Enhanced thermo-mechanical stability and conductive response are essential when developing carbon nanotube/elastomer-based nanocomposites for flexible sensing applications. To improve performance of such materials, it is crucial to understand structure–property relations. By using advanced experimental approaches on multi-walled carbon nanotubes/thermoplastic polyurethane system, we were able to reveal main building blocks and network’s morphology (plasma etching and SEM); identify mechanisms of network formation, and the nature of building blocks (rheological analysis); as well as determine the impacts on the thermo-mechanical (thermal and viscoelastic analysis) and conductive (electrical analysis) performance of such nanocomposites. Results showed that the network is in majority constructed from MWCNT bundles. The inherent nature of elastomeric system forces bundles and network to retain random distribution. Bundles may be considered as stiff rod-like Brownian entities, which geometrically entangle at volume fraction of ΦV,cG≈0.46%, indicating network formation. The network was considered as fully established at concentration of ΦV,cCP≈1%, as cross-over point of dynamic moduli. Finally, it was found that thermo-mechanical and conductive performance of the nanocomposite corresponds to the fully established network (and not network formation), allowing force (∼10× increase of moduli), and electron (∼108× increase of conductivity) transfer, while improving thermo-mechanical stability within operating temperatures (increase of glass transition for 25 °C).

The present research addresses the modeling of viscoelastic–viscoplastic behavior of polymers with a theoretical expansion of Schapery’s nonlinear viscoelastic model by incorporating two components of irrecoverable processes, displaying material flow and viscoplastic behavior (structure- and load-related irrecoverable process). The theory is accompanied by an experimental and analytical framework for identifying model parameters. Introduced multi-scale analysis allows evaluation of pure linear and nonlinear viscoelastic, as well as viscoplastic behavior, enabling the study of their contribution to overall material response. Model performance was examined with creep recovery tests on two versatile and well-established thermoplastic polymers with different morphological structures: amorphous ABS exhibiting notable flow and semi-crystalline POM, where flow may be neglected. Results show extremely accurate predictions and exceptional agreement with experimental data, as the error was found to be less than 5% ranging from infinitesimally small to relatively high loading magnitudes (from 0.1 to 15 MPa of shear stress) at 70 °C (maximum operating temperature). Notably, viscoplastic strains were detected even within linear viscoelastic domain, suggesting that these effects are not related to yield phenomena (associated with progressive/damaging mechanisms), but rather provide an explanation for the material’s inability to fully recover. With its predictive capability and adaptability, the model demonstrates to be a powerful tool for capturing realistic material responses not only for the considered but also applicable to other molecular systems.

The present study examined the nonlinear time-dependent behavior of rheodictic polymers, a class of noncrosslinked materials that exhibit flow. Such behavior was addressed with extended Schapery's nonlinear viscoelastic model by introducing new physical quantities, i.e., the flow term Φflow and corresponding nonlinear shift parameter g2,flow. While Φflow portrays irrecoverable deformation, g2,flow depicts a nonlinear contribution to flow acceleration. This theory was accompanied by analytical and experimental methodologies for identifying all the parameters in the linear and nonlinear viscoelastic domains. Predictions of long-term time-dependent behavior (in shear) at various stress states show excellent agreement with the experimental data, i.e., within 5% error, obtained for polycarbonate at 130°C. Surprisingly, the newly introduced g2,flow indicates that flow retardation occurs with increasing stress, implying that a highly deformed entangled system hinders molecular reptation/disentanglement. Nevertheless, the proposed extension of Schapery's nonlinear viscoelastic model not only allows accurate predictions of the nonlinear time-dependent behavior of rheodictic polymers but also enables a detailed outlook on the underlying molecular mechanisms under severe environmental and loading conditions.

The properties of thin polymer films are influenced by the size of the fillers, their morphology, the surface properties and their distribution/interaction in the polymer matrix. In this work, thin polymer composite films with MoO3 or SiO2 nano and micro fillers in PVDF-HFP/PVP polymer matrix were successfully fabricated using the solvent casting method. The effects of different types, sizes and morphologies of the inorganic fillers on the crystallization of the PVDF-HFP polymer were investigated, as well as the effects on the thermal and mechanical properties of the composites. Scanning electron microscopy, ATR-FTIR spectroscopy, differential scanning calorimetry, nanoindentation and uniaxial mechanical tests were used for characterization. The results showed that MoO3 nanowires thermally stabilized the polymer matrix, induced crystallization of the PVDF-HFP polymer in all three polymorphs (α-, β-, γ-phase) and formed a geometrical network in the polymer matrix, resulting in the highest elastic moduli, hardness and Young’s modulus.

In households, considerable costs are related to energy losses, which are a consequence of maintaining comfortable living temperatures. Improved isolation and utilization of energy harvesting devices is the key to reducing energy losses and the related costs. Polymeric solar absorbers are cost-effective solar energy harvesters that can significantly reduce the energy cost for individual households. One of the concerns related to polymers is their flammability. To mitigate the flammability risk, the present work explores the development of solar absorber paints with flame-retardant properties. Bridged 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) derivatives (NED and PHED) in concertation ranges of 10-15 wt% were used in a polyurethane-based matrix to demonstrate the effect of additives on the fire retardancy of the material. Additionally, the rheological and thermal properties of the composite materials were evaluated and described. Furthermore, aluminium and PPS (polyethylene sulphide) substrates were coated with solar absorber paint based on a 15% FR (fire retardant) additive formulation, for which the thermal stability at 150 degrees C for 655 h was evaluated. It was discovered that PHED is more compatible with the polyurethane matrix than NED, and as expected, a greater amount of FR additives resulted in improved flame retardancy. The long-term stability of absorber paint coatings on Al and PPS was also successfully confirmed by confirming stable solar absorptance and thermal emittance. In future prospects, we believe that the flame retardancy of polyurethane-based coatings could be further improved, and the utilization of covalently bonded FRs should also be considered.

A novel facile and eco-friendly procedure for fabrication of multifunctional antibacterial and ultraviolet (UV) protective cotton surface was presented, including premodification of cellulose fibres with a polysiloxane matrix, followed by green in situ biosynthesis of silver nanoparticles (Ag NPs) in the presence of sumac leaf extract as a reducing and stabilising agent. During the biosynthesis, face-centred cubic Ag NPs with an average size of 52-105 nm were generated on the cotton fibres. Increasing the concentration of the AgNO3 precursor resulted in increased concentration of Ag NPs of 50-11,000 mg/kg. The chemically modified cotton surface exhibited excellent antimicrobial and UV protection properties. The additive antibacterial activity of Ag NPs and sumac leaf extract showed biocidal activity against S. aureus even at the lowest Ag NP concentration of 50 mg/kg, and in the case of E. coli, biocidal activity was achieved at a concentration of 340 mg/kg. The presence of both Ag NPs and sumac leaf extract provided UV protection factor greater than 40, irrespective of Ag NP concentration. The increase in Ag NP concentration significantly improved the durability of the coating.

This work presents a unique approach for the preparation of a flame retardant (FR) polyamide 6 (PA6) polymer with chemically bonded 9,10-dihydro-9,10-oxa-10-phosphaphenanthrene-10-oxide (DOPO) as a pendant group bridged to the polymer via an -NH- group. A novel phosphonamidate co-monomer (DOPO-A-CLM) was synthesized from DOPO and alpha-amino-epsilon-caprolactam (A-CLM). This co-monomer was subsequently used in the hydrolytic polymerization with epsilon-caprolactam (CLM) in different weight ratios to prepare DOPO-NH-functionalized PA6 (PA6-xDC, x = 7, 10, and 15 wt% DOPO-A-CLM). Chemical incorporation of DOPO-A-CLM into the PA6 backbone decreased the molecular weight of the polymer from 15387 for neat PA6 to 12375, 10516 and 9316 for PA6-7DC, PA6-10DC and PA6-15DC, respectively. The DOPO-NH- pendant group accelerated start of the PA6 thermal decomposition and increased the char residues at 500 degrees C from 1% for PA6 to 4.6, 4.9, and 5.0% for the PA6-7DC, PA6-10DC, and PA6-15DC samples, respectively, indicating crosslinking reactions in the condensed phase. The evolved phosphorus-active species in the gas phase inhibited the PA6 depolymerization, resulting in increased thermo-oxidative stability and about a fourfold higher residue at 500 degrees C in the case of PA6-15DC compared to PA6. The intrinsically flame retardant PA6 filament yarns with chemically bound FR pendant group were successfully melt spun from PA6-10DC, drawn and wound on bobbin. The DOPO-NH- pendant group decreased filament flammability and inhibited flame propagation, resulting in immediate self-extinguishment after flame removal. Incorporation of DOPO-A-CLM decreased the filament tensile properties compared to the neat PA6, which correlates with the decreased polymer molecular weight.

The aim of this study was to evaluate the antibacterial and antifungal activity, cytotoxicity, leaching, and ecotoxicity of novel flame retardant polyamide 6 (PA6) textile fibers developed by our research group. The textile fibers were produced by the incorporation of flame-retardant bridged 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) derivative (PHED) in the PA6 matrix during the in situ polymerization process at concentrations equal to 10 and 15 wt% (PA6/10PHED and PA6/15PHED, respectively). Whilst the nanodispersed PHED provided highly efficient flame retardancy, its biological activity led to excellent antibacterial activity against Escherichia coli and Staphylococcus aureus, as well as excellent antifungal activity against Aspergillus niger and Candida albicans. The results confirmed leaching of the PHED, but the tested leachates did not cause any measurable toxic effect to the duckweed Lemna minor. The in vitro cytotoxicity of the leached PHED from the PA6/15PHED sample was confirmed for human cells from adipose tissue in direct and prolonged contact. The targeted biological activity of the organophosphinate flame retardant could be beneficial for the development of PA6 textile materials with multifunctional properties and the low ecotoxicity profile, while the PHED's leaching and cytotoxicity limit their application involving the washing processes and direct contact with the skin.

A bio-epoxy surface adhesive for adherence of the metal component species to glass substrate with desirable adhesion strength, converted controlled removal upon request, and bio-based resource inclusion was developed. For the development of resin, three different lignin-based aromatic monophenols, guaiacol, cresol, and vanillin, were used in the chemical epoxidation reaction with epichlorohydrin. The forming transformation process was studied by viscoelasticity, in situ FTIR monitoring, and Raman. Unlike other hydroxyl phenyls, guaiacol showed successful epoxide production, and stability at room temperature. Optimization of epoxide synthesis was conducted by varying NaOH concentration or reaction time. The obtained product was characterized by nuclear magnetic resonance and viscosity measurements. For the production of adhesive, environmentally problematic bisphenol A (BPA) epoxy was partially substituted with the environmentally acceptable, optimized guaiacol-based epoxy at 20, 50, and 80 wt.%. Mechanics, rheological properties, and the possibility of adhered phase de-application were assessed on the bio-substitutes and compared to commercially available polyepoxides or polyurethanes. Considering our aim, the sample composed of 80 wt.% bio-based epoxy/20 wt.% BPA thermoset was demonstrated to be the most suitable among those analyzed, as it was characterized by low BPA, desired boundary area and recoverability using a 10 wt.% acetic acid solution under ultrasound.

Self-healing anticorrosion composite coatings containing isophorone diisocyanate-loaded polyurethane microcapsules were developed, and comprehensive research on prepolymer and microcapsules synthesis, as well as functional composite coatings preparation and characterization, was performed. The influence of the prepolymer type and the concentration of the stabilizing agent used in the synthesis procedure on the properties of the microcapsules was studied in detail. For this purpose, three different prepolymers were prepared from toluene-2,4-diisocyanate (TDI) and either glycerol, 1,4-butanediol, or 1,6-hexanediol, and their chemical properties were investigated. Microcapsules were synthesized from the obtained prepolymers, according to the oil-in-water polymerization method, where 1,6-hexanediol was used as a chain extender, while the concentration of the stabilizing agent in the synthesis procedure was varied. Microcapsules prepared from TDI-glycerol prepolymer, synthesized in the presence of 10 wt% of the stabilizing agent, showed superior chemical, morphological, and thermo-gravimetrical properties; thus, they were incorporated into the coating in the concentration of 20 wt%. The prepared composite coatings demonstrated self-healing and anticorrosion properties, and thus the developed microcapsules show great potential for the incorporation into the composite anticorrosion coatings at critical points where damage can easily occur, providing longer and more efficient anticorrosion protection.

The production of sustainable and effective flame retardant (FR) polyamide 6 (PA6) fibrous materials requires the establishment of a novel approach for the production of polyamide 6/FR nanodispersed systems. This research work explores the influence of three different flame-retardant bridged 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) derivatives on the comprehensive properties of in situ produced PA6/FR systems. To this end, in situ water-catalyzed ring-opening polymerization of ε-caprolactam was conducted in the presence of three different bridged DOPO derivatives, e.g., one P−N bond phosphonamidate derivative and two P−C bond phosphinate derivatives. The selected bridged DOPO derivatives mainly act in the gas phase at the temperatures that relatively match the PA6 pyrolysis specifics. The effects of the FRs on the dispersion state, morphological, molecular, structural, melt-rheological, and thermal properties of the in situ synthesized PA6 were evaluated. The specific advantage of this approach is one-step production of PA6 with uniformly distributed nanodispersed FR, which was obtained in the case of all three applied FRs. However, the applied FRs differently interacted with monomer and polymer during the polymerization, which was reflected in the length of PA6 chains, crystalline structure, and melt-rheological properties. The applied FRs provided a comparable effect on the thermal stability of PA6 and stabilization of the PA6/FR systems above 450 °C in the oxygen-assisted pyrolysis. However, only with the specifically designed FR molecule were the comprehensive properties of the fiber-forming PA6 satisfied for the continuous conduction of the melt-spinning process.

Versatile product protective coatings that deliver faster drying times and shorter minimum overcoat intervals that enable curing at faster line speeds and though lower energy consumption are often desired by coating manufacturers. Product protective coatings, based on silsesquioxane-modified diglycidyl ether of bisphenol-A (DGEBA) epoxy resin, are prepared through a glycidyl ring-opening polymerization using dicyandiamide (DICY) as a curing agent. As silsesquioxane modifier serves the octaglycidyl-polyhedral oligomeric silsesquioxane (GlyPOSS). To decrease the operational temperature of the curing processes, three different accelerators for crosslinking are tested, i.e., N,N-benzyl dimethylamine, 2-methylimidazole, and commercial Curezol 2MZ-A. Differential scanning calorimetry, temperature-dependent FT-IR spectroscopy, and rheology allow differentiation among accelerators’ effectiveness according to their structure. The former only contributed to epoxy ring-opening, while the latter two, besides participate in crosslinking. The surface roughness of the protective coatings on aluminum alloy substrate decreases when the accelerators are applied. The scanning electron microscopy (SEM) confirms that coatings with accelerators are more homogeneous. The protective efficiency is tested with a potentiodynamic polarization technique in 0.5 M NaCl electrolyte. All coatings containing GlyPOSS, either without or with accelerators, reveal superior protective efficiency compared to neat DGEBA/DICY coating.

Studies of the production of fiber-forming polyamide 6 (PA6)/graphene composite material and melt-spun textile fibers are scarce, but research to date reveals that achieving the high dispersion state of graphene is the main challenge to nanocomposite production. Considering the significant progress made in the industrial mass production of graphene nanoplatelets (GnPs), this study explored the feasibility of production of PA6/GnPs composite fibers using the commercially available few-layer GnPs. To this aim, the GnPs were pre-dispersed in molten ε-caprolactam at concentrations equal to 1 and 2 wt %, and incorporated into the PA6 matrix by the in situ water-catalyzed ring-opening polymerization of ε-caprolactam, which was followed by melt spinning. The results showed that the incorporated GnPs did not markedly influence the melting temperature of PA6 but affected the crystallization temperature, fiber bulk structure, crystallinity, and mechanical properties. Furthermore, GnPs increased the PA6 complex viscosity, which resulted in the need to adjust the parameters of melt spinning to enable continuous filament production. Although the incorporation of GnPs did not provide a reinforcing effect of PA6 fibers and reduced fiber tensile properties, the thermal stability of the PA6 fiber increased. The increased melt viscosity and graphene anti-dripping properties postponed melt dripping in the vertical flame spread test, which consequently prolonged burning within the samples.

A novel flame retardant polyamide 6 (PA6)/bridged 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO)-derivative (PHED) nanocomposite textile filament yarns were developed. The scalable production approach includes in situ water-catalyzed ring-opening polymerization of e-caprolactam in the presence of the flame retardant PHED followed by melt-spinning of nanocomposite filament yarns and production of knitted fabrics: The specific chemical structure of the PHED additive enabled its excellent miscibility with molten e-caprolactam and the uninterrupted polymerization of e-caprolactam. The produced PA6/PHED nanocomposite was characterized by the preserved molecular structure of the polyamide 6 and uniformly distributed nano-dispersed FR at concentrations of 10 and 15 wt %. The PA6/PHED nanocomposite structure was successfully preserved after the melt-spinning processing. The PA6 nanocomposite filament yarns at the applied 15 wt %. loading of PHED showed (a) increased thermooxidative stability compared to neat PA6 up to 500 degrees C, with a 43% higher residue at 500 degrees C and (b) self-extinguishment of fiber strand and knitted samples within 1 s in standard vertical flame spread tests (ASTM D6413), followed by the significant reduction of the melt-dripping and the melt-drop flammability. Additionally, 1.2 mm-tick PA6/PHED bar samples achieved a V0 rating in UL94 vertical burning test at the applied 10 wt % concentration of PHED. This innovative and scalable approach could pave the way for the production of new-generation nanocomposite PA6 filament yarns with self-extinguishing properties at the macro-scale, which would be highly beneficial for increasing fire safety, whilst maintaining the use of a DOPO derivative at the minimum level. (C) 2019 Elsevier Ltd. All rights reserved.

PVC or poly(vinyl chloride) is one of the most widely used synthetic materials in the world. Its usage ranges from biomedical devices, electrical cable and telecommunication cables and wires, insulation, construction, clothing, non–food packaging, heritage collections, artificial leather for automotive interiors and many other products where rubber can be replaced, e.g. [1]. PVC long-term stability depends on loading conditions. The literature contains reports presenting mechanical and electrical stability studies [2].

A new approach to optimization of dye-sensitized solar cell, DSSC, performance, based on addition of POSS-based ionic liquid as an additive for I-/I-3(-) electrolyte systems is proposed. Iodide PEO-POSS Its are presented as conductive and thermally stable additives for DSSC electrolytes. Multifunctional M(EO)(n) Im(+)I(-) PIB7T8 POSS ILs with polyethylene oxide, PEO, chains of different lengths, n = 1-7 for M(PEG350), were synthesized, characterized and used as electrolyte additives for DSSCs, based on MPIm(+)I(-) or M(EO)(2)PIm(+)I(-)/butyronitrile electrolyte systems. The amphiphilic PEO ionic liquid-functionalized POSS molecules are considered as a potential POSS-based anodic surface modifier. The beneficial orientation of the PEO-POSS IL additive with the longest PEO chain at the anodic surface enabled a 7% increase in DSSC conversion efficiency. The positive influence of the additives' specific structure and anodic surface orientation on DSSC performance will be revealed in this research.

Two temperature and pH responsive submicron hydrogels based on poly(N- methylenebisacrylamide), chitosan and β-cyclodextrines (PNCS/CD hydrogel) with varying poly(N-isopropylacrylamide) to chitosan ratios were synthesized according to a simplified procedure, reflecting improved stimuli responsive properties and excellent bio-barrier properties, granted by incorporated chitosan. Hydrogels were applied to cotton-cellulose fabric as active coatings. Subsequently, antimicrobially active savory essential oil (EO) was embedded into the hydrogels in order to develop temperature- and pH-responsive cotton-cellulose fabric with double antimicrobial activity, i.e., bio-barrier formation of chitosan along with the proactive release of savory EO at predetermined conditions. The influence of the hydrogels chemical composition on stimuli responsive and antibacterial properties were assessed. Both PNCS/CD hydrogels showed stimuli responsiveness along with controlled release of savory EO. The chemical composition of the hydrogels strongly influenced the size of the hydrogel particles, their temperature and pH responsiveness, and the bio-barrier forming activity. The increased concentration of chitosan resulted in superior overall stimuli responsiveness and excellent synergy between the antimicrobial activities of the hydrogel and released savory EO.