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Synthesis, Characterization, and Applications of Polymer Nanocomposites

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A special issue of Nanomaterials (ISSN 2079-4991).

Deadline for manuscript submissions: closed (30 November 2018) | Viewed by 63930

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Special Issue Editor

Prof. Dr. Carola Esposito Corcione

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Guest Editor

Department of Innovation Engineering, University of Salento, Via per Monteroni, 73100 Lecce, Italy
Interests: polymers; nanocomposite; recycle
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

The combination of two different materials, is a simple route for combining attractive features from different materials in order to enhance the deficient characteristics of a particular material. Many common examples of composite materials can be found in the world around us. Wood and bone are examples of natural composites. Recent and successful examples of improved properties that can be achieved using these procedures are offered by adding to a polymeric phase of organic and inorganic filler, for instance, hyperbranched polymers and inorganic nanofillers.

In particular, polymer composites reinforced with inorganic fillers of dimensions in the nanometer scale, known as nanocomposites, have attracted a great deal of interest from researchers, due to unexpected synergistic properties derived from the two components. The most-studied polymer nanocomposites (PN) are composed of thermoplastic or thermosetting matrices, organically-modified montmorillonite (OMMT), and modified boehmite or carbon nanotubes (CNTs). The present Special Issue will be focused on the “Synthesis, Characterization, and Applications of Polymer Nanocomposites”. Papers referring to the thermal, physical and mechanical characterization of polymer nanocomposites are welcome. Theoretical analyses with model predictions of experimental data are also welcome.

Dr. Carola Esposito Corcione
Guest Editor

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Keywords

nanocomposites
thermal analysis
DSC
TGA
TMA
DTA, rheology, kinetic, mechanical properties

Published Papers (11 papers)

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Research

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21 pages, 4851 KiB

Open AccessArticle

Higher-Order Thermo-Elastic Analysis of FG-CNTRC Cylindrical Vessels Surrounded by a Pasternak Foundation

by Masoud Mohammadi, Mohammad Arefi, Rossana Dimitri and Francesco Tornabene

Nanomaterials 2019, 9(1), 79; https://doi.org/10.3390/nano9010079 - 08 Jan 2019

Cited by 41 | Viewed by 3876

Abstract

This study analyses the two-dimensional thermo-elastic response of functionally graded carbon nanotube-reinforced composite (FG-CNTRC) cylindrical pressure vessels, by applying the third-order shear deformation theory (TSDT). The effective properties of FG-CNTRC cylindrical pressure vessels are computed for different patterns of reinforcement, according to the rule of mixture. The governing equations of the problem are derived from the principle of virtual works and are solved as a classical eigenproblem under the assumption of clamped supported boundary conditions. A large parametric investigation aims at showing the influence of some meaningful parameters on the thermo-elastic response, such as the type of pattern, the volume fraction of CNTs, and the Pasternak coefficients related to the elastic foundation. Full article

(This article belongs to the Special Issue Synthesis, Characterization, and Applications of Polymer Nanocomposites)

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19 pages, 2740 KiB

Open AccessArticle

Wave Propagation of Porous Nanoshells

by Behrouz Karami, Davood Shahsavari, Maziar Janghorban, Rossana Dimitri and Francesco Tornabene

Nanomaterials 2019, 9(1), 22; https://doi.org/10.3390/nano9010022 - 24 Dec 2018

Cited by 57 | Viewed by 3701

Abstract

This study aims at investigating the wave propagation of porous nanoshells. The Bi-Helmholtz non-local strain gradient theory is employed in conjunction with a higher-order shear deformation shell theory, in order to include the size-dependent effects. The nanoshells are made of a porous functionally graded material (P-FGM), whose properties vary continuously along the thickness direction. A variational approach is here applied to handle the governing equations of the problem, which are solved analytically to compute the wave frequencies and phase velocities as function of the wave numbers. The sensitivity of the wave response is analyzed for a varying porosity volume fraction, material properties, non-local parameters, strain gradient length scales, temperature, humidity, and wave numbers. Based on the results, it is verified that the size-dependence of the response is almost the same to the one of plates, beams and tubes. Full article

(This article belongs to the Special Issue Synthesis, Characterization, and Applications of Polymer Nanocomposites)

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22 pages, 5050 KiB

Open AccessArticle

Graphene Based Poly(Vinyl Alcohol) Nanocomposites Prepared by In Situ Green Reduction of Graphene Oxide by Ascorbic Acid: Influence of Graphene Content and Glycerol Plasticizer on Properties

by Mónica Cobos, M. Jesús Fernández and M. Dolores Fernández

Nanomaterials 2018, 8(12), 1013; https://doi.org/10.3390/nano8121013 - 06 Dec 2018

Cited by 40 | Viewed by 4971

Abstract

The enhanced properties of polymer nanocomposites as compared with pure polymers are only achieved in the presence of well-dispersed nanofillers and strong interfacial adhesion. In this study, we report the preparation of nanocomposite films based on poly(vinyl alcohol) (PVA) filled with well dispersed graphene sheets (GS) by in situ reduction of graphene oxide (GO) dispersed in PVA solution using ascorbic acid (L-AA) as environmentally friendly reductant. The combined effect of GS content and glycerol as plasticizer on the structure, thermal, mechanical, water absorption, and water barrier properties of PVA/GS nanocomposite films is studied for the first time. Higher glass transition temperature, lower crystallinity, melting, and crystallization temperature, higher mechanical properties, and remarkable improvement in the thermal stability compared to neat PVA are obtained as a result of strong interfacial interactions between GS and PVA by hydrogen bonding. PVA/GS composite film prepared by ex situ process is more brittle than its in situ prepared counterpart. The presence of GS improves the water barrier and water resistance properties of nanocomposite films by decreasing water vapor permeability and water absorption of PVA. This work demonstrates that the tailoring of PVA/GS nanocomposite properties is enabled by controlling GS and glycerol content. The new developed materials, particularly those containing plasticizer, could be potential carriers for transdermal drug delivery. Full article

(This article belongs to the Special Issue Synthesis, Characterization, and Applications of Polymer Nanocomposites)

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13 pages, 2444 KiB

Open AccessArticle

Effects of Protonation, Hydroxylamination, and Hydrazination of g-C₃N₄ on the Performance of Matrimid^®/g-C₃N₄ Membranes

by María Soto-Herranz, Mercedes Sánchez-Báscones, Antonio Hérnandez-Giménez, José I. Calvo-Díez, Jesús Martín-Gil and Pablo Martín-Ramos

Nanomaterials 2018, 8(12), 1010; https://doi.org/10.3390/nano8121010 - 05 Dec 2018

Cited by 19 | Viewed by 4865

Abstract

One of the challenges to continue improving polymeric membranes properties involves the development of novel chemically modified fillers, such as nitrogen-rich 2-D nanomaterials. Graphitic carbon nitride (g-C₃N₄) has attracted significant interest as a new class of these fillers. Protonation is known to afford it desirable functionalities to form unique architectures for various applications. In the work presented herein, doping of Matrimid^® with protonated g-C₃N₄ to yield Matrimid^®/g-C₃N₄ mixed matrix membranes was found to improve gas separation by enhancing the selectivity for CO₂/CH₄ by up to 36.9% at 0.5 wt % filler doping. With a view to further enhancing the contribution of g-C₃N₄ to the performance of the composite membrane, oxygen plasma and hydrazine monohydrate treatments were also assayed as alternatives to protonation. Hydroxylamination by oxygen plasma treatment increased the selectivity for CO₂/CH₄ by up to 52.2% (at 2 wt % doping) and that for O₂/N₂ by up to 26.3% (at 0.5 wt % doping). Hydrazination led to lower enhancements in CO₂/CH₄ separation, by up to 11.4%. This study suggests that chemically-modified g-C₃N₄ may hold promise as an additive for modifying the surface of Matrimid^® and other membranes. Full article

(This article belongs to the Special Issue Synthesis, Characterization, and Applications of Polymer Nanocomposites)

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18 pages, 5963 KiB

Open AccessArticle

Peculiarities of Synthesis and Properties of Lignin–Silica Nanocomposites Prepared by Sol-Gel Method

by Tetyana M. Budnyak, Selda Aminzadeh, Ievgen V. Pylypchuk, Anastasia V. Riazanova, Valentin A. Tertykh, Mikael E. Lindström and Olena Sevastyanova

Nanomaterials 2018, 8(11), 950; https://doi.org/10.3390/nano8110950 - 18 Nov 2018

Cited by 34 | Viewed by 6696

Abstract

The development of advanced hybrid materials based on polymers from biorenewable sources and mineral nanoparticles is currently of high importance. In this paper, we applied softwood kraft lignins for the synthesis of lignin/SiO₂ nanostructured composites. We described the peculiarities of composites formation in the sol-gel process through the incorporation of the lignin into a silica network during the hydrolysis of tetraethoxysilane (TEOS). The initial activation of lignins was achieved by means of a Mannich reaction with 3-aminopropyltriethoxysilane (APTES). In the study, we present a detailed investigation of the physicochemical characteristics of initial kraft lignins and modified lignins on each step of the synthesis. Thus, 2D-NMR, ³¹P-NMR, size-exclusion chromatography (SEC) and dynamic light scattering (DLS) were applied to analyze the characteristics of pristine lignins and lignins in dioxan:water solutions. X-Ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FTIR) were used to confirm the formation of the lignin–silica network and characterize the surface and bulk structures of the obtained hybrids. Termogravimetric analysis (TGA) in nitrogen and air atmosphere were applied to a detailed investigation of the thermal properties of pristine lignins and lignins on each step of modification. SEM confirmed the nanostructure of the obtained composites. As was demonstrated, the activation of lignin is crucial for the sol-gel formation of a silica network in order to create novel hybrid materials from lignins and alkoxysilanes (e.g., TEOS). It was concluded that the structure of the lignin had an impact on its reactivity during the activation reaction, and consequently affected the properties of the final hybrid materials. Full article

(This article belongs to the Special Issue Synthesis, Characterization, and Applications of Polymer Nanocomposites)

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15 pages, 5737 KiB

Open AccessArticle

Interfacial Adhesion and Mechanical Properties of PET Fabric/PVC Composites Enhanced by SiO₂/Tributyl Citrate Hybrid Sizing

by Dandan Pu, Fuyao Liu, Yubing Dong, Qingqing Ni and Yaqin Fu

Nanomaterials 2018, 8(11), 898; https://doi.org/10.3390/nano8110898 - 01 Nov 2018

Cited by 7 | Viewed by 3194

Abstract

Poly(ethylene terephthalate) (PET) fabric-reinforced polyvinyl chloride (PVC) composites have a wide range of applications, but the interface bonding of PET fabric/PVC composites has remained a challenge. In this work, a new in-situ SiO₂/tributyl citrate sizing agent was synthesized according to the principle of “similar compatibility.” The developed sizing agent was used as a PET surface modifier to enhance the interfacial performance of PET fabric/PVC composites. The morphology and structure of the PET filaments, the wettability and tensile properties of the PET fabric, the interfacial adhesion, and the tensile and tearing properties of the PET fabric/PVC composites were investigated. Experimental results showed that many SiO₂ nanoparticles were scattered on the surface of the modified PET filaments. Moreover, the surface roughness of the modified PET filaments remarkably increased in comparison with that of the untreated PET filaments. The contact angle of the modified PET filaments was also smaller than that of the untreated ones. The peeling strength of the modified PET fabrics/PVC composites was 0.663 N/mm, which increased by 62.50% in comparison with the peeling strength of the untreated ones (0.408 N/mm). This work provides a new approach to the surface modification of PET and improves the properties of PET fabric/PVC composites. Full article

(This article belongs to the Special Issue Synthesis, Characterization, and Applications of Polymer Nanocomposites)

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20 pages, 3905 KiB

Open AccessArticle

Effects of the Nanofillers on Physical Properties of Acrylonitrile-Butadiene-Styrene Nanocomposites: Comparison of Graphene Nanoplatelets and Multiwall Carbon Nanotubes

by Sithiprumnea Dul, Alessandro Pegoretti and Luca Fambri

Nanomaterials 2018, 8(9), 674; https://doi.org/10.3390/nano8090674 - 29 Aug 2018

Cited by 50 | Viewed by 5260

Abstract

The effects of carbonaceous nanoparticles, such as graphene (GNP) and multiwall carbon nanotube (CNT) on the mechanical and electrical properties of acrylonitrile–butadiene–styrene (ABS) nanocomposites have been investigated. Samples with various filler loadings were produced by solvent free process. Composites ABS/GNP showed higher stiffness, better creep stability and processability, but slightly lower tensile strength and electrical properties (low conductivity) when compared with ABS/CNT nanocomposites. Tensile modulus, tensile strength and creep stability of the nanocomposite, with 6 wt % of GNP, were increased by 47%, 1% and 42%, respectively, while analogous ABS/CNT nanocomposite showed respective values of 23%, 12% and 20%. The electrical percolation threshold was achieved at 7.3 wt % for GNP and 0.9 wt % for CNT. The peculiar behaviour of conductive CNT nanocomposites was also evidenced by the observation of the Joule’s effect after application of voltages of 12 and 24 V. Moreover, comparative parameters encompassing stiffness, melt flow and resistivity were proposed for a comprehensive evaluation of the effects of the fillers. Full article

(This article belongs to the Special Issue Synthesis, Characterization, and Applications of Polymer Nanocomposites)

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12 pages, 2983 KiB

Open AccessArticle

Barrier Properties of Layered-Silicate Reinforced Ethylenepropylenediene Monomer/Chloroprene Rubber Nanorubbers

by Chang Mou Wu, Wen Yen Hsieh, Kuo Bin Cheng, Chiu-Chun Lai and Kuei Chi Lee

Nanomaterials 2018, 8(5), 314; https://doi.org/10.3390/nano8050314 - 09 May 2018

Cited by 6 | Viewed by 3704

Abstract

The triacetin and nitroglycerin barrier properties of layered-silicate reinforced ethylenepropylenediene monomer/chloroprene rubber (EPDM/CR) nanorubbers were investigated as rocket-propellant inhibitors. EPDM/CR nanorubbers with intercalated structures were formulated and prepared by the melt-compounding method. The triacetin permeability and nitroglycerin absorption were observed to decrease with increasing layered-silicate content. The layered silicates also improved the flame retardancies of the nanorubbers by forming silicate reinforced carbonaceous chars. Layered-silicate reinforced EPDM/CR nanorubbers are potentially effective rocket propellant-inhibiting materials. Full article

(This article belongs to the Special Issue Synthesis, Characterization, and Applications of Polymer Nanocomposites)

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18 pages, 2066 KiB

Open AccessArticle

Production of Curcumin-Loaded Silk Fibroin Nanoparticles for Cancer Therapy

by Mercedes G. Montalbán, Jeannine M. Coburn, A. Abel Lozano-Pérez, José L. Cenis, Gloria Víllora and David L. Kaplan

Nanomaterials 2018, 8(2), 126; https://doi.org/10.3390/nano8020126 - 24 Feb 2018

Cited by 137 | Viewed by 10770

Abstract

Curcumin, extracted from the rhizome of Curcuma longa, has been widely used in medicine for centuries due to its anti-inflammatory, anti-cancer, anti-oxidant and anti-microbial effects. However, its bioavailability during treatments is poor because of its low solubility in water, slow dissolution rate and rapid intestinal metabolism. For these reasons, improving the therapeutic efficiency of curcumin using nanocarriers (e.g., biopolymer nanoparticles) has been a research focus, to foster delivery of the curcumin inside cells due to their small size and large surface area. Silk fibroin from the Bombyx mori silkworm is a biopolymer characterized by its biocompatibility, biodegradability, amphiphilic chemistry, and excellent mechanical properties in various material formats. These features make silk fibroin nanoparticles useful vehicles for delivering therapeutic drugs, such as curcumin. Curcumin-loaded silk fibroin nanoparticles were synthesized using two procedures (physical adsorption and coprecipitation) more scalable than methods previously described using ionic liquids. The results showed that nanoparticle formulations were 155 to 170 nm in diameter with a zeta potential of approximately −45 mV. The curcumin-loaded silk fibroin nanoparticles obtained by both processing methods were cytotoxic to carcinogenic cells, while not decreasing viability of healthy cells. In the case of tumor cells, curcumin-loaded silk fibroin nanoparticles presented higher efficacy in cytotoxicity against neuroblastoma cells than hepatocarcinoma cells. In conclusion, curcumin-loaded silk fibroin nanoparticles constitute a biodegradable and biocompatible delivery system with the potential to treat tumors by local, long-term sustained drug delivery. Full article

(This article belongs to the Special Issue Synthesis, Characterization, and Applications of Polymer Nanocomposites)

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Review

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21 pages, 7473 KiB

Open AccessReview

Natural Rubber Nanocomposites: A Review

by Liliane Bokobza

Nanomaterials 2019, 9(1), 12; https://doi.org/10.3390/nano9010012 - 22 Dec 2018

Cited by 114 | Viewed by 10170

Abstract

This paper reviews studies carried out on natural rubber filled with nanofillers such as spherical silica particles (generated by the sol gel reaction), clays and carbon nanostructures. It is shown that the mechanical response of NR is influenced by several parameters including the processing conditions, the state of filler dispersion, the polymer-filler interactions and the filler morphological aspects. Even if the sol gel process conducted in vulcanized rubber yields almost ideal dispersions, rod-shaped particles such as clay, carbon fibers or carbon nanotubes are by far more efficient in terms of mechanical reinforcement on account of their anisotropic character and their ability to orientate in the direction of stretch. The efficiency of layered fillers such as clays or graphitic structures clearly depends on the way they are dispersed (exfoliated) in the rubber. Complete exfoliation still remains difficult to achieve which limits the tremendous nanoreinforcement expected from a single layer of clay or graphite. In all cases, the onset of crystallization is observed at a lower strain value than that of the unfilled matrix due to strain amplification effects. Full article

(This article belongs to the Special Issue Synthesis, Characterization, and Applications of Polymer Nanocomposites)

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21 pages, 3041 KiB

Open AccessReview

Nanostructured Polymeric Materials with Protein-Repellent and Anti-Caries Properties for Dental Applications

by Ning Zhang, Ke Zhang, Xianju Xie, Zixiang Dai, Zeqing Zhao, Satoshi Imazato, Yousif A. Al-Dulaijan, Faisal D. Al-Qarni, Michael D. Weir, Mark A. Reynolds, Yuxing Bai, Lin Wang and Hockin H. K. Xu

Nanomaterials 2018, 8(6), 393; https://doi.org/10.3390/nano8060393 - 01 Jun 2018

Cited by 38 | Viewed by 5631

Abstract

Dental caries is prevalent worldwide. Tooth cavity restorations cost more than $46 billion annually in the United States alone. The current generation of esthetic polymeric restorations have unsatisfactory failure rates. Replacing the failed restorations accounts for 50–70% of all the restorations. This article reviewed developments in producing a new generation of bioactive and therapeutic restorations. This includes: Protein-repellent and anti-caries polymeric dental composites, especially the use of 2-methacryloyloxyethyl phosphorylcholine (MPC) and dimethylaminododecyl methacrylate (DMAHDM); protein-repellent adhesives to greatly reduce biofilm acids; bioactive cements to inhibit tooth lesions; combining protein-repellency with antibacterial nanoparticles of silver; tooth surface coatings containing calcium phosphate nanoparticles for remineralization; therapeutic restorations to suppress periodontal pathogens; and long-term durability of bioactive and therapeutic dental polymers. MPC was chosen due to its strong ability to repel proteins. DMAHDM was selected because it had the most potent antibacterial activity when compared to a series of antibacterial monomers. The new generation of materials possessed potent antibacterial functions against cariogenic and periodontal pathogens, and reduced biofilm colony-forming units by up to 4 logs, provided calcium phosphate ions for remineralization and strengthening of tooth structures, and raised biofilm pH from a cariogenic pH 4.5 to a safe pH 6.5. The new materials achieved a long-term durability that was significantly beyond current commercial control materials. This new generation of bioactive and nanostructured polymers is promising for wide applications to provide therapeutic healing effects and greater longevity for dental restorations. Full article

(This article belongs to the Special Issue Synthesis, Characterization, and Applications of Polymer Nanocomposites)

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