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Nanocomposites of Polymers and Inorganic Particles 2016

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A special issue of Polymers (ISSN 2073-4360).

Deadline for manuscript submissions: closed (30 October 2016) | Viewed by 101417

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Prof. Dr. Walter Remo Caseri

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Department of Materials, ETH Zürich, HCI F 515, Vladimir-Prelog-Weg 5, CH-8093 Zürich, Switzerland
Interests: inorganic polymers; organometallic polymers; nanocomposites
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Special Issue Information

Dear Colleagues,

Nanocomposites of polymers and inorganic particles offer a tremendous spectrum of properties and (potential) applications due to the versatility of combinations of characteristics of polymers and inorganic materials. Thus, generation of uncommon (multifunctional) materials with tailored characteristics can be created for a multitude of future technologies. In addition to this, general effects inherent in nanoparticles, peculiarities of nanocomposites, are also promoted by size-dependent properties of inorganic nanoparticles, by incorporation of anisotropic particles (e.g., rods or platelets), or by orientation. Over all, nanocomposites can be obtained with properties that are not inherent in corresponding composites with particles in the micrometer range or above. Accordingly, nanocomposites have found pronounced attention in various core scientific disciplines, such as chemistry, physics, biology (including biomedicine), and materials science. Considerable research has been undertaken with a view to widen the basic understanding of nanocomposites in all areas, and, on the other hand, novel (potential) applications are also envisaged in scientific studies.

This Special Issue addresses all kinds and aspects of nanocomposites comprising inorganic particles in a matrix of synthetic polymers or biopolymers. The systems should be well characterized, both with respect to the employed polymer and the inorganic particles, in order to allow reproduction and application of the results by other laboratories. The focus on this Special Issue is devoted to research. Hence, scientific impact is essential. Of course, applications are appreciated, but are in no way a prerequisite for study of basic aspects of nanocomposites. If an application is claimed, it should be demonstrated that the investigated materials themselves are promising. Please, note that the sole optimization of recipes, ingredients or procedures for the development of (commercial) products is not within the scope of this Special Issue. Original articles, as well as reviews are appreciated. The contributions may emphasize particular aspects of nanocomposites, for example with regard to preparation, structural features, physical properties, materials properties (including biologic or biomedical properties) or processing.

Prof. Dr. Walter Caseri
Guest Editor

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Keywords

nanocomposites
polymers
inorganic particles
nanoparticles
surface-modified particles
synthesis
physical properties
materials properties
biological properties
biomedical properties
processing

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Published Papers (12 papers)

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Research

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2421 KiB

Open AccessArticle

Catalytic Activity of Oxidized Carbon Black and Graphene Oxide for the Crosslinking of Epoxy Resins

by Maria Rosaria Acocella, Carola Esposito Corcione, Antonella Giuri, Mario Maggio, Gaetano Guerra and Alfonso Maffezzoli

Polymers 2017, 9(4), 133; https://doi.org/10.3390/polym9040133 - 7 Apr 2017

Cited by 11 | Viewed by 6606

Abstract

This article compares the catalytic activities of oxidized carbon black (oCB) and graphene oxide (eGO) samples on the kinetics of a reaction of diglycidyl ether of bisphenol A (DGEBA) with a diamine, leading to crosslinked insoluble networks. The study is mainly conducted by rheometry and Differential Scanning Calorimetry (DSC). Following the same oxidation procedure, CB samples are more efficiently oxidized than graphite samples. For instance, CB and graphite samples with high specific surface areas (151 and 308 m²/g), as oxidized by the Hummers’ method, exhibit O/C wt/wt ratios of 0.91 and 0.62, respectively. Due to the higher oxidation levels, these oCB samples exhibit a higher catalytic activity toward the curing of epoxy resins than fully exfoliated graphene oxide. Full article

(This article belongs to the Special Issue Nanocomposites of Polymers and Inorganic Particles 2016)

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10837 KiB

Open AccessArticle

Antibacterial Property and Cytotoxicity of a Poly(lactic acid)/Nanosilver-Doped Multiwall Carbon Nanotube Nanocomposite

by Chi-Hui Tsou, Wei-Hua Yao, Yi-Cheng Lu, Chih-Yuan Tsou, Chin-San Wu, Jian Chen, Ruo Yao Wang, Chaochin Su, Wei-Song Hung, Manuel De Guzman and Maw-Cherng Suen

Polymers 2017, 9(3), 100; https://doi.org/10.3390/polym9030100 - 10 Mar 2017

Cited by 50 | Viewed by 6752

Abstract

A novel method was used to synthesize a nanosilver-doped multiwall carbon nanotube (MWCNT-Ag), and subsequently, the novel poly(lactic acid) (PLA)- and MWCNT-Ag-based biocompatible and antimicrobial nanocomposites were prepared by melt blending. Based on energy dispersive X-ray spectrometry images, an MWCNT-Ag was successfully synthesized. The effect of the MWCNT-Ag on the PLA bionanocomposites was investigated by evaluating their thermal and mechanical properties, antifungal activity, and cytotoxicity. The nanocomposites exhibited a high degree of biocompatibility with the MWCNT-Ag content, which was less than 0.3 phr. Furthermore, tensile strength testing, thermogravimetric analysis, differential scanning calorimetry, and antibacterial evaluation revealed that the tensile strength, thermostability, glass transition temperature, and antibacterial properties were enhanced by increasing the MWCNT-Ag content. Finally, hydrolysis analysis indicated that the low MWCNT-Ag content could increase the packing density of PLA. Full article

(This article belongs to the Special Issue Nanocomposites of Polymers and Inorganic Particles 2016)

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3962 KiB

Open AccessArticle

Electrodeposition of Mn-Co/Polypyrrole Nanocomposites: An Electrochemical and In Situ Soft-X-ray Microspectroscopic Investigation

by Benedetto Bozzini, Patrizia Bocchetta, George Kourousias and Alessandra Gianoncelli

Polymers 2017, 9(1), 17; https://doi.org/10.3390/polym9010017 - 6 Jan 2017

Cited by 20 | Viewed by 6928

Abstract

Understanding the lateral variations in the elemental and chemical state of constituents induced by electrochemical reactions at nanoscales is crucial for the advancement of electrochemical materials science. This requires in situ studies to provide observables that contribute to both modeling beyond the phenomenological level and exactly transducing the functionally relevant quantities. A range of X-ray coherent diffraction imaging (CDI) approaches have recently been proposed for imaging beyond the diffraction limit with potentially dramatic improvements in time resolution with chemical sensitivity. In this paper, we report a selection of ptychography results obtained in situ during the electrodeposition of a metal–polymer nanocomposite. Our selection includes dynamic imaging during electrochemically driven growth complemented with absorption and phase spectroscopy with high lateral resolution. We demonstrate the onset of morphological instability feature formation and correlate the chemical state of Mn with the local growth rate controlled by the current density distribution resulting from morphological evolution. Full article

(This article belongs to the Special Issue Nanocomposites of Polymers and Inorganic Particles 2016)

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4840 KiB

Open AccessArticle

Characterization of Thermoplastic Polyurethane (TPU) and Ag-Carbon Black TPU Nanocomposite for Potential Application in Additive Manufacturing

by Steven T. Patton, Chenggang Chen, Jianjun Hu, Lawrence Grazulis, Amanda M. Schrand and Ajit K. Roy

Polymers 2017, 9(1), 6; https://doi.org/10.3390/polym9010006 - 29 Dec 2016

Cited by 33 | Viewed by 12775

Abstract

Electromechanical, adhesion, and viscoelastic properties of polymers and polymer nanocomposites (PNCs) are of interest for additive manufacturing (AM) and flexible electronics. Development/optimization of inks for AM is complex, expensive, and substrate/interface dependent. This study investigates properties of free standing films of a thermoplastic polyurethane (TPU) polymer and an Ag–carbon black (Ag-CB) TPU PNC in a lightly loaded low strain compression contact as a rough measure of their suitability for AM. The TPU exhibited high hysteresis and a large viscoelastic response, and sufficient dwell time was needed for polymer chain relaxation and measurable adhesion. A new discovery is that large enough contact area is needed to allow longer time constant polymer ordering in the contact that led to higher adhesion and better performance/reliability. This has previously unknown implications for interface size relative to polymer chain length in AM design. The standard linear model was found to be a good fit for the viscoelastic behavior of the TPU. The PNC exhibited no adhesion (new result), low electrical resistance, and relatively small viscoelastic response. This implies potential for AM electrical trace as well as switch applications. Full article

(This article belongs to the Special Issue Nanocomposites of Polymers and Inorganic Particles 2016)

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3426 KiB

Open AccessArticle

Creep and Recovery Behaviour of Polyolefin-Rubber Nanocomposites Developed for Additive Manufacturing

by Fugen Daver, Mladenko Kajtaz, Milan Brandt and Robert A. Shanks

Polymers 2016, 8(12), 437; https://doi.org/10.3390/polym8120437 - 15 Dec 2016

Cited by 39 | Viewed by 12536

Abstract

Nanocomposite application in automotive engineering materials is subject to continual stress fields together with recovery periods, under extremes of temperature variations. The aim is to prepare and characterize polyolefin-rubber nanocomposites developed for additive manufacturing in terms of their time-dependent deformation behaviour as revealed in creep-recovery experiments. The composites consisted of linear low density polyethylene and functionalized rubber particles. Maleic anhydride compatibilizer grafted to polyethylene was used to enhance adhesion between the polyethylene and rubber; and multi-walled carbon nanotubes were introduced to impart electrical conductivity. Various compositions of nanocomposites were tested under constant stress in creep and recovery. A four-element mechanistic Burger model was employed to model the creep phase of the composites, while a Weibull distribution function was employed to model the recovery phase of the composites. Finite element analysis using Abaqus enabled numerical modelling of the creep phase of the composites. Both analytical and numerical solutions were found to be consistent with the experimental results. Creep and recovery were dependent on: (i) composite composition; (ii) compatibilizers content; (iii) carbon nanotubes that formed a percolation network. Full article

(This article belongs to the Special Issue Nanocomposites of Polymers and Inorganic Particles 2016)

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13443 KiB

Open AccessArticle

Polyetheretherketone Hybrid Composites with Bioactive Nanohydroxyapatite and Multiwalled Carbon Nanotube Fillers

by Chen Liu, Kai Wang Chan, Jie Shen, Cheng Zhu Liao, Kelvin Wai Kwok Yeung and Sie Chin Tjong

Polymers 2016, 8(12), 425; https://doi.org/10.3390/polym8120425 - 8 Dec 2016

Cited by 42 | Viewed by 7052

Abstract

Polyetheretherketone (PEEK) hybrid composites reinforced with inorganic nanohydroxyapatite (nHA) and multiwalled carbon nanotube (MWNT) were prepared by melt-compounding and injection molding processes. The additions of nHA and MWNT to PEEK were aimed to increase its elastic modulus, tensile strength, and biocompatibility, rendering the hybrids suitable for load-bearing implant applications. The structural behavior, mechanical property, wettability, osteoblastic cell adhesion, proliferation, differentiation, and mineralization of the PEEK/nHA-MWNT hybrids were studied. X-ray diffraction and SEM observation showed that both nHA and MWNT fillers are incorporated into the polymer matrix of PEEK-based hybrids. Tensile tests indicated that the elastic modulus of PEEK can be increased from 3.87 to 7.13 GPa by adding 15 vol % nHA and 1.88 vol % MWNT fillers. The tensile strength and elongation at break of the PEEK/(15% nHA)-(1.88% MWNT) hybrid were 64.48 MPa and 1.74%, respectively. Thus the tensile properties of this hybrid were superior to those of human cortical bones. Water contact angle measurements revealed that the PEEK/(15% nHA)-(1.88% MWNT) hybrid is hydrophilic due to the presence of nHA. Accordingly, hydrophilic PEEK/(15% nHA)-(1.88% MWNT) hybrid promoted the adhesion, proliferation, differentiation, and mineralization of murine MC3T3-E1 osteoblasts on its surface effectively on the basis of cell culture, fluorescence microscopy, MTT assay, WST-1 assay, alkaline phosphatase activity, and Alizarin red staining tests. Thus the PEEK/(15% nHA)-(1.88% MWNT) hybrid has the potential to be used for fabricating load-bearing bone implants. Full article

(This article belongs to the Special Issue Nanocomposites of Polymers and Inorganic Particles 2016)

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6901 KiB

Open AccessArticle

Effect of Microwave Treatment of Graphite on the Electrical Conductivity and Electrochemical Properties of Polyaniline/Graphene Oxide Composites

by Yanjun Tang, Xiulan Hu, Dongdong Liu, Daliang Guo and Junhua Zhang

Polymers 2016, 8(11), 399; https://doi.org/10.3390/polym8110399 - 16 Nov 2016

Cited by 17 | Viewed by 8029

Abstract

Polyaniline (PANI)/graphene oxide (GO) composites were synthesized via in situ polymerization of aniline in the presence of GO. The effect of microwave treatment of graphite on the electrical conductivity and electrochemical properties of PANI/GO composites was highlighted, and the morphology and microstructure were subsequently characterized using transmission electron microscopy, scanning electron microscopy, Fourier-transformed infrared spectroscopy, X-ray diffraction, and thermogravimetric analysis. The results demonstrated that microwave treatment of graphite imparted a well-dispersed, highly ordered layered structure to the as-prepared GO, and in turn facilitated strong bonding between the GO and PANI nanosheets, which may be responsible for the improved electrical conductivity and electrochemical properties of the resulting PANI/GO composites. The desired PANI/GO composites possessed an electrical conductivity of 508 S/m, an areal capacitance of 172.8 mF/cm², and a retained capacitance of 87.4% after cycling, representing percentage increases of 102, 232, and 112, respectively, as a result of the microwave treatment of graphite. The resulting composites are promising electrode materials for high-performance and ecofriendly electrical energy storage devices. Full article

(This article belongs to the Special Issue Nanocomposites of Polymers and Inorganic Particles 2016)

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6593 KiB

Open AccessArticle

Influence of Organically-Modified Montmorillonite and Synthesized Layered Silica Nanoparticles on the Properties of Polypropylene and Polyamide-6 Nanocomposites

by Moisés Gómez, Humberto Palza and Raúl Quijada

Polymers 2016, 8(11), 386; https://doi.org/10.3390/polym8110386 - 31 Oct 2016

Cited by 22 | Viewed by 5594

Abstract

Nanocomposites of layered silica nanoparticles (LSN) obtained by the sol–gel method, and commercial montmorillonite clay Cloisite^®20A with polypropylene (PP) and Cloisite^®30B with polyamide-6 (PA6) were prepared by melt blending in order to study their effects on barrier, mechanical properties, and thermal stability. Transmission electron microscopy (TEM) showed that all of the nanocomposites present agglomerated nanoparticles with some degree of individual particles. In barrier properties, LSN dramatically increased the oxygen and water vapor permeability of PP at low loadings (<5 wt %) due to the percolation effect. However, in PP and PA6 nanocomposites with clays, the permeability showed increases and decreases depending on the solubility of the permeating gases with the clays and the polymers. Tensile stress-strain tests otherwise showed that the nanocomposites with clays present an enhancement in the elastic modulus. Meanwhile, with the LSN, a decrease was found due to the formation of agglomerations and voids. Finally, thermogravimetric analysis under inert conditions showed the nanoparticles do not have a significant effect on the thermal stability of the nanocomposites. These results expose the relevance of the type of layered nanoparticle and polymer matrix on the barrier, mechanical, and thermal behaviors of the resulting nanocomposites. Full article

(This article belongs to the Special Issue Nanocomposites of Polymers and Inorganic Particles 2016)

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7896 KiB

Open AccessArticle

Microwave-Assisted Hydrothermal Synthesis of Cellulose/Hydroxyapatite Nanocomposites

by Lian-Hua Fu, Yan-Jun Liu, Ming-Guo Ma, Xue-Ming Zhang, Zhi-Min Xue and Jie-Fang Zhu

Polymers 2016, 8(9), 316; https://doi.org/10.3390/polym8090316 - 20 Sep 2016

Cited by 25 | Viewed by 9085

Abstract

In this paper, we report a facile, rapid, and green strategy for the synthesis of cellulose/hydroxyapatite (HA) nanocomposites using an inorganic phosphorus source (sodium dihydrogen phosphate dihydrate (NaH₂PO₄·2H₂O)), or organic phosphorus sources (adenosine 5′-triphosphate disodium salt (ATP), creatine phosphate disodium salt tetrahydrate (CP), or D-fructose 1,6-bisphosphate trisodium salt octahydrate (FBP)) through the microwave-assisted hydrothermal method. The effects of the phosphorus sources, heating time, and heating temperature on the phase, size, and morphology of the products were systematically investigated. The experimental results revealed that the phosphate sources played a critical role on the phase, size, and morphology of the minerals in the nanocomposites. For example, the pure HA was obtained by using NaH₂PO₄·2H₂O as phosphorus source, while all the ATP, CP, and FBP led to the byproduct, calcite. The HA nanostructures with various morphologies (including nanorods, pseudo-cubic, pseudo-spherical, and nano-spherical particles) were obtained by varying the phosphorus sources or adjusting the reaction parameters. In addition, this strategy is surfactant-free, avoiding the post-treatment procedure and cost for the surfactant removal from the product. We believe that this work can be a guidance for the green synthesis of cellulose/HA nanocomposites in the future. Full article

(This article belongs to the Special Issue Nanocomposites of Polymers and Inorganic Particles 2016)

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1547 KiB

Open AccessArticle

Enhanced Optoelectronic Properties of PFO/Fluorol 7GA Hybrid Light Emitting Diodes via Additions of TiO₂ Nanoparticles

by Bandar Ali Al-Asbahi, Mohammad Hafizuddin Haji Jumali and Mohamad Saleh AlSalhi

Polymers 2016, 8(9), 334; https://doi.org/10.3390/polym8090334 - 6 Sep 2016

Cited by 28 | Viewed by 6827

Abstract

The effect of TiO₂ nanoparticle (NP) content on the improvement of poly(9,9′-di-n-octylfluorenyl-2,7-diyl) (PFO)/Fluorol 7GA organic light emitting diode (OLED) performance is demonstrated here. The PFO/Fluorol 7GA blend with specific ratios of TiO₂ NPs was prepared via a solution blending method before being spin-coated onto an indium tin oxide (ITO) substrate to act as an emissive layer in OLEDs. A thin aluminum layer as top electrode was deposited onto the emissive layer using the electron beam chamber. Improvement electron injection from the cathode was achieved upon incorporation of TiO₂ NPs into the PFO/Fluorol 7GA blend, thus producing devices with intense luminance and lower turn-on voltage. The ITO/(PFO/Fluorol 7GA/TiO₂)/Al OLED device exhibited maximum electroluminescence intensity and luminance at 25 wt % of TiO₂ NPs, while maximum luminance efficiency was achieved with 15 wt % TiO₂ NP content. In addition, this work proved that the performance of the devices was strongly affected by the surface morphology, which in turn depended on the TiO₂ NP content. Full article

(This article belongs to the Special Issue Nanocomposites of Polymers and Inorganic Particles 2016)

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2911 KiB

Open AccessArticle

Well-Defined Polypropylene/Polypropylene-Grafted Silica Nanocomposites: Roles of Number and Molecular Weight of Grafted Chains on Mechanistic Reinforcement

by Masahito Toyonaga, Patchanee Chammingkwan, Minoru Terano and Toshiaki Taniike

Polymers 2016, 8(8), 300; https://doi.org/10.3390/polym8080300 - 12 Aug 2016

Cited by 30 | Viewed by 7327

Abstract

Grafting terminally functionalized polypropylene (PP) to nanofillers provides well-defined PP-based nanocomposites plausibly featured with a physical cross-linkage structure. In this paper, a series of PP-grafted silica nanoparticles (PP-g-SiO₂) were synthesized by varying the number of grafted chains per silica particle, and influences of the number and the molecular weight of grafted chains were studied on physical properties of PP/PP-g-SiO₂ nanocomposites. We found that only 20–30 chain/particle was sufficient to exploit benefits of the PP grafting for the nanoparticle dispersion, the nucleation, and the Young’s modulus. Meanwhile, the yield strength was sensitive to both of the number and the molecular weight of grafted PP: Grafting longer chains at a higher density led to greater reinforcement. Full article

(This article belongs to the Special Issue Nanocomposites of Polymers and Inorganic Particles 2016)

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Review

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9724 KiB

Open AccessReview

Bulk Heterojunction Solar Cells Based on Blends of Conjugated Polymers with II–VI and IV–VI Inorganic Semiconductor Quantum Dots

by Ryan Kisslinger, Weidi Hua and Karthik Shankar

Polymers 2017, 9(2), 35; https://doi.org/10.3390/polym9020035 - 26 Jan 2017

Cited by 41 | Viewed by 10950

Abstract

Bulk heterojunction solar cells based on blends of quantum dots and conjugated polymers are a promising configuration for obtaining high-efficiency, cheaply fabricated solution-processed photovoltaic devices. Such devices are of significant interest as they have the potential to leverage the advantages of both types of materials, such as the high mobility, band gap tunability and possibility of multiple exciton generation in quantum dots together with the high mechanical flexibility and large molar extinction coefficient of conjugated polymers. Despite these advantages, the power conversion efficiency (PCE) of these hybrid devices has remained relatively low at around 6%, well behind that of all-organic or all-inorganic solar cells. This is attributed to major challenges that still need to be overcome before conjugated polymer–quantum dot blends can be considered viable for commercial application, such as controlling the film morphology and interfacial structure to ensure efficient charge transfer and charge transport. In this work, we present our findings with respect to the recent development of bulk heterojunctions made from conjugated polymer–quantum dot blends, list the ongoing strategies being attempted to improve performance, and highlight the key areas of research that need to be pursued to further develop this technology. Full article

(This article belongs to the Special Issue Nanocomposites of Polymers and Inorganic Particles 2016)

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