Organic-inorganic Hybrid Sol-gel Research Articles

Hybrid organic–inorganic sol–gel coatings with interpenetrating network for corrosion protection of tinplate

Novel hybrid organic–inorganic coatings with interpenetrating network were synthesized by the acid-catalyzed hydrolytic co-polycondensation of tetraethoxysilane and 3-metacryloxypropyltrimethoxysilane, followed by radical polymerization with methyl methacrylate and triallyl isocyanurate (TAIC). The hybrid coatings were characterized by Fourier transformed infrared spectroscopy, thermogravimetric analysis and scanning electron microscope, and their anti-corrosion behaviors were evaluated by potentiodynamic polarization, electrochemical impedance spectroscopy and salt spray test. The results indicated that the hybrid coatings exhibited excellent anti-corrosion ability by forming a physical barrier between metal and its external environment. Thermal stability of the hybrid coatings was increased after the addition of TAIC. Furthermore, hydrophobic properties of the hybrid coatings were examined by measuring the contact angles, and the change in wetting characteristics of the hybrid coatings was not obvious.

Electrochemical Evaluation of Hot-Dip Galvanized Steel (HDGS) Coated with Organic-Inorganic Hybrid Sol-Gel in Cementitious Materials

Chromate based chemical conversion layers (CCC) are commonly used as surface treatments as they exhibit enhanced corrosion resistance and improved coating adhesion. However, the restrictions imposed on the use of hexavalent chromium, due to health and environmental concerns, has led to R&D efforts in the last few decades to search for new coating materials that fulfill the regulations and economic constraints imposed. Among these new coating materials, sol-gel methods are shown to be environmentally and economically advantageous in producing coatings that can provide effective corrosion protection. This work describes the studies performed for applying a sol-gel method to the production of organic-inorganic hybrid (OIH) coatings over HDGS reinforcement. The evaluation of their efficiency as a corrosion protection layer, to prevent the initial excessive reaction between mortar and the zinc, during the first days after concreting was studied.

Influence of pH on the Corrosion Protection of Epoxy-Silica-Zirconia Sol-Gel Coatings Applied on EN AW-6063 Aluminium Alloy

Aluminium alloys of 6000 series can suffer severe corrosion in polluted (acidic) and/or marine environments and in contact with alkaline media like fresh cementitious materials. Therefore, architectural aluminium components are often coated, what requires its surface pre-treatment. Organic-inorganic hybrid (OIH) sol-gel coatings have been proposed as an effective, environmental compliant new pre-treatment for aluminium coating. In this work, an epoxy-silica-zirconia sol-gel coating was synthesized and applied on EN AW-6063 alloy. Cerium nitrate was incorporated as corrosion inhibitor. Cerium doped and undoped OIH coatings were exposed to neutral, acidic (pH~3) and alkaline (pH~10) chloride solutions. Electrochemical impedance spectroscopy (EIS) and SEM/EDS characterization of coated samples revealed that the best performance is achieved in the neutral and the worst in the acidic solution. In the alkaline solution, the cerium doped coatings exhibited much better anticorrosive performance than the undoped ones, clearly evidencing the beneficial role of the corrosion inhibitor in this media.

Development and characterization of novel organic–inorganic hybrid sol–gel films

Organic–inorganic hybrid films were fabricated by reacting 3-glycidoxypropyltrimethoxysilane with 4,4′-diaminodiphenylether by hydrolysis and condensation reaction with acid catalysis. The chemical bonding between the organic and inorganic phases provides reinforcement to the films, and tetraethoxysilane was added in such a way that silica contents varied from 1 wt% to 3 wt% in the films. Structural characterization of the hybrid films was performed using Fourier transform infrared and nuclear magnetic resonance spectroscopic techniques. The thermal properties studied using thermogravimetric analysis, indicate an improved thermal stability for the films according to the percentage concentration of silica present in them. The water absorption was also found to be reduced for the films with increased silica content. The surface morphology was investigated by means of x-ray diffraction and scanning electron microscopic techniques. The films transparency and homogeneity seem to have been affected severely when the silica content kept on increasing and ultimately led to opaqueness in film.

Preparation of novel fibre–silica–Ag composites: the influence of fibre structure on sorption capacity and antimicrobial activity

Novel fibre–silica–Ag composites with biocidal activity were successfully produced by chemical modifying cotton (CO), wool (WO), silk (SE), polyamide (PA) and polyester (PES) fabrics and CO/PES and WO/PES fabric blends. A silica–Ag coating was prepared using a two-step procedure that included the creation of a silica matrix on the fibre surface via the application of an inorganic–organic hybrid sol–gel precursor [reactive binder (RB)] using a pad-dry-cure method, followed by the in situ synthesis of AgCl particles within the RB-treated fibres from solutions of 0.10 mM and 0.50 mM AgNO3 and NaCl. The presence of the coating on the fibres was verified by scanning electron microscopy and energy-dispersive X-ray spectroscopy. The bulk concentration of Ag in the coated fibres was determined using inductively coupled plasma mass spectroscopy. The antimicrobial activity was determined for the bacteria Escherichia coli and Staphylococcus aureus and the fungus Aspergillusniger. The results show that the chemical and morphological structures of the fibres directly influenced their absorptivity and affinity for the Ag compound particles. As the amorphous molecular structure of the fibres and the amount of functional groups available as binding sites for Ag+ were increased, both the silver solution uptake and the concentration of the absorbed Ag compound particles increased. The chemical binding of Ag to the fibres significantly reduced the effectiveness of the antimicrobial activity of the Ag compound particles. Accordingly, an increase in the concentration of absorbed Ag was required to achieve a biocidal effect.

A hybrid organic–inorganic sol–gel coating for protecting aluminium alloy 7075-T6 against corrosion in Harrison’s solution

A two-step procedure for synthesizing a new type of hybrid coating is presented. Coatings were synthesized from tetraethyl orthosilicate, 3-(trimethoxysilyl)propyl methacrylate and zirconium(IV) propoxide (ZTP). Zirconium(IV) propoxide was chelated with methacrylic acid. The synthesis, which proceeded at room temperature, was optimized using in situ Fourier transform infrared spectroscopy (FTIR). The effects of ZTP content, ageing and Zr/Si ratio were investigated. The viscosity of the sols increased with the ratio of Zr to Si. The terminal stability of the hybrid coatings was determined by thermogravimetric analysis and their composition and morphology analyzed by FTIR and scanning electron microscopy combined with energy dispersive X-ray spectroscopy. Sols were deposited on the aluminium AA7075-T6 substrate by spin-coating. The corrosion properties in dilute Harrison’s solution of samples coated by hybrid coatings were determined by electrochemical polarization methods. The coatings substantially improved the corrosion resistance of the substrate, as shown by a broad range of passivity extending up to high electrode potentials. The degree of protection was dependent on the content of zirconium and the time of ageing. The strong corrosion protection was ascribed to the bonding between silicon, oxygen and zirconium (Si–O–Si, Si–O–Zr), as proved by the FTIR analysis.

Triethylphosphite as a network forming agent enhances in vitro biocompatibility and corrosion protection of hybrid organic–inorganic sol–gel coatings for Ti6Al4V alloys

The biocompatibility and life of metallic implants can be enhanced through improving the biocompatibility and corrosion protection characteristics of the coatings used with these materials. In this study, triethylphosphite (TEP) was used to introduce phosphorus into organic-inorganic hybrid silica based sol-gel coatings prepared using γ-methacryloxypropyltrimethoxysilane and tetramethylorthosilicate. Addition of TEP dramatically increased the rate of intermolecular condensation and resulted in materials showing greater cross-linking. Protein (fibrinogen) uptake, osteoblast in vitro biocompatibility and corrosion resistance was enhanced in coatings containing TEP. Although higher concentrations of phosphorus supported the greatest improvement in biocompatibility, a compromise in the phosphorus concentration used would be required if corrosion resistance was most desirable parameter for optimisation. Films prepared by dip coating on Ti6Al4V alloys from these sols offer a promising alternative to wholly metallic prostheses.

Enhancing in vitro biocompatibility and corrosion protection of organic-inorganic hybrid sol-gel films with nanocrystalline hydroxyapatite.

Application of novel organic-inorganic hybrid sol-gel coatings containing dispersed hydroxyapatite (HAp) particles improves the biocompatibility, normal human osteoblast (NHOst) response in terms of osteoblast viability and adhesion of a Ti6Al4V alloy routinely used in medical implants. The incorporation of HAp particles additionally results in more effective barrier proprieties and improved corrosion protection of the Ti6Al4V alloy through higher degree of cross-linking in the organopolysiloxane matrix and enhanced film thickness.

Multifunctional sol-gel coatings for protection of wood

Organic–inorganic hybrid sol-gel coatings derived from sols synthesized using two organically modified precursors were generated on wood specimens using dip and spray coating techniques. One of the sols was synthesized using methacryloxypropyltrimethoxysilane (MPTMS) and nanoscaled boehmite particles and the other was synthesized using dimethyldiethoxysilane (DMDEOS) and tetraethoxysilane (TEOS). The coatings were generated on the wood specimens by dipping into the sols for specific time periods and by using spray coating method. The coatings were cured at different temperatures for varying soaking times. The dipping times, curing temperature, and soaking times were varied between 24–96 h, 130–200°C and 1–5 h, respectively. The coated samples were characterized for their water contact angles, microstructure, and resistance to water uptake. The coatings derived from MPTMS+boehmite sol were seen to exhibit better performance than DMDEOS+TEOS sol by forming a good barrier on the wood surface, thereby providing superior resistance to water and weather. Dipping of wood into the sol was seen to provide better protection when compared to spray coating. Dipping into the MPTMS+boehmite sol for 24 h and curing at 130°C for 2 h were found to be the optimal processing parameters yielding the best properties.

Organic–inorganic hybrid sol–gel pretreatments for corrosion protection of mild steel in neutral and acidic solutions

This work aims to develop and study sol–gel-derived anticorrosion films for mild steel. Epoxy bis-silane precursor has been prepared by reaction of liquid epoxy resin and aminopropyl triethoxysilane. A pretreatment application bath (Sol) has been prepared by dissolving epoxy-silane precursor at constant solid content and fixed water/ethanol ratio, and the solution was adjusted to acidic pH. The organic–inorganic hybrid films were deposited on mild steel by dip-coating technique, by immersion of sample panels into the sol and their withdrawal at controlled rate to facilitate the desired and uniform film. Films were subsequently cured at room temperature. The anticorrosion properties of the coatings were studied using electrochemical impedance spectroscopy, DC polarisation techniques and neutral salt spray test. This study shows that very dense and protective hybrid coatings on mild steel can be obtained by controlling the resin/silane ratio during synthesis of the precursor.

Electrochemical Evaluation of Hot-Dip Galvanized Steel (HDGS) Coated With Organic-Inorganic Hybrid Sol-Gel in Cementitious Materials

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Study of flame-retardant finishing of cellulose fibres: Organic–inorganic hybrid versus conventional organophosphonate

The aim of this study was to introduce a non-formaldehyde inorganic–organic hybrid sol–gel flame-retardant precursor (SiOP) containing phosphorous, nitrogen, and silicon and to compare its functional properties with those of the conventional formaldehyde-containing organic flame-retardant agent, organophosphonate (OP). SiOP was used at concentrations of 2%, 4%, and 8%, and OP was used at a concentration of 200 g/dm3. Both agents were applied to 100% cotton (CO) woven fabric by the pad-dry-cure method under the appropriate conditions. The presence of the SiOP and OP coatings on the CO fabric was confirmed by scanning electron microscopy, energy dispersive X-ray spectroscopy and Fourier-transform infrared spectroscopy. The results of the vertical tests of flammability and the thermogravimetric analyses showed that the presence of the SiOP coating changed the thermal degradation pathway of the CO fabric and resulted in an increase in the thermo-oxidative stability of the cellulose fibres. The thermo-oxidative stability was enhanced by the addition of higher amount of dry solids. At comparable dry solids contents, OP preserved significantly greater flame retardancy and thermo-oxidative stability than did SiOP. These results indicated that the SiOP precursor could not act as an effective alternative to the OP agent in the flame-retardant protection of CO fabric.

Hybrid sol–gel layers containing CeO2 nanoparticles as UV-protection of plastic lenses for concentrated photovoltaics

Fresnel lenses made of polymethylmethacrylate (PMMA) represent a cost-effective approach for concentrated photovoltaic (CPV) panels. The lens must sustain suitable working performance during the whole lifetime of the photovoltaic plant, as UV photodegradation is the main issue to be avoided. In this work, PMMA sheets were covered with a hybrid organic–inorganic sol–gel coating consisting of a matrix of an organically modified silicate (ORMOSIL) in which CeO2 nanoparticles 10–20nm in size were dispersed, acting as the UV-absorbing agent. Ceria contents up to 40% w/w were studied and blended with the precursor ORMOSIL solution before deposition and in-situ polymerization at 80°C. The UV–visible spectra were analyzed between 200 and 800nm. Furthermore, the effect of the aging on outdoor weathering was investigated for the coated PMMA sheets and compared to the unprotected sample. The results show that a load of 30% w/w of ceria nanoparticles provides a reasonable compromise in terms of UV protection and absorption in the visible range. The weathering test also demonstrates enhanced protection against UV degradation for the coated PMMA sheet compared to the bare substrate, although the adherence should be further improved for optimum performance.

Development of water-repellent organic–inorganic hybrid sol–gel coatings on aluminum using short chain perfluoro polymer emulsion

The development of an organic–inorganic sol–gel coating system (thickness∼2μm) on aluminum is reported. The coating uses glycidoxytrimethoxysilane (GPTMS) and methyltrimethoxysilane (MTMS) as silane precursors, crosslinked with hexamethylmethoxymelamine (HMMM) and followed by hydrophobic modification using a water base short chain per-fluoro emulsion (FE). Such coating resulted in enhanced hydrophobicity with a contact angle of about 120° and sliding angle of 25° for a 20μL water droplet. Potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) measurements showed reduced corrosion upon coated substrates than the bare; correlated with both a higher degree of water repellency and formation of low permeable crosslinked sol–gel network. The structure of the coatings deposited was analyzed using Fourier transform infrared (FTIR) and X-ray photoelectron (XPS) spectroscopy, revealing replacement of hydrophillic surface hydroxyls groups with low energy per-fluoro groups.

Antimicrobial wool, polyester and a wool/polyester blend created by silver particles embedded in a silica matrix

A two-step antimicrobial finishing procedure was applied to wool (WO) and polyester (PES) fabrics and a WO/PES fabric blend, in which the pad-dry-cure method was performed to create a functional silica matrix through the application of an inorganic–organic hybrid sol–gel precursor (RB) followed by the in situ synthesis of AgCl particles on the RB-treated fibres using 0.10 and 0.50mM AgNO3 and NaCl. The bulk concentration of Ag on the cotton fibres was determined by inductively coupled plasma mass spectroscopy. The antimicrobial activity was determined for the bacteria Escherichia coli and Staphylococcus aureus, and the fungus Aspergillus niger. The results showed that the highest concentration of the adsorbed Ag compound particles was on the WO samples followed by the WO/PES and PES samples. The antimicrobial activity of the finished fabric samples strongly depended not only on the amount of adsorbed Ag but also on the properties of the fabric samples. Whereas Ag biocidal activity was generated for the finished PES samples at Ag particle concentrations of less than 10mg/kg, the 34-times higher Ag particle concentration on the WO samples was insufficient to impart satisfactory antimicrobial activity because Ag chemically binds to the thiol groups on wool. The presence of wool fibres in WO/PES samples decreased the antimicrobial protection of the fabric blend compared with that of the PES fabric. A lethal concentration of adsorbed Ag compound particles for bacteria and fungi was produced only through the treatment of the WO and WO/PES samples with 0.5mM AgNO3.

Structure and magnetic properties of SiO2/PCL novel sol–gel organic–inorganic hybrid materials

Abstract Organic–inorganic nanocomposite materials have been synthesized via sol–gel. They consist of an inorganic SiO 2 matrix, in which different percentages of poly(e-caprolactone) (PCL) have been incorporated. The formation of H-bonds among the carbonyl groups of the polymer chains and Si–OH group of the inorganic matrix has been proved by means of Fourier transform infrared spectroscopy (FT-IR) analysis and has been confirmed by solid-state nuclear magnetic resonance (NMR). X-Ray diffraction (XRD) analysis highlighted the amorphous nature of the synthesized materials. Scanning electron microscope (SEM) micrograph and atomic force microscope (AFM) topography showed their homogeneous morphology and nanostructure nature. Considering the opportunity to synthesize these hybrid materials under microgravity conditions by means of magnetic levitation, superconducting quantum interference device (SQUID) magnetometry has been used to quantify their magnetic susceptibility. This measure has shown that the SiO 2 /PCL hybrid materials are diamagnetic and that their diamagnetic susceptibility is independent of temperature and increases with the PCL amount.

Effect of Nanoparticle Addition in Hybrid Sol-Gel Silane Coating on Corrosion Resistance of Low Carbon Steel

Chromium pre-treatments of metal have been replaced by silane pre-treatments as more environmental friendly option. Nanoparticles can be added in the silane sol-gel network have been reported to improve corrosion resistance. In this work, the electrochemical corrosion resistance of low carbon steel coated with hybrid organic-inorganic sol-gel film filled with nanoparticles was evaluated. The sol-gel films have been synthesized from 3-glycidoxy-propyl-trimethoxy-silane (3-GPTMS) and tetra-ethyl-ortho-silicate (TEOS) precursors. These films have been impregnated with 300 ppm of silica or alumina nanoparticles. The electrochemical behavior of the coated steel was evaluated by means of electrochemical impedance spectroscopy (EIS) and scanning electron microscopy (SEM). Equivalent circuit modeling, used for quantifying the EIS measurements showed that sol-gel films containing silica nanoparticles improved the barrier properties of the silane coating. The silica nanoparticle-containing films showed highest initial pore resistance over the five days of immersion in 0.05M NaCl.

Single mode ridge waveguides based on vinyltriethoxysilane hybrid sol–gel material

In this work, fabrication and characterization of a single-mode vinyltriethoxysilane (VTES) based hybrid organic–inorganic sol–gel ridge waveguide is reported. VTES based hybrid sol–gel material has been deposited by multiple spin-coating process on quartz substrate. Channel waveguides have been fabricated by UV photopolymerization followed by wet etching process. Optical guided mode was observed to ensure the single mode condition while cut-back technique was performed for loss propagation measurement. Optical propagation losses were measured to be 1.6dB/cm at 1.31μm wavelength. This value shows that this material is a promising choice for the development of integrated optical circuits for telecommunication field.

Aggregation of dipolar molecules in SiO2 hybrid organic–inorganic films: use of silver nanoparticles as inhibitors of molecular aggregation

The technological implementation of hybrid organic–inorganic materials in second order nonlinear optical photonic devices depends strongly on the ability of the host matrixes to contain high loads of dipolar molecules without aggregation. Some organic molecules are often used to diminish the attracting interactions between dipolar molecules in such kind of materials, but their efficiency as inhibitors of molecular aggregation is limited by their polarizability. In this work, we report the use of silver nanoparticles as inhibitors of molecular aggregation in hybrid organic–inorganic films doped with dipolar molecules. The large polarizability of the silver nanoparticles makes them ideal moieties for the inhibition of the electrostatic interactions between dipolar nonlinear optical molecules. The average size of the silver nanoparticles in this work was 70.5 nm in diameter, they were synthesized using silver nitrate (AgNO3) as precursor and aminoethylaminopropyltrimethoxysilane as reducing agent. These nanoparticles were immersed in SiO2 hybrid organic–inorganic sol–gel films doped with dipolar chromophores to study their effect as inhibitors of dipolar chromophores aggregation. The presence of the silver nanoparticles in the solid films was confirmed by transmission electronic microscopy and UV–Visible spectroscopy. UV–Visible spectroscopy was also used to monitor the dipolar chromophores aggregation in the SiO2 films. We found that, at room temperature, silver nanoparticles are good inhibiting chromophores aggregation in comparison with the performance of organic inhibitors.

High-Energy-Density Sol–Gel Thin Film Based on Neat 2-Cyanoethyltrimethoxysilane

Hybrid organic-inorganic sol-gel dielectric thin films from a neat 2-cyanoethyltrimethoxysilane (CNETMS) precursor have been fabricated and their permittivity, dielectric strength, and energy density characterized. CNETMS sol-gel films possess compact, polar cyanoethyl groups and exhibit a relative permittivity of 20 at 1 kHz and breakdown strengths ranging from 650 V/μm to 250 V/μm for film thicknesses of 1.3 to 3.5 μm. Capacitors based on CNETMS films exhibit extractable energy densities of 7 J/cm(3) at 300 V/μm, as determined by charge-discharge and polarization-electric field measurements, as well as an energy extraction efficiency of ~91%. The large extractable energy resulting from the linear dielectric polarization behavior suggests that CNETMS films are promising sol-gel materials for pulsed power applications.