Polymers

17 pages, 4515 KiB

Open AccessArticle

Synergistic Effect of Binary Mixed-Pluronic Systems on Temperature Dependent Self-assembly Process and Drug Solubility

by Chin-Fen Lee, Hsueh-Wen Tseng, Pratap Bahadur and Li-Jen Chen

Polymers 2018, 10(1), 105; https://doi.org/10.3390/polym10010105 - 22 Jan 2018

Cited by 23 | Viewed by 6263

Mixed Pluronic micelles from very hydrophobic and very hydrophilic copolymers were selected to scrutinize the synergistic effect on the self-assembly process as well as the solubilization capacity of ibuprofen. The tendency of mixing behavior between parent copolymers was systematically examined from two perspectives: [...] Read more.

Mixed Pluronic micelles from very hydrophobic and very hydrophilic copolymers were selected to scrutinize the synergistic effect on the self-assembly process as well as the solubilization capacity of ibuprofen. The tendency of mixing behavior between parent copolymers was systematically examined from two perspectives: different block chain lengths at same hydrophilicity (L92 + F108, +F98, +F88, and +F68), as well as various hydrophobicities at the same PPO moiety (L92 + F88, +F87, and +P84). Temperature-dependent micellization in these binary systems was clearly inspected by the combined use of high sensitivity differential scanning calorimeter (HSDSC) and dynamic light scattering (DLS). Changes in heat capacity and size of aggregates at different temperatures during the whole micellization process were simultaneously observed and examined. While distinction of block chain length between parent copolymers increases, the monodispersity of the binary Pluronic systems decreases. However, parent copolymers with distinct PPO moieties do not affirmatively lead to non-cooperative binding, such as the L92 + P84 system. The addition of ibuprofen promotes micellization as well as stabilizes aggregates in the solution. The partial replacement of the hydrophilic Pluronic by a more hydrophobic Pluronic L92 would increase the total hydrophobicity of mixed Pluronics used in the system to substantially enhance the solubility of ibuprofen. The solubility of ibuprofen in the 0.5 wt % L92 + 0.368 wt % P84 system is as high as 4.29 mg/mL, which is 1.4 times more than that of the 0.868 wt % P84 system and 147 times more than that in pure water at 37 °C. Full article

(This article belongs to the Special Issue Polymer Micelles)

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8 pages, 3032 KiB

Open AccessCommunication

Magnetically Tunable Vibration Transmissibility for Polyurethane Magnetic Elastomers

by Hiroyuki Endo, Shunsuke Kato, Mayuko Watanebe, Takehito Kikuchi, Mika Kawai and Tetsu Mitsumata

Polymers 2018, 10(1), 104; https://doi.org/10.3390/polym10010104 - 22 Jan 2018

Cited by 10 | Viewed by 6383

Abstract

The effect of a weak magnetic field on vibration transmissibility was investigated for magnetic elastomers with various volume fractions of magnetic particles. Polyurethane elastomers without magnetic particles exhibited a natural frequency at 53 Hz and were insensitive to a magnetic field of 60 [...] Read more.

The effect of a weak magnetic field on vibration transmissibility was investigated for magnetic elastomers with various volume fractions of magnetic particles. Polyurethane elastomers without magnetic particles exhibited a natural frequency at 53 Hz and were insensitive to a magnetic field of 60 mT. The natural frequency for magnetic elastomers with a volume fraction of 0.23 was 115 Hz at 0 mT, and increased to 134 Hz at 60 mT. The vibration transmissibility was independent of the magnetic field. A linear relation between the natural frequency and (G/m)^1/2 was observed (G: storage modulus, m: mass), indicating that the observed vibration is basically described by a simple harmonic oscillation. Full article

(This article belongs to the Special Issue Elastomers)

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16 pages, 3462 KiB

Open AccessArticle

Designing High-Refractive Index Polymers Using Materials Informatics

by Vishwesh Venkatraman and Bjørn Kåre Alsberg

Polymers 2018, 10(1), 103; https://doi.org/10.3390/polym10010103 - 22 Jan 2018

Cited by 32 | Viewed by 11580

Abstract

A machine learning strategy is presented for the rapid discovery of new polymeric materials satisfying multiple desirable properties. Of particular interest is the design of high refractive index polymers. Our in silico approach employs a series of quantitative structure–property relationship models that facilitate [...] Read more.

A machine learning strategy is presented for the rapid discovery of new polymeric materials satisfying multiple desirable properties. Of particular interest is the design of high refractive index polymers. Our in silico approach employs a series of quantitative structure–property relationship models that facilitate rapid virtual screening of polymers based on relevant properties such as the refractive index, glass transition and thermal decomposition temperatures, and solubility in standard solvents. Exploration of the chemical space is carried out using an evolutionary algorithm that assembles synthetically tractable monomers from a database of existing fragments. Selected monomer structures that were further evaluated using density functional theory calculations agree well with model predictions. Full article

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17 pages, 3663 KiB

Open AccessArticle

Highly Zeolite-Loaded Polyvinyl Alcohol Composite Membranes for Alkaline Fuel-Cell Electrolytes

by Po-Ya Hsu, Ting-Yu Hu, Selvaraj Rajesh Kumar, Chia-Hao Chang, Kevin C.-W. Wu, Kuo-Lun Tung and Shingjiang Jessie Lue

Polymers 2018, 10(1), 102; https://doi.org/10.3390/polym10010102 - 22 Jan 2018

Cited by 39 | Viewed by 8749

Abstract

Having a secure and stable energy supply is a top priority for the global community. Fuel-cell technology is recognized as a promising electrical energy generation system for the twenty-first century. Polyvinyl alcohol/zeolitic imidazolate framework-8 (PVA/ZIF-8) composite membranes were successfully prepared in this work [...] Read more.

Having a secure and stable energy supply is a top priority for the global community. Fuel-cell technology is recognized as a promising electrical energy generation system for the twenty-first century. Polyvinyl alcohol/zeolitic imidazolate framework-8 (PVA/ZIF-8) composite membranes were successfully prepared in this work from direct ZIF-8 suspension solution (0–45.4 wt %) and PVA mixing to prevent filler aggregation for direct methanol alkaline fuel cells (DMAFCs). The ZIF-8 fillers were chosen for the appropriate cavity size as a screening aid to allow water and suppress methanol transport. Increased ionic conductivities and suppressed methanol permeabilities were achieved for the PVA/40.5% ZIF-8 composites, compared to other samples. A high power density of 173.2 mW cm⁻² was achieved using a KOH-doped PVA/40.5% ZIF-8 membrane in a DMAFC at 60 °C with 1–2 mg cm⁻² catalyst loads. As the filler content was raised beyond 45.4 wt %, adverse effects resulted and the DMAFC performance (144.9 mW cm⁻²) was not improved further. Therefore, the optimal ZIF-8 content was approximately 40.5 wt % in the polymeric matrix. The specific power output was higher (58 mW mg⁻¹) than most membranes reported in the literature (3–18 mW mg⁻¹). Full article

(This article belongs to the Special Issue Polymeric Membranes)

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16 pages, 4061 KiB

Open AccessArticle

A Combined Self-Consistent Method to Estimate the Effective Properties of Polypropylene/Calcium Carbonate Composites

by Zhongqiang Xiong, Shaorong Lu, Junkun Liu, Guangsheng Lv, Yuqi Li and Jinhong Yu

Polymers 2018, 10(1), 101; https://doi.org/10.3390/polym10010101 - 21 Jan 2018

Cited by 7 | Viewed by 4278

Abstract

In this work, trying to avoid difficulty of application due to the irregular filler shapes in experiments, self-consistent and differential self-consistent methods were combined to obtain a decoupled equation. The combined method suggests a tenor γ independent of filler-contents being an important connection [...] Read more.

In this work, trying to avoid difficulty of application due to the irregular filler shapes in experiments, self-consistent and differential self-consistent methods were combined to obtain a decoupled equation. The combined method suggests a tenor γ independent of filler-contents being an important connection between high and low filler-contents. On one hand, the constant parameter can be calculated by Eshelby’s inclusion theory or the Mori–Tanaka method to predict effective properties of composites coinciding with its hypothesis. On the other hand, the parameter can be calculated with several experimental results to estimate the effective properties of prepared composites of other different contents. In addition, an evaluation index

σ_{f}^{'}

of the interactional strength between matrix and fillers is proposed based on experiments. In experiments, a hyper-dispersant was synthesized to prepare polypropylene/calcium carbonate (PP/CaCO₃) composites up to 70 wt % of filler-content with dispersion, whose dosage was only 5 wt % of the CaCO₃ contents. Based on several verifications, it is hoped that the combined self-consistent method is valid for other two-phase composites in experiments with the same application progress as in this work. Full article

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13 pages, 1960 KiB

Open AccessArticle

Temperature-Responsive Polymer Microgel-Gold Nanorods Composite Particles: Physicochemical Characterization and Cytocompatibility

by Aslam Khan, Tajdar Husain Khan, Maqusood Ahamed, Ahmed Mohamed El-Toni, Ali Aldalbahi, Javed Alam and Tansir Ahamad

Polymers 2018, 10(1), 99; https://doi.org/10.3390/polym10010099 - 20 Jan 2018

Cited by 13 | Viewed by 6843

Abstract

In this paper, we report an easy route for preparing new metal nanorod-polymer composites consisting of gold nanorods, Au NRs, and temperature responsive copolymer “microgel” particles. The microgel particles of ~200 nm in size, which contain carboxylic acid groups, were prepared by surfactant-free [...] Read more.

In this paper, we report an easy route for preparing new metal nanorod-polymer composites consisting of gold nanorods, Au NRs, and temperature responsive copolymer “microgel” particles. The microgel particles of ~200 nm in size, which contain carboxylic acid groups, were prepared by surfactant-free emulsion polymerization of a selected mixture made of N-isopropylacylamide and acrylic acid in the presence of a cross-linker N,N′-methylenebisacrylamide. The electrostatic interactions between the cationic cetyltrimethylammonium bromide (CTAB) stabilized Au NRs and anionic microgel particles were expected to occur in order to prepare stable Au NRs-microgel composite particles. The optical and structural characterization of the composite was achieved using UV-Vis spectroscopy, Field emission scanning electron microscopy (FESEM), Transmission electron microscopy (TEM) and dynamic light scattering (DLS). TEM image shows that Au NRs are attached on the surface of the microgel particles. Dynamic light scattering measurements prove that the composite particles are temperature responsive, which means the particles undergo a decrease in size as the temperature increases above its phase transition temperature. In vitro cytotoxicity of the composite materials were tested by 3-(4,5-Dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT), Lactate dehydrogenase (LDH), and hemolysis assay, which showed non-toxicity (biocompatibility). Full article

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

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19 pages, 16132 KiB

Open AccessArticle

Flexural Behaviour of Carbon Textile-Reinforced Concrete with Prestress and Steel Fibres

by Yunxing Du, Xinying Zhang, Lingling Liu, Fen Zhou, Deju Zhu and Wei Pan

Polymers 2018, 10(1), 98; https://doi.org/10.3390/polym10010098 - 20 Jan 2018

Cited by 41 | Viewed by 6143

Abstract

Four-point bending tests were adopted to investigate the influences of the number of textile layers, volume content of steel fibres, and prestress on the flexural behaviour of carbon textile-reinforced concrete (TRC). The failure mode of the specimen changed from debonding failure to shear [...] Read more.

Four-point bending tests were adopted to investigate the influences of the number of textile layers, volume content of steel fibres, and prestress on the flexural behaviour of carbon textile-reinforced concrete (TRC). The failure mode of the specimen changed from debonding failure to shear failure, accompanied by the matrix-textile interfacial debonding with an increasing number of textile layers. The interfacial bonding performance between the textile and matrix improved with the addition of steel fibres in the TRC specimens. The presence of prestress or steel fibres improved first-crack and ultimate stresses of the TRC specimen. In comparison with the first-crack stress, a more pronounced enhancement in the ultimate stress was achieved by the addition of steel fibres. However, the effect of prestress on the first-crack stress was found to be more significant than on the ultimate stress. The prestress combined with steel fibres further improved the flexural behaviour of the TRC specimens. The prestressed TRC specimens with 1% volume content of steel fibres effectively avoided debonding. Thus, the utilization of the textiles could be improved. Full article

(This article belongs to the Special Issue Textile and Textile-Based Materials)

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11 pages, 3767 KiB

Open AccessArticle

Synthesis of Molecularly Imprinted Cryogels to Deplete Abundant Proteins from Bovine Serum

by Chun Yang, Yan Zhang, Wei-Qin Cao, Xiao-Feng Ji, Jian Wang, Ya-Nan Yan, Tao-Lin Zhong and Yu Wang

Polymers 2018, 10(1), 97; https://doi.org/10.3390/polym10010097 - 20 Jan 2018

Cited by 14 | Viewed by 4490

Abstract

Molecularly imprinted polyacrylamide cryogels were synthesized with pending templates (bovine serums of different concentrations). As the serum concentrations increased in the monomer solutions, the resulting cryogels could adsorb and deplete more proteins from serum samples. Due to the addition of vinyltriethoxysilane (VTEOS) in [...] Read more.

Molecularly imprinted polyacrylamide cryogels were synthesized with pending templates (bovine serums of different concentrations). As the serum concentrations increased in the monomer solutions, the resulting cryogels could adsorb and deplete more proteins from serum samples. Due to the addition of vinyltriethoxysilane (VTEOS) in the prepolymerizing solutions, the polymers came as organic–inorganic hybrid materials. It endued the silica-modified amphoteric polyacrylamide cryogels with improved mechanical strengths. Scanning electron micrography (SEM), Infrared (IR) spectrometry, thermogravimetry-differential thermal analysis (TG-DTA), and X-ray photoelectron spectroscopy (XPS) were carried out to characterize these macroporous polymers. Amphoteric cryogels proved to be favorable materials recognizing and binding proteins. When used as liquid chromatography stationary phases, they were capable of simultaneously adsorbing various serum proteins. Electrophoresis showed that abundant proteins were gradually depleted by the cryogels prepared from increased ratios of bovine serums in the monomer solutions. As abundant proteins are always imprinted first, this sample per se imprinting method provides an effective and convenient way to deplete abundant proteins from complex samples such as serums, meanwhile concentrating and collecting scarce species therein. Full article

(This article belongs to the Special Issue Molecularly Imprinted Polymers)

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19 pages, 1968 KiB

Open AccessArticle

Novel Antibacterial Polyglycidols: Relationship between Structure and Properties

by Fabian Marquardt, Cornelia Stöcker, Rita Gartzen, Elisabeth Heine, Helmut Keul and Martin Möller

Polymers 2018, 10(1), 96; https://doi.org/10.3390/polym10010096 - 20 Jan 2018

Cited by 8 | Viewed by 5779

Abstract

Antimicrobial polymers are an attractive alternative to low molecular weight biocides, because they are non-volatile, chemically stable, and can be used as non-releasing additives. Polymers with pendant quaternary ammonium groups and hydrophobic chains exhibit antimicrobial properties due to the electrostatic interaction between polymer [...] Read more.

Antimicrobial polymers are an attractive alternative to low molecular weight biocides, because they are non-volatile, chemically stable, and can be used as non-releasing additives. Polymers with pendant quaternary ammonium groups and hydrophobic chains exhibit antimicrobial properties due to the electrostatic interaction between polymer and cell wall, and the membrane disruptive capabilities of the hydrophobic moiety. Herein, the synthesis of cationic–hydrophobic polyglycidols with varying structures by post-polymerization modification is presented. The antimicrobial properties of the prepared polyglycidols against E. coli and S. aureus are examined. Polyglycidol with statistically distributed cationic and hydrophobic groups (cationic–hydrophobic balance of 1:1) is compared to (i) polyglycidol with a hydrophilic modification at the cationic functionality; (ii) polyglycidol with both—cationic and hydrophobic groups—at every repeating unit; and (iii) polyglycidol with a cationic–hydrophobic balance of 1:2. A relationship between structure and properties is presented. Full article

(This article belongs to the Special Issue Antimicrobial Polymers)

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8 pages, 2583 KiB

Open AccessCommunication

Photoluminescence Enhancement of Poly(3-methylthiophene) Nanowires upon Length Variable DNA Hybridization

by Jingyuan Huang, Jinho Choi, Gil Sun Lee, Fengchun Chen, Chunzhi Cui, Long Yi Jin and Dong Hyuk Park

Polymers 2018, 10(1), 100; https://doi.org/10.3390/polym10010100 - 20 Jan 2018

Cited by 5 | Viewed by 4948

Abstract

The use of low-dimensional inorganic or organic nanomaterials has advantages for DNA and protein recognition due to their sensitivity, accuracy, and physical size matching. In this research, poly(3-methylthiophene) (P3MT) nanowires (NWs) are electrochemically prepared with dopant followed by functionalization with probe DNA (pDNA) [...] Read more.

The use of low-dimensional inorganic or organic nanomaterials has advantages for DNA and protein recognition due to their sensitivity, accuracy, and physical size matching. In this research, poly(3-methylthiophene) (P3MT) nanowires (NWs) are electrochemically prepared with dopant followed by functionalization with probe DNA (pDNA) sequence through electrostatic interaction. Various lengths of pDNA sequences (10-, 20- and 30-mer) are conjugated to the P3MT NWs respectively followed with hybridization with their complementary target DNA (tDNA) sequences. The nanoscale photoluminescence (PL) properties of the P3MT NWs are studied throughout the whole process at solid state. In addition, the correlation between the PL enhancement and the double helix DNA with various lengths is demonstrated. Full article

(This article belongs to the Special Issue Polymer Based Bio-Sensors)

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18 pages, 2687 KiB

Open AccessArticle

Toughening of Poly(lactic acid) and Thermoplastic Cassava Starch Reactive Blends Using Graphene Nanoplatelets

by Anibal Bher, Ilke Uysal Unalan, Rafael Auras, Maria Rubino and Carlos E. Schvezov

Polymers 2018, 10(1), 95; https://doi.org/10.3390/polym10010095 - 19 Jan 2018

Cited by 47 | Viewed by 7049

Abstract

Poly(lactic acid) (PLA) was reactively blended with thermoplastic cassava starch (TPCS) and functionalized with commercial graphene (GRH) nanoplatelets in a twin-screw extruder, and films were produced by cast-film extrusion. Reactive compatibilization between PLA and TPCS phases was reached by introducing maleic anhydride and [...] Read more.

Poly(lactic acid) (PLA) was reactively blended with thermoplastic cassava starch (TPCS) and functionalized with commercial graphene (GRH) nanoplatelets in a twin-screw extruder, and films were produced by cast-film extrusion. Reactive compatibilization between PLA and TPCS phases was reached by introducing maleic anhydride and a peroxide radical during the reactive blending extrusion process. Films with improved elongation at break and toughness for neat PLA and PLA-g-TPCS reactive blends were obtained by an addition of GRH nanoplatelets. Toughness of the PLA-g-TPCS-GRH was improved by ~900% and ~500% when compared to neat PLA and PLA-g-TPCS, respectively. Crack bridging was established as the primary mechanism responsible for the improvement in the mechanical properties of PLA and PLA-g-TPCS in the presence of the nanofiller due to the high aspect ratio of GRH. Scanning electron microscopy images showed a non-uniform distribution of GRH nanoplatelets in the matrix. Transmittance of the reactive blend films decreased due to the TPCS phase. Values obtained for the reactive blends showed ~20% transmittance. PLA-GRH and PLA-g-TPCS-GRH showed a reduction of the oxygen permeability coefficient with respect to PLA of around 35% and 50%, respectively. Thermal properties, molecular structure, surface roughness, XRD pattern, electrical resistivity, and color of the films were also evaluated. Biobased and compostable reactive blend films of PLA-g-TPCS compounded with GRH nanoplatelets could be suitable for food packaging and agricultural applications. Full article

(This article belongs to the Special Issue Processing-Structure-Properties Relationships in Polymers)

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10 pages, 2493 KiB

Open AccessArticle

Temperature Scanning Stress Relaxation of an Autonomous Self-Healing Elastomer Containing Non-Covalent Reversible Network Junctions

by Amit Das, Aladdin Sallat, Frank Böhme, Essi Sarlin, Jyrki Vuorinen, Norbert Vennemann, Gert Heinrich and Klaus Werner Stöckelhuber

Polymers 2018, 10(1), 94; https://doi.org/10.3390/polym10010094 - 19 Jan 2018

Cited by 34 | Viewed by 8016

Abstract

In this work, we report about the mechanical relaxation characteristics of an intrinsically self-healable imidazole modified commercial rubber. This kind of self-healing rubber was prepared by melt mixing of 1-butyl imidazole with bromo-butyl rubber (bromine modified isoprene-isobutylene copolymer, BIIR). By this melt mixing [...] Read more.

In this work, we report about the mechanical relaxation characteristics of an intrinsically self-healable imidazole modified commercial rubber. This kind of self-healing rubber was prepared by melt mixing of 1-butyl imidazole with bromo-butyl rubber (bromine modified isoprene-isobutylene copolymer, BIIR). By this melt mixing process, the reactive allylic bromine of bromo-butyl rubber was converted into imidazole bromide salt. The resulting development of an ionic character to the polymer backbone leads to an ionic association of the groups which ultimately results to the formation of a network structure of the rubber chains. The modified BIIR thus behaves like a robust crosslinked rubber and shows unusual self-healing properties. The non-covalent reversible network has been studied in detail with respect to stress relaxation experiments, scanning electron microscopic and X-ray scattering. Full article

(This article belongs to the Special Issue Elastomers)

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11 pages, 1714 KiB

Open AccessFeature PaperArticle

Aggregation of Cationic Amphiphilic Block and Random Copoly(vinyl ether)s with Antimicrobial Activity

by Yukari Oda, Kazuma Yasuhara, Shokyoku Kanaoka, Takahiro Sato, Sadahito Aoshima and Kenichi Kuroda

Polymers 2018, 10(1), 93; https://doi.org/10.3390/polym10010093 - 19 Jan 2018

Cited by 12 | Viewed by 5837

Abstract

In this study, we investigated the aggregation behaviors of amphiphilic poly(vinyl ether)s with antimicrobial activity. We synthesized a di-block poly(vinyl ether), B38₂₆, composed of cationic primary amine and hydrophobic isobutyl (iBu) side chains, which previously showed antimicrobial activity against [...] Read more.

In this study, we investigated the aggregation behaviors of amphiphilic poly(vinyl ether)s with antimicrobial activity. We synthesized a di-block poly(vinyl ether), B38₂₆, composed of cationic primary amine and hydrophobic isobutyl (iBu) side chains, which previously showed antimicrobial activity against Escherichia coli. B38₂₆ showed similar uptake behaviors as those for a hydrophobic fluorescent dye, 1,6-diphenyl-1,3,5-hexatriene, to counterpart polymers including homopolymer H44 and random copolymer R40₂₅, indicating that the iBu block does not form strong hydrophobic domains. The cryo-TEM observations also indicated that the polymer aggregate of B38₂₆ appears to have low-density polymer chains without any defined microscopic structures. We speculate that B38₂₆ formed large aggregates by liquid-liquid separation due to the weak association of polymer chains. The fluorescence microscopy images showed that B38₂₆ bonds to E. coli cell surfaces, and these bacterial cells were stained by propidium iodide, indicating that the cell membranes were significantly damaged. The results suggest that block copolymers may provide a new platform to design and develop antimicrobial materials that can utilize assembled structures and properties. Full article

(This article belongs to the Special Issue Polymer Micelles)

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12 pages, 3370 KiB

Open AccessArticle

Thermo-Responsive Starch-g-(PAM-co-PNIPAM): Controlled Synthesis and Effect of Molecular Components on Solution Rheology

by Yifei Fan, Nadia Boulif and Francesco Picchioni

Polymers 2018, 10(1), 92; https://doi.org/10.3390/polym10010092 - 19 Jan 2018

Cited by 28 | Viewed by 8316

Abstract

A series of highly branched random copolymers of acrylamide (AM) and N-isopropylacrylamide (NIPAM) have been prepared from a waxy potato starch-based macroinitiator by aqueous Cu⁰-mediated living radical polymerization (Cu⁰-mediated LRP). The NIPAM intake in the copolymer was varied [...] Read more.

A series of highly branched random copolymers of acrylamide (AM) and N-isopropylacrylamide (NIPAM) have been prepared from a waxy potato starch-based macroinitiator by aqueous Cu⁰-mediated living radical polymerization (Cu⁰-mediated LRP). The NIPAM intake in the copolymer was varied between 0% and 50 mol % to evaluate the influence of chain composition on the aqueous rheological properties as well as their low critical solution temperature (LCST). The viscosity of the copolymer was found to increase with the NIPAM intake and an LCST can be observed when the NIPAM content is high enough (e.g., 50 mol %). In addition, thermo-thickening behavior was observed at a low shear rate (γ ≤ 10 s⁻¹) and higher NIPAM content was found to shift the onset of thermo-thickening behavior to a lower temperature. However, the absolute increase in viscosity values is reduced with the NIPAM intake. Besides this, an interesting significant thermo-thickening behavior was also observed on highly branched starch-g-polyacrylamide at high temperatures (>80 °C), which has not been previously reported. Rheology tests also revealed a good salt-resistant property in copolymers with low NIPAM content (e.g., <25 mol %). Considering the viscosity profile in saline as compared to that in pure water, this NIPAM intake seems to represent an optimum balance of viscosity and salt-resistance performance. Full article

(This article belongs to the Collection Polysaccharides)

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28 pages, 8031 KiB

Open AccessReview

Synthesis, Characterization, and Applications of Magnetic Nanoparticles Featuring Polyzwitterionic Coatings

by Philip Biehl, Moritz Von der Lühe, Silvio Dutz and Felix H. Schacher

Polymers 2018, 10(1), 91; https://doi.org/10.3390/polym10010091 - 18 Jan 2018

Cited by 154 | Viewed by 14091

Abstract

Throughout the last decades, magnetic nanoparticles (MNP) have gained tremendous interest in different fields of applications like biomedicine (e.g., magnetic resonance imaging (MRI), drug delivery, hyperthermia), but also more technical applications (e.g., catalysis, waste water treatment) have been pursued. Different surfactants and polymers [...] Read more.

Throughout the last decades, magnetic nanoparticles (MNP) have gained tremendous interest in different fields of applications like biomedicine (e.g., magnetic resonance imaging (MRI), drug delivery, hyperthermia), but also more technical applications (e.g., catalysis, waste water treatment) have been pursued. Different surfactants and polymers are extensively used for surface coating of MNP to passivate the surface and avoid or decrease agglomeration, decrease or modulate biomolecule absorption, and in most cases increase dispersion stability. For this purpose, electrostatic or steric repulsion can be exploited and, in that regard, surface charge is the most important (hybrid) particle property. Therefore, polyelectrolytes are of great interest for nanoparticle coating, as they are able to stabilize the particles in dispersion by electrostatic repulsion due to their high charge densities. In this review article, we focus on polyzwitterions as a subclass of polyelectrolytes and their use as coating materials for MNP. In the context of biomedical applications, polyzwitterions are widely used as they exhibit antifouling properties and thus can lead to minimized protein adsorption and also long circulation times. Full article

(This article belongs to the Special Issue Polymers and Block Copolymers at Interfaces and Surfaces)

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13 pages, 3363 KiB

Open AccessArticle

Effect of Hydroxyl Monomers on the Enzymatic Degradation of Poly(ethylene succinate), Poly(butylene succinate), and Poly(hexylene succinate)

by Zhenhui Bai, Yun Liu, Tingting Su and Zhanyong Wang

Polymers 2018, 10(1), 90; https://doi.org/10.3390/polym10010090 - 18 Jan 2018

Cited by 56 | Viewed by 6335

Abstract

Poly(ethylene succinate) (PES), poly(butylene succinate) (PBS), and poly(hexylene succinate) (PHS), were synthesized using succinic acid and different dihydric alcohols as materials. Enzymatic degradability by cutinase of the three kinds of polyesters was studied, as well as their solid-state properties. The biodegradation behavior relied [...] Read more.

Poly(ethylene succinate) (PES), poly(butylene succinate) (PBS), and poly(hexylene succinate) (PHS), were synthesized using succinic acid and different dihydric alcohols as materials. Enzymatic degradability by cutinase of the three kinds of polyesters was studied, as well as their solid-state properties. The biodegradation behavior relied heavily on the distance between ester groups, crystallinity, and the hydrophilicity-hydrophobicity balance of polyester surfaces. The weight loss through degradation of the three kinds of polyesters with different hydroxyl monomers took place in the order PHS > PBS > PES. The degradation behavior of the polyesters before and after degradation was analyzed by scanning electron microscopy, differential scanning calorimetry, powder X-ray diffraction, Fourier transform infrared spectroscopy, gel permeation chromatography, and thermogravimetric analysis. The decrease in relative intensity at 1800–1650 estedpolyesters were degraded simultaneously. The frequencies of the crystalline and amorphous bands were almost identical before and after degradation. Thus, enzymatic degradation did not change the crystalline structure but destroyed it, and the degree of crystallinity markedly decreased. The molecular weight and polydispersity index only changed slightly. The thermal stability of the three kinds of polyesters decreased during enzymatic degradation. Full article

(This article belongs to the Special Issue Biodegradable and Biobased Polyesters)

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16 pages, 5122 KiB

Open AccessArticle

Poly(carbonate urethane)-Based Thermogels with Enhanced Drug Release Efficacy for Chemotherapeutic Applications

by Benjamin Qi Yu Chan, Hongwei Cheng, Sing Shy Liow, Qingqing Dou, Yun-Long Wu, Xian Jun Loh and Zibiao Li

Polymers 2018, 10(1), 89; https://doi.org/10.3390/polym10010089 - 18 Jan 2018

Cited by 33 | Viewed by 6021

Abstract

In this study, we report the synthesis and characterisation of a thermogelling poly(carbonate urethane) system comprising poly(ethylene glycol) (PEG), poly(propylene glycol) (PPG) and poly(polytetrahydrofuran carbonate) (PTHF carbonate). The incorporation of PTHF carbonate allowed for the control of the lower critical solution temperature (LCST) [...] Read more.

In this study, we report the synthesis and characterisation of a thermogelling poly(carbonate urethane) system comprising poly(ethylene glycol) (PEG), poly(propylene glycol) (PPG) and poly(polytetrahydrofuran carbonate) (PTHF carbonate). The incorporation of PTHF carbonate allowed for the control of the lower critical solution temperature (LCST) and decreased critical gelation concentration (CGC) of the thermogels significantly. In addition, the as-prepared thermogels displayed low toxicity against HepG2, L02 and HEK293T cells. Drug release studies were carried out using doxorubicin (Dox). Studies conducted using nude mice models with hepatocellular carcinoma revealed that the Dox-loaded poly(PEG/PPG/PTHF carbonate urethane) thermogels showed excellent in vivo anti-tumour performance and effectively inhibited tumour growth in the tested model. Full article

(This article belongs to the Special Issue Polymers for Therapy and Diagnostics)

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14 pages, 2316 KiB

Open AccessArticle

One-Pot Synthesis of Waterborne Polymeric Dispersions Stabilized with Alkali-Soluble Resins

by Massimo Bandiera, Roelof Balk and Maria J. Barandiaran

Polymers 2018, 10(1), 88; https://doi.org/10.3390/polym10010088 - 18 Jan 2018

Cited by 16 | Viewed by 5832

Abstract

Alkali-soluble resins (ASRs) are a type of electrosteric emulsifiers of high interest because they can profitably improve the features of waterborne dispersions. In this work, they have been synthesized in-situ through a one-pot approach and they have been used as polymeric surfactants for [...] Read more.

Alkali-soluble resins (ASRs) are a type of electrosteric emulsifiers of high interest because they can profitably improve the features of waterborne dispersions. In this work, they have been synthesized in-situ through a one-pot approach and they have been used as polymeric surfactants for a second emulsion polymerization step in the same reactor. This strategy provides some advantages compared to other polymerization techniques, like the intensification of the process and the absence of organic solvents. Their use can also further reduce the environmental impact of formulations for film-forming applications, since grafting reactions with the particles have been observed and quantified in relation with the synthetic parameters. These chemical linkages with the particles may reduce the leaching and the release of surfactants from polymeric films, for example in water-based coatings or adhesives. The systems have been also studied from the kinetics point of view, finding relevant differences with other electrosterically stabilized processes from the literature, as well as concerns the nucleation mechanism. Full article

(This article belongs to the Special Issue Emulsion Polymerization)

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21 pages, 3205 KiB

Open AccessReview

Integration of Heterogeneous Materials for Wearable Sensors

by Yaser M. Haddara and Matiar M. R. Howlader

Polymers 2018, 10(1), 60; https://doi.org/10.3390/polym10010060 - 18 Jan 2018

Cited by 20 | Viewed by 6427

Abstract

Wearable sensors are of interest for several application areas, most importantly for their potential to allow for the design of personal continuous health monitoring systems. For wearable sensors, flexibility is required and imperceptibility is desired. Wearable sensors must be robust to strain, motion, [...] Read more.

Wearable sensors are of interest for several application areas, most importantly for their potential to allow for the design of personal continuous health monitoring systems. For wearable sensors, flexibility is required and imperceptibility is desired. Wearable sensors must be robust to strain, motion, and environmental exposure. A number of different strategies have been utilized to achieve flexibility, imperceptibility, and robustness. All of these approaches require the integration of materials having a range of chemical, mechanical, and thermal properties. We have given a concise review of the range of materials that must be incorporated in wearable sensors regardless of the strategies adopted to achieve wearability. We first describe recent advances in the range of wearable sensing materials and their processing requirements and then discuss the potential routes to the integration of these heterogeneous materials. Full article

(This article belongs to the Special Issue Wearable Sensor)

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14 pages, 27800 KiB

Open AccessArticle

Mechanical Properties Changes of Irradiated Thermoplastic Elastomer

by David Manas, Ales Mizera, Miroslav Manas, Martin Ovsik, Lenka Hylova, Stanislav Sehnalek and Pavel Stoklasek

Polymers 2018, 10(1), 87; https://doi.org/10.3390/polym10010087 - 17 Jan 2018

Cited by 15 | Viewed by 6212

Abstract

Some polymers need a cross-linking agent for the controlled cross-linking process of polymers with a tendency to degradation during the radiation cross-linking process. While, on the other hand, other polymers do not need a cross-linking agent—predominantly there are cross-linking polymers. The Thermo-Plastic Elastomer [...] Read more.

Some polymers need a cross-linking agent for the controlled cross-linking process of polymers with a tendency to degradation during the radiation cross-linking process. While, on the other hand, other polymers do not need a cross-linking agent—predominantly there are cross-linking polymers. The Thermo-Plastic Elastomer (TPE) that was used belongs to this group of predominantly cross-linking polymers; however, this agent is added because of faster reaction times and smaller irradiation doses. Microindentation–tensile and tensile impact tests were carried out on a thermoplastic sample—with, and without, a cross-linking agent. Small changes were measured between these materials at low radiation doses, (up to 66 kGy); nevertheless, at higher doses, the influence of the cross-linking agent on the mechanical properties is significant. Full article

(This article belongs to the Special Issue Elastomers)

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18 pages, 3589 KiB

Open AccessArticle

The Effect of Reactive Ionic Liquid or Plasticizer Incorporation on the Physicochemical and Transport Properties of Cellulose Acetate Propionate-Based Membranes

by Edyta Rynkowska, Kateryna Fatyeyeva, Joanna Kujawa, Krzysztof Dzieszkowski, Andrzej Wolan and Wojciech Kujawski

Polymers 2018, 10(1), 86; https://doi.org/10.3390/polym10010086 - 17 Jan 2018

Cited by 29 | Viewed by 6816

Abstract

Pervaporation is a membrane-separation technique which uses polymeric and/or ceramic membranes. In the case of pervaporation processes applied to dehydration, the membrane should transport water molecules preferentially. Reactive ionic liquid (RIL) (3-(1,3-diethoxy-1,3-dioxopropan-2-yl)-1-methyl-1H-imidazol-3-ium) was used to prepare novel dense cellulose acetate propionate [...] Read more.

Pervaporation is a membrane-separation technique which uses polymeric and/or ceramic membranes. In the case of pervaporation processes applied to dehydration, the membrane should transport water molecules preferentially. Reactive ionic liquid (RIL) (3-(1,3-diethoxy-1,3-dioxopropan-2-yl)-1-methyl-1H-imidazol-3-ium) was used to prepare novel dense cellulose acetate propionate (CAP) based membranes, applying the phase-inversion method. The designed polymer-ionic liquid system contained ionic liquid partially linked to the polymeric structure via the transesterification reaction. The various physicochemical, mechanical, equilibrium and transport properties of CAP-RIL membranes were determined and compared with the properties of CAP membranes modified with plasticizers, i.e., tributyl citrate (TBC) and acetyl tributyl citrate (ATBC). Thermogravimetric analysis (TGA) testified that CAP-RIL membranes as well as CAP membranes modified with TBC and ATBC are thermally stable up to at least 120 °C. Tensile tests of the membranes revealed improved mechanical properties reflected by reduced brittleness and increased elongation at break achieved for CAP-RIL membranes in contrast to pristine CAP membranes. RIL plasticizes the CAP matrix, and CAP-RIL membranes possess preferable mechanical properties in comparison to membranes with other plasticizers investigated. The incorporation of RIL into CAP membranes tuned the surface properties of the membranes, enhancing their hydrophilic character. Moreover, the addition of RIL into CAP resulted in an excellent improvement of the separation factor, in comparison to pristine CAP membranes, in pervaporation dehydration of propan-2-ol. The separation factor β increased from ca. 10 for pristine CAP membrane to ca. 380 for CAP-16.7-RIL membranes contacting an azeotropic composition of water-propan-2-ol mixture (i.e., 12 wt % water). Full article

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14 pages, 2479 KiB

Open AccessArticle

Mucoadhesive Interpolyelectrolyte Complexes for the Buccal Delivery of Clobetasol

by Venera R. Garipova, Chiara G. M. Gennari, Francesca Selmin, Francesco Cilurzo and Rouslan I. Moustafine

Polymers 2018, 10(1), 85; https://doi.org/10.3390/polym10010085 - 17 Jan 2018

Cited by 29 | Viewed by 4991

Abstract

This work aimed to investigate the feasibility to design: (a) a mucoadhesive interpolyelectrolyte complex (IPEC) loaded with clobetasol propionate (CP) intended to treat oral lichen planus and (b) individuate an orodispersible dosage form suitable for its administration. IPECs were synthesized by mixing Eudragit [...] Read more.

This work aimed to investigate the feasibility to design: (a) a mucoadhesive interpolyelectrolyte complex (IPEC) loaded with clobetasol propionate (CP) intended to treat oral lichen planus and (b) individuate an orodispersible dosage form suitable for its administration. IPECs were synthesized by mixing Eudragit^® E PO (EPO) and different grades of cross-linked polyacrylate derivatives, in different molar ratios, namely 1:1, 1:2, and 2:1. All IPECs resulted at nanoscale independently of their composition (120–200 nm). Both zeta-potentials (ζ) and mucoadhesive performances were influenced by the ratio between polymers. On the bases of the preliminary data, IPECs made of Polycarbophil and EPO in the 1:2 ratio were loaded with CP. The encapsulation efficiency was up 88% independently of the CP-IPEC ratio. The drug encapsulation caused IPEC destabilization in water, as it was noticed by the increase of ζ values and the formation of aggregates. Oral lyophilisates were prepared by freeze-drying slurries made of placebo or CP loaded IPECs, maltodextrin with a dextrose equivalent 38 and Span^®80. The optimized formulation permitted to obtain a fast disintegration upon contact with water reducing the tendency of IPECs to aggregate. Moreover, oral lyophilisates allowed improving the apparent solubility of CP throughout the in vitro release experiment. Full article

(This article belongs to the Special Issue Advances in Mucoadhesive Polymers and Formulations for Transmucosal Drug Delivery)

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15 pages, 4258 KiB

Open AccessArticle

Enhanced Oxidation Resistance of Polyphenylene Sulfide Composites Based on Montmorillonite Modified by Benzimidazolium Salt

by Jian Xing, Zhenzhen Xu and Bingyao Deng

Polymers 2018, 10(1), 83; https://doi.org/10.3390/polym10010083 - 17 Jan 2018

Cited by 48 | Viewed by 6599

Abstract

Organic montmorillonite (MMT) modified by 1,3-dihexadecyl-3H-benzimidazolium bromide (Bz) was used to prepare polyphenylene sulfide (PPS)/MMT composites by melting intercalation. The PPS/MMT composites showed mixed morphology, being comprised of exfoliated and intercalated structures with slight agglomerates. The tensile property of PPS/MMT composites [...] Read more.

Organic montmorillonite (MMT) modified by 1,3-dihexadecyl-3H-benzimidazolium bromide (Bz) was used to prepare polyphenylene sulfide (PPS)/MMT composites by melting intercalation. The PPS/MMT composites showed mixed morphology, being comprised of exfoliated and intercalated structures with slight agglomerates. The tensile property of PPS/MMT composites was significantly improved due to the good dispersion of the MMT nanolayers. The test results showed that the tensile strength retention of PPS/MMT composites was higher than that of pure PPS after the oxidation treatment. Moreover, FTIR and XPS analyses were also used to evaluate the oxidation resistance of PPS composites. The FTIR analysis confirmed that adding MMT could better limit the damage of the C–S group and retard the generation of sulfuryl groups (–SO₂–) during the oxidation treatment compared to pure PPS. The XPS analysis also suggested that the addition of MMT could reduce the chemical combination of the elements sulfur (S) and oxygen (O) during oxidation treatment. Furthermore, the MMT nanolayers could also promote the transfer of S from a C–S bond into an –SO₂– group. Full article

(This article belongs to the Special Issue Polymer-Clay (Nano)Composites)

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25 pages, 1341 KiB

Open AccessArticle

Microphase Segregation of Diblock Copolymers Studied by the Self-Consistent Field Theory of Scheutjens and Fleer

by Merve Mocan, Marleen Kamperman and Frans A. M. Leermakers

Polymers 2018, 10(1), 78; https://doi.org/10.3390/polym10010078 - 17 Jan 2018

Cited by 8 | Viewed by 5369

Abstract

We used the self-consistent field (SCF) formalism of Scheutjens and Fleer (SF-SCF) to complement existing theoretical investigations on the phase behavior of block copolymer melts. This method employs the freely jointed chain (FJC) model for finite chain length and systematic differences exist compared [...] Read more.

We used the self-consistent field (SCF) formalism of Scheutjens and Fleer (SF-SCF) to complement existing theoretical investigations on the phase behavior of block copolymer melts. This method employs the freely jointed chain (FJC) model for finite chain length and systematic differences exist compared to the classical SCF predictions. We focus on the critical and hexagonal (HEX) to lamellar (LAM) phase transition region at intermediate and strong segregations. Chain length (N) dependence of the critical point (

χ^{c r}

) was found to be

χ^{c r} N = 10.495 (1 + 4 / N)

. The characteristic spacing (D) of LAM was found as

D = 4 / 3 \sqrt{N}

at the critical conditions. We present SF-SCF predictions for the phases single gyroid (SG), double gyroid (DG) and hexagonally perforated lamellar (HPL), in the region where HEX and LAM compete. At

χ N = 30

,

N = 300

; we found SG and HPL were metastable with respect to LAM or HEX, DG was stable in a narrow region of the asymmetry ratio. In contrast to the latest predictions, at strong segregation

χ N = 120

, DG was found to be metastable. From the structural evolution of HPL, we speculate that this may be an intermediate phase that allows the system to go through various connectivity regimes between minority and majority blocks. Full article

(This article belongs to the Special Issue RAFT Living Radical Polymerization and Self-Assembly)

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17 pages, 15625 KiB

Open AccessArticle

EBR Strengthening Technique for Concrete, Long-Term Behaviour and Historical Survey

by Christoph Czaderski and Urs Meier

Polymers 2018, 10(1), 77; https://doi.org/10.3390/polym10010077 - 17 Jan 2018

Cited by 19 | Viewed by 6137

Abstract

Epoxy bonded steel plates (externally bonded reinforcemen: EBR) for the strengthening of concrete structures were introduced to the construction industry in the late 1960s, and the use of fibre reinforced polymers (FRPs) was introduced in the 1990s, which means that these techniques have [...] Read more.

Epoxy bonded steel plates (externally bonded reinforcemen: EBR) for the strengthening of concrete structures were introduced to the construction industry in the late 1960s, and the use of fibre reinforced polymers (FRPs) was introduced in the 1990s, which means that these techniques have already been used in construction for 50 and 25 years, respectively. In the first part of the paper, a historical survey of the development and introduction of these strengthening techniques into the construction industry are presented. The monitoring of such applications in construction is very important and gives more confidence to this strengthening technique. Therefore, in the second part of the paper, two long-term monitoring campaigns over an extraordinarily long duration will be presented. Firstly, a 47-year monitoring campaign on a concrete beam with an epoxy bonded steel plate and, secondly, a 20-year monitoring campaign on a road bridge with epoxy bonded CFRP (carbon fibre reinforced polymers) strips are described. The paper is an expanded version of the paper presented at the SMAR2017 Conference. Full article

(This article belongs to the Special Issue Selected Papers from "SMAR 2017")

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10 pages, 2201 KiB

Open AccessArticle

Quartz Microcrystal-Hybridized Organosilicone Encapsulant with Enhanced Optical and Thermal Performances

by Xin Chen, Yancong Feng, Xiao Wang, En Li, Yao Wang, Lingling Shui, Hao Li, Nan Li and Guofu Zhou

Polymers 2018, 10(1), 84; https://doi.org/10.3390/polym10010084 - 16 Jan 2018

Cited by 3 | Viewed by 4245

Abstract

Encapsulant is one determining factor underpinning the device lifetimes of organic optoelectronics. However, encapsulant seriously needs improvement in optical, thermal, and mechanical properties, especially to develop organic light emitting diodes. In this study, we prepared an in situ crosslinked organosilane composite containing benzyloxy [...] Read more.

Encapsulant is one determining factor underpinning the device lifetimes of organic optoelectronics. However, encapsulant seriously needs improvement in optical, thermal, and mechanical properties, especially to develop organic light emitting diodes. In this study, we prepared an in situ crosslinked organosilane composite containing benzyloxy and glycidyl-modified quartz microcrystal (mQMC) as high performance encapsulant. In the present work, methylphenylsilanediol (MPSD) was introduced as a novel crosslinker to impart appropriate structural strength. Along with increasing mQMC fillers, this organosilane system shows improved properties, such as refractive index, thermal stability, and storage modulus. Specifically, these hybridized mQMCs in the organosilane framework may facilitate an approximate two-fold increase (0.238 W/(m·K)) in overall thermal conductivity at the determined concentration. Full article

(This article belongs to the Special Issue Siloxane-Based Polymers)

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16 pages, 5750 KiB

Open AccessArticle

Electrical, Mechanical and Electromechanical Properties of Graphene-Thermoset Polymer Composites Produced Using Acetone-DMF Solvents

by Alessandro Giuseppe D’Aloia, Alessandro Proietti, Hossein Cheraghi Bidsorkhi, Alessio Tamburrano, Giovanni De Bellis, Fabrizio Marra, Agnese Bregnocchi and Maria Sabrina Sarto

Polymers 2018, 10(1), 82; https://doi.org/10.3390/polym10010082 - 16 Jan 2018

Cited by 13 | Viewed by 5222

Abstract

Recently, graphene-polymer composites gained a central role in advanced stress and strain sensing. A fundamental step in the production of epoxy-composites filled with graphene nanoplatelets (GNPs) consists in the exfoliation and dispersion of expanded graphite in a proper solvent, in the mixing of [...] Read more.

Recently, graphene-polymer composites gained a central role in advanced stress and strain sensing. A fundamental step in the production of epoxy-composites filled with graphene nanoplatelets (GNPs) consists in the exfoliation and dispersion of expanded graphite in a proper solvent, in the mixing of the resulting GNP suspension with the polymer matrix, and in the final removal of the solvent from the composite before curing through evaporation. The effects of traces of residual solvent on polymer curing process are usually overlooked, even if it has been found that even a small amount of residual solvent can affect the mechanical properties of the final composite. In this paper, we show that residual traces of N,N′-Dimethylformamide (DMF) in vinylester epoxy composites can induce relevant variations of the electrical, mechanical and electromechanical properties of the cured GNP-composite. To this purpose, a complete analysis of the morphological and structural characteristics of the composite samples produced using different solvent mixtures (combining acetone and DMF) is performed. Moreover, electrical, mechanical and electromechanical properties of the produced composites are assessed. In particular, the effect on the piezoresistive response of the use of DMF in the solvent mixture is analyzed using an experimental strain dependent percolation law to fit the measured electromechanical data. It is shown that the composites realized using a higher amount of DMF are characterized by a higher electrical conductivity and by a strong reduction of Young’s Modulus. Full article

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12 pages, 4003 KiB

Open AccessArticle

Suitability of Different Variants of Polyethylene Glycol Impregnation for the Dimensional Stabilization of Oak Wood

by Tillmann Meints, Christan Hansmann and Wolfgang Gindl-Altmutter

Polymers 2018, 10(1), 81; https://doi.org/10.3390/polym10010081 - 16 Jan 2018

Cited by 37 | Viewed by 6126

Abstract

The common method to impregnate wood with polyethylene glycol (PEG) is to store the samples for several weeks in aqueous PEG-solution, allowing for diffusion of PEG into the wood. As this method is poorly suited for industrial application, an alternative approach based on [...] Read more.

The common method to impregnate wood with polyethylene glycol (PEG) is to store the samples for several weeks in aqueous PEG-solution, allowing for diffusion of PEG into the wood. As this method is poorly suited for industrial application, an alternative approach based on vacuum-pressure treatment is evaluated in the present study. Using European oak wood and three variants of PEG, including silane-functionalized PEG, impregnation experiments at different PEG concentrations were performed. Significant uptake of PEG resulted in clearly altered wood-water relations and improved dimensional stability of oak wood. These results are discussed in terms of stability in humid and aqueous environments, and in terms of effects of the anatomy of oak wood on differences in dimensional stabilization observed along the radial and tangential anatomical directions, respectively. While both of the PEG variants perform better with an anti-shrinkage efficiency of up to 80%, the PEG-silane variant performs less effectively in this respect; however PEG-silane is clearly predominant in case of water extraction. Full article

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10 pages, 2113 KiB

Open AccessArticle

Accurately Determining the Extent of Coupling in Post Polymerization Reactions of Polystyrene

by Ching Pan and Eric Tillman

Polymers 2018, 10(1), 80; https://doi.org/10.3390/polym10010080 - 16 Jan 2018

Cited by 3 | Viewed by 5410

Abstract

Polymers prepared by controlled radical polymerization (CRP) can be employed in subsequent chain-end joining reactions, yet accurately assessing the extent of coupling in mechanistically unique paths is not straightforward. Precisely known mixtures of polystyrene standards were prepared and analyzed by gel permeation chromatography [...] Read more.

Polymers prepared by controlled radical polymerization (CRP) can be employed in subsequent chain-end joining reactions, yet accurately assessing the extent of coupling in mechanistically unique paths is not straightforward. Precisely known mixtures of polystyrene standards were prepared and analyzed by gel permeation chromatography (GPC), mimicking the coupled product and precursor that could be present after a post-polymerization, chain-end joining reaction. The exactly known percentages of each polymer in the mixture allowed for comparison of the true “extent of coupling” (X_c) to that determined by a commonly used equation, which is based on number average molecular weights (M_n) of the precursor and coupled product. The results indicated that an improvement in accuracy could be achieved by instead using refractive index (RI) signal height ratios under the peak molecular weight (M_p) of each component, with all calculations being within 0.05 of the true X_c of the fabricated “product” mixture (compared to greater than 0.10 average error using the more established method) when the sample mixture had nominal molecular weights of 2500 and 5000 Da. Moreover, when “precursor” and “coupled” pairs mixed were not related as a simple doubling of molecular weight, the calculation method presented here remained effective at determining the content of the mixture, especially at higher X_c values (>0.45). This second case is important for experiments that may link polymer chains together with a spacer, such as a radical trap, a triazole, or even larger structure such as an oligomer. Full article

(This article belongs to the Special Issue Living Polymerization)

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18 pages, 2757 KiB

Open AccessArticle

Antimicrobial Carvacrol-Containing Polypropylene Films: Composition, Structure and Function

by Max Krepker, Ofer Prinz-Setter, Rotem Shemesh, Anita Vaxman, David Alperstein and Ester Segal

Polymers 2018, 10(1), 79; https://doi.org/10.3390/polym10010079 - 16 Jan 2018

Cited by 51 | Viewed by 7541

Abstract

Significant research has been directed toward the incorporation of bioactive plant extracts or essential oils (EOs) into polymers to endow the latter with antimicrobial functionality. EOs offer a unique combination of having broad antimicrobial activity from a natural source, generally recognized as safe [...] Read more.

Significant research has been directed toward the incorporation of bioactive plant extracts or essential oils (EOs) into polymers to endow the latter with antimicrobial functionality. EOs offer a unique combination of having broad antimicrobial activity from a natural source, generally recognized as safe (GRAS) recognition in the US, and a volatile nature. However, their volatility also presents a major challenge in their incorporation into polymers by conventional high-temperature-processing techniques. Herein, antimicrobial polypropylene (PP) cast films were produced by incorporating carvacrol (a model EO) or carvacrol, loaded into halloysite nanotubes (HNTs), via melt compounding. We studied the composition-structure-property relationships in these systems, focusing on the effect of carvacrol on the composition of the films, the PP crystalline phase and its morphology and the films’ mechanical and antimicrobial properties. For the first time, molecular dynamics simulations were applied to reveal the complex interactions between the components of these carvacrol-containing systems. We show that strong molecular interactions between PP and carvacrol minimize the loss of this highly-volatile EO during high-temperature polymer processing, enabling semi-industrial scale production. The resulting films exhibit outstanding antimicrobial properties against model microorganisms (Escherichia coli and Alternaria alternata). The PP/(HNTs-carvacrol) nanocomposite films, containing the carvacrol-loaded HNTs, display a higher level of crystalline order, superior mechanical properties and prolonged release of carvacrol, in comparison to PP/carvacrol blends. These properties are ascribed to the role of HNTs in these nanocomposites and their effect on the PP matrix and retained carvacrol content. Full article

(This article belongs to the Special Issue Antimicrobial Polymers)

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