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ABSTRACT Three-dimensional fluorinated pentablock poly( l-lactide- co-ε-caprolactone)-based scaffolds were successfully produced by the incorporation of thermally exfoliated graphene oxide (TEGO) as an antimicrobial agent with an electrospinning technique. In a ring-opening polymerization, the fluorinated groups in the middle of polymer backbone were attached with a perfluorinated reactive stabilizer having oxygen-carrying ability. The fiber diameter and its morphologies were optimized through changes in TEGO amount, voltage, polymer concentration, and solvent type to obtain an ideal scaffold structure. Instead of the widely used graphene oxide synthesized by Hummer's method, TEGO sheets having a low amount of oxygen produced by thermal expansion were integrated into the fiber structure to investigate the effect of the oxygen functional groups of TEGO sheets on the degradation and antimicrobial activity of the scaffolds. There was no antimicrobial activity in TEGO-reinforced scaffolds in the in vitro tests in contrast to the literature. This study confirmed that a low number of oxygen functional groups on the surface of TEGO restricted the antimicrobial activity of the fabricated composite scaffolds. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43490. [ABSTRACT FROM AUTHOR]

Acrylonitrile was polymerized by an insertion process on being added to solutions containing the adduct of the reaction of tetrakis(dimethylamino) titanium (T4) and azobisisobutyronitrile (AIBN). The obtained azo-linked polyacrylonitrile has appropriate initiating functionality for a subsequent vinyl polymerization. [ABSTRACT FROM AUTHOR]

The morphology of nanostructures is a vital parameter to consider in components comprised of materials exhibiting specific functionalities. The number of process steps and the need for high temperatures can often be a limiting factor when targeting a specific morphology. Here, we demonstrate a repeatable synthesis of different morphologies of a highly crystalline monoclinic phase of vanadium dioxide (VO2(M)) using a one-step hydrothermal method. By adjusting the synthesis parameters, such as pH, temperature, and reducing agent concentration in the precursor, VO2 nanostructures with high uniformity and crystallinity are achieved. Some of these morphologies were obtained via the choice of the reducing agent that allowed us to skip the annealing step. Our results indicate that the morphologies of the nanostructures are very sensitive to the hydrazine hydrate (N2H4.H2O) concentration. Another reducing agent, dodecylamine, was used to achieve well-organized and high-quality VO2(M) nanotubes. Differential scanning calorimetry (DSC) experiments revealed that all samples display the monoclinic-to-tetragonal structural transition (MTST) regardless of the morphology, albeit at different temperatures that can be interpreted as the variations in overheating and undercooling limits. VO2(M) structures with a higher surface to volume ratio exhibit a higher overheating limit than those with low ratios. [ABSTRACT FROM AUTHOR]

Rice husk ash (RHA) having a porous sructure and a high amount of amorphous silica nanoparticles (4 nm) decorated on the surface of carbon nanosheets is a suitable and cheap candidate for the use of a grout additive. In this study, neat RHA and functionalized RHA (f-RHA) with three different loadings were successfully incorporated into the cement-bentonite based grouts by adjusting the water to cement ratio. The workability of the developed grouts having RHA-based additives was analyzed in terms of bleeding, density, flow spread, and Marsh cone time. Additionally, the thermal and prolongation of hydration performances of the cementitious grout were enriched by successful attachment of amino-silane functional groups on the RHA surface. The heat of hydration performances of RHA and functionalized RHA introduced cementitious grout composite were assessed by isothermal calorimetry tests, and especially the kinetics of hydration was increased by the addition of RHA. The presence of amino silane groups in f-RHA intensified the heat adsorption by reacting with cement constituents, and thus resulted in the retardation and reduction in the heat flow. Therefore, using an amino-silane coupling agent increased the induction period and hindered the heat of hydration compared to the reference grout. On the other hand, the incorporation of RHA and f-RHA into the cement matrix did not affect the thermal conductivity of the grouts. [ABSTRACT FROM AUTHOR]

An amorphous poly(urethane-urea) copolymer composed of 70 wt% poly(ethylene oxide) (PEO) soft segments (SS) (M w = 2000 g mol−1) and 30 wt% cycloaliphatic hard segments (HS) was subjected to in-situ X-Rays during tensile deformation. Mechanical hardening at room temperature was attributed to strain induced crystallization (SIC) of the PEO SS through the multiplication of aligned crystallites. The permanent nature of these crystals after stress removal indicates a certain mechanical stability, which we related here to the concomitant effect of superstraining of the SS crystallites and the HS reorganization upon deformation. This is in marked contrast to previous studies which reported the crystalline phase to be temporary upon unloading. A manifestation of such enhanced stability is the memory effect evidenced by an increased crystallizability of PEO segments during incremental cyclic loading. These results offer a way to (i) tune the mechanical properties of TPUs via the formation of mechanically stable pre-oriented SS crystals and to (ii) tune the thermally/water activated shape memory properties of TPUs (shape fixity, kinetics of shape memory recovery). [Display omitted] • Mechanical hardening in TPU due to strain induced crystallization (SIC) of PEO SS. • SIC is found permanent after stress removal for sufficiently applied load. • The SS crystals keep the memory of their strain induced orientation. • Improved mechanical performance of pre-stretched TPU containing PEO crystals. [ABSTRACT FROM AUTHOR]

In this study, condensation characteristics of water vapor on micro-structured surfaces at different pressures and subcooling temperature has been investigated experimentally. This work represents a basic study in order to design a secondary evaporator section in a refrigeration cycle. A set of surfaces has been manufactured over copper substrates with one sample used as unstructured (smooth) reference surface and two micro-structured surfaces with longitudinal grooves having V-shape and square cross-sections. As the second step, the surfaces have been modified by using a polymer coating to achieve stronger hydrophobicity at the surface and hence to influence wettability such that increased heat transfer rates should be reached. The polymer coating has been created with a dip coating process by applying a mixture of perfluoroalkyl triethoxysilane. Concerning the wettability, a high-speed flow visualization study has been performed for the interpretation of heat transfer results. Experimental results showed that an increase in the droplet contact angle by applying the polymer coating over surfaces, while the largest droplet contact angle was obtained (130.9°±2.0°) for the surface with V-shaped micro-structuring compared to other surfaces. The comparison of heat transfer performance reveals an enhancement in heat transfer coefficient for the coated version of unstructured, square-grooved and V-grooved surface by 34.5%, 61.8%, and 73.4%, respectively. • Pf-IPTES coat leads to heat transfer increase at comparable operating conditions. • Hydrophobicity resulted in heat transfer augmentation for all surfaces used. • At p max = 1.25 Bar, contribution of Pf-IPTES to heat transfer increase was weak. • Heat transfer performance using micro-structures was similar/lower than bare surface. • Steady condensation is strongly sensitive to vapor pressure. [ABSTRACT FROM AUTHOR]

This study reports the synthesis of highly branched poly(arylene ether sulfone)s (HBPAES) and their incorporation into linear poly(arylene ether sulfone) (LPAES) to investigate the effect of branched topology on the morphological and mechanical properties of final polymer blends. The A 2 + B 3 polymerization was utilized to synthesize HBPAESs with varying distance between branch points by reacting monomeric 4,4′-dichlorodiphenyl sulfone (DCDPS) or pre-synthesized chlorine terminated linear oligomers with various degrees of polymerization as the A₂ species with 1,1,1-tris(4-hydroxyphenyl)ethane (THPE) as the B₃ monomer. The chemical structure and the degree of branching of synthesized HBPAESs were characterized by 1H Nuclear Magnetic Resonance (NMR) spectroscopy, while Size Exclusion Chromatography (SEC) and Differential Scanning Calorimetry (DSC) were used for the determination of their molecular weight and glass transition temperatures. Polymer blends of HBPAES and LPAES (10/90 w/w) were solution cast into free-standing, dry films and characterized by tensile tests, Dynamic Mechanical Analysis (DMA), Atomic Force (AFM) and Scanning Electron (SEM) Microscopies. Complementary to experimental studies, these blends were modeled with dissipative particle dynamics (DPD) simulations to explain their microphase behavior, miscibility, and morphology. The experimental and computational studies together revealed that understanding the effect of the degree of branching on the intermolecular interactions of highly branched polymers with their linear analogues is critical to obtain final polymer blends with tunable mechanical properties and enhanced fracture behavior. Image 1 • A set of HBPAESs was synthesized with varying distance between branch points via the A 2 +B 3 polymerization at a A 2 :B 3 ratio of 0.85. • Blends of LPAES and HBPAESs were miscible with a single T g value, which was also supported by DPD simulations. • The incorporation of HBPAES into LPAES changed the fracture behavior of resulting blend films depending on the degree of branching (DB) of the HBPAES component. • The physical form of HBPAES was found to change from spherical to rod-like structures in blends as a function of the DB. [ABSTRACT FROM AUTHOR]

One-component epoxy resins (OCERs) with improved stability (shelf life) and controlled curing temperatures were prepared using epoxy resins and polyoxazoline-imidazole (POZ-Im) based thermal latent curing agents (TLCs). POZ homopolymers with molar masses of 1000, 2000, and 5000 g/mol were obtained via cationic ring-opening polymerization (CROP) of 2-ethyl-2-oxazoline, 2-propyl-2-oxazoline, 2-pentyl-2-oxazoline, and 2-phenyl-2-oxazoline. TLCs were prepared by physically entrapping imidazole, the curing agent, in the POZ matrix at the homopolymer/Im (HP/Im) ratios of 1:1 and 5:1 and characterized by FTIR and TGA. TLCs were then mixed with bisphenol A diglycidyl ether (DGEBA) to obtain OCERs with Im concentrations of 1, 3, and 5 wt %. Dynamic DSC tests were performed to determine the effect of the pendant group and molar mass of POZ, the POZ/Im ratio, and Im concentration on the curing behavior of the OCERs, whereas isothermal DSC tests were carried out to examine their thermal stability and optimal curing temperatures. Optical microscopy was performed to study the compatibility of the TLCs with DGEBA. This study showed that the dispersion quality of TLCs is highly associated with the compatibility of POZs and DGEBA, which affected the release of Im, thus left limit temperatures of curing. In addition, higher left limit temperatures were obtained when the POZ/Im ratio increased. Isothermal DSC results conformed to the improved stability and better thermal latency of the samples with a POZ/Im ratio of 5:1. Moreover, the higher left limit temperatures were obtained with the lowest molar mass of POZ due to the better interaction between the -OH end group of POZ and Im. The shelf life of PEOZ 1K-Im 5:1 1% OCER was predicted at -20, 0, and 20 °C, with an estimated 15.3 days at 20 °C using isothermal DSC and rheology at 50, 60, and 70 °C. Overall, this research contributes to the development of OCERs by introducing POZ-Im complexes as novel TLCs. The findings shed light on the importance of compatibility in achieving optimal dispersion and release of Im and the role of the POZ/Im ratio and POZ molar mass in controlling left limit temperatures, ultimately influencing the curing behavior of OCERs., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

One-component epoxy resins (OCERs) are proposed to overcome the energy inefficiency and processing difficulties of conventional two-component epoxy resins by employing latent curing agents, specifically thermal latent curing agents (TLCs). Despite recent progress, the need for TLCs with a simple preparation method for different curing agents, epoxy resins, and process conditions remains. Here, tailorable TLCs were prepared by forming complexes between imidazole (Im) and amphiphilic polyoxazoline copolymers with tunable structures and properties by a solvent evaporation method. The obtained TLCs were manually mixed with DGEBA to prepare OCERs. The miscibility of the complexes with DGEBA was studied, considering the functionalities of copolymers. The curing behaviors of TLCs were compared using dynamic Differential Scanning Calorimetry (DSC) studies considering the side chain and composition of the copolymers, copolymer:Im ratio, and concentration of Im in DGEBA. The curing behavior of the promising OCERs was studied by isothermal DSC studies to investigate their stability at different temperatures and curing rate at elevated temperatures revealing the stability of these OCERs., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

Poly(ethylene oxide) (PEO)-based polymer electrolytes are a promising class of materials for use in lithium-ion batteries due to their high ionic conductivity and flexibility. In this study, the effects of polymer architecture including linear, star, and hyperbranched and salt (lithiumbis(trifluoromethanesulfonyl)imide (LiTFSI)) concentration on the glass transition ( T g ), microstructure, phase diagram, free volume, and bulk viscosity, all of which play a significant role in determining the ionic conductivity of the electrolyte, have been systematically studied for PEO-based polymer electrolytes. The branching of PEO widens the liquid phase toward lower salt concentrations, suggesting decreased crystallization and improved ion coordination. At high salt loadings, ion clustering is common for all electrolytes, yet the cluster size and distribution appear to be strongly architecture-dependent. Also, the ionic conductivity is maximized at a salt concentration of [Li/EO ≈ 0.085] for all architectures, and the highly branched polymers displayed as much as three times higher ionic conductivity (with respect to the linear analogue) for the same total molar mass. The architecture-dependent ionic conductivity is attributed to the enhanced free volume measured by positron annihilation lifetime spectroscopy. Interestingly, despite the strong architecture dependence of ionic conductivity, the salt addition in the highly branched architectures results in accelerated yet similar monomeric friction coefficients for these polymers, offering significant potential toward decoupling of conductivity from segmental dynamics of polymer electrolytes, leading to outstanding battery performance., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

Wastewater from the textile industry contains high concentrations of pollutants, so the wastewater must be treated before it is discharged. In addition, the reuse of treated wastewater should be considered from an environmental point of view, as large volumes of wastewater are produced. Since textile wastewater mainly contains dyestuffs, it must be treated effectively using environmentally friendly technologies. Membrane processes are widely used in textile wastewater treatment as they have distinct advantages over conventional wastewater treatment methods. This study reports the pilot-scale manufacturing and characterization of three different NF membranes. Three different types of membranes were fabricated. The fabricated membranes were compared through characterization by surface properties, chemical structure and morphology. Membranes were tested for pure water flux. Then the synthetic wastewater (SWW) was tested for flux and rejection. Lastly, the textile wastewater was tested. The textile wastewater flux of pure piperazine (PIP), 60% S-DADPS and 0.04% halloysite nanotubes (HNTs) were 22.42, 79.58 and 40.06 L m -2 h -1 . It has been proven that the 60% s-DADPS membrane provides up to four times improvement in wastewater flux and simultaneously. In addition, NF membranes produced using HNT and sDADPS on a pilot scale have brought innovation to the literature with the good results obtained.

Poly(2-oxazoline)s (POZs) are widely investigated for their applications in various fields due to their unique properties. To exploit and combine different characteristics of the POZ family, 2-oxazoline monomers can be copolymerized to prepare tailor-made copolymers with the desired glass transition temperature ( T g ), melting temperature ( T m ), amphiphilicity, and functionality. Here, we report the synthesis and characterization of 2-oxazoline monomers and a range of POZ copolymers produced, thereof. 2-Propyl-2-oxazoline (PrOZ) and 2-pentyl-2-oxazoline (PeOZ) monomers were synthesized by two different methods starting from nitriles or carboxylic acids. A number of POZ copolymers were synthesized by copolymerization of 2-ethyl-2-oxazoline (EOZ) with either one of PrOZ, PeOZ, or 2-phenyl-2-oxazoline (PhOZ) at three different compositions (25:75, 50:50, and 75:25) and three molecular weights (1000, 2000, and 5000 Da). The successful synthesis of the monomers and copolymers was demonstrated through their structural analysis by 1 H NMR and FTIR. SEC results confirmed the targeted molar masses of the copolymers and living nature of the polymerization by showing low dispersity values. Thermal properties of the copolymers were studied using DSC and TGA. DSC studies revealed the amorph and random state of the copolymers with obtained T g values for the copolymers in the range of -3 to 84 °C depending on their molecular weight and type of the side chain. While the presence of longer aliphatic side chains resulted in lower T g values, the presence of 2-phenyl substituents on the polymer led to higher T g values. The decomposition temperatures determined by TGA were in the range of 328 to 383 °C depending on the molecular weight, composition, and side chain of the copolymers. It was observed that higher molecular weights led to higher T g values and decomposition temperatures. While copolymers with aliphatic side chains exhibited a single-step decomposition profile, the decomposition of copolymers having aromatic side chains occurred in multiple steps. The variations in the molecular weight, composition, and side chains of the copolymers resulted in a library of tailorable amphiphilic copolymers suitable for multiple applications ranging from biomedical applications to composite manufacturing., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

This paper reports the synthesis of nanocomposite agarose hydrogels with improved bioactivity with the incorporation of anisotropic 2D nanosilicates (Laponite) to promote cell binding, growth and proliferation. Rheological measurements showed that the incorporation of nanosilicates slightly increased the gelation temperature (T gel ). The use of higher nanosilicate content at the constant agarose concentration improved the mechanical properties of the gels. Due to the non-swelling nature of agarose, the addition of nanosilicates did not result in any remarkable change in the swelling properties of the agarose gels, while collapsed agarose nanofibers were observed with the incorporation of nanosilicates. EDX analysis confirmed the presence of the embedded nanosilicates in the gel matrix. The existence of physical interactions between nanosilicate and agarose was demonstrated by FTIR over the shifting of SiO stretching band to a lower frequency. The encapsulated NIH/3T3 fibroblast cells showed enhanced proliferation and spreading in the presence of nanosilicates., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

We report molecular dynamics in the rigid amorphous fraction (RAF) of the polymer bound at the interfaces with nanoparticles in polymer nanocomposites and calculate the glass transition temperature, T g , for this bound layer of polymer. We follow the '3-phase-model' for semicrystalline polymers where the polymer matrix consists of the crystalline fraction (CF), the mobile amorphous fraction (MAF) and the RAF. While the amorphous polymer bound by crystallites is completely rigid, neither contributing to the glass transition, nor displaying molecular dynamics, the amorphous polymer bound at the interfaces with filler displays decelerated dynamics, as compared to the bulk polymer. Reports in the literature suggest a discrepancy between T g values obtained by Differential Scanning Calorimetry (DSC) and by Dielectric Relaxation Spectroscopy (DRS). As a plausible explanation we suggest that DRS results in T g values taking into account the bound polymer, whereas DSC does not. For this investigation we use semicrystalline polyurethane-urea/SiO 2 nanocomposites and employ, next to DSC and DRS, SEM, SAXS and WAXS for morphological characterization. It is our intention to use DRS as a tool for investigating the RAF.