Polymers

6984 KiB

Open AccessArticle

Conformation Change, Tension Propagation and Drift-Diffusion Properties of Polyelectrolyte in Nanopore Translocation

by Pai-Yi Hsiao

Polymers 2016, 8(10), 378; https://doi.org/10.3390/polym8100378 - 24 Oct 2016

Cited by 10 | Viewed by 5999

Using Langevin dynamics simulations, conformational, mechanical and dynamical properties of charged polymers threading through a nanopore are investigated. The shape descriptors display different variation behaviors for the cis- and trans-side sub-chains, which reflects a strong cis-trans dynamical asymmetry, especially when the [...] Read more.

Using Langevin dynamics simulations, conformational, mechanical and dynamical properties of charged polymers threading through a nanopore are investigated. The shape descriptors display different variation behaviors for the cis- and trans-side sub-chains, which reflects a strong cis-trans dynamical asymmetry, especially when the driving field is strong. The calculation of bond stretching shows how the bond tension propagates on the chain backbone, and the chain section straightened by the tension force is determined by the ratio of the direct to the contour distances of the monomer to the pore. With the study of the waiting time function, the threading process is divided into the tension-propagation stage and the tail-retraction stage. At the end, the drift velocity, diffusive property and probability density distribution are explored. Owing to the non-equilibrium nature, translocation is not a simple drift-diffusion process, but exhibits several intermediate behaviors, such as ballistic motion, normal diffusion and super diffusion, before ending with the last, negative-diffusion behavior. Full article

(This article belongs to the Special Issue Semiflexible Polymers)

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13110 KiB

Open AccessArticle

Low Band Gap Donor–Acceptor Type Polymers Containing 2,3-Bis(4-(decyloxy)phenyl)pyrido[4,3-b]pyrazine as Acceptor and Different Thiophene Derivatives as Donors

by Yan Zhang, Xuezhong Liu, Min Wang, Xiaoli Liu and Jinsheng Zhao

Polymers 2016, 8(10), 377; https://doi.org/10.3390/polym8100377 - 24 Oct 2016

Cited by 12 | Viewed by 7214

Abstract

Four donor–acceptor type conducting polymers, namely poly(2,3-bis(4-decyloxy)phenyl)-5,8-bis(4-thiophen-2-yl)pyrido[4,3-b]pyrazine) (P1), poly(2,3-bis(4-decyloxy)phenyl)-5,8-bis(4-butylthiophen-2-yl)pyrido[4,3-b]pyrazine) (P2), poly(2,3-bis(4-(decyloxy)phenyl)-5,8-bis(4-hexyloxythiophen-2-yl)pyrido[4,3-b]pyrazine) (P3) and poly(2,3-bis(4-(decyloxy)phenyl)-5,8-bis(2,3-dihydrothieno[3,4-b][1,4]dioxin-7-yl)pyrido[4,3-b]pyrazine) (P4), containing thiophene or its derivative as the donor and pyrido[4,3-b]pyrazine as the acceptor were prepared and characterized by cyclic voltammetry, scanning electron microscopy, and UV-Vis spectroscopy to detect [...] Read more.

Four donor–acceptor type conducting polymers, namely poly(2,3-bis(4-decyloxy)phenyl)-5,8-bis(4-thiophen-2-yl)pyrido[4,3-b]pyrazine) (P1), poly(2,3-bis(4-decyloxy)phenyl)-5,8-bis(4-butylthiophen-2-yl)pyrido[4,3-b]pyrazine) (P2), poly(2,3-bis(4-(decyloxy)phenyl)-5,8-bis(4-hexyloxythiophen-2-yl)pyrido[4,3-b]pyrazine) (P3) and poly(2,3-bis(4-(decyloxy)phenyl)-5,8-bis(2,3-dihydrothieno[3,4-b][1,4]dioxin-7-yl)pyrido[4,3-b]pyrazine) (P4), containing thiophene or its derivative as the donor and pyrido[4,3-b]pyrazine as the acceptor were prepared and characterized by cyclic voltammetry, scanning electron microscopy, and UV-Vis spectroscopy to detect the influence of the donor units’ strength on the electrochromic performances. The results demonstrated that all of the polymers could be reversibly reduced and oxidized by p-type doping and n-type doping, and showed near-infrared activities and different color changes in p-type doping process. Especially, P3 and P4 showed lower optical band gap than P1 and P2 due to the strong electron-donating hexyloxythiophen group of P3 and ethylenedioxythiophene group of P4. Besides, P3 and P4 displayed the saturated green color at the neutral state and the desirable transparency at the oxidized state. All the polymers displayed desirable optical contrasts, satisfactory coloration efficiency, excellent stability and short switching time, which made the polymers fascinating candidates in the electrochromic device applications. Full article

(This article belongs to the Special Issue Conjugated Polymers 2016)

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15129 KiB

Open AccessArticle

Effect of Saponification Condition on the Morphology and Diameter of the Electrospun Poly(vinyl acetate) Nanofibers for the Fabrication of Poly(vinyl alcohol) Nanofiber Mats

by Seong Baek Yang, Jong Won Kim and Jeong Hyun Yeum

Polymers 2016, 8(10), 376; https://doi.org/10.3390/polym8100376 - 21 Oct 2016

Cited by 7 | Viewed by 7728

Abstract

Novel poly(vinyl alcohol) (PVA) nanofiber mats were prepared for the first time through heterogeneous saponification of electrospun poly(vinyl acetate) (PVAc) nanofibers. The effect of varying the saponification conditions, including temperature, time, and concentration of the alkaline solution, on the morphology of the saponified [...] Read more.

Novel poly(vinyl alcohol) (PVA) nanofiber mats were prepared for the first time through heterogeneous saponification of electrospun poly(vinyl acetate) (PVAc) nanofibers. The effect of varying the saponification conditions, including temperature, time, and concentration of the alkaline solution, on the morphology of the saponified PVA fibers were evaluated by field-emission scanning electron microscopy. At 25 °C, the saponified PVA fibers exhibited a broad diameter distribution. The average fiber diameter, however, was found to decrease with increasing saponification temperature. When the saponification time was increased from 6 to 30 h, the average fiber diameter decreased gradually from 1540 to 1060 nm. In addition, the fiber diameter and morphology were also affected by the concentration of the alkaline saponification solution. The most optimal conditions for fabrication of thin, uniform, and smooth PVA nanofibers corresponded to an alkaline solution containing 10 g each of NaOH, Na₂SO₄, and methanol per 100 g of water, a temperature of 25 °C, and a saponification time of 24 h. Full article

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18626 KiB

Open AccessArticle

FRP-Confined Recycled Coarse Aggregate Concrete: Experimental Investigation and Model Comparison

by Yingwu Zhou, Jingjing Hu, Mali Li, Lili Sui and Feng Xing

Polymers 2016, 8(10), 375; https://doi.org/10.3390/polym8100375 - 21 Oct 2016

Cited by 48 | Viewed by 7781

Abstract

The in situ application of recycled aggregate concrete (RAC) is of great significance in environmental protection and construction resources sustainability. However, it has been limited to nonstructural purposes due to its poor mechanical performance. External confinement using steel tubes and fiber-reinforced polymer (FRP) [...] Read more.

The in situ application of recycled aggregate concrete (RAC) is of great significance in environmental protection and construction resources sustainability. However, it has been limited to nonstructural purposes due to its poor mechanical performance. External confinement using steel tubes and fiber-reinforced polymer (FRP) can significantly improve the mechanical performance of RAC and thus the first-ever study on the axial compressive behavior of glass FRP (GFRP)-confined RAC was recently reported. To have a full understanding of FRP-confined RAC, this paper has extended the type of FRP and presents a systematic experimental study on the axial compressive performance of carbon FRP (CFRP)-confined RAC. The mechanical properties of CFRP-confined RAC from the perspective of the failure mode, ultimate strength and strain, and stress–strain relationship responses were analyzed. Integrated with existing experimental data of FRP-confined RAC, the paper compiles a database for the mechanical properties of FRP-confined RAC. Based on the database, the effects of FRP type (i.e., GFRP and CFRP) and the replacement ratio of recycled coarse aggregate were investigated. The results indicated that the stress–stain behavior of FRP-confined RAC depended heavily on the unconfined concrete strength and the FRP confining pressure instead of the replacement ratio. Therefore, this study adopted eleven high-performance ultimate strength and strain models developed for FRP-confined normal aggregate concrete (NAC) to predict the mechanical properties of FRP-confined RAC. All the predictions had good agreement with the test results, which further confirmed similar roles played by FRP confinement in improving the mechanical properties of RAC and improving those of NAC. On this basis, this paper finally recommended a stress–strain relationship model for FRP-confined RAC. Full article

(This article belongs to the Collection Fiber-Reinforced Polymer Composites in Structural Engineering)

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2713 KiB

Open AccessArticle

Synthesis of Thermo-Responsive Polymer via Radical (Co)polymerization of N,N-Dimethyl-α-(hydroxymethyl)acrylamide with N,N-Diethylacrylamide

by Yasuhiro Kohsaka and Yoshiaki Tanimoto

Polymers 2016, 8(10), 374; https://doi.org/10.3390/polym8100374 - 20 Oct 2016

Cited by 11 | Viewed by 6693

Abstract

α-Functionalized acrylamides have not been considered as an effective monomer design due to their poor polymerizability, although the analogues, α-functionalized acrylates, are attractive monomers of which polymers exhibit characteristic properties. In this article, we report the first example of radical polymerization of α-functionalized [...] Read more.

α-Functionalized acrylamides have not been considered as an effective monomer design due to their poor polymerizability, although the analogues, α-functionalized acrylates, are attractive monomers of which polymers exhibit characteristic properties. In this article, we report the first example of radical polymerization of α-functionalized N,N-disubstituted acrylamide affording thermo-responsive hydrophilic polymers. N,N-dimethyl-α-(hydroxymethyl)acrylamide (DMαHAA) was (co)polymerized with N,N-diethylacrylamide (DEAA). Although the homopolymerization did not afford a polymeric product, the copolymerizations with various feed ratios yielded a series of the copolymers containing 0%–65% of DMαHAA units. The obtained copolymers exhibited a lower critical solution temperature (LCST) in water; the cloud points (T_cs) were linearly elevated as the contents of DMαHAA units from 32 to 64 °C, indicating that DMαHAA functioned as a more hydrophilic monomer than DEAA. The linear relationship between T_c and DMαHAA content suggests that the homopolymer, poly(DMαHAA), should have T_c at ca. 80 °C, although it is not available by direct radical homopolymerization. Full article

(This article belongs to the Special Issue Responsive Polymers for Drug Delivery, Imaging and Theranostic Functions)

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10156 KiB

Open AccessReview

Emerging Multifunctional NIR Photothermal Therapy Systems Based on Polypyrrole Nanoparticles

by Mozhen Wang

Polymers 2016, 8(10), 373; https://doi.org/10.3390/polym8100373 - 20 Oct 2016

Cited by 55 | Viewed by 14197

Abstract

Near-infrared (NIR)-light-triggered therapy platforms are now considered as a new and exciting possibility for clinical nanomedicine applications. As a promising photothermal agent, polypyrrole (PPy) nanoparticles have been extensively studied for the hyperthermia in cancer therapy due to their strong NIR light photothermal effect [...] Read more.

Near-infrared (NIR)-light-triggered therapy platforms are now considered as a new and exciting possibility for clinical nanomedicine applications. As a promising photothermal agent, polypyrrole (PPy) nanoparticles have been extensively studied for the hyperthermia in cancer therapy due to their strong NIR light photothermal effect and excellent biocompatibility. However, the photothermal application of PPy based nanomaterials is still in its preliminary stage. Developing PPy based multifunctional nanomaterials for cancer treatment in vivo should be the future trend and object for cancer therapy. In this review, the synthesis of PPy nanoparticles and their NIR photothermal conversion performance were first discussed, followed by a summary of the recent progress in the design and implementation on the mulitifunctionalization of PPy or PPy based therapeutic platforms, as well as the introduction of their exciting biomedical applications based on the synergy between the photothermal conversion effect and other stimulative responsibilities. Full article

(This article belongs to the Special Issue Responsive Polymers for Drug Delivery, Imaging and Theranostic Functions)

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7095 KiB

Open AccessArticle

New Vistas on the Anionic Polymerization of Styrene in Non-Polar Solvents by Means of Density Functional Theory

by Hideo Morita and Marcel Van Beylen

Polymers 2016, 8(10), 371; https://doi.org/10.3390/polym8100371 - 20 Oct 2016

Cited by 7 | Viewed by 7753

Abstract

The elementary processes of anionic styrene polymerization in the gas phase and in cyclohexane were studied using M062X (a recently developed density functional theory (DFT) method) combined with the 6-31+G(d) basis sets, in order to clarify the complicated phenomena caused by the association [...] Read more.

The elementary processes of anionic styrene polymerization in the gas phase and in cyclohexane were studied using M062X (a recently developed density functional theory (DFT) method) combined with the 6-31+G(d) basis sets, in order to clarify the complicated phenomena caused by the association of the active chain-ends and elucidate the details of the polymerization mechanism. Three types of HSt₂Li (a model structure of polystyryllithium chain-ends) were obtained; the well-known first structure in which Li is coordinated to the side chain, the second structure in which Li is coordinated to the phenyl ring, (both without the penultimate unit coordination), and the third structure in which Li is coordinated to both the chain-end unit and the penultimate styrene unit. Although the third HSt₂Li is the most stable as expected, the free energy for the transition state of its reaction with styrene is higher than those for the other two transition states due to its steric hindrance. The free energy for the transition state of the reaction of the second HSt₂Li with styrene is the lowest, suggesting that the route through it is the predominant reaction path. The penultimate unit effect, slower addition of styrene to HSt₂Li than to HStLi, is attributed to coordination of the penultimate styrene units of the polystyryllithium dimer (one of the starting materials) to its Li atoms. The calculated enthalpy for the reaction barrier of the second HSt₂Li with styrene in cyclohexane was found to agree with the observed apparent activation energy in benzene. Full article

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2743 KiB

Open AccessArticle

CaLB Catalyzed Conversion of ε-Caprolactone in Aqueous Medium. Part 1: Immobilization of CaLB to Microgels

by Stefan Engel, Heidi Höck, Marco Bocola, Helmut Keul, Ulrich Schwaneberg and Martin Möller

Polymers 2016, 8(10), 372; https://doi.org/10.3390/polym8100372 - 19 Oct 2016

Cited by 18 | Viewed by 8949

Abstract

The enzymatic ring-opening polymerization of lactones is a method of increasing interest for the synthesis of biodegradable and biocompatible polymers. In the past it was shown that immobilization of Candida antarctica lipase B (CaLB) and the reaction medium play an important role in [...] Read more.

The enzymatic ring-opening polymerization of lactones is a method of increasing interest for the synthesis of biodegradable and biocompatible polymers. In the past it was shown that immobilization of Candida antarctica lipase B (CaLB) and the reaction medium play an important role in the polymerization ability especially of medium ring size lactones like ε-caprolactone (ε-CL). We investigated a route for the preparation of compartmentalized microgels based on poly(glycidol) in which CaLB was immobilized to increase its esterification ability. To find the ideal environment for CaLB, we investigated the acceptable water concentration and the accessibility for the monomer in model polymerizations in toluene and analyzed the obtained oligomers/polymers by NMR and SEC. We observed a sufficient accessibility for ε-CL to a toluene like hydrophobic phase imitating a hydrophobic microgel. Comparing free CaLB and Novozym^® 435 we found that not the monomer concentration but rather the solubility of the enzyme, as well as the water concentration, strongly influences the equilibrium of esterification and hydrolysis. On the basis of these investigations, microgels of different polarity were prepared and successfully loaded with CaLB by physical entrapment. By comparison of immobilized and free CaLB, we demonstrated an effect of the hydrophobicity of the microenvironment of CaLB on its enzymatic activity. Full article

(This article belongs to the Special Issue Enzymatic Polymer Synthesis)

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19702 KiB

Open AccessArticle

Material Evaluation and Process Optimization of CNT-Coated Polymer Powders for Selective Laser Sintering

by Shangqin Yuan, Jiaming Bai, Chee Kai Chua, Jun Wei and Kun Zhou

Polymers 2016, 8(10), 370; https://doi.org/10.3390/polym8100370 - 19 Oct 2016

Cited by 103 | Viewed by 12192

Abstract

Multi-walled carbon nanotubes (CNTs) as nano-reinforcements were introduced to facilitate the laser sintering process and enhance the thermal and mechanical properties of polymeric composites. A dual experimental-theoretical method was proposed to evaluate the processability and predict the process parameters of newly developed CNT-coated [...] Read more.

Multi-walled carbon nanotubes (CNTs) as nano-reinforcements were introduced to facilitate the laser sintering process and enhance the thermal and mechanical properties of polymeric composites. A dual experimental-theoretical method was proposed to evaluate the processability and predict the process parameters of newly developed CNT-coated polyamide 12 (CNTs/PA12) powders. The thermal conductivity, melt viscosity, phase transition and temperature-dependent density and heat capacity of PA12 and CNTs/PA12 powders were characterized for material evaluation. The composite powders exhibited improved heat conduction and heat absorption compared with virgin polymer powders, and the stable sintering range of composite powders was extended and found to be favourable for the sintering process. The microstructures of sintered composites revealed that the CNTs remained at the powder boundaries and formed network architectures, which instantaneously induced the significant enhancements in tensile strength, elongation at break and toughness without sacrificing tensile modulus. Full article

(This article belongs to the Special Issue Three-Dimensional Structures: Fabrication and Application)

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5303 KiB

Open AccessArticle

Copolymers Based on 1,3-Bis(carbazol-9-yl)benzene and Three 3,4-Ethylenedioxythiophene Derivatives as Potential Anodically Coloring Copolymers in High-Contrast Electrochromic Devices

by Chung-Wen Kuo, Teng-Lu Wu, Yuan-Chung Lin, Jeng-Kuei Chang, Ho-Rei Chen and Tzi-Yi Wu

Polymers 2016, 8(10), 368; https://doi.org/10.3390/polym8100368 - 19 Oct 2016

Cited by 23 | Viewed by 6077

Abstract

In this study, copolymers based on 1,3-bis(carbazol-9-yl)benzene (BCz) and three 3,4-ethylenedioxythiophene derivatives (3,4-ethylenedioxythiophene (EDOT), 3,4-(2,2-dimethylpropylenedioxy)thiophene (ProDOT-Me₂), and 3,4-ethylenedithiathiophene (EDTT)) were electrochemically synthesized and their electrochemical and electrochromic properties were characterized. The anodic copolymer P(BCz-co-ProDOT) with BCz/ProDOT-Me₂ = 1/1 [...] Read more.

In this study, copolymers based on 1,3-bis(carbazol-9-yl)benzene (BCz) and three 3,4-ethylenedioxythiophene derivatives (3,4-ethylenedioxythiophene (EDOT), 3,4-(2,2-dimethylpropylenedioxy)thiophene (ProDOT-Me₂), and 3,4-ethylenedithiathiophene (EDTT)) were electrochemically synthesized and their electrochemical and electrochromic properties were characterized. The anodic copolymer P(BCz-co-ProDOT) with BCz/ProDOT-Me₂ = 1/1 feed molar ratio showed high optical contrast (ΔT%) and coloring efficiency (η), measured as 52.5% and 153.5 cm²∙C⁻¹ at 748 nm, respectively. Electrochromic devices (ECDs) based on P(BCz-co-EDOT), P(BCz-co-ProDOT), and P(BCz-co-EDTT) as anodic polymer layers, and poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonic acid) (PEDOT-PSS) as cathodic polymer layer were fabricated. P(BCz-co-ProDOT)/triple-layer PEDOT-PSS ECD showed three different colors (light yellow, yellowish-blue, and dark blue) at different applied potentials. In addition, the highest optical contrast (ΔT%) of P(BCz-co-ProDOT)/triple-layer PEDOT-PSS ECD was found to be 41% at 642 nm and the coloration efficiency was calculated to be 416.5 cm²∙C⁻¹ at 642 nm. All ECDs showed satisfactory optical memories and electrochemical cyclic stability. Full article

(This article belongs to the Special Issue Functionally Responsive Polymeric Materials)

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2346 KiB

Open AccessArticle

Preparation and Characterization of High Surface Area Activated Carbon Fibers from Lignin

by Jian Lin and Guangjie Zhao

Polymers 2016, 8(10), 369; https://doi.org/10.3390/polym8100369 - 18 Oct 2016

Cited by 32 | Viewed by 9098

Abstract

Activated carbon fibers (ACFs) were successfully prepared from softwood lignin, which was isolated with polyethylene glycol 400 (PEG-400) as a solvolysis reagent, by water steam activation. The pore characterization and adsorption property of ACFs were investigated. The results showed that all the ACFs [...] Read more.

Activated carbon fibers (ACFs) were successfully prepared from softwood lignin, which was isolated with polyethylene glycol 400 (PEG-400) as a solvolysis reagent, by water steam activation. The pore characterization and adsorption property of ACFs were investigated. The results showed that all the ACFs with more micropores exhibited high specific surface area and total pore volume which increased with the activation time prolonging; the highest ones were around 3100 m²/g and 1.5 mL/g, respectively. The specific surface area and total pore volume were much larger than those of other types of lignin-based ACFs and activated charcoal. Besides, with increasing activation time, the amount of graphitic carbon, which was the main compound on the surface of ACFs, decreased, while the amount of functional groups containing C–O slightly increased. In addition, the adsorption capacity of ACFs for methylene blue was highly increased as the activation time increased. Accordingly, lignin isolated with PEG is a promising precursor for ACF production. Full article

(This article belongs to the Special Issue Polymeric Fibers)

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2107 KiB

Open AccessArticle

Multiresponsive Behavior of Functional Poly(p-phenylene vinylene)s in Water

by Kanykei Ryskulova, Anupama Rao Gulur Srinivas, Thomas Kerr-Phillips, Hui Peng, David Barker, Jadranka Travas-Sejdic and Richard Hoogenboom

Polymers 2016, 8(10), 365; https://doi.org/10.3390/polym8100365 - 18 Oct 2016

Cited by 6 | Viewed by 7154

Abstract

The multiresponsive behavior of functionalized water-soluble conjugated polymers (CPs) is presented with potential applications for sensors. In this study, we investigated the aqueous solubility behavior of water-soluble CPs with high photoluminescence and with a particular focus on their pH and temperature responsiveness. For [...] Read more.

The multiresponsive behavior of functionalized water-soluble conjugated polymers (CPs) is presented with potential applications for sensors. In this study, we investigated the aqueous solubility behavior of water-soluble CPs with high photoluminescence and with a particular focus on their pH and temperature responsiveness. For this purpose, two poly(phenylene vinylene)s (PPVs)—namely 2,5-substituted PPVs bearing both carboxylic acid and methoxyoligoethylene glycol units—were investigated, with different amount of carboxylic acid units. Changes in the pH and temperature of polymer solutions led to a response in the fluorescence intensity in a pH range from 3 to 10 and for temperatures ranging from 10 to 85 °C. Additionally, it is demonstrated that the polymer with the largest number of carboxylic acid groups displays upper critical solution temperature (UCST)-like thermoresponsive behavior in the presence of a divalent ion like Ca²⁺. The sensing capability of these water-soluble PPVs could be utilized to design smart materials with multiresponsive behavior in biomedicine and soft materials. Full article

(This article belongs to the Special Issue Young Talents in Polymer Science)

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2707 KiB

Open AccessReview

A Review of Thermo- and Ultrasound-Responsive Polymeric Systems for Delivery of Chemotherapeutic Agents

by Az-Zamakhshariy Zardad, Yahya Essop Choonara, Lisa Claire Du Toit, Pradeep Kumar, Mostafa Mabrouk, Pierre Pavan Demarco Kondiah and Viness Pillay

Polymers 2016, 8(10), 359; https://doi.org/10.3390/polym8100359 - 18 Oct 2016

Cited by 78 | Viewed by 10124

Abstract

There has been an exponential increase in research into the development of thermal- and ultrasound-activated delivery systems for cancer therapy. The majority of researchers employ polymer technology that responds to environmental stimuli some of which are physiologically induced such as temperature, pH, as [...] Read more.

There has been an exponential increase in research into the development of thermal- and ultrasound-activated delivery systems for cancer therapy. The majority of researchers employ polymer technology that responds to environmental stimuli some of which are physiologically induced such as temperature, pH, as well as electrical impulses, which are considered as internal stimuli. External stimuli include ultrasound, light, laser, and magnetic induction. Biodegradable polymers may possess thermoresponsive and/or ultrasound-responsive properties that can complement cancer therapy through sonoporation and hyperthermia by means of High Intensity Focused Ultrasound (HIFU). Thermoresponsive and other stimuli-responsive polymers employed in drug delivery systems can be activated via ultrasound stimulation. Polyethylene oxide/polypropylene oxide co-block or triblock polymers and polymethacrylates are thermal- and pH-responsive polymer groups, respectively but both have proven to have successful activity and contribution in chemotherapy when exposed to ultrasound stimulation. This review focused on collating thermal- and ultrasound-responsive delivery systems, and combined thermo-ultrasonic responsive systems; and elaborating on the advantages, as well as shortcomings, of these systems in cancer chemotherapy. The mechanisms of these systems are explicated through their physical alteration when exposed to the corresponding stimuli. The properties they possess and the modifications that enhance the mechanism of chemotherapeutic drug delivery from systems are discussed, and the concept of pseudo-ultrasound responsive systems is introduced. Full article

(This article belongs to the Special Issue Responsive Polymers for Drug Delivery, Imaging and Theranostic Functions)

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4066 KiB

Open AccessReview

Heteroatom-Doped Carbon Nanostructures Derived from Conjugated Polymers for Energy Applications

by Yanzhen He, Xijiang Han, Yunchen Du, Bin Zhang and Ping Xu

Polymers 2016, 8(10), 366; https://doi.org/10.3390/polym8100366 - 17 Oct 2016

Cited by 44 | Viewed by 9878

Abstract

Heteroatom-doped carbon materials have been one of the most remarkable families of materials with promising applications in fuel cells, supercapacitors, and batteries. Among them, conjugated polymer (CP)-derived heteroatom-doped carbon materials exhibit remarkable electrochemical performances because the heteroatoms can be preserved at a relatively [...] Read more.

Heteroatom-doped carbon materials have been one of the most remarkable families of materials with promising applications in fuel cells, supercapacitors, and batteries. Among them, conjugated polymer (CP)-derived heteroatom-doped carbon materials exhibit remarkable electrochemical performances because the heteroatoms can be preserved at a relatively high content and keep stable under harsh working conditions. In this review, we summarized recent advances in the rational design and various applications of CP-derived heteroatom-doped carbon materials, including polyaniline (PANI), polypyrrole (PPy), and their ramification-derived carbons, as well as transition metal-carbon nanocomposites. The key point of considering CP-derived heteroatom-doped carbon materials as important candidates of electrode materials is that CPs contain only nonmetallic elements and some key heteroatoms in their backbones which provide great chances for the synthesis of metal-free heteroatom-doped carbon nanostructures. The presented examples in this review will provide new insights in designing and optimizing heteroatom-doped carbon materials for the development of anode and cathode materials for electrochemical device applications. Full article

(This article belongs to the Special Issue Conjugated Polymers 2016)

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2390 KiB

Open AccessArticle

Aromatic Copolyamides with Anthrazoline Units in the Backbone: Synthesis, Characterization, Pervaporation Application

by Galina A. Polotskaya, Alexandra Yu. Pulyalinа, Mikhail Ya. Goikhman, Irina V. Podeshvo, Irina A. Valieva and Alexander M. Toikka

Polymers 2016, 8(10), 362; https://doi.org/10.3390/polym8100362 - 17 Oct 2016

Cited by 12 | Viewed by 5562

Abstract

Copolyamides with anthrazoline units in the backbone (coPA) were synthesized and dense nonporous films were prepared by solvent evaporation. Glass transition temperature, density, and fractional free volume were determined for the dense nonporous films composed of polyamide and two of its copolymers containing [...] Read more.

Copolyamides with anthrazoline units in the backbone (coPA) were synthesized and dense nonporous films were prepared by solvent evaporation. Glass transition temperature, density, and fractional free volume were determined for the dense nonporous films composed of polyamide and two of its copolymers containing 20 and 30 mol % anthrazoline units in the backbone. Transport properties of the polymer films were estimated by sorption and pervaporation tests toward methanol, toluene, and their mixtures. An increase in anthrazoline fragments content leads to an increasing degree of methanol sorption but to a decreasing degree of toluene sorption. Pervaporation of a methanol–toluene mixture was studied over a wide range of feed concentration (10–90 wt % methanol). Maximal separation factor was observed for coPA-20 containing 20 mol % fragments with anthrazoline units; maximal total flux was observed for coPA-30 with the highest fractional free volume. Full article

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2539 KiB

Open AccessArticle

Synthesis of Novel Cobalt-Containing Polysilazane Nanofibers with Fluorescence by Electrospinning

by Qian Zhang, Dechang Jia, Zhihua Yang, Xiaoming Duan, Qingqing Chen and Yu Zhou

Polymers 2016, 8(10), 350; https://doi.org/10.3390/polym8100350 - 17 Oct 2016

Cited by 9 | Viewed by 8145

Abstract

Emission in the nanostructured materials is important in micro/nanoelectronic devices. We report here a strategy for the processing of micron and submicron fibers from a cobalt-containing hyperbranched polysilazane by electrospinning. The electrospun nanofibers have uniform average diameters of ~600 nm and lengths of [...] Read more.

Emission in the nanostructured materials is important in micro/nanoelectronic devices. We report here a strategy for the processing of micron and submicron fibers from a cobalt-containing hyperbranched polysilazane by electrospinning. The electrospun nanofibers have uniform average diameters of ~600 nm and lengths of ~10 μm. The photophysical properties of polycobaltsilazane (PCSN) are studied using UV-VIS and photoluminescence spectroscopies. PCSN fibers display a series of emission peaks between 490 and 615 nm. The Co(II) doping into polysilazane leads to the emission from 465 to 415 nm. The emission wavelength shift of Co(III)-containing polysilazane is specific under 340 and 470 nm excitation wavelengths, respectively, while it is not observed with metal-free polysilazane. Thermogravimetric analysis-Differentical thermal analysis (TGA-DTA) profiles also show good thermostability of the PCSN fibers at 800 °C under Ar atmosphere. The use of PCSN offers both enhanced ceramic yields against ~5 wt % starting material and the fluorescence intensity of polymeric fibers. Full article

(This article belongs to the Special Issue Conjugated Polymers 2016)

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5982 KiB

Open AccessArticle

Relaxation Oscillation with Picosecond Spikes in a Conjugated Polymer Laser

by Wafa Musa Mujamammi, Saradh Prasad, Mohamad S. AlSalhi and Vadivel Masilamani

Polymers 2016, 8(10), 364; https://doi.org/10.3390/polym8100364 - 14 Oct 2016

Cited by 8 | Viewed by 5784

Abstract

Optically pumped conjugated polymer lasers are good competitors for dye lasers, often complementing and occasionally replacing them. This new type of laser material has broad bandwidths and high optical gains comparable to conventional laser dyes. Since the Stokes’ shift is unusually large, the [...] Read more.

Optically pumped conjugated polymer lasers are good competitors for dye lasers, often complementing and occasionally replacing them. This new type of laser material has broad bandwidths and high optical gains comparable to conventional laser dyes. Since the Stokes’ shift is unusually large, the conjugated polymer has a potential for high power laser action, facilitated by high concentration. This paper reports the results of a new conjugated polymer, the poly[(9,9-dioctyl-2,7-divinylenefluorenylene)-alt-co-{2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylene}](PFO-co-MEH-PPV) material, working in the green region. Also discussed are the spectral and temporal features of the amplified spontaneous emissions (ASE) from the conjugated polymer PFO-co-MEH-PPV in a few solvents. When pumped by the third harmonic of the Nd:YAG laser of 10 ns pulse width, the time-resolved spectra of the ASE show relaxation oscillations and spikes of 600 ps pulses. To the best of our knowledge, this is the first report on relaxation oscillations in conjugated-polymer lasers. Full article

(This article belongs to the Special Issue Conjugated Polymers 2016)

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978 KiB

Open AccessArticle

Highly Branched Bio-Based Unsaturated Polyesters by Enzymatic Polymerization

by Hiep Dinh Nguyen, David Löf, Søren Hvilsted and Anders Egede Daugaard

Polymers 2016, 8(10), 363; https://doi.org/10.3390/polym8100363 - 14 Oct 2016

Cited by 17 | Viewed by 8753

Abstract

A one-pot, enzyme-catalyzed bulk polymerization method for direct production of highly branched polyesters has been developed as an alternative to currently used industrial procedures. Bio-based feed components in the form of glycerol, pentaerythritol, azelaic acid, and tall oil fatty acid (TOFA) were polymerized [...] Read more.

A one-pot, enzyme-catalyzed bulk polymerization method for direct production of highly branched polyesters has been developed as an alternative to currently used industrial procedures. Bio-based feed components in the form of glycerol, pentaerythritol, azelaic acid, and tall oil fatty acid (TOFA) were polymerized using an immobilized Candida antarctica lipase B (CALB) and the potential for an enzymatic synthesis of alkyds was investigated. The developed method enables the use of both glycerol and also pentaerythritol (for the first time) as the alcohol source and was found to be very robust. This allows simple variations in the molar mass and structure of the polyester without premature gelation, thus enabling easy tailoring of the branched polyester structure. The postpolymerization crosslinking of the polyesters illustrates their potential as binders in alkyds. The formed films had good UV stability, very high water contact angles of up to 141° and a glass transition temperature that could be controlled through the feed composition. Full article

(This article belongs to the Special Issue Enzymatic Polymer Synthesis)

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2347 KiB

Open AccessArticle

Atomistic Modelling of Confined Polypropylene Chains between Ferric Oxide Substrates at Melt Temperature

by Ali Gooneie, Joamin Gonzalez-Gutierrez and Clemens Holzer

Polymers 2016, 8(10), 361; https://doi.org/10.3390/polym8100361 - 14 Oct 2016

Cited by 19 | Viewed by 8390

Abstract

The interactions and conformational characteristics of confined molten polypropylene (PP) chains between ferric oxide (Fe₂O₃) substrates were investigated by molecular dynamics (MD) simulations. A comparative analysis of the adsorbed amount shows strong adsorption of the chains on the high-energy [...] Read more.

The interactions and conformational characteristics of confined molten polypropylene (PP) chains between ferric oxide (Fe₂O₃) substrates were investigated by molecular dynamics (MD) simulations. A comparative analysis of the adsorbed amount shows strong adsorption of the chains on the high-energy surface of Fe₂O₃. Local structures formed in the polymer film were studied utilizing density profiles, orientation of bonds, and end-to-end distance of chains. At interfacial regions, the backbone carbon-carbon bonds of the chains preferably orient in the direction parallel to the surface while the carbon-carbon bonds with the side groups show a slight tendency to orient normal to the surface. Based on the conformation tensor data, the chains are compressed in the normal direction to the substrates in the interfacial regions while they tend to flatten in parallel planes with respect to the surfaces. The orientation of the bonds as well as the overall flattening of the chains in planes parallel to the solid surfaces are almost identical to that of the unconfined PP chains. Also, the local pressure tensor is anisotropic closer to the solid surfaces of Fe₂O₃ indicating the influence of the confinement on the buildup imbalance of normal and tangential pressures. Full article

(This article belongs to the Special Issue Computational Modeling and Simulation in Polymer)

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1800 KiB

Open AccessArticle

Structure–Property Studies on a New Family of Halogen Free Flame Retardants Based on Sulfenamide and Related Structures

by Teija Tirri, Melanie Aubert, Weronika Pawelec, Anton Holappa and Carl-Eric Wilén

Polymers 2016, 8(10), 360; https://doi.org/10.3390/polym8100360 - 14 Oct 2016

Cited by 20 | Viewed by 8530

Abstract

A wide variety of molecules containing S–N or S–N–S cores were synthesized, and their flame retardant properties in polypropylene (PP), low density polyethylene (LDPE) and polystyrene (PS) were investigated. In addition, polymers or oligomers bearing the sulfenamide functionality (SN) were also synthesized. It [...] Read more.

A wide variety of molecules containing S–N or S–N–S cores were synthesized, and their flame retardant properties in polypropylene (PP), low density polyethylene (LDPE) and polystyrene (PS) were investigated. In addition, polymers or oligomers bearing the sulfenamide functionality (SN) were also synthesized. It was shown that this radical generator family based on sulfenamides is very versatile in terms of structural modifications, and the thermal decomposition range can be easily adjusted by changing the R groups attached to the core. The thermal stabilities of the different sulfenamides were examined by thermogravimetric analysis (TGA). Radicals generated by the homolytic cleavage of the S–N or S–N–S bonds at an elevated temperature can effectively interact with the intermediate products of polymer thermolysis and provide excellent flame retardant properties. The choice of most suitable SN-structure varies depending on the polymer type. For polypropylene DIN 4102-1 B2 and UL94 VTM-2 classifications were achieved with only 0.5 to 1 wt % of sulfenamide, and, in some cases, no flaming dripping was observed. Also for LDPE thin films, sulfenamides offered the DIN 4102-1 B2 rating at low dosage. In the case of polystyrene, the very stringent UL94 V-0 classification was even achieved at a loading of 5 wt % of sulfenamide. Full article

(This article belongs to the Special Issue Recent Advances in Flame Retardancy of Textile Related Products)

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Enhancing the Compatibility, Hydrophilicity and Mechanical Properties of Polysulfone Ultrafiltration Membranes with Lignocellulose Nanofibrils

by Zhaodong Ding, Xuejiao Liu, Yang Liu and Liping Zhang

Polymers 2016, 8(10), 349; https://doi.org/10.3390/polym8100349 - 14 Oct 2016

Cited by 54 | Viewed by 7178

Abstract

Lignocellulose nanofibrils (LCN) and cellulose nanofibrils (CNF) are popular nanometer additives to improve mechanical properties and hydrophilic abilities; moreover, lignocellulose has potential as a natural adhesion promoter in fiber-reinforced composites. LCN and CNF were blended into polysulfone (PSF) to prepare ultrafiltration membranes via [...] Read more.

Lignocellulose nanofibrils (LCN) and cellulose nanofibrils (CNF) are popular nanometer additives to improve mechanical properties and hydrophilic abilities; moreover, lignocellulose has potential as a natural adhesion promoter in fiber-reinforced composites. LCN and CNF were blended into polysulfone (PSF) to prepare ultrafiltration membranes via the phase inversion method. These additives were characterized by Fourier transform infrared spectroscopy and transmission electron microscopy, and the rheological properties such as shear viscosity and non-Newtonian fluid index of the casting solutions were analyzed using a rotational rheometer. The performance of ultrafiltration membranes was characterized using Fourier transform infrared spectroscopy, thermogravimetric analysis and scanning electron microscopy. The pure water flux, bovine serum albumin retention ratio, water contact angle, surface energy, molecular weight cut-off, pore size and mechanical properties were measured. The equilibrium contact angle of water decreased from 63.5° on the PSF membrane to 42.1° on the CNF/PSF membrane and then decreased to 33.9° on the LCN/PSF membrane when the nanometer additives content was 0.8 wt %. The results reveal that LCN and CNF were successfully combined with PSF. Moreover, the combination of LCN/PSF ultrafiltration membranes was more promising than that of CNF/PSF ultrafiltration membranes. Full article

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Open AccessArticle

Mapping the Mechanical Properties of Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) Banded Spherulites by Nanoindentation

by Patricia Enrique-Jimenez, Juan F. Vega, Javier Martínez-Salazar, Fernando Ania and Araceli Flores

Polymers 2016, 8(10), 358; https://doi.org/10.3390/polym8100358 - 12 Oct 2016

Cited by 7 | Viewed by 5943

Abstract

Nanoindentation provides clear evidence that spherulite banding can be associated with a continuous modulation of mechanical properties from the more compliant peaks to the stiffer valleys. The structural arrangement in polymer-banded spherulites has intrigued scientists for many decades, and the debate has been [...] Read more.

Nanoindentation provides clear evidence that spherulite banding can be associated with a continuous modulation of mechanical properties from the more compliant peaks to the stiffer valleys. The structural arrangement in polymer-banded spherulites has intrigued scientists for many decades, and the debate has been recently intensified with the advent of new experimental evidence. The present paper approaches this issue by exploring the local mechanical properties of poly(3-hydroxybutyrate-co-3-hydroxyvalerate)-ringed spherulites via nanoindentation and discussing the confidence of the results. It was found that storage modulus and hardness across the banding morphology can be described as a sequence of regular oscillations with a periodicity that exactly matches the one observed using optical and atomic force microscopy. Results are consistent with the model of regular twisting of the lamellae, with flat-on arrangement in the low regions and edge-on lamellae in the crests. Full article

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Open AccessReview

Recent Advances in the Design of Water Based-Flame Retardant Coatings for Polyester and Polyester-Cotton Blends

by Jenny Alongi, Federico Carosio and Paul Kiekens

Polymers 2016, 8(10), 357; https://doi.org/10.3390/polym8100357 - 11 Oct 2016

Cited by 47 | Viewed by 8999

Abstract

Over the last ten years a new trend of research activities regarding the flame retardancy of polymeric materials has arisen. Indeed, the continuous search for new flame retardant systems able to replace the traditional approaches has encouraged alternative solutions, mainly centred on nanotechnology. [...] Read more.

Over the last ten years a new trend of research activities regarding the flame retardancy of polymeric materials has arisen. Indeed, the continuous search for new flame retardant systems able to replace the traditional approaches has encouraged alternative solutions, mainly centred on nanotechnology. In this context, the deposition of nanostructured coatings on fabrics appears to be the most appealing and performance suitable approach. To this aim, different strategies can be exploited: from the deposition of a single monolayer consisting of inorganic nanoparticles (single-step adsorption) to the building-up of more complex architectures derived from layer by layer assembly (multi-step adsorption). The present paper aims to review the application of such systems in the field of polyester and polyester-cotton blend fabrics. The results collated by the authors are discussed and compared with those published in the literature on the basis of the different deposition methods adopted. A critical analysis of the advantages and disadvantages exhibited by these approaches is also presented. Full article

(This article belongs to the Special Issue Recent Advances in Flame Retardancy of Textile Related Products)

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3133 KiB

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The Effect of Crystallinity on Compressive Properties of Al-PTFE

by Bin Feng, Xiang Fang, Huai-Xi Wang, Wen Dong and Yu-Chun Li

Polymers 2016, 8(10), 356; https://doi.org/10.3390/polym8100356 - 11 Oct 2016

Cited by 50 | Viewed by 8821

Abstract

Al-PTFE (Al-polytetrafluoroethene) is an important kind of Reactive Material (RM), however only limited importance was placed to the effect of crystallinity of PTFE on the mechanical and reactive behavior. This paper investigated the influence of crystallinity on the compression behavior of Al-PTFE at [...] Read more.

Al-PTFE (Al-polytetrafluoroethene) is an important kind of Reactive Material (RM), however only limited importance was placed to the effect of crystallinity of PTFE on the mechanical and reactive behavior. This paper investigated the influence of crystallinity on the compression behavior of Al-PTFE at strain rates range from 10⁻² to 3 × 10³ s⁻¹. Two kinds of samples were prepared by different sintering procedures to acquire different crystallinity. The samples’ crystallinity was characterized by the density method and X-ray diffraction method. The samples were tested using an electro-hydraulic press for quasi-static loading, and split Hopkinson pressure bars (SHPBs) for high strain rates. Low crystalline samples have consistently higher strength and toughness than the high crystalline samples. The phenomenon was explained by an “elastic-plastic network” model combined with the effect of chain entanglement density. A bilinear dependence of true stress on log

\dot{ε}

was observed, and Johnson-Cook models were fitted separately according to the different strain rate sensitivity. Finally, a close connection between fracture and initiation of Al-PTFE was confirmed in quasi-static tests, SHPB tests, and drop weight tests. It was hypothesized that the high temperature at the crack tips of PTFE is an important promoting factor of initiation. Full article

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23981 KiB

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Biphasic Polyurethane/Polylactide Sponges Doped with Nano-Hydroxyapatite (nHAp) Combined with Human Adipose-Derived Mesenchymal Stromal Stem Cells for Regenerative Medicine Applications

by Krzysztof Marycz, Monika Marędziak, Jakub Grzesiak, Anna Lis and Agnieszka Śmieszek

Polymers 2016, 8(10), 339; https://doi.org/10.3390/polym8100339 - 11 Oct 2016

Cited by 20 | Viewed by 7475

Abstract

Cartilage and bone tissue injuries are common targets in regenerative medicine. The degeneration of cartilage tissue results in tissue loss with a limited ability to regenerate. However, the application of mesenchymal stem cells in the course of such condition makes it possible to [...] Read more.

Cartilage and bone tissue injuries are common targets in regenerative medicine. The degeneration of cartilage tissue results in tissue loss with a limited ability to regenerate. However, the application of mesenchymal stem cells in the course of such condition makes it possible to manage this disorder by improving the structure of the remaining tissue and even stimulating its regeneration. Nevertheless, in the case of significant tissue loss, standard local injection of cell suspensions is insufficient, due to the low engraftment of transplanted cells. Introduction of mesenchymal stem cells on the surface of a compatible biomaterial can be a promising tool for inducing the regeneration by both retaining the cells at the desired site and filling the tissue gap. In order to obtain such a cell-biomaterial hybrid, we developed complex, biphasic polymer blend biomaterials composed of various polyurethane (PU)-to-polylactide (PLA) ratios, and doped with different concentrations of nano-hydroxyapatite (nHAp). We have determined the optimal blend composition and nano-hydroxyapatite concentration for adipose mesenchymal stem cells cultured on the biomaterial. We applied biological in vitro techniques, including cell viability assay, determination of oxidative stress factors level, osteogenic and chondrogenic differentiation potentials as well as cell proteomic analysis. We have shown that the optimal composition of biphasic scaffold was 20:80 of PU:PLA with 20% of nHAp for osteogenic differentiation, and 80:20 of PU:PLA with 10% of nHAp for chondrogenic differentiation, which suggest the optimal composition of final biphasic implant for regenerative medicine applications. Full article

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6281 KiB

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The Effect of Injection Molding Temperature on the Morphology and Mechanical Properties of PP/PET Blends and Microfibrillar Composites

by Maja Kuzmanović, Laurens Delva, Ludwig Cardon and Kim Ragaert

Polymers 2016, 8(10), 355; https://doi.org/10.3390/polym8100355 - 9 Oct 2016

Cited by 55 | Viewed by 11503

Abstract

Within this research the effect of injection molding temperature on polypropylene (PP)/poly(ethylene terephthalate) (PET) blends and microfibrillar composites was investigated. Injection molding blends (IMBs) and microfibrillar composites (MFCs) of PP/PET have been prepared in a weight ratio 70/30. The samples were processed at [...] Read more.

Within this research the effect of injection molding temperature on polypropylene (PP)/poly(ethylene terephthalate) (PET) blends and microfibrillar composites was investigated. Injection molding blends (IMBs) and microfibrillar composites (MFCs) of PP/PET have been prepared in a weight ratio 70/30. The samples were processed at three different injection molding temperatures (T_im) (210, 230, 280 °C) and subjected to extensive characterization. The observations from the fracture surfaces of MFCs showed that PET fibers can be achieved by three step processing. The results indicated that T_im has a big influence on morphology of IMBs and MFCs. With increasing the T_im, distinctive variations in particle and fiber diameters were noticed. The differences in mechanical performances were obtained by flexural and impact tests. Establishing relationships between the processing parameters, properties, and morphology of composites is of key importance for the valorization of MFC polymers. Full article

(This article belongs to the Special Issue Polymeric Fibers)

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3617 KiB

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Low Density Wood-Based Particleboards Bonded with Foamable Sour Cassava Starch: Preliminary Studies

by Sandra Monteiro, Jorge Martins, Fernão D. Magalhães and Luísa Carvalho

Polymers 2016, 8(10), 354; https://doi.org/10.3390/polym8100354 - 8 Oct 2016

Cited by 29 | Viewed by 7105

Abstract

This work investigates the feasibility of producing low density particleboards using an adhesive system based on sour cassava starch, taking advantage of its adhesive and self-expansion properties. Relevant properties of the produced particleboards were evaluated according to European Standards including: density, internal bond, [...] Read more.

This work investigates the feasibility of producing low density particleboards using an adhesive system based on sour cassava starch, taking advantage of its adhesive and self-expansion properties. Relevant properties of the produced particleboards were evaluated according to European Standards including: density, internal bond, moisture content and thickness swelling. Low density particleboards were produced with densities between 207 kg/m³ and 407 kg/m³. The best performance corresponded to particleboard with a density of 318 kg/m³, an internal bond strength of 0.67 N/mm², and a thickness swelling of 8.7%. These values meet the standard requirements of general purpose lightweight boards for use in dry conditions. Heat post-treatment (24 h at 80 °C) led to lower internal bond strength, due to retrogradation (recrystallization of amylose and amylopectin chains upon cooling) causing higher rigidity of the starch binder. However, it showed to have a significant effect on decreasing the thickness swelling. Full article

(This article belongs to the Special Issue Renewable Polymeric Adhesives)

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1763 KiB

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Dynamics of DNA Squeezed Inside a Nanochannel via a Sliding Gasket

by Aiqun Huang, Walter Reisner and Aniket Bhattacharya

Polymers 2016, 8(10), 352; https://doi.org/10.3390/polym8100352 - 29 Sep 2016

Cited by 10 | Viewed by 6062

Abstract

We use Brownian dynamics (BD) simulation of a coarse-grained (CG) bead-spring model of DNA to study the nonequilibrim dynamics of a single DNA molecule confined inside a rectangular nanochannel being squeezed with a sliding gasket piston or “nanodozer”. From our simulations we extract [...] Read more.

We use Brownian dynamics (BD) simulation of a coarse-grained (CG) bead-spring model of DNA to study the nonequilibrim dynamics of a single DNA molecule confined inside a rectangular nanochannel being squeezed with a sliding gasket piston or “nanodozer”. From our simulations we extract the nonequilibrim density profile

c (x, t)

of the squeezed molecule along the channel axis (x-coordinate) and then analyze the non-equilibrium profile using a recently introduced phenomenological Nonlinear Partial Differential Equation (NPDE) model. Since the NPDE approach also fits the experimental results well and is numerically efficient to implement, the combined BD + NPDE methods can be a powerful approach to analyze details of the confined molecular dynamics. In particular, the overall excellent agreement between the two complementary sets of data provides a strategy for carrying out large scale simulation on semi-flexible biopolymers in confinement at biologically relevant length scales. Full article

(This article belongs to the Special Issue Semiflexible Polymers)

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434 KiB

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Microstructure of Sheared Entangled Solutions of Semiflexible Polymers

by Marc Lämmel, Evelin Jaschinski, Rudolf Merkel and Klaus Kroy

Polymers 2016, 8(10), 353; https://doi.org/10.3390/polym8100353 - 28 Sep 2016

Cited by 3 | Viewed by 5803

Abstract

We study the influence of finite shear deformations on the microstructure and rheology of solutions of entangled semiflexible polymers theoretically and by numerical simulations and experiments with filamentous actin. Based on the tube model of semiflexible polymers, we predict that large finite shear [...] Read more.

We study the influence of finite shear deformations on the microstructure and rheology of solutions of entangled semiflexible polymers theoretically and by numerical simulations and experiments with filamentous actin. Based on the tube model of semiflexible polymers, we predict that large finite shear deformations strongly affect the average tube width and curvature, thereby exciting considerable restoring stresses. In contrast, the associated shear alignment is moderate, with little impact on the average tube parameters, and thus expected to be long-lived and detectable after cessation of shear. Similarly, topologically preserved hairpin configurations are predicted to leave a long-lived fingerprint in the shape of the distributions of tube widths and curvatures. Our numerical and experimental data support the theory. Full article

(This article belongs to the Special Issue Semiflexible Polymers)

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5104 KiB

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Study of Non-Isothermal Crystallization of Polydioxanone and Analysis of Morphological Changes Occurring during Heating and Cooling Processes

by Yolanda Márquez, Lourdes Franco, Pau Turon, Juan Carlos Martínez and Jordi Puiggalí

Polymers 2016, 8(10), 351; https://doi.org/10.3390/polym8100351 - 28 Sep 2016

Cited by 19 | Viewed by 8018

Abstract

Non-isothermal crystallization kinetics of polydioxanone (PDO), a polymer with well-established applications as bioabsorbable monofilar suture, was investigated by Avrami, Mo, and isoconversional methodologies. Results showed Avrami exponents appearing in a relatively narrow range (i.e., between 3.76 and 2.77), which suggested a three-dimensional spherulitic [...] Read more.

Non-isothermal crystallization kinetics of polydioxanone (PDO), a polymer with well-established applications as bioabsorbable monofilar suture, was investigated by Avrami, Mo, and isoconversional methodologies. Results showed Avrami exponents appearing in a relatively narrow range (i.e., between 3.76 and 2.77), which suggested a three-dimensional spherulitic growth and instantaneous nucleation at high cooling rates. The nucleation mechanism changed to sporadic at low rates, with both crystallization processes being detected in the differential scanning calorimetry (DSC) cooling traces. Formation of crystals was hindered as the material crystallized because of a decrease in the motion of molecular chains. Two secondary nucleation constants were derived from calorimetric data by applying the methodology proposed by Vyazovkin and Sbirrazzuoli through the estimation of effective activation energies. In fact, typical non-isothermal crystallization analysis based on the determination of crystal growth by optical microscopy allowed secondary nucleation constants of 3.07 × 10⁵ K² and 1.42 × 10⁵ K² to be estimated. Microstructure of sutures was characterized by a stacking of lamellae perpendicularly oriented to the fiber axis and the presence of interlamellar and interfibrillar amorphous regions. The latter became enhanced during heating treatments due to loss of partial chain orientation and decrease of electronic density. Degradation under various pH media revealed different macroscopic morphologies and even a distinct evolution of lamellar microstructure during subsequent heating treatments. Full article

(This article belongs to the Special Issue Biodegradable Polymers)

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Polymers, Volume 8, Issue 10 (October 2016) – 33 articles

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