Polymers

15 pages, 3238 KiB

Open AccessArticle

Understanding the Polymerization of Polyfurfuryl Alcohol: Ring Opening and Diels-Alder Reactions

by Gianluca Tondi, Nicola Cefarin, Thomas Sepperer, Francesco D’Amico, Raphael J. F. Berger, Maurizio Musso, Giovanni Birarda, Andreas Reyer, Thomas Schnabel and Lisa Vaccari

Polymers 2019, 11(12), 2126; https://doi.org/10.3390/polym11122126 - 17 Dec 2019

Cited by 49 | Viewed by 6834

Abstract

Polyfurfuryl alcohol (PFA) is one of the most intriguing polymers because, despite its easy polymerization in acid environment, its molecular structure is definitely not obvious. Many studies have been performed in recent decades, and every time, surprising aspects came out. With the present [...] Read more.

Polyfurfuryl alcohol (PFA) is one of the most intriguing polymers because, despite its easy polymerization in acid environment, its molecular structure is definitely not obvious. Many studies have been performed in recent decades, and every time, surprising aspects came out. With the present study, we aim to take advantage of all of the findings of previous investigations and exploit them for the interpretation of the completely cured PFA spectra registered with three of the most powerful techniques for the characterization of solid, insoluble polymers: Solid-State ¹³C-NMR, Attenuated Total Reflectance (ATR), Fourier Transform Infrared (FTIR) spectroscopy, and UV-resonant Raman spectroscopy at different excitation wavelengths, using both an UV laser source and UV synchrotron radiation. In addition, the foreseen structures were modeled and the corresponding ¹³C-NMR and FTIR spectra were simulated with first-principles and semi-empiric methods to evaluate their matching with experimental ones. Thanks to this multi-technique approach, based on complementary analytical tools and computational support, it was possible to conclude that, in addition to the major linear unconjugated polymerization, the PFA structure consists of Diels-Alder rearrangements occurring after the opening of some furanic units, while the terminal moieties of the chain involves γ-lactone arrangements. The occurrence of head-head methylene ether bridges and free hydroxyl groups (from unreacted furfuryl alcohol, FA, or terminal chains) could be excluded, while the conjugated systems could be considered rather limited. Full article

(This article belongs to the Special Issue State-of-the-Art Polymer Science and Technology in Italy (2019,2020))

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13 pages, 2937 KiB

Open AccessArticle

A Methodology Towards Mechanical Properties Optimization of Three-Component Polymers by the Gradual Variation of Feed Composition in Semi-Continuous Emulsion-Free Radical Polymerization

by Francisco J. Rivera-Gálvez, Luis J. González-Ortiz, Miguel A. López-Manchado, María E. Hernández-Hernández and Carlos F. Jasso-Gastinel

Polymers 2019, 11(12), 2125; https://doi.org/10.3390/polym11122125 - 17 Dec 2019

Cited by 2 | Viewed by 2584

Abstract

In this work, a new methodology for the synthesis of three-component polymers (TCPs) was developed using a seeded, semi-continuous free-radical emulsion polymerization towards the optimization of the moduli–ultimate deformation performance and energy dissipation capacity for a styrene (S), n-butyl acrylate (BA), and 4-vinylbenzyl [...] Read more.

In this work, a new methodology for the synthesis of three-component polymers (TCPs) was developed using a seeded, semi-continuous free-radical emulsion polymerization towards the optimization of the moduli–ultimate deformation performance and energy dissipation capacity for a styrene (S), n-butyl acrylate (BA), and 4-vinylbenzyl chloride (VBC) system. The three components were sequentially fed in pairs, varying feed composition along the conversion using S as the common monomer. To prepare a reference material, an industrial method was utilized with those monomers, using an equivalent global composition in a two-stage batch process (TS). Nanophase formation in the particles was observed by transmission electron microscopy (TEM), while the separation of the phases in the solid samples was observed by atomic force microscopy (AFM). The changes in glass transition temperature were determined by differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA). The latter was primarily used to compare mechanodynamic properties as a function of temperature for the two synthesis methods used. Thus, the higher toughness of the forced composition three-component polymeric materials was evaluated by means of their energy dissipation capacity, toughness, and stress–strain measurements at several temperatures. Full article

(This article belongs to the Section Polymer Analysis and Characterization)

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16 pages, 2144 KiB

Open AccessArticle

Selected Physicochemical and Pharmaceutical Properties of Poly-ε-caprolactone and Poly(d,l-lactide-co-ε-caprolactone) Conjugates of Lamivudine Synthesized via Ring-Opening Polymerization

by Tomasz Urbaniak and Witold Musiał

Polymers 2019, 11(12), 2124; https://doi.org/10.3390/polym11122124 - 17 Dec 2019

Cited by 1 | Viewed by 2999

Abstract

The modification of drug fate after administration may be achieved by the covalent coupling of active pharmaceutical ingredients with macromolecules. To prolong or delay the release, slowly degrading polymers such as polyesters may be applied for conjugation. The detachment of a covalently conjugated [...] Read more.

The modification of drug fate after administration may be achieved by the covalent coupling of active pharmaceutical ingredients with macromolecules. To prolong or delay the release, slowly degrading polymers such as polyesters may be applied for conjugation. The detachment of a covalently conjugated drug from the polymeric matrix relies mostly on the material degradation profile and barely on the weak interaction between the drug and macromolecules. In the present study, lamivudine was conjugated via ring-opening polymerization with poly-ε-caprolactone and poly(d,l-lactide-co-ε-caprolactone). The influence of the reaction parameters on the course of the polymerization and physicochemical properties of obtained conjugates were investigated. Subsequently, selected reaction products were formulated into submicron particles, and drug release profiles in physiological-like conditions were investigated. The course of the reaction was monitored via gel permeation chromatography. The structure and physicochemical properties of products were evaluated via spectroscopic, calorimetric, and diffractometric methods. The profile of the drug release from particles prepared by the slow evaporation of conjugate solution from o/w emulsion was monitored with high-performance liquid chromatography. Both an elevated reaction temperature and higher catalyst concentration increased the polymerization rate and simultaneously promoted the side reactions, resulting in a broad molecular weight distribution of products in the range from 1.30 to 2.15. The physicochemical properties of conjugates obtained in different conditions varied and had a direct influence on the drug release. The release curve of lamivudine from particles based on low molecular weight conjugates achieved a plateau between 18.9 and 22.2 μg per mg of conjugate within a month. Drug detachment from particles composed of high molecular weight conjugates exhibited a distinct delay period preceded by a drug burst release at a maximal level of 13.3 μg per mg of conjugate. Conjugate chemical composition and the degree of crystallinity were also found to influence the release. Full article

(This article belongs to the Special Issue Biodegradable Polymers for Biomedical Application)

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24 pages, 13466 KiB

Open AccessArticle

Investigation of Piezoelectricity and Resistivity of Surface Modified Barium Titanate Nanocomposites

by Udhay Sundar, Zichen Lao and Kimberly Cook-Chennault

Polymers 2019, 11(12), 2123; https://doi.org/10.3390/polym11122123 - 17 Dec 2019

Cited by 16 | Viewed by 4600

Abstract

Polymer-ceramic nanocomposite piezoelectric and dielectric films are of interest because of their possible application to advanced embedded energy storage devices for printed wired electrical boards. The incompatibility of the two constituent materials; hydrophilic ceramic filler, and hydrophobic epoxy limit the filler concentration, and [...] Read more.

Polymer-ceramic nanocomposite piezoelectric and dielectric films are of interest because of their possible application to advanced embedded energy storage devices for printed wired electrical boards. The incompatibility of the two constituent materials; hydrophilic ceramic filler, and hydrophobic epoxy limit the filler concentration, and thus, their piezoelectric properties. This work aims to understand the role of surfactant concentration in establishing meaningful interfacial layers between the epoxy and ceramic filler particles by observing particle surface morphology, piezoelectric strain coefficients, and resistivity spectra. A comprehensive study of nanocomposites, comprising non-treated and surface treated barium titanate (BTO), embedded within an epoxy matrix, was performed. The surface treatments were performed with two types of coupling agents: Ethanol and 3-glycidyloxypropyltrimethoxysilan. The observations of particle agglomeration, piezoelectric strain coefficients, and resistivity were compared, where the most ideal properties were found for concentrations of 0.02 and 0.025. This work demonstrates that the interfacial core-shell processing layer concentration influences the macroscopic properties of nanocomposites, and the opportunities for tuning interfacial layers for desirable characteristics of specific applications. Full article

(This article belongs to the Special Issue Piezoelectric, Flexoelectric and Electrostrictive Effects in Polymers: From Material Synthesis to Practical Applications)

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13 pages, 2450 KiB

Open AccessArticle

Giving a Second Opportunity to Tire Waste: An Alternative Path for the Development of Sustainable Self-Healing Styrene–Butadiene Rubber Compounds Overcoming the Magic Triangle of Tires

by Javier Araujo-Morera, Marianella Hernández Santana, Raquel Verdejo and Miguel Angel López-Manchado

Polymers 2019, 11(12), 2122; https://doi.org/10.3390/polym11122122 - 17 Dec 2019

Cited by 52 | Viewed by 8002

Abstract

Current regulations demand tires with long lifetime and reduced fuel consumption without sacrificing car safety. However, tire technology still needs to reach a suitable balance between these three indicators. Here, we address them by developing a self-healing tire compound using styrene–butadiene rubber (SBR) [...] Read more.

Current regulations demand tires with long lifetime and reduced fuel consumption without sacrificing car safety. However, tire technology still needs to reach a suitable balance between these three indicators. Here, we address them by developing a self-healing tire compound using styrene–butadiene rubber (SBR) as the matrix and reclaimed tire waste as the sustainable filler. The addition of ground tire rubber (GTR) to the matrix simultaneously improved the rolling resistance and maintained both wet grip and healing ability. We provide an in-depth analysis of the healing behavior of the material at a scale close to the relevant molecular processes through a systematic dynamic-mechanical and dielectric analysis. We found that SBR and SBR/GTR compounds show a complete recovery of stiffness and relaxation dynamics after being damaged by cyclic deformation, resulting in a heterogeneous repaired rubber network. This new development could well overcome the so-called magic triangle of tires, which is certainly one of the key objectives of the tire industry. Full article

(This article belongs to the Special Issue Advances in Rubber Composites)

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10 pages, 1448 KiB

Open AccessArticle

A Complexed Initiating System AlCl₃·Phenetole/TiCl₄·H₂O with Dominant Synergistic Effect for Efficient Synthesis of High Molecular Weight Polyisobutylene

by Yulong Jin, Liang Chen, Xing Guo, Linfeng Xu, Zhihua Zhu, Zhen Liu, Ruihua Cheng and Boping Liu

Polymers 2019, 11(12), 2121; https://doi.org/10.3390/polym11122121 - 17 Dec 2019

Cited by 2 | Viewed by 3004

Abstract

A complexed initiating system AlCl₃·phenetole/TiCl₄·H₂O was prepared by simply compounding AlCl₃/phenetole and TiCl₄/H₂O and used for cationic polymerization of isobutylene. It was found AlCl₃·phenetole/TiCl₄·H₂O exhibited [...] Read more.

A complexed initiating system AlCl₃·phenetole/TiCl₄·H₂O was prepared by simply compounding AlCl₃/phenetole and TiCl₄/H₂O and used for cationic polymerization of isobutylene. It was found AlCl₃·phenetole/TiCl₄·H₂O exhibited activities 1.2–3 times higher than those of AlCl₃/phenetole, and more than an order of magnitude higher than those of TiCl₄/H₂O, which indicated a notable synergistic effect produced in the complexed system. In addition, due to the higher activity of AlCl₃·phenetole/TiCl₄·H₂O, lower coinitiator concentration and polymerization temperature, as well as higher monomer concentration were more favored for this complexed initiating system to produce polyisobutylene (PIB) with reasonable molecular weight (M_w) and molecular weight distribution (MWD). Furthermore, high molecular weight polyisobutylene (HPIB) with M_w = 1–3 × 10⁵ g·mol⁻¹ could be successfully produced by the complexed catalyst system at T_p = −60 to −40 °C. As a whole, the high activity as well as the simple preparation procedures of the complexed initiating system offer us a unique approach for the production of HPIB with improved efficiency. Full article

(This article belongs to the Section Polymer Chemistry)

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27 pages, 9337 KiB

Open AccessArticle

Influence of the Design Solutions of Extruder Screw Mixing Tip on Selected Properties of Wheat Bran-Polyethylene Biocomposite

by Emil Sasimowski, Łukasz Majewski and Marta Grochowicz

Polymers 2019, 11(12), 2120; https://doi.org/10.3390/polym11122120 - 17 Dec 2019

Cited by 11 | Viewed by 4973

Abstract

The study investigated the impact of the extruder screw design solution—the intensive mixing tip used—on the course of the extrusion process and the properties of the obtained biocomposite extrudate. A lignocellulosic wheat bran biocomposite based on a low-density polyethylene matrix was extruded. Three [...] Read more.

The study investigated the impact of the extruder screw design solution—the intensive mixing tip used—on the course of the extrusion process and the properties of the obtained biocomposite extrudate. A lignocellulosic wheat bran biocomposite based on a low-density polyethylene matrix was extruded. Three mixing tips of the screw were used interchangeably: apineapple tip, a cut rings tip, and a Maddock tip. The experimental tests carried out included the production of an extrudate with a mass content of bran altered within the range from 10% to 50%. Processing properties such as the melt flow rate (MFR) and mass flow rate of the extruded biocomposite were determined. Selected physical, mechanical, and structural properties of the biocomposite extrudate obtained with the use of the three tested mixing tips at five bran contents were tested. Full article

(This article belongs to the Section Polymer Processing and Engineering)

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11 pages, 5055 KiB

Open AccessArticle

Microfibrillated Cellulose Suspension and Its Electrorheology

by Kisuk Choi, Jae Do Nam, Seung Hyuk Kwon, Hyoung Jin Choi, Md Sakinul Islam and Nhol Kao

Polymers 2019, 11(12), 2119; https://doi.org/10.3390/polym11122119 - 17 Dec 2019

Cited by 18 | Viewed by 3533

Abstract

Microfibrillated cellulose (MFC) particles were synthesized by a low-pressure alkaline delignification process, and their shape and chemical structure were investigated by SEM and Fourier transformation infrared spectroscopy, respectively. As a novel electrorheological (ER) material, the MFC particulate sample was suspended in insulating oil [...] Read more.

Microfibrillated cellulose (MFC) particles were synthesized by a low-pressure alkaline delignification process, and their shape and chemical structure were investigated by SEM and Fourier transformation infrared spectroscopy, respectively. As a novel electrorheological (ER) material, the MFC particulate sample was suspended in insulating oil to fabricate an ER fluid. Its rheological properties—steady shear stress, shear viscosity, yield stress, and dynamic moduli—under electric field strength were characterized by a rotational rheometer. The MFC-based ER fluid demonstrated typical ER characteristics, in which the shear stresses followed the Cho–Choi–Jhon model well under electric field strength. In addition, the solid-like behavior of the ER fluid was investigated with the Schwarzl equation. The elevated value of both dynamic and elastic yield stresses at applied electric field strengths was well described using a power law model (~E^1.5). The reversible and quick response of the ER fluid was also illustrated through the on–off test. Full article

(This article belongs to the Special Issue Cellulose and Renewable Materials)

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26 pages, 12095 KiB

Open AccessArticle

The Potential of Agglomerated Cork for Sandwich Structures: A Systematic Investigation of Physical, Thermal, and Mechanical Properties

by Claudia Sergi, Jacopo Tirillò, Fabrizio Sarasini, Enrique Barbero Pozuelo, Sonia Sanchez Saez and Christoph Burgstaller

Polymers 2019, 11(12), 2118; https://doi.org/10.3390/polym11122118 - 17 Dec 2019

Cited by 16 | Viewed by 4407

Abstract

Considering the major role played by sandwich structures in many fields where high stiffness-to-weight ratio is required, the selection of a suitable core material is of paramount importance. In order to face the environmental problems related to waste disposal, the selection of an [...] Read more.

Considering the major role played by sandwich structures in many fields where high stiffness-to-weight ratio is required, the selection of a suitable core material is of paramount importance. In order to face the environmental problems related to waste disposal, the selection of an eco-friendly core material is now included in the design criteria of sandwich structures. Agglomerated cork is recognized as a good solution that combines satisfactory mechanical performances and eco-sustainability. Many research studies individually addressed cork’s morphological, thermal, and mechanical features without providing a comprehensive overview of the relationships that exist between them. In this work, the investigation of the peculiar cork morphology allowed learning more about its good insulation capacity and its impressive recovery capability. The use of dynamic mechanical analysis (DMA) and thermogravimetric analysis (TGA) clarified the influence of temperature on both flexural and compressive performances. The effect of testing parameters such as temperature and speed on agglomerated cork properties was validated through statistical analysis. Moreover, to highlight agglomerated cork advantages and drawbacks, the work provides also a comparison with more traditional polyvinylchloride (PVC) foams commonly used in industrial applications. Full article

(This article belongs to the Section Polymer Applications)

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11 pages, 2072 KiB

Open AccessArticle

Improving Performance of Electrospun Nylon 6,6 Nanofiber Membrane for Produced Water Filtration via Solvent Vapor Treatment

by Nur Syakinah Abd Halim, Mohd Dzul Hakim Wirzal, Muhammad Roil Bilad, Nik Abdul Hadi Md Nordin, Zulfan Adi Putra, Nonni Soraya Sambudi and Abdull Rahim Mohd Yusoff

Polymers 2019, 11(12), 2117; https://doi.org/10.3390/polym11122117 - 17 Dec 2019

Cited by 37 | Viewed by 6502

Abstract

Electrospun nanofiber membrane (NFM) has a high potential to be applied as a filter for produced water treatment due to its highly porous structure and great permeability. However, it faces fouling issues and has low mechanical properties, which reduces the performance and lifespan [...] Read more.

Electrospun nanofiber membrane (NFM) has a high potential to be applied as a filter for produced water treatment due to its highly porous structure and great permeability. However, it faces fouling issues and has low mechanical properties, which reduces the performance and lifespan of the membrane. NFM has a low integrity and the fine mat easily detaches from the sheet. In this study, nylon 6,6 was selected as the polymer since it offers great hydrophilicity. In order to increase mechanical strength and separation performance of NFM, solvent vapor treatment was implemented where the vapor induces the fusion of fibers. The fabricated nylon 6,6 NFMs were treated with different exposure times of formic acid vapor. Results show that solvent vapor treatment helps to induce the fusion of overlapping fibers. The optimum exposure time for solvent vapor is 5 h to offer full retention of dispersed oil (100% of oil rejection), has 62% higher in tensile strength (1950 MPa) compared to untreated nylon 6,6 NFM (738 MPa), and has the final permeability closest to the untreated nylon 6,6 NFM (733 L/m².h.bar). It also took more time to get fouled (220 min) compared to untreated NFM (160 min). Full article

(This article belongs to the Special Issue Electrospun Nanofibers: Theory and Its Applications)

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9 pages, 10300 KiB

Open AccessArticle

Modified Epoxy Resin Synthesis from Phosphorus—Containing Polyol and Physical Changes Studies in the Synthesized Products

by Jeong Beom Jang, Tae Hee Kim, Taeyoon Kim, Hye Jin Kim, Bongkuk Seo, Choong-Sun Lim and Wonjoo Lee

Polymers 2019, 11(12), 2116; https://doi.org/10.3390/polym11122116 - 16 Dec 2019

Cited by 5 | Viewed by 5137

Abstract

Epoxy resins are commonly used to manufacture the molding compounds, reinforced plastics, coatings, or adhesives required in various industries. However, the demand for new epoxy resins has increased to satisfy diverse industrial requirements such as enhanced mechanical properties, thermal stability, or electrical properties. [...] Read more.

Epoxy resins are commonly used to manufacture the molding compounds, reinforced plastics, coatings, or adhesives required in various industries. However, the demand for new epoxy resins has increased to satisfy diverse industrial requirements such as enhanced mechanical properties, thermal stability, or electrical properties. Therefore, in this study, we synthesized new epoxy resin (PPME) by modifying phosphorous-containing polyol. The prepared resin was analyzed and added to epoxy compositions in various quantities. The compositions were cured at high temperatures to obtain plastics to further test the mechanical and thermal properties of the epoxy resin. The measured tensile and flexural strength of epoxy compositions were similar to the composition without synthesized epoxy resin. However, the heat release rates of the compositions exhibited tendencies of a decrease proportional to the amount of PPME. Full article

(This article belongs to the Special Issue Thermosets II)

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16 pages, 4496 KiB

Open AccessArticle

Experimental, Numerical, and Analytical Study on The Effect of Graphene Oxide in The Mechanical Properties of a Solvent-Free Reinforced Epoxy Resin

by Sergio Horta Muñoz, María del Carmen Serna Moreno, José Miguel González-Domínguez, Pablo Antonio Morales-Rodríguez and Ester Vázquez

Polymers 2019, 11(12), 2115; https://doi.org/10.3390/polym11122115 - 16 Dec 2019

Cited by 9 | Viewed by 3435

Abstract

This paper presents a methodology for manufacturing nanocomposites from an epoxy resin reinforced with graphene oxide (GO) nanoparticles. A scalable and sustainable fabrication process, based on a solvent-free method, is proposed with the objective of achieving a high level of GO dispersion, while [...] Read more.

This paper presents a methodology for manufacturing nanocomposites from an epoxy resin reinforced with graphene oxide (GO) nanoparticles. A scalable and sustainable fabrication process, based on a solvent-free method, is proposed with the objective of achieving a high level of GO dispersion, while maintaining matrix performance. The results of three-point bending tests are examined by means of an analytical technique which allows determining the mechanical response of the material under tension and compression from flexural data. As result, an increase of 39% in the compressive elastic modulus of the nanocomposite is found with the addition of 0.3 wt % GO. In parallel, we described how the strain distribution and the failure modes vary with the amount of reinforcement based on digital image correlation (DIC) techniques and scanning electron microscopy (SEM). A novel analytical model, capable of predicting the influence of GO content on the elastic properties of the material, is obtained. Numerical simulations considering the experimental conditions are carried out. the full strain field given by the DIC system is successfully reproduced by means of the finite element method (FEM). While, the experimental failure is explained by the crack growth simulations using the eXtended finite element method (XFEM). Full article

(This article belongs to the Special Issue Processing and Molding of Polymers)

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21 pages, 8163 KiB

Open AccessArticle

Compression-Responsive Photonic Crystals Based on Fluorine-Containing Polymers

by Julia Kredel and Markus Gallei

Polymers 2019, 11(12), 2114; https://doi.org/10.3390/polym11122114 - 16 Dec 2019

Cited by 10 | Viewed by 4392

Abstract

Fluoropolymers represent a unique class of functional polymers due to their various interesting and important properties such as thermal stability, resistance toward chemicals, repellent behaviors, and their low refractive indices in comparison to other polymeric materials. Based on the latter optical property, fluoropolymers [...] Read more.

Fluoropolymers represent a unique class of functional polymers due to their various interesting and important properties such as thermal stability, resistance toward chemicals, repellent behaviors, and their low refractive indices in comparison to other polymeric materials. Based on the latter optical property, fluoropolymers are particularly of interest for the preparation of photonic crystals for optical sensing application. Within the present study, photonic crystals were prepared based on core-interlayer-shell particles focusing on fluoropolymers. For particle assembly, the melt-shear organization technique was applied. The high order and refractive index contrast of the individual components of the colloidal crystal structure lead to remarkable reflection colors according to Bragg’s law of diffraction. Due to the special architecture of the particles, consisting of a soft core, a comparably hard interlayer, and again a soft shell, the resulting opal films were capable of changing their shape and domain sizes upon applied pressure, which was accompanied with a (reversible) change of the observed reflection colors as well. By the incorporation of adjustable amounts of UV cross-linking agents into the opal film and subsequent treatment with different UV irradiation times, stable and pressure-sensitive opal films were obtained. It is shown that the present strategy led to (i) pressure-sensitive opal films featuring reversibly switchable reflection colors and (ii) that opal films can be prepared, for which the written pattern—resulting from the compressed particles—could be fixed upon subsequent irradiation with UV light. The herein described novel fluoropolymer-containing photonic crystals, with their pressure-tunable reflection color, are promising candidates in the field of sensing devices and as potential candidates for anti-counterfeiting materials. Full article

(This article belongs to the Section Polymer Chemistry)

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26 pages, 5925 KiB

Open AccessArticle

Poly(Glycerol Sebacate)–Poly(l-Lactide) Nonwovens. Towards Attractive Electrospun Material for Tissue Engineering

by Piotr Denis, Michał Wrzecionek, Agnieszka Gadomska-Gajadhur and Paweł Sajkiewicz

Polymers 2019, 11(12), 2113; https://doi.org/10.3390/polym11122113 - 16 Dec 2019

Cited by 33 | Viewed by 7525

Abstract

Two types of poly(glycerol sebacate) (PGS) prepolymers were synthesized and electrospun with poly(l-lactic acid) (PLA), resulting in bicomponent nonwovens. The obtained materials were pre-heated in a vacuum, at different times, to crosslink PGS and investigate morphological and structural dependencies in that [...] Read more.

Two types of poly(glycerol sebacate) (PGS) prepolymers were synthesized and electrospun with poly(l-lactic acid) (PLA), resulting in bicomponent nonwovens. The obtained materials were pre-heated in a vacuum, at different times, to crosslink PGS and investigate morphological and structural dependencies in that polymeric, electrospun system. As both PGS and PLA are sensitive to pre-heating (crosslinking) conditions, research concerns both components. More interest is focused on the properties of PGS, considering further research for mechanical properties and subsequent experiments with PGS synthesis. Electrospinning of PGS blended with PLA does not bring difficulties, but obtaining elastomeric properties of nonwovens is problematic. Even though PGS has many potential advantages over other polyesters when soft tissue engineering is considered, its full utilization via the electrospinning process is much harder in practice. Further investigations are ongoing, especially with the promising PGS prepolymer with a higher esterification degree and its variations. Full article

(This article belongs to the Special Issue Biodegradable Polymer Scaffolds for Tissue Engineering)

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15 pages, 1297 KiB

Open AccessArticle

Hydrofilm Polyurethane Films Reduce Radiation Dermatitis Severity in Hypofractionated Whole-Breast Irradiation: An Objective, Intra-Patient Randomized Dual-Center Assessment

by Leonard Christopher Schmeel, David Koch, Frederic Carsten Schmeel, Bettina Bücheler, Christina Leitzen, Birgit Mahlmann, Dorothea Kunze, Martina Heimann, Dilini Brüser, Alina-Valik Abramian, Felix Schoroth, Thomas Müdder, Fred Röhner, Stephan Garbe, Brigitta Gertrud Baumert, Hans Heinz Schild and Timo Martin Wilhelm-Buchstab

Polymers 2019, 11(12), 2112; https://doi.org/10.3390/polym11122112 - 16 Dec 2019

Cited by 29 | Viewed by 11201

Abstract

Radiation-induced skin injury represents the most frequent side effect in breast cancer patients undergoing whole-breast irradiation (WBI). Numerous clinical studies on systemic and topical treatments for radiation dermatitis have failed to provide sustainable treatment strategies. While protective skin products such as dressings are [...] Read more.

Radiation-induced skin injury represents the most frequent side effect in breast cancer patients undergoing whole-breast irradiation (WBI). Numerous clinical studies on systemic and topical treatments for radiation dermatitis have failed to provide sustainable treatment strategies. While protective skin products such as dressings are undoubtedly the standard of care in wound care management, their utilization as preventive treatment in radiotherapy has been somewhat neglected in recent years. In this prospective, intra-patient randomized observational study, Hydrofilm polyurethane films were prophylactically applied to either the medial or lateral breast-half of 74 patients with breast cancer undergoing hypofractionated whole-breast irradiation following breast-preserving surgery. Maximum radiation dermatitis severity was assessed using Common Terminology Criteria for Adverse Events (CTCAE) v4.03 toxicity scores, photospectrometric erythema and pigmentation measurements and patient-assessed modified Radiation-Induced Skin Reaction Assessment Scale (RISRAS) scale. Phantom studies revealed a clinically negligible dose build-up of less than 0.1% with Hydrofilm. Compared to the control compartments physician-assessed radiation dermatitis severity was reduced in the hydrofilm compartments (mean 0.54 vs. 1.34; p = < 0.001). Objective photospectrometric skin measurements showed decreased erythema (p = 0.0001) and hyperpigmentation (p = 0.002) underneath Hydrofilm. Hydrofilm also completely prevented moist desquamation, and significantly reduced patients’ treatment-related symptoms of itching, burning, pain, and limitations of day-to-day-activities. Significant beneficial effects were observed in terms of radiation dermatitis severity, erythema, hyperpigmentation as well as subjective treatment-related symptom experiences, while adverse reactions were rare and minor. Therefore, a prophylactic application of Hydrofilm polyurethane films can be suggested in hypofractionated WBI. Full article

(This article belongs to the Special Issue Advances in Functional Polyurethanes)

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13 pages, 2094 KiB

Open AccessArticle

Removal of Pb(II) Ions Using Polymer Inclusion Membranes Containing Calix[4]resorcinarene Derivative as Ion Carrier

by Iwona Zawierucha, Anna Nowik-Zajac and Cezary A. Kozlowski

Polymers 2019, 11(12), 2111; https://doi.org/10.3390/polym11122111 - 16 Dec 2019

Cited by 11 | Viewed by 2780

Abstract

Stricter environmental regulations regarding the discharge of toxic metals require developing various technologies for the removal of these metals from polluted effluents. The removal of toxic metal ions using immobilized membranes with doped ligands is a promising approach for enhancing environmental quality, because [...] Read more.

Stricter environmental regulations regarding the discharge of toxic metals require developing various technologies for the removal of these metals from polluted effluents. The removal of toxic metal ions using immobilized membranes with doped ligands is a promising approach for enhancing environmental quality, because of the high selectivity and removal efficiency, high stability, and low energy requirements of the membranes. Cellulose triacetate-based polymer inclusion membranes (PIMs), with calix[4]resorcinarene derivative as an ion carrier, were analyzed to determine their ability for removal of Pb(II) ions from aqueous solutions. The effects of ion carrier concentration, plasticizer amount, pH of source aqueous phase, and receiving agents on the effective transport of Pb(II) were determined. All studied parameters were found to be important factors for the transport of Pb(II) ions. The PIM containing calix[4]resorcinarene derivative as an ion carrier showed high stability and excellent transport activity for selective removal of Pb(II) from the battery industry effluent, with a separation efficiency of 90%. Full article

(This article belongs to the Special Issue Polymer-Based Membrane Technology and Applications)

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14 pages, 1940 KiB

Open AccessArticle

Synthesis and Application of H-ZSM-5 Zeolites with Different Levels of Acidity as Synergistic Agents in Flame Retardant Polymeric Materials

by Felipe Reis Bernardes, Michelle Jakeline Cunha Rezende, Victor de Oliveira Rodrigues, Regina Sandra Veiga Nascimento and Simone Pereira da Silva Ribeiro

Polymers 2019, 11(12), 2110; https://doi.org/10.3390/polym11122110 - 16 Dec 2019

Cited by 11 | Viewed by 3349

Abstract

Several studies show a synergistic effect between intumescent formulations and aluminosilicates, such as zeolites and clays, but little is known about the effect of acidity of these additives on the synergistic action. In this work, H-ZSM-5 zeolite was submitted to desilication treatments for [...] Read more.

Several studies show a synergistic effect between intumescent formulations and aluminosilicates, such as zeolites and clays, but little is known about the effect of acidity of these additives on the synergistic action. In this work, H-ZSM-5 zeolite was submitted to desilication treatments for 30 min and for 2 h, and silicalite-1 was synthesized. The objective was to obtain samples of equivalent crystalline structure, but with different amounts of acid sites, in order to evaluate the effect of acid concentration of H-ZSM-5 zeolites on the synergistic action with an intumescent formulation composed by ammonium polyphosphate and pentaerythritol in polypropylene. H-ZSM-5 zeolites and silicalite were characterized by X-ray diffraction, nitrogen adsorption analysis and temperature-programmed desorption of ammonia. The desilication produced H-ZSM-5 zeolites with similar volumes of mesopores in both treatments, but the zeolite resulting from 2 h of desilication presented a higher concentration of acid sites than the zeolite from 30 min. The flame-retardant properties were evaluated by UL-94 classification, limiting oxygen index, glow-wire, thermogravimetric analysis and heating microscopy. The results showed that increasing the concentration and accessibility of the acid sites of H-ZSM-5 zeolites the flame-retardant properties of the studied composites improved. It is suggested that the increase of acid site concentration positively influences the catalysis of the reaction between ammonium polyphosphate and pentaerythritol, favoring the production of the precursors of the intumescent layer. Full article

(This article belongs to the Section Polymer Applications)

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17 pages, 3468 KiB

Open AccessArticle

Plasma Treatment of Polymer Powder as an Effective Tool to Functionalize Polymers: Case Study Application on an Amphiphilic Polyurethane

by Rossella Laurano, Monica Boffito, Alessandro Torchio, Claudio Cassino, Valeria Chiono and Gianluca Ciardelli

Polymers 2019, 11(12), 2109; https://doi.org/10.3390/polym11122109 - 16 Dec 2019

Cited by 20 | Viewed by 4814

Abstract

Plasma treatment is a widely applied, easy, fast, and highly reproducible surface modification technique. In this work powder plasma treatment was exploited to expose carboxylic groups along the backbone of a water soluble polymer. Specifically, a custom-made amphiphilic poly(ether urethane) containing Poloxamer^® [...] Read more.

Plasma treatment is a widely applied, easy, fast, and highly reproducible surface modification technique. In this work powder plasma treatment was exploited to expose carboxylic groups along the backbone of a water soluble polymer. Specifically, a custom-made amphiphilic poly(ether urethane) containing Poloxamer^® 407 blocks (M_w = 54,000 Da) was first synthesized and its powders were plasma treated in the presence of Acrylic Acid vapor. To maximize –COOH group exposure while preventing polymer degradation, different Ar gas flow rates (i.e., 10, 30, and 50 sccm) were investigated. Upon gas flow increase, significant polymer degradation was observed, with a 35% molecular weight reduction at 50 sccm Ar flow rate. On the other hand, the highest number of exposed carboxylic groups (5.3 × 10¹⁸ ± 5.5 × 10¹⁷ units/g_polymer) was obtained by setting gas flow at 10 sccm. Hence, a gas flow of 10 sccm turned out to be the best set-up to maximize –COOH exposure while preventing degradation phenomena. Additionally, upon plasma treatment, no detrimental effects were observed in the thermoresponsiveness of polymer aqueous solutions, which was ensured by Poloxamer^® 407 blocks. Therefore, the newly developed technology here applied on an amphiphilic poly(ether urethane) could pave the way to the tailored design of a plethora of different multifunctional hydrogels. Full article

(This article belongs to the Special Issue Stimuli Responsive Polymers II)

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13 pages, 4620 KiB

Open AccessArticle

Allylamine PECVD Modification of PDMS as Simple Method to Obtain Conductive Flexible Polypyrrole Thin Films

by Robert Texidó and Salvador Borrós

Polymers 2019, 11(12), 2108; https://doi.org/10.3390/polym11122108 - 15 Dec 2019

Cited by 5 | Viewed by 4380

Abstract

In this paper, we report a one-step method to obtain conductive polypyrrole thin films on flexible substrates. To do this, substrates were modified through allylamine plasma grafting to create a high amount of reactive amine groups on PDMS surface. These groups are used [...] Read more.

In this paper, we report a one-step method to obtain conductive polypyrrole thin films on flexible substrates. To do this, substrates were modified through allylamine plasma grafting to create a high amount of reactive amine groups on PDMS surface. These groups are used during polypyrrole particle synthesis as anchoring points to immobilize the polymeric chains on the substrate during polymerization. Surface morphology of polypyrrole thin films are modified, tailoring the polyelectrolyte used in the polypyrrole synthesis obtaining different shapes of nanoparticles that conform to the film. Depending on the polyelectrolyte molecular weight, the shape of polypyrrole particles go from globular (500 nm diameter) to a more constructed and elongated shape. The films obtained with this methodology reflected great stability under simple bending as well as good conductivity values (between 2.2 ± 0.7 S/m to 5.6 ± 0.2 S/cm). Full article

(This article belongs to the Special Issue Conducting Polymers for Advanced Applications)

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16 pages, 4101 KiB

Open AccessArticle

Surface Modification of Bamboo Fibers to Enhance the Interfacial Adhesion of Epoxy Resin-Based Composites Prepared by Resin Transfer Molding

by Dong Wang, Tian Bai, Wanli Cheng, Can Xu, Ge Wang, Haitao Cheng and Guangping Han

Polymers 2019, 11(12), 2107; https://doi.org/10.3390/polym11122107 - 15 Dec 2019

Cited by 42 | Viewed by 5439

Abstract

Bamboo fibers (BFs)-reinforced epoxy resin (EP) composites are prepared by resin transfer molding (RTM). The influence of BFs surface modification (NaOH solution or coupling agents, i.e., KH550 and KH560) on interfacial properties of BFs/EP composites is systematically investigated. The synergistic effect of hydrolysis, [...] Read more.

Bamboo fibers (BFs)-reinforced epoxy resin (EP) composites are prepared by resin transfer molding (RTM). The influence of BFs surface modification (NaOH solution or coupling agents, i.e., KH550 and KH560) on interfacial properties of BFs/EP composites is systematically investigated. The synergistic effect of hydrolysis, peeling reaction of BFs, and the condensation reaction of hydrolyzed coupling agents are confirmed by FTIR. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) reveal that the interfacial compatibility of NaOH- and silane-modified BFs/EP composites was significantly improved. KH550-modified BFs/EP composite renders optimal tensile, flexural, and impact strength values of 68 MPa, 86 MPa, and 226 J/m. The impact resistance mechanism at the interface of BFs/EP composites was proposed. Moreover, the dynamic mechanical properties, creep behavior, and differential scanning calorimetry of BFs/EP composites have also been carried out to understand thermal stabilities. Overall, the surface-modified BFs-reinforced EP composites exhibited superior interfacial bonding. Full article

(This article belongs to the Special Issue Epoxy Resins and Composites)

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31 pages, 7630 KiB

Open AccessReview

Fundamentals of Global Modeling for Polymer Extrusion

by Krzysztof Wilczyński, Andrzej Nastaj, Adrian Lewandowski, Krzysztof J. Wilczyński and Kamila Buziak

Polymers 2019, 11(12), 2106; https://doi.org/10.3390/polym11122106 - 15 Dec 2019

Cited by 55 | Viewed by 20265

Abstract

A review paper is presented on modeling for polymer extrusion for both single screw and twin-screw extrusion. An issue of global modeling is discussed, which includes modeling for solid conveying, melting, melt flow, and co-operation of the screw/die system. The classical approach to [...] Read more.

A review paper is presented on modeling for polymer extrusion for both single screw and twin-screw extrusion. An issue of global modeling is discussed, which includes modeling for solid conveying, melting, melt flow, and co-operation of the screw/die system. The classical approach to global modeling of the extrusion process, which is based on separate models for each section of the screw, i.e., solid transport section, melting and pre-melting sections, and the melt flow section is presented. In this case, the global model consists of the elementary models. A novel continuous concept of global modeling based on CFD (Computational Fluids Dynamics) computations is also presented, and a concept of using the DEM (Discrete Element Method) computation coupled with CFD computations is discussed. Full article

(This article belongs to the Special Issue Advances in Screw Processing of Polymeric Materials - In Memory of Professor James Lindsay White)

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20 pages, 7594 KiB

Open AccessArticle

Modification of Poly(Ethylene 2,5-Furandicarboxylate) with Poly(Ethylene glycol) for Biodegradable Copolyesters with Good Mechanical Properties and Spinnability

by Peng Ji, Danping Lu, Shengming Zhang, Wanying Zhang, Chaosheng Wang and Huaping Wang

Polymers 2019, 11(12), 2105; https://doi.org/10.3390/polym11122105 - 14 Dec 2019

Cited by 21 | Viewed by 5256

Abstract

Using 2,5-furandicarboxylic acid, ethylene glycol, and poly(ethylene glycol) as raw materials and ethylene glycol antimony as a catalyst, poly(ethylene furandicarboxylate) (PEF) and polyethylene glycol (PEG) copolymers (PEGFs) were synthesized by transesterification by changing the molecular weight of PEG (from 600 to 10,000 g/mol) [...] Read more.

Using 2,5-furandicarboxylic acid, ethylene glycol, and poly(ethylene glycol) as raw materials and ethylene glycol antimony as a catalyst, poly(ethylene furandicarboxylate) (PEF) and polyethylene glycol (PEG) copolymers (PEGFs) were synthesized by transesterification by changing the molecular weight of PEG (from 600 to 10,000 g/mol) and the PEG content (from 10 to 60 wt %). The thermal, hydrophilic, degradation, and spinnility characteristics of these copolymers were then investigated. Thermogravimetric analysis shows that PEGF is thermally stable at 62 °C, much lower than the temperature for PEF. The intrinsic viscosity of the obtained copolyester was between 0.67 and 0.99 dL/g, which is higher than the viscosity value of PEF. The contact angle experiment shows that the hydrophilicity of PEGFs is improved (the surface contact angle is reduced from 91.9 to 63.3°), which gives PEGFs a certain degradability, and the maximum mass loss can reach approximately 15%. Melt spinning experiments show that the PEGF polymer has poor spinnability, but the mechanical properties of the polymer monofilament are better. Full article

(This article belongs to the Special Issue Synthesis and Characterization of Bio-Based Polymers)

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17 pages, 2488 KiB

Open AccessArticle

Chemically Denatured Structures of Porcine Pepsin using Small-Angle X-ray Scattering

by Yecheol Rho, Jun Ha Kim, Byoungseok Min and Kyeong Sik Jin

Polymers 2019, 11(12), 2104; https://doi.org/10.3390/polym11122104 - 14 Dec 2019

Cited by 13 | Viewed by 4323

Abstract

Porcine pepsin is a gastric aspartic proteinase that reportedly plays a pivotal role in the digestive process of many vertebrates. We have investigated the three-dimensional (3D) structure and conformational transition of porcine pepsin in solution over a wide range of denaturant urea concentrations [...] Read more.

Porcine pepsin is a gastric aspartic proteinase that reportedly plays a pivotal role in the digestive process of many vertebrates. We have investigated the three-dimensional (3D) structure and conformational transition of porcine pepsin in solution over a wide range of denaturant urea concentrations (0–10 M) using Raman spectroscopy and small-angle X-ray scattering. Furthermore, 3D GASBOR ab initio structural models, which provide an adequate conformational description of pepsin under varying denatured conditions, were successfully constructed. It was shown that pepsin molecules retain native conformation at 0–5 M urea, undergo partial denaturation at 6 M urea, and display a strongly unfolded conformation at 7–10 M urea. According to the resulting GASBOR solution models, we identified an intermediate pepsin conformation that was dominant during the early stage of denaturation. We believe that the structural evidence presented here provides useful insights into the relationship between enzymatic activity and conformation of porcine pepsin at different states of denaturation. Full article

(This article belongs to the Section Polymer Analysis and Characterization)

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15 pages, 5923 KiB

Open AccessArticle

Evolution of Interfacial Friction Angle and Contact Area of Polymer Pellets during the Initial Stage of Ultrasonic Plasticization

by Bingyan Jiang, Yang Zou, Guomeng Wei and Wangqing Wu

Polymers 2019, 11(12), 2103; https://doi.org/10.3390/polym11122103 - 14 Dec 2019

Cited by 7 | Viewed by 3326

Abstract

Interfacial friction heating is one of the leading heat generation mechanisms during the initial stage of ultrasonic plasticization of polymer pellets, which has a significant influence on the subsequent viscoelastic heating according to our previous study. The interfacial friction angle and contact area [...] Read more.

Interfacial friction heating is one of the leading heat generation mechanisms during the initial stage of ultrasonic plasticization of polymer pellets, which has a significant influence on the subsequent viscoelastic heating according to our previous study. The interfacial friction angle and contact area of polymer pellets are critical boundary conditions for the analysis of interfacial frictional heating of polymer pellets. However, the duration of the interfacial friction heating is extremely short in ultrasonic plasticization, and the polymer pellets are randomly distributed in the cylindrical barrel, resulting in the characterization of the distribution of the interfacial friction angle and contact area to be a challenge. In this work, the interfacial friction angle of the polymer pellets in the partially plasticized samples of polymethyl methacrylate (PMMA), polypropylene (PP), and nylon66 (PA66) were characterized by a super-high magnification lens zoom 3D microscope. The influence of trigger pressure, plasticizing pressure, ultrasonic amplitude, and vibration time on the interfacial friction angle and the contact area of the polymer pellets were studied by a single factor experiment. The results show that the compaction degree of the plasticized samples could be enhanced by increasing the level of the process parameters. With the increasing parameter level, the proportion of interfacial friction angle in the range of 0–10° and 80–90° increased, while the proportion in the range of 30–60° decreased accordingly. The proportion of the contact area of the polymer pellets was increased up to 50% of the interfacial friction area which includes the upper, lower, and side area of the cylindrical plasticized sample. Full article

(This article belongs to the Special Issue Tribology of Polymers)

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15 pages, 4864 KiB

Open AccessArticle

Thiol–Ene Click Reaction Initiated Rapid Gelation of PEGDA/Silk Fibroin Hydrogels

by Jianwei Liang, Xiaoning Zhang, Zhenyu Chen, Shan Li and Chi Yan

Polymers 2019, 11(12), 2102; https://doi.org/10.3390/polym11122102 - 14 Dec 2019

Cited by 20 | Viewed by 5524

Abstract

In this work, poly(ethylene glycol) diacrylate (PEGDA) molecules were grafted to silk fibroin (SF) molecules via a thiol–ene click reaction under 405 nm UV illumination for the fabrication of a PEGDA/SF composite hydrogel. The composite hydrogels could be prepared in a short and [...] Read more.

In this work, poly(ethylene glycol) diacrylate (PEGDA) molecules were grafted to silk fibroin (SF) molecules via a thiol–ene click reaction under 405 nm UV illumination for the fabrication of a PEGDA/SF composite hydrogel. The composite hydrogels could be prepared in a short and controllable gelation time without the use of a photoinitiator. Features relevant to the drug delivery of the PEGDA/SF hydrogels were assessed, and the hydrogels were characterized by various techniques. The results showed that the prepared PEGDA/SF hydrogels demonstrated a good sustained-release performance with limited swelling behavior. It was found that a prior cooling step can improve the compressive strength of the hydrogels effectively. Additionally, the MTT assay indicated the prepared PEGDA/SF hydrogel is non-cytotoxic. Subcutaneous implantation of the PEGDA/SF hydrogel in Kunming mice did not induce an obvious inflammation, which revealed that the prepared PEGDA/SF hydrogel possessed good biocompatibility. Furthermore, the mechanism of the gelation process was discussed. Full article

(This article belongs to the Section Biobased and Biodegradable Polymers)

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9 pages, 1905 KiB

Open AccessArticle

Development of Multi-Functional Graphene Polymer Composites Having Electromagnetic Interference Shielding and De-Icing Properties

by Ji-Hwan Ha, Soon-Kook Hong, Jae-Kwan Ryu, Joonwon Bae and Sung-Hoon Park

Polymers 2019, 11(12), 2101; https://doi.org/10.3390/polym11122101 - 14 Dec 2019

Cited by 40 | Viewed by 4437

Abstract

We developed a multi-functional graphene composite with electromagnetic interference (EMI) shielding and de-icing properties. Two-dimensional graphene fillers were homogeneously dispersed in a polymer by three-roll milling. The electrical properties and percolation threshold of the graphene composites were measured with various graphene contents. The [...] Read more.

We developed a multi-functional graphene composite with electromagnetic interference (EMI) shielding and de-icing properties. Two-dimensional graphene fillers were homogeneously dispersed in a polymer by three-roll milling. The electrical properties and percolation threshold of the graphene composites were measured with various graphene contents. The variation in the EMI shielding properties of the graphene composites with respect to the filler content was measured. The shielding efficiency improved with increasing graphene filler content. Furthermore, we conducted electrical heating tests on the graphene composites. The composites could be heated rapidly to 200 °C by electrical Joule heating with low electric power because of the high electrical conductivity of the composite. Moreover, the composite film was suitable for application in a de-icing unit because of its rapid and homogenous heating performance. Full article

(This article belongs to the Special Issue Carbon Nanomaterial-Modified Polymer Composites)

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13 pages, 4422 KiB

Open AccessArticle

Examination of Poly (Styrene-Butadiene-Styrene)-Modified Asphalt Performance in Bonding Modified Aggregates Using Parallel Plates Method

by Xiangbing Gong, Zejiao Dong, Zhiyang Liu, Huanan Yu and Kaikai Hu

Polymers 2019, 11(12), 2100; https://doi.org/10.3390/polym11122100 - 14 Dec 2019

Cited by 2 | Viewed by 2772

Abstract

Although asphalt-aggregate bonding provides contacting strength for hot mix asphalt (HMA), it is still ignorant in dynamic shear test, due to the only use of metal parallel plate. Modified parallel plates cored from different types of aggregate were provided to simulate aggregate-asphalt-aggregate (AAA) [...] Read more.

Although asphalt-aggregate bonding provides contacting strength for hot mix asphalt (HMA), it is still ignorant in dynamic shear test, due to the only use of metal parallel plate. Modified parallel plates cored from different types of aggregate were provided to simulate aggregate-asphalt-aggregate (AAA) sandwich in HMA, aiming at the comprehensive interpretation on bonding’s influence. This study began with an experimental design, aggregate plates, and joint clamps were processed to be installed into the rheometer. Aggregate type and loading conditions were set as essential variables. Subsequently, microscopic tests were utilized to obtain chemical components of aggregate, micro morphology of interface, and roughness of plates. The shearing tests for poly (styrene-butadiene-styrene)-modified asphalt were conducted in bonding with aggregate plates. Meanwhile, contrasting groups adopting metal plates followed the same experimental procedures. The results indicate that the influence of aggregate type on binder’s rheological characteristics is dependent on the experimental variables, and microscopic characteristics and component differences should be taken into consideration when selecting aggregates in designing asphalt mixtures. Full article

(This article belongs to the Special Issue Functional Polymer Solutions and Gels–Physics and Novel Applications)

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19 pages, 2430 KiB

Open AccessArticle

Development of Injection-Molded Polylactide Pieces with High Toughness by the Addition of Lactic Acid Oligomer and Characterization of Their Shape Memory Behavior

by Diego Lascano, Giovanni Moraga, Juan Ivorra-Martinez, Sandra Rojas-Lema, Sergio Torres-Giner, Rafael Balart, Teodomiro Boronat and Luis Quiles-Carrillo

Polymers 2019, 11(12), 2099; https://doi.org/10.3390/polym11122099 - 14 Dec 2019

Cited by 26 | Viewed by 4442

Abstract

This work reports the effect of the addition of an oligomer of lactic acid (OLA), in the 5–20 wt% range, on the processing and properties of polylactide (PLA) pieces prepared by injection molding. The obtained results suggested that the here-tested OLA mainly performs [...] Read more.

This work reports the effect of the addition of an oligomer of lactic acid (OLA), in the 5–20 wt% range, on the processing and properties of polylactide (PLA) pieces prepared by injection molding. The obtained results suggested that the here-tested OLA mainly performs as an impact modifier for PLA, showing a percentage increase in the impact strength of approximately 171% for the injection-molded pieces containing 15 wt% OLA. A slight plasticization was observed by the decrease of the glass transition temperature (T_g) of PLA of up to 12.5 °C. The OLA addition also promoted a reduction of the cold crystallization temperature (T_cc) of more than 10 °C due to an increased motion of the biopolymer chains and the potential nucleating effect of the short oligomer chains. Moreover, the shape memory behavior of the PLA samples was characterized by flexural tests with different deformation angles, that is, 15°, 30°, 60°, and 90°. The obtained results confirmed the extraordinary effect of OLA on the shape memory recovery (R_r) of PLA, which increased linearly as the OLA loading increased. In particular, the OLA-containing PLA samples were able to successfully recover over 95% of their original shape for low deformation angles, while they still reached nearly 70% of recovery for the highest angles. Therefore, the present OLA can be successfully used as a novel additive to improve the toughness and shape memory behavior of compostable packaging articles based on PLA in the new frame of the Circular Economy. Full article

(This article belongs to the Special Issue Advances in Manufacturing and Characterization of Functional Polyesters)

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20 pages, 4262 KiB

Open AccessReview

Progress in the Synthesis of Bifunctionalized Polyhedral Oligomeric Silsesquioxane

by Mingyue Wang, Hong Chi, Joshy K.S. and Fuke Wang

Polymers 2019, 11(12), 2098; https://doi.org/10.3390/polym11122098 - 14 Dec 2019

Cited by 51 | Viewed by 7007

Abstract

Polyhedral oligomeric silsesquioxane (POSS) has been considered as one of the most promising nanofillers in academic and industrial research due to its unique multifunctional nanostructure, easy functionalization, hybrid nature, and high processability. The progress of POSS has been extensive, particularly applications based on [...] Read more.

Polyhedral oligomeric silsesquioxane (POSS) has been considered as one of the most promising nanofillers in academic and industrial research due to its unique multifunctional nanostructure, easy functionalization, hybrid nature, and high processability. The progress of POSS has been extensive, particularly applications based on single- or multiple-armed POSS. In polymer hybrids, in order to enhance the properties, bifunctional POSS has been incorporated into the backbone chain of the polymer. This review summarizes recent developments in the synthesis, modification, and application of bifunctional POSS-containing composite materials. This includes amino-POSS, hydroxyl-POSS, aromatic ring-POSS, ether-POSS, and vinyl groups-POSS and their applications, exemplified by polyurethanes (PUs) and polyimides (PIs). In addition, the review highlights the enhancement of thermal, mechanical, and optical properties of the composites. Full article

(This article belongs to the Collection Silicon-Containing Polymeric Materials)

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14 pages, 2839 KiB

Open AccessArticle

A Novel Class of Cost Effective and High Performance Composites Based on Terephthalate Salts Reinforced Polyether Ether Ketone

by Franco Dominici, Debora Puglia, Francesca Luzi, Fabrizio Sarasini, Marco Rallini and Luigi Torre

Polymers 2019, 11(12), 2097; https://doi.org/10.3390/polym11122097 - 14 Dec 2019

Cited by 10 | Viewed by 2930

Abstract

Poly(ether ether ketone) (PEEK)-based nanocomposites have been realized with incorporation (0–30 wt %) of anhydrous calcium terephthalate salts (CATAS), synthetized by reaction of terephtalic acid with the metal (Ca) oxide, by means of a melt processing. Their structure, morphology, thermal, and mechanical properties [...] Read more.

Poly(ether ether ketone) (PEEK)-based nanocomposites have been realized with incorporation (0–30 wt %) of anhydrous calcium terephthalate salts (CATAS), synthetized by reaction of terephtalic acid with the metal (Ca) oxide, by means of a melt processing. Their structure, morphology, thermal, and mechanical properties have been investigated. Scanning electron microscopy observations confirmed homogeneous dispersion of nanometer-sized fillers and a toughened fracture morphology even at the higher content, while thermal characterization confirmed an unvaried thermal stability and unmodified crystalline structure of the reference PEEK matrix. A negligible nucleating effect was evidenced, while a blocking effect of the amorphous phase fraction provide composites with increased stiffness, confirmed by enhanced values of G’ and shifts of glass transition peak to higher temperatures, for restriction in chain mobility imposed by CATAS. The proposed solutions aimed to enlarge the application range of high performance costly PEEK-based composites, by using thermally stable nanofillers with limited costs and easily controllable synthesis phase. Full article

(This article belongs to the Section Polymer Analysis and Characterization)

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