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Smart and Modern Thermoplastic Polymer Materials

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

Deadline for manuscript submissions: closed (20 July 2018) | Viewed by 47121

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Special Issue Editor

Prof. Dr. Andrea Pucci

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Guest Editor

Department of Chemistry and Industrial Chemistry, University of Pisa, Via G. Moruzzi 13, 56124 Pisa, Italy
Interests: smart polymeric materials; sensor nanocomposites; mechanochromic materials; self-healing composites
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

This Special Issue aims to provide the current state-of-the-art of thermoplastic polymer materials with smart features for modern applications. Research into smart thermoplastic polymers has increased greatly over the last few decades, principally owing to the spreading interest on upgraded materials for new and modern applications. Inputs are generally triggered by scientific and research aspects that are often intertwined with societal issues and demands.

The Special Issue covers fundamental research and applications of modern thermoplastic materials within novel scopes related to self-healing materials, energy harvesting and sensors. The use of thermoplastic polymers with smart features is widespread, ranging from polymers for photovoltaics, to optical sensing, nanocomposites with graphitic fillers, thermoreversible materials, and many others.

Papers are aimed at highlighting the latest research in the area or summarizing selected areas of the different topics. The preparation of smart thermoplastic polymers including polymer nanocomposites, their detailed characterization and their ultimate applications are reported and discussed to provide the most illustrative information.

Different properties and applications are intertwined throughout the Special issue. All of the authors contribute examples of modern and smart thermoplastic polymer materials that are relevant and illustrative for academic scientists, researchers and industry.

Prof. Andrea Pucci
Guest Editor

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

Dye-doped polymers
Polymers for optical sensing
Polymers for light harvesting
Polymers filled with graphitic materials
Self-healing polymers

Published Papers (10 papers)

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Editorial

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3 pages, 298 KiB

Open AccessEditorial

Smart and Modern Thermoplastic Polymer Materials

by Andrea Pucci

Polymers 2018, 10(11), 1211; https://doi.org/10.3390/polym10111211 - 31 Oct 2018

Cited by 6 | Viewed by 2818

Abstract

Smart and modern thermoplastic polymer materials are defined as novel thermoplastic materials that are capable of responding to external stimuli through a macroscopic output in which the energy of the stimulus is transduced appropriately as a function of external interference. [...] Full article

(This article belongs to the Special Issue Smart and Modern Thermoplastic Polymer Materials)

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Research

Jump to: Editorial

13 pages, 3017 KiB

Open AccessArticle

Mechanochemically Carboxylated Multilayer Graphene for Carbon/ABS Composites with Improved Thermal Conductivity

by Laura Burk, Matthias Gliem, Fabian Lais, Fabian Nutz, Markus Retsch and Rolf Mülhaupt

Polymers 2018, 10(10), 1088; https://doi.org/10.3390/polym10101088 - 1 Oct 2018

Cited by 14 | Viewed by 3435

Abstract

Dry ball milling of graphite under carbon dioxide pressure affords multilayer-functionalized graphene (MFG) with carboxylic groups as nanofiller for composites of carbon and acrylonitrile–butadiene–styrene copolymers (ABSs). Produced in a single-step process without requiring purification, MFG nanoplatelets are uniformly dispersed in ABS even in the absence of compatibilizers. As compared to few-layer graphene oxide, much larger amounts of MFG are tolerated in ABS melt processing. Unparalleled by other carbon nanofillers and non-functionalized micronized graphite, the addition of 15 wt % MFG simultaneously results in a Young’s modulus of 2550 MPa (+68%), a thermal conductivity of 0.321 W∙m⁻¹∙K⁻¹ (+200%), and a heat distortion temperature of 99 °C (+9%) with respect to neat ABS, without encountering massive embrittlement and melt-viscosity build-up typical of few-layer graphene oxide. With carbon filler at 5 wt %, the Young’s modulus increases with increasing aspect ratio of the carbon filler and is superior to spherical hydroxyl-functionalized MFG, which forms large agglomerates. Both MFG and micronized graphite hold promise for designing carbon/ABS compounds with improved thermal management in lightweight engineering applications. Full article

(This article belongs to the Special Issue Smart and Modern Thermoplastic Polymer Materials)

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15 pages, 4913 KiB

Open AccessArticle

Electrically-Responsive Reversible Polyketone/MWCNT Network through Diels-Alder Chemistry

by Rodrigo Araya-Hermosilla, Andrea Pucci, Patrizio Raffa, Dian Santosa, Paolo P. Pescarmona, Régis Y. N. Gengler, Petra Rudolf, Ignacio Moreno-Villoslada and Francesco Picchioni

Polymers 2018, 10(10), 1076; https://doi.org/10.3390/polym10101076 - 28 Sep 2018

Cited by 21 | Viewed by 4795

Abstract

This study examines the preparation of electrically conductive polymer networks based on furan-functionalised polyketone (PK-Fu) doped with multi-walled carbon nanotubes (MWCNTs) and reversibly crosslinked with bis-maleimide (B-Ma) via Diels-Alder (DA) cycloaddition. Notably, the incorporation of 5 wt.% of MWCNTs results in an increased modulus of the material, and makes it thermally and electrically conductive. Analysis by X-ray photoelectron spectroscopy indicates that MWCNTs, due to their diene/dienophile character, covalently interact with the matrix via DA reaction, leading to effective interfacial adhesion between the components. Raman spectroscopy points to a more effective graphitic ordering of MWCNTs after reaction with PK-Fu and B-Ma. After crosslinking the obtained composite via the DA reaction, the softening point (tan(δ) in dynamic mechanical analysis measurements) increases up to 155 °C, as compared to the value of 130 °C for the PK-Fu crosslinked with B-Ma and that of 140 °C for the PK-Fu/B-Ma/MWCNT nanocomposite before resistive heating (responsible for crosslinking). After grinding the composite, compression moulding (150 °C/40 bar) activates the retro-DA process that disrupts the network, allowing it to be reshaped as a thermoplastic. A subsequent process of annealing via resistive heating demonstrates the possibility of reconnecting the decoupled DA linkages, thus providing the PK networks with the same thermal, mechanical, and electrical properties as the crosslinked pristine systems. Full article

(This article belongs to the Special Issue Smart and Modern Thermoplastic Polymer Materials)

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13 pages, 2727 KiB

Open AccessArticle

Synthesis of High Molar Mass Poly(phenylene methylene) Catalyzed by Tungsten(II) Compounds

by Andreas Braendle, Carina Vidovič, Nadia C. Mösch-Zanetti, Markus Niederberger and Walter Caseri

Polymers 2018, 10(8), 881; https://doi.org/10.3390/polym10080881 - 7 Aug 2018

Cited by 7 | Viewed by 4220

Abstract

Poly(phenylene methylene)s (PPMs) with high molar masses were isolated by polymerization of benzyl chloride catalyzed with tungsten(II) compounds and subsequent fractionation. Four different tungsten(II) catalysts were successfully exploited for the polymerization, for which a strict temperature profile was developed. The PPMs possessed roughly a trimodal molar mass distribution. Simple fractionation by phase separation of 2-butanone solutions allowed to effectively segregate the products primarily into PPM of low molar mass (M_n = 1600 g mol⁻¹) and high molar mass (M_n = 167,900 g mol⁻¹); the latter can be obtained in large quantities up to 50 g. The evolution of the trimodal distribution and the monomer conversion was monitored by gel permeation chromatography (GPC) and ¹H NMR spectroscopy, respectively, over the course of the polymerization. The results revealed that polymerization proceeded via a chain-growth mechanism. This study illustrates a new approach to synthesize PPM with hitherto unknown high molar masses which opens the possibility to explore new applications, e.g., for temperature-resistant coatings, fluorescent coatings, barrier materials or optical materials. Full article

(This article belongs to the Special Issue Smart and Modern Thermoplastic Polymer Materials)

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18 pages, 3234 KiB

Open AccessFeature PaperArticle

Functional Poly(dihalopentadiene)s: Stereoselective Synthesis, Aggregation-Enhanced Emission and Sensitive Detection of Explosives

by Ting Han, Yun Zhang, Benzhao He, Jacky W. Y. Lam and Ben Zhong Tang

Polymers 2018, 10(8), 821; https://doi.org/10.3390/polym10080821 - 25 Jul 2018

Cited by 9 | Viewed by 3837

Abstract

The development of polymeric materials with novel structures and unique properties and functionalities is of both academic and industrial significance. In this work, functional poly(dihalopentadiene)s were synthesized by boron trihalide-mediated multicomponent polymerization routes in a stereoselective manner. The polymerizations of tetraphenylethylene-containing diyne, BX₃ (X = Cl, Br) and p-tolualdehyde proceed smoothly in dichloromethane under mild conditions to afford high molecular weight poly(dihalopentadiene)s with a predominant (Z,Z)-configuration in moderate to good yields. The reaction conditions and the boron trihalide used were found to have great effects on the stereochemistry of the resulting polymer structures. The obtained poly(1,5-dihalo-(Z,Z)-1,4-pentadiene)s possess high thermal stability and good film-forming ability. Their thin films show high refractive index of 1.9007–1.6462 in a wide wavelength region of 380–890 nm with low optical dispersion. The polymers are weakly emissive in dilute solutions but become highly emissive upon aggregated, demonstrating a unique phenomenon of aggregation-enhanced emission. Their nanoaggregates in aqueous media can serve as sensitive fluorescent chemosensors for the detection of explosives with a superamplification effect and a low detection limit. Full article

(This article belongs to the Special Issue Smart and Modern Thermoplastic Polymer Materials)

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15 pages, 4801 KiB

Open AccessArticle

Preparation of Graphene-Perfluoroalkoxy Composite and Thermal and Mechanical Properties

by Wanlong Zhang, Haibin Zuo, Xinru Zhang, Jingsong Wang, Longfei Guo and Xing Peng

Polymers 2018, 10(7), 700; https://doi.org/10.3390/polym10070700 - 25 Jun 2018

Cited by 19 | Viewed by 4354

Abstract

Perfluoroalkoxy (PFA) material exhibits perfect corrosion resistance under both acid or alkaline circumstances; thus, steel heat exchangers are being substituted by those made of PFA in high corrosion atmospheres. However, the low thermal conductivity of PFA degrades its heat transfer efficiency. Based on the extremely high heat conductivity of graphene, a novel grapheme-PFA composite was proposed to simultaneously meet the demands of heat transfer and corrosion resistance. Ultrasonic dispersion technology was used to disperse the aggregated graphene in the composite. Graphene–PFA composites with different graphene contents and using different dispersing solvents were prepared with a hot pressing method, and thermal conductivity, abrasion resistance, crystallization and pyrolysis properties were investigated. The thermal conductivity of PFA composites with graphene content of 20 wt % reached 5.017 W (m·k)⁻¹, which is 21.88 times that of pure PFA. The relationship between the abrasion loss and the friction coefficient of the composites with different graphene contents was obtained. A thermogravimetric analyzer was used to investigate the crystallization and pyrolysis behavior of the composites; correspondingly, the temperature range that composites work in was determined. The heat conduction mechanism was analyzed through the thermal conductivity model of composite materials. The composite material is expected to play an important role in the development of high-performance thermal equipment. Full article

(This article belongs to the Special Issue Smart and Modern Thermoplastic Polymer Materials)

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16 pages, 4976 KiB

Open AccessArticle

Effect of the Polyketone Aromatic Pendent Groups on the Electrical Conductivity of the Derived MWCNTs-Based Nanocomposites

by Nicola Migliore, Lorenzo Massimo Polgar, Rodrigo Araya-Hermosilla, Francesco Picchioni, Patrizio Raffa and Andrea Pucci

Polymers 2018, 10(6), 618; https://doi.org/10.3390/polym10060618 - 5 Jun 2018

Cited by 14 | Viewed by 5534

Abstract

Electrically conductive plastics with a stable electric response within a wide temperature range are promising substitutes of conventional inorganic conductive materials. This study examines the preparation of thermoplastic polyketones (PK30) functionalized by the Paal–Knorr process with phenyl (PEA), thiophene (TMA), and pyrene (PMA) pendent groups with the aim of optimizing the non-covalent functionalization of multiwalled carbon nanotubes (MWCNTs) through π–π interactions. Among all the aromatic functionalities grafted to the PK30 backbone, the extended aromatic nuclei of PMA were found to be particularly effective in preparing well exfoliated and undamaged MWCNTs dispersions with a well-defined conductive percolative network above the 2 wt % of loading and in freshly prepared nanocomposites as well. The efficient and superior π–π interactions between PK30PMA and MWCNTs consistently supported the formation of nanocomposites with a highly stable electrical response after thermal solicitations such as temperature annealing at the softening point, IR radiation exposure, as well as several heating/cooling cycles from room temperature to 75 °C. Full article

(This article belongs to the Special Issue Smart and Modern Thermoplastic Polymer Materials)

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15 pages, 3953 KiB

Open AccessArticle

Microwave Attenuation of Graphene Modified Thermoplastic Poly(Butylene adipate-co-terephthalate) Nanocomposites

by Sima Kashi, S. Ali Hadigheh and Russell Varley

Polymers 2018, 10(6), 582; https://doi.org/10.3390/polym10060582 - 25 May 2018

Cited by 22 | Viewed by 4127

Abstract

With the widespread development and use of electronics and telecommunication devices, electromagnetic radiation has emerged as a new pollution. In this study, we fabricated flexible multifunctional nanocomposites by incorporating graphene nanoplatelets into a soft thermoplastic matrix and investigated its performance in attenuating electromagnetic radiation over frequency ranges of C (5.85–8.2 GHz), X (8.2–12.4 GHz), and Ku bands (12.4–18 GHz). Effects of nanofiller loading, sample thickness, and radiation frequency on the nanocomposites shielding effectiveness (SE) were investigated via experimental measurements and simulation. The highest rate of increase in SE was observed near percolation threshold of graphene. Comparison of reflectivity and absorptivity revealed that reflection played a major role in nanocomposites shielding potential for all frequencies while the low absorptivity was due to high power reflection at nanocomposite surface and thin thickness. Subsequently, effective absorbance calculations revealed the great potential of nanocomposites for absorbing microwaves, reaching more than 80%. Simulations confirmed the observed nanocomposites SE behaviours versus frequency. Depending on thickness, different frequency dependency behaviours were observed; for thin samples, SE remained unchanged, while for thicker samples it exhibited either increasing or decreasing trends with increasing frequency. At any fixed frequency, increasing the thickness resulted in sine-wave periodic changes in SE with a general increasing trend. Full article

(This article belongs to the Special Issue Smart and Modern Thermoplastic Polymer Materials)

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19 pages, 4943 KiB

Open AccessArticle

One-Pot Synthesis and Characterization of Novel Shape-Memory Poly(ε-Caprolactone) Based Polyurethane-Epoxy Co-networks with Diels–Alder Couplings

by Katalin Czifrák, Csilla Lakatos, József Karger-Kocsis, Lajos Daróczi, Miklós Zsuga and Sándor Kéki

Polymers 2018, 10(5), 504; https://doi.org/10.3390/polym10050504 - 6 May 2018

Cited by 20 | Viewed by 4887

Abstract

The present work aimed at the preparation and investigation of different epoxy-polyurethane (EP-PU) co-networks. The EP-PU co-networks were obtained by applying two different synthetic strategies, in which the coupling element, the Diels–Alder (DA) adduct, was prepared previously or formed “in situ” in the reaction between furan functionalized polyurethane and furfuryl amine-diglycidyl ether bisphenol-A oligomers (FA_DGEBA). For the synthesis of these EP-PU networks, poly(ε-caprolactone)-diol (PCD, M_n = 2 kg/mol) and poly(ε-caprolactone) (PCL) with different molecular weights (M_n = 10, 25 and 50 kg/mol) and 1,6-hexamethylenediisocyanate (HDI) were used. The EP-PU co-networks were characterized by Attenuated Total Reflectance Fourier-Transform Infrared spectroscopy (AT-FT-IR), differential scanning calorimetry (DSC) and dynamical mechanical analysis (DMA). Scanning electron microscopy (SEM) was applied to assess the morphology of the EP-PU samples. It was demonstrated that the stress–strain curves for the EP-PUs could be interpreted based on the Standard Linear Solid (SLS) model. The DMA traces of some EP-PUs (depending on the composition and the synthetic method) revealed a plateau-like region above the melting temperature (T_m) of PCL confirming the presence of cross-linked structure. This feature predicted shape memory (SM) behavior for these EP-PU samples. Indeed, very good shape fixity and moderate shape recovery were obtained. The shape recovery processes of these EP-PU samples were described using double exponential decay functions. Full article

(This article belongs to the Special Issue Smart and Modern Thermoplastic Polymer Materials)

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15 pages, 1780 KiB

Open AccessArticle

Cost-Effective Double-Layer Hydrogel Composites for Wound Dressing Applications

by Javad Tavakoli, Samaneh Mirzaei and Youhong Tang

Polymers 2018, 10(3), 305; https://doi.org/10.3390/polym10030305 - 12 Mar 2018

Cited by 39 | Viewed by 8100

Abstract

Although poly vinyl alcohol-poly acrylic acid (PVA-PAA) composites have been widely used for biomedical applications, their incorporation into double-layer assembled thin films has been limited because the interfacial binding materials negatively influence the water uptake capacity of PVA. To minimize the effect of interfacial binding, a simple method for the fabrication of a double-layered PVA-PAA hydrogel was introduced, and its biomedical properties were evaluated in this study. Our results revealed that the addition of PAA layers on the surface of PVA significantly increased the swelling properties. Compared to PVA, the equilibrium swelling ratio of the PVA-PAA hydrogel increased (p = 0.035) and its water vapour permeability significantly decreased (p = 0.04). Statistical analysis revealed that an increase in pH value from 7 to 10 as well as the addition of PAA at pH = 7 significantly increased the adhesion force (p < 0.04). The mechanical properties—including ultimate tensile strength, modulus, and elongation at break—remained approximately untouched compared to PVA. A significant increase in biocompatibility was found after day 7 (p = 0.016). A higher release rate for tetracycline was found at pH = 8 compared to neutral pH. Full article

(This article belongs to the Special Issue Smart and Modern Thermoplastic Polymer Materials)

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