A facile and green method for the production of novel and potentially biocompatible poly(amide-imide)/ZrO2–poly(vinyl alcohol) nanocomposites containing trimellitylimido-l-leucine linkages

We have reported the synthesis of nanocomposites (NCs) based on chiral poly(amide-imide) (PAI) and modified zirconium nanoparticles (ZrO₂ NPs) with poly(vinyl alcohol) (PVA). The optically active PAI was prepared under the green condition via the direct polycondensation of biocompatible trimellitylimido-l-leucine diacid and 4,4′-diaminediphenylsulfone in the presence of tetrabutylammonium bromide and triphenyl phosphite as the green solvent and the activating agents. NPs, due to a high surface to volume ratio, have a great tendency to agglomerate in the polymer matrix. So, at first, the surface of ZrO₂ NPs was modified with the PVA as the biodegradable and biocompatible polymer. Afterward, the modified NPs were added into the PAI matrix in the ethanol solution under ultrasonic irradiations. The obtained PAI/ZrO₂–PVA NCs (PZ–PNC)s were characterized by various techniques. The Fourier transform infrared proved the formation of PZ–PNCs. Field emission-scanning electron microscopy exhibited that ZrO₂ NPs had good dispersion in the PAI matrix, and transmission electron microscopy indicated that ZrO₂ NPs were coated by a nanometer-thick layer of PVA that was about 10 nm. X-ray diffraction analysis showed that the ZrO₂ NPs retained their crystalline structure after they were added in the PAI matrix. Thermogravimetric analysis illustrated that the prepared PZ–PNCs had a better thermal stability than the neat PAI.     

Ultrasonic assisted organo-modification of mesoporous SBA-15 with N-trimellitylimido-l-methionine and preparation of the poly(amide–imide)/SBA nanocomposites

Mesoporous SBA-15 materials were functionalized with N-trimellitylimido-l-methionine through ultrasonic irradiation, and the resulting functionalized materials were investigated as reinforcing agent for the preparation of the polymer based nanocomposites (NCs). An optically active and organo-soluble l-methionine containing poly(amide–imide) (PAI) was synthesized by the direct step-growth polymerization reaction of the above chiral diacid and 3,5-diamino-N-(pyridin-3-yl) benzamide in molten tetrabutylammonium bromide as a green solvent. A simple solution blending process was used to efficiently disperse modified-SBA into the chiral PAI to obtain PAI/modified-SBA NCs. The obtained NCs were characterized by Fourier transform-infrared spectroscopy, thermogravimetry analysis (TGA), X-ray diffraction, field emission-scanning electron microscopy, and transmission electron microscopy (TEM) techniques. TGA data indicated an increasing in thermal stability of the NCs when compared to the pure polymer. TEM images show well-ordered hexagonal arrays of mesopores SBA and the average distances between neighboring pores is around 3–5 nm.     

The utilization of poly(amide-imide)/SiO2 nanocomposite as nanofiller for strengthening of mechanical and thermal properties of poly(vinyl alcohol) nanocomposite films

The present investigation reports the preparation and characterization of the thermally stable poly(vinyl alcohol)/(poly(amide-imide)-SiO₂) nanocomposite (PVA/PAI-SiO₂ NC) films. For this reason, the surface of SiO₂ nanoparticles (NPs) was modified with N-trimellitylimido-l-methionine and subsequently, 5 wt.% of modified SiO₂ NPs were dispersed in the PAI matrix via sonochemical reaction. The resulting NC was studied by different techniques. Finally, the PAI-SiO₂ NC was employed as nanofiller and was incorporated into the PVA matrix for the enhancement of its mechanical and thermal properties. The synthesized NCs were studied by Fourier transform infrared and X-ray diffraction spectroscopy analysis. The surface topography and morphology of the NCs were studied by atomic force microscopy techniques, field emission scanning electron microscopy and transmission electron microscopy. The micrographs demonstrated that the nanofillers were homogeneously dispersed in the PVA matrix. The thermo gravimetric analysis curves indicated that the thermal decomposition of the PVA/PAI-SiO₂ NC films shifted toward higher temperature in comparison with the pure PVA. The effect of nanofiller on the mechanical properties of NC films was also explored.     

Synthesis,characterization, and photocatalytic properties of ZnO nano-flower containing TiO2 NPs

In this study, TiO₂-impregnated ZnO nano-flowers were synthesized by one-pot hydrothermal process. Aqueous suspension containing ZnO precursor and commercial TiO₂ NPs (P25) is heated at 140 °C for 2 h. The morphology and structure of as-synthesized particles were characterized by field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), and X-ray diffraction (XRD), which revealed that TiO₂ NPs were attached on the surface of ZnO flower. It was observed that the presence of TiO₂ NPs in the hydrothermal solution could sufficiently decrease the size of ZnO flower. The hybrid nanostructure, with unique morphology, obtained from this convenient method (low temperature, less time, and less number of reagents) was found to be effective photocatalyst under UV-irradiation.     

Preparation and characterization of reinforced poly(vinyl alcohol) films by a nanostructured,chiral, L-leucine based poly(amide-imide)/ZrO2 nanocomposite through a green method

In the present investigation, at first, the surface of ZrO₂ nanoparticles was modified with a bioactive and biocompatible diacid based on leucine amino acid as a coupling agent. The grafting of diacid on the surface of ZrO₂ was confirmed by Fourier transform infrared spectroscopy and thermogravimetric analysis. Then, the synthesis of poly(amide-imide)/ZrO₂ nanocomposite (PAI/ZrO₂ NC) was performed through ultrasonic technique. The obtained NCs demonstrated good thermal stability. Field emission scanning electron microscopy and transmission electron microscopy analysis showed that the average diameter of NP was around 15–20 nm. Finally, the resulting NC, was used as a nano-filler and was incorporated into the poly(vinyl alcohol) (PVA) in order to improve its mechanical and thermal properties. The PVA/PAI–ZrO₂ NC films were characterized by different techniques. The data indicated that the thermal and mechanical properties of the PVA/PAI–ZrO₂ NC were enhanced. It was attributed to the good dispersion of filler into the PVA matrix as a result of hydrogen bonding.     

Electrical conductivity of carbon nanotube/poly(vinylidene fluoride) composites prepared by high-speed mechanical mixing

Electrically conductive multi-walled nanotube (MWCNT)/poly(vinylidene fluoride) (PVDF) composites with a segregated structure were prepared by high-speed mechanical mixing method. It was found that MWCNTs were uniformly dispersed on polymer particle surfaces. At the MWCNTs composition of 0.1 vol.%, the composites exhibited a dramatic enhancement in electrical conductivity by 11 orders of magnitude. A low percolation threshold was achieved at the CNT concentration of 0.078 vol.%. The mechanical mixing method presented can be adapted to other CNT/polymer composites with a segregated structure.     

Supercritical antisolvent micronization of PVP and ibuprofen sodium towards tailored solid dispersions

The supercritical antisolvent technology is used to precipitate polyvinylpyrrolidone (PVP) particles and crystallise ibuprofen sodium (IS) crystals separately and in the form of solid dispersion together. Supercritical carbon dioxide (scCO₂) is used as antisolvent. For PVP particle generation, ethanol, acetone and mixtures of ethanol and acetone are used as solvents. The initial concentration of PVP in the solution was varied between 0.5 wt% and 1.5 wt%, the operation pressure between 10 MPa and 30 MPa and the composition of ethanol/acetone solvent mixtures between 100 wt% and 0 wt% of ethanol at a constant temperature of 313 K. Furthermore, the mean molecular weight of the polymer was varied between 40 kg mol⁻¹, 360 kg mol⁻¹ and 1300 kg mol⁻¹. An increase of the content of the poor solvent acetone in the initial solvent mixture as well as the usage of PVP with a higher molecular weight, leads to a significant decrease in mean particle size. At all the investigated parameters always fully amorphous PVP powder precipitates. For IS, only ethanol was used as the solvent, the initial IS concentration in the solution was varied between 1 wt% and 3 wt% and the operation pressure between 10 MPa and 16 MPa. A variation of these parameters leads to a manipulation of the size and the morphology of the crystallised IS crystals. Irrespective of the parameters used, always the same polymorphic form of ibuprofen sodium is produced. The solid dispersions were generated at different compositions of PVP to IS and with two different molecular weights of PVP at otherwise constant conditions. Fully amorphous solid dispersions consisting of IS and PVP together were generated at different ratios of PVP to IS.The mechanisms that control the final particle properties are discussed taking into account two different models for “ideal” and “non-ideal” solutes. Furthermore, the study of the “unconventional” SAS parameters, molecular weight and solvation power of the solvent shows that these parameters qualify to tailor polymer particle properties via SAS processing. Next to the investigation into the behaviour of both solutes separately, fully amorphous solid dispersions consisting of IS and PVP together were generated. While X-ray diffraction was used to analyze the crystalline structure of the particles, respectively, solid dispersions, their morphology was analysed using scanning electron microscopy (SEM).     

Nanocomposite polyHIPEs with magnetic nanoparticles: Preparation and heating effect

Emulsion templating of high internal phase emulsions (HIPEs) was used to synthesise microcellular poly(styrene-co-divinylbenzene) magnetic nanoparticle composites with open, interconnected, porous structures. The emulsions were stabilised by a combination of a surfactant and maghemite/magnetite (uncoated or coated with oleic acid) nanoparticles and then cured thermally. Up to 23 wt% (with regards to complete composite mass) of magnetic nanoparticles were incorporated into the polymer matrix. Composite polymers exhibited magnetic properties with a saturation magnetisation of 13 emu/g and a substantial heating effect at the AC magnetic field of 3.8 kA/m and a frequency of 104 kHz. A nanocomposite polyHIPE sample with coated nanoparticles exhibited a higher hyperthermia effect. Samples retained typical polyHIPE morphology with cavity diameters of approx. 8 μm and interconnecting pores of around 0.8 μm in diameter. Compared to styrene/divinylbenzene polyHIPEs without nanoparticles, the openness (interconnecting pore size to cavity size ratio) was slightly reduced. Materials were characterised with gas adsorption porosimetry, XRD, TGA/DSC, SEM, TEM.     

Bio-inspired cross-linking with borate for enhancing gas-barrier properties of poly(vinyl alcohol)/graphene oxide composite films

The demand for flexible and transparent barrier films in industries has been increasing. Learning from nature, borate ions were used to cross-link poly(vinyl alcohol) (PVA) and graphene oxide (GO) to produce flexible, transparent high-barrier composite films with a bio-inspired structure. PVA/GO films with only 0.1 wt% GO and 1 wt% cross-linker exhibited an O₂ transmission rate <0.005 cc m⁻² day⁻¹, an O₂ permeability <5.0 × 10⁻²⁰ cm³ cm cm⁻² Pa⁻¹ s⁻¹, and a transmittance at 550 nm >85%; thus, they can be used for flexible electronics. Fourier transform infrared spectrometry and X-ray photoelectron spectroscopy indicated that the outstanding barrier properties are attributed to the formation of chemical cross-linking involving borate ions, GO sheets, and PVA, similar to the borate cross-links in high-order plants. Comparing our experimental data with the Cussler model, we found that the effective aspect ratio was significantly increased after cross-linking, suggesting that cross-linking networks connected GO with each other to form ultra-large impermeable regions. A feasible green technique, with potential for commercial production of barrier films for flexible electronics was presented.     

Effect of silane modified nano ZnO on UV degradation of polyurethane coatings

Nanosized ZnO modified by 2-aminoethyl-3-aminopropyltrimethoxysilane (APS) was prepared using the precipitation method. Modified nano ZnO by silane (ZnO-APS) was characterized by XRD, SEM, TEM and UV–vis measurements. The degradation of the polyurethane coating, the polyurethane coatings containing 0.1 wt% nano ZnO and the polyurethane coatings containing nano ZnO-APS at two concentrations (0.1 and 0.5 wt%) during QUV test was evaluated by gloss measurement and electrochemical impedance spectroscopy. The coating surface after QUV test was observed with SEM. The results show that nano ZnO-APS has spherical structure with particle size around 10–15 nm. Nano ZnO improved the UV resistance of the PU coating and surface treatment by APS enhanced the effect of nano ZnO. The presence of nano ZnO-APS at 0.1 wt% concentration significantly improved the UV resistance of polyurethane coating.     

High performance holographic gratings formed with novel photopolymer films containing hyper-branched silsesquioxane

A transparent photopolymer film was prepared by embedding the epoxy cured octaaminophenylsilsesquioxane (hyper-branched POSS) into poly(vinyl chloride) (PVC) matrix containing vinyl monomers. Holographic gratings were successfully generated in that films by irradiation of laser light with 532 nm wavelength.The diffraction efficiency was increased with increasing the hyper-branched POSS concentration up to 15 wt%. DSC and TG analysis indicated the plasticizing effect of POSS in photopolymer that loosened the polymer matrix. This plasticizing effect made the monomer diffusion much more effective providing higher diffraction efficiency (D.E. ∼ 80%) compared to the film without hyper-branched POSS (D.E. ∼ 50%). The diffraction efficiency started to decrease with further higher concentration of POSS, because the polymer film became less transparent.Low volume shrinkage of 1.64% could be also obtained in recording of slanted holographic gratings.     

Electrochemical synthesis of a novel poly(2,5-dimethoxy aniline) nanorod for ultrasensitive glucose biosensor application

We report for the first time a rapid electrochemical synthesis of one-dimensional poly(2,5-dimethoxyaniline) nanorods (PDMA-NR) in the presence of surfactant. FE-SEM and TEM images confirm the PDMA-NR formation and the average diameter of single rod sizes in the range of ∼200–300 nm. An enzymatic glucose biosensor was fabricated through immobilizing glucose oxidase (GOx) into PDMA-NR matrix. The amperometric current response of PDMA-NR/GOx to glucose is linear in the concentration range between 1 and 10 μM with a detection limit of 0.5 μM (S/N = 3). The PDMA-NR/GOx electrode possesses high sensitivity (5.03 μA/μM), selectivity, stability, and reproducibility toward glucose.     

Reaction kinetics of hydrothermal depolymerization of poly(ethylene naphthalate), poly(ethylene terephthalate), and polycarbonate with aqueous ammonia solution

Poly(ethylene naphthalate) (PEN), poly(ethylene terephthalate) (PET) and poly(carbonate) (PC) were depolymerized in a semi-batch reactor with a 0.6 M aqueous ammonia solution under hydrothermal conditions, at 433–553 K and 10 MPa, compared with aqueous alkaline (NaOH and KOH) solutions and water alone. The polymers studied were almost completely converted into monomers in an aqueous ammonia solution as well as aqueous NaOH and KOH solutions under hydrothermal conditions. The depolymerization reactions for the three polymers consisted of the initial induction stage, where the reactions proceeded very slowly, and the major depolymerization stage thereafter. The induction times were correlated with temperature. In the latter stage the overall depolymerization rate for each polymer was represented by 2/3-order reaction kinetics with respect to the amount of unreacted polymer, suggesting that the reaction occurred on the polymer surface. The depolymerization rates for PC with a 0.6 M aqueous ammonia solution were much faster than those with a 0.6 M aqueous NaOH solution.     

Synthesis of organic–inorganic polymer hybrids from poly(vinyl chloride) and polyhedral oligomeric silsesquioxane via CH/π interaction

The synthesis of poly(vinyl chloride) (PVC)/polyhedral oligomeric silsesquioxane (POSS) polymer hybrids was performed utilizing CH/π interaction. Poly(vinyl chloride) as an organic component was dissolved in THF with octaphenethylsilsesquioxane (Phenethyl-POSS) or octacyclohexylsilsesquioxane (Cyclohexyl-POSS) as an inorganic component. The resulting mixture was placed at 40 °C for 2 weeks. The obtained polymer hybrid was dried in vacuo at 60 °C for 2 days. The transparent polymer hybrids were obtained when Phenethyl-POSS was employed as an inorganic component. In contrast, polymer hybrid became turbid when Cyclohexyl-POSS was used. These results suggest that the CH/π interaction was found to act as an important role for the dispersion of Phenethyl-POSS in the PVC matrix.     

Sintering behaviour of silicon carbide matrix composites reinforced with multilayer graphene

The scope of this paper includes preparation and characterisation of dense silicon carbide matrix composites reinforced with multilayer graphene (MLG). Application of graphene as a reinforcement phase should simultaneously improve mechanical properties of SiC matrix composites and act as one of the sintering activators. In the present work the mechanical properties and the microstructure changes of samples sintered with different additions of graphene (0.5, 1, 2, 3, 4 wt%) and boron (0.3, 1 and 2 wt%) were examined. The composites were consolidated at two different temperatures (1800 °C and 1900 °C) using the Spark Plasma Sintering method (SPS). Reference samples with the addition of graphite as a source of carbon (1 and 3 wt%) were also sintered in the same conditions. The abovementioned amounts of graphite are an optimal content which is essential to obtain high density of samples [1], [2], [3], [4], [5], [6], [7], [8], [9]. The influence of MLG on density, mechanical properties and phase structure of the sintered samples were investigated. A high rate of densification for the composites with 0.3 wt% of B and 1 wt% of MLG sintered at 1900 °C was observed. Moreover, these composites showed the highest average of microhardness (2663 HV0.5) and single-phase structure.     

Effect of concentration and degree of saturation on co-precipitation of catechin and poly(l-lactide) by the RESOLV process

Rapid expansion of subcritical solutions into liquid solvents (RESOLV) was able to consistently produce catechin (CTC)-loaded poly(l-lactide) (PLLA) nanoparticles. The effects of CTC concentration and processing conditions – pre-expansion temperature and pressure, and degree of saturation – on the size and morphology of CTC-loaded PLLA nanoparticles were investigated, as well as the loading capacity (LC), entrapment efficiency (EE), and release of CTC. RESOLV experiments were carried out with 0.1 wt% CTC + 0.2 wt% PLLA and 0.2 wt% CTC + 0.2 wt% PLLA solutions in mixtures of EtOH and CO₂ (3:2, wt/wt) with pre-expansion temperature and pressure of 60–100 °C and 265–325 bar, respectively. The obtained CTC-loaded PLLA nanoparticles were spherical, with average sizes, LC, and EE ranges of ∼30–40 nm, 2.4–7.3%, and 4.7–22.0%, respectively. CTC concentration, pre-expansion temperature, and degree of saturation had significant effects on LC and EE of CTC, without affecting the size of composite nanoparticles. The LC and EE of CTC increased with increasing pre-expansion temperature and degree of saturation, and with decreasing CTC concentration. The release profiles of CTC from the nanoparticles exhibited an initial stage of burst release (first 8 h) followed by a sustained release (∼1–9 days). Furthermore, the fraction of CTC being released from the nanoparticles decreased with increasing the degree of saturation of subcritical solutions prior to rapid expansion and with increasing the LC of CTC.     

Dispersion polymerization of MMA in supercritical CO2 in the presence of poly(poly(ethylene glycol) methacrylate-co-1H,1H,2H,2H-perfluorooctylmethacrylate)

Various random copolymers of poly(poly(ethylene glycol) methacrylate-co-1H,1H,2H,2H-perfluorooctylmethacrylate) (p(PEGMA-co-FOMA)) with different poly(ethylene glycol) (PEG) chain length (M_n = 300, 475, and 1100) and different FOMA content have been synthesized in supercritical carbon dioxide (scCO₂) via free-radical polymerization. The copolymers containing above 50 wt% FOMA could be used as a stabilizer for the polymerization of methyl methacrylate (MMA) in scCO₂. For PEGMA (300) and PEGMA (475) copolymers, the copolymeric stabilizer with 67–69 wt% FOMA content was shown to be optimal to produce micrometer-size spherical PMMA powder. The size of pendant PEG group and the composition of copolymer as well as the concentration of MMA affected on the size of PMMA particles and the stability of PMMA latexes in CO₂.     

New polymer electrolyte for electrochemical application

A solid polymer electrolyte consisting of poly vinylpyrrolidone (PVP) and potassium iodide (KI) were developed, characterized for possible application in dye sensitized solar cell (DSSC) as an electrolyte. Complex impedance spectroscopy revealed the enhancement in electrical conductivity (σ) by salt doping and a conductivity maximum was obtained at 30 wt% KI concentration. Dielectric phenomena also support the σ data. Fourier transform infrared spectroscopy (FTIR) confirmed the composite nature of polymer electrolyte film. Using maximum electrical conductivity film we have fabricated a DSSC which shows 0.14% efficiency at 1 sun condition.     

Jatropha curcas oil based alkyd/epoxy/graphene oxide (GO) bionanocomposites: Effect of GO on curing,mechanical and thermal properties

Jatropha curcas oil based alkyd/epoxy/GO bionanocomposites were prepared by direct solution blending of alkyd/epoxy blend matrix with GO nano filler. Structures and properties of the bionanocomposites were characterized with Fourier transform infrared spectroscopy, X-ray diffraction, transmission electron microscopy, differential scanning calorimetry, thermogravimetric analysis, and tensile testing. X-ray diffraction and transmission electron microscopy study demonstrates the formation of highly exfoliated GO layers and its homogeneous dispersion throughout the polymer matrix with 1 and 3 wt% GO. However, the intercalated structure is predominant with 5 wt% GO. The homogeneous dispersion and the strong interaction of the GO layers and the polymer matrix induced the significant improvement in thermal and mechanical properties of the bionanocomposites. The tensile strength and elastic modulus of the bionanocomposite increased by 133% and 68% respectively with 3 wt% GO loading. The thermal stability of the bionanocomposite improved by 39 °C and T_g is shifted toward higher temperature by 20 °C as compared to the pristine polymer. Incorporation of GO significantly decreases the curing time of the alkyd/epoxy resin blend.     

Formation of PVP hollow fibers by electrospinning in one-step process at sub and supercritical CO2

It was well known that electrospinning is one of the simple technical methods for the production of polymer nanoparticles and nanofibers. Various polymers have been successfully electrospun into ultrafine particles and fibers in recent years mostly in solvent solution and some in melt form. In this work, hollow fibers with walls made of organic polymer composites have been formed by electrospinning in a single processing step under pressurized carbon dioxide (CO₂). The experiments were conducted at 313 K and ∼8 MPa. The capability and feasibility of this technique was demonstrated by the production of polyvinylpyrrolidone (PVP) fibers whose size and wall thickness could be independently varied by controlling a set of experimental parameters. The PVP fibers had an average pore diameter 2–4 μm. At low pressures (<5 MPa; subcritical conditions), the solid fibers were formed, the baloon-like structures of PVP was formed with increasing pressure of CO₂ at 8 MPa (supercritical condition)