Polymers, Volume 10, Issue 2 (February 2018) – 121 articles

Auxetic plied yarns are specially constructed with two types of single yarns of different sizes and moduli. This paper investigates how to use these types of yarns to produce woven fabrics with auxetic effects. Four-ply auxetic yarns were first incorporated into a series of woven fabrics with different design parameters to study their auxetic behavior and percent open area during extension. Effects of auxetic plied yarn arrangement, single component yarn properties, weft yarn type, and weave structure were then evaluated. Additional double helical yarn (DHY) and 6-ply auxetic yarn woven fabrics were also made for comparison. The results show that the alternative arrangement of S- and Z-twisted 4-ply auxetic yarns in a woven fabric can generate a higher negative Poisson’s ratio (NPR) of the fabric. While the higher single stiff yarn modulus of auxetic yarn can result in greater NPR behavior, finer soft auxetic yarn does not necessarily generate such an effect. Weft yarns with low modulus and short float over the 4-ply auxetic yarns in fabric structure are favorable for producing high NPR behavior. The weft cover factor greatly affects the variation of the percent open area of the 4-ply auxetic yarn fabrics during extension. When different kinds of helical auxetic yarns (HAYs) are made into fabrics, the fabric made of DHY does not have the highest NPR effect but it has the highest percent open area, which increases with increasing tensile strain. Full article

A series of poly(ether-block-amide) (PEBAX)/polyethylene glycol (PEG) composite films (PBXPG) were prepared by solution casting technique. This study demonstrates how the incorporation of different molecular weight PEG into PEBAX can improve the as-prepared composite film performance in gas permeability as a function of temperature. Additionally, we investigated the effect of PEG with different molecular weights on gas transport properties, morphologies, thermal properties, and water sorption. The thermal stability of the composite films increased with increasing molecular weight of PEG, whereas the water sorption and total surface energy decreased. As the temperature increased from 10 to 80 °C, the low (L)-PBXPG and medium (M)-PBXPG films showed a trend similar to the pure PEBAX film. However, the high (H)-PBXPG film with relatively high molecular weight exhibited a distinct permeation jump in the phase change region of H-PEG, which is related to the temperature dependent changes in the morphology structure such as crystallinity and the chemical affinity between the polymer film and gas molecule. Based on these results, it can be expected that H-PBXPG composite films can be used as self-ventilating materials in microwave cooking. Full article

Well-defined poly(tert-butyldimethylsilyl methacrylate)s (TBDMSMA) were prepared by the reversible addition-fragmentation chain transfer (RAFT) process using cyanoisopropyl dithiobenzoate (CPDB) as chain-transfer agents (CTA). The experimentally obtained molecular weight distributions are narrow and shift linearly with monomer conversion. Propagation rate coefficients (k_p) and termination rate coefficients (k_t) for free radical polymerization of TBDMSMA have been determined for a range of temperature between 50 and 80 °C using the pulsed laser polymerization-size-exclusion chromatography (PLP-SEC) method and the kinetic method via steady-state rate measurement, respectively. The CPDB-mediated RAFT polymerization of TBDMSMA has been subjected to a combined experimental and PREDICI modeling study at 70 °C. The rate coefficient for the addition reaction to RAFT agent (k_β1, k_β2) and to polymeric RAFT agent (k_β) is estimated to be approximately 1.8 × 10⁴ L·mol⁻¹·s⁻¹ and for the fragmentation reaction of intermediate RAFT radicals in the pre-equilibrium (k_-β1, k_-β2) and main equilibrium (k_-β) is close to 2.0 × 10⁻² s⁻¹. The transfer rate coefficient (k_tr) to cyanoisopropyl dithiobenzoate is found to be close to 9.0 × 10³ L·mol⁻¹·s⁻¹ and the chain-transfer constant (C_tr) for CPDB-mediated RAFT polymerization of TBDMSMA is about 9.3. Full article

The copolymers of ethylene (E) with open-caged iso-butyl-substituted tri-alkenyl-silsesquioxanes (POSS-6-3 and POSS-10-3) and phenyl-substituted tetra-alkenyl-silsesquioxane (POSS-10-4) were synthesized by copolymerization over the ansa-metallocene catalyst. The influence of the kind of silsesquioxane and of the copolymerization conditions on the reaction performance and on the properties of the copolymers was studied. In the case of copolymerization of E/POSS-6-3, the positive comonomer effect was observed, which was associated with the influence of POSS-6-3 on transformation of the bimetallic ion pair to the active catalytic species. Functionality of silsesquioxanes and polymerization parameters affected the polyhedral oligomeric silsesquioxanes (POSS) contents in the copolymers which varied in the range of 1.33–7.43 wt %. Tri-alkenyl-silsesquioxanes were incorporated into the polymer chain as pendant groups while the tetra-alkenyl-silsesquioxane derivative could act as a cross-linking agent which was proved by the changes in the contents of unsaturated end groups, by the glass transition temperature values, and by the gel contents (up to 81.3% for E/POSS-10-4). Incorporation of multi-alkenyl-POSS into the polymer chain affected also the melting and crystallization behaviors. Full article

Carbon nanoparticles tend to form agglomerates with considerable cohesive strength, depending on particle morphology and chemistry, thus presenting different dispersion challenges. The present work studies the dispersion of three types of graphite nanoplates (GnP) with different flake sizes and bulk densities in a polypropylene melt, using a prototype extensional mixer under comparable hydrodynamic stresses. The nanoparticles were also chemically functionalized by covalent bonding polymer molecules to their surface, and the dispersion of the functionalized GnP was studied. The effects of stress relaxation on dispersion were also analyzed. Samples were removed along the mixer length, and characterized by microscopy and dielectric spectroscopy. A lower dispersion rate was observed for GnP with larger surface area and higher bulk density. Significant re-agglomeration was observed for all materials when the deformation rate was reduced. The polypropylene-functionalized GnP, characterized by increased compatibility with the polymer matrix, showed similar dispersion effects, albeit presenting slightly higher dispersion levels. All the composites exhibit dielectric behavior, however, the alternate current (AC) conductivity is systematically higher for the composites with larger flake GnP. Full article

The poly(ethylene glycol)-based benzoxazine polymers were synthesized via a polycondensation reaction between Bisphenol-A, paraformaldehyde, and poly(ether diamine)/(Jeffamine^®). The structures of the polymers were confirmed by proton nuclear magnetic resonance spectroscopy (¹H-NMR), indicating the presence of a cyclic benzoxazine ring. The polymer solutions were casted on the glass plate and cross-linked via thermal treatment to produce tough and flexible films without using any external additives. Thermal properties and the crosslinking behaviour of these polymers were studied by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). Single gas (H₂, O₂, N₂, CO₂, and CH₄) transport properties of the crosslinked polymeric membranes were measured by the time-lag method. The crosslinked PEG-based polybenzoxazine membranes show improved selectivities for CO₂/N₂ and CO₂/CH₄ gas pairs. The good separation selectivities of these PEG-based polybenzoxazine materials suggest their utility as efficient thin film composite membranes for gas and liquid membrane separation technology. Full article

Adsorption of the polyelectrolyte polydiallyldimethylammonium chloride (PDADMAC) onto nanosilica (SiO₂) fabricated from rice husk was studied in this work. Nanosilica was characterized by X-ray diffraction, Fourier-transform infrared spectroscopy (FTIR), and scanning electron microscopy (SEM). Adsorption of PDADMAC onto SiO₂ increased with increasing pH because the negative charge of SiO₂ is higher at high pH. Adsorption isotherms of PDADMAC onto silica at different KCl concentrations were fitted well by a two-step adsorption model. Adsorption mechanisms of PDADMAC onto SiO₂ are discussed on the basis of surface charge change, evaluation by ζ potential, surface modification by FTIR measurements, and the adsorption isotherm. The application of PDADMAC adsorption onto SiO₂ to remove amoxicillin antibiotic (AMX) was also studied. Experimental conditions such as contact time, pH, and adsorbent dosage for removal of AMX using SiO₂ modified with PDADMAC were systematically optimized and found to be 180 min, pH 10, and 10 mg/mL, respectively. The removal efficiency of AMX using PDADMAC-modified SiO₂ increased significantly from 19.1% to 92.3% under optimum adsorptive conditions. We indicate that PDADMAC-modified SiO₂ rice husk is a novel adsorbent for removal of antibiotics from aqueous solution. Full article

A key for the preparation of polyacrylate-based polyurethane is the synthesis of hydroxyl-terminated polyacrylate. To our knowledge, exactly one hydroxyl group of every polyacrylate chain has not been reported. The hydroxyl-terminated poly(butyl acrylate) (PBA) has been successfully synthesized by degenerative iodine transfer polymerization (DITP) of the n-butyl acrylate (n-BA) using 4,4′-azobis(4-cyano-1-pentanol) (ACPO) and diiodoxylene (DIX) as initiator and chain transfer agent, respectively, and subsequently substituted reaction of the iodine-terminated PBA with β-mercaptoethanol in alkaline condition. The latter reaction was highly efficient, and the terminal iodine at the end of polymer chains were almost quantitatively transformed to a hydroxyl group. 2,2′-Azobis(isobutyronitrile) (AIBN) and ACPO were used as initiators in the DITPs of n-BA. The results demonstrated that they had a significant influence on the terminal groups of the formed polymer chains. The structure, molecular weight, and molecular weight distribution of the hydroxyl-terminated PBA have been studied by ¹H, ¹³C NMR, and GPC results. The components of hydroxyl-terminated PBA were determined by MALDI-TOF MS spectra, and their formation is discussed. The broad molecular weight distribution of the PBA and the difference in the polymerization behaviors from typical living radical polymerization are explained based on the results of ¹H NMR and MALDI-TOF MS spectra. The hydroxyl-terminated PBA has been successfully used in the preparation of PBA-based polyurethane dispersions (PUDs). The aqueous PUDs were stable, and based on the DSC results it can be said that the miscibility of hard segments with PBA chains was improved. Full article

Complex surface topographies control, define, and determine the properties of insect cuticles. In some cases, these nanostructured materials are a direct extension of chitin-based cuticles. The cellular mechanisms that generate these elaborate chitin-based structures are unknown, and involve complicated cellular and biochemical “bottom-up” processes. We demonstrated that a synthetic “top-down” fabrication technique—nanosphere lithography—generates surfaces of chitin or chitosan that mimic the arrangement of nanostructures found on the surface of certain insect wings and eyes. Chitin and chitosan are flexible and biocompatible abundant natural polymers, and are a sustainable resource. The fabrication of nanostructured chitin and chitosan materials enables the development of new biopolymer materials. Finally, we demonstrated that another property of chitin and chitosan—the ability to self-assemble nanosilver particles—enables a novel and powerful new tool for the nanosphere lithographic method: the ability to generate a self-masking thin film. The scalability of the nanosphere lithographic technique is a major limitation; however, the silver nanoparticle self-masking enables a one-step thin-film cast or masking process, which can be used to generate nanostructured surfaces over a wide range of surfaces and areas. Full article

Graphene (G) and its derivatives, graphene oxide (GO) and reduced graphene oxide (rGO) have enormous potential for energy applications owing to their 2D structure, large specific surface area, high electrical and thermal conductivity, optical transparency, and huge mechanical strength combined with inherent flexibility. The combination of G-based materials with polymers leads to new nanocomposites with enhanced structural and functional properties due to synergistic effects. This review briefly summarizes recent progress in the development of G/polymer nanocomposites for use in polymer solar cells (PSCs). These nanocomposites have been explored as transparent conducting electrodes (TCEs), active layers (ALs) and interfacial layers (IFLs) of PSCs. Photovoltaic parameters, such as the open-circuit voltage (V_oc), short-circuit current density (J_sc), fill factor (FF) and power-conversion efficiency (PCE) are compared for different device structures. Finally, future perspectives are discussed. Full article

In this article, the molecularly imprinted polymers (MIPs) of ginsenoside Re (Re) were synthesized by suspension polymerization with Re as the template molecule, methacrylic acid (MAA) as the functional monomers, and ethyl glycol dimethacrylate (EGDMA) as the crosslinker. The MIPs were characterized by Fourier transform infrared spectroscopy (FTIR), Field emission scanning electron microscopy (FESEM), and surface porosity detector, and the selective adsorption and specific recognition of MIPs were analyzed using the theory of kinetics and thermodynamics. The experimental results showed that compared with non-imprinted polymers (NIPs), MIPs had a larger specific surface area and special pore structure and that different from the Langmuir model of NIPs, the static adsorption isotherm of MIPs for Re was in good agreement with the Freundlich model based on the two adsorption properties of MIPs. The curves of the adsorption dynamics and the lines of kinetic correlation indicate that there was a fast and selective adsorption equilibrium for Re because of the affinity of MIPs to the template rather than its analogue of ginsenoside Rg1 (Rg1). The study of thermodynamics indicate that the adsorption was controlled by enthalpy and that MIPs had higher enthalpy and entropy than NIPs, which contributed to the specific recognition of MIPs. Full article

Polymerization via Suzuki coupling under microwave (µW) irradiation has been studied for the synthesis of poly{1,4-(2/3-aminobenzene)-alt-2,7-(9,9-dihexylfluorene)} (PAF), chosen as molecular model. Briefly, µW-assisted procedures accelerated by two orders of magnitude the time required when using classical polymerization processes, and the production yield was increased (>95%). In contrast, although the sizes of the polymers that were obtained by non-conventional heating reactions were reproducible and adequate for most applications, with this methodology the molecular weight of final polymers were not increased with respect to conventional heating. Asymmetric orientation of the amine group within the monomer and the assignments of each dyad or regioregularity, whose values ranged from 38% to 95% with this molecule, were analysed using common NMR spectroscopic data. Additionally, the synthesis of a new cationic polyelectrolyte, poly{1,4-(2/3-aminobenzene)-co-alt-2,7-[9,9´-bis(6’’-N,N,N-trimethylammonium-hexyl)fluorene]} dibromide (PAFAm), from poly{1,4-(2/3-aminobenzene)-co-alt-2,7-[9,9´-bis(6’’-bromohexyl)fluorene]} (PAFBr) by using previously optimized conditions for µW-assisted heating procedures was reported. Finally, the characterization of the final products from these batches showed unkown interesting solvatochromic properties of the PAF molecule. The study of the solvatochromism phenomena, which was investigated as a function of the polarity of the solvents, showed a well-defined Lippert correlation, indicating that the emission shift observed in PAF might be due to its interaction with surrounding environment. Proven high sensitivity to changes of its environment makes PAF a promising candidate of sensing applications. Full article

Well-defined novel, linear, biodegradable, amphiphilic thermo-responsive ABA-type triblock copolymers, poly[2-(2-methoxyethoxy) ethyl methacrylate-co-oligo(ethylene glycol) methacrylate]-b-poly(ε-caprolactone)-b-poly[2-(2-methoxyethoxy) ethyl methacrylate-co-oligo(ethylene glycol) methacrylate] [P(MEO₂MA-co-OEGMA)-b-PCL-b-P(MEO₂MA-co-OEGMA)] (tBPs), were synthesized via a combination of ring-opening polymerization (ROP) of ε-caprolactone (εCL) and reversible addition-fragmentation chain transfer polymerization (RAFT) of MEO₂MA and OEGMA comonomers. The chemical structures and compositions of these copolymers were characterized using Fourier transform infrared spectroscopy (FT-IR) and proton nuclear magnetic resonance (¹H NMR). The molecular weights of the copolymers were obtained using gel permeation chromatography (GPC) measurements. Thermo-responsive micelles were obtained by self-assembly of copolymers in aqueous medium. The temperature sensitivity and micelllization behavior of amphiphilic triblock copolymers solutions were studied by transmittance, fluorescence probe, surface tension, dynamic light scattering (DLS) and transmission electron microscopy (TEM). A hydrophobic drug, anethole, was encapsulated in micelles by using the dialysis method. The average particle sizes of drug-loaded micelles were determined by dynamic light scattering measurement. In vitro, the sustained release of the anethole was performed in pH 7.4 phosphate-buffered saline (PBS) at different temperatures. Results showed that the triblock copolymer’s micelles were quite effective in the encapsulation and controlled release of anethole. The vial inversion test demonstrated that the triblock copolymers could trigger the sol-gel transition which also depended on the temperature, and its sol-gel transition temperature gradually decreased with increasing concentration. The hydrogel system could also be used as a carrier of hydrophobic drugs in medicine. Full article

Marine resources are well recognized for their biologically active substances with great potential applications in the cosmeceutical industry. Among the different compounds with a marine origin, chitin and its deacetylated derivative—chitosan—are of great interest to the cosmeceutical industry due to their unique biological and technological properties. In this review, we explore the different functional roles of chitosan as a skin care and hair care ingredient, as an oral hygiene agent and as a carrier for active compounds, among others. The importance of the physico-chemical properties of the polymer in its use in cosmetics are particularly highlighted. Moreover, we analyse the market perspectives of this polymer and the presence in the market of chitosan-based products. Full article

The limited availability of materials with special properties represents one of the main limitations to a wider application of polymer-based additive manufacturing technologies. Filled resins are usually not suitable for vat photo-polymerization techniques such as stereolithography (SLA) or digital light processing (DLP) due to a strong increment of viscosity derived from the presence of rigid particles within the reactive suspension. In the present paper, the possibility to in situ generate silver nanoparticles (AgNPs) starting from a homogeneous liquid system containing a well dispersed silver salt, which is subsequently reduced to metallic silver during stereolithographic process, is reported. The simultaneous photo-induced cross-linking of the acrylic resin produces a filled thermoset resin with thermal-mechanical properties significantly enhanced with respect to the unfilled resin, even at very low AgNPs concentrations. With this approach, the use of silver salts having carbon-carbon double bonds, such as silver acrylate and silver methacrylate, allows the formation of a nanocomposite structure in which the release of by-products is minimized due to the active role of all the reactive components in the three dimensional (3D)-printing processes. The synergy, between this nano-technology and the geometrical freedom offered by SLA, could open up a wide spectrum of potential applications for such a material, for example in the field of food packaging and medical and healthcare sectors, considering the well-known antimicrobial effects of silver nanoparticles. Full article

The incidence of heart failure (HF) is increasing worldwide and myocardial infarction (MI), which follows ischemia and reperfusion (I/R), is often at the basis of HF development. Nanocarriers are interesting particles for their potential application in cardiovascular disease. Impaired drug delivery in ischemic disease is challenging. Cyclodextrin nanosponges (NS) can be considered innovative tools for improving oxygen delivery in a controlled manner. This study has developed new α-cyclodextrin-based formulations as oxygen nanocarriers such as native α-cyclodextrin (α-CD), branched α-cyclodextrin polymer (α-CD POLY), and α-cyclodextrin nanosponges (α-CD NS). The three different α-CD-based formulations were tested at 0.2, 2, and 20 µg/mL to ascertain their capability to reduce cell mortality during hypoxia and reoxygenation (H/R) in vitro protocols. H9c2, a cardiomyoblast cell line, was exposed to normoxia (20% oxygen) or hypoxia (5% CO₂ and 95% N₂). The different formulations, applied before hypoxia, induced a significant reduction in cell mortality (in a range of 15% to 30%) when compared to samples devoid of oxygen. Moreover, their application at the beginning of reoxygenation induced a considerable reduction in cell death (12% to 20%). α-CD NS showed a marked efficacy in controlled oxygenation, which suggests an interesting potential for future medical application of polymer systems for MI treatment. Full article

Exuding wound care requires a dressing to quickly absorb exudates and properly manage moisture during the healing process. In this study, the superabsorbent spacer fabrics were designed and fabricated for application in exuding wound dressings. The fabric structure consists of three layers, including two outer hydrophobic layers made of polyester/spandex yarns and one superabsorbent middle layer made of superabsorbent yarns. In order to confirm the performance of these superabsorbent spacer fabrics, their dressing properties were tested and compared with two commercial foam dressings. The results showed that all the superabsorbent spacer fabrics had much faster wetting speeds (less than 2 s) than the foam dressings (6.04 s for Foam A and 63.69 s for Foam B). The absorbency of the superabsorbent spacer fabrics was at least twice higher than that of the foam dressings. The air permeability of the superabsorbent spacer fabrics (higher than 15 mL/s/cm² at 100 Pa) was much higher than that of the foam dressings which had a too low permeability to be measured by the testing device. In addition, the water vapor permeability, thermal insulation, and conformability of superabsorbent spacer fabrics were comparable to foam dressings. The study indicates that the superabsorbent spacer fabrics are suitable for exuding wound dressing applications. Full article

We herein selected a 3D metal–organic framework decorated with carboxylate groups as an adsorbent to remove the pharmaceutical molecules of diclofenac sodium and chlorpromazine hydrochloride from water. The experiment aimed at exploring the effect factors of initial concentration, equilibrium time, temperature, pH and adsorbent dosage on the adsorption process. The adsorption uptake rate of the diclofenac sodium is much higher than that of the chlorpromazine hydrochloride. This paper presents the high adsorption capacity of diclofenac sodium, in which porous MOFs are used for the removal of drug contaminants from water. According to linear fitting with adsorption isotherm equation and kinetic equations, diclofenac sodium conforms to the Langmuir model and pseudo-first-order kinetic equation, while chlorpromazine hydrochloride accords with the Temkin model and pseudo-second-order kinetic equation. The results of the study indicate that the title compound could be a promising hybrid material for removing diclofenac sodium and chlorpromazine hydrochloride from wastewater. Full article

The aim of the present work was the development of heart patches based on gelatin (G) and chondroitin sulfate (CS) to be used as implants to improve heart recovery after corrective surgery for critical congenital heart defects (CHD). Patches were prepared by means of electrospinning to obtain nanofibrous scaffolds and they were loaded with platelet lysate (PL) as a source of growth factors to further enhance the repair process. Scaffolds were characterized for morphology and mechanical properties and for the capability to support in vitro adhesion and proliferation of dermal fibroblasts in order to assess the system’s general biocompatibility. Adhesion and proliferation of endothelial cells and cardiac cells (cardiomyocytes and cardiac fibroblasts from rat fetuses) onto PL-loaded patches was evaluated. Patches presented good elasticity and high stiffness suitable for in vivo adaptation to heart contraction. CS improved adhesion and proliferation of dermal fibroblasts, as proof of their biocompatibility. Moreover, they enhanced the adhesion and proliferation of endothelial cells, a crucial mediator of cardiac repair. Cell adhesion and proliferation could be related to elastic properties, which could favor cell motility. The presence of platelet lysate and CS was crucial for the adhesion and proliferation of cardiac cells and, in particular, of cardiomyocytes: G/CS scaffold embedded with PL appeared to selectively promote proliferation in cardiomyocytes but not cardiac fibroblasts. In conclusion, G/CS scaffold seems to be a promising system to assist myocardial-repair processes in young patient, preserving cardiomyocyte viability and preventing cardiac fibroblast proliferation, likely reducing subsequent uncontrolled collagen deposition by fibroblasts following repair. Full article

Polyamide 6.6 is one of the most widely used polymers in the textile industry due to its durability; however, it has rather limited modification potential. In this work, the controlled surface modification of polyamide 6.6 fibres using the solvent system CaCl2/H2O/EtOH was studied. The effects of solvent composition (relative proportions of the three components) and treatment time on fibre properties were studied both in situ (with fibres in solvent) and ex situ (after the solvent was washed off). The fibres swell and/or dissolve in the solvent depending on its composition and the treatment time. We believe that the fibre–solvent interaction is through complex formation between the fibre carbonyl groups and the CaCl2. On washing, there is decomplexation and precipitation of the polymer. The treated fibres exhibit greater diameters and surface roughness, structural difference between an outer shell and an inner core is observable, and water retention is higher. The solvent system is more benign than current alternatives, and through suitable tailoring of the treatment conditions, e.g., composition and time, it may be used in the design of advanced materials for storage and release of active substances. Full article

Long poly-diacetylene chains are excellent candidates for planar, on-surface synthesized molecular electronic wires. Since hexagonal-Boron Nitride (h-BN) was identified as the best available atomically flat insulator for the deposition of poly-diacetylene precursors, we demonstrate the polymerization patterns and rate on it under UV-light irradiation, with subsequent polymer identification by atomic force microscopy. The results on h-BN indicate self-sensitization which yields blocks comprised of several polymers, unlike on the well-studied graphite/diacetylene system, where the polymers are always isolated. In addition, the photo-polymerization proceeds at least 170 times faster on h-BN, where it also results in longer polymers. Both effects are explained by the h-BN bandgap, which is larger than the diacetylene electronic excitation energy, thus allowing the transfer of excess energy absorbed by polymerized wires to adjacent monomers, triggering their polymerization. This work sets the stage for conductance measurements of single molecular poly-diacetylene wires on h-BN. Full article

An amphoteric random copolymer (P(SA)₉₁) composed of anionic sodium 2-acrylamido-2-methylpropanesulfonate (AMPS, S) and cationic 3-acrylamidopropyl trimethylammonium chloride (APTAC, A) was prepared via reversible addition-fragmentation chain transfer (RAFT) radical polymerization. The subscripts in the abbreviations indicate the degree of polymerization (DP). Furthermore, AMPS and APTAC were polymerized using a P(SA)₉₁ macro-chain transfer agent to prepare an anionic diblock copolymer (P(SA)₉₁S₆₇) and a cationic diblock copolymer (P(SA)₉₁A₈₈), respectively. The DP was estimated from quantitative 13C NMR measurements. A stoichiometrically charge neutralized mixture of the aqueous P(SA)₉₁S₆₇ and P(SA)₉₁A₈₈ formed water-soluble polyion complex (PIC) micelles comprising PIC cores and amphoteric random copolymer shells. The PIC micelles were in a dynamic equilibrium state between PIC micelles and charge neutralized small aggregates composed of a P(SA)₉₁S₆₇/P(SA)₉₁A₈₈ pair. Interactions between PIC micelles and fetal bovine serum (FBS) in phosphate buffered saline (PBS) were evaluated by changing the hydrodynamic radius (R_h) and light scattering intensity (LSI). Increases in R_h and LSI were not observed for the mixture of PIC micelles and FBS in PBS for one day. This observation suggests that there is no interaction between PIC micelles and proteins, because the PIC micelle surfaces were covered with amphoteric random copolymer shells. However, with increasing time, the diblock copolymer chains that were dissociated from PIC micelles interacted with proteins. Full article

A low cost composite material was synthesized for neodymium recovery from dilute aqueous solutions. The in-situ production of the composite containing chitosan and iron(III) hydroxide (ChiFer(III)) was improved and the results were compared with raw chitosan particles. The sorbent was characterized using Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy-energy dispersive X-ray analyses (SEM-EDX). The equilibrium studies were performed using firstly a batch system, and secondly a continuous system. The sorption isotherms were fitted with the Langmuir, Freundlich, and Sips models; experimental data was better described with the Langmuir equation and the maximum sorption capacity was 13.8 mg g-1 at pH 4. The introduction of iron into the biopolymer matrix increases by four times the sorption uptake of the chitosan; the individual sorption capacity of iron (into the composite) was calculated as 30.9 mg Nd/g Fe. The experimental results of the columns were fitted adequately using the Thomas model. As an approach to Nd-Fe-B permanent magnets effluents, a synthetic dilute effluent was simulated at pH 4, in order to evaluate the selectivity of the sorbent material; the overshooting of boron in the column system confirmed the higher selectivity toward neodymium ions. The elution step was carried out using MilliQ-water with the pH set to 3.5 (dilute HCl solution). Full article

The effects of octakis[(3-glycidoxypropyl)dimethylsiloxy]octasilsesquioxane (GPOSS) on the crystallinity, crystal structure, morphology, and mechanical properties of polyoxymethylene (POM) and POM/GPOSS composites were investigated. The POM/GPOSS composites with varying concentrations of GPOSS nanoparticles (0.05–0.25 wt %) were prepared via melt blending. The structure of POM/GPOSS composites was characterized by differential scanning calorimetry (DSC), wide angle X-ray diffraction (WAXD), and polarized light microscopy (PLM). The mechanical properties were determined by standardized tensile tests. The morphology and dispersion of GPOSS nanoparticles in the POM matrix were investigated with scanning electron microscopy (SEM) and energy dispersive X-ray (EDX) analysis. It was observed that the dispersion of the GPOSS nanoparticles was uniform. Based on DSC studies, it was found that the melting temperature, lamellar thickness, and the degree of crystallinity of the POM/GPOSS composites increased. The POM/GPOSS composites showed an increased Young’s modulus and tensile strength. Finally, compared with the pure POM, the addition of GPOSS reduced the spherulites’ size and improved the crystallinity of the POM, which demonstrates that the nucleation effect of GPOSS is favorable for the mechanical properties of POM. Full article

Poly(lactic acid) (PLA), a well-known biodegradable and compostable polymer, was used in this study as a model system to determine if the addition of nanoclays affects its biodegradation in simulated composting conditions and whether the nanoclays impact the microbial population in a compost environment. Three different nanoclays were studied due to their different surface characteristics but similar chemistry: organo-modified montmorillonite (OMMT), Halloysite nanotubes (HNT), and Laponite® RD (LRD). Additionally, the organo-modifier of MMT, methyl, tallow, bis-2-hydroxyethyl, quaternary ammonium (QAC), was studied. PLA and PLA bio-nanocomposite (BNC) films were produced, characterized, and used for biodegradation evaluation with an in-house built direct measurement respirometer (DMR) following the analysis of evolved CO2 approach. A biofilm formation essay and scanning electron microscopy were used to evaluate microbial attachment on the surface of PLA and BNCs. The results obtained from four different biodegradation tests with PLA and its BNCs showed a significantly higher mineralization of the films containing nanoclay in comparison to the pristine PLA during the first three to four weeks of testing, mainly attributed to the reduction in the PLA lag time. The effect of the nanoclays on the initial molecular weight during processing played a crucial role in the evolution of CO2. PLA-LRD5 had the greatest microbial attachment on the surface as confirmed by the biofilm test and the SEM micrographs, while PLA-QAC0.4 had the lowest biofilm formation that may be attributed to the inhibitory effect also found during the biodegradation test when the QAC was tested by itself. Full article

We synthesized a series of plant-based and renewable, eugenol-modified polystyrene (PEUG#) (# = 20, 40, 60, 80, and 100, in which # is the molar content of the eugenol moiety in the side group). Eugenol is extracted from clove oil. We used polymer modification reactions to determine the liquid crystal (LC) orientation properties of the polymer films. In general, the LC cells fabricated using the polymer films with a higher molar content of eugenol side groups exhibited vertical LC orientation behavior. The vertical orientation behavior was well correlated with the surface energy value of the polymer films. The vertical LC orientation could be formed due to the low polar surface energy value on the polymer film generated by the nonpolar carbon group. Electro-optical performances (e.g., voltage holding ratio (VHR), residual DC voltage (R-DC), and thermal orientation stabilities) were good enough to be observed for LC cells using PEUG100 polymer as an eco-friendly LC orientation material. Full article

This work focused on the evaluation of the kinetics of dyeing polyester fabrics with high molecular weight disperse dyes, at low temperature by solvent microemulsion. This study also compared the effect of two non-toxic agro-sourced auxiliaries (o-vanillin and coumarin) using a non-toxic organic solvent. A dyeing bath consisting of a micro-emulsion system involving a small proportion of n-butyl acetate was used, and the kinetics of dyeing were analysed at four temperatures (83, 90, 95 and 100 °C). Moreover, the dyeing rate constants, correlation coefficient and activation energies were proposed for this system. It was found that o-vanillin yielded higher dye absorption levels than coumarin, leading to exhaustions of 88% and 87% for Disperse Red 167 and Disperse Blue 79, respectively. K/S values of dyed polyester were also found to be higher for dye baths containing o-vanillin with respect to the ones with coumarin. In terms of hot pressing fastness and wash fastness, generally no adverse influence on fastness properties was reported, while o-vanillin showed slightly better results compared to coumarin. Full article

Thiolated poly(aspartic acid) is known as a good mucoadhesive polymer in aqueous ophthalmic formulations. In this paper, cyclodextrin-modified thiolated poly(aspartic acid) was synthesized for the incorporation of prednisolone, a lipophilic ophthalmic drug, in an aqueous in situ gellable mucoadhesive solution. This polymer combines the advantages of cyclodextrins and thiolated polymers. The formation of the cyclodextrin-drug complex in the gels was analyzed by X-ray powder diffraction. The ocular applicability of the polymer was characterized by means of physicochemical, rheological and drug diffusion tests. It was established that the chemical bonding of the cyclodextrin molecule did not affect the complexation of prednisolone, while the polymer solution preserved its in situ gellable and good mucoadhesive characteristics. The chemical immobilization of cyclodextrin modified the diffusion profile of prednisolone and prolonged drug release was observed. The combination of free and immobilized cyclodextrins provided the best release profile because the free complex can diffuse rapidly, while the bonded complex ensures a prolonged action. Full article

Crystalline morphology and structure of nylon 4 9 have been studied by means of optical and transmission electron microscopies, and X-ray diffraction. Rhombic crystals were characteristic of crystallization from glycerin dilute solutions, although the final morphology was dependent on the crystallization temperature. In any case, a single electron diffraction pattern was always obtained, being characteristic a 2 mm symmetry and reflections at spacings that were indicative of a projected rectangular unit cell with hydrogen bonds established along two planar directions (i.e., the diagonals of the unit cell), as it was determined from related polyamides. Crystallization from the melt gave rise to negative birefringent spherulites with a morphology (axialitic, speckled or ringed) that was dependent on the crystallization temperature. Kinetic analysis indicated that melt crystallization took place according to two growth mechanisms (Regimes II and III), which reflect distinct secondary nucleation rates. A complex polymorphic behavior on heating and cooling processes was evidenced by real time synchrotron experiments, being determined an intermediate crystalline structure as well as the typical pseudohexagonal arrangement associated to the Brill transition. Polymorphic transitions were highly dependent on the initial crystalline structure, being enhanced the structural transition from the low temperature structure to the intermediate one when traces of the latter were initially present. Calorimetric and infrared studies supported also the detected thermal transitions of nylon 4 9. Full article

At present, research on the relationship of comb-like polymer phase change material structures and their heat storage performance is scarce. Therefore, this relationship from both micro and macro perspectives will be studied in this paper. In order to achieve a high phase change enthalpy, ethylene glycol segments were introduced between the vinyl and the alkyl side chains. A series of poly(mono/diethylene glycol n-tetradecyl ether vinyl ethers) (PC₁₄E_nVEs) (n = 1, 2) with various molecular weights were polymerized by living cationic polymerization. The results of PC₁₄E₁VE and PC₁₄E₂VE showed that the minimum number of carbon atoms required for side-chain crystallization were 7.7 and 7.2, which were lower than that reported in the literature. The phase change enthalpy 89 J/g (for poly(mono ethylene glycol n-tetradecyl ether vinyl ethers)) and 86 J/g (for poly(hexadecyl acrylate)) were approximately equal. With the increase of molecular weight, the melting temperature, the melting enthalpy, and the initial thermal decomposition temperature of PC₁₄E₁VE changed from 27.0 to 28.0 °C, from 95 to 89 J/g, and from 264 to 287 °C, respectively. When the number average molar mass of PC₁₄E_nVEs exceeded 20,000, the enthalpy values remained basically unchanged. The introduction of the ethylene glycol chain was conducive to the crystallization of alkyl side chains. Full article