Water‐dispersed graphene oxide sheets were used to prepare graphene/poly(ethylene glycol) diacrylate resin composites by photopolymerization. It was found that graphene sheets undergo excellent morphological distribution within the resin system, giving rise to transparent composites with unaltered thermal properties with respect to the neat resin, that are electrically conductive at loading ratios as low as 0.02 wt.‐% of graphene oxide. The proposed strategy based on photopolymerization provides an easy, energy‐saving and environmental friendly technique that can find a wide application in coating technology, mainly for electromagnetic shielding and antistatic coatings.
A new route for the manufacturing of silica/poly(benzimidazole) (PBI) nanocomposites fibers is described. PBI was synthesized via melt polycondensation and polycondensation in poly(phosphoric acid). Solutions of PBI and silica nanoparticles in N,N‐dimethylacetamide (DMAc) were electrospun to fibers and non‐wovens. The resulting materials were analyzed by ATR‐IR spectroscopy, small‐angle X‐ray scattering (SAXS) and nitrogen sorption measurements. The non‐wovens could be processed towards dense, cross‐linked membranes by hot pressing and treatment with p‐xylylene dichloride.
This review presents the state of the art regarding the improvement of scratch resistance of polymeric coatings. In particular, our attention is focused on the effect of inorganic nanometric fillers on the scratch resistance of organic coatings. Two main strategies are described for the achievement of such nanostructured hybrid organic/inorganic coatings: either a top‐down or a bottom‐up approach.
In this comparative study, the charge storage performance of commercial high‐temperature polymer films was evaluated and correlated with their chemical structure. Isothermal surface potential decay measurements after annealing periods at 90 °C revealed that amorphous polyetherimide (PEI) films showed the best charge storage behavior. Polyimide films showed reduced charge storage performance, whereas sulfur‐containing polymer films are not suitable as electrets due to their fast charge decay. Additionally, the effect of water content in PEI films in the range of 0.02–0.79 wt.‐% was studied. Increasing amounts of water decreased the charge storage properties proportionally, but only by a relatively smaller amount: the highest investigated water content of 0.79 wt.‐% reduced the charge by only 30%.
Temperature‐responsive PVCL homopolymers and functional PVCL polymers containing carboxylic acids are prepared in organic and aqueous solutions. PVCL bulk polymers are characterized using 1H NMR, photometry, ATR‐FTIR, and thermal analysis. A finite phase transition at 37–40 °C occurs in aqueous solutions of PVCL and PVCL‐COOH. PVCL and PVCL‐COOH polymers are electrospun into fibers ranging from 100 to 2300 nm in diameter. PVCL/cellulose bi‐component films are obtained by electrospinning of CA and PVCL followed by alkaline hydrolysis. These tunable thermo‐responsive PVCL/cellulose nanofibers have potential applications in developing affinity membranes.
Short electrospun fibers were obtained by using UV cutting method. Either polymers with double bonds with a photocross‐linker (CL) and photoinitiator (PI) or known photochemistry of coumarin ([2 + 2] cycloaddition reaction) without the addition of CL and PI is utilized for making short electrospun fibers. The electrospun fibers were irradiated by UV light in the presence of a mask with a defined width of slits. The uncovered parts of fibers were cross‐linked and therefore became insoluble. The non‐cross‐linked parts were removed by immersion of the fibers into an appropriate solvent. The length of obtained short fibers can be controlled by changing the width of the slits of the employed mask.
Nanocomposites of poly(ethylene terephthalate) and two different montmorillonite‐based organoclays were prepared by a co‐rotating twin screw extruder. Dispersion of nanoclays in the polymer matrix was examined by TEM and XRD. Nanocomposites with lower content of organoclay showed exfoliated morphology while by increasing the amount of organoclay the intercalated morphology was more prevalent. Both organoclays had a good intercalation with PET and were uniformly dispersed within the polymer. Oxygen permeability of thin films of nanocomposites showed that the nanocomposites had better oxygen barrier properties than the neat PET. Tensile and impact properties of the nanocomposites also were measured.
High‐strength conductive pristine graphene/epoxy composites are prepared by two simple processing methods – freeze dry/mixing and solution processing. PVP‐stabilized graphene is aggregation‐resistant and allows for excellent dispersion in both the resin and final composite, as confirmed by optical microscopy and SEM images. The superior dispersion quality results in excellent nanofiller/matrix load transfer, with a 38% increase in strength and a 37% improvement in modulus for 0.46 vol% graphene loading. The composites have a very low electrical percolation threshold of 0.088 vol%. Despite the effectiveness of both methods, the freeze‐drying method is more promising and versatile enough to be used for graphene dispersion in a wide range of other composite precursors.
A facile and easily industrialized approach for preparing highly dispersed MMT/polymer nanocomposites is developed by combining the latex compounding method and a spray‐drying process. Clay particles are successfully delaminated into layers, and layer re‐stacking is effectively prevented. HR‐TEM and XRD results confirm that MMT layers achieve exfoliated or nearly exfoliated dispersion in both MMT/styrene‐butadiene rubber and MMT/PS nanocomposites. Compared with melt‐blended MMT/SBR composites, MMT/SBR nanocomposites prepared by this new strategy exhibit extremely high dynamic modulus.
In this study, novel protein/biodegradable polymer blend biomaterials‐gelatin/poly(ethylene oxide) blend films with compositional gradients were successfully fabricated by a dissolution/diffusion method. Two kinds of compositional gradient films, which were different in gradient structure, were prepared. The compositional gradient structure in the films was characterized by polarized optic microscopy, ATR‐FTIR, and trans‐FT‐IR mapping measurement. In addition, the mechanical properties of the gradient films were characterized with reference to their gradient structure. It is found that the compositional gradient films have better mechanical properties than the pure gelatin film. These protein/biodegradable polymer compositional gradient films have a potential for many biomedical applications.
A new concept of top‐down electrospinning is described. A dedicated apparatus was designed including the adaptation of a movable needle system in combination with a thin conveyor belt made of an insulation material on the top of the grounded collector plate. The new design, termed ‘needle printing’, permits to electrospin mats with increased size, homogeneous and controllable thicknesses. Due to the increase of bending instability and to the ‘needle printing’, the produced fibres are more regular in shape, longer and are deposited more stretched. In contrast to traditional electrospinning, the fibre population is the same in all regions of the mats imparting the same morphological and mechanical properties to each point of the produced structures.
Castor‐oil‐based anionic PU dispersions are post‐cured using a multiaziridine‐based crosslinker CX‐100. Thermal and mechanical properties of the resulting films are studied by DMA, DSC, TGA, and tensile tests. Mechanical properties are dramatically improved by the crosslinker. For example, the Young's modulus and tensile strength increase from 14.5 to 125 MPa and 13.1 to 18.1 MPa, respectively, when the aziridine fraction increases from 0 to 100%. The onset decomposition temperature of the films, T5, increases from 162 to 209 °C, indicating a significant increase in the thermal stability as the amount of aziridine is increased. This work provides an effective way of curing biorenewable anionic PU dispersions to prepare high performance, environmentally friendly coatings.
Three series of composite films based on polyimide and MWNTs were prepared by conversion of pyromellitic dianhydride and 4,4′‐oxydianiline in the presence of the nanotubes, followed by thermal imidization. Carboxy‐ and amino‐functionalized as well as unmodified nanotubes were used. It was demonstrated that just 0.5 wt.‐% of nanotubes increased the tensile properties of the composite films distinctly. Surprisingly, a significant influence of the functional groups on the mechanical performance of the composite films could not be demonstrated. However, it was shown that functional groups may reduce the conductivity of the films. Furthermore, the influence of ultrasonication is discussed.
The efficiency of epoxy/CNT nanocomposites as photocatalyst on adsorbed, aqueous and gas phases is investigated. Epoxy films containing SWNTs in the range between 0.1 and 0.3 wt% are prepared by means of UV‐induced polymerization and the achieved materials are used as photocatalysts on adsorbed, aqueous, and gas phases. The activity of this new photocatalytic materials is evaluated in the adsorbed state by using the methylene blue target molecule, in the aqueous phase by following the photodegradation of phenol and 3,5‐dichlorophenol, and in the gas phase using nitrogen monoxide as probe molecule. It is demonstrated that the catalyst is suitable for both oxidative and reductive degradation reactions.
The intercalation of cationic copolymer into a smectic clay, montmorillonite, has been used to produce polymerically modified organoclays. The organoclays of different lamellar morphology and content of quaternary ammonium groups have been prepared by altering the clay/polymer ratio. The organoclays prepared have been explored in the design of antimicrobial materials based on clay/polymer nanotechnology. Polyamide nanocomposites containing organoclays with incorporated cationic polymer showed an antimicrobial activity and improved mechanical properties. The antimicrobial efficiency and the mechanical properties of the nanocomposites were controlled by the variation of the content of the cationic polymer incorporated into the organoclay and organoclay loading.
Chitosan‐functionalized graphene oxides (FGOCs) were successfully synthesized. FGOCs were found to significantly improve the solubility of the GO in aqueous acidic media. The presence of organic groups was confirmed by means of XPS and TGA. Restoration of the sp2 carbon network and exfoliation of graphene sheets were confirmed by Raman spectroscopy, UV‐visible spectroscopy and WAXD. The SEM and AFM investigations of the resultant FGOCs showed that most of the graphene sheets were individual and few were layered. Controlled release behavior of Ibuprofen and 5‐fluorouracil was then investigated. We found that FGOCs are a promising new material for biological and medical applications.
Copolymers of 3,4‐ethylenedioxythiophene and 3‐methylthiophene have been prepared by recurrent potential pulses using monomer mixtures with various concentration ratios, their properties being compared with those of the corresponding homopolymers. In addition, different technological applications have been tested for the generated copolymers. Results indicate that the properties of the copolymers are closer to those of poly(3,4‐ethylenedioxythiophene) than to those poly(3‐methylthiophene). Furthermore, the ability of the copolymers to store charge and to interact with plasmid DNA suggest that they are very promising materials.
Cross‐linked alginate capsules a few millimeters in diameter have been formed by immersion in a CaCl2 solution. When adding cellulose whiskers or microfibrillated cellulose to the aqueous alginate solution, nanocomposite capsules containing 40 wt.% cellulosic nanoparticles were obtained. The morphology and compression strength of these capsules were investigated by microscopic observations and crushing tests, respectively. The capsules were extruded with a thermoplastic polymer. Visual inspection of the ensuing films shows a nonhomogeneous dispersion of the capsules that kept their integrity after extrusion. It results in preliminary disappointing mechanical properties of the composite films. However, further investigation is in progress to optimize this simple and ecofriendly process.
A pronounced and distinctive increase in the conductivity of polyetherimide nanocomposite films containing CNF agglomerates is reported. It is demonstrated that a variation of the CNF network can have a dramatic effect on the AC conductivity of PEI composites. The effect is found in composites containing relatively large and strongly entangled CNF agglomerates, and it is suggested that is is due to a new mechanism of electrical conduction. The observed behavior may reveal the distinctive response of electrons in strongly entangled CNF networks in polymer films to an AC field in contrast to a DC field, and could also result in a negative dielectric response.
Epoxy/BaTiO3 hybrid materials are prepared as good candidates for organic capacitors. The hybrid system is cured by using camphorquinone and a iodonium salt through a free‐radical promoted cationic polymerization using a long‐wavelength tungsten halogen lamp. The cured films are fully characterized. Morphological characterization shows a well‐dispersed inorganic phase within the organic matrix. Electrical characterization demonstrates a linear increase of the dielectric constant with increasing filler content, while low dielectric loss values are obtained.
