation is further confirmed by the T_g measurements and the ATR‐FTIR studies. The increase in wet‐adhesion is attributed to late H₂O‐catalyzed curing of the previously partially cured polymers (epoxy ring opening), as well as the formation of nanocomposite layer within the epoxy primer matrix, because of precipitation of the nanocrystals including zinc ammine complexes formed as a result of dissolution of the zinc/aluminum alloy as well as the metal oxide pigments by the amine crosslinker. High activation energy of ～100 kJ mol^?1 indicated a chemical process to be responsible for the adhesion gain. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3318–3327, 2006     

Optimization of thermoelectric properties of metal‐oxide‐based polymer composites

Thermoelectric modules can be used for thermal energy harvesting. Common rigid thermoelectric stacks usually contain heavy metal alloys such as Bi₂Te₃. In order to substitute conventional materials and to reduce manufacturing costs, nontoxic, inexpensive and abundant materials using low‐cost processes are first choice. This study deals with polymer composites consisting of a polysiloxane matrix filled with thermoelectric Sn_0.85Sb_0.15O₂ particles in micrometer scale. Thin composite sheets have been prepared by doctor blade technique and the Seebeck coefficient, the electrical and thermal conductivity, and the porosity were measured. Platelet‐type particles, consisting of Sn_0.85Sb_0.15O₂‐coated insulating mica substrate and globular Sn_0.85Sb_0.15O₂ particles have been varied in size, coating thickness and were mixed with each other in different ratios. The filler content was varied in order to maximize the figure of merit, ZT, to 1.9 × 10^?5 ± 4 × 10^?6. Owing to their low raw material costs and the high degree of design freedom of polymer composites, one may use these materials in thermoelectric generators for remote low‐power demanding applications. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2014 , 131, 40038.     

Some properties of styrene‐based ionomers. I

Some properties of styrene‐based ionomers containing alkali metal salts of acrylic acid or methacrylic acid have been investigated. A study has been conducted to examine the influence of the acidic content and nature (acrylic or methacrylic) and the nature of the alkali metal salt on the glass transition temperature, density, melt index and activation energy of a flow of the styrene‐based ionomers. The present studies have indicated that the temperature of glass transition (T_g) of sodium ionomers increases as the sodium content rises and the region of the glass transition broadens. The T_g's of the styrene‐acrylic acid (S‐AA) ionomers do not depend on the nature of the alkali metal introduced into the copolymer. The density of films rises with the content of acid or salt introduced to the polystyrene chain. The melt index of the investigated ionomers depends on the amount and type of the introduced acid and salt as well as on the molecular weight of the initial copolymer. The energy of activation of the flow is independent of the polymer molecular weight; however, the energy of activation of flow of the ionomers increases with larger ionic radii of the introduced alkali metal. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 55–62, 2003     

Moisture diffusion properties of HFPE‐II‐52 polyimide

Moisture diffusion properties of the polyimide HFPE‐II‐52 were determined using weight gain, weight loss, and swelling experiments over a temperature range of 25–200°C. Below 100°C, diffusivity was measured using standard weight loss and weight gain methods. Above 100°C, diffusivity is found by weight loss experiments performed by placing moisture saturated samples in an oven and recording weight loss dynamically. The diffusivity of the polyimide was found to obey the Arrhenius relation over the entire range of temperature. Weight gain experiments were performed to determine the equilibrium level of moisture absorbed by the polyimide as a function of relative humidity. Swelling experiments were performed to measure swelling strain as a function of moisture absorption. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3471‐3479, 2006     

Effect of different treatments on the thermal behavior of reinforced phenol–formaldehyde polymer composites

Thermal behavior of oil palm fiber‐reinforced phenol–formaldehyde (PF) resins with different chemical treatments were analyzed using Differential Scanning Calorimeter (DSC). A well‐defined peak of crystallization was observed in all the samples. However, in one of them a second exothermic peak also emerged, which indicates some structural changes at high temperature. Crystallization kinetics has been studied in terms of activation energy of crystallization, dimensionality of growth and stability using various recent theories developed for nonisothermal crystallization. The results indicate the surface nucleation and crystallization through one‐dimensional growth. Thermal stability of PF composites increases after chemical treatment, and is maximum for resin treated with peroxide PF composite in comparison to fiber‐treated PF composites. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 603–608, 2000     

Some properties of styrene‐based ionomers II

Some properties of styrene‐based ionomers obtained from copolymers styrene (S) and acrylic acid (AA) or methacrylic acid (MA) obtained in emulsion containing alkali metal salts have been investigated. A study has been conducted to examine the influence of the acid content and nature (acrylic or methacrylic) and nature of alkali metal salt on the glass transition temperature, density, melt index, and activation energy of flow of the styrene‐based ionomers. The present studies have indicated that the temperature of glass transition (T_g) of sodium ionomers increases as the sodium content rises, but the increase is lower than in the case of the ionomers based on copolymers obtained in bulk. The density of films rises with the content of alkali metal salt introduced to the polystyrene chain, and it is higher than in the case of the ionomers based on copolymers obtained in bulk containing almost the same content of alkali metal salts. Styrene ionomers containing alkali metal acrylates have higher densities than those containing alkali metal methacrylates. The melt index of the investigated ionomers depends on the amount and type of introduced acid and salt, as well as on the molecular weight of the initial copolymer. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 268–275, 2005     

Guidelines for dryer design based on results from non‐Fickian model

In polymer solution coatings below the glass transition temperature of the pure polymer, the coating can go undergo a glass transition and develop stresses during drying. When stresses develop, a non‐Fickian model accurately describes solvent mass transport in drying polymer coatings. The non‐Fickian model includes the solvent transport due to both stress and concentration gradients. This article presents a non‐Fickian model, which predicts a lower residual solvent than does the corresponding Fickian model. We showed in an earlier article that the non‐Fickian model predicts trapping skinning (higher residual solvent under more intense operating conditions) at higher drying gas‐flow rates. In this article, the non‐Fickian model was used to investigate how the gas‐flow rate, dry film thickness, and substrate thickness affect the residual solvent for a single‐zone dryer. This work recommends guidelines for choosing gas‐flow rates, gas temperatures, and substrate thickness to minimize the residual solvent. The model predictions show that, at any gas temperature, the residual solvent is minimum at an intermediate gas‐flow rate. The trapping skinning effect is less evident in thicker coatings and substrates. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 477–486, 2003     

Study of the isothermal curing of an epoxy prepreg by near‐infrared spectroscopy

The commercial epoxy prepreg SPX 8800, containing diglycidyl ether of bisphenol A, dicyanodiamide, diuron, and reinforcing glass fibers, was isothermally cured at different temperatures from 75 to 110°C and monitored via in situ near‐infrared Fourier transform spectroscopy. Two cure conditions were investigated: curing the epoxy prepreg directly (condition 1) and curing the epoxy prepreg between two glass plates (condition 2). Under both curing conditions, the epoxy group could not reach 100% conversion with curing at low temperatures (75–80°C) for 24 h. A comparison of the changes in the epoxy, primary amine, and hydroxyl groups during the curing showed that the samples cured under condition 2 had lower initial epoxy conversion rates than those cured under condition 1 and that more primary amine–epoxy addition occurred under condition 2. In addition, the activation energy under cure condition 2 (104–97 kJ/mol) was higher than that under condition 1 (93–86 kJ/mol), but a lower glass‐transition temperature of the cured samples was observed via differential scanning calorimetry. The moisture in the prepreg was assumed to account for the different reaction kinetics observed and to have led to different reaction mechanisms. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 2295–2305, 2003     

Relationship between surface energy and adhesion strength in polyethylene—paper composites

This work reports adhesion behaviour of polyethylene on paper, and deals with the surface energy of the materials involved in the manufacture of these composites, and its influence on the adhesion strength, at constant roughness, for the paper substrates. The surface energy of different papers treated with various sizing agents was determined by measuring contact angles according to the Owens-Wendt method. The peeling energy was shown to follow a linear relationship versus the reversible energy of adhesion. This result is explained by the fact that rupture takes place at the interface and that the size of the defect at the interface depends on the spreading coefficient. Corona treatment, applied to strongly sized papers before making the composites, restored the adhesion strength to its original range of values, again demonstrating the thermodynamic character of adhesion in thermoplastic-paper composites.     

Synthesis and characterization of poly[methyl methacrylate‐co‐2‐ethylhexyl acrylate‐co‐poly(propylene glycol diacrylate)] latices

The emulsion polymerization of the monomers methyl methacrylate (MMA) and 2‐ethylhexyl acrylate (EHA) was studied to investigate the effect of the crosslinkable monomer poly(propylene glycol diacrylate) (PPGDA). IR spectroscopy, NMR, differential scanning calorimetry, gel permeation chromatography, and scanning electron microscopy were used to characterize the synthesized polymers. These polymers were coated on glass panels and cured at appropriate temperatures to study the physical properties, swelling behavior, surface tension, and contact angle of these polymer latices. The results show that as the concentration of EHA monomer increased, the surface tension of the latices decreased. The copolymers were characterized by ¹H‐NMR spectroscopy to ensure the absence of unreacted monomer, and the results confirm the incorporation of EHA units in the copolymer. The contact angle of the latices on the glass substrate was smaller than that on the metal. The swelling mechanism of the film showed that the Fickian diffusion coefficient with 10 wt % PPGDA was at a minimum value and was the most highly crosslinked polymer among the samples. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation and characterization of UV‐cured hybrid coatings by triethoxysilane‐modified dimethacrylate based on bisphenol‐s epoxy

Novel hybrid oligomers based on a UV‐curable bisphenol‐S epoxy dimethacrylate (DBSMA) were synthetized. DBSMA was modified with various amount of (3‐isocyanatopropyl)triethoxysilane coupling agent. The modification degree of the hybrid oligomer was varied from 0 to70 wt %. The photopolymerization kinetics was monitored by a real‐time infrared spectroscopy. The conversion and rate of hybrid coatings increased with the increase in modification degree. UV‐curable, hard, and transparent organic–inorganic hybrid coatings were prepared. They were performed by the analyses of various properties such as surface and mechanical properties. Results from the mechanical measurements showed that the properties of hybrid coatings improved with the increase in modification degree. The thermal behavior of coatings was also investigated. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Influence of vibrations on interface delamination in metal–polymer composites

The main objective of this work was the study of vibration effects on the viscoelastic coating protecting the steel layer in a metal–polymer composite, with simulated conditions of the transportation of food containers. Mechanical resonance tests in metal–polymer [electrolytic chromium-coated steel–poly(ethylene terephthalate) (PET)] sheets were performed to generate vibration conditions to induce structural modifications in the viscoelastic layer covering the surface of the plates. Consequently, schematic representations of the areas affected by these modifications were made. The modified structures were later analyzed by electron microscopy to detect and evaluate alterations in the morphology of the material. In addition, vibrational Raman spectroscopy analyses were performed to assess the chemical and structural changes on the protective PET at the metal–polymer interface level. The results of this study are expected to provide basic information on the mechanisms and nature of the delamination processes taking place in metal–polymer laminates employed in food-container applications. These damages have previously been detected in some food containers made of PET materials. The study of these damages can lead to the improvement of current composites or the development of higher quality materials. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Glass‐transition temperature–conversion relationship for an epoxy–hexahydro‐4‐methylphthalic anhydride system

The DGEBA–MHHPA epoxy system has found increasing applications in microelectronics packaging, making crucial the ability to understand and model the cure kinetics mechanism accurately. The present article reports on work done to elucidate an appropriate model, modified from the empirical DiBenedetto's equation, to relate the glass‐transition temperature (T_g) to the degree of conversion for a DGEBA–MHHPA epoxy system. This model employs the ratio of segmental mobility for crosslinked and uncrosslinked polymers, λ, to fit the model curve to the data obtained. A higher ratio value was shown to indicate a more consistent rate of increase of T_g in relation to the degree of conversion, while a lower value indicated that the rate of T_g increase was disproportionately higher at higher degrees of conversion. The best fit value of λ determined by regression analysis for the DGEBA–MHHPA epoxy system was 0.64, which appeared to be higher than for those previously obtained for other epoxy systems, which ranged from 0.43–0.58. The highest T_g value obtained experimentally, T_{g max}, was 146°C, which is significantly below the derived theoretical maximum T_g∞ value of 170. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 511–516, 2000     

Glass‐transition and gas‐transport characteristics of polymer nanocomposites based on crosslinked poly(ethylene oxide)

The glass‐transition and gas‐transport properties of rubbery polymer nanocomposites based on crosslinked poly(ethylene oxide) and metal oxide nanoparticles were studied. Nanocomposite samples were prepared by the UV photopolymerization of poly(ethylene glycol) diacrylate (n ～ 14) in the presence of magnesium oxide or silica nanoparticles. The thermomechanical properties of the composites were investigated with dynamic mechanical and dielectric spectroscopy methods. The inclusion of nanoparticles in the crosslinked poly(ethylene glycol) diacrylate network led to a systematic increase in rubbery modulus and a modest positive offset (～6°C) in the measured glass‐transition temperature for both systems. Bulk density measurements indicated only minimal void volume fraction in the composites, and CO₂ and light gas permeability decreased with particle loading; for example, the CO₂ infinite dilution permeability at 35°C decreased from 106 barrer in the unfilled polymer to 55 barrer in a nanocomposite containing 30 wt % magnesium oxide nanoparticles. The inclusion of toluene diluent in the prepolymerization mixtures produced a limited enhancement in sample permeability, but the sizeable increases in gas transport with particle loading reported for certain other rubbery nanocomposite systems were not realized in the crosslinked poly(ethylene glycol) diacrylate composites. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

UV‐activated hydrosilation reaction for silicone polymer crosslinking

In this article hydrosilation was employed to achieve a fully cured three‐dimensional silicone network. The UV‐activated hydrosilation reaction was investigated focusing on the curing conditions and their relationships to physical properties. After finding the optimum catalyst concentration, it was observed that by decreasing the molecular weight of the vinyl oligomer a slight increase of the T_g value was achieved together with a complete suppression of the Tm. It was possible to fully cure samples up to 4 cm of thickness. The dark curing process was evaluated by FTIR analyses and it was evidenced an important increase on dark‐polymerization, which is dependent on the length of the UV‐irradiation time. This result shows the versatility of UV‐curing technique for silicone network formation. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Chemical oxidation of high-density polyethylene: Surface energy,functionality, and adhesion to liquid epoxy

The application of polyolefins has increased significantly over the past few decades. However, their chemical inertness and low surface energy limits their application in many industries where high adhesion to polar materials is required, such as for composites and protective coatings. Herein, six different acids are used to create polar functional groups on High-Density Polyethylene's (HDPE) surface and to increase its adhesion to liquid epoxy (LE). Contact angle measurements, Fourier Transform Infrared Spectroscopy (FTIR), X-ray Photoelectron Spectroscopy (XPS), and pull-off strength measurements are used to analyze the surface energy and functionality of HDPE and to measure its adhesion to LE. The results show that each acid increases both the polar and disperse surface energies of HDPE to a different extent, but that this is not necessarily a function of acid strength. Chlorosulfonic acid and chromic acid increase the oxygen to carbon ratio by a factor of 8 and increase HDPE's adhesion to LE by more than 400%. Furthermore, a comparison between predicted work of adhesion values from the OWRK model and experimental results shows that the latter are significantly higher than what is predicted, especially with increasing surface polarity.     

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     

Synthesis and characterization of multi‐hollow opaque polymer pigments

A new generation multihollow opaque polymer pigment was synthesized by suspension polymerization of “water‐in‐oil‐in‐water” emulsion method, where methyl methacrylate and ethylene glycol dimethacrylate monomer mixture was used as oil phase. The effects of surfactant and cosurfactant composition in terms of “hydrophilic/lipophilic balance” on the stability of the “water‐in‐oil” emulsion and the size of water droplets were studied. Low droplet sizes and the optimum stability were obtained with “Span 80&Tween 80” surfactant mixture at an HLB value of 8. The desired size distribution was obtained at “monomer/surfactant/water” ratio of 75.5/9.4/15.1 at an ultrasonic mixing power of 80 W lasting for 30 s. The surface morphology and hollow structure of polymer pigments were analyzed by scanning and transmission electron microscopy techniques. L*a*b color and gloss properties of polymer pigments were examined. The opacity values were assessed by contrast ratio measurements, and the pigments provided up to 97.3% opacity with 50% v/v solid content in resin. In addition, the pigments exhibited low gloss values and yielded matte films. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43696.     

Hydrolyzable‐emulsifier‐containing polymer latices as dispersants and binders for waterborne carbon black paint

Poly(styrene‐co‐butyl methacrylate) and poly(styrene‐co‐butyl acrylate) latices were prepared by emulsion polymerization with alkali‐hydrolyzable and nonhydrolyzable cationic emulsifiers and were used as a dispersant and binder for waterborne carbon black (CB) paint. CB was dispersed in the latex solutions and then coated on filter paper pretreated with dilute aqueous Na₂CO₃ under mild conditions. The styrene (St)‐rich rigid copolymer latices easily dispersed the CB but fixed a little amount of the pigment on the paper surface. In contrast, the methacrylate‐ and acrylate‐rich soft latices tended to increase the adhesibility on it. We also demonstrated that the hydrolyzable‐emulsifier‐containing latices always had a higher adhesibility than the nonhydrolyzable‐emulsifier‐containing ones. Thus, the hydrolyzable‐emulsifier‐containing latices with an appropriate St content had the highest paintability, rapid adhesion, quick drying, reduced fading, superior fastness, and so on. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3869–3873, 2013