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Sol-Gel Chemistry in Polymers Research

A special issue of Polymers (ISSN 2073-4360). This special issue belongs to the section "Polymer Chemistry".

Deadline for manuscript submissions: closed (20 January 2021) | Viewed by 23948

Special Issue Editor


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Guest Editor
Department of Chemical Materials and Industrial Production Engineering (DICMaPI), University of Naples Federico II, P.le Tecchio 80, 80125 Naples, Italy
Interests: sol–gel chemistry; electrospinning; biocomposites; surface treatments
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Special Issue Information

Dear Colleagues,

I have been asked by the Editor of Polymers (MDPI) to coordinate a Special Issue entitled “Sol–Gel Chemistry in Polymers Research”.

As you know, the sol–gel synthesis route has been extensively exploited since the 1970s, in combination with polymer synthesis methodologies, to produce not only  inorganic materials (glassy or ceramic) but also hybrid organic/inorganic composites in the form of aerogels, monoliths, coatings, fibers, and particles.

The strategy takes advantage of the fact that almost all the important oxides MOn (where M is a metal or semimetal and n is not necessarily an integer), as well as many mixed oxides, have been prepared by the sol–gel process through reactions occurring at low temperatures starting from precursors that are commercially available at high purity. Moreover, a great number of organometallic compounds are available, allowing easy surface functionalization and interface tailoring. Sol–gel synthesis also allows the easy production of particles at the nanoscale, where materials properties change: ferromagnetic materials become superparamagnetic, band gaps of semiconductors and light absorption and scattering properties change, etc.

Many synthesis routes have been proposed in the literature to produce not only composites but also organic/inorganic hybrid particles where sol–gel chemistry gives the inorganic phase or plays a fundamental role in the coupling: heterocoagulation, layer-by-layer assembly, molecular recognition assembly, grafting through coupling agents, polymerization in multiphase systems, surface-initiated polymerization, sol–gel nanocoating. The mild sol–gel synthesis conditions also allow the inherent difficulty in combining organic with glass and ceramic chemistries due to the traditional wide gap in the typical process temperatures to be overcome. In particular new perspectives are opened by the so-called in situ processes where the inorganic phase is produced in the presence of a polymer or a monomer. The mild synthesis conditions also allow the proposal of facile sol–gel protocols for the bioencapsulation of relevant functional biomacromolecules.

Generally speaking, the applications include both structural and functional materials spanning very different fields: catalysis, biomaterials, biology, sensors, etc.

This Issue is open to all contributions where sol–gel chemistry is combined with polymer chemistry, with aims of both deepening our knowledge of processes and finding new applications. The objective is to highlight the progress in this outstanding research field.

Considering your prominent contribution to this interesting research field, I would like to cordially invite you to submit a paper to this Special Issue through the webpage of the journal (S.I.:  Sol–Gel Chemistry in Polymers Research).

Prof. Francesco Branda
Guest Editor

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Polymers is an international peer-reviewed open access semimonthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2700 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

Sol-Gel;

Polymerization;

Stöber method;

Hybrid materials;

Nanocomposites;

Surface functionalization;

Compatibilization;

Interface tailoring;

Nanoparticles;

Hybrid organic/inorganic particles;

In situ synthesis;

Bioencapsulation

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Published Papers (4 papers)

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Research

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13 pages, 3501 KiB  
Article
Thermal and Fire Behavior of a Bio-Based Epoxy/Silica Hybrid Cured with Methyl Nadic Anhydride
by Aurelio Bifulco, Angela Marotta, Jessica Passaro, Aniello Costantini, Pierfrancesco Cerruti, Gennaro Gentile, Veronica Ambrogi, Giulio Malucelli and Francesco Branda
Polymers 2020, 12(8), 1661; https://doi.org/10.3390/polym12081661 - 26 Jul 2020
Cited by 27 | Viewed by 4552
Abstract
Thermosetting polymers have been widely used in many industrial applications as adhesives, coatings and laminated materials, among others. Recently, bisphenol A (BPA) has been banned as raw material for polymeric products, due to its harmful impact on human health. On the other hand, [...] Read more.
Thermosetting polymers have been widely used in many industrial applications as adhesives, coatings and laminated materials, among others. Recently, bisphenol A (BPA) has been banned as raw material for polymeric products, due to its harmful impact on human health. On the other hand, the use of aromatic amines as curing agents confers excellent thermal, mechanical and flame retardant properties to the final product, although they are toxic and subject to governmental restrictions. In this context, sugar-derived diepoxy monomers and anhydrides represent a sustainable greener alternative to BPA and aromatic amines. Herein, we report an “in-situ” sol–gel synthesis, using as precursors tetraethylorthosilicate (TEOS) and aminopropyl triethoxysilane (APTS) to obtain bio-based epoxy/silica composites; in a first step, the APTS was left to react with 2,5-bis[(oxyran-2-ylmethoxy)methyl]furan (BOMF) or diglycidyl ether of bisphenol A (DGEBA)monomers, and silica particles were generated in the epoxy in a second step; both systems were cured with methyl nadic anhydride (MNA). Morphological investigation of the composites through transmission electron microscopy (TEM) demonstrated that the hybrid strategy allows a very fine distribution of silica nanoparticles (at nanometric level) to be achieved within a hybrid network structure for both the diepoxy monomers. Concerning the fire behavior, as assessed in vertical flame spread tests, the use of anhydride curing agent prevented melt dripping phenomena and provided high char-forming character to the bio-based epoxy systems and their phenyl analog. In addition, forced combustion tests showed that the use of anhydride hardener instead of aliphatic polyamine results in a remarkable decrease of heat release rate. An overall decrease of the smoke parameters, which is highly desirable in a context of greater fire safety was observed in the case of BOMF/MNA system. The experimental results suggest that the effect of silica nanoparticles on fire behavior appears to be related to their dispersion degree. Full article
(This article belongs to the Special Issue Sol-Gel Chemistry in Polymers Research)
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17 pages, 4982 KiB  
Article
Tuning Functional Behavior of Humic Acids through Interactions with Stöber Silica Nanoparticles
by Giulio Pota, Virginia Venezia, Giuseppe Vitiello, Paola Di Donato, Valentina Mollo, Aniello Costantini, Joshua Avossa, Assunta Nuzzo, Alessandro Piccolo, Brigida Silvestri and Giuseppina Luciani
Polymers 2020, 12(4), 982; https://doi.org/10.3390/polym12040982 - 23 Apr 2020
Cited by 20 | Viewed by 3887
Abstract
Humic acids (HA) exhibit fascinating multifunctional features, yet degradation phenomena as well as poor stability in aqueous environments strongly limit their use. Inorganic nanoparticles are emerging as a powerful interface for the development of robust HA bio-hybrid materials with enhanced chemical stability and [...] Read more.
Humic acids (HA) exhibit fascinating multifunctional features, yet degradation phenomena as well as poor stability in aqueous environments strongly limit their use. Inorganic nanoparticles are emerging as a powerful interface for the development of robust HA bio-hybrid materials with enhanced chemical stability and tunable properties. Hybrid organic-inorganic SiO2/HA nanostructures were synthesized via an in-situ sol-gel route, exploiting both physical entrapment and chemical coupling. The latter was achieved through amide bond formation between carboxyl groups of HA and the amino group of 3-aminopropyltriethoxysilane (APTS), as confirmed by Fourier-Transform Infrared (FTIR) and Nuclear Magnetic Resonance (NMR) spectroscopy. Monodisperse hybrid nanoparticles about 90 nm in diameter were obtained in both cases, yet Electron Paramagnetic Resonance (EPR) spectroscopy highlighted the different supramolecular organization of HA. The altered HA conformation was reflected in different antioxidant properties of the conjugated nanoparticles that, however, resulted in being higher than for pure HA. Our findings proved the key role of both components in defining the morphology of the final system, as well as the efficacy of the ceramic component in templating the HA supramolecular organization and consequently tuning their functional features, thus defining a green strategy for bio-waste valorization. Full article
(This article belongs to the Special Issue Sol-Gel Chemistry in Polymers Research)
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26 pages, 7871 KiB  
Article
Acrylate-Based Hybrid Sol-Gel Coating for Corrosion Protection of AA7075-T6 in Aircraft Applications: The Effect of Copolymerization Time
by Peter Rodič, Romana Cerc Korošec, Barbara Kapun, Alenka Mertelj and Ingrid Milošev
Polymers 2020, 12(4), 948; https://doi.org/10.3390/polym12040948 - 19 Apr 2020
Cited by 25 | Viewed by 4756
Abstract
Pre-hydrolysed/condensed tetraethyl orthosilicate (TEOS) was added to a solution of methyl methacrylate (MMA) and 3-methacryloxypropyltrimethoxysilane (MAPTMS), and then copolymerised for various times to study the influence of the latter on the structure of hybrid sol-gel coatings as corrosion protection of aluminium alloy 7075-T6. [...] Read more.
Pre-hydrolysed/condensed tetraethyl orthosilicate (TEOS) was added to a solution of methyl methacrylate (MMA) and 3-methacryloxypropyltrimethoxysilane (MAPTMS), and then copolymerised for various times to study the influence of the latter on the structure of hybrid sol-gel coatings as corrosion protection of aluminium alloy 7075-T6. The reactions taking place during preparation were characterised using real-time Fourier transform infrared spectroscopy, dynamic light scattering and gel permeation chromatography. The solution characteristics were evaluated, using viscosimetry, followed by measurements of thermal stability determined by thermogravimetric analysis. The optimal temperature for the condensation reaction was determined with the help of high-pressure differential scanning calorimetry. Once deposited on 7075-T6 substrates, the coatings were evaluated using a field emission scanning electron microscope coupled to an energy dispersive spectrometer to determine surface morphology, topography, composition and coating thickness. Corrosion properties were tested in dilute Harrison’s solution (3.5 g/L (NH4)2SO4 and 0.5 g/L NaCl) using electrochemical impedance spectroscopy. The copolymerization of MMA and MAPTMS over 4 h was optimal for obtaining 1.4 µm thick coating with superior barrier protection against corrosion attack (|Z10 mHz| ~ 1 GΩ cm2) during three months of exposure to the corrosive medium. Full article
(This article belongs to the Special Issue Sol-Gel Chemistry in Polymers Research)
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Review

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33 pages, 7363 KiB  
Review
Hybrid Sol–gel Coatings for Corrosion Mitigation: A Critical Review
by Rita B. Figueira
Polymers 2020, 12(3), 689; https://doi.org/10.3390/polym12030689 - 19 Mar 2020
Cited by 82 | Viewed by 9962
Abstract
The corrosion process is a major source of metallic material degradation, particularly in aggressive environments, such as marine ones. Corrosion progression affects the service life of a given metallic structure, which may end in structural failure, leakage, product loss and environmental pollution linked [...] Read more.
The corrosion process is a major source of metallic material degradation, particularly in aggressive environments, such as marine ones. Corrosion progression affects the service life of a given metallic structure, which may end in structural failure, leakage, product loss and environmental pollution linked to large financial costs. According to NACE, the annual cost of corrosion worldwide was estimated, in 2016, to be around 3%–4% of the world’s gross domestic product. Therefore, the use of methodologies for corrosion mitigation are extremely important. The approaches used can be passive or active. A passive approach is preventive and may be achieved by emplacing a barrier layer, such as a coating that hinders the contact of the metallic substrate with the aggressive environment. An active approach is generally employed when the corrosion is set in. That seeks to reduce the corrosion rate when the protective barrier is already damaged and the aggressive species (i.e., corrosive agents) are in contact with the metallic substrate. In this case, this is more a remediation methodology than a preventive action, such as the use of coatings. The sol-gel synthesis process, over the past few decades, gained remarkable importance in diverse areas of application. Sol–gel allows the combination of inorganic and organic materials in a single-phase and has led to the development of organic–inorganic hybrid (OIH) coatings for several applications, including for corrosion mitigation. This manuscript succinctly reviews the fundamentals of sol–gel concepts and the parameters that influence the processing techniques. The state-of-the-art of the OIH sol–gel coatings reported in the last few years for corrosion protection, are also assessed. Lastly, a brief perspective on the limitations, standing challenges and future perspectives of the field are critically discussed. Full article
(This article belongs to the Special Issue Sol-Gel Chemistry in Polymers Research)
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