Hybrids of cellulose acetate and sol–gel silica: Morphology,thermomechanical properties,water permeability,and biodegradation evaluation

Hybrids based on cellulose acetate (CA) and SiO₂ were prepared by hydrolysis of tetraethoxysilane (TEOS). More rigid films were obtained with an inorganic phase incorporation. The thermal stability of the hybrids was similar to pure CA. Composite membranes were prepared by casting of CA/TEOS mixtures onto a poly(vinylidene fluoride) support. The water permeation decreased with the incorporation of the inorganic phase. Hybrid membranes were able to retain solutes with a molar mass of ?9000 g/mol (?98% retention). Hybrids were submitted to biodegradation tests. The presence of the inorganic phase did not inhibit the growth of Thricoderma harzianum fungi. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2196–2205, 2002     

Hybrid ternary organic-inorganic films based on interpolymer complexes and silica

Homogeneous transparent hybrid films consisting of chitosan (CHI), poly(monomethyl itaconate) (PMMI) and silica were obtained indicating the absence of microphase separation. These ternary hybrid materials are very interesting since materials with high functionality can be obtained presenting different properties from those of the starting materials but with the advantage of preserving the inherent property of each component. The inorganic phase was prepared by sol-gel process of tetraethoxysilane (TEOS). Most of the amine groups from CHI (pK_b 7.7) are quaternized in the acidic medium used in the preparations (pH=2), where a physical crosslinking via hydrogen bonding could occur through carboxyl groups from PMMI. Silica gel obtained from TEOS has been intercalated as a very fine dispersion in the polymer complex formed between CHI and PMMI. Transmission electron microscopy and atomic force microscopy was used to examine the homogeneity of the ternary polymer hybrids (CHI/PMMI/SiO₂), obtained as self-supported films. The results support the nanometer scale dispersion of the phases. Porous silica films with high BET area were obtained by calcination of the hybrid films. The mean pore diameter of these silica films corresponds to the dimension of the polymer domains observed in the pristine hybrid films. Moreover, it was found that the swelling behavior of the samples was influenced by the organic and inorganic phases, where the inorganic phase tends to diminish the swelling.     

Influence of silane structure on curing behavior and surface properties of sol–gel based UV-curable organic–inorganic hybrid coatings

In this study, three usual silane precursors, tetraethoxysilane (TEOS), vinyltrimethoxysilane (VTMS), and 3-methacryloxypropyltrimethoxysilane (MPS), and different binary and triplet blends of them were polymerized via a sol–gel method under acidic conditions. ²⁹Si NMR spectroscopy was used to characterize and quantify the degree of condensation of oligomers. The organic phase was based on a three-acrylate monomer trimethylolpropane triacrylate (TMPTA). The effect of prepared oligomers on the curing behavior of hybrid materials and the interaction between organic and inorganic phases were monitored via photo differential scanning calorimetry (Photo-DSC). Atomic force microscopy (AFM) was used to investigate the surface properties of UV-cured hybrid materials. Photo-DSC results showed that the addition of functionalized oligomers can increase both the photopolymerization rate and the final degree of conversion. They also indicated that oligomers containing MPS are more compatible with the organic phase than other oligomers. Topography and phase trace images of AFM showed that oligomers containing VTMS migrate to the surface of films and affect the water contact angle. In contrast to VTMS, the presence of MPS in oligomers causes the formation of covalent bonds between the organic and inorganic phases in the bulk of the film, and so the surface properties of the film remain unchanged.     

Acid-catalyzed moisture-curing polyurea/polysiloxane ceramer coatings

The para-toluene sulfonic acid (p-TSA) was used to catalyze the moisture curing of an organic/inorganic hybrid coating system. The organic phase was based on the isocyanurate of 1,6-hexamethylene of diisocyanate (HDI). The inorganic phase was based on the prepolymerized oligomers of tetraethyl orthosilicate (TEOS). An alkoxysilane-functionalized HDI isocyanate was added into the coating formulation to aid in phase miscibility. The general coating and tensile properties were evaluated as a function of the acid catalyst concentration. In addition, the films were analyzed using differential scanning calorimetry (DSC) and dynamical mechanical thermal analysis (DMTA). The results indicated that the acid catalyst enhanced the adhesive properties of the hybrid coatings. The addition of the acid catalyst increased the changed crosslink density of films and decreased the crystallinity of the organic phase.     

Scratch resistance and oxygen barrier properties of acrylate-based hybrid coatings on polycarbonate substrate

Organic/inorganic hybrid coating materials were synthesized using acrylate end-capped polyester, 1,6-hexanediolacrylate, tetraethoxysilane (TEOS), and 3-trimethoxysilylpropylmethacrylate (TMSPM). The hybrid materials were cast onto a polycarbonate (PC) substrate and cured by UV irradiation to give a hybrid film with covalent linkage between the inorganic and the organic networks. The coating layer was characterized by FT-IR and ²⁹Si-NMR, and pencil hardness and oxygen permeation rate of coated films were investigated. The pencil hardness of all samples examined in this study was higher than 1H, whereas that of uncoated PC substrate was 6B. The hardness enhancement after coating may due to incorporation of organic acrylate resin. The oxygen permeability coefficient of the film coated with hybrid material on 3-aminopropyltriethoxysilane (APTEOS) pretreated polycarbonate substrate was 1.67×10⁻³ GPU, the lowest value in this work, whereas that of uncoated PC substrate was 8.07×10⁻³ GPU. The lower oxygen permeation rates of these films are attributed to the good adhesion between organic/inorganic hybrid coating layer and PC substrate and a dense structure induced by an increase of network density.     

Dual‐curable unsaturated polyester inorganic/organic hybrid films

An unsaturated polyester, based on maleic anhydride, 1,6‐hexanediol, and trimethylol propane, was formulated with tetraethylorthosilicate (TEOS) oligomers and a coupling agent to prepare inorganic/organic hybrid films. TEOS oligomers were prepared through the hydrolysis and condensation of TEOS with water, and 3‐(triethoxysilyl)propylisocyanate was used as the coupling agent between the organic and inorganic phases. The hybrid materials were cured by moisture via sol–gel chemistry and by the UV curing of unsaturated polyesters. To compare the properties of the moisture‐cured inorganic/organic hybrid films, a conventional 2K polyurethane system was also prepared. The tensile, adhesion, abrasion, and fracture toughness properties were investigated as functions of the coupling agent and relative amount of UV cure versus thermal cure. Although no difference could be observed in the tensile properties, the abrasion resistance, fracture toughness, and adhesion were enhanced by the incorporation of TEOS oligomers into polyurethane films. Also, the abrasion resistance, fracture toughness, and tensile properties were increased with both moisture and UV exposure. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 115–126, 2006     

Organic–Inorganic Hybrid Films Based on Hydroxylated Soybean Oils

Hybrid organic–inorganic films were prepared using four different hydroxylated soybean oils (HSO) or epoxidized soybean oil as organic precursor and tetraethyl orthosilicate (TEOS) as inorganic precursor in a mass ratio of HSO:TEOS of 90:10. The films were macroscopically homogeneous and were characterized by swelling and extraction in solvent, thermogravimetric analysis (TGA), scanning electron microscopy (SEM) including energy dispersive spectroscopy (EDX), adhesion and hardness. Their properties varied as a function of the number of OH groups present in the HSO. The best hybrid system was HSOF198/TEOS, with an OH value of 198 mg of KOH/g, which presents lower swelling coefficient, very good adhesion on aluminium surface and good hardness.     

Properties of organic–inorganic composite materials prepared from acrylic resin emulsions and colloidal silicas

To design an organic–inorganic composite material with colloidal silica as the inorganic component, an acrylic resin emulsion and an organic silane hybridized acrylic resin emulsion were prepared by emulsion polymerization. The organic–inorganic composite films were prepared by blending the emulsion and the colloidal silica. The contact angles for water, gloss at 60°, and the transparencies of those films were measured. The dispersion state of colloidal silica in films was observed with a scanning electron microscope (SEM) and a transmission electron microscope (TEM). From these results, the contact angle for water of the organic–inorganic composite film obtained from the silane hybridized acrylic resin emulsion was lower than that of the organic–inorganic composite film obtained from an acrylic resin emulsion. The contact angles for water in organic–inorganic composite films with colloidal silicas were lower than those of the films without the colloidal silicas. The films prepared from silane hybridized acrylic resin emulsion composites with colloidal silicas of less than 100 nm were more hydrophilic. SEM and TEM observations demonstrated that some aggregations of the small colloidal particle silica were densely dispersed on the film surface. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2051–2056, 2006     

Hybrid films synthesised from epoxidised castor oil, γ-glycidoxypropyltrimethoxysilane and tetraethoxysilane

Novel organic–inorganic hybrid films were synthesised through the reaction of epoxidised castor oil (ECO) with γ-glycidoxypropyltrimethoxysilane (GPTMS) and tetraethoxysilane (TEOS). The amounts of GPTMS employed were sufficient to react with 25, 50 or 75% of the epoxy groups present in the ECO, whilst the mass proportions of ECO to TEOS varied from 90:10 to 70:30. Films were pre-cured at room temperature under an inert atmosphere, and subsequently submitted to thermal curing. Macro and microscopic properties of the films, including adhesion, hardness, swelling in toluene, microstructure (scanning electron microscopy) and thermal properties were determined as a function of the proportion of organic to inorganic precursor. Morphologic studies showed that the hybrid films were microscopically homogeneous when lower proportions of inorganic precursors were employed. Hardness and tensile strength increased, and swelling in toluene decreased, with the increase in the concentration of inorganic precursors. Good adhesion of the films to an aluminium surface was observed throughout the hybrid series.     

Electrochemical study of TEOS,TEOS/MPTS,MPTS/MMA and TEOS/MPTS/MMA films on tin coated steel in 3.5% NaCl solution

This work compares the anticorrosion features of siloxane layers as eco-friendly alternatives for chromium passivation process on industrials tin coated steel and unravels the influence of each component of the film. The films were prepared with synergistic blends of siloxanes as tetraethyl orthosilane (TEOS), 3-methacryloxy-propyl-trimethoxysilane (MPTS) and methyl methacrylate (MMA). To assess the influence of each component, five different films were prepared: TEOS-based, MPTS-based, TEOS/MPTS, MPTS/MMA and TEOS/MPTS/MMA. The corrosion resistance of the coatings was evaluated by means of open circuit potential, anodic polarization curves and electrochemical impedance spectroscopy measurements, and the anticorrosion properties discussed based on electrical equivalent circuit fitting. Coated surfaces were analyzed using atomic force microscopy and the coatings’ thicknesses were evaluated by means of glow discharge optical emission spectroscopy. The results plainly showed the efficiency of the anticorrosion properties of the film in a 3.5 wt.% NaCl solution and have clearly revealed the improvement of the protective properties of the coating when the MPTS was added to the formulations, pointing this component as the main responsible for the coating anticorrosion action. The addition of MMA to the formulation led to formation of coatings with low long term anticorrosion protection, which was ascribed to the low thickness.     

Corrosion protection of aluminum alloy substrate with nano-silica reinforced organic–inorganic hybrid coatings

Organic–inorganic hybrid (OIH) thin films derived from the sol–gel process have emerged as sustainable metal pretreatment alternatives to toxic heavy metal-based systems. In recent years, such OIH systems based on Si, Zr, and Ti have been successfully developed and commercialized for pretreatment of aluminum alloys, galvanized steel, cold-rolled steel, and many other metals and alloys, for improving adhesion and corrosion resistance performance. A variety of approaches are being used to further enhance performance of such OIH systems to match or surpass that obtained from chromate-based systems. In the present study, a novel bis-silane compound has been synthesized and used as a primary sol–gel precursor for OIH coatings. In order to further improve their mechanical and corrosion resistance performance, colloidal nanoparticles have been incorporated. The microstructure of the deposited films as a function of their composition and formation of Si–O–Si structural network has been studied by Confocal Raman spectroscopic technique. The chemical structure of the OIH films has been characterized by FTIR analysis. Electrochemical impedance spectroscopy, DC polarization measurements, and accelerated neutral salt-fog test (ASTM B117) have been used to evaluate corrosion resistance performance of coatings on industrial aluminum alloy AA 3003 H14. Nano-indentation tests of these OIH films have been performed to study the effect of colloidal nanoparticles on coating micro/nano structure and their mechanical properties. The study reveals that colloidal nanoparticles improve the corrosion resistance of OIH coatings by formation of a protective barrier to diffusion of corrosive species to the metal surface. The optimum content of colloidal nanoparticles that can provide best corrosion protection has been determined. Electrochemical study provides useful insight into the significance of interaction between the sol–gel hybrid and silica particles in the corrosion protection mechanism.     

Interface-driven phase-separated coatings

A homogeneous mixture of two polymers dissolved in a common solvent or a mixture of solvents was applied as a thin film. The first component was a bisphenol-A based epoxide derivative modified with tetraethoxysilane (TEOS) oligomer and the second component was a high-solids fluorinated acrylic copolymer. The thin films were coated on steel substrates and were thermally crosslinked using a methylated melamine formaldehyde and/or a polyamide-amine curing agent. The films were evaluated via x-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) with integrated energy dispersive spectroscopy (EDS). It was found that the molecular weight of the resins, fluorine content, epoxide inorganic modification, and curing agent affected the degree of stratification.     

Effect of nonsolvent on the structures and properties of poly(arylene ether nitrile) films prepared by the phase inversion method

In this study, a series of nonsolvents including ethyl acetate (EAC), acetic acid (HAC), n-butyl alcohol (NBA), iso-propyl alcohol (IPA) and ethanol (EA) were selected during the phase inversion process of poly(arylene ether nitrile) (PEN) films. The mechanism of film formation was tightly related with the interactions among polymer, solvent and nonsolvent. In the case of EAC, the aggregated sphere in P-EAC confirmed the in situ aggregate mechanism of polymer chains during the phase inversion process. As the nonsolvent-polymer interaction increases from HAC, NBA, IPA to EA, the phase inversion mechanism was gradually changed from the delayed to transient, as verified by the morphology transformation from spongy-like to finger-like. Dielectric, mechanical properties of these PEN films are tightly related with the morphological features, while their thermal properties are similar. Among them, P-EAC show the optimal properties for potential application in the low-k films, with a dielectric constant, T_d5%, tensile strength of 1.99, 515.84°C, and 36.08 MPa, respectively. This work can provide references for tailoring the structures and properties of PEN films through rational selection of nonsolvent via the phase inversion method.     

Synthesis and characterization of emulsion polymerized mixed matrix aluminum silicate/poly(2,6‐dimethyl 1,4‐phenylene oxide) films

A series of poly (2,6‐dimethyl‐1,4‐phenylene oxide) (PPO)‐based organic/inorganic films for the potential application in membrane gas separation were prepared by employing a method in which aluminum hydroxonitrate contained in a stable water‐in‐oil (W/O) emulsion, the oil phase being a solution of PPO in trichloroethylene, was mixed with a homogeneous solution of PPO in trichloroethylene containing tetraethyl orthosilicate (TEOS). Inorganic polymerization occurred in or at the surface of the aqueous droplets of the W/O emulsion. Subsequently, thin films were prepared by a spin coating technique, and they were referred to as emulsion polymerized mixed matrix (EPMM) films. Scanning electron micrographs taken from a film cross section indicated the presence of particles in the PPO matrix, and energy dispersive X‐ray measurements showed that the embedded particles contained Al and Si elements. Differential scanning calorimetry analysis showed a decrease in the glass transition of the EPMM films with increase of TEOS loading. The compatibility between aluminum silicate nanoparticles and PPO in the EPMM films was confirmed by air separation tests. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Surlyn®/silicate hybrid materials. I. Polymer in situ sol–gel process and structure characterization

We report the creation of a new organic/inorganic hybrid material that results from sol–gel reactions for tetraethylorthosilicate (TEOS) within poly[ethylene‐co‐methacrylic acid], as well as within a Zn⁺² partially neutralized form of this copolymer (Surlyn®). FTIR and ²⁹Si solid‐state NMR spectroscopic probes yield information regarding molecular connectivity within the in situ grown silicate structures. FTIR analyses of Surlyn® matrix bands suggest that strong molecular level interactions between the organic and inorganic phases are not present, although there is other evidence that these phases are mechanically coupled on a larger dimensional scale. The ²⁹Si solid‐state NMR analyses indicate mainly Q₃ and Q₄ coordination states about the SiO₄ substructures, regardless of silicate content, which is in general agreement with the interpretation of the FTIR results that show incomplete condensation. Environmental scanning electron microscopy and energy dispersive X‐ray analysis results reinforce the conclusion that a significant silicate component is incorporated deep within TEOS‐treated films. Differential scanning calorimetry studies of Surlyn®‐Zn⁺²/silicate hybrids suggest that silicate incorporation essentially does not disrupt crystallinity. Thermogravimetric analyses show practically no change in the degradation onset temperature, which is consistent with organic/inorganic phase separation. The general conclusion is that a silicate phase can indeed be incorporated within this acid copolymer, as well as its Zn⁺² ionomeric form, via in situ sol–gel processes. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2832–2844, 2000     

Ethoxysilyl-modified hyperbranched polyesters as mulitfunctional coupling agents for epoxy-silica hybrid coatings

Partially ethoxysilyl-modified hyperbranched aliphatic-aromatic polyesters (HBPs) were effectively used as toughening as well as multi-site coupling agents in the preparation of organic-inorganic UV-thermal dual-cured epoxy/TEOS coatings. Through chain transfer reaction of the phenolic terminal units of the HBPs effective incorporation in the epoxy resin is achieved in the photo-initiated cationic polymerization whereas the ethoxysilane groups allow effective formation of a strongly interconnected inorganic-organics network during the in-situ sol-gel process with TEOS by binding the organic to the inorganic phase. Under those conditions, the addition of the inorganic precursor to the epoxy/HPB (20 wt%) system induced an increase of the storage modulus and more important, an improvement of the viscoelastic properties by extending the performance of the elastic modulus to higher temperatures. Thus, highly transparent hybrid coatings with enhanced thermal-mechanical and surface hardness properties resulted by the use of the partially ethoxysilyl-modified HBPs as multifunctional coupling agents.     

Phase separation and morphology in ethylcellulose/cellulose acetate phthalate blends

This article discusses the phase separation and morphology of ethylcellulose/cellulose acetate phthalate blended films cast from methanol/methylene chloride (50/50 v/v) solvent mixture. The solvent system has been shown to be a cosolvent for CAP and a solvent/nonsolvent for EC. The two polymers have been shown to phase separate for all blend compositions via nucleation and growth. The morphology of these systems consists of a dispersion of broad size distribution of the minor component in a matrix of the major one. The formation of two layers due to coalescence of the dispersed phases and their eventual precipitation has been observed for the middle blend compositions. Finally, the phase separation in this system is discussed in terms of the Flory–Huggins theory and changes in the solvency mechanism during film casting. Enrichment of the solvent system in methanol at relatively early stages of film casting leads to changes in the system viscosity, relative chain conformation in solution, and chain diffusion. The effect of these parameters on the final morphology are discussed in terms of deviations from the equilibrium binodal decomposition.     

Optimization of UV curable acrylated polyester-polyurethane/polysiloxane ceramer coatings using a response surface methodology

Dual UV and moisture curable acrylated polyester, organic/inorganic hybrid coatings were prepared using a coupling agent and tetraethylorthosilicate (TEOS) oligomers. An acrylated polyester resin based on adipic acid, neopentyl glycol, trimethylolpropane, and acrylic acid was synthesized. TEOS oligomers were prepared through the hydrolysis and condensation of TEOS with water and 3-(triethoxysilyl)propylisocyanate (TEOSPI) was used as the coupling agent between organic and inorganic phases. Trimethylolpropane triacrylate (TMPTA) was used as a reactive diluent. The formulations were cured into films by utilizing UV, followed by moisture curing. The resultant coatings were evaluated in terms of tensile and fracture toughness properties by using ANOVA. Effects of the TEOS oligomers, TEOSPI, and TMPTA on the free radical UV polymerization kinetics were also investigated. The experiments were planned according to the three-factor, three-level Box-Behnken design. Reaction kinetics, fracture toughness, and tensile properties were evaluated in terms of the concentrations of TEOS oligomers, TEOSPI, and TMPTA concentrations. Presented at the 82nd Annual Meeting of the Federation of Societies for Coatings Technology, October 25–27, 2004, in Chicago, IL.     

Effect of nonsolvent coagulant on the morphology and radionuclide detection efficiency of CAYS‐impregnated polysulfone films

Single‐ or double‐layered porous films consisting of polysulfone (PSF) and cerium‐activated yttrium silicate (CAYS) were prepared through the phase inversion of polymeric solutions. For a single‐layered structure, a casting solution including n‐methylpyrrolidone (NMP) as a solvent was cast on a glass substrate and solidified by immersing into a nonsolvent bath. In a double‐layered structure, the bottom layer is a dense PSF film, prepared by vacuum coagulation of a methylene chloride/PSF solution. The top layer was formulated by coagulating the NMP solution, cast over the dense film, in a nonsolvent bath. The morphology and the radionuclide detection efficiency of the prepared films were significantly affected by the nonsolvent coagulants used. The water‐coagulated, double‐layered film showed a relatively clear‐cut interface between the two layers, indicating the rapid coagulation of the second layer. On the contrary, the film coagulated by isopropanol retained well‐developed sponge structures highly intertwined in the interface, associated with the delayed precipitation of the second layer. When spotted on the prepared films, radionuclides stayed mainly on the top surface of the isopropanol‐coagulated film, but went deep into the substructure of the film coagulated with water. In comparison with the mono‐layered films, the double‐layered ones improved the detection capacity of the spotted radionuclides, owing to the dense support layer. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99:1903–1909, 2006     

Organic–Inorganic Coatings Based on Epoxidised Castor Oil/APTES/TEOS

Two series of organic–inorganic hybrid films were prepared from epoxidised castor oil (ECO) and the inorganic precursor 3-aminopropyltriethoxysilane (APTES), and the combination of APTES with tetraethoxysilane (TEOS) with different organic to inorganic proportions. Films were pre-cured at room temperature under inert atmosphere and subsequently submitted to thermal curing. The macro- and microscopic properties of the films, including adhesion, hardness, microstructure and thermal properties, were determined as a function of the proportion of ECO to inorganic precursors. Morphologic studies showed that the hybrid films were microscopically homogeneous. The hardness and tensile strength of the films increased with increased concentrations of inorganic precursor. All of the films exhibited good adhesion to an aluminium surface and worked as an efficient barrier against corrosion.