Polymers, Volume 12, Issue 1 (January 2020) – 250 articles

Modeling and analyzing the sports equipment for injury prevention, reduction in cost, and performance enhancement have gained considerable attention in the sports engineering community. In this regard, the structure study of on-water sports board (surfboard, kiteboard, and skimboard) is vital due to its close relation with environmental and human health as well as performance and safety of the board. The aim of this paper is to advance the on-water sports board through various bio-inspired core structure designs such as honeycomb, spiderweb, pinecone, and carbon atom configuration fabricated by three-dimensional (3D) printing technology. Fused deposition modeling was employed to fabricate complex structures from polylactic acid (PLA) materials. A 3D-printed sample board with a uniform honeycomb structure was designed, 3D printed, and tested under three-point bending conditions. A geometrically linear analytical method was developed for the honeycomb core structure using the energy method and considering the equivalent section for honeycombs. A geometrically non-linear finite element method based on the ABAQUS software was also employed to simulate the boards with various core designs. Experiments were conducted to verify the analytical and numerical results. After validation, various patterns were simulated, and it was found that bio-inspired functionally graded honeycomb structure had the best bending performance. Due to the absence of similar designs and results in the literature, this paper is expected to advance the state of the art of on-water sports boards and provide designers with structures that could enhance the performance of sports equipment. Full article

Thermodynamic, structural, and transport properties of tetrabutylphosphonium hydroxide (TBPH) and tetrabutylphosphonium chloride (TBPCl)–water mixtures have been investigated using all-atom molecular dynamics simulations in response to recent experimental work showing the TBPH–water mixtures capability as a cellulose solvent. Multiple transitional states exist for the water—ionic liquid (IL) mixture between 70 and 100 mol% water, which corresponds to a significant increase in water hydrogen bonds. The key transitional region, from 85 to 92.5 mol% water, which coincides with the mixture’s maximum cellulose solubility, reveals small and distinct water veins with cage structures formed by the TBP⁺ ions, while the hydroxide and chloride ions have moved away from the P atom of TBP⁺ and are strongly hydrogen bonded to the water. The maximum cellulose solubility of the TBPH–water solution at approximately 91.1 mol% water, appears correlated with the destruction of the TBP’s interlocking structure in the simulations, allowing the formation of water veins and channeling structures throughout the system, as well as changing from a subdiffusive to a near-normal diffusive regime, increasing the probability of the IL’s interaction with the cellulose polymer. A comparison is made between the solution properties of TBPH and TBPCl with those of alkylimidazolium-based ILs, for which water appears to act as anti-solvent rather than a co-solvent. Full article

As a material for application in the life sciences, a new composite material, geopolymer/CeO₂ (GP_CeO₂), was synthesized as a potential low-cost solid electrolyte for application in solid oxide fuel cells operating in intermediate temperature (IT-SOFC). The new materials were obtained from alkali-activated metakaolin (calcined clay) in the presence of CeO₂ powders (x = 10%). Besides the commercial CeO₂ powder, as a source of ceria, two differently synthesized CeO₂ powders also were used: CeO₂ synthesized by modified glycine nitrate procedure (MGNP) and self-propagating reaction at room temperature (SPRT). The structural, morphological, and electrical properties of pure and GP_CeO₂-type samples were investigated by X-ray powder diffraction (XRPD), Fourier transform infrared (FTIR), BET, differential thermal and thermogravimetric analysis (DTA/TGA), scanning electron microscopy (FE-SEM), energy dispersive spectrometer (EDS), and method complex impedance (EIS). XRPD and matrix-assisted laser desorption and ionization time-of-flight (MALDI-TOF) analysis confirmed the formation of solid phase CeO₂. The BET, DTA/TGA, FE-SEM, and EDS results indicated that particles of CeO₂ were stabile interconnected and form a continuous conductive path, which was confirmed by the EIS method. The highest conductivity of 1.86 × 10⁻² Ω⁻¹ cm⁻¹ was obtained for the sample GP_CeO₂_MGNP at 700 °C. The corresponding value of activation energy for conductivity was 0.26 eV in the temperature range 500–700 °C. Full article

A low-water-sensitive Artemisia sphaerocephala Krasch. gum (ASKG) based intelligent film was developed. Red cabbage extracts (RCE) was selected as a natural pH-sensitive indicator, and anionic cellulose nanofiber (ACNF) was added as a hydrophobic and locking host. The zeta potential, rheology, Fourier-transform infrared spectroscopy, X-ray diffractometry, and release results indicated that the RCE was locked by the ACNF via electrostatic interactions, moreover, broke the original complicated network and ordered arrangement of polymer molecules in the developed intelligent films. RCE addition decreased the tensile strength, oxygen, and water vapor barrier properties and light transmission of the developed intelligent films, while increasing the elongation at break. The films could respond to buffer solutions and NH₃ through different color changes. The developed intelligent film was hydrophobic, which could precisely detect the freshwater shrimp freshness in real time via color changes, which indicated that the films have potential in intelligent packaging and gas-sensing label fields. Full article

This manuscript presents an experimental and numerical analysis of the mechanical structural behavior of Nylstrong GF-PA6, a plastic material manufactured using FDM (fused deposition modeling) technology for a compression uniaxial stress field. Firstly, an experimental test using several test specimens fabricated in the Z and X-axis allows characterizing the elastic behavior of the reinforced GF-PA6 according to the ISO 604 standard for uniaxial compression stress environments in both Z and X manufacturing orientations. In a second stage, an experimental test analyzes the structural behavior of an industrial part manufactured under the same conditions as the test specimens. The experimental results for the test specimens manufactured in the Z and X-axis present differences in the stress-strain curve. Z-axis printed elements present a purely linear elastic behavior and lower structural integrity, while X-axis printed elements present a nonlinear elastic behavior typical of plastic and foam materials. In order to validate the experimental results, numerical analysis for an industrial part is carried out, defining the material GF-PA6 as elastic and isotropic with constant Young’s compression modulus according to ISO standard 604. Simulations and experimental tests show good accuracy, obtaining errors of 0.91% on the Z axis and 0.56% on the X-axis between virtual and physical models. Full article

Paper recycling has increased in recent years. A principal consequence of this process is the problem of addressing some polymeric components known as stickies. A deep characterization of stickies sampled over one year in a recycled paper industry in México was performed. Based on their chemical structure, an enzymatic assay was performed using lipases. Compounds found in stickies by Fourier-transform infrared spectrometry were poly (butyl-acrylate), dioctyl phthalate, poly (vinyl-acetate), and poly (vinyl-acrylate). Pulp with 4% (w/w) consistency and pH = 6.2 was sampled directly from the mill once macrostickies were removed. Stickies were quantified by counting the tacky macrostructures in the liquid fraction of the pulp using a Neubauer chamber before the paper was made, and they were analyzed with rhodamine dye and a UV lamp. Of the two commercial enzymes evaluated, the best treatment condition used Lipase 30 G (Specialty Enzymes & Biotechnologies Co^®, Chino, CA, USA) at a concentration of 0.44 g/L, which decreased 35.59% of stickies. SebOil DG (Specialty Enzymes & Biotechnologies^®) showed a stickies reduction of 21.5% when used at a concentration of 0.33 g/L. Stickies in kraft paper processes were actively controlled by the action of lipases, and future research should focus on how this enzyme recognizes its substrate and should apply synthetic biology to improve lipase specificity. Full article

An insulated metallopolymer that undergoes phosphorescence-to-fluorescence conversion between complementary colors by an acid-stimulus is proposed as a color-tunable material. A Pt-based phosphorescent metallopolymer, where the conjugated polymeric backbone is insulated by a cyclodextrin, is depolymerized by HCl via acidic cleavage of Pt-acetylide bonds to form a fluorescent monomer. The insulation enables phosphorescence-to-fluorescence conversion to take place in the solid film. Rapid color change was achieved by accelerating the reaction between the metallopolymer and HCl by UV irradiation. These approaches are expected to provide new guidelines for the development of next-generation color-tunable materials and printable sensors based on precise molecular engineering. Full article

This study aimed to fabricate core/sheath-structured composite nanofibers containing cinnamon oil by emulsion electrospinning and to investigate their acaricidal effect on house dust mites as well as their antibacterial and antifungal properties in relation to cinnamon oil concentration in the nanofibers. An oil-in-water emulsion, which comprised cinnamon oil and poly(vinyl alcohol) solution as oil and water phases, respectively, was used to prepare core/sheath-structured nanofibers. The morphology and the inner structure of the electrospun nanofibers were observed by scanning electron microscopy and confocal laser scanning microscopy. Core/sheath-structured nanofibers containing cinnamon oil were successfully prepared by emulsion electrospinning. The composite nanofibers prepared from an emulsion containing 20 wt% of cinnamon oil exhibited a strong acaricidal effect against house dust mites (Dermatophagoides farinae). The composite nanofibers fabricated from an emulsion containing 4.29 wt% of cinnamon oil showed excellent antimicrobial effects against Staphylococcus aureus and a series of fungi that can trigger respiratory- and skin-related diseases. The release profile of cinnamon oil from the core/sheath-structured nanofibers showed a continuous release of functional ingredients over 28 days. Our findings demonstrate that the use of such fibrous structures could be a promising approach for delivering naturally derived bioactive agents in a controlled way. Full article

The study of laser processing of acrylic intra-ocular lenses (IOL) by using femtosecond laser pulses delivered at high-repetition rate is presented in this work. An ultra-compact air-cooled femtosecond diode laser (HighQ2-SHG, Spectra-Physics) delivering 250 fs laser pulses at the fixed wavelength of 520 nm with a repetition rate of 63 MHz was used to process the samples. Laser inscription of linear periodic patterns on the surface and inside the acrylic substrates was studied as a function of the processing parameters as well as the optical absorption characteristics of the sample. Scanning Electron Microscopy (SEM) Energy Dispersive X-ray Spectroscopy (EDX), and micro-Raman Spectroscopy were used to evaluate the compositional and microstructural changes induced by the laser radiation in the processed areas. Diffractive characterization was used to assess 1st-order efficiency and the refractive index change. Full article

Excellent quadratic non-linear optical (ONL-2) properties of the poly(2,5-bis(but-2-ynyloxy) benzoate, containing a polar diacetylene as a chromophore, were found. According with the Maker fringes method, oriented polymer films showing an order parameter of ∼0.23 can display outstanding and stable Second Harmonic Generation (SHG) effects under off-resonant conditions (SHG-532 nm). Also, the macroscopic non-linear optical (NLO)-coefficients were evaluated under the rod-like molecular approximation, obtaining: χ_zzz⁽²⁾ and χ_zxx⁽²⁾ in the order of 280 ± 10 and 100 ± 10 pm V⁻¹, respectively. The mechanical and chemical properties, in addition to the large ONL-2 coefficients exhibited by this polymer, make it a promising organic material in the development of optoelectronic/photonic devices. Full article

Antibiotic resistance of bacteria stimulates the development of new treatment approaches. Piezoelectric-catalysis has attracted much attention due to the possibility to effectively provide antibacterial effect via generation of reactive oxygen species. However, the influence of the surface charge or potential of a piezopolymer on bacteria has not been sufficiently studied so far. This study reports the fabrication and characterization of thin films of piezoelectric polyhydroxybutyrate, polyvinylidene fluoride, and polyvinylidene fluoride trifluoroethylene as well as non-piezoelectric polycaprolactone polymers fabricated using solution casting approach. The piezoelectric coefficient (d₃₃) and surface electric peak-to-peak potential generated by the cyclic mechanical stress applied to the films were measured. Neither any toxic effect of the polymer films nor ultrasound influence on Escherichia coli bacteria behavior is observed. However, significant inhibition of the growth of bacteria is revealed during mechanical stimulation of piezoelectric samples via ultrasound treatment. Thus, this study demonstrates clear bacteriostatic effect of piezoelectric polymers for different tissue engineering applications. Full article

Commonly synthetic polyethylene glycol polyurethane (PEG–PU) hydrogels possess poor mechanical properties, such as robustness and toughness, which limits their load-bearing application. Hence, it remains a challenge to prepare PEG–PU hydrogels with excellent mechanical properties. Herein, a novel double-crosslinked (DC) PEG–PU hydrogel was fabricated by combining chemical with physical crosslinking, where trimethylolpropane (TMP) was used as the first chemical crosslinker and polyphenol compound tannic acid (TA) was introduced into the single crosslinked PU network by simple immersion process. The second physical crosslinking was formed by numerous hydrogen bonds between urethane groups of PU and phenol hydroxyl groups in TA, which can endow PEG–PU hydrogel with good mechanical properties, self-recovery and a self-healing capability. The research results indicated that as little as a 30 mg·mL⁻¹ TA solution enhanced the tensile strength and fracture energy of PEG–PU hydrogel from 0.27 to 2.2 MPa, 2.0 to 9.6 KJ·m⁻², respectively. Moreover, the DC PEG–PU hydrogel possessed good adhesiveness to diverse substrates because of TA abundant catechol groups. This work shows a simple and versatile method to prepare a multifunctional DC single network PEG–PU hydrogel with excellent mechanical properties, and is expected to facilitate developments in the biomedical field. Full article

With the per capita growth of energy demand, there is a significant need for alternative and sustainable energy resources. Efficient electrochemical catalysis will play an important role in sustaining that need, and nanomaterials will play a crucial role, owing to their high surface area to volume ratio. Electrospun nanofiber is one of the most promising alternatives for producing such nanostructures. A section of key nano-electrocatalysts comprise of transition metals (TMs) and their derivatives, like oxides, sulfides, phosphides and carbides, etc., as well as their 1D composites with carbonaceous elements, like carbon nanotubes (CNTs) and carbon nanofiber (CNF), to utilize the fruits of TMs’ electronic structure, their inherent catalytic capability and the carbon counterparts’ stability, and electrical conductivity. In this work, we will discuss about such TM derivatives, mostly TM-based ceramics, grown on the CNF substrates via electrospinning. We will discuss about manufacturing methods, and their electrochemical catalysis performances in regards to energy conversion processes, dealing mostly with water splitting, the metal–air battery fuel cell, etc. This review will help to understand the recent evolution, challenges and future scopes related to electrospun transition metal derivative-based CNFs as electrocatalysts. Full article

In this study, feather was used as the source of protein and combined with copper and boron salts to prepare wood preservatives with nano-hydroxyapatite or nano-graphene oxide as nano-carriers. The treatability of preservative formulations, the changes of chemical structure, micromorphology, crystallinity, thermal properties and chemical composition of wood cell walls during the impregnation and decay experiment were investigated by retention rate of the preservative, Fourier transform infrared spectroscopy (FT-IR), scanning electronic microscopy-energy dispersive spectrometer (SEM-EDS), X-ray diffraction (XRD), thermoanalysis (TG), and confocal Raman microscopy (CRM) techniques. Results revealed that the preservatives (particularly with nano-carrier) successfully penetrated wood blocks, verifying the enhanced effectiveness of protein-based preservative with nano-carrier formulations. Decay experiment demonstrated that the protein-based wood preservative can remarkably improve the decay resistance of the treated wood samples, and it is an effective, environmentally friendly wood preservative. Further analysis of these three preservative groups confirmed the excellent function of nano-hydroxyapatite as a nano-carrier, which can promote the chelation of preservatives with higher content of effective preservatives. Full article

In this study, activated carbon microsphere (SLACM) was prepared from powdered sodium lignosulfonate (SL) and polystyrene by the Mannich reaction and ZnCl₂ activation, which can be used to remove Cr(VI) from the aqueous solution without adding any binder. The SLACM was characterized and the batch experiments were conducted under different initial pH values, initial concentrations, contact time durations and temperatures to investigate the adsorption performance of Cr(VI) onto SLACM. The results indicated that the SLACM surface area and average pore size were 769.37 m²/g and 2.46 nm (the mesoporous material), respectively. It was found that the reduced initial pH value, the increased temperature and initial Cr(VI) concentration were beneficial to Cr(VI) adsorption. The maximum adsorption capacity of Cr(VI) on SLACM was 227.7 mg/g at an initial pH value of 2 and the temperature of 40 °C. The adsorption of SLACM for Cr(VI) mainly occurred during the initial stages of the adsorption process. The adsorption kinetic and isotherm experimental data were thoroughly described by Elovich and Langmuir models, respectively. SL could be considered as a potential raw material for the production of activated carbon, which had a considerable potential for the Cr(VI) removal from wastewater. Full article

The crystallization behavior of fully biobased poly(butylene isophthalate) (PBI) has been investigated using calorimetric and microscopic techniques. PBI is an extremely slow crystallizing polymer that leads, after melt-crystallization, to the formation of lamellar crystals and rather large spherulites, due to the low nuclei density. Based upon quantitative analysis of the crystal-nucleation behavior at low temperatures near the glass transition, using Tammann’s two-stage nuclei development method, a nucleation pathway for an acceleration of the crystallization process and for tailoring the semicrystalline morphology is provided. Low-temperature annealing close to the glass transition temperature (T_g) leads to the formation of crystal nuclei, which grow to crystals at higher temperatures, and yield a much finer spherulitic superstructure, as obtained after direct melt-crystallization. Similarly to other slowly crystallizing polymers like poly(ethylene terephthalate) or poly(l-lactic acid), low-temperature crystal-nuclei formation at a timescale of hours/days is still too slow to allow non-spherulitic crystallization. The interplay between glass relaxation and crystal nucleation at temperatures slightly below T_g is discussed. Full article

In this work, the supercritical antisolvent (SAS) process was used to coprecipitate Eudragit L100-55 (EUD) with diclofenac (DICLO) and theophylline (THEOP), with the aim of obtaining composite microparticles with a prolonged drug release for oral delivery. Working at the optimized conditions in terms of pressure and overall concentration in the liquid solution (10.0 MPa and 50 mg/mL), microparticles of EUD/DICLO 20/1 and 10/1 w/w were produced with a mean size of 2.92 µm and 1.53 µm, respectively. For the system EUD/THEOP, well-defined spherical microspheres with a mean diameter ranging from 3.75 µm and 5.93 µm were produced at 12.0 MPa. The produced composite systems were characterized by various techniques, such as scanning electron microscopy, differential scanning calorimetry, X-ray microanalysis, FT-IR and UV–vis spectroscopy. Dissolution studies showed the potential of EUD to prolong the drug release, significantly, up to a few days. Full article

In this paper, we consider the interphase regions surrounding the dispersed and networked carbon nanotubes (CNT) to develop and simplify the expanded Takayanagi model for tensile modulus of polymer CNT nanocomposites (PCNT). The moduli and volume fractions of dispersed and networked CNT and the surrounding interphase regions are considered. Since the modulus of interphase region around the dispersed CNT insignificantly changes the modulus of nanocomposites, this parameter is removed from the developed model. The developed model shows acceptable agreement with the experimental results of several samples. “E_R” as nanocomposite modulus per the modulus of neat matrix changes from 1.4 to 7.7 at dissimilar levels of “f” (CNT fraction in the network) and network modulus. Moreover, the lowest relative modulus of 2.2 is observed at the smallest levels of interphase volume fraction ( ${\varphi }_i$ < 0.017), while the highest “ ${\varphi }_i$ ” as 0.07 obtains the highest relative modulus of 11.8. Also, the variation of CNT size (radius and length) significantly changes the relative modulus from 2 to 20. Full article

In this paper, we studied the laser and optical properties of conjugated oligomer (CO) 1,4-bis(9-ethyl-3-carbazo-vinylene)-9,9-dihexyl-fluorene (BECV-DHF) thin films, which were cast onto a quartz substrate using a spin coating technique. BECV-DHF was dissolved in chloroform at different concentrations to produce thin films with various thicknesses. The obtained results from the absorption spectrum revealed one sharp peak at 403 nm and two broads at 375 and 428 nm. The photoluminescence (PL) spectra were recorded for different thin films made from different concentrations of the oligomer solution. The threshold, laser-induced fluorescence (LIF), and amplified spontaneous emission (ASE) properties of the CO BECV-DHF thin films were studied in detail. The ASE spectrum was achieved at approximately 482.5 nm at a suitable concentration and sufficient pump energy. The time-resolved spectroscopy of the BECV-DHF films was demonstrated at different pump energies. Full article

This study reports on the production and characterization of highly porous (up to 91%) composite foams for potential bone tissue engineering (BTE) applications. A calcium phosphate-based glass particulate (PGP) filler of the formulation 50P₂O₅-40CaO-10TiO₂ mol.%, was incorporated into biodegradable poly(d,l-lactic acid) (PDLLA) at 5, 10, 20, and 30 vol.%. The composites were fabricated by melt compounding (extrusion) and compression molding, and converted into porous structures through solid-state foaming (SSF) using high-pressure gaseous carbon dioxide. The morphological and mechanical properties of neat PDLLA and composites in both nonporous and porous states were examined. Scanning electron microscopy micrographs showed that the PGPs were well dispersed throughout the matrices. The highly porous composite systems exhibited improved compressive strength and Young’s modulus (up to >2-fold) and well-interconnected macropores (up to ~78% open pores at 30 vol.% PGP) compared to those of the neat PDLLA foam. The pore size of the composite foams decreased with increasing PGPs content from an average of 920 µm for neat PDLLA foam to 190 µm for PDLLA-30PGP. Furthermore, the experimental data was in line with the Gibson and Ashby model, and effective microstructural changes were confirmed to occur upon 30 vol.% PGP incorporation. Interestingly, the SSF technique allowed for a high incorporation of bioactive particles (up to 30 vol.%—equivalent to ~46 wt.%) while maintaining the morphological and mechanical criteria required for BTE scaffolds. Based on the results, the SSF technique can offer more advantages and flexibility for designing composite foams with tunable characteristics compared to other methods used for the fabrication of BTE scaffolds. Full article

In this paper, we focus on the synthesis and characterization of novel stable nanolayers made of star methacrylate polymers. The effect of nanolayer modification on its antibacterial properties was also studied. A covalent immobilization of star poly(N,N′-dimethylaminoethyl methacrylate) (PDMAEMA) to benzophenone functionalized glass or silicon supports was carried out via a “grafting to” approach using UV irradiation. To date, star polymer UV immobilization has never been used for this purpose. The thickness of the resulting nanolayers increased from 30 to 120 nm with the molar mass of the immobilized stars. The successful bonding of star PDMAEMA to the supports was confirmed by surface sensitive quantitative spectroscopic methods. Next, amino groups in the polymer layer were quaternized with bromoethane, and the influence of this modification on the antibacterial properties of the obtained materials was analyzed using a selected reference strain of bacteria. The resulting star nanolayer surfaces exhibited higher antimicrobial activity against Bacillus subtilis ATCC 6633 compared to that of the linear PDMAEMA analogues grafted onto a support. These promising results and the knowledge about the influence of the topology and modification of PDMAEMA layers on their properties may help in searching for new materials for antimicrobial applications in medicine. Full article

Epoxy resin plays a key role in composite matrices and DGEBA is the major precursor used. With the aim of favouring the use of bio resources, epoxy resins can be prepared from lignin. In particular, diglycidyl ether of isoeugenol derivatives are good candidates for the replacement of DGEBA. This article presents an effective and eco-friendly way to prepare epoxy resin derived from isoeugenol (BioIgenox), making its upscale possible. BioIgenox has been totally characterized by NMR, FTIR, MS and elemental analyses. Curing of BioIgenox and camphoric anhydride with varying epoxide function/anhydride molar ratios has allowed determining an optimum ratio near 1/0.9 based on DMA and DSC analyses and swelling behaviours. This thermoset exhibits a Tg measured by DMA of 165 °C, a tensile storage modulus at 40 °C of 2.2 GPa and mean 3-point bending stiffness, strength and strain at failure of 3.2 GPa, 120 MPa and 6.6%, respectively. Transposed to BioIgenox/hexahydrophtalic anhydride, this optimized formulation gives a thermoset with a Tg determined by DMA of 140 °C and a storage modulus at 40 °C of 2.6 GPa. The thermal and mechanical properties of these two thermosets are consistent with their use as matrices for structural or semi-structural composites. Full article

Poly(ε-caprolactone) (PCL) and poly(lactic acid) (PLA) blends were compatibilized by reactive blending and by copolymers formed during reaction in the solution. The reactive blending of PCL/PLA was performed using di-(2-tert-butyl-peroxyisopropyl)benzene (BIB) or dicumyl peroxide (DCP) as radical initiator. PCL-g-PLA copolymers were prepared using 1.0 wt. % of DCP or BIB via reaction in solution, which was investigated through a Fourier transform infrared spectrometry (FTIR) and nuclear magnetic resonance (NMR) in order to better understand the occurring mechanisms. The effect of different additions such as PCL-g-PLA copolymers, DCP, or BIB on the properties of PCL/PLA blends was studied. The unmodified PCL/PLA blends showed a sea-island morphology typical of incompatible blends, where PLA droplets were dispersed in the PCL matrix. Application of organic peroxides improved miscibility between PCL and PLA phases. A similar effect was observed for PCL/PLA blend compatibilized by PCL-g-PLA copolymer, where BIB was used as initiator. However, in case of application of the peroxides, the PCL/PLA blends were cross-linked, and it has been confirmed by the gel fraction and melt flow index measurements. The thermal and mechanical properties of the blends were also investigated by means of differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA), and tensile strength. Full article

The interaction between gum rosin and gum rosin derivatives with Mater-Bi type bioplastic, a biodegradable and compostable commercial bioplastic, were studied. Gum rosin and two pentaerythritol esters of gum rosin (Lurefor 125 resin and Unik Tack P100 resin) were assessed as sustainable compatibilizers for the components of Mater-Bi^® NF 866 polymeric matrix. To study the influence of each additive in the polymeric matrix, each gum rosin-based additive was compounded in 15 wt % by melt-extrusion and further injection molding process. Then, the mechanical properties were assessed, and the tensile properties and impact resistance were determined. Microscopic analyses were carried out by field emission scanning electron microscopy (FE-SEM), atomic force microscopy (AFM) and atomic force microscopy with nanomechanical assessment (AFM-QNM). The oxygen barrier and wettability properties were also assayed. The study revealed that the commercial thermoplastic starch is mainly composed of three phases: A polybutylene adipate-co-terephthalate (PBAT) phase, an amorphous phase of thermoplastic starch (TPSa), and a semi-crystalline phase of thermoplastic starch (TPSc). The poor miscibility among the components of the Mater-Bi type bioplastic was confirmed. Finally, the formulations with the gum rosin and its derivatives showed an improvement of the miscibility and the solubility of the components depending on the additive used. Full article

Intending to expand the thermo-physical properties of bio-based polymers, furan-based thermoplastic polyesters were synthesized following the melt polycondensation method. The resulting polymers, namely, poly(ethylene 2,5-furandicarboxylate) (PEF), poly(propylene 2,5-furandicarboxylate) (PPF), poly(butylene 2,5-furandicarboxylate) (PBF) and poly(1,4-cyclohexanedimethylene 2,5-furandicarboxylate) (PCHDMF) are used in blends together with various polymers of industrial importance, including poly(ethylene terephthalate) (PET), poly(ethylene 2,6-naphthalate) (PEN), poly(L-lactic acid) (PLA) and polycarbonate (PC). The blends are studied concerning their miscibility, crystallization and solid-state characteristics by using wide-angle X-ray diffractometry (WAXD), differential scanning calorimetry (DSC) and polarized light microscopy (PLM). PEF blends show in general dual glass transitions in the DSC heating traces for the melt quenched samples. Only PPF–PEF blends show a single glass transition and a single melt phase in PLM. PPF forms immiscible blends except with PEF and PBF. PBF forms miscible blends with PCHDMF and PPF, whereas all other blends show dual glass transitions in DSC and phase separation in PLM. PCHDMF–PEF and PEN–PEF blends show two glass transition temperatures, but they shift to intermediate temperature values depending on the composition, indicating some partial miscibility of the polymer pairs. Full article

Carbon-fiber-reinforced plastic is an important building material; however, its application is limited because of its brittleness, leading to vulnerability under shock. Thus, the strength performance of carbon-fiber-reinforced plastics needs to be improved. Here, the drop impact test was conducted to analyze the impact energy and fracture characteristics of carbon-fiber-reinforced plastics and ethylene vinyl acetate sheets. The compression after impact test was performed to assess the residual compressive strength. The thermal energy generated was measured as change in temperature at the time of fracture to investigate the relationship between thermal and mechanical properties. The impact absorption efficiency of 100% was achieved when the carbon-fiber-reinforced plastics specimen was laminated with four or more sheets of ethylene vinyl acetate. The thermal energy generated during impact, the impact load, and the compression after impact test strength was reduced with the increasing number of laminated ethylene vinyl acetate layers. Our results showed that, by carefully selecting the optimal conditions of fabricating the carbon-fiber-reinforced plastic/ethylene vinyl acetate composites, carbon composite materials can be used for impact mitigation. Full article

Dental caries (tooth decay) is the most frequent oral disease in humans. Filling cavities with a dental restorative material is the most common treatment, and glass ionomer cements are the main fluoride ion release restorative materials. The goal of this study was to develop a restorative compound with superior fluoride ion release and recharge abilities. Previously developed fluorinated bentolite and hydrophobized 3YSZ were used as two different inorganic fillers mixed in a bisphenol A-glycidyl methacrylate (Bis-GMA) matrix. XRD, FTIR, and TGA were used to determine the hydrophobic modification of these two inorganic fillers. In mechanical tests, including diameter tensile strength, flexural strength, and wear resistance, the developed composite resin was significantly superior to the commercial control. A WST-1 assay was used to confirm that the material displayed good biocompatibility. Furthermore, the simulation of the oral environment confirmed that the composite resin had good fluoride ion release and reloading abilities. Thus, the composite resin developed in this study may reduce secondary caries and provide a new choice for future clinical treatments. Full article

Hyperbranched polyoxetanes are a relatively new class of polymers. These are branched polyethers that are synthesized from oxetanes—four-member cyclic ethers bearing hydroxymethyl groups—via ring-opening polymerization. Four series of polyoxetanes were synthesized from 3-ethyl-3-(hydroxymethyl)oxetane and 1,1,1-tris(hydroxymethyl)propane as a core molecule. Reagents ratios ranged from 1:5 to 1:50, theoretical molar mass ranged from 714 g/mol to 5942 g/mol, and dispersities ranged from 1.77 to 3.75. The morphology of the macromolecules was investigated by a matrix-assisted laser desorption/ionization time of flight technique. The polyoxetanes’ adhesive interactions with polar materials were analyzed and provided results as follows: the work of adhesion was 101–105 mJ/m², the bond-line tensile shear strengths were 0.39–1.32 MPa, and there was a brittle fracture mode within the polymer. The findings confirmed a good adhesion to polar substrates, but further research on polyoxetane modifications toward a reduction of brittleness is necessary. Full article

The composition and structure of polyacrylonitrile (PAN) precursors play an important role during thermal stabilization, which influences the properties of the resulting carbon fibers. In this paper, PAN homopolymer and PAN-itaconic (IA) copolymers with different IA contents were synthesized by aqueous phase precipitation polymerization. The effects of IA content on the structure and thermal properties were studied using scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). The morphology of PAN polymers showed that the average size of the PAN particles increased with the increase of IA content in the feed. The content of the IA comonomer on the copolymers was quantitatively characterized by the relative absorbance intensity (A₁₇₃₅/A₂₂₄₃) in FTIR spectrum. With the increase of IA content in the feed, PAN-IA copolymers exhibited lower degree of crystallinity and crystal size than the control PAN homopolymer. The results from DSC curves indicated that PAN-IA1.0 copolymers had lower initial exothermic temperature (192.4 °C) and velocity of evolving heat (6.33 J g⁻¹ °C⁻¹) in comparison with PAN homopolymer (T_i = 238.1 °C and ΔH/ΔT = 34.6 J g⁻¹ °C⁻¹) in an air atmosphere. TGA results suggested that PAN-IA1.0 copolymers had higher thermal stability than PAN homopolymer, which can form a ladder structure easier during thermal processing. Therefore, PAN-IA1.0 copolymers would be a suitable candidate for preparing high performance PAN based carbon fibers. Full article