Search

Reinforcement steel extensively applied in civil construction is susceptible to corrosion due to the carbonation process in reinforced concrete and chloride ions diffusion. Epoxy-silica-based coatings are a promising option to guarantee the long-term stability of reinforced concrete structures. In this study, the influence of the proportion between the poly (bisphenol-A-co-epichlorhydrin) resin (DGEBA) and the curing agent diethylenetriamine (DETA) on the structural, morphological, and barrier properties of epoxy–silica nanocomposites were evaluated. To simulate different stages of concrete aging, electrochemical impedance spectroscopy (EIS) assays were performed for coated samples in a 3.5 wt.% NaCl solution (pH 7) and in simulated concrete pore solutions (SCPS), which represent the hydration environment in fresh concrete (SCPS2, pH 14) and after carbonation (SCPS1, pH 8). The results showed that coatings with an intermediate DETA to DGEBA ratio of 0.4, presented the best long-term corrosion protection with a low-frequency impedance modulus of up to 3.8 GΩ cm2 in NaCl and SCPS1 solutions. Small-angle X-ray scattering and atomic force microscopy analysis revealed that the best performance observed for the intermediate DETA proportion is associated with the presence of larger silica nanodomains, which act as a filler in the cross-linked epoxy matrix, thus favoring the formation of an efficient diffusion barrier.

Made available in DSpace on 2022-05-01T13:41:37Z (GMT). No. of bitstreams: 0 Previous issue date: 2022-02-25 In the absence of preventive maintenance, corrosion of structural steel by the deterioration of the passive layer due to exposure to aggressive environments is the main failure factor of reinforced concrete. To overcome economic, safety, and environmental implications, present research efforts focus on eco-friendly organic-inorganic hybrid coatings to achieve effective protection of reinforcing steel. Nanostructured PMMA (poly(methyl methacrylate))-silica coatings developed by combining reactions of the polymerization of methyl methacrylate and 3-[(methacryloxy)propyl]trimethoxysilane with the sol-gel hydrolytic condensation of tetraethyl orthosilicate using isopropanol as a solvent represent a promising approach to accomplish this goal. The nanoscale dispersion of silica nodes covalently conjugated with PMMA chains led to transparent, homogeneous, and pore-free coatings deposited with a thickness of 15 μm on 2D and 3D reinforcing steel. Mechanical, thermal, and surface analyses showed a strong adhesion of the coating to the substrate surface (15.9 MPa), a thermal stability of up to 256 °C, and a contact angle of about 75°. Electrochemical assays in standard 3.5 wt % NaCl solution, simulated carbonated, and alkaline concrete pore solutions confirmed effective corrosion protection, with an impedance modulus of up to 100 Gω cm2(at 4 mHz) and a lifetime of more than 670 days. Hence, PMMA-silica hybrid coatings are an eco-friendly and efficient alternative to protect reinforcing steel against corrosion, helping to prevent structural failures and fatal accidents. São Paulo State University (UNESP) Institute of Chemistry São Paulo State University (UNESP) Institute of Chemistry

Made available in DSpace on 2022-05-01T09:30:59Z (GMT). No. of bitstreams: 0 Previous issue date: 2021-12-01 Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) Organic-inorganic hybrids are considered an effective and environmentally compliant alternative to chromate-based anticorrosive coatings, currently banned due to the high toxicity of hexavalent chromium. In this work, hybrid nanocomposites based on poly(methyl methacrylate) (PMMA), covalently bonded to cerium oxide nanoparticles through the 2-hydroxyethyl methacrylate (HEMA) coupling agent, were tailored by carefully tuning the inorganic colloidal precursor to provide films with active corrosion protection for metallic substrates. Lithium hydroxide was exploited as oxidizing agent of cerium nitrate to form ceria nanoparticles. Precursor solutions and solid nanocomposites with different LiOH to Ce(NO3)3.6H2O molar ratios were analyzed using spectroscopic and electron microscopy techniques and theoretical simulations. Electrochemical impedance spectroscopy (EIS) was used to study the anticorrosive performance of the coatings on carbon steel and 7075 aluminum alloy. The results showed that increasing amounts of LiOH lead to the formation of higher ceria content and larger primary nanoparticles, ranging from 1.7 to 2.8 nm. The homogenous ~20 μm-thick coatings present excellent anticorrosive performance on carbon steel and AA7075 substrates. Coatings on carbon steel with low LiOH loading (1Li:1Ce) showed long-term durability and high impedance modulus of up to 29 GΩ cm2 after 1 day in saline solution. On the AA7075 alloy, the presence of larger cerium oxide particles at higher LiOH content (3Li:1Ce) acted as effective reservoirs of cerium ions, providing high barrier coatings (395 GΩ cm2) with active corrosion protection. São Paulo State University (UNESP) Institute of Chemistry São Paulo State University (UNESP) Institute of Chemistry CAPES: 001 CNPq: 142305/2020-0 FAPESP: 2015/09342-7 FAPESP: 2015/11907-2 FAPESP: 2019/13871-6 CNPq: 307905/2018-7 CNPq: 309419/2020-4 CNPq: 421081/2016-3 CNPq: 424133/2016-4 CNPq: 430758/2018-9

Made available in DSpace on 2020-12-12T02:34:44Z (GMT). No. of bitstreams: 0 Previous issue date: 2020-05-01 Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) Ti6Al4V is the mostly applied metallic alloy for orthopedic and dental implants, however, its lack of osseointegration and poor long-term corrosion resistance often leads to a secondary surgical intervention, recovery delay and toxicity to the surrounding tissue. As a potential solution of these issues poly(methyl methacrylate)-silicon dioxide (PMMA-silica) coatings have been applied on a Ti6Al4V alloy to act simultaneously as an anticorrosive barrier and bioactive film. The nanocomposite, composed of PMMA covalently bonded to the silica phase through 3-(trimethoxysilyl)propyl methacrylate (MPTS), has been synthesized combining the sol-gel process with radical polymerization of methyl methacrylate. The 5 μm thick coatings deposited on Ti6Al4V have a smooth surface, are homogeneous, transparent, free of pores and cracks, and show a strong adhesion to the metallic substrate (11.6 MPa). Electrochemical impedance spectroscopy results proved an excellent anticorrosive performance of the coating, with an impedance modulus of 26 GΩ cm2 and long-term durability in simulated body fluid (SBF) solution. Moreover, after 21 days of immersion in SBF, the PMMA-silica coating presented apatite crystal deposits, which suggests in vivo bone bioactivity. This was confirmed by biological characterization showing enhanced osteoblast proliferation, explained by the increased surface free energy and protein adsorption. The obtained results suggest that PMMA-silica hybrids can act in a dual role as efficient anticorrosive and bioactive coating for Ti6Al4V alloys. São Paulo State University (UNESP) Institute of Chemistry Federal University of Piauí (UFPI) Interdisciplinary Laboratory for Advanced Materials (LIMAV) Department of Materials Engineering Department of Chemical Engineering Northeastern University São Paulo State University (UNESP) Institute of Chemistry CNPq: 303752/2017-3