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.
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.
A processing method based on stretching of molten polymer nanocomposites was applied to prepare dichroic films. First, dodecanethiol‐capped gold particles were embedded in low density polyethylene. The resulting isotropic films were stretched in the melt under uniaxial loading using an elongational rheometer. The melt elongation technique resulted in reproducible characteristics of the optical properties and can be directly transferred to an industrial scale. The organic coating of the metal particles plays an important role in the generation of the dichroism. A reactive surface (adsorbed perfluorophenyl azide) led to strongly agglomerated particles which obviously did not lead to dichroic films.
Two novel cationic RAFT agents, PCDBAB and DCTBAB, were anchored onto MMT clay to yield RAFT‐MMT clays. The RAFT‐MMT clays were then dispersed in styrene where thermal self‐initiation polymerization of styrene to give rise to exfoliated PS/clay nanocomposites occurred. The RAFT agents anchored onto the clay layers successfully controlled the polymerization process resulting in controlled molecular masses and narrow polydispersity indices. The nanocomposites prepared showed enhanced thermal stability, which was a function of the clay loading, clay morphology, and slightly on molecular mass.
EVA copolymer/organoclay nanocomposites were prepared using melt‐compounding. Organoclays were obtained using wet and semi‐wet modification methods. These methods enable us to obtain organoclays with adequate modifier incorporation, but organoclays with a homogeneous and narrow agglomeration size distribution were obtained only with the wet method. TS and EB were higher for nanocomposites obtained with organoclays prepared using the wet method. Analysis of Limiting Oxygen Index, UL94 test and Cone Calorimeter test showed that the retardant properties of nanocomposites were also influenced by the kind of modifiers and the modification method.
The influence of Ca‐stearate‐coated CaCO3 and talc on the quiescent and flow‐induced crystallization of iPP is studied using different methods. Comparison of rheometry and DSC shows that rheometry is an interesting tool to monitor crystallization kinetics. It is observed that the Ca‐stearate coating degrades at commonly used annealing temperatures, influencing the crystallization behavior of the CaCO3‐containing polymer. WAXD indicates that the CaCO3 does not significantly influence the degree of crystallinity. As shear intensifies, both the pure and particle‐containing polymers crystallize faster; however, their behavior also becomes increasingly similar. There are indications that shear influences the organization of the CaCO3 aggregates.
Morphological analyses of nanocomposites based on TPU and polyhedral oligomeric silsesquioxanes (POSS) was performed using different techniques (transmission electron microscopy, small‐ and wide‐angle X‐ray scattering, differential scanning calorimetry) as a function of molecular weight of poly(ethylene glycol) (PEG) and PEG/POSS mol ratio. A strong interdependence in crystallisation behaviour between the two (POSS and the soft segments of TPU) specified to be able to crystallise in TPU/POSS was found. The mechanical properties determined by using recording microindentation techniques at room temperature were significantly improved by POSS for two material formulations.
A novel zirconia polyester nanocomposite is prepared using an in situ approach. Surface‐functionalized zirconia nanoparticles are obtained by attaching 3‐phosphonopropionic acid to the metal oxide. Neat and surface‐covered metal oxide particles are incorporated at the beginning of the polyesterification reaction of isophthalic acid and neopentyl glycol resulting in zirconia/poly(neopentyl isophthalate) (PNI) nanocomposites. TEM shows that the dispersibility of the inorganic filler is improved by covering the zirconia surface with carboxylic acid groups. These results are verified by SAXS. Rheological measurements reveal that the viscosities are increasing compared to pristine PNI at particle loads of 10 wt% (neat zirconia) and 5 wt% (phosphonic‐acid‐capped zirconia), respectively.
Novel fluoroalkyl end‐capped oligomer/hydroxyapatite nanocomposites have been easily prepared by the reaction of disodium hydrogenphosphate and calcium chloride in the presence of self‐assembled molecular aggregates formed by fluoroalkyl end‐capped oligomers in aqueous media. The fluorinated hydroxyapatite nanocomposites thus obtained were found to exhibit a good dispersibility in a variety of media, and were applied to the surface modification of glass.
The effect of both sulfur and peroxide curing on the intercalation and exfoliation process of layered silicate was studied to find a suitable vulcanization package for acrylonitrile butadiene rubber. X‐ray diffraction and transmission electron microscopy studies showed that proper selection of a curing package could lead the layered silicates to have excellent dispersion in intercalated form. The curing characteristics, physical properties, dynamic mechanical properties, and thermogravimetric analysis of layered silicate‐acrylonitrile butadiene rubber nanocomposites were explored. Finally, the effect of different types of zinc accelerators in sulfur vulcanization process was investigated on the intercalation‐exfoliation process of the layered silicates.
PET/PE blends are prepared with and without different types of organo‐modified montmorillonites (OMMT) using a extrusion process. The droplet size of PE dispersed phase decreases upon organoclays addition, however without any direct dependence on the organoclay initial surface tension. To assess the effect of the organomodifier without MMT, PET/PE blends are then compounded adding solely the surfactants (similar to those used to modify the various organoclays). Whatever the chemical nature of the surfactant, a refinement of the PE droplets is observed, interestingly similar to those previously observed in presence of clay. This shows unambiguously that the key factor for organoclay compatibilization efficiency, in the case of PET/PE blends, is the surfactant modifier itself and not the MMT platelets.
In the present work, the functionalisation of oxidised SWCNTs and MWCNTs is studied. The functionalised fillers are characterised by Raman spectroscopy and TGA. The functionalised fillers are dispersed in a PBT‐PTMO thermoplastic elastomer matrix via in situ polymerisation. The functionalisation causes a fine filler dispersion right at beginning of nanocomposite manufacturing. The fillers act as nucleating agents for crystallisation and evidences for a grafting from PBT at the surface of the functionalised nanotubes are found. An outstanding reinforcement effect by the functionalised CNTs is confirmed by tensile tests.
The preparation of new rubber based nanocomposites by using properly modified organophilic clays is described. A commercial organophilic montmorillonite containing a hydroxylated ammonium ion is reacted with LPBs. The reaction causes a decrease of the polarity of the clay and a great increase of the interlayer distance. The modified organoclays are successfully dispersed into rubber matrices (SBR or BR) by melt blending in an internal batch mixer. SAXS analyses and TEM micrographs revealed the formation of highly exfoliated nanocomposites containing intercalated stacks made of few lamellae.
PCL‐based nanoclay (layered silicate) nanocomposites are prepared using a small scale intermeshing co‐rotating twin‐screw extruder. Improving the level of nanoclay dispersion in PCL nanocomposites is obtained by changing the extrusion parameters. Increasing the screw speed and decreasing the throughput leads to an improved dispersion quality, as observed from the improved mechanical properties of the nanocomposites as well as from their clearly affected rheological and crystallization behavior. Furthermore, a commercially available software that simulates the twin‐screw extrusion process (LUDOVIC) is used to asses the processing parameters applied for making the nanocomposites.
The present study is aimed to investigate the effect of multiple extrusions of iPP/WF composites with and without EBAGMA used as compatibilizer. The degradation induced by the recycling processes was evaluated through changes in molecular structure, morphology, rheology, thermal and mechanical properties. The results showed that after six cycles, the presence of WF imparts stability to the composite materials. This effect was enhanced for the compatibilized samples. Further, SEM revealed better dispersion of the WF in the matrix. In contrast, it was confirmed that after the first recycling, both the molecular weight and the properties of PP drastically decreased due to chain scission resulting from degradation.
This work reviews principles of Raman and infrared imaging, as well as applications of the art to understand physiochemical phenomena in polymer systems. Image sequences may be assessed in terms of spatial or spectral changes that occur over time, either within a specific region or across the field of view. As such, the methods have enabled the analysis of diffusion and dissolution processes at polymer interfaces, drug release from polymer matrices, and structural transitions among others. Despite analytical limitations imposed by resolution (spectral or spatial) and sample preparation, Raman and infrared imaging are powerful tools for relating performance attributes to molecular‐level characteristics.
Poly(ε‐caprolactone) nanocomposites, PCLOC25A and PCLOC30B, with organoclays (OCs) having nonpolar and polar organic modifiers, respectively, were prepared by the melt mixing method and additional heat treatment. WXRD analysis revealed that both nanocomposites were exfoliated, irrespective of the OC polarity. However, WXRD failed to show the degree of exfoliation of the nanocomposites, because the d001 peaks disappeared. Thus, dynamic mechanical analysis (DMA) was carried out to compare the degree of exfoliation of the PCL nanocomposites. From DMA, PCLOC30B showed higher elasticity, storage moduli, viscosity, and activation energy than PCLOC25A, indicating that PCLOC30B had a more exfoliated structure than PCLOC25A. This is due to the polar interaction in PCLOC30B, as verified by the plots of aT versus temperature. Thus, it was confirmed that DMA provides an alternative approach to evaluating the degree of exfoliation of nanocomposites.
Novel materials were prepared from dual photo and thermal polymerization of hybrid thiol‐ene/cationic systems. In the first stage, the thiol‐ene system proceeded to high conversions, while the cationic photopolymerization was inhibited. The formation of sulfides during this stage was the main factor for the inhibition of the cationic photopolymerization of the epoxy monomers. Once those sulfides were formed, they reacted with the oxonium‐terminated growing polyether chains to form trialkylsulfonium salts. These salts promoted the thermal polymerization of the epoxy monomers in the second stage. The viscoelastic properties of the resulting polymers were measured by DMA.
A fabrication setup was specially designed so that one stream of sol of polyvinyl pyrrolidone (PVP), electrospun to form a bundle of fibers, acted as an axis between two rotating needles, and a second stream of PVP sol containing copper nitrate was electrospun around the fiber bundle axis to form a coil. This was turned into a coiled ribbon upon treatment in moisture. After calcination and reduction, a helical microcoil of nanocopper ribbon was produced, with controlled diameter and pitch. The width and thickness of the ribbon could be varied by manipulating the diameter of the coiled fiber and its treatment time in moisture.
A new melt‐processable PTFE material is presented and characterized that provides new and economical solutions in polymer technology while bridging the gap between perfluorinated PTFE and fluorothermoplastic materials such as perfluoroalkoxy resins. Thermal transitions, MW and MWD, and microstructures of the melt‐processable PTFE materials are investigated and compared to standard PTFE, modified PTFE, and PFA materials. The influence of the polymerization type used for the preparation of the melt‐processable PTFE (emulsion and suspension polymerization) on the MWD and the comonomer distribution are discussed.
