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Nanocomposites of Polymers and Inorganic Particles

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A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Nanochemistry".

Deadline for manuscript submissions: closed (31 October 2019) | Viewed by 43372

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Dr. Marinella Striccoli

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Institute for Physical and Chemical Processes, IPCF-National Research Council, CNR, Bari Division, c/o Chemistry Department, University of Bari “Aldo Moro”, 70125 Bari, Italy
Interests: nanomaterials; colloidal nanoparticles; quantum dots; carbon dots; perovskite nanocrystals; hybrids; nanocomposites; optical properties; self assembly and nanocrystal organization; chemical functionalization
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Prof. Dr. Roberto Comparelli

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National Research Council–Institute for Physical Chemical Processes (CNR-IPCF), Bari, Italy
Interests: photocatalysis; visible light active photocatalysts; inorganic nanocrystals; hybrid nanocomposites; plasmonics nanoparticles; nanocrystal functionalization; solar energy conversion
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Dr. Annamaria Panniello

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CNR-IPCF Division of Bari, Bari, Italy
Interests: nanomaterials; nanocomposites; organic-inorganic hybrids; carbon nanoparticles; surface functionalization; spectroscopy
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Dear Colleagues,

In the last few years, significant efforts have been devoted to design, fabricate and exploit nanocomposite materials based on inorganic nanoparticles incorporated in a polymer matrix. The extraordinary interest in such materials relies on the large range of properties that can arise from the synergic combination of the features of nanoparticles and host polymer. Indeed, the original size dependent physical and chemical properties of nanomaterials (semicondunting, metals, oxides and magnetic nanoparticles), joint with the high processability, the defined chemistry and the morphology of polymers and block copolymers, finally turn out in innovative materials, with high technological impact in a variety of advanced application in photonic, optoelectronics, sensing, environmental, energy conversion, biological and biomedical fields.

The aim of the Special Issue is to focus on recent developments, advancements and future prospectives of such a fascinating and largely multidisciplinar field. Topics will include preparative approaches, functionalization strategies of nanoparticles and polymers, integration of nanocomposites in devices, additive manufacturing materials and processes and nanocomposite advanced application. Authors are welcomed to provide their contribution on the aforementioned aspects and on other subjects relevant for the theme. Review articles will be also welcome.

Dr. Marinella Striccoli
Dr. Roberto Comparelli
Dr. Annamaria Panniello
Guest Editors

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Keywords

Inorganic nanoparticles
Nanocrystals
Polymers
Hybrid nanostructures
Nano-fillers
Matrix
Multiphases

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Published Papers (9 papers)

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Research

9 pages, 2800 KiB

Open AccessArticle

Fabrication of Spherical Titania Inverse Opal Structures Using Electro-Hydrodynamic Atomization

by Jong-Min Lim and Sehee Jeong

Molecules 2019, 24(21), 3905; https://doi.org/10.3390/molecules24213905 - 30 Oct 2019

Cited by 1 | Viewed by 4168

Abstract

Spherical PS/HEMA opal structure and spherical titania inverse opal structure were fabricated by self-assembly of colloidal nanoparticles in uniform aerosol droplets generated with electro-hydrodynamic atomization method. When a solution of PS/HEMA nanoparticles with uniform size distribution was used, PS/HEMA nanoparticles self-assembled into a face-centered cubic (FCC) structure by capillary force with the evaporation of the solvent in aerosol droplet, resulting in a spherical opal structure. When PS/HEMA nanoparticles and anatase titania nanoparticles were dispersed simultaneously into the solution, titania nanoparticles with relatively smaller size were assembled at the interstitial site of PS/HEMA nanoparticles packed in the FCC structure, resulting in a spherical opal composite structure. Spherical titania inverse opal structure was fabricated after removing PS/HEMA nanoparticles from the spherical opal composite structure by calcination. Full article

(This article belongs to the Special Issue Nanocomposites of Polymers and Inorganic Particles)

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15 pages, 5582 KiB

Open AccessArticle

Magnetic Polyurea Nano-Capsules Synthesized via Interfacial Polymerization in Inverse Nano-Emulsion

by Suzana Natour, Anat Levi-Zada and Raed Abu-Reziq

Molecules 2019, 24(14), 2663; https://doi.org/10.3390/molecules24142663 - 23 Jul 2019

Cited by 14 | Viewed by 6432

Abstract

Polyurea (PU) nano-capsules have received voluminous interest in various fields due to their biocompatibility, high mechanical properties, and surface functionality. By incorporating magnetic nanoparticle (MNPs) into the polyurea system, the attributes of both PU and MNPs can be combined. In this work, we describe a facile and quick method for preparing magnetic polyurea nano-capsules. Encapsulation of ionic liquid-modified magnetite nanoparticles (MNPs), with polyurea nano-capsules (PU NCs) having an average size of 5–20 nm was carried out through interfacial polycondensation between amine and isocyanate monomers in inverse nano-emulsion (water-in-oil). The desired magnetic PU NCs were obtained utilizing toluene and triple-distilled water as continuous and dispersed phases respectively, polymeric non-ionic surfactant cetyl polyethyleneglycol/polypropyleneglycol-10/1 dimethicone (ABIL EM 90), diethylenetriamine, ethylenediamine diphenylmethane-4,4′-diisocyanate, and various percentages of the ionic liquid-modified MNPs. High loading of the ionic liquid-modified MNPs up to 11 wt% with respect to the dispersed aqueous phase was encapsulated. The magnetic PU NCs were probed using various analytical instruments including electron microscopy, infrared spectroscopy, X-ray diffraction, and nuclear magnetic spectroscopy. This unequivocally manifested the successful synthesis of core-shell polyurea nano-capsules even without utilizing osmotic pressure agents, and confirmed the presence of high loading of MNPs in the core. Full article

(This article belongs to the Special Issue Nanocomposites of Polymers and Inorganic Particles)

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12 pages, 3075 KiB

Open AccessArticle

Polymerization Assisted by Upconversion Nanoparticles under NIR Light

by Polina Demina, Natalya Arkharova, Ilya Asharchuk, Kirill Khaydukov, Denis Karimov, Vasilina Rocheva, Andrey Nechaev, Yuriy Grigoriev, Alla Generalova and Evgeny Khaydukov

Molecules 2019, 24(13), 2476; https://doi.org/10.3390/molecules24132476 - 5 Jul 2019

Cited by 23 | Viewed by 5015

Abstract

Photopolymerization of nanocomposite materials using near infrared light is one of the unique technologies based on the luminescent properties of lanthanide-doped upconversion nanoparticles (UCNPs). We explored the UCNP-triggered radical polymerization both in oligomer bulk and on the nanoparticle surface in aqueous dispersion. Core/shell UCNPs NaYF₄:Yb³⁺ and Tm³⁺/NaYF₄ with emitting lines in the ultraviolet and blue regions were used to activate a photoinitiator. The study of the bulk photopolymerization in an initially homogeneous reaction mixture showed the UCNP redistribution due to gradient density occurring in the volume, which led to formation of UCNP superlattices and spheres “frozen” in a polymer matrix. We also developed a strategy of “grafting from” the surface, providing polymer shell growth directly on the nanoparticles. The photosensitization of the endogenous water-soluble photoinitiator riboflavin by the resonance energy transfer from UCNPs was demonstrated in the course of monomer glycidyl methacrylate polymerization followed by photocrosslinking with poly(ethylene glycol) diacrylate on the nanoparticle surface. Full article

(This article belongs to the Special Issue Nanocomposites of Polymers and Inorganic Particles)

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14 pages, 2186 KiB

Open AccessArticle

Polyolefin/ZnO Composites Prepared by Melt Processing

by Alojz Anžlovar, Mateja Primožič, Iztok Švab, Maja Leitgeb, Željko Knez and Ema Žagar

Molecules 2019, 24(13), 2432; https://doi.org/10.3390/molecules24132432 - 2 Jul 2019

Cited by 6 | Viewed by 3470

Abstract

Composites of polyolefin matrices (HDPE and PP) were prepared by melt processing using two commercially available nano ZnO powders (Zinkoxyd aktiv and Zano 20). The mechanical and thermal properties, UV-Vis stability, and antibacterial activity of composites were studied. Tensile testing revealed that both nano ZnO types have no particular effect on the mechanical properties of HDPE composites, while some positive trends are observed for the PP-based composites, but only when Zano 20 was used as a nanofiller. Minimal changes in mechanical properties of composites are supported by an almost unaffected degree of crystallinity of polymer matrix. All polyolefin/ZnO composites exposed to artificial sunlight for 8–10 weeks show more pronounced color change than pure matrices. This effect is more evident for the HDPE than for the PP based composites. Color change also depends on the ZnO concentration and type; composites with Zano 20 show more intense color changes than those prepared with Zinkoxyd aktiv. Results of the antibacterial properties study show very high activity of polyolefin/ZnO composites against Staphylococcus aureus regardless of the ZnO surface modification, while antibacterial activity against Escherichia coli shows only the composites prepared with unmodified ZnO. This phenomenon is explained by different membrane structure of gram-positive (S. aureus) and gram-negative (E. coli) bacteria. Full article

(This article belongs to the Special Issue Nanocomposites of Polymers and Inorganic Particles)

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19 pages, 7316 KiB

Open AccessArticle

The Influence of Graft Length and Density on Dispersion, Crystallisation and Rheology of Poly(ε-caprolactone)/Silica Nanocomposites

by Maria Eriksson, Joris Hamers, Ton Peijs and Han Goossens

Molecules 2019, 24(11), 2106; https://doi.org/10.3390/molecules24112106 - 3 Jun 2019

Cited by 14 | Viewed by 3780

Abstract

Different techniques of grafting polymer chains to filler surfaces are often employed to compatibilise filler and polymer matrices. In this paper the influence of graft length and graft density on the state of dispersion, crystallisation and rheological properties of poly(ε-caprolactone) (PCL)/silica (SiO₂) nanocomposites are reported. Grafted silica nanoparticles were prepared through polymerisation of PCL from the nanoparticle surface. Graft length was controlled by the reaction time, while the grafting density was controlled by the monomer-to-initiator ratio. Grafted nanoparticles were mixed with PCL of different molecular weights and the state of dispersion was assessed. Different matrix-to-graft molecular weight ratios resulted in different states of dispersion. Composites based on the higher molecular weight matrix exhibited small spherical agglomerates while the lower molecular weight matrix revealed more sheet-like microstructures. The state of dispersion was found to be relatively independent of graft length and density. Under quiescent conditions the grafts showed increased nucleation ability in the higher molecular weight PCL, while in the lower molecular weight matrix the effect was less pronounced. Rheological experiments showed an increase in viscosity with increased filler content, which was beneficial for the formation of oriented structures in shear-induced crystallisation. Full article

(This article belongs to the Special Issue Nanocomposites of Polymers and Inorganic Particles)

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9 pages, 2214 KiB

Open AccessArticle

Vacuum Casting and Mechanical Characterization of Nanocomposites from Epoxy and Oxidized Multi-Walled Carbon Nanotubes

by Gerald Singer, Philipp Siedlaczek, Gerhard Sinn, Patrick H. Kirner, Reinhard Schuller, Roman Wan-Wendner and Helga C. Lichtenegger

Molecules 2019, 24(3), 510; https://doi.org/10.3390/molecules24030510 - 31 Jan 2019

Cited by 5 | Viewed by 3240

Abstract

Sample preparation is an important step when testing the mechanical properties of materials. Especially, when carbon nanotubes (CNT) are added to epoxy resin, the increase in viscosity complicates the casting of testing specimens. We present a vacuum casting approach for different geometries in order to produce specimens from functional nanocomposites that consist of epoxy matrix and oxidized multi-walled carbon nanotubes (MWCNTs). The nanocomposites were characterized with various mechanical tests that showed improved fracture toughness, bending and tensile properties performance by addition of oxidized MWCNTs. Strengthening mechanisms were analyzed by SEM images of fracture surfaces and in-situ imaging by digital image correlation (DIC). Full article

(This article belongs to the Special Issue Nanocomposites of Polymers and Inorganic Particles)

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11 pages, 4450 KiB

Open AccessArticle

Polydopamine-Based Surface Modification of ZnO Nanoparticles on Sericin/Polyvinyl Alcohol Composite Film for Antibacterial Application

by Lisha Ai, Yejing Wang, Gang Tao, Ping Zhao, Ahmad Umar, Peng Wang and Huawei He

Molecules 2019, 24(3), 503; https://doi.org/10.3390/molecules24030503 - 30 Jan 2019

Cited by 32 | Viewed by 4726

Abstract

Silk sericin (SS) is a type of natural macromolecular protein with excellent hydrophilicity, biocompatibility and biodegradability, but also has very poor mechanical properties. To develop sericin-based wound dressings, we utilized polyvinyl alcohol (PVA) to reinforce the mechanical property of sericin by blending PVA and sericin, then modified zinc oxide nanoparticles (ZnO NPs) on SS/PVA film with the assistance of polydopamine (PDA) to endow SS/PVA film with antibacterial activity. Scanning electron microscopy, energy dispersive spectroscopy and X-ray powder diffraction demonstrated ZnO NPs were well grafted on PDA-SS/PVA film. Fourier transform infrared spectra suggested PDA coating and ZnONPs modification did not alter the structure of sericin and PVA. Water contact angle and swelling tests indicated the excellent hydrophilicity and swellability of ZnO NPs-PDA-SS/PVA composite film. Mass loss analysis showed ZnO NPs-PDA-SS/PVA film had excellent stability. The mechanical performance test suggested the improved tensile strength and elongation at break could meet the requirement of ZnO NPs-PDA-SS/PVA film in biomaterial applications. The antibacterial assay suggested the prepared ZnO NPs-PDA-SS/PVA composite film had a degree of antimicrobial activity against Escherichia coli and Staphylococcus aureus. The excellent hydrophilicity, swellability, stability, mechanical property and antibacterial activity greatly promote the possibility of ZnO NPs-PDA-SS/PVA composite film in antibacterial biomaterials application. Full article

(This article belongs to the Special Issue Nanocomposites of Polymers and Inorganic Particles)

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12 pages, 3295 KiB

Open AccessArticle

Effect of CaCO₃ Nanoparticles on the Mechanical and Photo-Degradation Properties of LDPE

by Paula A. Zapata, Humberto Palza, Boris Díaz, Andrea Armijo, Francesca Sepúlveda, J. Andrés Ortiz, Maria Paz Ramírez and Claudio Oyarzún

Molecules 2019, 24(1), 126; https://doi.org/10.3390/molecules24010126 - 31 Dec 2018

Cited by 42 | Viewed by 5491

Abstract

CaCO₃ nanoparticles of around 60 nm were obtained by a co-precipitation method and used as filler to prepare low-density polyethylene (LDPE) composites by melt blending. The nanoparticles were also organically modified with oleic acid (O-CaCO₃) in order to improve their interaction with the LDPE matrix. By adding 3 and 5 wt% of nanofillers, the mechanical properties under tensile conditions of the polymer matrix improved around 29%. The pure LDPE sample and the nanocomposites with 5 wt% CaCO₃ were photoaged by ultraviolet (UV) irradiation during 35 days and the carbonyl index (CI), degree of crystallinity (χ_c), and Young’s modulus were measured at different times. After photoaging, the LDPE/CaCO₃ nanocomposites increased the percent crystallinity (χ_c), the CI, and Young’s modulus as compared to the pure polymer. Moreover, the viscosity of the photoaged nanocomposite was lower than that of photoaged pure LDPE, while scanning electron microscopy (SEM) analysis showed that after photoaging the nanocomposites presented cavities around the nanoparticles. These difference showed that the presence of CaCO₃ nanoparticles accelerate the photo-degradation of the polymer matrix. Our results show that the addition of CaCO₃ nanoparticles into an LDPE polymer matrix allows future developments of more sustainable polyethylene materials that could be applied as films in agriculture. These LDPE-CaCO₃ nanocomposites open the opportunity to improve the low degradation of the LDPE without sacrificing the polymer’s behavior, allowing future development of novel eco-friendly polymers. Full article

(This article belongs to the Special Issue Nanocomposites of Polymers and Inorganic Particles)

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14 pages, 5004 KiB

Open AccessArticle

A Novel AgNPs/Sericin/Agar Film with Enhanced Mechanical Property and Antibacterial Capability

by Yejing Wang, Rui Cai, Gang Tao, Peng Wang, Hua Zuo, Ping Zhao, Ahmad Umar and Huawei He

Molecules 2018, 23(7), 1821; https://doi.org/10.3390/molecules23071821 - 23 Jul 2018

Cited by 37 | Viewed by 6125

Abstract

Silk sericin is a protein from a silkworm’s cocoon. It has good biocompatibility, hydrophilicity, bioactivity, and biodegradability. However, sericin could not be used in biomedical materials directly because of its frangible characteristic. To develop multifunctional sericin-based materials for biomedical purposes, we prepared a sericin/agar (SS/agar) composite film through the blending of sericin and agar and repetitive freeze-thawing. Then, we synthesized silver nanoparticles (AgNPs) in situ on the surface of the composite film to endow it with antibacterial activity. Water contact angle, swelling and losing ratio, and mechanical properties analysis indicated that the composite film had excellent mechanical property, hydrophilicity, hygroscopicity, and stability. Scanning electron microscopy and X-ray photoelectron spectroscopy analysis confirmed the successful modification of AgNPs on the composite film. X-ray powder diffraction showed the face-centered cubic structures of the AgNPs. This AgNPs modified composite film exhibited an excellent antibacterial capability against Escherichia coli and Staphylococcus aureus. Our study develops a novel AgNPs/sericin/agar composite film with enhanced mechanical performance and an antimicrobial property for potential biomedical applications. Full article

(This article belongs to the Special Issue Nanocomposites of Polymers and Inorganic Particles)

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