Polymers

17 pages, 5436 KiB

Open AccessArticle

3D-Printing of Microfibrous Porous Scaffolds Based on Hybrid Approaches for Bone Tissue Engineering

by Ranjith Kumar Kankala^1,2,†

, Xiao-Ming Xu^1,†, Chen-Guang Liu¹, Ai-Zheng Chen^1,2,*

and Shi-Bin Wang^1,2,*

¹ Institute of Biomaterials and Tissue Egineering, Huaqiao University, Xiamen 361021, China

² Fujian Provincial Key Laboratory of Biochemical Technology (Huaqiao University), Xiamen 361021, China

^† These authors contributed equally to this work.

Polymers 2018, 10(7), 807; https://doi.org/10.3390/polym10070807 - 23 Jul 2018

Cited by 71 | Viewed by 8160

Abstract

In recent times, tremendous progress has been evidenced by the advancements in various methods of generating three-dimensional (3D) porous scaffolds. However, the applicability of most of the traditional approaches intended for generating these biomimetic scaffolds is limited due to poor resolution and strict [...] Read more.

In recent times, tremendous progress has been evidenced by the advancements in various methods of generating three-dimensional (3D) porous scaffolds. However, the applicability of most of the traditional approaches intended for generating these biomimetic scaffolds is limited due to poor resolution and strict requirements in choosing materials. In this work, we fabricated 3D porous scaffolds based on the composite inks of gelatin (Gel), nano-hydroxyapatite (n-HA), and poly(lactide-co-glycolide) (PLGA) using an innovative hybrid strategy based on 3D printing and freeze-drying technologies for bone tissue engineering. Initially, the PLGA scaffolds were printed using the 3D printing method, and they were then coated with the Gel/n-HA complex, yielding the Gel/n-HA/PLGA scaffolds. These Gel/n-HA/PLGA scaffolds with exceptional biodegradation, mechanical properties, and biocompatibility have enabled osteoblasts (MC3T3-E1) for their convenient adhesion as a layer and have efficiently promoted their growth, as well as differentiation. We further demonstrated the bone growth by measuring the particular biomarkers that act as key players in the ossification process (i.e., alkaline phosphatase (ALP), osteocalcin (OC), and collagen type-I (COL-I)) and the total proteins of the MC3T3-E1 cells. We anticipate that the convenient generation of highly porous 3D scaffolds based on Gel/n-HA/PLGA fabricated through an innovative combinatorial approach of 3D printing technology and freeze-drying methods may undoubtedly find widespread applications in regenerative medicine. Full article

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22 pages, 6096 KiB

Open AccessArticle

Rational Development of a Novel Hydrogel as a pH-Sensitive Controlled Release System for Nifedipine

by Fabián Avila-Salas^1,*, Yeray A. Rodriguez Nuñez², Adolfo Marican^2,3, Ricardo I. Castro^4,5, Jorge Villaseñor³, Leonardo S. Santos³

, Sergio Wehinger^6,7 and Esteban F. Durán-Lara^2,8,*

¹ Centro de Nanotecnología Aplicada, Facultad de Ciencias, Universidad Mayor, Huechuraba 8580000, Región Metropolitana, Chile

² BioNanoMaterials Lab|Drug Delivery and Controlled Release, Universidad de Talca, Talca 3460000, Maule, Chile

³ Instituto de Química de Recursos Naturales, Universidad de Talca, Talca 3460000, Maule, Chile

⁴ Multidisciplinary Agroindustry Research Laboratory, Universidad Autónoma de Chile, Talca 3460000, Maule, Chile

⁵ Carrera de Ingeniería en Construcción e Instituto de Ciencias Biomédicas, Universidad Autónoma de Chile, Talca 3460000, Maule, Chile

⁶ Department of Clinical Biochemistry and Immunohematology, Faculty of Heatlh Sciences, Universidad de Talca, Talca 3460000, Maule, Chile

⁷ Center for Studies of Exercise, Metabolism and Cancer (CEMC), Universidad de Chile, Independencia 8380000, Región Metropolitana, Chile

⁸ Departamento de Microbiología, Facultad de Ciencias de la Salud, Universidad de Talca, Talca 3460000, Maule, Chile

Polymers 2018, 10(7), 806; https://doi.org/10.3390/polym10070806 - 23 Jul 2018

Cited by 22 | Viewed by 5365

Abstract

This work depicts the rational development (in-silico design, synthesis, characterization and in-vitro evaluation) of polyvinyl alcohol hydrogels (PVAH) cross-linked with maleic acid (MA) and linked to γ-cyclodextrin molecules (γ-CDPVAHMA) as systems for the controlled and sustained release of nifedipine (NFD). Through computational studies, [...] Read more.

This work depicts the rational development (in-silico design, synthesis, characterization and in-vitro evaluation) of polyvinyl alcohol hydrogels (PVAH) cross-linked with maleic acid (MA) and linked to γ-cyclodextrin molecules (γ-CDPVAHMA) as systems for the controlled and sustained release of nifedipine (NFD). Through computational studies, the structural blocks (PVA chain + dicarboxylic acid + γ-CD) of 20 different hydrogels were evaluated to test their interaction energies (ΔE) with NFD. According to the ΔE obtained, the hydrogel cross-linked with maleic acid was selected. To characterize the intermolecular interactions between NFD and γ-CDPVAHMA, molecular dynamics simulation studies were carried out. Experimentally, three hydrogel formulations with different proportions of γ-CD (2.43%, 3.61% and 4.76%) were synthesized and characterized. Both loading and release of NFD from the hydrogels were evaluated at acid and basic pH. The computational and experimental results show that γ-CDs linked to the hydrogels were able to form 1:1 inclusion complexes with NFD molecules. Finally, γ-CDPVAHMA-3 demonstrated to be the best pH-sensitive release platform for nifedipine. Its effectiveness could significantly reduce the adverse effects caused by the anticipated release of NFD in the stomach of patients. Full article

(This article belongs to the Special Issue Polymers: Design, Function and Application)

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9 pages, 2561 KiB

Open AccessArticle

Coupling of Defect Modes in Cholesteric Liquid Crystals Separated by Isotropic Polymeric Layers

by Shaohua Gao¹, Yanzi Zhai¹, Xinzheng Zhang^1,*

, Xiao Song¹, Jiayi Wang¹, Irena Drevensek-Olenik^2,*

, Romano A. Rupp^1,3 and Jingjun Xu^1,4

¹ The MOE Key Laboratory of Weak-Light Nonlinear Photonics, TEDA Institute of Applied Physics and School of Physics, Nankai University, Tianjin 300457, China

² Faculty of Mathematics and Physics, University of Ljubljana, Jadranska 19 and Department of Complex Matter, J. Stefan Institute, Jamova cesta 39, 1000 Ljubljana, Slovenia

³ Faculty of Physics, Vienna University, Boltzmanngasse 5, A-1090 Wien, Austria

⁴ Synergetic Innovation Center of Chemical Science and Engineering, Tianjin 300071, China

Polymers 2018, 10(7), 805; https://doi.org/10.3390/polym10070805 - 23 Jul 2018

Cited by 16 | Viewed by 7856

Abstract

Cholesteric liquid crystal structures with multiple isotropic defect layers exhibit localized optical modes (defect modes). Coupling effects between these modes were simulated using the finite difference time domain method. Analogous to the well-known result of the tight-binding approximation in solid state physics, splitting [...] Read more.

Cholesteric liquid crystal structures with multiple isotropic defect layers exhibit localized optical modes (defect modes). Coupling effects between these modes were simulated using the finite difference time domain method. Analogous to the well-known result of the tight-binding approximation in solid state physics, splitting of the defect modes takes place, as soon as the structure contains more than one defect layer. The dispersion relation of the mini-bands forming within the photonic band gap of the structure is calculated numerically. The structures might have promising applications for multiwavelength filters and low-threshold lasers. Full article

(This article belongs to the Special Issue Liquid Crystalline Polymers)

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13 pages, 4776 KiB

Open AccessArticle

In Vivo Investigation into Effectiveness of Fe₃O₄/PLLA Nanofibers for Bone Tissue Engineering Applications

by Wei-Yi Lai¹, Sheng-Wei Feng², Ya-Hui Chan³, Wei-Jen Chang^3,4, Hsin-Ta Wang^1,* and Haw-Ming Huang^3,5,*

¹ School of Organic and Polymeric, National Taipei University of Technology, Taipei 10608, Taiwan

² School of Oral Hygiene, College of Oral Medicine, Taipei Medical University, Taipei 11031, Taiwan

³ School of Dentistry, College of Oral Medicine, Taipei Medical University, Taipei 11031, Taiwan

⁴ Dental Department, Taipei Medical University Shuang-Ho Hospital, New Taipei City 23561, Taiwan

⁵ Graduate Institute of Biomedical Optomechatronics, College of Biomedical Engineering, Taipei 11031, Taiwan

Polymers 2018, 10(7), 804; https://doi.org/10.3390/polym10070804 - 22 Jul 2018

Cited by 34 | Viewed by 5063

Abstract

Fe₃O₄ nanoparticles were loaded into poly-l-lactide (PLLA) with concentrations of 2% and 5%, respectively, using an electrospinning method. In vivo animal experiments were then performed to evaluate the potential of the Fe₃O₄/PLLA nanofibrous material [...] Read more.

Fe₃O₄ nanoparticles were loaded into poly-l-lactide (PLLA) with concentrations of 2% and 5%, respectively, using an electrospinning method. In vivo animal experiments were then performed to evaluate the potential of the Fe₃O₄/PLLA nanofibrous material for bone tissue engineering applications. Bony defects with a diameter of 4 mm were prepared in rabbit tibias. Fe₃O₄/PLLA nanofibers were grafted into the drilled defects and histological examination and computed tomography (CT) image detection were performed after an eight-week healing period. The histological results showed that the artificial bony defects grafted with Fe₃O₄/PLLA nanofibers exhibited a visibly higher bone healing activity than those grafted with neat PLLA. In addition, the quantitative results from CT images revealed that the bony defects grafted with 2% and 5% Fe₃O₄/PLLA nanofibers, respectively, showed 1.9- and 2.3-fold increases in bone volume compared to the control blank sample. Overall, the results suggest that the Fe₃O₄/PLLA nanofibers fabricated in this study may serve as a useful biomaterial for future bone tissue engineering applications. Full article

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13 pages, 6335 KiB

Open AccessArticle

Improve the Performance of Mechanoelectrical Transduction of Ionic Polymer-Metal Composites Based on Ordered Nafion Nanofibres by Electrospinning

by Yang Zhao¹

, Jiazheng Sheng¹, Di Xu¹, Minzhong Gao², Qinglong Meng¹, Dezhi Wu¹, Lingyun Wang¹, Wenlong Lv^1,3, Qinnan Chen¹, Jingjing Xiao^1,* and Daoheng Sun¹

¹ Department of Mechanical and Electrical Engineering, Xiamen University, Xiamen 361102, China

² School of Aerospace Engineering, Beijing Institute of Technology, Beijing 100081, China

³ Pen-Tung Sah Institute of Micro-Nano Science and Technology, Xiamen University, Xiamen 361005, China

Polymers 2018, 10(7), 803; https://doi.org/10.3390/polym10070803 - 21 Jul 2018

Cited by 13 | Viewed by 5065

Abstract

An ionic polymer–metal composite (IPMC) is a kind of soft material. The applications of IPMC in actuators, environmental sensing, and energy harvesting are currently increasing rapidly. In this study, an ordered Nafion nanofibre mat prepared by electrospinning was used to investigate the characteristics [...] Read more.

An ionic polymer–metal composite (IPMC) is a kind of soft material. The applications of IPMC in actuators, environmental sensing, and energy harvesting are currently increasing rapidly. In this study, an ordered Nafion nanofibre mat prepared by electrospinning was used to investigate the characteristics of the mechanoelectrical transduction of IPMC. The morphologies of the Nafion nanofibre mat were characterized. The proton conductivity, ion exchange capacities, and water uptake potential of the Nafion nanofibre mat were compared to traditional IPMC, respectively. A novel mechanism of Nafion nanofibre IPMC was designed and the open circuit voltage and short circuit current were measured. The maximum voltage value reached 100 mv. The output power was 3.63 nw and the power density was up to 42.4 μW/Kg under the load resistance. The Nafion nanofibre mat demonstrates excellent mechanoelectrcical transduction behavior compared to traditional IPMC and could be used for the development of self-powered devices in the future. Full article

(This article belongs to the Special Issue Electrospinning of Nanofibres)

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10 pages, 578 KiB

Open AccessArticle

GC-MS Screening Analysis for the Identification of Potential Migrants in Plastic and Paper-Based Candy Wrappers

by Soraya Galmán Graíño, Raquel Sendón

, Julia López Hernández

and Ana Rodríguez-Bernaldo de Quirós^*

Department of Analytical Chemistry, Nutrition and Food Science, Faculty of Pharmacy, University of Santiago de Compostela, 15782-Santiago de Compostela, Spain

Polymers 2018, 10(7), 802; https://doi.org/10.3390/polym10070802 - 21 Jul 2018

Cited by 40 | Viewed by 10403

Abstract

Food packaging materials may be a potential source of contamination through the migration of components from the material into foodstuffs. Potential migrants can be known substances such as additives (e.g., plasticizers, stabilizers, antioxidants, etc.), monomers, and so on. However, they can also be [...] Read more.

Food packaging materials may be a potential source of contamination through the migration of components from the material into foodstuffs. Potential migrants can be known substances such as additives (e.g., plasticizers, stabilizers, antioxidants, etc.), monomers, and so on. However, they can also be unknown substances, which could be non-intentionally added substances (NIAS). In the present study, non-targeted analysis using mass spectrometry coupled to gas chromatography (GC-MS) for the identification of migrants in plastic and paper-based candy wrappers was performed. Samples were analyzed after extraction with acetonitrile. Numerous compounds including N-alkanes, phthalates, acetyl tributyl citrate, tributyl aconitate, bis(2-ethylhexyl) adipate, butylated hydroxytoluene, etc. were identified. Many of the compounds detected in plastic samples are not included in the positive list of the authorized substances. One non-intentionally added substance, 7,9-Di-tert-butyl-1-oxaspiro(4,5)deca-6-9-diene-2,8-dione, which has been reported as a degradation product of the antioxidant Irganox 1010, was found in several samples of both plastic and paper packaging. The proposed method was shown to be a useful approach for the identification of potential migrants in packaging samples. The toxicity of the compounds identified was estimated according to Cramer rules. Then, a second targeted analysis was also conducted in order to identify photoinitiators; among the analyzed compounds, only 2-hydroxybenzophenone was found in five samples. Full article

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

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16 pages, 4109 KiB

Open AccessArticle

Micro-Structure and Thermomechanical Properties of Crosslinked Epoxy Composite Modified by Nano-SiO₂: A Molecular Dynamics Simulation

by Qing Xie^1,*, Kexin Fu¹

, Shaodong Liang¹

, Bowen Liu¹, Lu Lu¹, Xueming Yang², Zhengyong Huang³ and Fangcheng Lü¹

¹ State Key Laboratory of Alternate Electrical Power System with Renewable Energy Sources, North China Electric Power University, Baoding 071000, China

² Department of Power Engineering, North China Electric Power University, Baoding 071003, China

³ State Key Laboratory of Power Transmission Equipment & System Security and New Technology, Chongqing University, Chongqing 400044, China

Polymers 2018, 10(7), 801; https://doi.org/10.3390/polym10070801 - 20 Jul 2018

Cited by 62 | Viewed by 6089

Abstract

Establishing the relationship among the composition, structure and property of the associated materials at the molecular level is of great significance to the rational design of high-performance electrical insulating Epoxy Resin (EP) and its composites. In this paper, the molecular models of pure [...] Read more.

Establishing the relationship among the composition, structure and property of the associated materials at the molecular level is of great significance to the rational design of high-performance electrical insulating Epoxy Resin (EP) and its composites. In this paper, the molecular models of pure Diglycidyl Ether of Bisphenol A resin/Methyltetrahydrophthalic Anhydride (DGEBA/MTHPA) and their nanocomposites containing nano-SiO₂ with different particle sizes were constructed. The effects of nano-SiO₂ dopants and the crosslinked structure on the micro-structure and thermomechanical properties were investigated using molecular dynamics simulations. The results show that the increase of crosslinking density enhances the thermal and mechanical properties of pure EP and EP nanocomposites. In addition, doping nano-SiO₂ particles into EP can effectively improve the properties, as well, and the effectiveness is closely related to the particle size of nano-SiO₂. Moreover, the results indicate that the glass transition temperature (T_g) value increases with the decreasing particle size. Compared with pure EP, the T_g value of the 6.5 Å composite model increases by 6.68%. On the contrary, the variation of the Coefficient of Thermal Expansion (CTE) in the glassy state demonstrates the opposite trend compared with T_g. The CTE of the 10 Å composite model is the lowest, which is 7.70% less than that of pure EP. The mechanical properties first increase and then decrease with the decreasing particle size. Both the Young’s modulus and shear modulus reach the maximum value at 7.6 Å, with noticeable increases by 12.60% and 8.72%, respectively compared to the pure EP. In addition, the thermal and mechanical properties are closely related to the Fraction of Free Volume (FFV) and Mean Squared Displacement (MSD). The crosslinking process and the nano-SiO₂ doping reduce the FFV and MSD value in the model, resulting in better thermal and mechanical properties. Full article

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7 pages, 765 KiB

Open AccessArticle

Influence of SiO₂/TiO₂ Nanocomposite on the Optoelectronic Properties of PFO/MEH-PPV-Based OLED Devices

by Bandar Ali Al-Asbahi^1,2

¹ Department of Physics & Astronomy, College of Science, King Saud University, Riyadh 11451, Saudi Arabia

² Research Chair in Laser Diagnosis of Cancers, College of Science, King Saud University, Riyadh 11451, Saudi Arabia

Polymers 2018, 10(7), 800; https://doi.org/10.3390/polym10070800 - 20 Jul 2018

Cited by 33 | Viewed by 5366

Abstract

The influence of SiO₂/TiO₂ nanocomposites on the performance of organic light-emitting diodes (OLEDs) based on poly(9,9′-di-n-octylfluorenyl-2,7-diyl) (PFO) and various amounts of poly(2-methoxy-5-(2-ethyl-hexyloxy)-1,4-phenylene-vinylene) (MEH-PPV) was investigated. Prior to the fabrication of the OLEDs on indium-tin oxide (ITO) substrates, the hybrids of [...] Read more.

The influence of SiO₂/TiO₂ nanocomposites on the performance of organic light-emitting diodes (OLEDs) based on poly(9,9′-di-n-octylfluorenyl-2,7-diyl) (PFO) and various amounts of poly(2-methoxy-5-(2-ethyl-hexyloxy)-1,4-phenylene-vinylene) (MEH-PPV) was investigated. Prior to the fabrication of the OLEDs on indium-tin oxide (ITO) substrates, the hybrids of PFO/MEH-PPV, in the presence and absence of the SiO₂/TiO₂ nanocomposites, were prepared via the solution blending technique. Improvement of the performances of the devices in the presence of the SiO₂/TiO₂ nanocomposites was detected. The existence of the SiO₂/TiO₂ nanocomposites led to better charge carrier injection and, thus, a significant reduction in the turn-on voltage of the devices. The enhancement of MEH-PPV electroluminescence peaks in the hybrids in the presence of SiO₂/TiO₂ nanocomposites is not only a result of the Förster resonance energy transfer, but also of hole-electron recombination, which is of greater significance. Moreover, the existence of the SiO₂/TiO₂ nanocomposites led to a shift of the CIE chromaticity coordinates of the devices. Full article

(This article belongs to the Special Issue Nanoparticle-Reinforced Polymers)

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12 pages, 3850 KiB

Open AccessArticle

Ball-Milled Recycled Lead-Graphite Pencils as Highly Stretchable and Low-Cost Thermal-Interface Materials

by Chun-An Liao¹

, Yee-Kwan Kwan¹, Tien-Chan Chang² and Yiin-Kuen Fuh^1,*

¹ Department of Mechanical Engineering, National Central University, No. 300, Jhongda Rd., Jhongli City, Taoyuan County 32001, Taiwan

² Institute of Nuclear Energy Research, Atomic Energy Council, Executive Yuan, No. 1000, Wenhua Rd., Jiaan Village, Longtan Township, Taoyuan County 32546, Taiwan

Polymers 2018, 10(7), 799; https://doi.org/10.3390/polym10070799 - 20 Jul 2018

Cited by 7 | Viewed by 4921

Abstract

A simple and sustainable production of nanoplatelet graphite at low cost is presented using carbon-based materials, including the recycled lead-graphite pencils. In this work, exfoliated graphite nanoplatelets (EGNs), ball-milled exfoliated graphite nanoplatelets (BMEGNs) and recycled lead-graphite pencils (recycled 2B), as well as thermally [...] Read more.

A simple and sustainable production of nanoplatelet graphite at low cost is presented using carbon-based materials, including the recycled lead-graphite pencils. In this work, exfoliated graphite nanoplatelets (EGNs), ball-milled exfoliated graphite nanoplatelets (BMEGNs) and recycled lead-graphite pencils (recycled 2B), as well as thermally cured polydimethylsiloxane (PDMS), are used to fabricate highly stretchable thermal-interface materials (TIMs) with good thermally conductive and mechanically robust properties. Several characterization techniques including scanning electron microscopy (SEM) and thermogravimetric analysis (TGA) showed that recycled nanoplatelet graphite with lateral size of tens of micrometers can be reliably produced. Experimentally, the thermal conductivity was measured for EGNs, BMEGNs and recycled 2B fillers with/without the effect of ball milling. The in-plane thermal conductivities of 12.97 W/mK (EGN), 13.53 W/mK (recycled 2B) and 14.56 W/mK (BMEGN) and through-plane thermal conductivities of 0.76 W/mK (EGN), 0.84 W/mK (recycled 2B) and 0.95 W/mK (BMEGN) were experimentally measured. Anisotropies were calculated as 15.31, 15.98 and 16.95 for EGN, recycled 2B and BMEGN, respectively. In addition, the mechanical robustness of the developed TIMs is such that they are capable of repeatedly bending at 180 degrees with outstanding flexibility, including the low-cost renewable material of recycled lead-graphite pencils. For heat dissipating application in high-power electronics, the TIMs of recycled 2B are capable of effectively reducing temperatures to approximately 6.2 °C as favorably compared with thermal grease alone. Full article

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

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12 pages, 2376 KiB

Open AccessArticle

Immobilizing Laccase on Modified Cellulose/CF Beads to Degrade Chlorinated Biphenyl in Wastewater

by Na Li^1,2,3, Quiyang Xia³, Yuan Li³

, Xiaobang Hou⁴, Meihong Niu¹, Qingwei Ping¹ and Huining Xiao^3,*

¹ Liaoning Province Key Laboratory of Plup and Papermaking Engineering, Dalian Polytechnic University, Dalian 116034, China

² Key Laboratory of Pulp and Paper Science & Technology of Ministry of Education/Shandong Province, Qilu University of Technology, Jinan 250353, China

³ Department of Chemical Engineering, University of New Brunswick, Fredericton, NB E3B 5A3, Canada

⁴ Department of Environment Science & Engineering, North China Electric Power University, Baoding 071003, China

Polymers 2018, 10(7), 798; https://doi.org/10.3390/polym10070798 - 19 Jul 2018

Cited by 27 | Viewed by 5585

Abstract

Novel modified cellulose/cellulose fibril (CF) beads (MCCBs) loaded with laccase were prepared to degrade polychlorinated biphenyls (PCBs) in wastewater. The proper porous structure in MCCBs was achieved by introducing nano CaCO₃ (as a pore forming agent) in cellulose/CF (CCBs) beads during the [...] Read more.

Novel modified cellulose/cellulose fibril (CF) beads (MCCBs) loaded with laccase were prepared to degrade polychlorinated biphenyls (PCBs) in wastewater. The proper porous structure in MCCBs was achieved by introducing nano CaCO₃ (as a pore forming agent) in cellulose/CF (CCBs) beads during the preparation process. Cellulose/CF composite beads were modified by maleic anhydride to introduce carboxyl groups. Laccase was immobilized on the MCCBs through electrostatic adsorption and covalent bonding. The effects of pH, laccase concentration and contact time on immobilization yields and recovered activity were investigated. The best conditions were pH 4, concentration 16 g/L and contact time 3 h. The immobilized laccase under these conditions showed a good performance in thermal and operational stability. The laccase immobilized on MCCB beads can remove 85% of 20 mg/L 4-hydroxy-3,5-dichlorobiphenyl (HO-DiCB) in wastewater. The results demonstrated that MCCBs, as a new type of green-based support, are very promising in material immobilizing laccase. This technology may be of potential advantage for the removal of polychlorinated biphenyls in wastewater from an environmental point of view. Full article

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12 pages, 2066 KiB

Open AccessArticle

Fabrication of Porous Polyvinylidene Fluoride/Multi-Walled Carbon Nanotube Nanocomposites and Their Enhanced Thermoelectric Performance

by Fei-Peng Du, Xuan Qiao, Yan-Guang Wu, Ping Fu, Sheng-Peng Liu, Yun-Fei Zhang^*

and Qiu-Yu Wang

School of Materials Science and Engineering, Key Laboratory of Green Chemical Process of Ministry of Education, Wuhan Institute of Technology, Wuhan 430205, China

Polymers 2018, 10(7), 797; https://doi.org/10.3390/polym10070797 - 19 Jul 2018

Cited by 28 | Viewed by 4584

Abstract

In this paper, a solvent vapor-induced phase separation (SVIPS) technique was used to create a porous structure in polyvinylidene fluoride/Multi-walled carbon nanotube (PVDF/MWNTs) composites with the aim of increasing the electrical conductivity through the incorporation of MWNTs while retaining a low thermal conductivity. [...] Read more.

In this paper, a solvent vapor-induced phase separation (SVIPS) technique was used to create a porous structure in polyvinylidene fluoride/Multi-walled carbon nanotube (PVDF/MWNTs) composites with the aim of increasing the electrical conductivity through the incorporation of MWNTs while retaining a low thermal conductivity. By using the dimethylformamide/acetone mixture, porous networks could be generated in the PVDF/MWNTs composites upon the rapid volatilization of acetone. The electrical conductivity was gradually enhanced by the addition of MWNTs. At the same time, the thermal conductivity of the PVDF film could be retained at 0.1546 W·m⁻¹·K⁻¹ due to the porous structure being even by loaded with a high content of MWNTs (i.e., 15 wt.%). Thus, the Seebeck coefficient, power factor and figure of merit (ZT) were subsequently improved with maximum values of 324.45 μV/K, 1.679 μW·m⁻¹·K⁻², and 3.3 × 10⁻³, respectively. The microstructures, thermal properties, and thermoelectric properties of the porous PVDF/MWNTs composites were studied. It was found that the enhancement of thermoelectric properties would be attributed to the oxidation of MWNTs and the porous structure of the composites. The decrease of thermal conductivity and the increase of Seebeck coefficient were induced by the phonon scattering and energy-filtering effect. The proposed method was found to be facile and effective in creating a positive effect on the thermoelectric properties of composites. Full article

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

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19 pages, 4051 KiB

Open AccessArticle

Star Shaped Long Chain Branched Poly (lactic acid) Prepared by Melt Transesterification with Trimethylolpropane Triacrylate and Nano-ZnO

by Le Yang¹, Zaijun Yang¹, Feng Zhang¹, Lijin Xie¹, Zhu Luo^1,*

and Qiang Zheng^2,*

¹ Department of Polymer Materials and Engineering, College of Materials and Metallurgy, Guizhou University, Guiyang 550025, China

² Department of Polymer Science and Engineering, Zhejiang University, Hangzhou 310027, China

Polymers 2018, 10(7), 796; https://doi.org/10.3390/polym10070796 - 19 Jul 2018

Cited by 25 | Viewed by 5987

Abstract

Long chain branched poly (lactic acid) (LCBPLA) was prepared via transesterification between high molecular weight poly (lactic acid) (PLA) and low molar mass monomer trimethylolpropane triacrylate (TMPTA) during melt blending in the presence of zinc oxide nanoparticles (nano-ZnO) as a transesterification accelerant in [...] Read more.

Long chain branched poly (lactic acid) (LCBPLA) was prepared via transesterification between high molecular weight poly (lactic acid) (PLA) and low molar mass monomer trimethylolpropane triacrylate (TMPTA) during melt blending in the presence of zinc oxide nanoparticles (nano-ZnO) as a transesterification accelerant in a torque rheometer. Compared with the traditional processing methods, this novel way is high-efficiency, environmentally friendly, and gel-free. The results revealed that chain restructuring reactions occurred and TMPTA was grafted onto the PLA backbone. The topological structures of LCBPLA were verified and investigated in detail. It was found that the concentration of the accelerants and the sampling occasion had very important roles in the occurrence of branching structures. When the nano-ZnO dosage was 0.4 phr and PLA was sampled at the time corresponding to the reaction peak in the torque curve, PLA exhibited a star-shaped topological structure with a high branching degree which could obviously affect the melt strength, extrusion foaming performances, and crystallization behaviors. Compared with pristine PLA, LCBPLA showed a higher melt strength, smaller cell diameter, and slower crystallization speed owing to the synergistic effects of nano-ZnO and the long chain branches introduced by the transesterification reaction in the system. However, severe degradation of the LCBPLAs would take place under a mixing time that was too long and lots of short linear chains generated due to the excessive transesterification reaction, with a sharp decline in melt strength. Full article

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15 pages, 3756 KiB

Open AccessArticle

Functionalized Graphene Oxide Modified Polyethersulfone Membranes for Low-Pressure Anionic Dye/Salt Fractionation

by Lifen Liu¹

, Xin Xie¹, Rahul S. Zambare²

, Antony Prince James Selvaraj^2,*, Bhuvana NIL Sowrirajalu², Xiaoxiao Song^1,*

, Chuyang Y. Tang³ and Congjie Gao¹

¹ Centre for Membrane and Water Science & Technology, Ocean College, Zhejiang University of Technology, Hangzhou 310014, China

² Environmental and Water Technology Centre of Innovation (EWTCOI), Ngee Ann Polytechnic, Singapore 599489, Singapore

³ Department of Civil Engineering, The University of Hong Kong, Pokfulam, Hong Kong, China

Polymers 2018, 10(7), 795; https://doi.org/10.3390/polym10070795 - 19 Jul 2018

Cited by 21 | Viewed by 4708

Abstract

In this study, polyelectrolyte assembled functionalized graphene oxide (PE-GO) membranes were fabricated through a one-step charge facilitated deposition method for high performance dye/salt separation. According to the intercalation of polydopamine (PDA) and (ionic liquid) IL functional moieties into the GO membranes, the pore [...] Read more.

In this study, polyelectrolyte assembled functionalized graphene oxide (PE-GO) membranes were fabricated through a one-step charge facilitated deposition method for high performance dye/salt separation. According to the intercalation of polydopamine (PDA) and (ionic liquid) IL functional moieties into the GO membranes, the pore size of the resulted PE-pGO and PE-iGO membrane increased from 2.69 nm to 4.13 nm and 6.54 nm, respectively. Correspondingly, a pure water flux of 13.8 ± 2.2, 36.7 ± 3.4, and 52.1 ± 6.7 L m⁻¹ h⁻¹ bar⁻¹ was achieved for PE-GO, PE-pGO and PE-iGO membrane, respectively. PE-iGO membrane with the largest pore size could be operated with significant water permeability (28.3 to 38.3 L m⁻¹ h⁻¹ bar⁻¹) at a low operating pressure range of 0.5–2 bar (dye concentration = 100 ppm, salt concentration = 5 g/L). More importantly, functionalities introduced to the GO nanosheets are found to impact the dye adsorption to the membrane surface. The IL intercalation promotes the elution of dye molecules from the IL moieties at elevated pH, therefore enhancing the efficiency of alkaline washing of the membrane. By contrast, the intercalation of PDA weakens such efficiency due to its strong adhesion force to the dye molecules even at the alkaline condition. Full article

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37 pages, 8129 KiB

Open AccessReview

Polysiloxane-Based Side Chain Liquid Crystal Polymers: From Synthesis to Structure–Phase Transition Behavior Relationships

by Lanying Zhang^1,2

, Wenhuan Yao³, Yanzi Gao¹, Cuihong Zhang¹ and Huai Yang^1,2,*

¹ Department of Materials Science and Engineering, College of Engineering, Peking University, Beijing 100871, China

² Key Laboratory of Polymer Chemistry and Physics of Ministry of Education, Peking University, Beijing 100871, China

³ College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou 730070, China

Polymers 2018, 10(7), 794; https://doi.org/10.3390/polym10070794 - 19 Jul 2018

Cited by 28 | Viewed by 8999

Abstract

Organosilicon polymer materials play an important role in certain applications due to characteristics of much lower glass transition temperatures (T_g), viscosities, surface energy, as well as good mechanical, thermal stabilities, and insulation performance stemming from the higher bond energy and [...] Read more.

Organosilicon polymer materials play an important role in certain applications due to characteristics of much lower glass transition temperatures (T_g), viscosities, surface energy, as well as good mechanical, thermal stabilities, and insulation performance stemming from the higher bond energy and the larger bond angles of the adjacent silicon-oxygen bond. This critical review highlights developments in the synthesis, structure, and phase transition behaviors of polysiloxane-based side chain liquid crystal polymers (PSCLCPs) of linear and cyclic polysiloxanes containing homopolymers and copolymers. Detailed synthetic strategies are elaborated, and the relationship between molecular structures and liquid crystalline phase transition behaviors is systematically discussed, providing theoretical guidance on the molecular design of the materials. Full article

(This article belongs to the Special Issue Liquid Crystalline Polymers)

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25 pages, 10129 KiB

Open AccessArticle

Synthesis of Low Melting Temperature Aliphatic-Aromatic Copolyamides Derived from Novel Bio-Based Semi Aromatic Monomer

by Syang-Peng Rwei^*

, Palraj Ranganathan, Whe-Yi Chiang and Yi-Huan Lee

Institute of Organic and Polymeric Materials, Research and Development Center for Smart Textile Technology, National Taipei University of Technology, Taipei 10608, Taiwan

Polymers 2018, 10(7), 793; https://doi.org/10.3390/polym10070793 - 19 Jul 2018

Cited by 26 | Viewed by 8495

Abstract

This work investigated the synthesis of a novel low melting temperature polyamide 6 (PA6) copolyamide (PA6-BABT/SA) with different aliphatic/aromatic units weight content using a melt poly-condensation process. The bio-based aromatic N¹,N⁴-bis(4-aminobutyl) terephthalamide diamine (BABT) and long-chain aromatic polyamide [...] Read more.

This work investigated the synthesis of a novel low melting temperature polyamide 6 (PA6) copolyamide (PA6-BABT/SA) with different aliphatic/aromatic units weight content using a melt poly-condensation process. The bio-based aromatic N¹,N⁴-bis(4-aminobutyl) terephthalamide diamine (BABT) and long-chain aromatic polyamide salt (BABT/SA, salt of BABT, and sebacic acid), components used for the synthesis of copolyamides, were obtained from bio-based monomers. For the first time, the pertinent BABT/SA aromatic polyamide salt was isolated as a white solid and completely characterized. By varying the weight ratio of BABT/SA salt, a series of copolyamides with different molecular weights and physical properties were prepared. The aromatic BABT/SA salt disrupted crystallization of the final copolyamides and lowered the onset of melting. The Fourier transform infrared spectroscopy and X-ray diffraction results indicated a steady decrease in the degrees of crystallinity with increasing BABT/SA salt segment ratio. Furthermore, compared to neat PA6, the obtained PA6-BABT/SA copolymers possessed a similar thermal stability and high transparency, but lower glass transition temperature around human body temperature. The PA6-BABT/SA copolymers with number-average molecular weight ≥30,000 Da presented good mechanical properties, specifically showing excellent tensile strength and elongation at break up to 105.2 MPa and 218.3%, respectively. Full article

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14 pages, 2158 KiB

Open AccessArticle

Dynamic and Static Mechanical Properties of Crosslinked Polymer Matrices: Multiscale Simulations and Experiments

by Daria V. Guseva¹, Vladimir Yu. Rudyak¹

, Pavel V. Komarov^2,3

, Boris A. Bulgakov^4,5, Alexander V. Babkin^4,5 and Alexander V. Chertovich^1,*

¹ Faculty of Physics, Lomonosov Moscow State University, Leninskie gory, 1-2, 119991 Moscow, Russia

² Department of General Physics, Tver State University, Sadovyj per., 35, 170002 Tver, Russia

³ Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilova st., 28, 119991 Moscow, Russia

⁴ Institute of New Carbon Materials and Technologies, Leninskie gory, 1-11, 119991 Moscow, Russia

⁵ Faculty of Chemistry, Lomonosov Moscow State University, Leninskie gory, 1-3, 119991 Moscow, Russia

Polymers 2018, 10(7), 792; https://doi.org/10.3390/polym10070792 - 19 Jul 2018

Cited by 21 | Viewed by 5765

Abstract

We studied the static and dynamic mechanical properties of crosslinked polymer matrices using multiscale simulations and experiments. We continued to develop the multiscale methodology for generating atomistic polymer networks, and applied it to the case of phthalonitrile resin. The mechanical properties of the [...] Read more.

We studied the static and dynamic mechanical properties of crosslinked polymer matrices using multiscale simulations and experiments. We continued to develop the multiscale methodology for generating atomistic polymer networks, and applied it to the case of phthalonitrile resin. The mechanical properties of the resulting networks were analyzed using atomistic molecular dynamics (MD) and dissipative particle dynamics (DPD). The Young’s and storage moduli increased with conversion, due both to the appearance of a network of covalent bonds, and to freezing of degrees of freedom and lowering of the glass transition temperature during crosslinking. The simulations’ data showed good quantitative agreement with experimental dynamic mechanical analysis measurements at temperatures below the glass transition. The data obtained in MD and DPD simulations at elevated temperatures were conformable. This makes it possible to use the suggested approach for the prediction of mechanical properties of a broad range of polymer matrices, including ones with high structural heterogeneity. Full article

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18 pages, 2307 KiB

Open AccessArticle

Surface Functionalization by Stimuli-Sensitive Microgels for Effective Enzyme Uptake and Rational Design of Biosensor Setups

by Larisa V. Sigolaeva^1,*

, Dmitry V. Pergushov¹

, Marina Oelmann², Simona Schwarz², Monia Brugnoni³

, Ilya N. Kurochkin^1,4, Felix A. Plamper³

, Andreas Fery^2,5 and Walter Richtering³

¹ Department of Chemistry, M.V. Lomonosov Moscow State University, Leninskie Gory 1/3, 119991 Moscow, Russia

² Leibniz-Institut für Polymerforschung Dresden e.V., Hohe Str. 6, 01069 Dresden, Germany

³ Institute of Physical Chemistry II, RWTH Aachen University, Landoltweg 2, 52056 Aachen, Germany

⁴ N.M. Emanuel Institute of Biochemical Physics, Russian Academy of Sciences, Kosygina Str. 4, 119334 Moscow, Russia

⁵ Physical Chemistry of Polymeric Materials, Technical University of Dresden, Hohe Str. 6, 01069 Dresden, Germany

Polymers 2018, 10(7), 791; https://doi.org/10.3390/polym10070791 - 19 Jul 2018

Cited by 38 | Viewed by 7812

Abstract

We highlight microgel/enzyme thin films that were deposited onto solid interfaces via two sequential steps, the adsorption of temperature- and pH-sensitive microgels, followed by their complexation with the enzyme choline oxidase, ChO. Two kinds of functional (ionic) microgels were compared in this work [...] Read more.

We highlight microgel/enzyme thin films that were deposited onto solid interfaces via two sequential steps, the adsorption of temperature- and pH-sensitive microgels, followed by their complexation with the enzyme choline oxidase, ChO. Two kinds of functional (ionic) microgels were compared in this work in regard to their adsorptive behavior and interaction with ChO, that is, poly(N-isopropylacrylamide-co-N-(3-aminopropyl)methacrylamide), P(NIPAM-co-APMA), bearing primary amino groups, and poly(N-isopropylacrylamide-co-N-[3-(dimethylamino) propyl]methacrylamide), P(NIPAM-co-DMAPMA), bearing tertiary amino groups. The stimuli-sensitive properties of the microgels in the solution were characterized by potentiometric titration, dynamic light scattering (DLS), and laser microelectrophoresis. The peculiarities of the adsorptive behavior of both the microgels and the specific character of their interaction with ChO were revealed by a combination of surface characterization techniques. The surface charge was characterized by electrokinetic analysis (EKA) for the initial graphite surface and the same one after the subsequent deposition of the microgels and the enzyme under different adsorption regimes. The masses of wet microgel and microgel/enzyme films were determined by quartz crystal microbalance with dissipation monitoring (QCM-D) upon the subsequent deposition of the components under the same adsorption conditions, on a surface of gold-coated quartz crystals. Finally, the enzymatic responses of the microgel/enzyme films deposited on graphite electrodes to choline were tested amperometrically. The presence of functional primary amino groups in the P(NIPAM-co-APMA) microgel enables a covalent enzyme-to-microgel coupling via glutar aldehyde cross-linking, thereby resulting in a considerable improvement of the biosensor operational stability. Full article

(This article belongs to the Special Issue Microgels and Hydrogels at Interfaces)

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11 pages, 6211 KiB

Open AccessArticle

Synthesis and Characterization of Fully Conjugated Ladder Naphthalene Bisimide Copolymers

by Feng Liu, Yonggang Wu^*, Chao Wang, Junshu Ma, Fan Wu, Ye Zhang and Xinwu Ba^*

College of Chemistry and Environmental Science, Hebei University, Baoding 071002, China

Polymers 2018, 10(7), 790; https://doi.org/10.3390/polym10070790 - 18 Jul 2018

Cited by 10 | Viewed by 5277

Abstract

Fully conjugated ladder copolymers have attracted considerable attention due to their unique fused-ring structure and optoelectronic properties. In this study, two fully conjugated ladder naphthalene diimide (NDI) copolymers, P(NDI-CZL) and P(NDI-TTL) with imine-bridged structures are presented in high yields. Both of the two [...] Read more.

Fully conjugated ladder copolymers have attracted considerable attention due to their unique fused-ring structure and optoelectronic properties. In this study, two fully conjugated ladder naphthalene diimide (NDI) copolymers, P(NDI-CZL) and P(NDI-TTL) with imine-bridged structures are presented in high yields. Both of the two copolymers have good solubility and high thermal stability. The corresponding compounds with the same structure as the copolymers were synthesized as model system. The yields for each step of the synthesis of the model compounds are higher than 95%. These results suggest that P(NDI-CZL) and P(NDI-TTL) can be synthesized successfully with fewer structural defects. The structures and optoelectronic properties of compounds and copolymers are investigated by NMR, fourier transform infrared spectroscopy (FTIR), ultraviolet-visible spectroscopy (UV-vis), and cyclic voltammetry (CV). Both in solution and as a thin film, the two copolymers show two UV-vis absorption bands (around 300–400 nm and 400–750 nm) and a very weak fluorescence. The collective results suggest that the two fully conjugated ladder copolymers can be used as potential acceptor materials. Full article

(This article belongs to the Special Issue Synthesis and Application of Conjugated Polymers)

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7 pages, 1757 KiB

Open AccessCommunication

Controlling the Internal Structures of Polymeric Microspheres via the Introduction of a Water-Soluble Organic Solvent

by Yanping He¹, Xin Li¹, Tianci Zhu¹, Mengxing Shan¹, Linhua Zhu¹, Tian Si¹, Hong Wang² and Yanlin Sun^1,*

¹ School of Chemical Engineering, Kunming University of Science and Technology, Chenggong Campus, Kunming 650504, China

² Faculty of Science, Kunming University of Science and Technology, Chenggong Campus, Kunming 650504, China

Polymers 2018, 10(7), 789; https://doi.org/10.3390/polym10070789 - 18 Jul 2018

Cited by 13 | Viewed by 5053

Abstract

Polymeric microspheres with different internal structures have been widely used because of their characteristics in the structures. This paper reports a method of controlling the internal structures of polymeric microspheres via the introduction of a water-soluble organic solvent to the continuous phase in [...] Read more.

Polymeric microspheres with different internal structures have been widely used because of their characteristics in the structures. This paper reports a method of controlling the internal structures of polymeric microspheres via the introduction of a water-soluble organic solvent to the continuous phase in the foam phase preparation of porous polymeric microspheres. The introduction of a water-soluble organic solvent enables the control of polymeric microspheres’ internal structures, from porous to hollow. Because a water-soluble organic solvent is introduced, the organic solvent may be diffused toward the interface because of the affinity between the organic solvent and the oil droplets, resulting an accumulation of organic solvent molecules at the interface to form an organic solvent layer. The presence of this layer may decrease the evaporation rate of the internal organic solvent in an oil droplet, which extends the time for the mingling of porogen droplets to form a few large pores or even an extremely large single pore inside. This method is also capable of altering the thickness of hollow microspheres’ shells in a desired way, with improved efficiency, yield and the capacity for continuous use on an industrial scale. Full article

(This article belongs to the Special Issue Microporous Organic Polymers: Synthesis, Characterization and Applications)

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13 pages, 1095 KiB

Open AccessArticle

Multi-Objective Optimization of Acoustic Performances of Polyurethane Foam Composites

by Shuming Chen¹, Wenbo Zhu¹

and Yabing Cheng^2,*

¹ State Key Laboratory of Automotive Simulation and Control, Jilin University, Changchun 130022, China

² School of Mechanical and Aerospace Engineering, Jilin University, Changchun 130022, China

Polymers 2018, 10(7), 788; https://doi.org/10.3390/polym10070788 - 18 Jul 2018

Cited by 34 | Viewed by 5333

Abstract

Polyurethane (PU) foams are widely used as acoustic package materials to eliminate vehicle interior noise. Therefore, it is important to improve the acoustic performances of PU foams. In this paper, the grey relational analysis (GRA) method and multi-objective particle swarm optimization (MOPSO) algorithm [...] Read more.

Polyurethane (PU) foams are widely used as acoustic package materials to eliminate vehicle interior noise. Therefore, it is important to improve the acoustic performances of PU foams. In this paper, the grey relational analysis (GRA) method and multi-objective particle swarm optimization (MOPSO) algorithm are applied to improve the acoustic performances of PU foam composites. The average sound absorption coefficient and average transmission loss are set as optimization objectives. The hardness and content of Ethylene Propylene Diene Monomer (EPDM) and the content of deionized water and modified isocyanate (MDI) are selected as design variables. The optimization process of GRA method is based on the orthogonal arrays

L_{9} (3^{4})

, and the MOPSO algorithm is based on the Response Surface (RS) surrogate model. The results show that the acoustic performances of PU foam composites can be improved by optimizing the synthetic formula. Meanwhile, the results that were obtained by GRA method show the degree of influence of the four design variables on the optimization objectives, and the results obtained by MOPSO algorithm show the specific effects of the four design variables on the optimization objectives. Moreover, according to the confirmation experiment, the optimal synthetic formula is obtained by MOPSO algorithm when the weight coefficient of the two objectives set as 0.5. Full article

(This article belongs to the Special Issue Polymeric Foams)

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25 pages, 572 KiB

Open AccessArticle

Dynamics of a Polymer Network Modeled by a Fractal Cactus

by Aurel Jurjiu^1,2,* and Mircea Galiceanu³

¹ National Institute for Research and Development of Isotopic and Molecular Technologies, Cluj-Napoca 400293, Romania

² Faculty of Physics, Babes-Bolyai University, Street Mihail Kogalniceanu 1, Cluj-Napoca 400084, Romania

³ Department of Physics, Federal University of Amazonas, Manaus 69077-000, Brazil

Polymers 2018, 10(7), 787; https://doi.org/10.3390/polym10070787 - 18 Jul 2018

Cited by 14 | Viewed by 4668

Abstract

In this paper, we focus on the relaxation dynamics of a polymer network modeled by a fractal cactus. We perform our study in the framework of the generalized Gaussian structure model using both Rouse and Zimm approaches. By performing real-space renormalization transformations, we [...] Read more.

In this paper, we focus on the relaxation dynamics of a polymer network modeled by a fractal cactus. We perform our study in the framework of the generalized Gaussian structure model using both Rouse and Zimm approaches. By performing real-space renormalization transformations, we determine analytically the whole eigenvalue spectrum of the connectivity matrix, thereby rendering possible the analysis of the Rouse-dynamics at very large generations of the structure. The evaluation of the structural and dynamical properties of the fractal network in the Rouse type-approach reveals that they obey scaling and the dynamics is governed by the value of spectral dimension. In the Zimm-type approach, the relaxation quantities show a strong dependence on the strength of the hydrodynamic interaction. For low and medium hydrodynamic interactions, the relaxation quantities do not obey power law behavior, while for slightly larger interactions they do. Under strong hydrodynamic interactions, the storage modulus does not follow power law behavior and the average displacement of the monomer is very low. Remarkably, the theoretical findings with respect to scaling in the intermediate domain of the relaxation quantities are well supported by experimental results from the literature. Full article

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9 pages, 2029 KiB

Open AccessArticle

Novel PSMA-Coated On-Off-On Fluorescent Chemosensor Based on Organic Dots with AIEgens for Detection of Copper (II), Iron (III) and Cysteine

by Rui Jiang, Na Liu, Fan Li, Wensheng Fu, Yun Zhou^* and Yan Zhang^*

Chongqing Key Laboratory of Green Synthesis and Applications, and Chongqing Key Laboratory of Inorganic Functional Materials, College of Chemistry, Chongqing Normal University, Chongqing 401331, China

Polymers 2018, 10(7), 786; https://doi.org/10.3390/polym10070786 - 17 Jul 2018

Cited by 17 | Viewed by 4801

Abstract

Herein, a novel on-off-on fluorescent chemosensor for copper (II) ion (Cu²⁺), iron (III) ion (Fe³⁺) and cysteine is developed simply by the nano-precipitation method. The prepared organic dots with AIEgens (AIE dots) are advantageous over other metal ions in [...] Read more.

Herein, a novel on-off-on fluorescent chemosensor for copper (II) ion (Cu²⁺), iron (III) ion (Fe³⁺) and cysteine is developed simply by the nano-precipitation method. The prepared organic dots with AIEgens (AIE dots) are advantageous over other metal ions in detecting Cu²⁺, Fe³⁺ with high selectivity and sensitivity by forming agglomerations (on-off). The agglomerations formed by AIE dots and Cu²⁺ redistributed and the fluorescence was obviously recovered in the presence of cysteine (off-on). This sensor has a wide linear range for Cu²⁺, Fe³⁺ and cysteine. The fluorescent detection limits of AIE dots are calculated to be 107 nM for Cu²⁺, 120 nM for Fe³⁺ and 78 nM for cysteine, respectively. These results indicate that the AIE dots can be used as a potential probe for Cu²⁺, Fe³⁺ and cysteine detection. Full article

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

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14 pages, 2051 KiB

Open AccessArticle

Poly(propylene 2,5-thiophenedicarboxylate) vs. Poly(propylene 2,5-furandicarboxylate): Two Examples of High Gas Barrier Bio-Based Polyesters

by Giulia Guidotti¹, Michelina Soccio¹, Nadia Lotti^1,*

, Massimo Gazzano²

, Valentina Siracusa^3,*

and Andrea Munari¹

¹ Department of Civil, Chemical, Environmental and Materials Engineering, University of Bologna, Via Terracini 28, 40131 Bologna, Italy

² Organic Synthesis and Photoreactivity Institute, ISOF-CNR, Via Gobetti 101, 40129 Bologna, Italy

³ Department of Chemical Science, University of Catania, Viale A. Doria 6, 95125 Catania, Italy

Polymers 2018, 10(7), 785; https://doi.org/10.3390/polym10070785 - 17 Jul 2018

Cited by 87 | Viewed by 6455

Abstract

Both academia and industry are currently devoting many efforts to develop high gas barrier bioplastics as substitutes of traditional fossil-based polymers. In this view, this contribution presents a new biobased aromatic polyester, i.e., poly(propylene 2,5-thiophenedicarboxylate) (PPTF), which has been compared with the furan-based [...] Read more.

Both academia and industry are currently devoting many efforts to develop high gas barrier bioplastics as substitutes of traditional fossil-based polymers. In this view, this contribution presents a new biobased aromatic polyester, i.e., poly(propylene 2,5-thiophenedicarboxylate) (PPTF), which has been compared with the furan-based counterpart (PPF). Both biopolyesters have been characterized from the molecular, thermo-mechanical and structural points of view. Gas permeability behavior has been evaluated with respect to 100% oxygen, carbon dioxide and nitrogen at 23 °C. In case of CO₂ gas test, gas transmission rate has been also measured at different temperatures. The permeability behavior at different relative humidity has been investigated for both biopolyesters, the thiophen-containing sample demonstrating to be better than the furan-containing counterpart. PPF’s permeability behavior became worse than PPTF’s with increasing RH, due to the more polar nature of the furan ring. Both biopolyesters under study are characterized by superior gas barrier performances with respect to PEF and PET. With the simple synthetic strategy adopted, the exceptional barrier properties render these new biobased polyesters interesting alternatives in the world of green and sustainable packaging materials. The different polarity and stability of heterocyclic rings was revealed to be an efficient tool to tailor the ability of crystallization, which in turn affects mechanical and barrier performances. Full article

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

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11 pages, 1949 KiB

Open AccessArticle

Modeling of Laser Beam Absorption in a Polymer Powder Bed

by Fuad Osmanlic^1,2,*,†, Katrin Wudy^2,3,†, Tobias Laumer^2,4,†, Michael Schmidt^2,4, Dietmar Drummer^2,3 and Carolin Körner^1,2,5

¹ Joint Institute of Advanced Materials and Processes, Friedrich-Alexander-Universität Erlangen-Nürnberg Dr.-Mack-Str. 81, 90762 Fuerth, Germany

² Collaborative Research Center 814-Additive Manufacturing, Friedrich-Alexander-Universität Erlangen-Nürnberg, Am Weichselgarten 9, 91058 Erlangen, Germany

³ Institute of Polymer Technology, Friedrich-Alexander-Universität Erlangen-Nürnberg, Am Weichselgarten 9, 91058 Erlangen, Germany

⁴ BLZ Bayerisches Laserzentrum GmbH, 91052 Erlangen, Germany

⁵ Chair of Materials Science and Engineering for Metals, Friedrich-Alexander-Universität Erlangen-Nürnberg, Martensstr. 5, 91058 Erlangen, Germany

^† These authors contributed equally to this work.

Polymers 2018, 10(7), 784; https://doi.org/10.3390/polym10070784 - 17 Jul 2018

Cited by 44 | Viewed by 7207

Abstract

In order to understand the absorption characteristic, a ray trace model is developed by taking into account the reflection, absorption and refraction. The ray paths are resolved on a sub-powder grid. For validation, the simulation results are compared to analytic solutions of the [...] Read more.

In order to understand the absorption characteristic, a ray trace model is developed by taking into account the reflection, absorption and refraction. The ray paths are resolved on a sub-powder grid. For validation, the simulation results are compared to analytic solutions of the irradiation of the laser beam onto a plain surface. In addition, the absorptance, reflectance and transmittance of PA12 powder layers measured by an integration sphere setup are compared with the numerical results of our model. It is shown that the effective penetration depth can be lower than the penetration depth in bulk material for polymer powders and, therefore, can increase the energy density at the powder bed surface. The implications for modeling of the selective laser sintering (SLS) process and the processability of fine powder distributions and high powder bed densities are discussed. Full article

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22 pages, 22531 KiB

Open AccessArticle

Enhancement of Colour Effects of Dyed-Yarn Mixed Fabrics Using Cramming Motion and Finer Polyester Yarns

by Lau Yiu Tang^†, Xiao Tian^† and Tao Hua^*

¹ Institute of Textiles and Clothing, The Hong Kong Polytechnic University, Hung Hom, Kowloon, Hong Kong, China

^† These authors contributed equally to this work.

Polymers 2018, 10(7), 783; https://doi.org/10.3390/polym10070783 - 16 Jul 2018

Cited by 14 | Viewed by 4702

Abstract

This paper reports the study of the effects of cramming motion implemented during weaving and finer weft yarns used on dyed-yarn mixed woven fabrics produced by using raw white warps and multicolored-wefts. The cramming motion was used to increase the dyed-weft yarns cover [...] Read more.

This paper reports the study of the effects of cramming motion implemented during weaving and finer weft yarns used on dyed-yarn mixed woven fabrics produced by using raw white warps and multicolored-wefts. The cramming motion was used to increase the dyed-weft yarns cover factor of fabric, and thus, to reduce the negative effect of white warp floats at the fabric face on the color attributes of fabric. The surface structure of fabric was characterized by using several key geometrical parameters that determined the resultant fabric color attributes. The effects of fabric structure and density, weft yarn count, and the introduction of black yarn on the fabric face layer on the fabric surface geometrical parameters, physical properties, as well as color attributes were investigated under the implementation of cramming motion on the fabric. The color attributes of fabrics using cramming motion and finer yarns were also compared to the fabrics without cramming motion. The experimental results indicate that the weft yarn density and cover factor of fabric face layer are increased by applying cramming motion and finer yarns for fabricating the blue-red and/or black mixed fabrics. Consequently, the fabric lightness can be further reduced for achieving a better color effect on colorful and figured woven fabrics mainly using dyed-wefts for color mixing. Full article

(This article belongs to the Special Issue Polymer Processing for Enhancing Textile Application)

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13 pages, 3911 KiB

Open AccessArticle

Synthesis of Benzene Tetracarboxamide Polyamine and Its Effect on Epoxy Resin Properties

by Seoyoon Yu, Wonjoo Lee, Bongkuk Seo^* and Chung-Sun Lim^*

Advanced Industrial Chemistry Research Center, Korea Research Institute of Chemical Technology, 45, Jongga-ro, Yugok dong, Jung-gu, Ulsan 44412, Korea

Polymers 2018, 10(7), 782; https://doi.org/10.3390/polym10070782 - 16 Jul 2018

Cited by 7 | Viewed by 6319

Abstract

Epoxy resins have found various industrial applications in high-performance thermosetting resins, high-performance composites, electronic-packaging materials, adhesives, protective coatings, etc., due to their outstanding performance, including high toughness, high-temperature performance, chemical and environmental resistance, versatile processability and adhesive properties. However, cured epoxy resins are [...] Read more.

Epoxy resins have found various industrial applications in high-performance thermosetting resins, high-performance composites, electronic-packaging materials, adhesives, protective coatings, etc., due to their outstanding performance, including high toughness, high-temperature performance, chemical and environmental resistance, versatile processability and adhesive properties. However, cured epoxy resins are very brittle, which limits their applications. In this work, we attempted to enhance the toughness of cured epoxy resins by introducing benzene tetracarboxamide polyamine (BTCP), synthesized from pyromellitic dianhydride (PMDA) and diamines in N-methyl-2-pyrrolidone (NMP) solvent. During this reaction, increased viscosity and formation of amic acid could be confirmed. The chemical reactions were monitored and evidenced using ¹H-NMR spectroscopy, FT-IR spectroscopy, water gel-phase chromatography (GPC) analysis, amine value determination and acid value determination. We also studied the effect of additives on thermomechanical properties using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), dynamical mechanical analysis (DMA), thermomechanical analysis (TMA) and by measuring mechanical properties. The BTCP-containing epoxy resin exhibited high mechanical strength and adhesion strength proportional to the amount of BTCP. Furthermore, field-emission scanning electron microscopy images were obtained for examining the cross-sectional morphology changes of the epoxy resin specimens with varying amounts of BTCP. Full article

(This article belongs to the Special Issue Hybrid Materials Based on Thermosets)

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16 pages, 4467 KiB

Open AccessArticle

The Synthesis of Low-Viscosity Organotin-Free Moisture-Curable Silane-Terminated Poly(Urethane-Urea)s

by Chen Tan

, Viivi Luona, Teija Tirri and Carl-Eric Wilen^*

Laboratory of Polymer Technology and Center for Functional Materials, Faculty of Science and Engineering/Chemical Engineering, Åbo Akademi University, Biskopsgatan 8, 20500 Turku, Finland

Polymers 2018, 10(7), 781; https://doi.org/10.3390/polym10070781 - 16 Jul 2018

Cited by 16 | Viewed by 7709

Abstract

This work explores the possibility of synthesizing moisture-curable silane-terminated poly(urethane-urea)s (SPURs) of low viscosity. First, NCO-terminated urethane prepolymers were prepared, followed by silane end-capping. The impact of polyol molecular weight and the ratio of isocyanate to polyol (NCO/OH) on viscosity and the properties [...] Read more.

This work explores the possibility of synthesizing moisture-curable silane-terminated poly(urethane-urea)s (SPURs) of low viscosity. First, NCO-terminated urethane prepolymers were prepared, followed by silane end-capping. The impact of polyol molecular weight and the ratio of isocyanate to polyol (NCO/OH) on viscosity and the properties of SPUR were examined. As alternatives to the organotin catalysts traditionally used for the polyurethane synthesis and curing processes, bismuth carboxylate catalysts were evaluated. In addition, the effect of organofunctional groups in the aminosilane structure (R1–NH–R2–Si(OR3)₃), i.e., R1 (alkyl, aryl or trimethoxysilyl-propyl), the spacer R2 (α or γ) and alkyl group R3 (methyl or ethyl), was examined. The chemical and physical structures of the SPUR were investigated by nuclear magnetic resonance spectroscopy (NMR), Fourier transform infrared spectroscopy (FT-IR) and the mechanical properties were evaluated by tensile tests. The results reveal that silane-terminated, moisture-curable polyurethanes can be successfully synthesized and cured with bismuth carboxylate catalysts. SPUR exhibiting low viscosity, with adequate tensile strength and elongation can be prepared using environmentally benign bismuth carboxylate catalyst having a high metal content of 19%–21%, by utilizing secondary aminosilane end-cappers and an optimal combination of the polyol molecular weight and NCO/OH ratio. Full article

(This article belongs to the Collection Polymeric Adhesives)

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17 pages, 7035 KiB

Open AccessArticle

Preparation of Molecularly Imprinted Microspheres as Biomimetic Recognition Material for In Situ Adsorption and Selective Chemiluminescence Determination of Bisphenol A

by Yan Xiong^1,2,*

, Qing Wang¹, Ming Duan^1,2,*, Jing Xu³, Jie Chen¹ and Shenwen Fang^1,2

¹ School of Chemistry and Chemical Engineering, Southwest Petroleum University, Chengdu 610500, China

² Oil and Gas Field Applied Chemistry Key Laboratory of Sichuan Province, Southwest Petroleum University, Chengdu 610500, China

³ Liaoning Entry-Exit Inspection and Quarantine Bureau, Dalian 116001, China

Polymers 2018, 10(7), 780; https://doi.org/10.3390/polym10070780 - 16 Jul 2018

Cited by 12 | Viewed by 4444

Abstract

Bisphenol A (BPA) is an endocrine disrupter in environments which can induce abnormal differentiation of reproductive organs by interfering with the action of endogenous gonadal steroid hormones. In this work, the bisphenol A (BPA) molecularly-imprinted microspheres (MIMS) were prepared and used as biomimetic [...] Read more.

Bisphenol A (BPA) is an endocrine disrupter in environments which can induce abnormal differentiation of reproductive organs by interfering with the action of endogenous gonadal steroid hormones. In this work, the bisphenol A (BPA) molecularly-imprinted microspheres (MIMS) were prepared and used as biomimetic recognition material for in situ adsorption and selective chemiluminescence (CL) determination of BPA. Through non-covalent interaction, the BPA-MIMS was successfully prepared by Pickering emulsion polymerization using a BPA template, 4-vinylpyridine (4-VP) monomer, ethylene glycol dimethacrylate (EGDMA) cross-linker, and a SiO₂ dispersion agent. The characterization of scanning electron microscopy (SEM) and energy-disperse spectroscopy (EDS) showed that the obtained MIMS possessed a regular spherical shape and narrow diameter distribution (25–30 μm). The binding experiment indicated BPA could be adsorbed in situ on the MIMS-packing cell with an apparent maximum amount Q_max of 677.3 μg g⁻¹. Then BPA could be selectively detected by its sensitive inhibition effect on the CL reaction between luminol and periodate (KIO₄), and the inhibition mechanism was discussed to reveal the CL reaction process. The CL intensity was linear to BPA concentrations in two ranges, respectively from 0.5 to 1.5 μg mL⁻¹ with a detection limit of 8.0 ng mL⁻¹ (3σ), and from 1.5 to 15 μg mL⁻¹ with a limit of detection (LOD) of 80 ng mL⁻¹ (3σ). The BPA-MIPMS showed excellent selectivity for BPA adsorption and the proposed CL method has been successfully applied to BPA determination in environmental water samples. Full article

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20 pages, 1075 KiB

Open AccessArticle

Structure-Properties Relations for Polyamide 6, Part 2: Influence of Processing Conditions during Injection Moulding on Deformation and Failure Kinetics

by Emanuele Parodi^1,2, Gerrit W. M. Peters¹

and Leon E. Govaert^1,*

¹ Department of Mechanical Engineering, Materials Technology Institute, Eindhoven University of Technology, P.O. Box 513, 5600 MB Eindhoven, The Netherlands

² Dutch Polymer Institute (DPI), P.O. Box 902, 5600 AX Eindhoven, The Netherlands

Polymers 2018, 10(7), 779; https://doi.org/10.3390/polym10070779 - 16 Jul 2018

Cited by 17 | Viewed by 6204

Abstract

The effect of processing conditions during injection on the structure formation and mechanical properties of injection molded polyamide 6 samples was investigated in detail. A large effect of the mold temperature on the crystallographic properties was observed. Also the the effect of pressure [...] Read more.

The effect of processing conditions during injection on the structure formation and mechanical properties of injection molded polyamide 6 samples was investigated in detail. A large effect of the mold temperature on the crystallographic properties was observed. Also the the effect of pressure and shear flow was taken in to consideration and analysed. The yield and failure kinetics, including time-to-failure, were studied by performing tensile and creep tests at several test temperatures and relative humidities. As far as mechanical properties are concerned, a strong influence of temperature and relative humidity on the yield stress and time-to-failure was found. A semi-empirical model, able to describe yield and failure kinetics, was applied to the experimental results and related to the crystalline phase present in the sample. In agreement with findings in the literature it is observed that for high mold temperatures the sample morphology is more stable with respect to humidity and temperature than in case of low mold temperatures and this effects could be successfully captured by the model. The samples molded at low temperatures showed, during mechanical testing, a strong evolution of the crystallographic properties when exposed to high testing temperature and high relative humidity, i.e., an increase of crystallinity or a crystal phase transition. This makes a full description of the mechanical behavior rather complicated. Full article

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

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22 pages, 4066 KiB

Open AccessArticle

Identification and Characterization of Novel Fc-Binding Heptapeptides from Experiments and Simulations

by Xiaoquan Sun¹, Justin Weaver², Sumith Ranil Wickramasinghe^2,3 and Xianghong Qian^1,*

¹ Department of Biomedical Engineering, University of Arkansas, Fayetteville, AR 72701, USA

² Department of Chemical and Biological Engineering, Colorado State University, Fort Collins, CO 80523, USA

³ Ralph E Martin Department of Chemical Engineering, University of Arkansas, Fayetteville, AR 72701, USA

Polymers 2018, 10(7), 778; https://doi.org/10.3390/polym10070778 - 16 Jul 2018

Cited by 6 | Viewed by 5157

Abstract

Purification of biologically-derived therapeutics is a major cost contributor to the production of this rapidly growing class of pharmaceuticals. Monoclonal antibodies comprise a large percentage of these products, therefore new antibody purification tools are needed. Small peptides, as opposed to traditional antibody affinity [...] Read more.

Purification of biologically-derived therapeutics is a major cost contributor to the production of this rapidly growing class of pharmaceuticals. Monoclonal antibodies comprise a large percentage of these products, therefore new antibody purification tools are needed. Small peptides, as opposed to traditional antibody affinity ligands such as Protein A, may have advantages in stability and production costs. Multiple heptapeptides that demonstrate Fc binding behavior that have been identified from a combinatorial peptide library using M13 phage display are presented herein. Seven unique peptide sequences of diverse hydrophobicity and charge were identified. All seven peptides showed strong binding to the four major human IgG isotypes, human IgM, as well as binding to canine, rat, and mouse IgG. These seven peptides were also shown to bind human IgG4 from DMEM cell culture media with 5% FCS and 5 g/L ovalbumin present. These peptides may be useful as surface ligands for antibody detection and purification purposes. Molecular docking and classical molecular dynamics (MD) simulations were conducted to elucidate the mechanisms and energetics for the binding of these peptides to the Fc region. The binding site was found to be located between the two glycan chains inside the Fc fragment. Both hydrogen bonding and hydrophobic interactions were found to be crucial for the binding interactions. Excellent agreement for the binding strength was obtained between experimental results and simulations. Full article

(This article belongs to the Special Issue Polymers for Bioseparations)

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Polymers, Volume 10, Issue 7 (July 2018) – 118 articles

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