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Polymers, Volume 10, Issue 7 (July 2018)

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Open AccessArticle Structure-Properties Relations for Polyamide 6, Part 2: Influence of Processing Conditions during Injection Moulding on Deformation and Failure Kinetics
Polymers 2018, 10(7), 779; https://doi.org/10.3390/polym10070779 (registering DOI)
Received: 30 May 2018 / Revised: 7 July 2018 / Accepted: 11 July 2018 / Published: 16 July 2018
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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
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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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Open AccessArticle Identification and Characterization of Novel Fc-Binding Heptapeptides from Experiments and Simulations
Polymers 2018, 10(7), 778; https://doi.org/10.3390/polym10070778 (registering DOI)
Received: 2 June 2018 / Revised: 11 July 2018 / Accepted: 12 July 2018 / Published: 16 July 2018
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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
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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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Open AccessArticle In Situ Strain and Damage Monitoring of GFRP Laminates Incorporating Carbon Nanofibers under Tension
Polymers 2018, 10(7), 777; https://doi.org/10.3390/polym10070777 (registering DOI)
Received: 5 June 2018 / Revised: 4 July 2018 / Accepted: 10 July 2018 / Published: 16 July 2018
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Abstract
In this study, conductive carbon nanofibers (CNFs) were dispersed into epoxy resin and then infused into glass fiber fabric to fabricate CNF/glass fiber-reinforced polymer (GFRP) laminates. The electrical resistance and strain of CNF/GFRP laminates were measured simultaneously during tensile loadings to investigate the
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In this study, conductive carbon nanofibers (CNFs) were dispersed into epoxy resin and then infused into glass fiber fabric to fabricate CNF/glass fiber-reinforced polymer (GFRP) laminates. The electrical resistance and strain of CNF/GFRP laminates were measured simultaneously during tensile loadings to investigate the in situ strain and damage monitoring capability of CNF/GFRP laminates. The damage evolution and conduction mechanisms of the laminates were also presented. The results indicated that the percolation threshold of CNFs content for CNF/GFRP laminates was 0.86 wt % based on a typical power law. The resistance response during monotonic tensile loading could be classified into three stages corresponding to different damage mechanisms, which demonstrated a good ability of in situ damage monitoring of the CNF/GFRP laminates. In addition, the capacity of in situ strain monitoring of the laminates during small strain stages was also confirmed according to the synchronous and reversible resistance responses to strain under constant cyclic tensile loading. Moreover, the analysis of the resistance responses during incremental amplitude cyclic tensile loading with the maximum strain of 1.5% suggested that in situ strain and damage monitoring of the CNF/GFRP laminates were feasible and stable. Full article
(This article belongs to the Special Issue Multi-functional Polymer Composites and Structures)
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Open AccessArticle Confirmation of Bioinformatics Predictions of the Structural Domains in Honeybee Silk
Polymers 2018, 10(7), 776; https://doi.org/10.3390/polym10070776 (registering DOI)
Received: 21 June 2018 / Revised: 11 July 2018 / Accepted: 12 July 2018 / Published: 16 July 2018
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Abstract
Honeybee larvae produce a silk made up of proteins in predominantly a coiled coil molecular structure. These proteins can be produced in recombinant systems, making them desirable templates for the design of advanced materials. However, the atomic level structure of these proteins is
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Honeybee larvae produce a silk made up of proteins in predominantly a coiled coil molecular structure. These proteins can be produced in recombinant systems, making them desirable templates for the design of advanced materials. However, the atomic level structure of these proteins is proving difficult to determine: firstly, because coiled coils are difficult to crystalize; and secondly, fibrous proteins crystalize as fibres rather than as discrete protein units. In this study, we synthesised peptides from the central structural domain, as well as the N- and C-terminal domains, of the honeybee silk. We used circular dichroism spectroscopy, infrared spectroscopy, and molecular dynamics to investigate the folding behaviour of the central domain peptides. We found that they folded as predicted by bioinformatics analysis, giving the protein engineer confidence in bioinformatics predictions to guide the design of new functionality into these protein templates. These results, along with the infrared structural analysis of the N- and C-terminal domain peptides and the comparison of peptide film properties with those of the full-length AmelF3 protein, provided significant insight into the structural elements required for honeybee silk protein to form into stable materials. Full article
(This article belongs to the Special Issue Protein Biopolymer)
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Open AccessReview Chain Trajectory, Chain Packing, and Molecular Dynamics of Semicrystalline Polymers as Studied by Solid-State NMR
Polymers 2018, 10(7), 775; https://doi.org/10.3390/polym10070775
Received: 3 June 2018 / Revised: 13 July 2018 / Accepted: 13 July 2018 / Published: 15 July 2018
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Abstract
Chain-level structure of semicrystalline polymers in melt- and solution-grown crystals has been debated over the past half century. Recently, 13C–13C double quantum (DQ) Nuclear Magnetic Resonance (NMR) spectroscopy has been successfully applied to investigate chain-folding (CF) structure and packing structure
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Chain-level structure of semicrystalline polymers in melt- and solution-grown crystals has been debated over the past half century. Recently, 13C–13C double quantum (DQ) Nuclear Magnetic Resonance (NMR) spectroscopy has been successfully applied to investigate chain-folding (CF) structure and packing structure of 13C enriched polymers after solution and melt crystallization. We review recent NMR studies for (i) packing structure, (ii) chain trajectory, (iii) conformation of the folded chains, (iv) nucleation mechanisms, (v) deformation mechanism, and (vi) molecular dynamics of semicrystalline polymers. Full article
(This article belongs to the Special Issue NMR in Polymer Science)
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Open AccessArticle A Roadmap towards Successful Nanocapsule Synthesis via Vesicle Templated RAFT-Based Emulsion Polymerization
Polymers 2018, 10(7), 774; https://doi.org/10.3390/polym10070774
Received: 3 July 2018 / Revised: 13 July 2018 / Accepted: 13 July 2018 / Published: 15 July 2018
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Abstract
Vesicle templated emulsion polymerization is a special form of emulsion polymerization where the polymer is grown from the outside of the vesicle, leading to nanocapsules. Cost effective nanocapsules synthesis is in high demand due to phasing out of older methods for capsule synthesis.
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Vesicle templated emulsion polymerization is a special form of emulsion polymerization where the polymer is grown from the outside of the vesicle, leading to nanocapsules. Cost effective nanocapsules synthesis is in high demand due to phasing out of older methods for capsule synthesis. Although the first indications of this route being successful were published some 10 years ago, until now a thorough understanding of the parameters controlling the morphologies resulting from the template emulsion polymerization was lacking. Most often a mixture of different morphologies was obtained, ranging from solid particles to pro-trusion structures to nanocapsules. A high yield of nanocapsules was not achieved until now. In this paper, the influence of initial vesicle dispersion, choice of the Reversible Addition-Fragmentation chain Transfer (RAFT) species and oligomer, monomer and crosslinker have been investigated. It turns out that good initial vesicle dispersion, molecular control of the RAFT process, a not too hydrophobic monomer and some crosslinking is needed to result in high yield of nanocapsules. In previous work, the level of RAFT control was often suboptimal and not properly verified and although nanocapsules were shown, other morphologies were also present. We now believe we have a full understanding of vesicle templated nanocapsules synthesis, relevant to many applications. Full article
(This article belongs to the Special Issue Emulsion Polymerization)
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Open AccessReview Nanostructured Composites Based on Liquid-Crystalline Elastomers
Polymers 2018, 10(7), 773; https://doi.org/10.3390/polym10070773
Received: 18 June 2018 / Revised: 9 July 2018 / Accepted: 10 July 2018 / Published: 14 July 2018
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Abstract
Liquid-crystalline elastomers (LCEs) are the object of many research investigations due to their reversible and controllable shape deformations, and their high potential for use in the field of soft robots and artificial muscles. This review focuses on recent studies about polymer composites based
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Liquid-crystalline elastomers (LCEs) are the object of many research investigations due to their reversible and controllable shape deformations, and their high potential for use in the field of soft robots and artificial muscles. This review focuses on recent studies about polymer composites based on LCEs and nanomaterials having different chemistry and morphology, with the aim of instilling new physical properties into LCEs. The synthesis, physico-chemical characterization, actuation properties, and applications of LCE-based composites reported in the literature are reviewed. Several cases are discussed: (1) the addition of various carbon nanomaterials to LCEs, from carbon black to carbon nanotubes, to the recent attempts to include graphene layers to enhance the thermo-mechanic properties of LCEs; (2) the use of various types of nanoparticles, such as ferroelectric ceramics, gold nanoparticles, conductive molybdenum-oxide nanowires, and magnetic iron-oxide nanoparticles, to induce electro-actuation, magnetic-actuation, or photo-actuation into the LCE-based composites; (3) the deposition on LCE surfaces of thin layers of conductive materials (i.e., conductive polymers and gold nanolayers) to produce bending actuation by applying on/off voltage cycles or surface-wrinkling phenomena in view of tunable optical applications. Some future perspectives of this field of soft materials conclude the review. Full article
(This article belongs to the Special Issue Liquid Crystalline Polymers)
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Open AccessArticle Development of Poly(HEMA-Am) Polymer Hydrogel Filler for Soft Tissue Reconstruction by Facile Polymerization
Polymers 2018, 10(7), 772; https://doi.org/10.3390/polym10070772
Received: 1 June 2018 / Revised: 6 July 2018 / Accepted: 11 July 2018 / Published: 13 July 2018
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Abstract
The number of breast reconstruction surgeries has been increasing due to the increase in mastectomies. Surgical implants (the standard polydimethylsiloxane (PDMS) implants) are widely used to reconstruct breast tissues, however, it can cause problems such as adverse immune reactions, fibrosis, rupture, and additional
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The number of breast reconstruction surgeries has been increasing due to the increase in mastectomies. Surgical implants (the standard polydimethylsiloxane (PDMS) implants) are widely used to reconstruct breast tissues, however, it can cause problems such as adverse immune reactions, fibrosis, rupture, and additional surgery. Hence, polymeric fillers have recently garnered increasing attention as strong alternatives for breast reconstruction materials. Polymeric fillers offer noninvasive methods of reconstruction, thereby reducing the possible adverse effects and simplifying the treatment. In this study, we synthesized a 2-hydroxylethylmethacrylate (HEMA) and acrylamide (Am) copolymer (Poly(HEMA-Am)) by redox polymerization to be used as a biocompatible filler material for breast reconstruction. The synthesized hydrogel swelled in phosphate buffered saline (PBS) shows an average modulus of 50 Pa, which is a characteristic similar to that of the standard dermal acrylamide filler. To investigate the biocompatibility and cytotoxicity of the Poly(HEMA-Am) hydrogel, we evaluated an in vitro cytotoxicity assay on human fibroblasts (hFBs) and human adipose-derived stem cells (hADSCs) with the hydrogel eluate, and confirmed a cell viability of over 80% of the cell viability with the Poly(HEMA-Am) hydrogel. These results suggest our polymeric hydrogel is a promising filler material in soft tissue augmentation including breast reconstruction. Full article
(This article belongs to the Special Issue Polymer Scaffolds for Biomedical Application)
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Open AccessArticle Enhanced Properties of Biodegradable Poly(Propylene Carbonate)/Polyvinyl Formal Blends by Melting Compounding
Polymers 2018, 10(7), 771; https://doi.org/10.3390/polym10070771
Received: 23 May 2018 / Revised: 3 July 2018 / Accepted: 10 July 2018 / Published: 13 July 2018
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Abstract
Polyvinyl formal (PVF) was first synthesized via the reaction of poly(vinyl alcohol) (PVA) and formaldehyde. The synthesized PVF exhibits a high decomposition temperature, glass transition temperature, and low melting point compared to pristine PVA. The synthesized PVF can be melt processed at temperatures
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Polyvinyl formal (PVF) was first synthesized via the reaction of poly(vinyl alcohol) (PVA) and formaldehyde. The synthesized PVF exhibits a high decomposition temperature, glass transition temperature, and low melting point compared to pristine PVA. The synthesized PVF can be melt processed at temperatures much lower than PVA. Poly(propylene carbonate) (PPC) and the as-made PVF were melt blended in a Haake mixer. The mechanical properties, thermal behaviors, and morphologies of PPC/PVF blends were investigated. Compared to the pure PPC, PPC/PVF blends show higher tensile strength and Vicat softening temperature. Thermogravimetric (TGA) result reveals that the thermal stabilities of PPC/PVF blends decreased with the increase of the content of PVF. Scanning electron microscopy (SEM) observation indicates that the interfacial compatibility of the PVF and PPC matrix is better than that of the PVA and PPC matrix. The PPC/PVF blends show much better comprehensive properties compared to pure commercial PPC, which provides a practical way to extend the application of PPC copolymer. Full article
(This article belongs to the Special Issue Polymers for Packaging Applications)
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Open AccessArticle A Combined XRD, Solvatochromic, and Cyclic Voltammetric Study of Poly (3,4-Ethylenedioxythiophene) Doped with Sulfonated Polyarylethersulfones: Towards New Conducting Polymers
Polymers 2018, 10(7), 770; https://doi.org/10.3390/polym10070770
Received: 14 June 2018 / Revised: 2 July 2018 / Accepted: 11 July 2018 / Published: 13 July 2018
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Abstract
Despite the poor solubility in organic solvents, poly (3,4-ethylenedioxythiophene) (PEDOT) is one of the most successful conducting polymers. To improve PEDOT conductivity, the dopants commonly used are molecules/polymers carrying sulfonic functionalities. In addition to these species, sulfonated polyarylethersulfone (SPAES), obtained via homogeneous synthesis
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Despite the poor solubility in organic solvents, poly (3,4-ethylenedioxythiophene) (PEDOT) is one of the most successful conducting polymers. To improve PEDOT conductivity, the dopants commonly used are molecules/polymers carrying sulfonic functionalities. In addition to these species, sulfonated polyarylethersulfone (SPAES), obtained via homogeneous synthesis with different degrees of sulfonation (DS), can be used thanks to both the tight control over the DS and the charge separation present in SPAES structure. Here, PEDOTs having enhanced solubility in the chosen reaction solvents (N,N-dimethylformamide, dimethylacetamide, dimethyl sulfoxide, and N-methyl-2-pyrrolidone) were synthesized via a high-concentration solvent-based emulsion polymerization with very low amounts of SPAES as dopant (1% w/w with respect to EDOT monomer), characterized by different DS. The influence of solvents and of the adopted doping agent was studied on PEDOT_SPAESs analyzing (i) the chemical structure, comparing via X-ray diffraction (XRD) the crystalline structures of undoped and commercial PEDOTs with PEDOT_SPAES’ amorphous structure; (ii) solvatochromic behavior, observing UV absorption wavelength variation as solvents and SPAES’ DS change; and (iii) electrochemical properties: voltammetric peak heights of PEDOT_SPAES cast onto glassy carbon electrodes differ for each solvent and in general are better than the ones obtained for neat SPAES, PEDOTs, and glassy carbon. Full article
(This article belongs to the Special Issue Polymers: Design, Function and Application)
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Open AccessArticle Influence of Macromolecular Architecture on the Optical and Humidity-Sensing Properties of Poly(N,N-Dimethylacrylamide)-Based Block Copolymers
Polymers 2018, 10(7), 769; https://doi.org/10.3390/polym10070769
Received: 13 June 2018 / Revised: 9 July 2018 / Accepted: 10 July 2018 / Published: 13 July 2018
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Abstract
The influence of the macromolecular architecture of block copolymers containing poly(N,N-dimethyl acrylamide) (PDMA) on the optical characteristics and sensing properties of corresponding thin films is discussed. Series of hydrophilic PDMA-based copolymers of different chemical composition and chain architecture such
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The influence of the macromolecular architecture of block copolymers containing poly(N,N-dimethyl acrylamide) (PDMA) on the optical characteristics and sensing properties of corresponding thin films is discussed. Series of hydrophilic PDMA-based copolymers of different chemical composition and chain architecture such as triblock, star-shaped, and branched were synthesized. The copolymers were characterized using conventional spectroscopic techniques as well as methods for characterization of copolymer macromolecular characteristics in solution, namely size-exclusion chromatography and static light scattering. Thin films of the copolymers of nanometer scale thickness were deposited on silicon substrates by the spin-coating method. The refractive index and extinction coefficient of the copolymer films were calculated from the reflectance spectra by using non-linear curve fitting methods and the composition-structure-optical properties relationships were evaluated. Humidity-sensing properties of the films were studied by measuring reflectance spectra of the films at a relative humidity range from 5 to 95%RH. The implementation of the copolymer films as optical sensors of humidity is justified and discussed. Full article
(This article belongs to the Special Issue Polymers: Design, Function and Application)
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Open AccessArticle Bioactive and Bioadhesive Catechol Conjugated Polymers for Tissue Regeneration
Polymers 2018, 10(7), 768; https://doi.org/10.3390/polym10070768
Received: 7 June 2018 / Revised: 3 July 2018 / Accepted: 11 July 2018 / Published: 13 July 2018
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Abstract
The effective treatment of chronic wounds constitutes one of the most common worldwide healthcare problem due to the presence of high levels of proteases, free radicals and exudates in the wound, which constantly activate the inflammatory system, avoiding tissue regeneration. In this study,
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The effective treatment of chronic wounds constitutes one of the most common worldwide healthcare problem due to the presence of high levels of proteases, free radicals and exudates in the wound, which constantly activate the inflammatory system, avoiding tissue regeneration. In this study, we describe a multifunctional bioactive and resorbable membrane with in-built antioxidant agent catechol for the continuous quenching of free radicals as well as to control inflammatory response, helping to promote the wound-healing process. This natural polyphenol (catechol) is the key molecule responsible for the mechanism of adhesion of mussels providing also the functionalized polymer with bioadhesion in the moist environment of the human body. To reach that goal, synthesized statistical copolymers of N-vinylcaprolactam (V) and 2-hydroxyethyl methacrylate (H) have been conjugated with catechol bearing hydrocaffeic acid (HCA) molecules with high yields. The system has demonstrated good biocompatibility, a sustained antioxidant response, an anti-inflammatory effect, an ultraviolet (UV) screen, and bioadhesion to porcine skin, all of these been key features in the wound-healing process. Therefore, these novel mussel-inspired materials have an enormous potential for application and can act very positively, favoring and promoting the healing effect in chronic wounds. Full article
(This article belongs to the Special Issue Polymers for Therapy and Diagnostics)
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Open AccessArticle Microwave Devulcanized Crumb Rubbers in Polypropylene Based Thermoplastic Dynamic Vulcanizates
Polymers 2018, 10(7), 767; https://doi.org/10.3390/polym10070767
Received: 13 June 2018 / Revised: 9 July 2018 / Accepted: 10 July 2018 / Published: 12 July 2018
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Abstract
Because of the chemically crosslinked 3D molecular structure of rubbers, their recycling is a challenging task, especially when cost efficiency is also considered. One of the most straightforward procedures is the grinding of discarded rubber products with subsequent devulcanization. The devulcanized rubber can
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Because of the chemically crosslinked 3D molecular structure of rubbers, their recycling is a challenging task, especially when cost efficiency is also considered. One of the most straightforward procedures is the grinding of discarded rubber products with subsequent devulcanization. The devulcanized rubber can be used as a feedstock for fresh rubber compounds or can be blended with uncured virgin rubber and thermoplastic polymers to form thermoplastic dynamic vulcanizates (TDVs). TDVs combine the beneficial (re)processability of thermoplastics and the elastic properties of rubbers. Our current work focuses on the development of polypropylene (PP)-based TDVs with the use of a tire model rubber (MR) composed of natural rubber (NR) and styrene-butadiene rubber (SBR) in a ratio of 70/30. The research target was the partial substitution of the above fresh MR by microwave devulcanized crumb rubber (dCR). TDVs were produced by continuous extrusion, and the effects of composition (PP/MR/dCR = 40/60/0…50/35/15) and processing parameters (different screw configurations, temperature profiles, the feeding method of PP) were investigated. Results showed that the fresh rubber compound can be replaced up to 10 wt % without compromising the mechanical properties of the resulting TDV. Full article
(This article belongs to the Special Issue Elastomers)
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Open AccessArticle Application of Melt-Blown Poly(lactic acid) Fibres in Self-Reinforced Composites
Polymers 2018, 10(7), 766; https://doi.org/10.3390/polym10070766
Received: 16 June 2018 / Revised: 10 July 2018 / Accepted: 10 July 2018 / Published: 12 July 2018
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Abstract
The aim of our research was to produce poly(lactic acid) (PLA) fibres with diameters in the micrometer size range, serving as the reinforcing phase in self-reinforced (SR) PLA composites. Nonwoven PLA mats were manufactured by solvent-free melt-blowing technology. Three types of PLA differing
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The aim of our research was to produce poly(lactic acid) (PLA) fibres with diameters in the micrometer size range, serving as the reinforcing phase in self-reinforced (SR) PLA composites. Nonwoven PLA mats were manufactured by solvent-free melt-blowing technology. Three types of PLA differing in d-lactide content were processed with a productivity as high as 36 g/h. The crystallinity of the PLA microfibres was enhanced by thermal annealing. A 2–3-fold increase in the degree of crystallinity was obtained, as measured by differential scanning calorimetry (DSC). Fibre diameters between 2–14 µm were revealed by scanning electron microscopy (SEM). Static tensile tests were performed on the nonwoven mats, showing the reduced moduli of the annealed fibres due the amorphous relaxation. The PLA mats were processed via the hot compaction technique and formed into SR–PLA composites. The morphological and mechanical properties of the obtained microstructural composites were comprehensively studied. Composites prepared from annealed, thermally more stable PLA nonwoven mats showed superior mechanical properties; the tensile strength improved by 47% due to the higher residual fibre content. Full article
(This article belongs to the Special Issue Polymers: Design, Function and Application)
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Open AccessArticle Mid-Chain Radical Migration in the Radical Polymerization of n-Butyl Acrylate
Polymers 2018, 10(7), 765; https://doi.org/10.3390/polym10070765
Received: 17 June 2018 / Revised: 5 July 2018 / Accepted: 9 July 2018 / Published: 12 July 2018
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Abstract
The occurrence of intramolecular transfer to polymer in the radical polymerization of acrylic monomers has been extensively documented in the literature. Whilst it has been largely assumed that intramolecular transfer to polymer leads to short chain branches, there has been some speculation over
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The occurrence of intramolecular transfer to polymer in the radical polymerization of acrylic monomers has been extensively documented in the literature. Whilst it has been largely assumed that intramolecular transfer to polymer leads to short chain branches, there has been some speculation over whether the mid-chain radical can migrate. Herein, by the matrix-assisted laser desorption/ionization time of flight (MALDI-TOF) mass spectrometry (MS) of poly(n-butyl acrylate) synthesized by solution polymerization under a range of conditions, it is shown that this mid-chain radical migration does occur in the radical polymerization of acrylates conducted at high temperatures, as is evident from the shape of the molecular weight distribution. Using a mathematical model, an initial approximation of the rate at which migration occurs is made and the distribution of branching lengths formed in this scenario is explored. It is shown that the polymerizations carried out under a low monomer concentration and at high temperatures are particularly prone to radical migration reactions, which may affect the rheological properties of the polymer. Full article
(This article belongs to the Special Issue Polymerization Kinetics)
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