Polymers, Volume 11, Issue 9 (September 2019) – 157 articles

Adhesive bonding of polyethylene gas pipelines is receiving increasing attention as a replacement for traditional electrofusion welding due to its potential to produce rapid and low-cost joints with structural integrity and pressure tight sealing. In this paper a mode-dependent cohesive zone model for the simulation of adhesively bonded medium density polyethylene (MDPE) pipeline joints is directly determined by following three consecutive steps. Firstly, the bulk stress-strain response of the MDPE adherend was obtained via tensile testing to provide a multi-linear numerical approximation to simulate the plastic deformation of the material. Secondly, the mechanical responses of double cantilever beam and end-notched flexure test specimens were utilised for the direct extraction of the energy release rate and cohesive strength of the adhesive in failure mode I and II. Finally, these material properties were used as inputs to develop a finite element model using a cohesive zone model with triangular shape traction separation law. The developed model was successfully validated against experimental tensile lap-shear test results and was able to accurately predict the strength of adhesively-bonded MPDE pipeline joints with a maximum variation of <3%. Full article

The reactivity and the reaction conditions of the ring-opening polymerization of ε-caprolactone (ε-CL) and L-lactide (LA) initiated by aluminum ketiminate complexes have been shown differently. Herein, we account for the observation by studying the mechanisms on the basis of density functional theory (DFT) calculations. The calculations show that the ring-opening polymerization of ε-CL and LA are rate-determined by the benzoxide insertion and the C–O bond cleavage step, respectively. Theoretical computations suggest that the reaction temperature of L–LA polymerization should be higher than that of ε-CL one, in agreement with the experimental data. To provide a reasonable interpretation of the experimental results and to give an insight into the catalyst design, the influence of the electronic, steric, and thermal effects on the polymerization behaviors will be also discussed in this study. Full article

Based on differential scanning calorimetry (DSC), X-ray diffraction (XRD) analysis, polarizing microscope (POM), and scanning electron microscopy (SEM) analysis, strategies to close the gap on applying conventional processing optimizations for the field of 3D printing and to specifically increase the mechanical performance of extrusion-based additive manufacturing of poly(lactic acid) (PLA) filaments by annealing and/or blending with poly(3-hydroxybutyrate) (PHB) were reported. For filament printing at 210 °C, the PLA crystallinity increased significantly upon annealing. Specifically, for 2 h of annealing at 100 °C, the fracture surface became sufficiently coarse such that the PLA notched impact strength increased significantly (15 kJ m⁻²). The Vicat softening temperature (VST) increased to 160 °C, starting from an annealing time of 0.5 h. Similar increases in VST were obtained by blending with PHB (20 wt.%) at a lower printing temperature of 190 °C due to crystallization control. For the blend, the strain at break increased due to the presence of a second phase, with annealing only relevant for enhancing the modulus. Full article

Herein, we report self-emulsifying anionic unsaturated polyester emulsions with different chain segments as novel sizing agents. The epoxy modified unsaturated polyester emulsions were synthesized via a self-emulsifying technique with no organic solvents. Emulsions were characterized by dynamic light scattering (DLS), Zeta potential, centrifuge, and cryo-scanning electron microscopy (Cryo-SEM). The results showed that the emulsions obtained were mono-dispersed nanospheres that had adequate colloidal stability. The maximum Zeta potential of the sizing agent is −52.88 mV. In addition, these emulsions were investigated as the sizing agents in order to improve interfacial adhesion between carbon fibers (CFs) and unsaturated polyester resin (UPR). Compared with the CFs sized with the commercial epoxy sizing agent, the interlaminar shear strength (ILSS) of CF/UPR composites from the CFs sized by these emulsion sizing agents with three different chain structures were enhanced by 25%, 29%, and 42%, respectively. The emulsion sizing agent composed of a flexible segment synthesized from adipic acid, neopentyl glycol, and maleic anhydride is most effective and can achieve the highest enhancement of the ILSS of CF/UPR composites. Full article

The influence of the pyrolysis temperature on the structural, textural, and electrochemical properties of carbon aerogels obtained from potato, maize, and rice starches was analyzed. The carbonization of organic precursors, followed by gelatinization, exchange of solvent, and drying process, was carried out in an argon atmosphere at temperatures ranging from 600 °C to 1600 °C. The nanostructured carbons were characterized by X-ray powder diffraction (XRD) as well as N₂-adsorption/desorption (N₂-BET) methods. The electrochemical behavior of Li-ion cells based on the fabricated carbon anodes was investigated using the galvanostatic charge/discharge tests (GCDT) and electrochemical impedance spectroscopy (EIS). The results show that the thermal treatment stage has a crucial impact on the proper formation of the aerogel material’s porous structures and also on their working parameters as anode materials. The highest relative development of the external surface was obtained for the samples pyrolysed at 700 °C, which exhibited the best electrochemical characteristics (the highest specific capacities as well as the lowest charge transfer resistances). Full article

Screen-printed ion-selective electrodes were designed and characterized for the assessment of cyromazine (CYR) pesticide. A novel approach is to design tailor-made specific recognition sites in polymeric membranes using molecularly imprinted polymers for cyromazine (CR) determination (sensor I). Another sensor (sensor II) is the plasticized PVC membrane incorporating cyromazine/tetraphenyl borate ion association complex. The charge-transfer resistance and water layer reached its minimal by incorporating Polyaniline (PANI) solid-contact ISE. The designed electrodes demonstrated Nernstain response over a linear range 1.0 × 10⁻²–5.2 × 10⁻⁶ and 1.0 × 10⁻²–5.7 × 10⁻⁵ M with a detection limit 2.2 × 10⁻⁶ and 8.1 × 10⁻⁶ M for sensors I and II, respectively. The obtained slopes were 28.1 ± 2.1 (r² = 0.9999) and 36.4 ± 1.6 (r² = 0.9991) mV/decade, respectively. The results showed that the proposed electrodes have a fast and stable response, good reproducibility, and applicability for direct measurement of CYR content in commercial pesticide preparations and soil samples sprayed with CYR pesticide. The results obtained from the proposed method are fairly in accordance with those using the standard official method. Full article

Polygalacturonase (EC. 3.2.1.15) is an enzyme that hydrolyzes the alpha-1,4 glycosidic bonds between galacturonic acid. In this study, an alkaline polygalacturonase producer Bacillus paralicheniformis CBS32 was isolated from kimchi (conventional Korean fermented food). The 16S rRNA sequence analysis of the isolated strain revealed that it was 99.92% identical to B. paralicheniformis KJ 16LBMN01000156. The polygalacturonase from B. paralicheniformis CBS32 was named PN32, and the purified PN32 showed a 16.8% yield and a 33-fold purity compared to the crude broth. The molecular mass, 110 kDa, was determined by SDS-PAGE, and the active band was confirmed by zymography analysis. The N-terminal amino acid sequence residues of PN32 were determined to be Gly–Val–Lys–Glu–Val–X–Gln–Thr–Phe. In the sequence comparison, PN32 was suggested as a novel polygalacturonase, since the sequence was not matched with the previous reports. In an application study, enzymatic depolymerization of ramie was performed for fiber degumming, and the result showed that the PN32 had a 28% higher depolymerization compared to the commercial pectinase. Overall, based on the results, PN32 has high potential for industrial applications. Full article

The inclusion of electrospun nanofiber veils was revealed as an effective method for enhancing the mechanical properties of fiber-reinforced epoxy resin composites. These veils will eventually allow the incorporation of nanomaterials not only for mechanical reinforcement but also in multifunctional applications. Therefore, this paper investigates the effect of electrospun nanofibrous veils made of polyamide 6 modified with TiO₂ nanoparticles on the mechanical properties of a carbon-fiber/epoxy composite. The nanofibers were included in the carbon-fiber/epoxy composite as a single structure. The effect of positioning these veils in different composite positions was investigated. Compared to the reference, the use of unmodified and TiO₂ modified veils increased the flexural stress at failure and the fracture toughness of composites. When TiO₂ modified veils were incorporated, new antibacterial properties were achieved due to the photocatalytic properties of the veils, widening the application area of these composites. Full article

In this study, corn, potato, and wrinkled pea starches were esterified with malic acid under high temperatures for different lengths of time. The degree of substitution (DS), granule morphology, crystal structure, gelatinization properties, and the digestibility of the malate starch were investigated. Fourier transform infrared spectroscopy (FT–IR) suggested that the malate starch showed a new infrared absorption peak near 1747 cm⁻¹, indicating the occurrence of an esterification reaction. With an increasing treatment time, the degree of substitution (DS) of the malate starch displayed an increasing trend. Scanning electron microscopy (SEM) demonstrated a significant change in the surface structure of the starch granules. X-ray diffractometry (XRD) reflected that the crystal structure of the malate starches was destroyed. The thermogravimetric (TG) curves showed that the maximum heat loss rate of the malate starch was ahead of that of native starch, which caused the decreased degree of crystallinity. These properties of malate starch could allow it to be used for the purpose of starch modification to produce resistant starch and to provide new applications for starch. Full article

We synthesized PPG-terminated tetra-carbamates as a new toughening additive for epoxy thermosets through facile addition reaction of hexamethylene diisocyanate (HDI) with poly(tetra-methylene glycols) (PTMG) and poly(propylene glycols) (PPG). The effects of prepared tetra-carbamates on the rheological behavior of neat epoxy resin were studied along with the various cured properties of their modified epoxy systems. Four carbamate groups (–NHCOO–) endow the prepared additives not only with good intramolecular interactions, but also with optimal intermolecular interactions with epoxy polymers. This results in the suitable miscibility of the additives with the epoxy matrix for the formation of the typical biphasic structure of microparticles dispersed in the epoxy matrix via polymerization-induced microphase separation. The impact strength and critical stress concentration factor (K_IC) of cured modified epoxy systems with the additives are significantly higher than those of unmodified epoxy systems, without sacrificing the processability (T_g) and flexural strength. The toughening mechanism is understood as a synergism combination among the phase separation mechanism, the in situ homogeneous toughening mechanism, and the particle cavitation mechanism. Full article

The correction of transcranial focused ultrasound aberrations is a relevant topic for enhancing various non-invasive medical treatments. Presently, the most widely accepted method to improve focusing is the emission through multi-element phased arrays; however, a new disruptive technology, based on 3D printed holographic acoustic lenses, has recently been proposed, overcoming the spatial limitations of phased arrays due to the submillimetric precision of the latest generation of 3D printers. This work aims to optimize this recent solution. Particularly, the preferred acoustic properties of the polymers used for printing the lenses are systematically analyzed, paying special attention to the effect of p-wave speed and its relationship to the achievable voxel size of 3D printers. Results from simulations and experiments clearly show that, given a particular voxel size, there are optimal ranges for lens thickness and p-wave speed, fairly independent of the emitted frequency, the transducer aperture, or the transducer-target distance. Full article

In this study, a novel hemocompatible coating on stainless steel substrates was prepared by electrochemically copolymerizing 3,4-ethylenedioxythiophene (EDOT) with graphene oxide (GO), polystyrene sulfonate (PSS), or heparin (HEP) on SUS316L stainless steel, producing an anti-fouling (anti-protein adsorption and anti-platelet adhesion) surface to avoid the restenosis of blood vessels. The negative charges of GO, PSS, and HEP repel negatively charged proteins and platelets to achieve anti-fouling and anti-clotting. The results show that the anti-fouling capability of the poly(3,4-ethylenedioxythiophene) (PEDOT)/PSS coating is similar to that of the PEDOT/HEP coating. The anti-fouling capability of PEDOT/GO is higher than those of PEDOT/HEP and PEDOT/PSS. The reason for this is that GO exhibits negatively charged functional groups (COO⁻). The highest anti-fouling capability was found with the PEDOT/GO/HEP coating, indicating that electrochemical copolymerization of PEDOT with GO and HEP enhances the anti-fouling capability. Furthermore, the biocompatibility of the PEDOT coatings was tested with 3T3 cells for 1–5 days. The results show that all PEDOT composite coatings exhibited biocompatibility. The blood clotting time (APTT) of PEDOT/GO/HEP was prolonged to 225 s, much longer than the 40 s of pristine SUS316L stainless steel (the control), thus greatly improving the anti-blood-clotting capability of cardiovascular stents. Full article

Multifunctional nanocomposite coatings were synthesized by reinforcing a polymeric matrix with halloysite nanotubes (HNTs) loaded with corrosion inhibitor (NaNO₃) and urea formaldehyde microcapsules (UFMCs) encapsulated with a self-healing agent (linseed oil (LO)). The developed polymeric nanocomposite coatings were applied on the polished mild steel substrate using the doctor’s blade technique. The structural (FTIR, XPS) and thermogravimetric (TGA) analyses reveal the loading of HNTs with NaNO₃ and encapsulation of UFMCs with linseed oil. It was observed that self-release of the inhibitor from HNTs in response to pH change was a time dependent process. Nanocomposite coatings demonstrate decent self-healing effects in response to the external controlled mechanical damage. Electrochemical impedance spectroscopic analysis (EIS) indicates promising anticorrosive performance of novel nanocomposite coatings. Observed corrosion resistance of the developed smart coatings may be attributed to the efficient release of inhibitor and self-healing agent in response to the external stimuli. Polymeric nanocomposite coatings modified with multifunctional species may offer suitable corrosion protection of steel in the oil and gas industry. Full article

The respiration rate (RR) is a key vital sign that links to adverse clinical outcomes and has various important uses. However, RR signals have been neglected in many clinical practices for several reasons and it is still difficult to develop low-cost RR sensors for accurate, automated, and continuous measurement. This study aims to fabricate, develop and evaluate a novel stretchable and wearable RR sensor that is low-cost and easy to use. The sensor is fabricated using the soft lithography technique of polydimethylsiloxane substrates (PDMS) for the stretchable sensor body and inkjet printing technology for creating the conductive circuit by depositing the silver nanoparticles on top of the PDMS substrates. The inkjet-printed (IJP) PDMS-based sensor was developed to detect the inductance fluctuations caused by respiratory volumetric changes. The output signal was processed in a Wheatstone bridge circuit to derive the RR. Six different patterns for a IJP PDMS-based sensor were carefully designed and tested. Their sustainability (maximum strain during measurement) and durability (the ability to go bear axial cyclic strains) were investigated and compared on an automated mechanical stretcher. Their repeatability (output of the sensor in repeated tests under identical condition) and reproducibility (output of different sensors with the same design under identical condition) were investigated using a respiratory simulator. The selected optimal design pattern from the simulator evaluation was used in the fabrication of the IJP PDMS-based sensor where the accuracy was inspected by attaching it to 37 healthy human subjects (aged between 19 and 34 years, seven females) and compared with the reference values from e-Health nasal sensor. Only one design survived the inspection procedures where design #6 (array consists of two horseshoe lines) indicated the best sustainability and durability, and went through the repeatability and reproducibility tests. Based on the best pattern, the developed sensor accurately measured the simulated RR with an error rate of 0.46 ± 0.66 beats per minute (BPM, mean ± SD). On human subjects, the IJP PDMS-based sensor and the reference e-Health sensor showed the same RR value, without any observable differences. The performance of the sensor was accurate with no apparent error compared with the reference sensor. Considering its low cost, good mechanical property, simplicity, and accuracy, the IJP PDMS-based sensor is a promising technique for continuous and wearable RR monitoring, especially under low-resource conditions. Full article

In the current study, we present methods of sodium hyaluronate, also denoted as hyaluronan (HA), nanofiber fabrication using a direct-current (DC) electric field. HA was spun in combination with poly(vinyl alcohol) (PVA) and polyethylene oxide (PEO) and as a pure polymer. Nonaggressive solvents were used due to the possible use of the fibers in life sciences. The influences of polymer concentration, average molecular weight (M_w), viscosity, and solution surface tension were analyzed. HA and PVA were fluorescent-labeled in order to examine the electrospun structures using fluorescence confocal microscopy. In this study, two intermediate solvent mixtures that facilitate HA electrospinning were found. In the case of polymer co-electrospinning, the effect of the surfactant content on the HA/PVA electrospinning process, and the effect of HA M_w on HA/PEO nanofiber morphology, were examined, respectively. Full article

This paper reported the development of polyoxymethylene (POM)/polylactide (PLA) blends for a potentially biodegradable material. A series of POM/PLA blends at different weight ratios were prepared by melt extrusion with a twin-screw extruder, and their mechanical properties, crystallization behavior and kinetics, thermal degradation kinetics and stability, lifespan prediction and enzymatic degradation behavior were investigated extensively. POM and PLA were found to be partially miscible in the melt state at low temperature and become phase-separated at elevated temperatures, and their blends exhibited a typical lower critical solution temperature behavior. There were two distinct glass transition temperatures (T_g) observed for POM/PLA blends at any mass ratios when quenched from the homogeneous state, and both POM and PLA domains showed an apparent depression in their respective T_g’s in the blends. Owing to the partial miscibility between two domains, the tensile strength and impact toughness of POM/PLA blends gradually decreased with an increase of PLA content, but their flexural strength and modulus presented an increasing trend with PLA content. The studies on non-isothermal and isothermal crystallization behaviors of the blends indicated that the crystallization rates of the blends decreased continually with increasing the PLA content, confirming that the crystallization of POM domain was controlled by the molecular-confined mechanism. The introduction of PLA into POM not only led to a slight increase of thermal stability of POM domain at low PLA contents but also shortened the lifespan of the blends, favoring the natural degradation of the blends. The POM/PLA blends exhibited an improvement in partially biodegradable performance with an increase of PLA content and their mass loss reached up to 25.3 wt % at the end of 48-h enzymatic degradation when 50 wt % of PLA was incorporated. Full article

More than one out of every three new cancers is a skin cancer, and the large majority are basal cell carcinomas (BCC). Targeted therapy targets the cancer’s specific genes, proteins, or tissue environment that contributes to cancer growth and survival and blocks the growth as well as the spread of cancer cells while limiting damage to healthy cells. Therefore, in the present study AS1411 aptamer-functionalized liposomes for the treatment of BCC were obtained and characterized. Aptamer conjugation increased liposome size, suggesting that the presence of an additional hydrophilic molecule on the liposomal surface increased the hydrodynamic diameter. As expected, the negatively charged DNA aptamer reduced the surface potential of the liposomes. Vertical Franz diffusion cells with artificial membranes were used to evaluate the in vitro release of 5-fluorouracil (5-FU). The aptamer moieties increase the stability of the liposomes and act as a supplementary steric barrier leading to a lower cumulative amount of the released 5-FU. The in vitro cell viability, targeting capability and apoptotic effects of liposomes on the human dermal fibroblasts and on the basal cell carcinoma TE 354.T cell lines were also evaluated. The results indicate that the functionalized liposomes are more efficient as nanocarriers than the non-functionalized ones. Full article

A method to modify polymers is that of introducing fibers in a matrix to produce a fiber-reinforced polymer (FRP). Consequently, the aim of this work was to study the compatibility effect of four coupling agents on wool FRP properties, using poly(lactic acid) plasticized with maleinized linseed oil as polymer matrix. The content of wool assessed was 1 phr. The compatibilizers were (3-(2-aminoethylamino)propyl)-trimethoxysilane, trimethoxy (2-(7-oxabicyclo (4.1.0)hept-3-yl) ethyl) silane, tris(2-methoxyethoxy)(vinyl) silane and titanium (IV) (triethanolaminate)isopropoxide. Initially, wool was modified with coupling agents in an acetone/water (50/50) solution. Mechanical properties were evaluated by tensile and flexural properties, hardness by Shore D measurement and impact resistance by Charpy’s energy. Differential scanning calorimetry, dynamic thermo-mechanical analysis, and thermogravimetric analysis were conducted to evaluate the interaction among components and the effect of the coupling agents on the thermal properties of the original material. Color, wettability and scanning electron microscopy were used to describe physical and microstructural properties. Modification of fibers allows achieving improved mechanical properties and changes the thermal properties of the FRPs slightly. Coupling agent treatment helps to formulate PLA–MLO and sheep wool materials and to improve their performance, thereby creating a broader spectrum of applications for PLA maintaining the bio-based character of the material. Full article

The aim of this study is the evaluation of partially sulfonated polystyrene nanoparticles (SPSNP) efficiency as nanocarriers for a non-ionic surfactant, oleic acid diethanolamide (OADA), in the reduction of the surfactant losses and the increase of oil recovery. The synthesized oleic acid diethanolamide was characterized by FTIR, ¹H NMR, ¹³C NMR, surface tension (γ = 36.6 mN·m⁻¹, CMC = 3.13 × 10⁻⁴ M) and interfacial tension of mineral oil/OADA aqueous solutions (IFT_eq = 0.07 mN·m⁻¹). The nanoparticles (SPSNP) were obtained by emulsion polymerization of styrene, DVB and sodium 4-styrenesulfonate (St-S) in the presence of OADA aqueous solution and were characterized by FTIR and PCS. The results show that the presence of ionic groups in the polymer structure promoted a better nanoparticles suspensions′ stability, smaller particles production and more pronounced IFT reduction. The SPSNP obtained with an OADA concentration twenty times its CMC and 0.012 mol % of St-S presented a particle size around 66 nm and can act as efficient nanocarriers decreasing the water/oil interfacial tension to low values (0.07 mN·m⁻¹) along the time, when in contact with the oil. Transport and oil recovery tests of the nanocarriers systems in an unconsolidated sand porous medium test show that the SPSNP do inhibit surfactant adsorption onto sand particles surface and induced an increase of oil recovery of up to about 13% relative to the water flooding oil recovery, probably due to a synergistic effect between the nanoparticles and surfactant action at the water/oil interface. Full article

In this paper, we synthesized MC(BeA-co-MMA) copolymer microcapsules through suspension polymerization. The pendent n-behenyl group of BeA is highly crystalline, and it acts as the side-chain in the structure of BeA-co-MMA copolymer. The highly crystalline n-behenyl side-chain provides BeA-co-MMA copolymer thermal-energy-storage capacity. In order to investigate the correlation between the thermal properties and crystal structure of the BeA-co-MMA copolymer, the effects of monomer ratio, temperature changing and the changing rate, as well as synthesis method were discussed. The monomer ratio influenced crystal transition behavior and thermal properties greatly. The DSC results proved that when the monomer ratio of BeA and MMA was 3:1, MC(BeA-co-MMA)3 showed the highest average phase change enthalpy ΔH (105.1 J·g^–1). It indicated that the n-behenyl side-chain formed a relatively perfect crystal region, which ensured a high energy storage capacity of the copolymer. All the DSC and SAXS results proved that the amount of BeA had a strong effect on the thermal-energy-storage capacity of the copolymer and the long spacing of crystals, but barely on the crystal lamella. It was found that MMA units worked like defects in the n-behenyl side-chain crystal structure of the BeA-co-MMA copolymer. Therefore, a lower fraction of MMA, that is, a higher fraction of BeA, contributed to a higher crystallinity of the BeA-co-MMA copolymer, providing a better energy storage capacity and thermoregulation property. ST(BeA-co-MMA) copolymer sheets with the same ingredients as microcapsules were also prepared through light-induced polymerization aiming at clarifying the effect of the synthesis method. The results proved that the synthesis method mainly influenced the copolymer chemical component, but lightly on the crystal packing of the n-behenyl side-chain. Full article

Coarse wool is a kind of goat wool that is difficult to further process in the textile industry due to its large diameter, dispersion, better strength, and less bending. Therefore, coarse wool is often discarded as waste or made into low-cost products. In this work, keratin was extracted from coarse wool by a high-efficiency method, and then, an Ag-doped keratin/PA6 composite nanofiber membrane with enhanced filtration and antibacterial performance was prepared using HCOOH as solvent and reductant. HAADF-STEM (high-angle annular dark field-scanning transmission electron microscopy) shows that AgNPs are uniformly distributed in keratin/PA6 (30/70) nanofibers. TGA (Thermogravimetric Analysis) and DSC (Differential Scanning Calorimetry) were employed to investigate the thermal stability of composite membranes with different keratin and AgNP contents. The present keratin as a dopant with polyamide-6 (PA6) was found not only to improve air filtration efficiency but also to enhance water–vapour transmission (WVT). The addition of the Ag nanoparticles (AgNPs) gave a strong antibacterial activity to the composite membrane against Staphylococcus aureus (99.62%) and Escherichia coli (99.10%). Bacterial filtration efficiency (BFE) of the composite membrane against S. aureus and E. coli were up to 96.8% and 95.6%, respectively. All of the results suggested a great potential for coarse wool extraction and application in the air filtration field. Full article

The cationic statistical copolymerization of n-butyl (be) and 2-chloroethyl vinyl ether (CEVE), is efficiently conducted using bis(η⁵-cyclopentadienyl)dimethyl zirconium (Cp₂ZrMe₂) in combination with tetrakis(pentafluorophenyl)borate dimethylanilinum salt [B(C₆F₅)₄]^–[Me₂NHPh]⁺, as an initiation system. The reactivity ratios are calculated using both linear graphical and non-linear methods. Structural parameters of the copolymers are obtained by calculating the dyad sequence fractions and the mean sequence length, which are derived using the monomer reactivity ratios. The glass transition temperatures (T_g) of the copolymers are measured by Differential Scanning Calorimetry (DSC), and the results are compared with predictions based on several theoretical models. The statistical copolymers are further employed as scaffolds for the synthesis of graft copolymers having poly(vinyl ether)s as a backbone and either poly(ε-caprolactone) (PCL) or poly(l-lactide) (PLLA) as side chains. Both the grafting “onto” and the grafting “from” methodologies are employed. The reaction sequence is monitored by Size Exclusion Chromatography (SEC), NMR and IR spectroscopies. The advantages and limitations of each approach are thoroughly examined. Full article

Boron removal was evaluated in the present work by using calcium alginate beads (CA) and a novel composite based on alginate–alumina (CAAl) as sorbents in a batch system. The effects of different parameters such as pH, temperature, contact time, and composition of alginate (at different concentrations of guluronic and mannuronic acids) on boron sorption were investigated. The results confirm that calcium alginate beads (CA) exhibited a better adsorption capacity in a slightly basic medium, and the composite alginate–alumina (CAAl) exhibited improved boron removal at neutral pH. Sorption isotherm studies were performed and the Langmuir isotherm model was found to fit the experimental data. The maximum sorption capacities were 4.5 mmol g⁻¹ and 5.2 mmol g⁻¹, using CA and CAAl, respectively. Thermodynamic parameters such as change in free energy (ΔG⁰), enthalpy (ΔH⁰), and entropy (ΔS⁰) were also determined. The pseudo-first-order and pseudo-second-order rate equations (PFORE and PSORE, respectively) were tested to fit the kinetic data; the experimental results can be better described with PSORE. The regeneration of the loaded sorbents was demonstrated by using dilute HCl solution (distilled water at pH 3) as eluent for metal recovery. Full article

To improve the adsorption selectivity towards hexavalent chromium anion (Cr(VI)), surface Cr(VI)-imprinted polypropylene (PP) fibers were fabricated by the plasma-mediated grafting strategy. Hence, a non-thermal Rradio frequency discharge plasma irradiation followed by a gaseous phase grafting was used to load acrylic acid (AA) onto PP fibers, which was afterwards amidated with triethylenetetramine and subjected to imprinting with a Cr(VI) template. The plasma irradiation conditions, i.e., gas species, output power, pressure, and time, were optimized and then the influence of grafting time, pressure, and temperature on the grafting degree of AA was investigated. Scanning electron microscopy and Fourier transform infrared spectroscopy were used for the characterization of pristine and modified fibers and to confirm the synthesis success. The hydrophilicity of modified fibers was greatly improved compared with pristine PP fibers. The adsorption thermodynamics and kinetics of Cr(VI) were investigated, as well as the elution efficiency and reusability. The prepared imprinted fibers showed superior adsorption selectivity to Cr(VI) compared with non-imprinted fibers. Finally, the stability of the imprinted fibers against the oxidation ability of Cr(VI) is discussed. Full article

The performance of solar-thermal conversion systems can be improved by incorporation of encapsulated phase change materials. In this study, for the first time, Crodatherm^TM 60 as a phase change material (PCM) was successfully encapsulated within polyurea as the shell supporting material. While preparing the slurry samples, graphite nanoplatelet (GNP) sheets were also incorporated to enhance the thermal and photothermal properties of the prepared materials. The morphology and chemical properties of these capsules were characterized by scanning electron microscopy (SEM) and Fourier transform infrared (FTIR) spectrum, respectively. The results show the spherical-like and core-shell structure of capsules with an average diameter size of 3.34 μm. No chemical interaction was observed between the core and the supporting materials. The thermal characteristics of the microencapsulated PCMs (MEPCMs), analyzed by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA), indicate that the prepared samples with 0.1 weight percentage of GNP possess the latent heat of 95.5 J/g at the phase transition temperature of about 64 °C. Analyzing the rheological properties of the prepared slurry with 16 wt % of MEPCMs proves that the prepared material meet the requirements given by the heat transfer applications. The thermal storage capacity, good thermal stability, and improved photothermal performance of the prepared material make it a potential candidate for using in direct absorption solar thermal applications. Full article

Induced desquamation of urinary bladder epithelial cells, also called urothelial cells, is frequently used in studies of bladder epithelial regeneration and also in treating recurrent bacterial cystitis. Positively charged polymer chitosan is known to cause large-scale desquamation of terminally differentiated urothelial cells called umbrella cells. Aiming to compare the desquamation ability of another polycation poly-L-lysine, we studied the effect of this polymer on the functional and structural integrity of the urothelium in ex vivo and in vivo experiments. The urothelium was analyzed by measuring transepithelial electrical resistance, and the structural changes of its luminal surface were analyzed with scanning electron microscopy. The results revealed a selective and concentration-dependent desquamation effect of poly-L-lysine on superficial urothelial cells followed by quick regeneration of the urothelium, which functionally and structurally recovers in 2 to 3 h after poly-L-lysine–induced injury. Poly-L-lysine was thus proven to be a promising polymer to be used when desquamation of urothelial cells is required in basic and potentially clinical studies. Full article

Zinc can enhance osteoblastic bone formation and stimulate osteogenic differentiation, suppress the differentiation of osteoclast precursor cells into osteoclasts, and inhibit pathogenic bacterial growth in a dose-dependent manner. In this study, simonkolleite, as a novel zinc resource, was coated on poly (amino acids) (PAA) via suspending PAA powder in different concentrations of zinc chloride (ZnCl₂) solution, and the simonkolleite-coated PAA (Zn–PAA) was characterized by SEM, XRD, FT-IR and XPS. Zinc ions were continuously released from the coating, and the release behavior was dependent on both the concentration of the ZnCl₂ immersing solution and the type of soak solutions (SBF, PBS and DMEM). The Zn–PAA was cultured with mouse bone marrow stem cells (BMSCs) through Transwell^TM plates, and the results indicated that the relative cell viability, alkaline phosphatase (ALP) activity and mineralization of BMSCs were significantly higher with Zn–PAA as compared to PAA. Moreover, the Zn–PAA was cultured with RAW264.7 cells, and the results suggested an inhibiting effect of Zn–PAA on the cell differentiation into osteoclasts. In addition, Zn–PAA exhibited an antibacterial activity against both S. aureus and E. coli. These findings suggest that simonkolleite coating with certain contents could promote osteogenesis, suppress osteoclast formation and inhibit bacteria, indicating a novel way of enhancing the functionality of synthetic bone graft material and identifying the underline principles for designing zinc-containing bone grafts. Full article

Inkjet printing on polyester fabric displays versatile environmental advantages. One of the significant benefits of inkjet printing is a dramatic enhancement of the printing quality. In this study, xanthan gum—a bio-based thickening agent accompanied by several salts—was adopted for the pretreatment of polyester fabric aiming at improving the sharpness and color depth of inkjet printed patterns. The influences of four metal salts (NaCl, KCl, CaCl₂ and MgCl₂) on inkjet printing performance were studied. More importantly, a quantitative method for evaluating the sharpness of an inkjet printed pattern was established according to the characteristics of anisotropy and isotropy of diffusion and adsorption of ink droplets on a fiber surface. Results showed that xanthan gum along with a low dosage of bivalent salts can significantly improve the color depth (K/S value) and sharpness of the printed polyester fabrics. It is feasible to evaluate the sharpness of inkjet printed polyester fabrics using a five-stage system, selecting the inkjet ellipse coefficient (T) and inkjet ellipse area (S), which can provide a quantitative and rapid evaluation method for defining inkjet printing. Full article

Polydopamine microspheres (PDAMs), synthesized using a biomimetic method, were used as a matrix for polyethylene glycol (PEG) to develop a novel high-efficient form-stable phase change material (PEG/PDAM) using a simple vacuum impregnation strategy. The PDAMs were first used as a support for the organic phase change materials, and the biomimetic synthesis of the PDAMs had the advantages of easy operation, mild conditions, and environmental friendliness. The characteristics and thermal properties of the PEG/PDAMs were investigated using SEM, FTIR, XRD, TGA, DSC, and XPS, and the results demonstrated that the PEG/PDAMs possessed favourable heat storage capacity, excellent thermal stability, and reliability, and the melting and freezing latent heats of PEG/PDAM-3 reached 133.20 ± 2.50 J/g and 107.55 ± 4.45 J/g, respectively. Therefore, the PEG/PDAMs possess great potential in real-world applications for thermal energy storage. Additionally, the study on the interaction mechanism between the PEG and PDAMs indicated that PEG was immobilized on the surface of PDAMs through hydrogen bonds between the PEG molecules and the PDAMs. Moreover, the PDAMs can also be used as a matrix for other organic materials for the preparation of form-stable phase change materials. Full article

A series of poly(l-lactide)/poly(d-lactide) blended chips (LD_C), as-spun LD fibers (LD_A) and hot-drawn LD fibers (LD_H) were prepared for investigating the homocrystallization and stereocomplex crystallization behaviors of LD_A and LD_H fibers during heating. Modulated differential scanning calorimetry (MDSC), hot stage polarized microscopy (HSPM), and real-time wide-angle X-ray diffraction (WAXD) were used for studying the crystallization and melting behaviors, fiber morphology, and crystalline structure evolution of the LD_A and LD_H fibers’ homocrystals and stereocomplex crystals during heating. The molecular chain orientations of the LD_A and LD_H fibers were obtained through spinning and improved through the hot drawing processes. When the molecular chain was oriented on the fiber axis, the homocrystals and stereocomplex crystals of the fibers began to form in turn as the heating temperature exceeded the glass transition temperature of the fiber. The side-by-side packing of the molecular chains was promoted by mixing the molecular chains with the extrusion screw during the spinning process, facilitating stereocomplex crystallization. When the LD_A fiber was heated above the glass transition temperature of the fiber, movement of the fiber molecular chain—including molecular chain orientation and relaxation, as well as crystallization, melting, and recrystallization of homocrystals and stereocomplex crystals—were investigated through HSPM. MDSC and real-time WAXD were used to observe the molecular chains of the melted poly(l-lactide) and poly(d-lactide) homocrystals of the fibers rearranging and transiting to form stereocomplex crystals during heating. Full article