Synthesis of high solid content waterborne polyurethanes with controllable bimodal particle size distribution

A series of waterborne polyurethane dispersions were synthesized by one‐pot reaction and step‐wise reaction, respectively. The effects of synthetic methods and DMPA content on the particle size distribution (PSD), solid contents and viscosity were studied by laser particle size analyzer, Brookfield viscometer and TEM analysis. High solid content and low viscosity waterborne polyurethanes (WPUs) with controllable bimodal PSD were prepared by one‐pot reaction using 2,2‐dimethylol propionic acid (DMPA) as the only self‐emulsifier. Meanwhile, 40% solid content WPUs with unimodal PSD were obtained by step‐wise reaction at the same formula. With the increment of DMPA content, the ratio of large particles to small particles decreased and two peaks of the particle size finally became one peak by one‐pot reaction while the PSD remained unimodal by step‐wise reaction. The reason leading to the difference of PSD between one‐pot reaction and step‐wise reaction was analyzed and the relationships among PSD, viscosity and solid content were discussed. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40420.     

Effects of small molecular weight silicon‐containing acrylate on kinetics,morphologies, and properties of free‐radical/cationic hybrid UV‐cured coatings

A series of UV‐curable, silicon‐containing mixtures were prepared by adding different micro amounts of small molecular weight silicon‐containing acrylate KH570 to an interpenetrating polymer network system composed of cycloaliphatic polyurethane acrylate, trimethylolpropane triacrylate, cycloaliphatic epoxy resin, free‐radical photoinitiator Irgacure 754 and cationic photoinitiator Irgacure 250 with a weight ratio of 15 : 15 : 65 : 1 : 4. Hybrid coatings with different addition amounts of KH570 (0.2, 0.6, 1.0 wt %) were cured from the mixtures by UV‐initiated free‐radical/cationic dual curing technique. Final reactant conversions and photopolymerization rates of the hybrid UV‐cured coatings were improved with the increase of KH570 content, as evaluated by conversion profiles. The morphologies and microstructures were characterized by scanning electron micro‐scopic, atomic force micrographic, and fourier transform infrared spectrophotometer measurements. Thermal, mechanical, and surface properties of the hybrid UV‐cured coatings were investigated. The increase in KH570 content caused a decrease in mechanical properties besides the breaking elongation. Thermo‐gravimetric analysis revealed that the incorporation of silicon into cross‐linked network structure resulted in high thermal stability. The surface properties of hybrid UV‐cured coatings, such as hardness, contact angle, flexibility, and glossiness were also examined. It is found that transparent hybrid coating with the addition of 1.0 wt % KH570 exhibited a relatively higher contact angle as a direct result of a relatively higher hydrophobic surface. These researches showed that micro amounts of small molecular weight silicon‐containing acrylate could greatly influence the morphologies of liquid nitrogen quenching cross sections and properties of hybrid UV‐cured coatings and could be used to modify UV‐cured coatings for some superior properties. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40655.     

The effect of side chains on the reactive rate and surface wettability of pentablock copolymers by ATRP

The reactive rate and surface wettability of three pentablock copolymers PDMS‐b‐(PMMA‐b‐PR)₂ (R = 3FMA, 12FMA, and MPS) obtained via ATRP for coatings are discussed. Poly(dimethylsiloxane) (PDMS) is used as difunctional macroinitiator, poly(methyl methacrylate) (PMMA) as the middle block, while poly(trifluoroethyl methacrylate) (P3FMA), poly(dodecafluoroheptyl methacrylate) (P12FMA) and poly(3‐(trimethoxysilyl)propyl methacrylate) (PMPS) as the end block, respectively. Their reactive rates obtained by gas chromatography (GC) analysis indicate that 3FMA gains 8.053 × 10^?5 s^?1 reactive rate and 75% conversion, higher than 12FMA (4.417 × 10^?5 s^?1, 35%), but MPS has 1.9389 × 10^?4 s^?1 reactive rate and 96% conversion. The wettability of pentablock copolymer films is characterized by water contact angles (WCA) and hexadecane contact angles (HCA). The PDMS‐b‐(PMMA‐b‐P12FMA)₂ film behaves much higher advancing and receding WAC (120° and 116°) and HCA (60° and 56°) than PDMS‐b‐(PMMA‐b‐P3FMA)₂ film (110° and 106° for WAC, 38° and 32° for HAC) because of its fluorine‐rich surface (20.9 wt % F). However, PDMS‐b‐(PMMA‐b‐PMPS)₂ film obtains 8° hysteretic contact angle in WAC (114°–106°) and HAC (32°–24°) due to its higher surface roughness (138 nm). Therefore, the fluorine‐rich and higher roughness surface could produce the lower water and oil wettability, but silicon‐rich surface will produce lower water wettability. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40209.     

Gradient and weather resistant hybrid super‐hydrophobic coating based on fluorinated epoxy resin

A weather resistant super‐hydrophobic coating that can offer good substrate adhesion and yet to be easily processed at large scale can be of practical use in emerging fields of self‐cleaning and anti‐icing paint, combing all these properties together remains challenging task. Here we describe a composite coating composed of a fluorinated epoxy resin emulsion with embedded in situ surface‐modified dual‐scale nano‐silica, which displayed durable super‐hydrophobicity and excellent adhesive strength. The as‐prepared coating possesses water contact angle of 158.6 ± 1°, sliding angle around 3.8 ± 0.2° which remain stable even under acidic/alkaline, heat/cool, and accelerated aging treatment. The results demonstrate that surface roughness had a micron‐ and nanometer scale distribution with increased particle loading beyond 40 wt %. Through quantitative comparison of surface Attenuated Total Reflection (ATR) with bulk FT‐IR transmission spectra, a gradient coating with surface enrichment of hydrophobic groups was determined. The air‐side fluorinated polysiloxane‐rich layer endows coating with weather‐resistance and ultra‐hydrophobicity while bottom epoxy resin layer enhances substrate adhesion. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40955.     

Acrylate–vinylidene chloride copolymers derived from corresponding water‐borne latexes: Influence of acrylate units on their potential as heavy‐duty anticorrosive coating materials

A series of aqueous latexes with solid contents of 56%–59% were synthesized by binary emulsion copolymerization of vinylidene chloride (VDC) with an acrylate, namely methyl acrylate (MA), ethyl acrylate (EA), butyl acrylate (BA), hexyl acrylate (HA), or 2‐ethylhexyl acrylate (EHA). Differential scanning calorimetry (DSC) and Fourier‐transform infrared (FTIR) spectroscopy showed that the acrylate units with short ester side‐chains, such as MA and EA, made the copolymers hard and the crystallization tendency of their PVDC segments was reduced. Hydrophobic acrylates with relatively long ester groups, such as HA and EHA, gave flexible copolymers, and favored the crystallization of their PVDC segments. BA endowed the copolymers with medium flexibility and crystallization tendency. As coating materials, the copolymers bearing MA and EA adhered poorly to the tinplate before or after 100 hr of salt‐spray corrosion, whereas those bearing BA, HA, or EHA showed good adhesion to tinplate when they had little or no crystallinity. After 100 hr of salt‐spray corrosion, only BA–VDC80, containing 80% VDC, retained both excellent adhesion to metal and excellent barrier performance. Further study demonstrated that BA–VDC80 could protect tinplate from rusting for at least 250 hr under harsh salt‐spray corrosion. Scanning electron microscopy, FTIR‐attenuated total reflectance spectroscopy and DSC were used to evaluate the corroded BA–VDC80 film. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40192.     

Theoretical and practical considerations in electrostatic depositioning of charged polymers

An interfacial engineering technology, based on the electrostatic deposition of charged polyelectrolytes onto surfaces of oppositely charged templates is reviewed with an emphasis on practical applications in the food, pharmaceutical and personal care industries. On interfaces of disperse systems consecutively deposited polymers provide major advantages in terms of physical and chemical stability of dispersions against superimposed stresses (pH, temperature, ionic strength, freezing, chilling, dehydration, lipid oxidation). The controlled deposition of multiple layers allows for a controlled and triggered release of incorporated functional components. This review highlights the basic principles of the layer‐by‐layer (LbL) electrostatic deposition method as well as some major advantages and drawbacks of this approach. An overview of several systems that can be used as templates for the deposition including emulsion droplets, liposomal vehicles, colloidal aggregates, and planar surfaces is given. Suitable substrates for the deposition are presented with a focus on charged biopolymers such as proteins or polysaccharides since they play an essential role in the formulation and stabilization of food, pharmaceutical and personal care applications. Issues and difficulties associated with implementing the technology on a larger, industrial scale are discussed. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40099.     

Mechanical and barrier properties of cardboard and 3D packaging coated with microfibrillated cellulose

Microfibrillated cellulose (MFC) is increasingly used with cellulosic substrates and especially with paper materials. Its use with cardboard remains not reported and the study of mechanical and barrier properties of MFC‐coated cardboard has been investigated in this article. The influence of coating process as well as the effect of MFC have been highlighted by comparing different MFC‐coated cardboard samples with PE‐coated cardboard samples. MFC was coated using bar coating process. Their distribution and homogeneity onto cardboard was observed using techniques such as SEM and FE‐SEM. Tests such as oxygen and air permeability, bending stiffness, and compressive strength have been carried out. The coating process used impacts significantly cardboard properties by two opposite ways: on one hand it damages the structure cohesion of cardboard decreasing its compressive strength; on the other hand it increases its bending stiffness by increasing considerably the samples thickness. The addition of MFC counterbalances the negative effects of the coating process: bending stiffness and compressive strength are indeed improved by 30% in machine direction. On the contrary, MFC does not enhance much cardboard barrier properties, although it considerably increases their water absorption. Within a framework of packaging application, MFC will rather have consequent effects on cardboard's properties as blend or as part of the multilayer structure. Other applications have to be considered for its use as top layer. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40106.     

Protective properties of PPy‐Au nanocomposite coatings prepared by sonoelectrochemisty and optimized by the Taguchi method

The polypyrrole (PPy) and polypyrrole‐Au (PPy‐Au) nanocomposite films have been sonoelectrochemically synthesized on St‐12 steel electrodes using the galvanostatic technique. Experimental design according to the Taguchi method has been applied to optimize the factors on the synthesis of PPy‐Au nanocomposite coating. Three factors were used to design an orthogonal array L9: Synthesis time (t), Current density (I), and Concentration of HAuCl₄ (C). The synthesized Au nanoparticles during polymerization were characterized by Ultraviolet–visible (UV‐visible) spectroscopy. Characterization of the surfaces was done by scanning electron microscope (SEM), energy dispersive X‐ray spectrum (EDX), and atomic force microscope (AFM). The scanning electron microscopy (SEM) image of PPy shows a smooth surface while PPy‐Au nanocomposite film has a compact morphology. Moreover, energy dispersive X‐ray spectrum (EDX) is evidence for the incorporation of Au nanoparticles. The corrosion protection of coatings was investigated by open circuit potential (OCP) time trends, potentiodynamic polarization technique, and electrochemical impedance spectroscopy (EIS) in a NaCl 3.5% solution. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41087.     

Synthesis of fluoroalkyl‐modified polyester and its application in improving the hydrophobicity and oleophobicity of cured polyester coatings

The fluoroalkyl‐modified polyester (PE‐F_n) was synthesized by the reaction of polyester resin (PE) and fluorinated isocyanate, and the structure of the synthesized product was characterized by proton nuclear magnetic resonance (¹H‐NMR) and fluorine nuclear magnetic resonance (¹⁹F‐NMR). The water and oil wettability of the cured PE coatings with PE‐F_n as additives was investigated by contact angle meter. The results showed that the introduction of an extremely low concentration of PE‐F_n into PE led to the increase in contact angle of water and diiodomethane on cured PE coatings, and the decrease in the surface free energy. The X‐ray photoelectron spectroscopic (XPS) analysis showed that the F/C molar ratio in the outer few nanometers was significantly higher than that in the bulk, indicating that the fluoroalkyl groups in PE‐F_n had enriched on the coating surface. It was also found that longer fluoroalkyl groups and fluoroalkyl groups with ? CF₃ at its end had the higher tendency to aggregate on the coating surface. The topological structures of the cured coatings were recorded by an atomic force microscope under tapping mode and the results revealed that there was a strong surface segregation of fluorinated species. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39812.     

Study the factors affecting the performance of organic–inorganic hybrid coatings

In this article, a series of hybrid organic–inorganic coatings based on silica‐epoxy composite resins were prepared with the sol‐gel method by using γ‐aminopropyl triethoxysilane as a coupling agent. Especially, the research emphasized on the factors that influenced on the properties of the prepared hybrid coatings. Firstly, epoxy resin was reacted with γ‐aminopropyl triethoxysilane at a specific feeding molar ratio; subsequently, the asprepared sol–gel precursor was cohydrolyzed with tetraethoxysilane (TEOS) at various contents to afford chemical bondings to form silica networks and give a series of organic–inorganic hybrid coatings. They were loaded and cured on steel panels and characterized for FTIR, TGA, DSC, water contact angles (WCA), pencil hardness, surface & three‐dimensional morphological studies, and potentiodynamic polarization tests. The surfaces of the hybrid coatings showed Sea‐Island or Inverting Sea‐Island morphologies at a certain relative content of two components, which made the coatings possess hydrophobic property. Due to the contribution of organic and inorganic components, the prepared hybrid coatings possess a lot of properties such as pencil hardness, thermotolerance, and corrosion resistance. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41010.