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Metal- and Metal Hybrid-Filled Polymer Nanocomposites

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

Deadline for manuscript submissions: closed (31 December 2020) | Viewed by 32694

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Prof. Dr. María Jesús Fernández

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Department of Polymer Science and Technology, University of the Basque Country UPV/EHU, 20018 San Sebastián, Spain
Interests: nanomaterials; synthesis and characterization of biodegradable polymer nanocomposites; graphene–metal and clay–metal hybrid materials; POSS; POSS–polymer hybrids

Prof. Dr. María Dolores Fernández

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Dear Colleagues,

Polymer nanocomposites have attracted considerable attention from both academic and industrial points of view owing to the enhanced properties that can be achieved for new materials as compared with unfilled polymers. Property enhancement depends on several factors, in particular on the dispersion state of the nanofiller. Metal nanoparticles are of great interest in nanotechnology due to their fascinating properties, small size, and surface plasmon behavior and are incorporated into polymer matrices to improve the performance properties. The method of incorporation of these nanoparticles is crucial since their properties are shape- and size-dependent. Metal-based hybrid fillers have been shown to be more effective in improving the performance of the nanocomposite than the individual components due to the synergetic effect. A wide range of applications has been found for metal nanoparticle composites that are dependent on the nanoparticle–polymer combination.

This Special Issue invites original papers and reviews reporting on recent progress in the following areas:

-Preparation methods for metal and metal oxide polymer nanocomposites;

-Preparation methods for metal hybrid polymer nanocomposites (clay–metal, carbon nanotubes–metal, graphene–metal);

-Morphology of metal nanoparticles, metal hybrids, and metal and metal hybrid polymer nanocomposites;

-Properties of metal and metal hybrid polymer nanocomposites;

-Applications of metal and metal hybrid polymer nanocomposites.

Prof. Dr. María Jesús Fernández
Prof. Dr. María Dolores Fernández
Guest Editors

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Keywords

Metal and metal oxide nanoparticles
Carbon–metal hybrids
Clay–metal hybrids
Synthesis and characterization
Properties
Applications
Biomedical applications
Environmental applications
Biosensing applications
Food packaging applications

Published Papers (10 papers)

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Research

19 pages, 3554 KiB

Open AccessArticle

New Construction of Functionalized CuO/Al₂O₃ Nanocomposite-Based Polymeric Sensor for Potentiometric Estimation of Naltrexone Hydrochloride in Commercial Formulations

by Amal M. Al-Mohaimeed, Gamal A. E. Mostafa and Maha F. El-Tohamy

Polymers 2021, 13(24), 4459; https://0-doi-org.brum.beds.ac.uk/10.3390/polym13244459 - 20 Dec 2021

Cited by 6 | Viewed by 2772

Abstract

Electrically conductive polymeric nanocomposites with nanoparticles are adaptable types of nanomaterials that are prospective for various applications. The extraordinary features of copper oxide (CuO) and aluminium oxide (Al₂O₃) nanostructures, encourages extensive studies to prospect these metal oxide nanocomposites as potential electroactive materials in sensing and biosensing applications. This study suggested a new CuO/Al₂O₃ nanocomposite-based polymeric coated wire membrane sensor for estimating naltrexone hydrochloride (NTX) in commercial formulations. Naltrexone hydrochloride and sodium tetraphenylborate (Na-TPB) were incorporated in the presence of polymeric polyvinyl chloride (PVC) and solvent mediator o-nitrophenyloctyl ether (o-NPOE) to form naltrexone tetraphenylborate (NTX-TPB) as an electroactive material. The modified sensor using NTX-TPB-CuO/Al₂O₃ nanocomposite displayed high selectivity and sensitivity for the discrimination and quantification of NTX with a linearity range 1.0 × 10⁻⁹–1.0 × 10⁻² mol L⁻¹ and a regression equation E_mV = (58.25 ± 0.3) log [NTX] + 754.25. Contrarily, the unmodified coated wire sensor of NTX-TPB exhibited a Nernstian response at 1.0 × 10⁻⁵–1.0 × 10⁻² mol L⁻¹ and a regression equation E_mV = (52.1 ± 0.2) log [NTX] + 406.6. The suggested modified potentiometric system was validated with respect to various criteria using the methodology recommended guidelines. Full article

(This article belongs to the Special Issue Metal- and Metal Hybrid-Filled Polymer Nanocomposites)

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19 pages, 4894 KiB

Open AccessArticle

Tribo-Mechanical Properties of the Antimicrobial Low-Density Polyethylene (LDPE) Nanocomposite with Hybrid ZnO–Vermiculite–Chlorhexidine Nanofillers

by Karla Čech Barabaszová, Sylva Holešová, Marianna Hundáková and Alena Kalendová

Polymers 2020, 12(12), 2811; https://0-doi-org.brum.beds.ac.uk/10.3390/polym12122811 - 27 Nov 2020

Cited by 10 | Viewed by 2093

Abstract

Materials made from low-density polyethylene (LDPE) in the form of packages or catheters are currently commonly applied medical devices. Antimicrobial LDPE nanocomposite materials with two types of nanofillers, zinc oxide/vermiculite (ZnO/V) and zinc oxide/vermiculite_chlorhexidine (ZnO/V_CH), were prepared by a melt-compounded procedure to enrich their controllable antimicrobial, microstructural, topographical and tribo-mechanical properties. X-ray diffraction (XRD) analysis and Fourier transform infrared spectroscopy (FTIR) revealed that the ZnO/V and ZnO/V_CH nanofillers and LDPE interacted well with each other. The influence of the nanofiller concentrations on the LDPE nanocomposite surface changes was studied through scanning electron microscopy (SEM), and the surface topology and roughness were studied using atomic force microscopy (AFM). The effect of the ZnO/V nanofiller on the increase in indentation hardness (HIT) was evaluated by AFM measurements and the Vickers microhardness (HV), which showed that as the concentration of the ZnO/V nanofiller increased, these values decreased. The ZnO/V and ZnO/V_CH nanofillers, regardless of the concentration in the LDPE matrix, slightly increased the average values of the friction coefficient (COF). The abrasion depths of the wear indicated that the LDPE_ZnO/V nanocomposite plates exhibited better wear resistance than LDPE_ZnO/V_CH. Higher HV and HIT microhardness values were measured for both nanofillers than the natural LDPE nanocomposite plate. Very positive antimicrobial activity against S. aureus and P. aeruginosa after 72 h was found for both nanofiller types. Full article

(This article belongs to the Special Issue Metal- and Metal Hybrid-Filled Polymer Nanocomposites)

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8 pages, 1862 KiB

Open AccessCommunication

Enhanced Olefin Transport by SiO₂ Particles for Polymer/Ag Metal/Electron Acceptor Composite Membranes

by Sang Wook Kang

Polymers 2020, 12(10), 2316; https://0-doi-org.brum.beds.ac.uk/10.3390/polym12102316 - 10 Oct 2020

Cited by 1 | Viewed by 1332

Abstract

We showed the potential of poly(ethylene-co-propylene) (EPR)/silver metal/p-benzoquinone composite membranes for propylene/propane mixtures, i.e., a selectivity of 10 and a mixed gas permeance of 0.5 GPU (1 GPU = 1 × 10⁻⁶ cm³ (STP)/(cm² s cmHg) in a previous study. In this study, we additionally found that the incorporation of fumed silica nanoparticles into EPR/silver metal/p-benzoquinone (p-BQ) composite membranes exhibited much higher permeance and selectivity for propylene/propane mixtures. The positive polarity of silver metal continuously increased with the increasing silica content up to the 0.1 weight ratio, as revealed by x-ray photoelectron spectroscopy (XPS). This increase in the polarity of silver metal was attributed to the enhanced interaction of p-BQ with the surface of Ag nanoparticles by the increased dispersion of p-BQ by fumed silica nanoparticles. Differential scanning calorimetry (DSC) also presented that the glass transition temperature (T_g) of the membranes was almost invariant. Therefore, the improvement of the permeance and selectivity with the silica nanoparticles was attributable to the increased polarity of the silver metal rather than the structural change. Full article

(This article belongs to the Special Issue Metal- and Metal Hybrid-Filled Polymer Nanocomposites)

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26 pages, 9049 KiB

Open AccessArticle

Aluminum-Filled Amorphous-PET, a Composite Showing Simultaneous Increase in Modulus and Impact Resistance

by Arfat Anis, Ahmed Yagoub Elnour, Mohammad Asif Alam, Saeed M. Al-Zahrani, Fayez AlFayez and Zahir Bashir

Polymers 2020, 12(9), 2038; https://0-doi-org.brum.beds.ac.uk/10.3390/polym12092038 - 08 Sep 2020

Cited by 17 | Viewed by 4590

Abstract

Metal-plastic composites have the potential to combine enhanced electrical and thermal conductivity with a lower density than a pure metal. The drawback has often been brittleness and low impact resistance caused by weak adhesion between the metal filler and the plastic. Based on our observation that aluminum foil sticks very strongly to poly(ethylene terephthalate) (PET) if it is used as a backing during compression moulding, this work set out to explore PET filled with a micro and a nano aluminum (Al) powder. In line with other composites using filler particles with low aspect-ratio, the tensile modulus increased somewhat with loading. However, unlike most particle composites, the strength did not decrease and most surprisingly, the Izod impact resistance increased, and in fact more than doubled with certain compositions. Thus, the Al particles acted as a toughening agent without decreasing the modulus and strength. This would be the first case where addition of a metal powder to a plastic increased the modulus and impact resistance simultaneously. The Al particles also acted as nucleating agents but it was not sufficient to make PET crystallize as fast as the injection moulding polyester, poly(butylene terephthalate) (PBT). Full article

(This article belongs to the Special Issue Metal- and Metal Hybrid-Filled Polymer Nanocomposites)

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14 pages, 12127 KiB

Open AccessArticle

Preparation of Antimicrobial Fibres from the EVOH/EPC Blend Containing Silver Nanoparticles

by Dorota Biniaś, Włodzimierz Biniaś, Alicja Machnicka and Monika Hanus

Polymers 2020, 12(8), 1827; https://0-doi-org.brum.beds.ac.uk/10.3390/polym12081827 - 14 Aug 2020

Cited by 5 | Viewed by 2579

Abstract

The article presents a new fabrication method for bioactive fibres with a microporous structure of ethylene–vinyl alcohol copolymers (EVOH)/ethylene−propylene copolymer (EPC) blends. The experimental work carried out resulted in obtaining EVOH/EPC polymer blends fibres with the addition of glycerol and sodium stearate. Different concentrations of glycerol (38%, 32%) and sodium stearate (2%, 8%) were used to prepare the fibres. The purpose of using different concentrations of stearate and glycerol was to evaluate the effect of additives on the structure and properties of the fibres. A significant influence of the additives used on the morphological structure of the fibres was found. The resulting fibres were modified with an AgNO₃ solution and reduced to silver nanoparticles (AgNPs), to give the fibres bioactive properties. The fibres obtained with the addition of 8% stearate have a more developed surface, which may influence the amount of adsorbed silver particles inside the fibre. However, the durability of depositing silver particles after multiple washes has not been tested. Three types of microorganisms were selected to assess the microbiological activity of the obtained fibres, i.e., Gram-positive Staphylococcus aureus and Gram-negative Pseudomonas aeruginosa and Escherichia coli. The fibres have antibacterial activity against gram positive and negative bacteria. The largest inhibition zones were obtained for gram-positive bacteria Staphylococcus aureus, ranging from 3 to 10 mm depending on the concentration of AgNPs. The morphology of the blends fibres was characterized by scanning electron microscopy (SEM) and optical microscopy (OM). The occurrence of elemental silver was analysed by energy dispersive spectroscopy (EDS) analysis. The changes of the polymer structure chemistry are studied by Fourier transform infrared spectroscopy (FTIR). Full article

(This article belongs to the Special Issue Metal- and Metal Hybrid-Filled Polymer Nanocomposites)

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15 pages, 3525 KiB

Open AccessArticle

Doxorubicin–Gelatin/Fe₃O₄–Alginate Dual-Layer Magnetic Nanoparticles as Targeted Anticancer Drug Delivery Vehicles

by Chiung-Hua Huang, Ting-Ju Chuang, Cherng-Jyh Ke and Chun-Hsu Yao

Polymers 2020, 12(8), 1747; https://0-doi-org.brum.beds.ac.uk/10.3390/polym12081747 - 05 Aug 2020

Cited by 30 | Viewed by 4151

Abstract

In this study, magnetic nanoparticles composed of a core (doxorubicin–gelatin) and a shell layer (Fe₃O₄–alginate) were developed to function as targeted anticancer drug delivery vehicles. The anticancer drug doxorubicin (DOX) was selected as a model drug and embedded in the inner gelatin core to obtain high encapsulation efficiency. The advantage of the outer magnetic layer is that it targets the drug to the tumor tissue and provides controlled drug release. The physicochemical properties of doxorubicin–gelatin/Fe₃O₄–alginate nanoparticles (DG/FA NPs) were characterized using scanning electron microscopy, Fourier transform infrared spectroscopy (FTIR), and X-ray diffraction. The mean diameter of DG/FA NPs, which was determined using a zeta potential analyzer, was 401.8 ± 3.6 nm. The encapsulation rate was 64.6 ± 11.8%. In vitro drug release and accumulation were also studied. It was found that the release of DOX accelerated in an acidic condition. With the manipulation of an external magnetic field, DG/FA NPs efficiently targeted Michigan Cancer Foundation-7 (MCF-7) breast cancer cells and showed in the nucleus after 6 h of incubation. After 12 h of incubation, the relative fluorescence intensity reached 98.4%, and the cell viability of MCF-7 cells decreased to 52.3 ± 4.64%. Dual-layer DG/FA NPs could efficiently encapsulate and deliver DOX into MCF-7 cells to cause the death of cancer cells. The results show that DG/FA NPs have the potential for use in targeted drug delivery and cancer therapy. Full article

(This article belongs to the Special Issue Metal- and Metal Hybrid-Filled Polymer Nanocomposites)

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14 pages, 3616 KiB

Open AccessArticle

Luminescent Properties of Lanthanoid-Poly(Sodium Acrylate) Composites: Insights on the Interaction Mechanism

by Alan F. Y. Matsushita, María José Tapia, Alberto A. C. C. Pais and Artur J. M. Valente

Polymers 2020, 12(6), 1314; https://0-doi-org.brum.beds.ac.uk/10.3390/polym12061314 - 09 Jun 2020

Cited by 5 | Viewed by 2047

Abstract

The interaction between polyelectrolytes and metal ions is governed by different types of interactions, leading to the formation of different phases, from liquid state to weak gels, through an appropriate choice of metal ion/polyelectrolyte molar ratio. We have found that lanthanide ions, europium(III) and terbium(III), are able to form polymer composites with poly(sodium acrylate). That interaction enhances the luminescent properties of europium(III) and terbium(III), showing that Eu³⁺/poly(sodium acrylate) (PSA) and Tb³⁺/PSA composites have a highly intense red and green emission, respectively. The effect of cations with different valences on the luminescent properties of the polymer composites is analyzed. The presence of metal ions tends to quench the composite emission intensity and the quenching process depends on the cation, with copper(II) being by far the most efficient quencher. The interaction mechanism between lanthanoid ions and PSA is also discussed. The composites and their interactions with a wide range of cations and anions are fully characterized through stationary and non-stationary fluorescence, high resolution scanning electronic microscopy and X-ray diffraction. Full article

(This article belongs to the Special Issue Metal- and Metal Hybrid-Filled Polymer Nanocomposites)

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18 pages, 15255 KiB

Open AccessEditor’s ChoiceArticle

Synthesis, Physical, Mechanical and Antibacterial Properties of Nanocomposites Based on Poly(vinyl alcohol)/Graphene Oxide–Silver Nanoparticles

by Mónica Cobos, Iker De-La-Pinta, Guillermo Quindós, María Jesús Fernández and María Dolores Fernández

Polymers 2020, 12(3), 723; https://0-doi-org.brum.beds.ac.uk/10.3390/polym12030723 - 24 Mar 2020

Cited by 72 | Viewed by 5026

Abstract

The design of new materials with antimicrobial properties has emerged in response to the need for preventing and controlling the growth of pathogenic microorganisms without the use of antibiotics. In this study, partially reduced graphene oxide decorated with silver nanoparticles (GO–AgNPs) was incorporated as a reinforcing filler with antibacterial properties to poly(vinyl alcohol) (PVA) for preparation of poly(vinyl alcohol)/graphene oxide-silver nanoparticles nanocomposites (PVA/GO–AgNPs). AgNPs, spherical in shape and with an average size of 3.1 nm, were uniformly anchored on the partially reduced GO surface. PVA/GO–AgNPs nanocomposites showed exfoliated structures with improved thermal stability, tensile properties and water resistance compared to neat PVA. The glass transition and crystallization temperatures of the polymer matrix increased with the incorporation of the hybrid. The nanocomposites displayed antibacterial activity against Staphylococcus aureus and Escherichia coli in a filler content- and time-dependent manner. S. aureus showed higher susceptibility to PVA/GO–AgNPs films than E. coli. Inhibitory activity was higher when bacterial cells were in contact with nanocomposite films than when in contact with leachates coming out of the films. GO–AgNPs based PVA nanocomposites could find application as wound dressings for wound healing and infection prevention. Full article

(This article belongs to the Special Issue Metal- and Metal Hybrid-Filled Polymer Nanocomposites)

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19 pages, 7486 KiB

Open AccessArticle

Surface and Structural Properties of Medical Acrylonitrile Butadiene Styrene Modified with Silver Nanoparticles

by Magdalena Ziąbka, Michał Dziadek and Kinga Pielichowska

Polymers 2020, 12(1), 197; https://0-doi-org.brum.beds.ac.uk/10.3390/polym12010197 - 12 Jan 2020

Cited by 7 | Viewed by 4124

Abstract

Acrylonitrile butadiene styrene/silver nanoparticles (ABS/AgNPs) composites were manufactured through the plastic processing method. Three different matrices were used to obtain polymer and composite samples containing 0.5 wt % and 1.0 wt % of silver nanoparticles, respectively. The aim of this study was to examine physicochemical properties and stability of the materials in the in vitro conditions for two years. The results showed that composites made from amorphous matrices had comparable mechanical properties after incorporation of AgNPs. The values of Young modulus and tensile strength increased after the first and second year of investigation. Silver nanoparticles did not alter the surface parameters—e.g., roughness and contact angle also retained stable values after the in vitro incubation in water solution. The scanning electron observation revealed homogeneous distribution of silver modifier in all the matrices. The 24-month incubation of materials proved the stability of the composites microstructure. The DSC analysis revealed that addition of AgNPs may decrease glass transition temperature of the composite materials which was also reduced after 12 and 24 months of incubation. The attenuated total reflectance–Fourier transform infrared (ATR-FTIR) spectroscopic studies did not indicate significant changes in the ABS matrices either upon their modification with AgNPs or after the long-term testing. The conducted studies proved that all the composites are stable and may be used for a long-term working period. Full article

(This article belongs to the Special Issue Metal- and Metal Hybrid-Filled Polymer Nanocomposites)

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14 pages, 3270 KiB

Open AccessArticle

Long-Lasting Examinations of Surface and Structural Properties of Medical Polypropylene Modified with Silver Nanoparticles

by Magdalena Ziąbka and Michał Dziadek

Polymers 2019, 11(12), 2018; https://0-doi-org.brum.beds.ac.uk/10.3390/polym11122018 - 05 Dec 2019

Cited by 9 | Viewed by 3162

Abstract

Composite materials based on polypropylene modified with silver nanoparticles (PP/AgNPs) were manufactured using injection molding and extrusion. Two different matrices were used to prepare the samples consisting of 0.5 and 1.0 wt. % of silver nanoparticles, respectively. The aim of this study was to assess whether silver nanoparticles (AgNPs) could influence the stability of a polymer matrix during the 24-month period of the in vitro testing. The results indicated that composites with silver nanoparticles displayed the significantly higher Young modulus and tensile strength after the first and second year of investigation. Moreover, the incorporation of nanoparticles into the matrix slightly increased the roughness and contact angle values and the parameters remained stable after the in vitro incubation. The two-year immersion of materials in the deionized water proved that the microstructure of composites did not change. The DSC analysis revealed that the material incubation resulted in a slight reduction in the melting temperature and degree of crystallinity of PP. The addition of nanoparticles to polymer matrices led to the increase in content of β crystals in the crystalline phase of PP, which was revealed in the long-term in vitro tests. The XRD measurement also showed the heightened surface crystallinity. The conducted studies have proved that all composites are stable over a period of 24 months. Such behavior suggests that the tested materials can be used as biomaterials. Full article

(This article belongs to the Special Issue Metal- and Metal Hybrid-Filled Polymer Nanocomposites)

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