Preparation and characterization of hybrid nanocomposite coatings by photopolymerization and sol-gel process

Organic-inorganic nanocomposite hybrid coatings were prepared through a dual-cure process involving cationic photopolymerization of epoxy groups and subsequent condensation of alkoxysilane groups. The kinetics of the photopolymerization and condensation reactions were investigated; suitable conditions for obtaining a complete conversion of both reactive groups were found. The obtained films are transparent to visible light. The T_g values of the hybrids increase by increasing the TEOS content in the photocurable formulation. Also, a significant increase in surface hardness could be obtained for the hybrid systems. AFM analysis gave evidence of a strong interaction between the organic and inorganic phase with the formation of silica domains in the nanoscale range.     

Ni-W/SiO2纳米复合镀层的制备与性能研究

采用电沉积的方法制备了Ni-W/SiO2纳米复合镀层,研究了镀液中SiO2纳米微粒的添加量和电流密度对镀层中微粒含量的影响,通过扫描电镜观察了Ni-W/SiO2纳米复合镀层的表面形貌.研究发现,纳米复合镀层的硬度随着镀层中SiO2纳米微粒含量的增加而提高.通过测量Ni-W/SiO2纳米复合镀层在NaCl溶液中的阳极极化曲线发现纳米复合镀层的耐蚀性能要优于合金镀层.     

Preparation and characterization of UV-curable epoxy/silica nanocomposite coatings

To enhance the interfacial interaction in silica nanoparticles filled polymer composites, the silica surface was firstly treated with glycidoxypropyl trimethoxysilane (GPTMS), and its structure was analyzed by ¹³C NMR and FTIR spectrophotometry. Then a series of GPTMS-modified silica/cycloaliphatic epoxy nanocomposite coatings with 0–6 wt% silica content were prepared by UV-induced cationic polymerization in the presence of a diaryliodonium photoinitiator and thioxanthone photosensitizer. The physical and mechanical properties such as hardness, adhesion, gloss, impact as well as tensile strength were examined. As a result, these composites demonstrated superior tensile strength and tensile modulus with increasing proportion of modified silica up to a certain level. An increase in abrasion resistance of nanocomposites with the addition of modified silica was observed. The thermal stability of nanocomposites was not enhanced with the addition of silica particles. SEM studies indicate that silica particles were dispersed homogenously through the polymer matrix.     

Preparation,characterization, and analysis of anti-corrosion subsea coatings

Within this work, a two-component anti-corrosive epoxy primer formulation, Sigmacover? 280, and its resulting films were prepared and evaluated. The optimum coating time following formulation was extended by adding an appropriate amount of solvent as a controlled thinner. The draw down coating method was identified to be a reproducible and a robust paint film deposition process. Gravimetric analysis, Differential scanning calorimetry (DSC), and through-dry testing were used in the characterization of the curing and drying behavior of each applied primer film. The shortest time for achieving a through-dry state occurred with thinner films cured at the higher temperature, as seen in the film curing/drying. The minimum covercoating time and full cure time of the paint films, cured under the different conditions, were evaluated by means of its dryness, hardness, and curing state studies/characterization.     

Preparation and characterization of polynorbornene/sepiolite hybrid nanocomposite films

Polynorbornene/sepiolite hybrid nanocomposite films were prepared using polynorbornene dicarboximide and modified sepiolite with 3‐ aminopropyltriethoxysilane (3‐APTES). Exo‐N‐(3,5‐dichlorophenylnorbornene)‐5,6‐dicarboxyimide (monomer) and their copolymers were synthesized via ring‐opening polymerization using ruthenium catalysts. Subsequently, the surface‐modified sepiolite by 3‐APTES was mixed with the polynorbornene copolymers to prepare hybrid nanocomposite films. The modified sepiolite particles were well dispersed in N,N‐dimethylacetamide and distributed randomly throughout the polynorbornene matrix in the hybrid films, which enhanced the dimensional stability and mechanical and oxygen barrier properties of the polynorbornene/sepiolite hybrid nanocomposite films. © 2014 Society of Chemical Industry     

Preparation and characterization of acrylic resin/titania hybrid nanocomposite coatings by photopolymerization and sol–gel process

Titania‐containing coatings were prepared through a dual‐cure process involving radical photopolymerization of a polysiloxane diacrylate and subsequent condensation of alkyltitanate groups. The kinetics of photopolymerization and condensation reaction was investigated as a function of the inorganic phase precursor (titanium tetraisopropoxide) content. AFM analysis gave evidence of a strong interaction between the organic and inorganic phase with the formation of titania domains in the nanoscale region. An increase of hydrophilicity in the coatings surface with increasing TiO₂ content was evidenced. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4659–4664, 2006     

Preparation and characterization of UV-cured polyurethane acrylate/ZnO nanocomposite films based on surface modified ZnO

A series of polyurethane acrylate (PUA)/ZnO nanocomposite films with different ZnO contents were prepared via a UV-curing system. To ensure good dispersion in the PUA matrix, ZnO nanoparticles were modified with a silane coupling agent and confirmed by FT-IR analysis. The morphological structures, thermal properties, mechanical properties and water transfer properties of the prepared films were investigated as a function of their ZnO concentration. WAXD and SEM analyses showed that the surface-modified ZnO nanoparticles were homogeneously dispersed in the PUA matrix and the molecular ordering increased with increasing ZnO content. Compared with neat PUA, the hardness and elastic modulus in films increased from 0.03 to 0.056 GPa and from 2.75 to 3.55 GPa, respectively. Additionally, the water uptake and WVTR in the PUA/ZnO nanocomposite films decreased as the ZnO content nanoparticles increased, which may come from enhanced molecular ordering and hydrophobicity in films. UV light below approximately 450 nm can be efficiently absorbed by incorporating ZnO nanoparticles into a PUA matrix, indicating that these composite films exhibit good weather ability and UV-shielding effects. The enhanced physical properties achieved by incorporating modified ZnO nanoparticles can be advantageous in various applications, whereas the thermal stability of the composite films should be increased.     

Preparation and characterization of Cu2S/CdS/ZnS nanocomposite in polymeric networks

Summary A novel inorganic semiconductor nanocomposite(Cu₂S/CdS/ZnS) were prepared in polymeric networks. The XPS data show that the mass content of Cu, Cd and Zn ions in polymeric networks were roughly 1.4%, 6.7% and 7.7% respectively. The particle sizes of Cu₂S, CdS and ZnS were about 2.8nm, 5.3nm and 7.1nm respectively determined by XRD, and they have monoclinic, hexagonal and hexagonal structures. Considering the densities, molar ratio and solubilities of these metal sulfides and compared with the TEM photograph, we can deduce that these three kinds of metal sulfides in polymeric networks formed a three-layered structure.     

Corrosion protection evaluation of silica/epoxy hybrid nanocomposite coatings to AA2024

Silica-based organic–inorganic hybrid nanocomposite films have been developed by sol–gel method for corrosion protection of AA2024 alloy. The sol–gel films have been synthesized from 3-glycidoxypropyltrimethoxysilane (GPTMS) and tetraethylorthosilicate (TEOS) precursors. Interlinked organic–inorganic networks can be formed because of the presence of both epoxy and silicon alkoxide functionalities in the precursor molecules. In order to investigate the effective factors on the properties of organically modified silicates films (Ormosils), different coatings with different organic and hydrolysis water content were developed. The films were prepared by dip-coating technique. The chemical composition and the structure of the hybrid sol–gel films were studied by energy dispersive spectroscopy (EDS) and scanning electron microscopy (SEM), respectively. The corrosion protection properties of the films were studied by potentiodynamic scanning (PDS) and salt spray tests. The results indicate that the hybrid films provided exceptional barrier and corrosion protection in comparison with untreated aluminium alloy substrate.     

Preparation and characterization of polymer/zirconia nanocomposite antistatic coatings on plastic substrates

Zirconia nanoparticles synthesized by the sol–gel method were surface modified by the coupling agent, 3-(trimethoxy silyl) propyl methacrylate (MSMA), containing C=C bonds. These particles were then UV-cured together with the hexa-functional monomer, dipentaethritol hexaacrylate (DPHA), to prepare transparent coatings that exhibited antistatic property on plastic substrates. FTIR and solid ²⁹SiNMR were used to analyze the chemical bonds in the formed particles and coatings. Dynamic light scattering measurement of the modified ZrO₂ sol indicated a relatively small particle size distribution, 1.5–20 nm, with a maximum intensity at ~5.5 nm. These particles dispersed uniformly in the organic host, poly(DPHA), as was manifested by the high resolution SEM images of the coatings. Antistatic performance of the coatings was examined based on the surface resistivity measurements. A resistivity of 7.74 × 10⁸ Ω/□ suited to common antistatic applications could be attained for coatings containing 10% inorganic component. In addition, all of the prepared coatings were very hard with pencil hardness 7H–8H, and they attached perfectly to the PMMA substrate according to the peel test.     

Preparation and characterization of water reducible alkyd resin/colloidal silica nanocomposite coatings

In this study, water reducible alkyd resins containing different amounts of colloidal silica were synthesized for the first time. In order to achieve this, alkyd resin, which has an oil content of 35%, was prepared with tall oil fatty acid, isophthalic acid, trimellitic anhydride, and trimethylolpropane. The alkyd resin was neutralized with triethylamine, and was dissolved in an isobutyl alcohol-isopropyl alcohol-butyl glycol mixture to produce 75% (wt.) solution, which was called stock alkyd resin. The stock alkyd resin was diluted with water to 50% (wt.) concentration with water and colloidal silica mixture in order to prepare an alkyd solution containing 0%, 5%, 10%, 15% and 20% colloidal silica. Then the effect of the silica nanoparticle addition on the surface coating properties, thermal behaviors and surface morphologies of water reducible alkyd resins was investigated. As a result, the addition of colloidal silica has improved surface coating properties and thermal behaviors of nanocomposite water reducible alkyd resin.     

Preparation and characterization of UV‐curable ZnO/polymer nanocomposite films

A series of novel nano‐ZnO/polymer composite films with different ZnO contents was prepared through incorporation of pre‐made colloidal ZnO particles into monomer mixtures of urethane‐methacrylate oligomer and 2‐hydroxyethyl methacrylate, followed by ultraviolet (UV) radiation‐initiated polymerization. The colloidal ZnO nanoparticles with a diameter of 3–5 nm were synthesized from zinc acetate and lithium hydroxide in ethanol via a wet chemical method. In order to stabilize and immobilize the ZnO particles into the polymer matrix, the ZnO nanoparticles were further capped using 3‐(trimethoxysilyl)propyl methacrylate. Thermogravimetric analyses show that the ZnO nanoparticles were successfully incorporated into the polymer matrix and these ZnO/polymer composites have a good thermal stability. Transmission electron microscopy studies indicate the ZnO nanoparticles were uniformly dispersed in the polymer and they remained at the original size (3–5 nm) before immobilization. All nanocomposite films with ZnO particle contents from 1 to 15 wt% show good transparency in the visible region and luminescent properties. In addition, composite films with high ZnO content (>7 wt%) are able to absorb UV irradiation below 350 nm, indicating that these composite films exhibit good UV screening effects. Copyright © 2006 Society of Chemical Industry     

High density hydrophilic and hydrophobic brush coatings using a polymeric primer layer

Polymer brush coatings, consisting of polymer chains covalently attached to a surface and being less than a hundred nanometer thick, allow the creation of functional surfaces without altering the inherent bulk properties or appearance of a product. Surface properties depend on the type and length of the polymer used, as well as on the grafting density of the polymer brush. By making use of a polymeric primer layer that is covalently linked to the substrate and creates a uniform and highly functionalized surface, polymer brush coatings with high grafting densities can be created. In this paper we report the preparation of hydrophilic as well as hydrophobic brush coatings on different substrates through the use of a poly(acrylic acid) primer layer. In addition, hydrophilic poly(ethylene glycol) brush coatings thus produced were shown to decrease adhesion of marine bacteria.     

Dielectric behavior characterization of a fibrous‐ZnO/PVDF nanocomposite

This study is focused on forming a fibrous‐zinc oxide/polyvinylidine fluoride (ZnO/PVDF) nanocomposite and characterizing its dielectric behavior. The nanocomposite is prepared in two steps. First, a network of nanoscale diameter ZnO fibers is produced by sintering electrospun PVA/Zinc Acetate fibers. Second, the ZnO fibrous nonwoven mat is sandwiched between two PVDF thermoplastic polymer films by hot‐press casting. Scanning electron microscope images of the nanocomposite show that hot‐press casting of the fibrous‐ZnO network breaks the network up into short fibers. The in‐plane distribution of the ZnO fillers (i.e., the short fibers) in the PVDF matrix appears to comply with that of the pristine ZnO fibers before hot‐pressing, indicating that the fillers remain well‐dispersed in the polymer matrix. To the authors' knowledge, the work reported herein is the first demonstration of the use of electrospinning to secure the dispersion and distribution of a network of inorganic fillers. Moreover, processing a fibrous‐ZnO/PVDF flexible composite as described in this report would facilitate material handling and enable dielectric property measurement, in contrast to that on a fibrous mat of pure ZnO. Because of the high surface area of the short ZnO fibers and their polycrystalline structure, interfacial polarization is pronounced in the nanocomposite film. The dielectric constant is enhanced significantly‐up to a factor of 10 at low frequencies compared to the dielectric constant of constituent materials (both bulk ZnO and PVDF), and up to a factor of two compared to a bulk‐ZnO/PVDF composite. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers     

Wear,thermal, and physical properties of fluorine-containing polyimide/silica hybrid nanocomposite coatings

This study prepared fluorine and SiO₂ particles containing organic–inorganic hybrid polyimide nanocomposite coatings (PISFs) with inorganic content in the range of 5–20% in pure polyimide solutions via the sol–gel process. Polyimide hybrid structures containing fluorine and SiO₂ particles were synthesized by using perfluorooctyltriethoxysilane and tetraethyl orthosilicate. These formulations were applied on aluminum sheets by using a 75 μm wire wound applicator, and the coatings were cured for 8 h at room temperature and then 24 h at 100 °C. Increased inorganic contents caused slight decreases in the initial decomposition temperatures, but the char yield values increased for PISF15 and PISF20. All samples exhibited hydrophobic properties. When all samples were compared, PISF5 and PISF10 exhibited hydrophobicity, high wear resistance and thermal properties. Additionally, PISF5 and PISF10 showed high adhesion, hardness, and methyl ethyl ketone solvent resistance. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47399.     

Preparation of supramolecular corrosion-inhibiting nanocontainers for self-protective hybrid nanocomposite coatings

The copolymers were prepared by the photo-induced copolymerization of methyl methacrylate (MMA, M ₁ ) with 4-methacryloyl-1,2,2,6,6-pentamethyl-piperidine (MPMP, M ₂ ) in benzene solution at ambient temperature. The reactivity ratios for these monomers were measured by running a series of reactions at various feed ratios of initial monomers, and the copolymer compositions were determined by ¹H NMR spectroscopy. The reactivity ratios of the monomers were found to be r ₁ ?=?0.28 and r ₂ ?=?1.63 by the application of extended Kelen-Tüdos method. The results showed that, MMA preferred to copolymerization while MPMP tended to homopolymerization in the copolymerization system. The sequence structures of the MMA/MPMP copolymers were characterized by ¹H NMR spectroscopy. The backbone structures of the MMA/MPMP copolymers were mainly composed of a syndiotactic and an isotactic configuration. Three kinds of the sequences of rr, rr’ and lr’ in the syndiotactic configuration and two kinds of the sequences of km’ and mm’ as the isotactic configuration were found. The sequential distribution and the sequence-length distribution in the MMA/MPMP copolymers were also obtained.     

Bio‐hybrid nanocomposite coatings from sonicated chitosan and nanoclay

Nanocomposite films and coatings with improved properties were produced from ultrasonic dispersed chitosan and hydrophilic bentonite nanoclay. Bio‐hybrid coatings were applied onto argon–plasma‐activated LDPE coated paper. The intercalation of chitosan in the silicate layers was confirmed by the decrease of diffraction angles as the chitosan/nanoclay ratio increased. Nanocomposite films and multilayer coatings had improved barrier properties against oxygen, water vapor, grease, and UV‐light transmission. Oxygen transmission was significantly reduced under all humidity conditions. In dry conditions, over 99% reduction and at 80% relative humidity almost 75% reduction in oxygen transmission rates was obtained. Hydrophilic chitosan was lacking the capability of preventing water vapor transmission, thus total barrier effect of nanoclay containing films was not more than 15% as compared with pure chitosan. Because to very thin coatings (≤1 μm), nanoclay containing chitosan did not have antimicrobial activity against test strains. All coating raw materials were “generally recognized as safe” (GRAS) and the calculated total migration was in all cases ≤6 mg/dm², thus the coatings met the requirements set by the packaging legislation. Processing of the developed bio‐hybrid nanocomposite coated materials was safe as the amounts of released particles under rubbing conditions were comparable with the particle concentrations in a normal office environment. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Linseed polyurethane/tetraethoxyorthosilane/fumed silica hybrid nanocomposite coatings: Physico-mechanical and potentiodynamic polarization measurements studies

The work presents the physico-mechanical properties and potentiodynamic polarization measurements studies of linseed oil based polyurethane/tetraethoxyorthosilane [LPU/TEOS] hybrid and polyurethane/tetraethoxyorthosilane/fumed silica NC [LPU/TEOS/FS] hybrid nanocomposite coatings. The best coating performance was obtained by the inclusion of 2 wt% FS in 2-LPU/TEOS hybrid. 2-LPU/TEOS/FS produced glossy, transparent, flexibility retentive, scratch-resistant and impact resistant coatings at ambient temperature relative to LPU/TEOS coatings. 2-LPU/TEOS/FS showed good scratch hardness (5.5 kg), impact resistance (250 lb/in.), flexibility (1/8 in.) as investigated by standard methods with corrosion rate obtained as 3.567 × 10⁻⁴ mm/year and 4.05 × 10⁻⁴ mm/year and inhibition efficiency as 99.816% and 99.710% in 3.5% NaOH and 3.5% HCl, respectively.     

Single-step prepared hybrid ZnO/CuO nanopowders for water repellent and corrosion resistant coatings

In this study, ZnO/CuO hybrid hydrophobic nanopowders were synthesized using a common single-step chemical precipitation route without using modifiers. Influence of initial ZnO:CuO precursor concentrations and alkaline agent type on the wettability behavior of the prepared samples were investigated. Wettability properties of the prepared samples were assessed by measuring the water contact angle and contact angle hysteresis values. Fourier transform infrared spectra, scanning electron microscope micrographs and X-ray diffraction patterns were applied to identify the surface chemistry and morphological features. Scanning electron microscope images of the synthesized ZnO/CuO nanocomposites indicated flower-like morphologies containing plenty of nano-needles, -rods, and -sheets with thicknesses lower than 90 nm. The sample prepared under the optimum conditions was superhydrophobic having water contact angle and contact angle hysteresis of 162.6°±1 and 2°, respectively. It was applied to coat the surface of stainless steel meshes by spray deposition method. The resultant superhydrophobic surface exhibited excellent self-cleaning (water repellency) property and a suitable stabilities under the ambient and saline solution (NaCl, 3.5%) media. Additionally, electrochemical corrosion tests confirmed that the corrosion resistance of the fabricated ZnO–CuO coating was higher than the initial bare mesh.