Polymers, Volume 11, Issue 2 (February 2019) – 200 articles

In this study, a long carbon chain dimer acid is introduced into a nylon 6 structure and is copolymerized with different structural amines to produce amorphous nylon 6 by 4,4′-methylenebis(2-methylcyclohexylamine) (MMCA) in different copolymerization ratios. The effect of different structures and copolymerization ratios on the properties of nylon 6 is determined, along with the thermal properties, crystallinity, water absorption, dynamic mechanical properties, and optical properties. It is found that the melting point and the thermal cracking temperature Td10 of nylon 6 are respectively between 176 °C and 213 °C and 378 °C to 405 °C. The effect of introducing a bicyclohexane group containing a methyl side chain is greater than that of a meta-benzene ring, so COMM (synthesized by Caprolactam (C), dimer oleic acid (OA), and 4,4′-Methylenebis(2-methylcyclohexylamine) (MMCA)) has the lowest melting point, enthalpy, and crystallinity. As the copolymerization ratio increases, its thermal properties decrease. 10% is the lowest crystallinity. The amine structure containing a bicycloalkyl group has lower water absorption and a 10% copolymerization ratio gives the lowest water absorption. It contains the bicycloalkyl group, COM (synthesized by Caprolactam (C), dimer oleic acid (OA) and 4,4′-Methylenebis(cyclohexylamine) (MCA)), which has the highest loss modulus. The lowest loss modulus is noted for a copolymerization ratio of 7% and the value of tan δ increases as the copolymerization ratio increases. The introduction of nylon 6 with the bicycloalkyl groups, COMM and COM, significantly increases transparency. As the copolymerization ratio increases, the transparency increases and the haze decreases. The best optical properties are achieved for 10% copolymerization. Full article

To reduce the intense terahertz (THz) wave absorption of water and increase the signal-to-noise ratio, the THz spectroscopy detection of biomolecules usually operates using the nanofluidic channel technologies in practice. The effects of confinement due to the existence of nanofluidic channels on the conformation and dynamics of biomolecules are well known. However, studies of confinement effects on the THz spectra of biomolecules are still not clear. In this work, extensive all-atom molecular dynamics simulations are performed to investigate the THz spectra of the glycine oligopeptide solutions in free and confined environments. THz spectra of the oligopeptide solutions confined in carbon nanotubes (CNTs) with different radii are calculated and compared. Results indicate that with the increase of the degree of confinement (the reverse of the radius of CNT), the THz absorption coefficient decreases monotonically. By analyzing the diffusion coefficient and dielectric relaxation dynamics, the hydrogen bond life, and the vibration density of the state of the water molecules in free solution and in CNTs, we conclude that the confinement effects on the THz spectra of biomolecule solutions are mainly to slow down the dynamics of water molecules and hence to reduce the THz absorption of the whole solution in confined environments. Full article

Flexible white organic light-emitting diodes (FWOLEDs) have considerable potential to meet the rapidly growing requirements of display and lighting commercialization. To achieve high-performance FWOLEDs, (i) the selection of effective flexible substrates, (ii) the use of transparent conducting electrodes, (iii) the introduction of efficient device architectures, and iv) the exploitation of advanced outcoupling techniques are necessary. In this review, recent state-of-the-art strategies to develop FWOLEDs have been summarized. Firstly, the fundamental concepts of FWOLEDs have been described. Then, the primary approaches to realize FWOLEDs have been introduced. Particularly, the effects of flexible substrates, conducting electrodes, device architectures, and outcoupling techniques in FWOLEDs have been comprehensively highlighted. Finally, issues and ways to further enhance the performance of FWOLEDs have been briefly clarified. Full article

In this paper, we present our work on high-efficiency multi-junction polymer and hybrid solar cells. The transfer matrix method is used for optical modeling of an organic solar cell, which was inspired by the McGehee Group in Stanford University. The software simulation calculates the optimal thicknesses of the active layers to provide the best short circuit current (J_SC) value. First, we show three designs of multi-junction polymer solar cells, which can absorb sunlight beyond the 1000 nm wavelengths. Then we present a novel high-efficiency hybrid (organic and inorganic) solar cell, which can absorb the sunlight with a wavelength beyond 2500 nm. Approximately 12% efficiency was obtained for the multi-junction polymer solar cell and 20% efficiency was obtained from every two-, three- and four-junction hybrid solar cell under 1 sun AM1.5 illumination. Full article

The effect of hydration in corona layer on temperature responsiveness of polymer micelles consisting of poly(N-vinyl pyrrolidone)-block-poly(n-octadecyl acrylate) (PVP-b-PODA) was investigated. Small-angle X-ray scattering and dynamic light scattering showed two-step shape change of PVP-b-PODA micelles around 45 and 65 °C with elevating temperature, although only one-step shape change was observed at 45 °C in cooling process. In the first step, shape of PVP-b-PODA micelles was changed from disk to ellipsoidal oblate at the melting temperature (T_m) of PODA, although similar micelles consisting of another amphiphilic block copolymers containing PODA simply changed from disk to sphere at the T_m with elevating temperature. PVP-b-PODA micelles changed to spherical shape above 65 °C. Two-dimensional (2D) ¹H-NMR showed the PVP chains were perfectly dehydrated above 65 °C. Therefore, it was suggested that the appearance of ellipsoidal shape between T_m of PODA and 65 °C was caused owing to shape memory effect of pseudo network of corona layer due to robust hydration of PVP chains. Full article

Delayed crosslinking polymer gel systems are widely utilized in deep profile control processes for water production control in oilfields. In this paper, a kind of delayed crosslinking amphiphilic polymer gel system with adjustable gelation time based on competitive inclusion was prepared and its delayed crosslinking gelling properties were studied. The amphiphilic polymer of P(acrylamide (AM)–sodium acrylate (NaA)–N-dodecylacrylamide (DDAM)) was synthesized and it showed much better salt resistance, temperature resistance, and shear resistance performance compared with hydrolyzed polyacrylamide (HPAM). Phenol can be controlled released from the the cavity of β-cyclodextrin (β-CD) ring in the presence of the hydrophobic group used as the competitive inclusion agent in the amphiphilic polymer backbone. Accordingly, the gelation time of the delayed crosslinking amphiphilic polymer gel system is closely related to release rate of the crosslinker from the the cavity of β-CD ring. This study screened an amphiphilic polymer with good salt resistance and temperature resistance performance, which can be used in high temperature and high salinity reservoirs, and provided a feasible way to control the gelation time of the polymer gel system by the competitive inclusion method. Full article

The flame retardant modification of epoxy (EP) is of great signification for aerospace, automotive, marine, and energy industries. In this study, a series of EP composites containing different variations of phosphorus-containing polysulfone (with a phosphorus content of approximately 1.25 wt %) were obtained. The obtained EP/polysulfone composites had a high glass transition temperature (T_g) and high flame retardancy. The influence of phosphorus-containing compounds (ArPN₂, ArPO₂, ArOPN₂ and ArOPO₂) on the thermal properties and flame retardancy of EP/polysulfone composites was investigated by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), a UL-94 vertical burning test, and cone calorimeter tests. The phosphorus-containing polysulfone enhanced the thermal stability of EP. The more stable porous char layer, less flammable gases, and a lower apparent activation energy at a high degree of conversion demonstrated the high gas inhibition effect of phosphorus-containing compounds. Moreover, the gas inhibition effect of polysulfone with a P–C bond was more efficient than the polysulfone with a P–O–C bond. The potential for optimizing flame retardancy while maintaining a high T_g is highlighted in this study. The flame-retardant EP/polysulfone composites with high thermal stability broaden the application field of epoxy. Full article

The use of biocompatible polymers such as Hydroxypropylmethylcellulose (HPMC), Hydroxyethylcellulose (HEC), Carboxymethylcellulose (CMC), and Carbopol in solid formulations results in mucoadhesive systems capable of promoting the prolonged and localized release of Active Pharmaceutical Ingredients (APIs). This strategy represents a technological innovation that can be applied to improving the treatment of oral infections, such as oral candidiasis. Therefore, the aim of this study was to develop a tablet of Ximenia americana L. from mucoadhesive polymers for use in the treatment of oral candidiasis. An X. americana extract (MIC of 125 μg·mL⁻¹) was obtained by turbolysis at 50% of ethanol, a level that demonstrated activity against Candida albicans. Differential Thermal Analysis and Fourier Transform Infrared Spectroscopy techniques allowed the choice of HPMC as a mucoadhesive agent, besides polyvinylpyrrolidone, magnesium stearate, and mannitol to integrate the formulation of X. americana. These excipients were granulated with an ethanolic solution 70% v/v at PVP 5%, and a mucoadhesive tablet was obtained by compression. Finally, mucoadhesive strength was evaluated, and the results demonstrated good mucoadhesive forces in mucin disk and pig buccal mucosa. Therefore, the study allowed a new alternative to be developed for the treatment of buccal candidiasis, one which overcomes the inconveniences of common treatments, costs little, and facilitates patients’ adhesion. Full article

Surface functionalization introduced by precisely-defined surface structures depended on the surface texture and quality. Laser treatment is an advanced, non-contact technique for improving the biomaterials surface characteristics. In this study, femtosecond laser modification was applied to fabricate diverse structures on biodegradable polymer thin films and their ceramic blends. The influences of key laser processing parameters like laser energy and a number of applied laser pulses (N) over laser-treated surfaces were investigated. The modification of surface roughness was determined by atomic force microscopy (AFM). The surface roughness (R_rms) increased from approximately 0.5 to nearly 3 µm. The roughness changed with increasing laser energy and a number of applied laser pulses (N). The induced morphologies with different laser parameters were compared via Scanning electron microscopy (SEM) and confocal microscopy analysis. The chemical composition of exposed surfaces was examined by FTIR, X-ray photoelectron spectroscopy (XPS), and XRD analysis. This work illustrates the capacity of the laser microstructuring method for surface functionalization with possible applications in improvement of cellular attachment and orientation. Cells exhibited an extended shape along laser-modified surface zones compared to non-structured areas and demonstrated parallel alignment to the created structures. We examined laser-material interaction, microstructural outgrowth, and surface-treatment effect. By comparing the experimental results, it can be summarized that considerable processing quality can be obtained with femtosecond laser structuring. Full article

Several types of polyaniline (PANI) and polypyrrole (Ppy) nanocomposites with embedded glucose oxidase (GOx) and gold nanoparticles (AuNPs) were formed by enzymatic polymerization of corresponding monomers (aniline and pyrrole) in the presence of 6 and 13 nm diameter colloidal gold nanoparticles (AuNPs_(6nm) or AuNPs_(13nm), respectively) or chloroaurate ions (AuCl₄⁻). Glucose oxidase in the presence of glucose generated H₂O₂, which acted as initiator of polymerization reaction. The influence of polymerization bulk composition and pH on the formation of PANI- and Ppy-based nanocomposites was investigated spectrophotometrically. The highest formation rate of PANI- and Ppy-based nanocomposites with embedded glucose oxidase and gold nanoparticles (PANI/AuNPs-GOx and Ppy/AuNPs-GOx, respectively) was observed in the solution of sodium acetate buffer, pH 6.0. It was determined that the presence of AuNPs or AuCl₄⁻ ions facilitate enzymatic polymerization of aniline and pyrrole. Full article

We have recently solved the tumbling-snake model for concentrated polymer solutions and entangled melts in the academic case of a monodisperse sample. Here, we extend these studies and provide the stationary solutions of the tumbling-snake model both analytically, for small shear rates, and via Brownian dynamics simulations, for a bidisperse sample over a wide range of shear rates and model parameters. We further show that the tumbling-snake model bears the necessary capacity to compare well with available linear and non-linear rheological data for bidisperse systems. This capacity is added to the already documented ability of the model to accurately predict the shear rheology of monodisperse systems. Full article

Methylsilsesquioxane (MSQ) aerogels with uniform mesopores were facilely prepared via a sol–gel process followed by microwave drying with methyltrimethoxysilane (MTMS) as a precursor, hydrochloric acid (HCl) as a catalyst, water and methanol as solvents, hexadecyltrimethylammonium chloride (CTAC) as a surfactant and template, and propylene oxide (PO) as a gelation agent. The microstructure, chemical composition, and pore structures of the resultant MSQ aerogels were investigated in detail to achieve controllable preparation of MSQ aerogels, and the thermal stability of MSQ aerogels was also analyzed. The gelation agent, catalyst, solvent, and microwave power have important roles related to the pore structures of MSQ aerogels. Meanwhile, the microwave drying method was found to not only have a remarkable effect on improving production efficiency, but also to be conducive to avoiding the collapse of pore structure (especially micropores) during drying. The resulting MSQ aerogel microwave-dried at 500 W possessed a specific surface area up to 821 m²/g and a mesopore size of 20 nm, and displayed good thermal stability. Full article

In order to enhance the interfacial adhesion of poly(p-phenylene terephthalamide) (PPTA) fibers to the rubber composites, a novel method to deposit multi-walled carbon nanotubes (MWCNTs) onto the surface of PPTA fibers has been proposed in this study. This chemical modification was performed through the introduction of epoxy groups by Friedel–Crafts alkylation on the PPTA fibers, the carboxylation of MWCNTs, and the ring-opening reaction between the epoxy groups and the carboxyl groups. The morphologies, chemical structures, and compositions of the surface of PPTA fibers were characterized by scanning electron microscope, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy. The results showed that MWCNTs were uniformly deposited onto the surface of PPTA fibers with the covalent bonds. The measurement of contact angles of the fibers with polar solvent and non-polar solvent indicated that the surface energy of deposited fibers significantly increased by 41.9% compared with the untreated fibers. An electronic tensile tester of single-filament and a universal testing machine were utilized to measure the strength change of the fibers after modification and the interfacial adhesion between the fibers and the rubber matrix, respectively. The results showed that the tensile strength had not been obviously reduced, and the pull-out force and peeling strength of the fibers to the rubber increased by 46.3% and 56.5%, respectively. Full article

A series of hybrid thermoplastic polyurethanes (PUs) were synthesized from bi-functional polyhedral oligomeric silsesquioxane (B-POSS) and polycaprolactone (PCL) using 1,6-hexamethylene diisocyanate (HDI) as a coupling agent for the first time. The newly synthesized hybrid materials were fully characterized in terms of structure, morphology, thermal and mechanical performance, as well as their toughening effect toward polyesters. Thermal gravimeter analysis (TGA) and differential scanning calorimetry (DSC) showed enhanced thermal stability by 76 °C higher in decomposition temperature (T_d) of the POSS PUs, and 22 °C higher glass transition temperature (T_g) when compared with control PU without POSS. Static contact angle results showed a significant increment of 49.8° and 53.4° for the respective surface hydrophobicity and lipophilicity measurements. More importantly, both storage modulus (G’) and loss modulus (G’’) are improved in the hybrid POSS PUs and these parameters can be further adjusted by varying POSS content in the copolymer. As a biodegradable hybrid filler, the as-synthesized POSS PUs also demonstrated a remarkable effect in toughening commercial polyesters, indicating a simple yet useful strategy in developing high-performance polyester for advanced biomedical applications. Full article

By the addition of a carbon-based electromagnetic absorbing agent during the foaming process, a novel electromagnetic absorbent polymethacrylimide (PMI) foam was obtained. The proposed foam exhibits excellent electromagnetic wave-absorbing properties, with absorptivity exceeding 85% at a large frequency range of 4.9–18 GHz. However, its poor mechanical properties would limit its application in load-carrying structures. In the present study, a novel enhancement approach is proposed by inserting metallic tubes into pre-perforated holes of PMI foam blocks. The mechanical properties of the tube-enhanced PMI foams were studied experimentally under compressive loading conditions. The elastic modulus, compressive strength, energy absorption per unit volume, and energy absorption per unit mass were increased by 127.9%, 133.8%, 54.2%, and 46.4%, respectively, by the metallic tube filling, and the density increased only by 5.3%. The failure mechanism of the foams was also explored. We found that the weaker interfaces between the foam and the electromagnetic absorbing agent induced crack initiation and subsequent collapses, which destroyed the structural integrity. The excellent mechanical and electromagnetic absorbing properties make the novel structure much more competitive in electromagnetic wave stealth applications, while acting simultaneously as load-carrying structures. Full article

As a renewable, biocompatible, and biodegradable polysaccharide, inulin has a good solubility in water and some physiological functions. Chemical modification is one of the important methods to improve the bioactivity of inulin. In this paper, based on 6-amino-6-deoxy-3,4-acetyl inulin (3), three kinds of Schiff bases of inulin bearing pyridine rings were successfully designed and synthesized. Detailed structural characterization was carried out using FTIR, ¹³C NMR, and ¹H NMR spectroscopy, and elemental analysis. Moreover, the antifungal activity of Schiff bases of inulin against three plant pathogenic fungi, including Botrytis cinerea, Fusarium oxysporum f.sp.niveum, and Phomopsis asparagi, were evaluated using in vitro hypha measurements. Inulin, as a natural polysaccharide, did not possess any antifungal activity at the tested concentration against the targeted fungi. Compared with inulin and the intermediate product 6-amino-6-deoxy-3,4-acetyl inulin (3), all the synthesized Schiff bases of inulin derivatives with >54.0% inhibitory index at 2.0 mg/mL exhibited enhanced antifungal activity. 3NS, with an inhibitory index of 77.0% exhibited good antifungal activity against Botrytis cinerea at 2.0 mg/mL. The synthesized Schiff bases of inulin bearing pyridine rings can be prepared for novel antifungal agents to expand the application of inulin. Full article

Although the tube framework has achieved remarkable success to describe entangled polymer dynamics, the chain motion assumed in tube theories is still a matter of discussion. Recently, Xu et al. [ACS Macro Lett. 2018, 7, 190–195] performed a molecular dynamics simulation for entangled bead-spring chains under a step uniaxial deformation and reported that the relaxation of gyration radii cannot be reproduced by the elaborated single-chain tube model called GLaMM. On the basis of this result, they criticized the tube framework, in which it is assumed that the chain contraction occurs after the deformation before the orientational relaxation. In the present study, as a test of their argument, two different slip-link simulations developed by Doi and Takimoto and by Masubuchi et al. were performed and compared to the results of Xu et al. In spite of the modeling being based on the tube framework, the slip-link simulations excellently reproduced the bead-spring simulation result. Besides, the chain contraction was observed in the simulations as with the tube picture. The obtained results imply that the bead-spring results are within the scope of the tube framework whereas the failure of the GLaMM model is possibly due to the homogeneous assumption along the chain for the fluctuations induced by convective constraint release. Full article

In this study we present polymeric microneedles composed of multiple layers to control drug release kinetics. Layered microneedles were fabricated by spraying poly(lactic-co-glycolic acid) (PLGA) and polyvinylpyrrolidone (PVP) in sequence, and were characterized by mechanical testing and ex vivo skin insertion tests. The compression test demonstrated that no noticeable layer separation occurred, indicating good adhesion between PLGA and PVP layers. Histological examination confirmed that the microneedles were successfully inserted into the skin and indicated biphasic release of dyes incorporated within microneedle matrices. Structural changes of a model protein drug, bovine serum albumin (BSA), in PLGA and PVP matrices were examined by circular dichroism (CD) and fluorescence spectroscopy. The results showed that the tertiary structure of BSA was well maintained in both PLGA and PVP layers while the secondary structures were slightly changed during microneedle fabrication. In vitro release studies showed that over 60% of BSA in the PLGA layer was released within 1 h, followed by continuous slow release over the course of the experiments (7 days), while BSA in the PVP layer was completely released within 0.5 h. The initial burst of BSA from PLGA was further controlled by depositing a blank PLGA layer prior to forming the PLGA layer containing BSA. The blank PLGA layer acted as a diffusion barrier, resulting in a reduced initial burst. The formation of the PLGA diffusion barrier was visualized using confocal microscopy. Our results suggest that the spray-formed multilayer microneedles could be an attractive transdermal drug delivery system that is capable of modulating a drug release profile. Full article

Environmentally friendly food packaging currently attracts much interest. Sodium trimetaphosphate (STMP) finds specialized applications in food, but it is rarely used as a crosslinking agent. In this study, STMP was used as a crosslinking agent to prepare chitosan/methylcellulose composite films. Both antibacterial and physicochemical properties of the composite film were improved by crosslinking with STMP. The crosslinked films, with good antibacterial activity (~99%), had increased tensile strength, a higher elongation at break, a lower swelling ratio and solubility, and a lower enzymatic degradation than the non-crosslinked films. Furthermore, the crosslinked films showed an excellent preservative effect on fresh-cut wax gourd after three days at room temperature. The obtained films crosslinked by STMP can be potentially applied to the food industry, such as food functional packaging, providing a novel alternative to traditional plastic packages. Full article

Bone tissue engineering is a rapidly growing field which is currently progressing toward clinical applications. Effective imaging methods for longitudinal studies are critical to evaluating the new bone formation and the fate of the scaffolds. Computed tomography (CT) is a prevailing technique employed to investigate hard tissue scaffolds; however, the CT signal becomes weak in mainly-water containing materials, which hinders the use of CT for hydrogels-based materials. Nevertheless, hydrogels such as gelatin methacrylate (GelMA) are widely used for tissue regeneration due to their optimal biological properties and their ability to induce extracellular matrix formation. To date, gold nanoparticles (AuNPs) have been suggested as promising contrast agents, due to their high X-ray attenuation, biocompatibility, and low toxicity. In this study, the effects of different sizes and concentrations of AuNPs on the mechanical properties and the cytocompatibility of the bulk GelMA-AuNPs scaffolds were evaluated. Furthermore, the enhancement of CT contrast with the cytocompatible size and concentration of AuNPs were investigated. 3D printed GelMA and GelMA-AuNPs scaffolds were obtained and assessed for the osteogenic differentiation of mesenchymal stem cells (MSC). Lastly, 3D printed GelMA and GelMA-AuNPs scaffolds were scanned in a bone defect utilizing µCT as the proof of concept that the GelMA-AuNPs are good candidates for bone tissue engineering with enhanced visibility for µCT imaging. Full article

This paper deals with a comparative study on the interpolymeric complexes of alginate poly(N-isopropyl acryl amide (PNIPAAm) and corresponding graft copolymers with various compositions in respect to their toxicity, biocompatibility and in vitro and in vivo release of theophylline (THP). Loading of the various matrices with theophylline and characterization of loaded matrices was studied by near infrared spectroscopy–chemical imaging (NIR–CI) analysis, scanning electron microscopy (SEM) and thermogravimetric analysis (TGA). It was appreciated that THP loading is higher than 40% and the drug is relatively homogeneous distributed within all matrices because of some specific interactions between components of the system. All samples have been found to be non-toxic and biocompatible. It was established that graft copolymers having a good stability show a better drug carrier ability, a higher THP loading, a prolonged release (longer release duration for graft copolymers of 235.4–302.3 min than that for IPC 72/28 of 77.6 min, which means approximately four times slower release from the graft copolymer-based matrices than from the interpolymeric complex) and a good bioavailability. The highest values for THP loading (45%), prolonged release (302.3 min) and bioavailability (175%) were obtained for graft copolymer AgA-g-PNIPAAm 68. The drug release mechanism varies with composition and architecture of the matrix. Full article

To find the effects of cross-linker phenol-formaldehyde (PF) resin on the performance of soy-based adhesives, the reaction between model compounds hydroxymethyl phenol (HPF) and glutamic acid were studied in this paper. HPF prepared in laboratory conditions showed higher content of hydroxymethyl groups than normal PF resin, which was proved by the results of Electrospray Ionization Mass Spectrometry (ESI-MS) and ¹³C Nuclear Magnetic Resonance (¹³C-NMR). The results of ESI-MS, Fourier transform infrared spectroscopy (FT-IR), and ¹³C-NMR based on resultant products obtained from model compounds showed better water resistance of the soy protein-based adhesive modified by PF-based resin, which indicated the reaction between PF resin and soy protein. However, it seemed that the soy-based adhesive cross-linked by HPF with the maximum content of hydroxymethyl groups did not show the best water resistance. Full article

In this work, a nylon 6 nanofibrous membrane was prepared via solution blowing technology and followed hot-press as scaffold for nanofiltration. The structure and properties of the hot-pressed nylon 6 nanofibrous membrane (HNM) were studied the effect of hot-pressing parameters and areal densities. Then an ultra-thin polyamide (PA) active layer was prepared by interfacial polymerization on HNM. The effects of nanofibrous scaffolds on the surface properties of ultra-thin nanofiltration membranes and their filtration performance were studied. Results showed that the nylon 6 nanofibers prepared at a concentration of 15 wt % had a good morphology and diameter distribution and the nanofibers were stacked more tightly and significantly reduced in diameter after hot pressing at 180 °C under the pressure of 15 MPa for 10 s. When the porous scaffold was prepared, HNM with an areal density of 9.4 and 14.1 g/m² has a better apparent structure, a smaller pore size, a higher porosity and a greater strength. At the same time, different areal densities of HNM have an important influence on the preparation and properties of nanofiltration membranes. With the increase of areal density, the uniformity of HNM increased while their surface roughness and pore size decreased, which is beneficial to the establishment of PA barrier layer. With areal density of 9.4 and 14.1 g/m², the as-prepared nanofiltration membrane has a smoother surface and more outstanding filtration performance. The pure water flux is 13.1 L m⁻² h⁻¹ and the filtration efficiencies for NaCl and Na₂SO₄ are 81.3% and 85.1%, respectively. Full article

Thermal degradation detection of cured epoxy resins and composites is currently limited to severe thermal damage in practice. Evaluating the change in mechanical properties after a short-time thermal exposure, as well as estimating the history of thermally degraded polymers, has remained a challenge until now. An approach to accurately predict the mechanical properties, as well as the thermal exposure time and temperature of epoxy resin, using Fourier-transform infrared spectroscopy (FTIR)-spectroscopy, data processing, and artificial neural networks, is presented here. Therefore, an epoxy resin has been fully cured and exposed to elevated temperatures for different time periods. A FTIR-spectrometer was used to measure molecular changes, using mid-IR (MIR)-FTIR for film samples and near-IR (NIR)-FTIR for bulk samples. A quantitative analysis of the thermally degraded film samples shows oxidation, chain-scission, and dehydration in the FTIR spectra in the MIR-range. Using NIR spectroscopy for the bulk samples, only minor changes in the FTIR spectra could be detected. However, using data processing, molecular information was extracted from the NIR range and a degradation model, using an artificial neural network, has been trained. Even though the changes due to thermal exposure were small, the presented model is capable of accurately predicting the time, temperature, and residual strength of the polymer. Full article

Today, the application of polyaniline in biomedicine is widely discussed. However, information about impurities released from polyaniline and about the cytotoxicity of its precursors aniline, aniline hydrochloride, and ammonium persulfate are scarce. Therefore, cytotoxicity thresholds for the individual precursors and their combinations were determined (MTT assay) and the type of cell death caused by exposition to the precursors was identified using flow-cytometry. Tests on fibroblasts revealed higher cytotoxicity of ammonium persulfate than aniline hydrochloride. Thanks to the synergic effect, both monomers in combination enhanced their cytotoxicities compared with individual substances. Thereafter, cytotoxicity of polyaniline doped with different acids (sulfuric, nitric, phosphoric, hydrochloric, and methanesulfonic) was determined and correlated with impurities present in respective sample (HPLC). The lowest cytotoxicity showed polyaniline doped with phosphoric acid (followed by sulfuric, methanesulfonic, and nitric acid). Cytotoxicity of polyaniline was mainly attributed to the presence of residual ammonium persulfate and low-molecular-weight polar substances. This is crucial information with respect to the purification of polyaniline and production of its cytocompatible form. Full article

A triptycene-based diamine, 1,3,6,8-tetramethyl-2,7-diamino-triptycene (TMDAT), was used for the synthesis of a novel solution-processable polyamide obtained via polycondensation reaction with 4,4′-(hexafluoroisopropylidene)bis(benzoic acid) (6FBBA). Molecular simulations confirmed that the tetrasubstitution with ortho-methyl groups in the triptycene building block reduced rotations around the C–N bond of the amide group leading to enhanced fractional free volume. Based on N₂ sorption at 77 K, 6FBBA-TMDAT revealed microporosity with a Brunauer–Emmett–Teller (BET) surface area of 396 m² g⁻¹; to date, this is the highest value reported for a linear polyamide. The aged 6FBBA-TMDAT sample showed moderate pure-gas permeabilities (e.g., 198 barrer for H₂, ~109 for CO₂, and ~25 for O₂) and permselectivities (e.g., αH₂/CH₄ of ~50) that position this polyamide close to the 2008 H₂/CH₄ and H₂/N₂ upper bounds. CO₂–CH₄ mixed-gas permeability experiments at 35 °C demonstrated poor plasticization resistance; mixed-gas permselectivity negatively deviated from the pure-gas values likely, due to the enhancement of CH₄ diffusion induced by mixing effects. Full article

This study analyzes the fundamental principles and characteristics of the microcellular foaming process (MCP) to minimize warpage in glass fiber reinforced polymer (GFRP), which is typically worse than that of a solid polymer. In order to confirm the tendency for warpage and the improvement of this phenomenon according to the glass fiber content (GFC), two factors associated with the reduction of the shrinkage difference and the non-directionalized fiber orientation were set as variables. The shrinkage was measured in the flow direction and transverse direction, and it was confirmed that the shrinkage difference between these two directions is the cause of warpage of GFRP specimens. In addition, by applying the MCP to injection molding, it was confirmed that warpage was improved by reducing the shrinkage difference. To further confirm these results, the effects of cell formation on shrinkage and fiber orientation were investigated using scanning electron microscopy, micro-CT observation, and cell morphology analysis. The micro-CT observations revealed that the fiber orientation was non-directional for the MCP. Moreover, it was determined that the mechanical and thermal properties were improved, based on measurements of the impact strength, tensile strength, flexural strength, and deflection temperature for the MCP. Full article

In the European Union, the demand for polyurethane is continually growing. In 2017, the estimated value of polyurethane production was 700,400 Tn, of which 27.3% is taken to landfill, which causes an environmental problem. In this paper, the behaviour of various polyurethane foams from the waste of different types of industries will be analyzed with the aim of assessing their potential use in construction materials. To achieve this, the wastes were chemically tested by means of CHNS, TGA, and leaching tests. They were tested microstructurally by means of SEM. The processing parameters of the waste was calculated after identifying its granulometry and its physical properties i.e., density and water absorption capacity. In addition, the possibility of incorporating these wastes in plaster matrices was studied by determining their rendering in an operational context, finding out their mechanical resistance to flexion and compression at seven days, their reaction to fire as well as their weight per unit of area, and their thermal behaviour. The results show that in all cases, the waste is inert and does not undergo leaching. The generation process of the waste determines the foam’s microstructure in addition to its physical-chemical properties, which directly affect building materials in which they are included, thus offering different ways in which they can be applied. Full article

The kinetic behaviors of ethylene and propylene polymerizations with the same MgCl₂-supported Ziegler–Natta (Z–N) catalyst containing an internal electron donor were compared. Changes of polymerization activity and active center concentration ([C*]) with time in the first 10 min were determined. Activity of ethylene polymerization was only 25% of that of propylene, and the polymerization rate (R_p) quickly decayed with time (t_p) in the former system, in contrast to stable R_p in the latter. The ethylene system showed a very low [C*]/[Ti] ratio (<0.6%), in contrast to a much higher [C*]/[Ti] ratio (1.5%–4.9%) in propylene polymerization. The two systems showed noticeably different morphologies of the nascent polymer/catalyst particles, with the PP/catalyst particles being more compact and homogeneous than the PE/catalyst particles. The different kinetic behaviors of the two systems were explained by faster and more sufficient catalyst fragmentation in propylene polymerization than the ethylene system. The smaller lamellar thickness (<20 nm) in nascent polypropylene compared with the size of nanopores (15–25 nm) in the catalyst was considered the key factor for efficient catalyst fragmentation in propylene polymerization, as the PP lamellae may grow inside the nanopores and break up the catalyst particles. Full article

The fluidity of a molten polymer plasticized by ultrasonic vibration was characterized by spiral flow testing based on an Archimedes spiral mold with microchannels. Mold inserts with various channel depths from 250 to 750 µm were designed and fabricated to represent the size effect under micro-scale. The effect of ultrasonic plasticizing parameters and the mold temperature on the flow length was studied to determine the rheological nature of polymers and control parameters. The results showed that the flow length decreased with reduced channel depth due to the size effect. By increasing ultrasonic amplitude, ultrasonic action time, plasticizing pressure, and mold temperature, the flow length could be significantly increased for both the amorphous polymer polymethyl methacrylate (PMMA) and the semi-crystalline polymers polypropylene (PP) and polyamide 66 (PA66). The enhanced fluidity of the ultrasonic plasticized polymer melt could be attributed to the significantly reduced shear viscosity. Full article