Polymers — Open Access Journal of Polymer Science

Graphene oxide (GO) has emerged as an ideal filler to reinforce polymeric matrices owing to its large specific surface area, transparency, flexibility, and very high mechanical strength. Nonetheless, functionalization is required to improve its solubility in common solvents and expand its practical uses. In this work, hexamethylene diisocyanate (HDI)-functionalized GO (HDI-GO) has been used as filler of a conductive polymer matrix, poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS). The nanocomposites have been prepared via a simple solution casting method, and have been characterized by scanning electron microscopy (SEM), UV–Vis and Raman spectroscopies, X-ray diffraction (XRD), thermogravimetric analysis (TGA), tensile tests, and four-point probe measurements to get information about how the HDI-GO functionalization degree (FD) and the HDI-GO concentration in the nanocomposite influence the final properties. SEM analysis showed a very homogenous dispersion of the HDI-GO nanosheets with the highest FD within the matrix, and the Raman spectra revealed the existence of very strong HDI-GO-PEDOT:PSS interactions. A gradual improvement in thermal stability was found with increasing HDI-GO concentration, with only a small loss in transparency. A reduction in the sheet resistance of PEDOT:PSS was found at low HDI-GO contents, whilst increasing moderately at the highest loading tested. The nanocomposites showed a good combination of stiffness, strength, ductility, and toughness. The optimum balance of properties was attained for samples incorporating 2 and 5 wt % HDI-GO with the highest FD. These solution-processed nanocomposites show considerably improved performance compared to conventional PEDOT:PSS nanocomposites filled with raw GO, and are highly suitable for applications in various fields, including flexible electronics, thermoelectric devices, and solar energy applications. Full article

In this work, we applied a fast and simple method to synthesize cellulose nanocrystal (CNC) aerogels, via a hydrothermal strategy followed by freeze drying. The characteristics and morphology of the obtained CNC-g-AA aerogels were affected by the hydrothermal treatment time, volume of added AA (acrylic acid), and the mass fraction of the CNCs. The formation mechanism of the aerogels involved free radical graft copolymerization of AA and CNCs with the cross-linker N,N′-methylene bis(acrylamide) (MBA) during the hydrothermal process. The swelling ratio of the CNC-g-AA aerogels was as high as 495:1, which is considerably greater than that of other polysaccharide-g-AA aerogels systems. Moreover, the CNC-g-AA aerogels exhibited an excellent methyl blue (MB) adsorption capacity and the ability to undergo rapid desorption/regeneration. The maximum adsorption capacity of the CNC-g-AA aerogels for MB was greater than 400 mg/g. Excellent regeneration performance further indicates the promise of our CNC-g-AA aerogels as an adsorbent for applications in environmental remediation. Full article

The aim of this study was to investigate the feasibility of large-scale preparation of porous polyvinyl alcohol/sodium alginate/graphene (Gr) (Gr-AP) nanofiber membranes using a copper wire needleless dynamic linear electrode electrospinning machine. Furthermore, the effects of Gr concentrations (0, 0.0375, 0.075, 0.25, 0.5, and 0.75 wt.%) on the morphology, electrical, hydrophilicity and thermal properties were evaluated. Results indicate that the dynamic linear electrospun Gr-AP membranes have a high yield of 1.25 g/h and are composed of porous finer nanofibers with a diameter of 141 ± 31 nm. Gr improved the morphology, homogeneity, hydrophobicity and thermal stability of Gr-AP nanofiber membranes. The critical conductive threshold is 0.075 wt.% for Gr, which provides the nanofiber membranes with an even distribution of diameter, an optimal conductivity, good hydrophilicity, appropriate specific surface area and optimal thermal stability. Therefore, needleless dynamic linear electrospinning is beneficial to produce high quality Gr-AP porous nanofiber membranes, and the optimal parameters can be used in artificial nerve conduits and serve as a valuable reference for mass production of nanofiber membranes. Full article

Rigid polyurethane foams (RPUFs) typically exhibit low thermal inertia, resulting in short ignition times and rapid flame spread. In this study, the fire phenomena of RPUFs were investigated using a multi-methodological approach to gain detailed insight into the fire behaviour of pentane- and water-blown polyurethane (PUR) as well as pentane-blown polyisocyanurate polyurethane (PIR) foams with densities ranging from 30 to 100 kg/m³. Thermophysical properties were studied using thermogravimetry (TG); flammability and fire behaviour were investigated by means of the limiting oxygen index (LOI) and a cone calorimeter. Temperature development in burning cone calorimeter specimens was monitored with thermocouples inside the foam samples and visual investigation of quenched specimens’ cross sections gave insight into the morphological changes during burning. A comprehensive investigation is presented, illuminating the processes taking place during foam combustion. Cone calorimeter tests revealed that in-depth absorption of radiation is a significant factor in estimating the time to ignition. Cross sections examined with an electron scanning microscope (SEM) revealed a pyrolysis front with an intact foam structure underneath, and temperature measurement inside burning specimens indicated that, as foam density increased, their burning behaviour shifted towards that of solid materials. The superior fire performance of PIR foams was found to be based on the cellular structure, which is retained in the residue to some extent. Full article

This article describes the synthesis of anionic polymer brushes and their mineralization with calcium phosphate. The brushes are based on poly(3-sulfopropyl methacrylate potassium salt) providing a highly charged polymer brush surface. Homogeneous brushes with reproducible thicknesses are obtained via surface-initiated atom transfer radical polymerization. Mineralization with doubly concentrated simulated body fluid yields polymer/inorganic hybrid films containing AB-Type carbonated hydroxyapatite (CHAP), a material resembling the inorganic component of bone. Moreover, growth experiments using Dictyostelium discoideum amoebae demonstrate that the mineral-free and the mineral-containing polymer brushes have a good biocompatibility suggesting their use as biocompatible surfaces in implantology or related fields. Full article

Hydrogen peroxide (H₂O₂)-sensitive layer-by-layer films were prepared based on combining phenyl boronic acid (PBA)-modified poly(allylamine) (PAH) with shikimic acid (SA)-modified-PAH through boronate ester bonds. These PBA-PAH/SA-PAH multilayer films could be prepared in aqueous solutions at pH 7.4 and 9.0 in the presence of NaCl. It is believed that the electrostatic repulsion between the SA-PAH and PBA-PAH was diminished and the formation of ester bonds between the SA and PBA was promoted in the presence of NaCl. These films readily decomposed in the presence of H₂O₂ because the boronate ester bonds were cleaved by an oxidation reaction. In addition, SA-PAH/PBA-PAH multilayer films combined with glucose oxidase (GOx) were decomposed in the presence of glucose because GOx catalyzes the oxidation of D-glucose to generate H₂O₂. The surfaces of CaCO₃ microparticles were coated with PAH/GOx/(SA-PAH/PBA-PAH)₅ films that absorbed insulin. A 1 mg quantity of these particles released up to 10 μg insulin in the presence 10 mM glucose under physiological conditions. Full article

An ultrafine particle aqueous-phase system of hot melt copolyester was prepared by an inverse emulsion–precipitation method. Laser particle size analysis showed that the diameter of the obtained copolyester particles was mostly distributed between 20 and 100 nm. The structure of the copolymer was characterized by FT–IR and ¹H-NMR, and the melting point of the particles was determined to be 125 °C, as measured by differential scanning calorimetry (DSC). Intrinsic viscosity analysis showed that the particle intrinsic viscosity decreased by 6.73% compared with that of the original copolyester. Polyester/cotton woven fabrics were padded with the ultrafine copolyester particles at different concentrations, and the corresponding SEM showed that the fibers were well bonded to each other. The pilling test results showed that these ultrafine copolyester granules improved the pilling performance of the polyester/cotton woven fabrics to a grade of 4.5–5. Full article

Lignin phenol formaldehyde (LPF) resols were produced using depolymerized lignin fractions at various levels of phenol substitution (50 to 70 wt %). To produce monomeric-rich (BCD-oil) and oligomeric (BCD-oligomers) bio-based phenolic compounds, softwood kraft lignin was base-catalysed degraded. These base-catalysed depolymerized (BCD) building blocks were further used to substitute phenol in the synthesis of phenolic resins and were characterized in detail (such as viscosity, free formaldehyde and phenol content, chemical composition, curing and bonding behaviour). The adhesive properties were compared to a phenol formaldehyde (PF) reference resin and a LPF with untreated kraft lignin. The resins synthesized with the two depolymerized lignin types differ significantly from each other with increasing phenol substitution. While with LPF-BCD-oligomers the viscosity increases and the bonding strength is not effected by increasing lignin content in the resin, a reduction of these properties could be observed with LPF-BCD-oil. Furthermore, LPF-BCD-oil showed similar curing behaviour and ultimate strength as the reference LPF. Adhesive bonds made using LPF-BCD-oligomers exhibited similar strength to those made using PF. Compared to the reference resins, it has been demonstrated that modified renewable lignin based phenolic components can be an equally performing alternative to phenol even for high degrees of substitution of 70%. Full article

We report on Flory–Huggins photonic sensors for the selective detection of volatile organic compounds without the use of any chemical functionalization. For this purpose, we employed periodic multilayers made of inert cellulose acetate alternated to active polystyrene films whose free volume was modified with silanized ZnO nanoparticles. The simple UV-visible (UV-vis) dynamic optical response of such polymer distributed Bragg reflectors during exposure to vapors of benzene, toluene, o-dichlorobenzene, and carbon tetrachloride allows their detection and recognition based on different chemico–physical affinity with the active polymer medium. Full article

Using supercritical carbon dioxide as the physical foaming agent, microcellular polypropylene (PP) nanocomposites were prepared in microcellular injection molding. The main purpose of this work is to study effects of content of nano-CaCO₃ on the crystallization, mechanical properties, and cell structure of PP nanocomposites in microcellular injection molding. The results show that adding nano-CaCO₃ to PP could improve its mechanical properties and cell structure. The thermal stability and crystallinity enhances with increase of nano-CaCO₃. As a bubble nucleating agent, adding nano-CaCO₃ to PP improves the cell structure in both the parallel sections and vertical sections. The mechanical properties increase first and then decrease with increase of nano-CaCO₃. The mechanical properties are affected by the cell structure, as well. The mechanical properties and cell structure are optimum when the content of nano-CaCO₃ is 6 wt %. Full article

Novel composite hydrogels based on the combination of alginate (Alg), soy protein isolate (SPI) and bioactive glass (BG) nanoparticles were developed for soft tissue engineering. Human umbilical vein endothelial cells (HUVEC) and normal human dermal fibroblasts were cultivated on hydrogels for 7, 14 and 21 days. Cell morphology was visualized using fluorescent staining at Days 7 and 14 for fibroblast cells and Days 14 and 21 for HUVEC. Metabolic activity of cells was analyzed using a colorimetric assay (water soluble tetrazolium (WST) assay). Compared to pure Alg, Alg/SPI and Alg/SPI/BG provided superior surfaces for both types of cells, supporting their attachment, growth, spreading and metabolic activity. Fibroblasts showed better colonization and growth on Alg/SPI/BG hydrogels compared to Alg/SPI hydrogels. The results indicate that such novel composite hydrogels might find applications in soft tissue regeneration. Full article

Silicone reverse dyeing technology provides an important means of saving water and salts-free in the textile dyeing industry. The interactions between dyes and surfactants may influence the hydrolysis of dye during dyeing. In this investigation, the effect of ethylene oxide content in nonionic surfactant on the hydrolytic reaction of reactive dye was firstly investigated in a siloxane reverse emulsion dyeing system. Compared with no surfactants, the hydrolytic reaction of vinyl sulfone reactive dye was a slowdown when some nonionic surfactants were used during dyeing. Usually, the hydrophobic groups in nonionic surfactants were dodecyl chains but their polar head groups were different. The hydrolytic reaction of vinyl sulfone dye showed that the longer of EO (ethylene oxide) chains, the faster the hydrolytic reaction of vinyl sulfone dye. From the absorption spectrum of dye, it could be concluded that more of dyes would be solubilized into the formed micelles, and dye-surfactant complexes were adhered to the surface of micelles if the molecular structure of surfactant had a shorter EO chains. Furthermore, the intramolecular or intermolecular hydrogen bond could be formed between dye and surfactant, which would further influence the hydrolytic reaction of vinyl sulfone dye. However, the solubility of surfactant in siloxane non-aqueous media would decrease with the increase of EO chains. Meanwhile, the dispersion of dye was enhanced as well as the hydrolytic reaction of dye. From this investigation, some surfactant can be used to improve the fixation of reactive dye during dyeing. Furthermore, washing times after dyeing and the ecological problems can be decreased. Full article

The effects of hydrothermal pretreatment (170–180 °C, 30–60 min) on the structural characteristics of enzymatic and extracted lignin from Triarrhena lutarioriparia (TL) during the integrated delignification process have been comprehensively investigated. Ion chromatography and NMR characterization showed that liquid products after mild hydrothermal process (170 °C, 30 min) were mainly composed of xylooligosaccharide (XOS) with different degrees of polymerization (DP ≥ 2). In addition, the structural changes of lignin during hydrothermal pretreatment and organic acid delignification process have been demonstrated by quantitative 2D heteronuclear single quantum coherence (2D-HSQC) and ³¹P-NMR techniques. Results showed that the structural changes of lignin (e.g., cleavage of β-O-4 linkages) induced by the hydrothermal pretreatment will facilitate the subsequent organic acid delignification process, and acetylated lignin could be obtained with a considerable yield, which can be used in lignin-based composite and candidate feedstock for catalytic upgrading of lignin. In short, the proposed process facilitates the producing of XOS and acetylated lignin for lignin valorization. Full article

In previous work by the authors, a new methodology was developed for Brownian dynamics/kinetic Monte Carlo (BD/kMC) simulations of polymer melts. In this study, this methodology is extended for dynamical simulations of crosslinked polymer networks in a coarse-grained representation, wherein chains are modeled as sequences of beads, each bead encompassing a few Kuhn segments. In addition, the C++ code embodying these simulations, entitled Engine for Mesoscopic Simulations for Polymer Networks (EMSIPON) is described in detail. A crosslinked network of cis-1,4-polyisoprene is chosen as a test system. From the thermodynamic point of view, the system is fully described by a Helmholtz energy consisting of three explicit contributions: entropic springs, slip springs and non-bonded interactions. Entanglements between subchains in the network are represented by slip springs. The ends of the slip springs undergo thermally activated hops between adjacent beads along the chain backbones, which are tracked by kinetic Monte Carlo simulation. In addition, creation/destruction processes are included for the slip springs at dangling subchain ends. The Helmholtz energy of non-bonded interactions is derived from the Sanchez–Lacombe equation of state. The isothermal compressibility of the polymer network is predicted from equilibrium density fluctuations in very good agreement with the underlying equation of state and with experiment. Moreover, the methodology and the corresponding C++ code are applied to simulate elongational deformations of polymer rubbers. The shear stress relaxation modulus is predicted from equilibrium simulations of several microseconds of physical time in the undeformed state, as well as from stress-strain curves of the crosslinked polymer networks under deformation. Full article

This paper presents a new approach to describe the mechanical behavior of semi-crystalline polymers, the plastic deformation of which is determined by their two-phase structure. To describe the plastic behavior of semi-crystalline polymers, a two-phase model is used. In the framework of this model, one phase is in a hard (crystalline) state, and the other in a soft (amorphous) state. The two-phase material is modeled by a single-phase homogeneous continuum based on the approximation of the effective medium. It is assumed that two infinitely close material points of the continuum are connected in series by elastic and viscous bonds, which corresponds to the Maxwell model. It is shown that, in this case, the Maxwell continuum is a pseudo-Euclidean space. Generalizing the definition of defects from a three-dimensional space to a four-dimensional pseudo-Euclidean space, we obtained a dynamic system of nonlinear, interrelated equations to describe the behavior of translational-type defects in the solid phase and dynamic defects in the amorphous phase. As an example of an application for these equations, the phenomenon of creep under uniaxial loading is considered. It is shown that the formalism of the proposed two-phase model makes it possible to describe creep phenomenon regularities, which correspond to both the aging theory and the flow theory. Full article

Calcium alginate (CaAlg) submicroparticles have a potential application in agricultural delivery systems. This study investigated the effects of CaAlg submicroparticles on seed germination and seedling growth of wheat. CaAlg submicroparticles with a Z-average diameter of around 250.4 nm and a measured zeta potential value of about −25.4 mV were prepared and characterized by dynamic light scattering (DLS), scanning electron microscopy (SEM) and energy dispersive X-ray spectrometer (EDS). After this, the effects of the concentration of CaAlg submicroparticles (10–500 μg/mL) on germination percentage, seedling length, the number of adventitious roots, chlorophyll content and soluble protein content were evaluated. The results demonstrated a significant increase in the level of germination percentage (9.0%), seedling index (50.3%), adventitious roots (27.5%), seedling length (17.0%), chlorophyll (8.7%) and soluble protein contents (4.5%) at a concentration of 100 μg/mL. However, an inhibitory effect was observed at a concentration of 500 μg/mL. The SEM examination showed that CaAlg submicroparticles could be successfully adsorbed onto the surface of the wheat seed. Further studies proved that CaAlg submicroparticles at a concentration of 100 μg/mL promoted the expression of indole-3-acetic acid (IAA)-related genes (YUCCA9, AUX1, ARF and UGT) in wheat, which resulted in an increase of 69% and 21% in IAA concentration in wheat roots and shoots, respectively. Full article

This paper aims to explore the mechanisms of the complex thermo-mechanical behavior of polymer glass across a wide range of temperature variations. To this end, the free vibration frequency spectrum of simply supported poly(methyl methacrylate) (PMMA) beams was thoroughly investigated with the aid of the impulse excitation technique. It was found that the amplitude ratio of the multiple peaks in the frequency spectrum is a strongly dependent on temperature, and that the peaks correspond to the multiple vibrational modes of the molecular network of PMMA. At a low temperature, the vibration is dominated by the overall microstructure of PMMA. With increasing the temperature, however, the contribution of the sub-microstructures is retarded by β relaxation. Above 80 °C, the vibration is fully dominated by the microstructure after relaxation. The relaxation time at the transition temperature is of the same order of the vibration period, confirming the contribution of β relaxation. These findings provide a precise method for establishing reliable physical-based constitutive models of polymer glass. Full article

The exploration of multifunctional electrode materials has been a hotspot for the development of high-performance supercapacitors. We have used carbon fiber plates recovered from construction waste to prepare high-quality flexible carbon fiber materials by pyrolysis of epoxy resin. The as-prepared recycled carbon fiber has a diameter of 8 μm and is the perfect substrate material for flexible electrode materials. Furthermore, polyaniline and manganese dioxide are uniformly deposited on the recycled carbon fiber by one-step electrodeposition to form an active film. The recycled carbon fiber/polyaniline/MnO₂ composite shows an excellent specific capacitance of 475.1 F·g⁻¹ and capacitance retention of 86.1% after 5000 GCD cycles at 1 A·g⁻¹ in 1 M Na₂SO₄ electrolyte. The composites optimized for electrodeposition time have more electroactive sites, faster ions and electron transfer, structural stability and higher conductivity, endowing the composites promising application prospect. Full article

Eugenol, used as bio-phenol, was designed to replace the hydrogen atom of hydrogenterminated siloxane by hydrosilylation reaction under the presence of alumina-supported platinum catalyst (Pt-Al₂O₃), silica-supported platinum catalyst (Pt-SiO₂) and carbon nanotube-supported platinum catalyst (Pt-CNT), respectively. The catalytic activities of these three platinum catalysts were measured by nuclear magnetic resonance hydrogen spectrometer (¹H NMR). The properties of bio-phenol siloxane were characterized by Fourier transform infrared spectrometer (FT–IR), UV-visible spectrophotometer (UV) and thermogravimeter (TGA), and its antibacterial property against Escherichia coli was also studied. The results showed that the catalytic activity of the catalyst Pt-CNT was preferable. When the catalyst concentration was 100 ppm, the reaction temperature was 80 °C and reaction time was 6 h, the reactant conversion rate reached 97%. After modification with bio-phenol, the thermal stability of the obtained bio-phenol siloxane was improved. For bio-phenol siloxane, when the ratio of weight loss reached 98%, the pyrolysis temperature was raised to 663 °C which was 60 °C higher than hydrogenterminated siloxane. Meanwhile, its autonomic antibacterial property against Escherichia coli was improved significantly. Full article