A large number of nano-sized oxides have been studied in the literature as fillers for polymeric membranes, such as Nafion^®. Superacidic sulfated oxides have been proposed and characterized. Once incorporated into polymer matrices, their beneficial effect on peculiar membrane properties has been demonstrated. The alteration of physical-chemical properties of composite membranes has roots in the intermolecular interaction between the inorganic filler surface groups and the polymer chains. In the attempt to tackle this fundamental issue, here we discuss, by a multi-technique approach, the properties of a nanosized sulfated titania material as a candidate filler for Nafion membranes. The results of a systematic study carried out by synchrotron X-ray diffraction, transmission electron microscopy, thermogravimetry, Raman and infrared spectroscopies are presented and discussed to get novel insights about the structural features, molecular properties, and morphological characteristics of sulphated TiO₂ nanopowders and composite Nafion membranes containing different amount of sulfated TiO₂ nanoparticles (2%, 5%, 7% w/w). Full article

This study deals with the fabrication of biodegradable porous materials from bacterial polyester, poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (P3HB3HH_x), via thermally induced phase separation. P3HB3HH_x monoliths with topological porous structure were prepared by dissolution of P3HB3HH_x in dimethyl sulfoxide (DMSO) at 85 °C and subsequent quenching. The microstructure of the resulting P3HB3HH_x monoliths was changed by the P3HB3HH_x concentration of the polymer solution. Differential scanning calorimetry and polarized optical microscope analysis revealed that the P3HB3HH_x monoliths crystallized during phase separation and the subsequent aging. The mechanical properties, such as compression modulus and stress, of the monoliths depended on the 3-hydroxyhexanoate content of P3HB3HH_x. Furthermore, the P3HB3HH_x monolith absorbed linseed oil in preference to water in a plant oil–water mixture. In combination with the biodegradable character of P3HB3HH_x, the present study is expected to contribute to the development of bio-based materials. Full article

A comprehensive understanding of the mechanical behavior of polycarbonate (PC) under high-rate loadings is essential for better design of PC products. In this work, the mechanical behavior of PC is studied during tensile loading at high strain rates, using a split Hopkinson tension bar (SHTB). A modified experimental technique based on the SHTB is proposed to perform the tension testing on PC at rates exceeding 1000 s⁻¹. The effect of strain rates on the tension stress–strain law of PC is investigated over a wide range of strain rates (0.0005–4500 s⁻¹). Based on the experiments, a physically based constitutive model is developed to describe the strain rate dependent tensile stress–strain law. The high rate tensile deformation mechanics of PC are further studied via finite element simulations using the LSDYNA code together with the developed constitutive model. Full article

Dear readers of Polymers, Finally, after an extensive voting period, we are proud to present the first winner of the Polymers Young Investigator Award to Dr. Luis M. Campos, who is an assistant professor at the Chemistry Department of Columbia University, USA.[...] Full article

“Pickering-type” emulsions were prepared using polydopamine (PDA) particles as a particulate emulsifier and n-dodecane, methyl myristate, toluene or dichloromethane as an oil phase. All the emulsions prepared were oil-in-water type and an increase of PDA particle concentration decreased oil droplet diameter. The PDA particles adsorbed to oil–water interface can be crosslinked using poly(ethylene imine) as a crosslinker, and the PDA particle-based colloidosomes were successfully fabricated. Scanning electron microscopy studies of the colloidosomes after removal of inner oil phase revealed a capsule morphology, which is strong evidence for the attachment of PDA particles at the oil–water interface thereby stabilizing the emulsion. The colloidosomes after removal of inner oil phase could retain their capsule morphology, even after sonication. On the other hand, the residues obtained after oil phase removal from the PDA particle-stabilized emulsion prepared in the absence of any crosslinker were broken into small fragments of PDA particle flocs after sonication. Full article

The objective of this study was to gain a deep understanding of composition and compatibilization effects on the properties of entirely sustainably sourced polymer blends based on polylactide (PLA) and polyamide 11 (PA11). Generally, PLA cannot challenge regular commodity polymers due to its weak thermo-mechanical properties and its poor elongation properties. With this work, however, we present a promising route to overcome these drawbacks in order to enhance the processability of PLA: blending the polymer with various compositions of other ductile biopolymers such as PA11, as well as mixing PLA/PA11 blends with various amounts of a chain extender, Joncryl ADR^®-4368, containing reactive epoxy functions, in a laboratory-scale twin-screw extruder. The effects on the rheological, morphological and mechanical properties were investigated. Results showed that a “self compatibilization” between PLA and PA11 chains can occur but it was found to be insufficient, contrary to recent work reported in the literature. The role of Joncryl as a compatibilizer for the PLA/PA11 system has been demonstrated by the significant decrease of particle size and interfacial tension as well as the improvement of ductile properties. Moreover, a new relaxation peak appeared in the relaxation spectrum, indicating the generation of a copolymer at the polymer-polymer interface. Full article

Ethylene-norbornene terpolymerization experiments using 5-alkyl-substituted norbornenes (5-pentyl-2-norbornene (C₅N) and 5-octyl-2-norbornene (C₈N)) or dicyclopentadiene (DCPD) were conducted with two ansa-metallocenes, [Zr{(η⁵-C₉H₆)₂C₂H₄}Cl2] (1) and [Zr{(η⁵-2,5-Me₂C₅H₂)₂CHEt}Cl₂] (2), activated by methylaluminoxane (MAO). The terpolymers obtained were investigated in detail by determining the microstructure and termonomer contents by ¹³C NMR, molar masses and thermal properties. Results were compared to those of ethylene (E)-norbornene (N) terpolymerizations with 1-octene. 2, with lower steric hindrance and a shorter bridge, gave the best activities, termonomer incorporation and molar masses. The size of the substituent in 5-alkyl substituted norbornene also plays a role. C₈N gives the highest activities and molar masses, while DCPD terpolymers have the highest cycloolefin content. Terpolymers are random; their molar masses, much higher than those in 1-octene terpolymers, are in a range useful for industrial applications. Finally, T_g values up to 152 °C were obtained. For similar N content, poly(E-ter-N-ter-C₈N)s and poly(E-ter-N-ter-DCPD)s have the lowest and the highest T_g values, respectively. Thus, the presence of an eight-carbon atom pendant chain in C₈N increases the flexibility of the polymer chain more than a five-carbon atom pendant chain in C₅N. The higher rigidity of C₅N may lead to lower activities and to increasing probability of σ-bond metathesis and chain termination, as evidenced by chain-end group analysis. Full article

The effect of acidic ionic liquid (IL) as a new catalyst on the properties of wood-based panels bonded with urea-glyoxal (UG) resins was investigated. Different levels of N-methyl-2-pyrrolidone hydrogen sulfate ([HNMP] HSO₄ (0, 1, 2, 3 wt %)) were added to prepared UG resin. The resin was then used for preparing laboratory particleboard panels. Then, the properties of the prepared panels were evaluated. The structure of the prepared UG resin was studied by ¹³C NMR, and thermal curing behavior of the resin before and after the addition of IL was measured by DSC. Additionally, the main oligomers formed in the UG reaction were identified by matrix-assisted laser desorption/ionization time-of-flight (MALDI TOF) mass spectroscopy. The results indicated that IL can be used as an efficient catalyst for UG resin. The physicochemical tests indicated that the addition of [HNMP] HSO₄ from 0 to 3 wt % decreased the pH value of the glue-mix, and the pH decreased on curing to the same level as urea-formaldehyde resins. The gel accelerated with increasing catalyst content and with the decreasing of the pH in the UG resin. The panels prepared with IL had higher mechanical strength and dimensional stability compared to those made from UG resins containing NH₄Cl. Scanning electron microscope (SEM) micrographs showed that the panels prepared with ionic liquid presented low porous. DSC analysis showed that the addition of IL to the UG resin decrease the energy of activation of the curing reaction to render possible cross-linking. The MALDI TOF results indicated a preponderant linearity of the oligomers formed, implying a high energy of activation of curing for UG resins. Full article

In this contribution, high ortho novolac resins modified with phenylboronic acid were synthesized. The thermal stability of novolac resins cured with hexamethylenetetramine (HMTA) and chemical states of B and N via a pyrolysis process were studied. For the cured o-novolac modified with phenylboronic acid, the temperature with maximum decomposition rate increased by 43.5 °C, and the char yield increased by 5.3% at 800 °C compared with cured o-novolac. Density functional theory (DFT) calculations show the existence of hydrogen bonding between N of HMTA and H of phenol in modified resin. Thus, N could still be found at high temperature and C=N structure could be formed via a pyrolysis process. B₂O₃ was obtained at 400 °C by the cleavage of B–O–C and B–C bonds and it reduces the oxygen loss which may take part in the formation of carbon oxides in the system. The melting B₂O₃ on the surface of the resin will prevent small molecules and carbon oxides from releasing. Moreover, introducing B into the system helps to decrease the interlayer distance and improve graphite structures via a pyrolysis process. Full article

Functional artificial vascular meshes from biodegradable polymers have been widely explored for certain tissue engineered meshes. Still, the foreign body reaction and limitation in endothelialization are challenges for such devices. Here, degradable meshes from phase-segregated multiblock copolymers consisting of poly(ε-caprolactone) (PCL) and polydepsipeptide segments are successfully prepared by electrospinning and electrospraying techniques. The pEGFP-ZNF580 plasmid microparticles (MPs-pZNF580) were loaded into the electrospun meshes to enhance endothelialization. These functional meshes were evaluated in vitro and in vivo. The adhesion and proliferation of endothelial cells on the meshes were enhanced in loaded mesh groups. Moreover, the hemocompatibility and the tissue response of the meshes were further tested. The complete tests showed that the vascular meshes modified with MPs-pZNF580 possessed satisfactory performance with an average fiber diameter of 550 ± 160 nm, tensile strength of 27 ± 3 MPa, Young’s modulus of 1. 9 ± 0.2 MPa, water contact angle of 95° ± 2°, relative cell number of 122% ± 1% after 7 days of culture, and low blood platelet adhesion as well as weak inflammatory reactions compared to control groups. Full article

Uniform small-sized (<10 μm) Konjac glucomanna (KGM) microspheres have great application prospects in bio-separation, drug delivery and controlled release. Premix membrane emulsification is an effective method to prepare uniform small-sized KGM microspheres. However, since KGM solution bears strong alkalinity, it requires the membrane to have a hydrophobic surface resistant to alkali. In this study, uniform small-sized KGM microspheres were prepared with epoxy-based polymer membrane (EP) we developed by premix membrane emulsification. It was found that emulsion coalescence and flocculation occurred frequently due to the high interface energy and sedimentation velocity of KGM emulsions. Emulsion stability had a significant influence on the uniformity and dispersity of the final KGM microspheres. To improve the stability of the emulsions, the effects of the concentration of the emulsifier, the viscosity of the KGM solution, the oil phase composition and the feeding method of epoxy chloropropane (EC) on the preparation results were studied. Under optimal preparation conditions (emulsifier 5 wt % PO-5s, KGM III (145.6 mPa·s), weight ratio of liquid paraffin (LP) to petroleum ether (PE) 11:1), uniform and stable KGM emulsions (d = 7.47 μm, CV = 15.35%) were obtained and crosslinked without emulsion-instable phenomena. Full article