Lithium phenyl (2,4,6-trimethylbenzoyl) phosphinate (LAP) is a free radical photo-initiator used to initiate free radical chain polymerization upon light exposure, and is combined with gelatin methacryloyl (GelMA) to produce a photopolymer used in bioprinting. The free radicals produced under bioprinting conditions are potentially cytotoxic and mutagenic. Since these photo-generated free radicals are highly-reactive but short-lived, toxicity assessments should be conducted with light exposure. In this study, photorheology determined that 10 min exposure to 9.6 mW/cm² 405 nm light from an LED light source fully crosslinked 10 wt % GelMA with >3.4 mmol/L LAP, conditions that were used for subsequent cytotoxicity and mutagenicity assessments. These conditions were cytotoxic to M-1 mouse kidney collecting duct cells, a cell type susceptible to lithium toxicity. Exposure to ≤17 mmol/L (0.5 wt %) LAP without light was not cytotoxic; however, concurrent exposure to ≥3.4 mmol/L LAP and light was cytotoxic. No condition of LAP and/or light exposure evaluated was mutagenic in bacterial reverse mutation assays using S. typhimurium strains TA98, TA100 and E. coli WP2 uvrA. These data indicate that the combination of LAP and free radicals generated from photo-excited LAP is cytotoxic, but mutagenicity was not observed in bacteria under typical bioprinting conditions. Full article

Mats of polyvinyl alcohol (PVA) core–shell nanofibers were produced using coaxial electrospinning in the presence of a thiosemicarbazone (TSC) N4-(S)-1-phenylethyl)-2-(pyridin-2-yl-ethylidene)hydrazine-1-carbothioamide (HapyTSCmB). Monolithic fibers with 0% or 5% TSC and core–shell fibers with 10% TSC in the spinning solution were studied to compare stability and release rates. SEM showed the formation of uniform, bead-free, cylindrical, and smooth fibers. NMR spectroscopy and thermal analysis (TG/DTA) gave proof for the chemical integrity of the TSC in the fiber mats after the electrospinning process. Attenuated total reflection Fourier-transform infrared (ATR-FTIR) spectroscopy showed no TSC on the surface of the PVA/TSC-PVA fibers confirming the core–shell character. The TSC release profiles of the fibers as studied using UV-vis absorption spectroscopy showed a slower release from the PVA/TSC-PVA core–shell structure compared with the monolithic PVA/TSC fibers as well as lower cumulative release percentage (17%). Out of several release models, the Korsmeyer–Peppas model gave the best fit to the experimental data. The main release phase can be described with a Fick-type diffusion mechanism. Antibacterial properties were tested against the Gram-positive Staphylococcus aureus bacterium and gave a minimal inhibitory concentration of 12.5 μg/mL. 3-(4,5-dimethyl-2-thiazolyl)-2,5-diphenyl-2H-tetrazoliumbromide (MTT)-based cytotoxicity experiments showed that the cell viability of fibroblast at different contents of TSC was slightly decreased from 1.5% up to 3.5% when compared to control cells. Full article

We applied black phosphorene (BP) and hexagonal boron nitride (BN) nanosheets as flame retardants to waterborne polyurethane to fabricate a novel black phosphorus/boron nitride/waterborne polyurethane composite material. The results demonstrated that the limiting oxygen index of the flame-retarded waterborne polyurethane composite increased from 21.7% for pure waterborne polyurethane to 33.8%. The peak heat release rate and total heat release of the waterborne polyurethane composite were significantly reduced by 50.94% and 23.92%, respectively, at a flame-retardant content of only 0.4 wt%. The superior refractory performances of waterborne polyurethane composite are attributed to the synergistic effect of BP and BN in the gas phase and condensed phase. This study shows that black phosphorus-based nanocomposites have great potential to improve the fire resistance of polymers. Full article

The aim of this work was to study the interfacial behavior of basalt-fiber-reinforced thermoplastic blends of polypropylene and poly(butylene terephthalate) (PP/PBT). We examined the effect of two compatibilizers and two basalt fiber (BF) sizings: commercial (REF) and experimental (EXP). Differential scanning calorimetry was used to assess the influence of BFs on the phase structure of obtained composites. Furthermore, dielectric relaxation spectroscopy was used for the first time to non-destructively study the interfacial adhesion within an entire volume of BF-reinforced composites by assessing the α relaxation, DC conductivity, and Maxwell–Wagner–Sillars (MWS) polarization. The fiber–matrix adhesion was further investigated using the Havriliak–Negami model. Using complex plane analysis, the dielectric strength, which is inversely related to the adhesion, was calculated. The composites reinforced with EXP fibers showed significantly lower values of dielectric strength compared to the REF fibers, indicating better adhesion between the reinforcement and blend matrix. Static bending tests also confirmed improved fiber adhesion with EXP fibers, while also suggesting a synergistic effect between compatibilizer and sizing in enhancing interfacial properties. Thus, we conclude that substantially improved adhesion of PP/PBT BF-reinforced composites is the result of mutual interactions of functional groups of blend matrix, mostly from blend compatibilizer, and fiber surface due to sizing. Full article

In this work, we study the imaging characteristics of an optical see-through display based on a holographic waveguide. To fabricate this device, two transmission holograms are recorded on a photopolymer material attached to a glass substrate. The role of the holograms is to couple the incident light between air and the glass substrate, accomplishing total internal reflection. The role of noise reflection gratings and shrinkage on the imaging characteristics of the device will be also explored. The holograms (slanted transmission gratings with a spatial frequency of 1690 lines/mm) were recorded on a polyvinyl alcohol acrylamide holographic polymer dispersed liquid crystal (HPDLC) material. We will show that sufficient refractive index modulation is achieved in the material, in order to obtain high diffraction efficiencies. We will demonstrate that the final device acts as an image formation system. Full article

We present a coarse-grained force field for modelling silica–polybutadiene interfaces and nanocomposites. The polymer, poly(cis-1,4-butadiene), is treated with a previously published united-atom model. Silica is treated as a rigid body, using one Si-centered superatom for each SiO ${}_2$ unit. The parameters for the cross-interaction between silica and the polymer are derived by Boltzmann inversion of the density oscillations at model interfaces, obtained from atomistic simulations of silica surfaces containing both $Q^4$ (hydrophobic) and $Q^3$ (silanol-containing, hydrophilic) silicon atoms. The performance of the model is tested in both equilibrium and non-equilibrium molecular dynamics simulations. We expect the present model to be useful for future large-scale simulations of rubber–silica nanocomposites. Full article

The specificity of activated carbon (AC) can be targeted by pretreatment of the precursors and/or activation conditions. Piassava (Leopoldinia piassaba and Attalea funifera Martius) are fibrous palms used to make brushes, and other products. Consolidated harvest and production residues provide economic feasibility for producing AC, a value-added product from forest and industrial residues. Corona electrical discharge and extraction pretreatments prior to AC activation were investigated to determine benefits from residue pretreatment. The resulting AC samples were characterized using elemental analyses and FTIR and tested for efficacy using methylene blue and phenol. All resulting AC had good adsorbent properties. Extraction as a pretreatment improved functionality in AC properties over Corona electrical discharge pretreatment. Due to higher lignin content, AC from L. piassaba had better properties than that from A. funifera. Full article

This work aims at developing polyamide 1010 (PA1010) composites with improved fire behavior using a halogen-free flame-retardant system based on melamine (Me) and gallic acid (GA) complexes (MA). The MA complexes were formed by hydrogen bonding, starting from 1:2, 1:1, 2:1 Me:GA molar ratios. PA1010 composites were obtained by melt mixing, followed by compression molding. MA provided a plasticizing effect on the PA1010 matrix by decreasing the glass transition temperature. The influence of MA on PA1010 chain packaging was highlighted in the X-ray diffraction patterns, mainly in the amorphous phase, but affected also the α and γ planes. This was reflected in the dynamic mechanical properties by the reduction of the storage modulus. H-bonds occurrence in MA complexes, improved the efficiency in the gaseous form during fire exposure, facilitating the gas formation and finally reflected in thermal stability, thermo-oxidative stability, LOI results, and vertical burning behavior results. PA1010 containing a higher amount of GA in the complex (MA12) displayed a limiting oxygen index (LOI) value of 33.6%, much higher when compared to neat PA1010 (25.8%). Vertical burning tests showed that all the composites can achieve the V-0 rating in contrast with neat PA1010 that has V-2 classification. Full article

Nitroxide-mediated polymerization is now a mature technique, at 35 years of age. During this time, several variants have been developed: electron spin capture polymerization (ESCP), photoNMP (NMP2), chemically initiated NMP (CI-NMP), spin label NMP (SL-NMP), and plasmon-initiated NMP (PI-NMP). This mini-review is devoted to the features and applications of these variants. Full article

In this study, a new class of thermal insulation composites was prepared by blending a modified hollow glass microsphere (HGM) with furan resin. The particle dispersion between the microparticles and resin matrix was improved using 3-methacryloxypropyltrimethoxy silane (KH-570). Furthermore, the structure and morphology of the modified HGM were characterised by Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM). In addition, the effects of the modified HGM on the thermal insulation, flame retardancy, and thermal properties of the composites were investigated. The thermal conductivity of the composites was lower than that of the native furan resin. The minimum thermal conductivity of the composites was 0.0274 W/m·K; the flame retardancy of the composites improved, and the limiting oxygen index become a maximum of 31.6%, reaching the refractory material level. Furthermore, the thermal analysis of the composites demonstrated enhanced thermal stability. This study demonstrates that the composite material exhibited good thermal insulation performance and flame retardancy and that it can be applied in the field of thermal insulation. Full article

Carbon fiber reinforced plastics (CFRP) have many mechanical properties that are superior to those of conventional structural materials and are becoming more and more widely used. Monitoring the curing process used to produce such composite material is important to ensure the quality of the process, especially for the characterization of residual strains after the material has been manufactured. In this study, we present a tilted fiber Bragg grating (TFBG) sensor used to monitor the curing of CFRP composite materials. The TFBG sensor was embedded into the layers of CFRP laminates to study the curing residual strain of the laminates. The experimental results showed that the curing residual stress was about −22.25 MPa, the axial residual strain was −281.351 με, and lateral residual strain of 89.91 με. The TFBG sensor was found to be sensitive to the curing residual strain of the CFRP, meaning that it has potential for use in applications involving composite curing processes. Moreover, it is indeed possible to improve the properties of composite materials via the optimization and monitoring of their curing parameters. Full article

Degeneration of articular cartilage (AC) is a common healthcare issue that can result in significantly impaired function and mobility for affected patients. The avascular nature of the tissue strongly burdens its regenerative capacity contributing to the development of more serious conditions such as osteoarthritis. Recent advances in bioprinting have prompted the development of alternative tissue engineering therapies for the generation of AC. Particular interest has been dedicated to scaffold-based strategies where 3D substrates are used to guide cellular function and tissue ingrowth. Despite its extensive use in bioprinting, the application of polycaprolactone (PCL) in AC is, however, restricted by properties that inhibit pro-chondrogenic cell phenotypes. This study proposes the use of a new bioprintable poly(ester urea) (PEU) material as an alternative to PCL for the generation of an in vitro model of early chondrogenesis. The polymer was successfully printed into 3D constructs displaying adequate substrate stiffness and increased hydrophilicity compared to PCL. Human chondrocytes cultured on the scaffolds exhibited higher cell viability and improved chondrogenic phenotype with upregulation of genes associated with type II collagen and aggrecan synthesis. Bioprinted PEU scaffolds could, therefore, provide a potential platform for the fabrication of bespoke, pro-chondrogenic tissue engineering constructs. Full article

The aim of this in vitro study was to evaluate the hardness and shrinkage stress (SS) of six bulk-fill resin composites. To evaluate microhardness (MH), ten 6 mm specimens were prepared using a metal mold for each selected bulk-fill resin composite and irradiated from the top side for 40 s using an LED light. After 24 h of storage, Vickers MH was evaluated on the upper, lower and lateral sides of the specimens. SS evaluation was then performed with a universal machine, which evaluated the contraction force generated by a bulk-fill composite specimen placed between two metal cylinders during and after light curing. The results were evaluated with a one-way ANOVA test with a post-hoc Bonferroni test and linear regression analysis (p < 0.05). All materials showed a significant MH decrease between the top and bottom surfaces. However, the bulk-fill materials tested performed differently when considering lateral depth progression. ANOVA tests for SS evaluation showed that both SDR and Venus Bulk Fill had significantly lower stress during irradiation than other tested materials. Further, MH decrease became significantly lower from the top surface at different depths in each tested group. Among the different resins, Venus Bulk Fill and SDR showed not only inferior hardness, but also a significant reduction in SS. Full article

An alternative approach for the synthesis of styrene butadiene rubber (SBR) copolymer latexes was explored in order to obtain low gel fractions and high solid contents. The ultra-turrax-assisted miniemulsion stabilized by in situ surfactant generation was adopted as the main strategy since this technique can inhibit the eventual presence of secondary nucleation producing polybutadiene particles and also control the cross-linking degree. Styrene monomer was first miniemulsified using an ultra-turrax and in situ generated surfactant using either hexadecane (HD) or octadecyl acrylate (ODA) as the hydrophobe. Dynamic light scattering (DLS) measurements of droplet size indicated faster stabilization and the production of smaller droplet diameters ca. 190 nm (PdI = 0.08) when employing in situ generated potassium oleate (K-Oleate) in comparison to SDS-based miniemulsions. High butadiene-level SBR latexes with ca. 50% solids content, a glass transition temperature (T_g) of −52 °C, and a butadiene to styrene weight ratio of 75:25, were then obtained using the miniemulsion droplets as seeds. Turbiscan and DLS measurements revealed a very stable resulting latex with SBR particle diameter of ca. 220 nm and a low polydispersity index (PdI). Secondary nucleation was prevented as indicated by the low N_p/N_d value. Cryo-TEM images showed a narrow distribution of particle size as well as the absence of agglomeration. The gel content was below 10% when tert-dodecyl mercaptan (t-DM) was used as chain transfer agent (CTA). Full article

Creating strong joints between dissimilar materials for high-performance hybrid products places high demands on modern adhesives. Traditionally, adhesion relies on the compatibility between surfaces, often requiring the use of primers and thick bonding layers to achieve stable joints. The coatings of polymer brushes enable the compatibilization of material surfaces through precise control over surface chemistry, facilitating strong adhesion through a nanometer-thin layer. Here, we give a detailed account of our research on adhesion promoted by polymer brushes along with examples from industrial applications. We discuss two fundamentally different adhesive mechanisms of polymer brushes, namely (1) physical bonding via entanglement and (2) chemical bonding. The former mechanism is demonstrated by e.g., the strong bonding between poly(methyl methacrylate) (PMMA) brush coated stainless steel and bulk PMMA, while the latter is shown by e.g., the improved adhesion between silicone and titanium substrates, functionalized by a hydrosilane-modified poly(hydroxyethyl methacrylate) (PHEMA) brush. This review establishes that the clever design of polymer brushes can facilitate strong bonding between metals and various polymer materials or compatibilize fillers or nanoparticles with otherwise incompatible polymeric matrices. To realize the full potential of polymer brush functionalized materials, we discuss the progress in the synthesis of polymer brushes under ambient and scalable industrial conditions, and present recent developments in atom transfer radical polymerization for the large-scale production of brush-modified materials. Full article