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Hybrid Polymeric Materials II

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

Deadline for manuscript submissions: closed (25 March 2022) | Viewed by 31700

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Special Issue Editors

Prof. Dr. Joannis K. Kallitsis

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Guest Editor

Department of Chemistry, University of Patras, GR-265 04 Rio-Patras, Greece
Interests: Polymer Science; Nanotechnology
Special Issues, Collections and Topics in MDPI journals

Dr. Aikaterini K. Andreopoulou

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Guest Editor

Department of Chemistry, University of Patras, University Campus, GR26504 Rio-Patras, Greece
Interests: dendronized polymers; metallopolymers; hybrid materials for optoelectronics; polymer electrolytes for PEM fuel cells

Special Issue Information

Dear Colleagues,

It is our pleasure to announce the edition of the Special Issue on “Hybrid Polymeric Materials II”. Combining synthetic organic polymers with inorganic materials, carbon nanostructures or nanoparticles at a molecular or a submicroscopic level gives rise to a unique class of materials namely the Hybrid Polymeric Materials. Multifaceted and with endless combinations, hybrid polymers take advantage of each component’s properties and special characteristics or even lead to new advantageous features otherwise not found in the constituting materials.

Hybrid polymeric materials represent a wide, rapidly growing research area targeting applications such as organic electronics, bioelectronics, energy conservation and production systems, diagnostics-imaging and sensing, to mention just a few.

This Special Issue, the second under this topic, aims to present recent trends and scientific results of modern polymer hybrids being devoted to the development up to the application of these fruitful materials. More specifically, functionalized polymers covalently attached to- or in close proximity and association using extended π-π stacking with- carbon nanostructures (such as fullerene, carbon nanotubes and graphene); polymeric metallocomplexes with transition metal ions, inorganic nanoparticles interconnected with polymeric entities, metal nanoparticles attached onto or associated to properly functionalized polymeric chain, etc are some of the subclasses of “Hybrid Polymeric Materials II” comprising this specially devoted issue.

We are looking forward to your valuable contribution in order to build together a successful issue that will give to the readers the state of the art activities and the future perspectives in the topic.

Prof. Joannis Kallitsis
Dr. Aikaterini K. Andreopoulou
Guest Editors

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

Fullerene–polymer hybrids
Carbon nanotube–polymer hybrids
Graphene–polymer hybrids
Metallic nanoparticle–polymer hybrids
Metaloxide–polymer hybrids
Polymer–transition metal complexes
Inorganic nanoparticles–polymer hybrids
Magnetic nanoparticles–polymer hybrids
Catalyst/nanocatalyst–polymer hybrids
Carbon nanodots–polymer hybrids

Published Papers (10 papers)

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Research

20 pages, 3086 KiB

Open AccessArticle

Static and Dynamic Behavior of Polymer/Graphite Oxide Nanocomposites before and after Thermal Reduction

by Kiriaki Chrissopoulou, Krystalenia Androulaki, Massimiliano Labardi and Spiros H. Anastasiadis

Polymers 2021, 13(7), 1008; https://doi.org/10.3390/polym13071008 - 25 Mar 2021

Cited by 5 | Viewed by 1753

Abstract

Nanocomposites of hyperbranched polymers with graphitic materials are investigated with respect to their structure and thermal properties as well as the dynamics of the polymer probing the effect of the different intercalated or exfoliated structure. Three generations of hyperbranched polyester polyols are mixed with graphite oxide (GO) and the favorable interactions between the polymers and the solid surfaces lead to intercalated structure. The thermal transitions of the confined chains are suppressed, whereas their dynamics show similarities and differences with the dynamics of the neat polymers. The three relaxation processes observed for the neat polymers are observed in the nanohybrids as well, but with different temperature dependencies. Thermal reduction of the graphite oxide in the presence of the polymer to produce reduced graphite oxide (rGO) reveals an increase in the reduction temperature, which is accompanied by decreased thermal stability of the polymer. The de-oxygenation of the graphite oxide leads to the destruction of the intercalated structure and to the dispersion of the rGO layers within the polymeric matrix because of the modification of the interactions between the polymer chains and the surfaces. A significant increase in the conductivity of the resulting nanocomposites, in comparison to both the polymers and the intercalated nanohybrids, indicates the formation of a percolated rGO network. Full article

(This article belongs to the Special Issue Hybrid Polymeric Materials II)

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9 pages, 1598 KiB

Open AccessCommunication

Nucleation Points: The Forgotten Parameter in the Synthesis of Hydrogel-Coated Gold Nanoparticles

by Adolfo Sepúlveda, Audrey Picard-Lafond, André Marette and Denis Boudreau

Polymers 2021, 13(3), 373; https://doi.org/10.3390/polym13030373 - 26 Jan 2021

Cited by 6 | Viewed by 1971

Abstract

The implementation of gold-hydrogel core-shell nanomaterials in novel light-driven technologies requires the development of well-controlled and scalable synthesis protocols with precisely tunable properties. Herein, new insights are presented concerning the importance of using the concentration of gold cores as a control parameter in the seeded precipitation polymerization process to modulate—regardless of core size—relevant fabrication parameters such as encapsulation yield, particle size and shrinkage capacity. Controlling the number of nucleation points results in the facile tuning of the encapsulation process, with yields reaching 99% of gold cores even when using different core sizes at a given particle concentration. This demonstration is extended to the encapsulation of bimodal gold core mixtures with equally precise control on the encapsulation yield, suggesting that this principle could be extended to encapsulating cores composed of other materials. These findings could have a significant impact on the development of stimuli-responsive smart materials. Full article

(This article belongs to the Special Issue Hybrid Polymeric Materials II)

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18 pages, 6791 KiB

Open AccessArticle

Injection Molded PP Foams Using Food Ingredients for Food Packaging Applications

by Artemis Tsagdi, Ioannis Drossos, Despoina Georgiou, Stylianos Exarhopoulos, Georgios Karasiotas, Joannis K. Kallitsis and Eleni P. Kalogianni

Polymers 2021, 13(2), 288; https://doi.org/10.3390/polym13020288 - 18 Jan 2021

Cited by 6 | Viewed by 2476

Abstract

A new approach to the creation of polypropylene (PP) based foaming materials was developed using food grade foaming agents that were coated on the PP pellets. More specifically, sodium bicarbonate and organic acids were used to coat PP pellets using either polyethyleneoxide (PEO) or lipid esters as coating stabilizers. In order to overcome the problem of the thermal decomposition of sodium bicarbonate at temperatures lower than the PP melting temperature, which makes the direct foaming during melt mixing impossible, the proposed methodology was proved quite efficient. Thus, new PP masterbatches were prepared, where the foaming agents were incorporated as coating at PP pellets at contents up to 10%, and initially used in Lab scale injection machines in order to find the best combination of materials that resulted in the production of foamed articles. Subsequently selected material combinations were tested in an industrial scale injection molding machine, where an optimization of the injection parameters was attempted. The outcome of this was the production of PP articles with significantly increased void fraction, up to 14%, decreased thermal conductivity, up to 20%, and various pore sizes as was observed via microscopic examination using SEM and CLSM. Full article

(This article belongs to the Special Issue Hybrid Polymeric Materials II)

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20 pages, 4960 KiB

Open AccessArticle

Bis-Tridendate Ir(III) Polymer-Metallocomplexes: Hybrid, Main-Chain Polymer Phosphors for Orange–Red Light Emission

by Konstantinos Andrikopoulos, Charalampos Anastasopoulos, Joannis K. Kallitsis and Aikaterini K. Andreopoulou

Polymers 2020, 12(12), 2976; https://doi.org/10.3390/polym12122976 - 13 Dec 2020

Cited by 2 | Viewed by 2537

Abstract

In this work, hybrid polymeric bis-tridentate iridium(III) complexes bearing derivatives of terpyridine (tpy) and 2,6-di(phenyl) pyridine as ligands were successfully synthesized and evaluated as red-light emitters. At first, the synthesis of small molecular bis-tridendate Ir(III) complexes bearing alkoxy-, methyl-, or hydroxy-functionalized terpyridines and a dihydroxyphenyl-pyridine moiety was accomplished. Molecular complexes bearing two polymerizable end-hydroxyl groups and methyl- or alkoxy-decorated terpyridines were copolymerized with difluorodiphenyl-sulphone under high temperature polyetherification conditions. Alternatively, the post-polymerization complexation of the terpyridine-iridium(III) monocomplexes onto the biphenyl-pyridine main chain homopolymer was explored. Both cases afforded solution-processable metallocomplex-polymers possessing the advantages of phosphorescent emitters in addition to high molecular weights and excellent film-forming ability via solution casting. The structural, optical, and electrochemical properties of the monomeric and polymeric heteroleptic iridium complexes were thoroughly investigated. The polymeric metallocomplexes were found to emit in the orange–red region (550–600 nm) with appropriate HOMO and LUMO levels to be used in conjunction with blue-emitting hosts. By varying the metal loading on the polymeric backbone, the emitter’s specific emission maxima could be successfully tuned. Full article

(This article belongs to the Special Issue Hybrid Polymeric Materials II)

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14 pages, 3842 KiB

Open AccessArticle

Poly(ethylene Terephthalate) Carbon-Based Nanocomposites: A Crystallization and Molecular Orientation Study

by Vasiliki F. Alexiou, George N. Mathioudakis, Konstantinos S. Andrikopoulos, Amaia Soto Beobide and George A. Voyiatzis

Polymers 2020, 12(11), 2626; https://doi.org/10.3390/polym12112626 - 08 Nov 2020

Cited by 19 | Viewed by 3477

Abstract

Hybrid polymeric materials incorporating carbon nanostructures or inorganic constituents stand as a promising class of materials exhibiting distinct but also complementary features. Carbon nanotubes have been proposed as unique candidates for polymer reinforcement; however, sustained efforts are further needed in order to make full use of their potential. The final properties of the reinforced polymer are controlled in part by the morphology and the eventual molecular orientation of the polymer matrix. In the present study, multiwall carbon nanotubes (MWCNTs) were utilized in order to reinforce polyethylene terephthalate (PET) composites. The effect of CNTs on the crystallization and the orientation of the structurally hybridized polymeric material has been investigated from the perspective of assessing their impact on the final properties of a relevant nanocomposite product. Functionalized MWCNTs were used to achieve their optimal dispersion in the polymer matrix. The physical properties of the composites (i.e., crystallinity and orientation) were characterized via differential scanning calorimetry, X-ray diffraction, and polarized Raman microscopy. The addition of well-dispersed CNTs acted as a nucleation agent, increasing the crystallization of the polyethylene terephthalate matrix and differentiating the orientation of both CNTs and macromolecular chains. Full article

(This article belongs to the Special Issue Hybrid Polymeric Materials II)

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13 pages, 2875 KiB

Open AccessArticle

A Facile Method for the Fabrication of Silver Nanoparticles Surface Decorated Polyvinyl Alcohol Electrospun Nanofibers and Controllable Antibacterial Activities

by Yan Yang, Zhijie Zhang, Menghui Wan, Zhihua Wang, Xueyan Zou, Yanbao Zhao and Lei Sun

Polymers 2020, 12(11), 2486; https://doi.org/10.3390/polym12112486 - 26 Oct 2020

Cited by 13 | Viewed by 2767

Abstract

Polyvinyl alcohol (PVA) electrospun nanofibers (NFs) are ideal carriers for loading silver nanoparticles (Ag NPs) serving as antibacterial materials. However, it is still a challenge to adjust the particles size, distribution, and loading density via a convenient and facile method in order to obtain tunable structure and antimicrobial activities. In this study, Ag NPs surface decorated PVA composite nanofibers (Ag/PVA CNFs) were fabricated by the solvothermal method in ethylene glycol, which plays the roles of both reductant and solvent. The morphology and structure of the as-fabricated Ag/PVA CNFs were characterized by scanning electron microscopy, transmission electron microscopy, selected area electron diffraction, X-ray diffraction, UV-visible spectroscopy, and Fourier transform infrared spectroscopy. Ag NPs had an average diameter of 30 nm, the narrowest size distribution and the highest loading density were successfully decorated on the surfaces of PVA NFs, at the AgNO₃ concentration of 0.066 mol/L. The antibacterial properties were evaluated by the methods of absorption, turbidity, and growth curves. The as-fabricated Ag/PVA hybrid CNFs exhibit excellent antimicrobial activities with antibacterial rates over 98%, especially for the sample prepared with AgNO₃ concentration of 0.066 mol/L. Meanwhile, the antibacterial effects are more significant in the Gram-positive bacteria of Staphylococcus aureus (S. aureus) than the Gram-negative bacteria of Escherichia coli (E. coli), since PVA is more susceptive to S. aureus. In summary, the most important contribution of this paper is the discovery that the particles size, distribution, and loading density of Ag NPs on PVA NFs can be easily controlled by adjusting AgNO₃ concentrations, which has a significant impact on the antibacterial activities of Ag/PVA CNFs. Full article

(This article belongs to the Special Issue Hybrid Polymeric Materials II)

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13 pages, 3595 KiB

Open AccessArticle

Highly Scattering Hierarchical Porous Polymer Microspheres with a High-Refractive Index Inorganic Surface for a Soft-Focus Effect

by Joonsik Yoon, Ji Hyun Lee, Jun Bae Lee and Jun Hyup Lee

Polymers 2020, 12(10), 2418; https://doi.org/10.3390/polym12102418 - 20 Oct 2020

Cited by 11 | Viewed by 5142

Abstract

Functional light scattering materials have received considerable attention in various fields including cosmetics and optics. However, a conventional approach based on optically active inorganic materials requires considerable synthetic effort and complicated dispersion processes for special refractive materials. Here, we report a simple and effective fabrication strategy for highly scattering hierarchical porous polymer microspheres with a high-refractive index inorganic surface that mitigates the disadvantages of inorganic materials, producing organic-inorganic hybrid particles with an excellent soft-focus effect. Hierarchical organic-inorganic hybrid particles were synthesized using the simple physical mixing of porous poly (methyl methacrylate) (PMMA) microparticles with different pore sizes and regularities as the organic core and titanium dioxide (TiO₂) nanoparticles with different particle sizes as the inorganic shell. The polar noncovalent interactions between polar PMMA microspheres and the polar surface of TiO₂ nanoparticles could induce the hierarchical core-shell structure of hybrid particles. The synthesized hybrid particles had increased diffuse reflectance properties of up to 160% compared with single inorganic particles. In addition, the light scattering efficiency and soft-focus effect could be increased further, depending on the size of the TiO₂ nanoparticles and the pore characteristics of the PMMA microspheres. The proposed study can provide a facile and versatile way to improve the light scattering performance for potential cosmetics. Full article

(This article belongs to the Special Issue Hybrid Polymeric Materials II)

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25 pages, 7584 KiB

Open AccessArticle

Hybrid Electromagnetic Nanomaterials Based on Polydiphenylamine-2-carboxylic Acid

by Sveta Zhiraslanovna Ozkan, Aleksandr Ivanovich Kostev, Galina Petrovna Karpacheva, Petr Aleksandrovich Chernavskii, Andrey Aleksandrovich Vasilev and Dmitriy Gennad’evich Muratov

Polymers 2020, 12(7), 1568; https://doi.org/10.3390/polym12071568 - 15 Jul 2020

Cited by 4 | Viewed by 2014

Abstract

Hybrid ternary nanomaterials based on conjugated polymer polydiphenylamine-2-carboxylic acid (PDPAC) (poly-N-phenylanthranilic acid), Fe₃O₄ nanoparticles and single-walled carbon nanotubes (SWCNT) were prepared for the first time. Polymer–metal–carbon Fe₃O₄/SWCNT/PDPAC nanocomposites were synthesized via in situ oxidative polymerization of diphenylamine-2-carboxylic acid (DPAC) by two different ways: in an acidic medium and in the interfacial process in an alkaline medium. In an alkaline medium (pH 11.4), the entire process of Fe₃O₄/SWCNT/PDPAC-1 synthesis was carried out in one reaction vessel without intermediate stages of product extraction and purification. In an acidic medium (pH 0.3), to prepare the Fe₃O₄/SWCNT/PDPAC-2 nanocomposites, prefabricated magnetite nanoparticles were deposited on the surface of obtained SWCNT/PDPAC-2. The phase composition of the nanocomposites does not depend on the synthesis reaction medium pH. The influence of the reaction medium pH on the structure, morphology, thermal, magnetic, and electrical properties of the obtained ternary nanocomposites was studied. Full article

(This article belongs to the Special Issue Hybrid Polymeric Materials II)

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11 pages, 3288 KiB

Open AccessArticle

Carbonization of Polydopamine-Coating Layers on Boron Nitride for Thermal Conductivity Enhancement in Hybrid Polyvinyl Alcohol (PVA) Composites

by Youjin Kim and Jooheon Kim

Polymers 2020, 12(6), 1410; https://doi.org/10.3390/polym12061410 - 24 Jun 2020

Cited by 22 | Viewed by 4452

Abstract

Inspired by mussel adhesion proteins, boron nitride (BN) particles coated with homogeneous polydopamine (BNPDA) were prepared, and through an annealing process, a carbonized PDA layer on the surface of BN was obtained, which exhibited a nanocrystalline graphite-like structure. The effect of carbonization of PDA coating layer on BN particles was characterized by various analytical techniques including SEM, TEM, Raman spectroscopy, and XPS. When the resulting particles were used as a thermally conductive filler for polyvinyl alcohol (PVA) composite films, enhanced thermal conductivity was observed compared to raw BN composite due to the ordered structure and improved solubility in water. Furthermore, the homogeneous dispersion of the filler and excellent flexibility of the modified composite film with 21 wt % filler may be attributed to compatibility with the PVA chain. As the whole fabrication process did not use toxic chemicals (mainly water was used as the solvent), it may contribute to green and sustainable chemistry. Full article

(This article belongs to the Special Issue Hybrid Polymeric Materials II)

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12 pages, 3478 KiB

Open AccessArticle

Dielectric Property and Space Charge Behavior of Polyimide/Silicon Nitride Nanocomposite Films

by Minghua Chen, Wenqi Zhou, Jiawei Zhang and Qingguo Chen

Polymers 2020, 12(2), 322; https://doi.org/10.3390/polym12020322 - 04 Feb 2020

Cited by 23 | Viewed by 4147

Abstract

Polymeric materials have many applications in multiple industries. In this paper, silicon nitride nanoparticles (Si₃N₄) were incorporated into a polyimide (PI) matrix to obtain composite films via the in situ polymerization method. The Si₃N₄ nanoparticles were consistently scattered in the composites, and the thickness of PI/Si₃N₄ films was around 50 µm. The effects of nanoparticle content on the dielectric constant, loss tangent and breakdown strength were simultaneously studied. A 3 wt.% doped PI/Si₃N₄ film revealled excellent dielectric properties, a dielectric constant (ε) of 3.62, a dielectric loss tangent (tanδ) of 0.038, and a breakdown strength of 237.42 MV/m. The addition of Si₃N₄ formed an interface layer inside PI, resulting in a large amount of space charge polarization in the electric field. The space charge of materials from the microscopic point of view was analyzed. The results show that there are trapenergy levels in the composites, which can be used as a composite carrier center and transport channel, effectively improving the performance of a small amount of nanoparticles film. Full article

(This article belongs to the Special Issue Hybrid Polymeric Materials II)

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