Characterization of Siloxane-poly(methyl methacrylate) Hybrid Films Obtained on a Tinplate Substrate Modified by the Addition of Organic and Inorganic Acids

Tinplate is used to food packaging and other types of packages. The corrosion resistance of the tinplate has been study due the necessity of an alternative to high environmental impact of chromatization process. Therefore protective coatings as hybrid films base elaborations with different acids are studied to improve the barrier effect against corrosion. The objective of this work is characterize hybrid films deposited on a tinplate from a sol made up of the alkoxide precursors 3-(trimethoxysilylpropyl) methacrylate (TMSM), tetraethoxysilane (TEOS) and poly(methyl methacrylate) (PMMA) together with one of three acids (acetic, hydrochloric or nitric acid) and to verify their action against the corrosion of the substrate. The films were obtained by a dip-coating process and cured for 3 hours at 160 °C. The film hydrophobicity was determined by contact angle measurements, and the morphology was evaluated by SEM. FTIR measurements were performed to characterize the chemical structures of the films. The electrochemical behavior of the coatings was evaluated by techniques open circuit potential monitoring (OCP), potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). The results demonstrate that the siloxane-PMMA films improve the protective properties of the tinplate, with the films obtained by acetic acid addition exhibiting the greatest improvement

Gelation of siloxane-poly(oxypropylene) composites

The viscoelastic properties of siloxane-poly(oxypropylene) (PPO) nanocomposites prepared by the sol-gel process has been analyzed during gelation by dynamic rheological measurements. The changes of storage and loss moduli, complex viscosity and phase angle has been measured as a function of time showing the newtonian viscosity of the sol in the initial step of gelation, and its progressive transformation to a viscoelastic gel. The rheologic properties have been correlated to mass fractal, nearly linear growth models and percolation theory. This study, completed by quasi-elastic light scattering and Si-29 solid state nuclear magnetic resonance measurements, shows that the mechanisms of gelation of siloxane-PPO hybrids depend on the molecular weight of the polymer and on the pH of the hybrid sol. For hybrids prepared in acid medium, a polymerization involving silicon reactive species located at the extremity of the polymer chains and presenting a functionality f = 2 occurs, forming a fractal structure during the first stage of sol-gel transition. For samples prepared under neutral pH, the fractal growth is only observed for hybrids containing short polymer chains (M-w similar to 130 gmol(-1)). The fractal dimensionality determined from the change in the rheological properties, indicates that the fractal growth mechanism changes from reaction-limited to diffusion-limited aggregation when the molecular weight of the PPO increases from 130 to 4000 gmol(-1) and as catalyst conditions change from acidic to neutral. Near the gel point, these hybrid gels have the typical scaling behavior expected from percolation theory. (C) 2002 Elsevier B.V. B.V. All rights reserved

Evolution of rheological properties and local structure during gelation of siloxane-polymethylmethacrylate hybrid materials

Hybrid siloxane-polymethylmethacrylate (PMMA) nanocomposites with covalent bonds between the inorganic (siloxane) and organic (polymer) phases were prepared by the sot gel process through hydrolysis and polycondensation of 3-(trimethoxysilyl)propylmethacrylate (TMSM) and polymerization of methylmethacrylate (MMA) using benzoyl peroxide (BPO) as initiator. The effect of MMA, BPO and water contents on the viscoelastic behaviour of these materials was analysed during gelation by dynamic rheological measurements. The changes in storage (G') and loss moduli (G), complex viscosity (eta*) and phase angle (6) were measured as a function of the reaction time showing the viscous character of the sot in the initial step of gelation and its progressive transformation to an elastic gel. This study was complemented by Si-29 and C-13 solid-state nuclear magnetic resonance (NMR/MAS) measurements of dried gel. The analysis of the experimental results shows that linear chains are formed in the initial step of the gelation followed by a growth of branched structures and formation of a three-dimensional network. Near the gel point this hybrid material demonstrates the typical scaling behaviour expected from percolation theory

Small-angle X-ray and nuclear-magnetic resonance study of siloxane-PMMA hybrids prepared by the sol-gel process

Transparent siloxane-polymethylmethacrylate (PMMA) hybrids were synthesized by the sol-gel process through hydrolysis of methacryloxyproyltrimethoxysilane (TMSM), tetramethoxysilane (TMOS) and polymerization of methylmethacrylate (MMA) using benzol peroxide (BPO) as catalyst. These composites have a good chemical stability due to the presence of covalent bonds between the inorganic (siloxane) and organic (PMMA) phases. The effects of siloxane content, pH of the initial sol and BPO content on the structure of the dried gels were analyzed by small-angle X-ray scattering (SAXS). SAXS results revealed the presence of an interference (or correlation) peak at medium q-range for all compositions, suggesting that siloxane groups located at the ends of PMMA chains form isolated clusters that are spatially correlated. The average intercluster distance - estimated from the q-value corresponding to the maximum in SAXS spectra - decreases for samples prepared with increasing amount of TMSM-TMOS. This effect was assigned to the expected increase in the number density of siloxane groups for progressively higher siloxane content. The increase of BPO content promotes a more efficient polymerization of MMA monomers but has no noticeable effect on the average intercluster distance. High pH favors polycondensation reactions between silicon species of both TMOS and TMSM silicon alcoxides, leading to a structure in which all siloxane clusters are bonded to PMMA chains. This effect was confirmed by Si-29 nuclear-magnetic resonance (NMR) measurements

Corrosion Mechanism Suggested Based on Electrochemical Analysis and SVET for Uncoated Tinplate and Post Coated With a Hybrid Film

<div><p>The tinplate, used in the packaging sector and formed from a metal substrate, comprises a steel base which has undergone a surface treatment to produce a thin layer of FeSn2, a tin layer and an oxide tin layer. Currently, packaging using surface treatment is based on the use of chromates because these metals provide an excellent corrosion resistance. Nontoxic alternatives to pre-treatments have been developed in recent years to replace the chromate process. The aim of this work is to analyze the performance of a new hybrid organic-inorganic film obtained from sol-gel consisting of the alkoxide precursors 3-(Trimethoxysilylpropyl)methacrylate (TMSM) and tetraethoxysilane (TEOS) with the addition of cerium nitrate with the scanning vibrating electrode technique (SVET), and electrochemical and morphological characterizations. Moreover, the evolution of the corrosion of the substrate was evaluated to propose a mechanism of corrosion. The results showed a galvanic coupling between the Sn/SnO2 coat (cathode) and the defects exposed at the ferrous base (anode). The organic-inorganic hybrid film containing a cathodic corrosion inhibitor was able to retard the corrosion of the tinplate.</p></div