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

Deadline for manuscript submissions: closed (31 August 2022) | Viewed by 24699

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Dr. Jesús-María García-Martínez

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Polymer Engineering Group (GIP), Polymer Science and Technology Institute (ICTP), Spanish Council for Scientific Research (CSIC), 28006 Madrid, Spain
Interests: polymers and environment; heterogeneous materials based on polymers; polyolefins; interfacial agents; interphase; interface; functionalization; plastic wastes; blends; composites
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Dr. Emilia P. Collar

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Dear Colleagues,

This Special Issue is devoted to one of the most attractive fields in material science and technology research. The concept of organic–inorganic hybrid materials can be applied to a wide variety of approaches at present, including those considering the matrix of inorganic or organic nature. Hence, the encapsulation of organic functionalities within inorganic matrices obtained by sol–gel processes, the polymerization of organoalkoxyxilanes, and the functionalization of inorganic substances such as micro or nanofillers with organic and/or inorganic molecules able to interact with organic matrixes to provide enhanced properties. In any case, it is the interphase between the components that becomes the critical aspect to consider in research activities with this type of advanced material, thus any effort to enhance and understand these interactions will be key to obtaining these materials with "tailor-made"organized structures at the subsequent nano, meso, micro and macro scales.

Dr. Jesús-María García-Martínez
Dr. Emilia P. Collar
Guest Editors

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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.

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Keywords

hybrid inorganic/organic polymer-based materials
heterogeneous materials based on polymers interfaces
interphase
functionalization
sol-gel
chemical modification
composites

Related Special Issue

Organic-Inorganic Hybrid Materials in Polymers (12 articles)

Published Papers (11 papers)

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Editorial

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3 pages, 208 KiB

Open AccessEditorial

Organic–Inorganic Hybrid Materials II: Some Additional Contributions to the Topic

by Jesús-María García-Martínez and Emilia P. Collar

Polymers 2021, 13(15), 2390; https://0-doi-org.brum.beds.ac.uk/10.3390/polym13152390 - 21 Jul 2021

Cited by 3 | Viewed by 1357

Abstract

By following the successful editorial pathway of the recently published former Special Issue dedicated to Organic–Inorganic Hybrid Materials [...] Full article

(This article belongs to the Special Issue Organic-Inorganic Hybrid Materials II)

Research

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19 pages, 3986 KiB

Open AccessFeature PaperArticle

Combined Effects from Dual Incorporation of ATBC as Plasticizer and Mesoporous MCM-41 as Nucleating Agent on the PLA Isothermal Crystallization in Environmentally-Friendly Ternary Composite Systems

by Enrique Blázquez-Blázquez, Rosa Barranco-García, Tamara M. Díez-Rodríguez, María L. Cerrada and Ernesto Pérez

Polymers 2023, 15(3), 624; https://0-doi-org.brum.beds.ac.uk/10.3390/polym15030624 - 25 Jan 2023

Cited by 4 | Viewed by 1182

Abstract

Different materials, based on an L-rich polylactide (PLA) as matrix, acetyl tri-n-butyl citrate (ATBC) as plasticizer, and mesoporous Mobile Crystalline Material.41 (MCM-41) particles as nucleating agent, were attained by melt extrusion. These materials are constituted by (a) binary blends of PLA and ATBC with different contents of the latest; (b) a dual compound of PLA and a given amount of MCM-41 silica (5 wt.%); and (c) ternary composites that include PLA, ATBC at several compositions and mesoporous MCM-41 at 5 wt.%. Influence of the incorporation of the plasticizer and nucleating particles has been comprehensively analyzed on the different phase transitions: glass transition, cold crystallization, melt crystallization and melting processes. Presence of both additives moves down the temperature at which PLA phase transitions take place, while allowing the PLA crystallization from the melt at 10 °C/min in the composites. This tridimensional ordering is not noticeable in the pristine PLA matrix and, accordingly, PLA crystallization rate is considerably increased under dynamic conditions and also after isothermal crystallization from either the melt or the glassy state. An important synergistic effect of dual action of ATBC and MCM-41 has been, therefore, found. Full article

(This article belongs to the Special Issue Organic-Inorganic Hybrid Materials II)

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14 pages, 3560 KiB

Open AccessArticle

Preparation and Properties of Fluorosilicone Fouling-Release Coatings

by Tong Wu, Yuhong Qi, Qi’an Chen, Chuanjun Gu and Zhanping Zhang

Polymers 2022, 14(18), 3804; https://0-doi-org.brum.beds.ac.uk/10.3390/polym14183804 - 11 Sep 2022

Cited by 1 | Viewed by 2200

Abstract

To improve the antifouling performance of silicone fouling-release coatings, some fluorosilicone and silicone fouling-release coatings were prepared and cured at room temperature with hydroxyl-terminated fluoropolysiloxane (FPS) or hydroxy-terminated polydimethylsiloxane (PDMS) as a film-forming resin, tetraethyl orthosilicate (TEOS) as a crosslinking agent, and dibutyltin dilaurate (DBTDL) as a catalyst. The chemical structure, surface morphology and roughness, tensile properties, and antifouling properties of the coating were studied by infrared spectroscopy, a laser confocal scanning microscope, contact angle measurement, tensile tests, and marine bacteria and benthic diatom attachment tests. The results showed that the FPS coatings were not only hydrophobic but also oleophobic, and the contact angles of the FPS coatings were larger than those of the PDMS coatings. The surface free energies of the FPS coatings were much lower than those of the PDMS coatings. Generally, the fluorine groups can improve the antifouling performance of the coating. Introducing nonreactive silicone oil into PDMS or FPS coatings can improve the antifouling performance of the coating to a certain extent. The prepared fluorosilicone fouling-release coatings showed good application prospects. Full article

(This article belongs to the Special Issue Organic-Inorganic Hybrid Materials II)

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14 pages, 2718 KiB

Open AccessArticle

Compositional Influence on the Morphology and Thermal Properties of Woven Non-Woven Mats of PLA/OLA/MgO Electrospun Fibers

by Adrián Leonés, Laura Peponi, Jesús-María García-Martínez and Emilia P. Collar

Polymers 2022, 14(10), 2092; https://0-doi-org.brum.beds.ac.uk/10.3390/polym14102092 - 20 May 2022

Cited by 3 | Viewed by 1317

Abstract

In the present work, a statistical study of the morphology and thermal behavior of poly(lactic acid) (PLA)/oligomer(lactic acid) (OLA)/magnesium oxide nanoparticles (MgO), electrospun fibers (efibers) has been carried out. The addition of both, OLA and MgO, is expected to modify the final properties of the electrospun PLA-based nanocomposites for their potential use in biomedical applications. Looking for the compositional optimization of these materials, a Box–Wilson design of experiment was used, taking as dependent variables the average fiber diameter as the representative of the fiber morphologies, as well as the glass transition temperature (T_g) and the degree of crystallinity (X_c) as their thermal response. The results show <r²> values of 73.76% (diameter), 88.59% (T_g) and 75.61% (X_c) for each polynomial fit, indicating a good correlation between both OLA and MgO, along with the morphological as well as the thermal behavior of the PLA-based efibers in the experimental space scanned. Full article

(This article belongs to the Special Issue Organic-Inorganic Hybrid Materials II)

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14 pages, 4416 KiB

Open AccessArticle

The Influence of Bi₂O₃ Nanoparticle Content on the γ-ray Interaction Parameters of Silicon Rubber

by Mahmoud I. Abbas, Ahmed M. El-Khatib, Mirvat Fawzi Dib, Hoda Ezzelddin Mustafa, M. I. Sayyed and Mohamed Elsafi

Polymers 2022, 14(5), 1048; https://0-doi-org.brum.beds.ac.uk/10.3390/polym14051048 - 06 Mar 2022

Cited by 23 | Viewed by 2089

Abstract

In this study, synthetic silicone rubber (SR) and Bi₂O₃ micro- and nanoparticles were purchased. The percentages for both sizes of Bi₂O₃ were 10, 20 and 30 wt% as fillers. The morphological, mechanical and shielding properties were determined for all the prepared samples. The Linear Attenuation Coefficient (LAC) values of the silicon rubber (SR) without Bi₂O₃ and with 5, 10, 30 and 30% Bi₂O₃ (in micro and nano sizes) were experimentally measured using different radioactive point sources in the energy range varying from 0.06 to 1.333 MeV. Additionally, we theoretically calculated the LAC for SR with micro-Bi₂O₃ using XCOM software. A good agreement was noticed between the two methods. The NaI (Tl) scintillation detector and four radioactive point sources (Am-241, Ba-133, Cs-137 and Co-60) were used in the measurements. Other shielding parameters were calculated for the prepared samples, such as the Half Value Layer (HVL), Mean Free Path (MFP) and Radiation Protection Efficiency (RPE), all of which proved that adding nano-Bi₂O₃ ratios of SR produces higher shielding efficiency than its micro counterpart. Full article

(This article belongs to the Special Issue Organic-Inorganic Hybrid Materials II)

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15 pages, 1865 KiB

Open AccessArticle

Unmodified Silica Nanoparticles Enhance Mechanical Properties and Welding Ability of Epoxy Thermosets with Tunable Vitrimer Matrix

by Anna I. Barabanova, Egor S. Afanas’ev, Vyacheslav S. Molchanov, Andrey A. Askadskii and Olga E. Philippova

Polymers 2021, 13(18), 3040; https://0-doi-org.brum.beds.ac.uk/10.3390/polym13183040 - 09 Sep 2021

Cited by 11 | Viewed by 2810

Abstract

Epoxy/silica thermosets with tunable matrix (vitrimers) were prepared by thermal curing of diglycidyl ether of bisphenol A (DGEBA) in the presence of a hardener—4-methylhexahydrophthalic anhydride (MHHPA), a transesterification catalyst—zinc acetylacetonate (ZAA), and 10–15 nm spherical silica nanoparticles. The properties of the resulting material were studied by tensile testing, thermomechanical and dynamic mechanical analysis. It is shown that at room temperature the introduction of 5–10 wt% of silica nanoparticles in the vitrimer matrix strengthens the material leading to the increase of the elastic modulus by 44% and the tensile stress by 25%. Simultaneously, nanoparticles enhance the dimensional stability of the material since they reduce the coefficient of thermal expansion. At the same time, the transesterification catalyst provides the thermoset with the welding ability at heating, when the chain exchange reactions are accelerated. For the first time, it was shown that the silica nanoparticles strengthen welding joints in vitrimers, which is extremely important, since it allows to repeatedly use products made of thermosets and heal defects in them. Such materials hold great promise for use in durable protective coatings, adhesives, sealants and many other applications. Full article

(This article belongs to the Special Issue Organic-Inorganic Hybrid Materials II)

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16 pages, 3084 KiB

Open AccessArticle

Hybrid Xerogels: Study of the Sol-Gel Process and Local Structure by Vibrational Spectroscopy

by Guillermo Cruz-Quesada, Maialen Espinal-Viguri, María Victoria López-Ramón and Julián J. Garrido

Polymers 2021, 13(13), 2082; https://0-doi-org.brum.beds.ac.uk/10.3390/polym13132082 - 24 Jun 2021

Cited by 10 | Viewed by 2230

Abstract

The properties of hybrid silica xerogels obtained by the sol-gel method are highly dependent on the precursor and the synthesis conditions. This study examines the influence of organic substituents of the precursor on the sol-gel process and determines the structure of the final materials in xerogels containing tetraethyl orthosilicate (TEOS) and alkyltriethoxysilane or chloroalkyltriethoxysilane at different molar percentages (RTEOS and ClRTEOS, R = methyl [M], ethyl [E], or propyl [P]). The intermolecular forces exerted by the organic moiety and the chlorine atom of the precursors were elucidated by comparing the sol-gel process between alkyl and chloroalkyl series. The microstructure of the resulting xerogels was explored in a structural theoretical study using Fourier transformed infrared spectroscopy and deconvolution methods, revealing the distribution of (SiO)₄ and (SiO)₆ rings in the silicon matrix of the hybrid xerogels. The results demonstrate that the alkyl chain and the chlorine atom of the precursor in these materials determines their inductive and steric effects on the sol-gel process and, therefore, their gelation times. Furthermore, the distribution of (SiO)₄ and (SiO)₆ rings was found to be consistent with the data from the X-ray diffraction spectra, which confirm that the local periodicity associated with four-fold rings increases with higher percentage of precursor. Both the sol-gel process and the ordered domains formed determine the final structure of these hybrid materials and, therefore, their properties and potential applications. Full article

(This article belongs to the Special Issue Organic-Inorganic Hybrid Materials II)

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15 pages, 13602 KiB

Open AccessArticle

New Insight on Photoisomerization Kinetics of Photo-Switchable Thin Films Based on Azobenzene/Graphene Hybrid Additives in Polyethylene Oxide

by Qais M. Al-Bataineh, Ahmad A. Ahmad, Ahmad M. Alsaad and Ahmad Telfah

Polymers 2020, 12(12), 2954; https://0-doi-org.brum.beds.ac.uk/10.3390/polym12122954 - 10 Dec 2020

Cited by 16 | Viewed by 2097

Abstract

In this work, we reported a new insight on the kinetics of photoisomerization and time evolution of hybrid thin films considering the azo-dye methyl red (MR) incorporated with graphene accommodated in polyethylene oxide (PEO). The kinetics of photoisomerization and time-evolution of hybrid thin films were investigated using UV-Vis s and FTIR spectroscopies, as well as appropriate models developed with new analytical methods. The existence of azo-dye MR in the complex is crucial for the resource action of the trans

\leftrightarrow

cis cycles through UV-illumination

\leftrightarrow

Visible-illumination relaxations. The results of the UV–Vis and the FTIR investigations prove the cyclical trans

\leftrightarrow

cis-states. Consequently, PEO-(MR-Graphene) hybrid composite thin films can be introduced as possible applicants for photochromic molecular switches, light-gated transistors, and molecular solar thermal energy storage media. Full article

(This article belongs to the Special Issue Organic-Inorganic Hybrid Materials II)

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14 pages, 3959 KiB

Open AccessArticle

Applying Membrane Distillation for the Recovery of Nitrate from Saline Water Using PVDF Membranes Modified as Superhydrophobic Membranes

by Fatemeh Ebrahimi, Yasin Orooji and Amir Razmjou

Polymers 2020, 12(12), 2774; https://0-doi-org.brum.beds.ac.uk/10.3390/polym12122774 - 24 Nov 2020

Cited by 15 | Viewed by 2797

Abstract

In this study, a flat sheet direct contact membrane distillation (DCMD) module was designed to eliminate nitrate from water. A polyvinylidene fluoride (PVDF) membrane was used in a DCMD process at an ambient pressure and at a temperature lower than the boiling point of water. The electrical conductivity of the feed containing nitrate increased, while the electrical conductivity of the permeate remained constant during the entire process. The results indicated that the nitrate ions failed to pass through the membrane and their concentration in the feed increased as pure water passed through the membrane. Consequently, the membrane was modified using TiO₂ nanoparticles to make a hierarchical surface with multi-layer roughness on the micro/nanoscales. Furthermore, 1H,1H,2H,2H-Perfluorododecyltrichlorosilane (FTCS) was added to the modified surface to change its hydrophobic properties into superhydrophobic properties and to improve its performance. The results for both membranes were compared and reported on a pilot scale using MATLAB. In the experimental scale (a membrane surface area of 0.0014 m², temperature of 77 °C, nitrate concentration of 0.9 g/Kg, and flow rate of 0.0032 Kg/s), the flux was 2.3 Kgm⁻²h⁻¹. The simulation results of MATLAB using these data showed that for the removal of nitrate (with a concentration of 35 g/Kg) from the intake feed with a flow rate of 1 Kg/s and flux of 0.96 Kgm⁻²h⁻¹, a membrane surface area of 0.5 m² was needed. Full article

(This article belongs to the Special Issue Organic-Inorganic Hybrid Materials II)

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14 pages, 4154 KiB

Open AccessArticle

3D Nanoarchitecture of Polyaniline-MoS₂ Hybrid Material for Hg(II) Adsorption Properties

by Hilal Ahmad, Ibtisam I. BinSharfan, Rais Ahmad Khan and Ali Alsalme

Polymers 2020, 12(11), 2731; https://0-doi-org.brum.beds.ac.uk/10.3390/polym12112731 - 17 Nov 2020

Cited by 17 | Viewed by 2274

Abstract

We report the facile hydrothermal synthesis of polyaniline (PANI)-modified molybdenum disulfide (MoS₂) nanosheets to fabricate a novel organic–inorganic hybrid material. The prepared 3D nanomaterial was characterized by field emission scanning electron microscopy, high-resolution transmission electron microscopy, energy-dispersive X-ray spectroscopy and X-ray diffraction studies. The results indicate the successful synthesis of PANI–MoS₂ hybrid material. The PANI–MoS₂ was used to study the extraction and preconcentration of trace mercury ions. The experimental conditions were optimized systematically, and the data shows a good Hg(II) adsorption capacity of 240.0 mg g⁻¹ of material. The adsorption of Hg(II) on PANI–MoS₂ hybrid material may be attributed to the selective complexation between the–S ion of PANI–MoS₂ with Hg(II). The proposed method shows a high preconcentration limit of 0.31 µg L⁻¹ with a preconcentration factor of 640. The lowest trace Hg(II) concentration, which was quantitatively analyzed by the proposed method, was 0.03 µg L⁻¹. The standard reference material was analyzed to determine the concentration of Hg(II) to validate the proposed methodology. Good agreement between the certified and observed values indicates the applicability of the developed method for Hg(II) analysis in real samples. The study suggests that the PANI–MoS₂ hybrid material can be used for trace Hg(II) analyses for environmental water monitoring. Full article

(This article belongs to the Special Issue Organic-Inorganic Hybrid Materials II)

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17 pages, 5024 KiB

Open AccessArticle

Synthesis, Optical and Electrical Characterization of Amino-alcohol Based Sol-gel Hybrid Materials

by Bárbara R. Gomes, Rita B. Figueira, Susana P. G. Costa, M. Manuela M. Raposo and Carlos J. R. Silva

Polymers 2020, 12(11), 2671; https://0-doi-org.brum.beds.ac.uk/10.3390/polym12112671 - 12 Nov 2020

Cited by 7 | Viewed by 3318

Abstract

This manuscript describes the synthesis and characterization of five new organic–inorganic hybrid (OIH) sol-gel materials that were obtained from a functionalized siloxane 3-glycidoxypropyltrimethoxysilane (GPTMS) by the reaction with the new Jeffamine^®, namely three different diamines, i.e., EDR-148, RFD-270, and THF-170, a secondary diamine, i.e., SD-2001, and a triamine, i.e., T-403. The OIH sol-gel materials were characterized by UV-visible absorption spectrophotometry, steady-state photoluminescence spectroscopy, and electrochemical impedance spectroscopy. The reported OIH sol-gel materials showed that, with the exception of the samples prepared with Jeffamine^® SD-2001, the transmittance values ranged between 61% and 79%. Regarding the capacitance data, the values reported changed between 0.008 and 0.013 nF cm⁻². Due to their optical and electrical properties these new OIH materials show promising properties for applications as support films in an optical sensor area such as fiber sensor devices. Studies to assess the chemical stability of the OIH materials in contact with cement pastes after 7, 14, and 28 days were also performed. The samples prepared with THF–170 and GPTMS, when compared to the samples prepared with RFD-270 and T-403, exhibited improved behavior in the cement paste (alkaline environment), showing promising properties for application as support film in optical fiber sensors in the civil engineering field. Full article

(This article belongs to the Special Issue Organic-Inorganic Hybrid Materials II)

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