Oriented precursors of MFCs consisting of HDPE and PA6 or PA12 are studied during strain‐controlled slow load‐cycling. In the PA6‐containing blends a strongly retarded nanostrain response is detected. Compatibilization induces nanostrain heterogenization. Stress fatigue is lower in the PA12 blends, but hardly decreased by the compatibilizer. Selective migration of the compatibilizer into a disordered semi‐crystalline fraction of the HDPE matrix can explain the findings. The semi‐crystalline HDPE entities in PA6 blends appear more disordered than in PA12‐blends. An analysis of the HDPE nanostructure evolution during cycling reveals epitaxial strain crystallization. Uncompatibilized PA6 blends cycled about high pre‐strain show plastic flow but nanoscopic shrinkage in the semi‐crystalline stacks.
Cellulose microfibers were modified with two different bi‐functional monomers. Composites of EVA copolymer with modified and unmodified cellulose were prepared by melt mixing. The samples were analyzed by SEM, XRD, FT‐IR, DSC, TGA, DMTA and tensile mechanical tests. SEM showed that the presence of reactive groups on cellulose surface enhanced the compatibility, improving the fiber/matrix interfacial adhesion. FT‐IR disclosed the occurrence of chemical reactions between the functionalized cellulose and polymer chains. The incorporation of fibers affected the crystallization behaviour and crystallinity of the polymer matrix. Composites with GMA modified cellulose displayed better compatibility, higher thermal and mechanical properties.
Artificial turf is robust, playable in all weathers and has a long service life. Polyamide (PA) flooring has excellent resilience but provokes abrasion injuries (friction burn); polyethylene (PE) monofilaments are skin‐friendly but tend to permanent deformation. To maximize resilience while minimizing the risk of skin abrasion, PA‐PE bicomponent fibers are developed. Numeric simulation is applied to find optimized fiber cross‐sections and material combinations, accompanied by melt‐spinning of respective filaments and validation of the model. The resulting artificial grass resembles natural turf with respect to playability and appearance and does not need any granular infill.
Unfilled and MWCNT‐filled PA fibers are prepared and the effect of the extensional flow on their mechanical performance and morphological variations is investigated. Morphological analyses using SEM, TEM, and SAXS suggest a stronger orientation of the MWCNTs along the fiber direction with increasing extensional flow. A particular MWCNT bundle formation in the PA drawn nanocomposite fibers is observed for the first time, and a pull‐out of the central nanotube in some bundles is noted. The maintenance of the “shish‐kebab” structure upon extensional flow is responsible for the mechanical improvements and dimensional stability in MWCNT‐filled PA fibers.
The traditional PA 6.6 production route, i.e. solution melt polymerization followed by extrusion, is applied to the in situ intercalation of PA 6.6/clay nanocomposites. Organoclays of different types are tested and the derived nanocomposites are thoroughly characterized in terms of molecular weight, thermal properties and morphology. Reaction acceleration is found in the presence of fully exchanged organoclays, which is attributed to a chain extension mechanism based on clay SiOH groups. Analysis of the nanocomposites' nanostructure indicates that the applied solution melt polymerization process results in some flocculation of the tested organoclays, which is improved in some cases after extrusion and leads to partially exfoliated nanocomposites.
PA nanocomposites are prepared from clays organophilized with a phosphonium and an ammonium salt, and sodium montmorillonite is used as reference. The analysis of mechanical and micromechanical properties of the composites reveal that several micromechanical deformation processes occur in the PA/MMT composites. The matrix cavitates at relatively small stress. Processes related to non‐exfoliated clay structural units are initiated at larger stresses. Sound is emitted mainly by the fracture of particles, but debonding may also occur. The plastic deformation of the matrix dominates at larger stresses and deformations. The various local deformations are independent of each other and composite properties are not determined by silicate related processes but by the deformation of the matrix.
The fabrication of nanocomposites by organic modification of clay during mixing into NR is reported. NR/OMMT nanocomposites show more intercalation and exfoliation at higher modifier content, increasing the tensile modulus primarily by improved filler reinforcement. Comparison with nominally identical pre‐modified OMMT shows similar microstructures and physical properties. No effect of mixing duration is observed, indicating that modification is rapid. Unlike montmorillonite, unmodified sepiolite disperses well in NR, so organo‐modification improves compatibility but does not affect the nanocomposite microstructure. This means that organo‐sepiolite offers relatively small improvements over sepiolite as a filler for NR.
A composite of boehmite alumina nanoparticles and a PP/PA12 blend is prepared. WAXD and SEM suggest that a low filler loading enhances the coalescence of PA12, whereas a higher loading reverses the situation. DSC, DMA and TGA reveal that the final properties of the blend composites such as crystallization temperatures, flexural storage moduli, or thermal degradation temperatures improve with increasing nanoparticle loading. The data are compared with the neat polymers and the compatibilized blend, and the results show that the compatibility increases only at high nanoparticle loading, and most of the thermal properties improve with increasing nanoparticle content in the blends. The presence of interfacial interactions between the polymer matrices and the filler was confirmed via FTIR.
The effect of hydrophilic and hydrophobic nanosilica on the morphological, mechanical and thermal properties of polyamide 6 (PA) and poly(propylene) (PP) blends is investigated by extrusion compounding. Depending on the difference between the polymer/nanoparticle interfacial tensions, different morphologies are obtained as highlighted by TEM and SEM. Hydrophobic nanosilica migrates mainly at the PA/PP interface, which leads to a clear refinement of PP droplet size. The macroscopic properties of the hybrid blends are discussed and interpreted in relation with the blend morphology and melt‐mixing procedure. The control over coalescence allows a morphology refinement of the blends and improves mechanical properties.
Solid‐state polymerization (SSP) of a poly(hexamethyleneadipamide) (PA 6.6)/clay nanocomposite system was studied. SSP runs were performed in a fixed‐bed reactor, at temperatures 160–200 °C and reaction times up to 8 h. The influence of clay presence on the PA 6.6 SSP rate constant was herewith quantified for the first time to prove significant acceleration of the SSP process. A catalysis mechanism was suggested, according to which the positive effect of clay is of a synergistic origin attributed to nucleated crystal morphology, that increased the concentration of reactive end groups in the amorphous regions, to chain extension performed by clay SiOH groups, and to thermal protection of the polyamide matrix due to the presence of the nanoparticles.
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 influence of the thermal history experienced during injection molding on the mechanical properties of polycarbonate is investigated. Distributions of the yield stress as they result from inhomogeneous cooling during processing, predicted by a previously developed modeling approach, are validated and are in good agreement with experiment. Predictions of the mechanical performance for different mold temperatures during processing are also validated over a range of applied strain and deformation rates and applied stresses and forces, for simple tensile bars and an actual product. Good agreement is found. It is shown that mold temperature has a tremendous influence on the life time of polymer products, which can differ by more than two orders of magnitude.
The oxidative degradation of PP/OMMT nanocomposites under γ‐irradiation was studied. Changes in structure and properties resulting from γ‐exposure in the range 0–100 kGy were investigated. The results were analyzed by comparing the influence of PP‐g‐MA and pristine OMMT on the oxidation kinetics of neat PP. γ‐Irradiation in the presence of air strongly degraded the properties of PP materials, particularly for radiation doses above 20 kGy. The rate of oxidative degradation of PP/OMMT/PP‐g‐MA nanocomposites was much faster than that of neat PP. This suggests that PP‐g‐MA and pristine OMMT components behave as oxidation catalysts, leading to the formation of free radicals in the polymer matrix.
Newly developed shape memory (SM) epoxies are unveiled with an improved deformability range, high strength with intrinsically good thermal and chemical stability, high thermal transition (i.e., SM transformation temperature), and qualitatively excellent SM characteristics, thereby providing a synthetic route for adding attractive properties to commonly used industrial and commodity resins. The impact of chemical composition on the failure strains of these SM epoxies is shown and the resulting SM behavior is discussed.
PA6 nanocomposite films with different nanoclay dispersion degrees are prepared by melt compounding and cast extrusion. The dispersion of the MMT platelets (homogeneity and degree of exfoliation) is evaluated qualitatively by TEM and quantitatively by rheology and NMR; it ranges from microcomposites to highly exfoliated nanocomposites. Compared to neat PA6, the optical properties (clarity, gloss, haze) are worse for the microcomposites and better for the nanocomposites. The mechanical properties depend strongly on the exfoliation level. Better exfoliation leads to higher stiffness. The strain at break decreases compared to neat PA6 films even in the case of highly exfoliated nanocomposites films. At low MMT content, the microcomposite has a higher ductility than well exfoliated nanocomposites films.
The electrospinnability of hordein and gliadin from acetic acid solutions is demonstrated and compared to that of zein. The relation between protein conformations in solution and the properties of post‐spun fibers are studied by means of CD, FTIR, TEM, DLS, viscosity measurements, SEM, and mechanical testing. The results show that both electrospinnability of the proteins and mechanical properties of post‐spun fibers are significantly influenced by solution protein conformations. Ultrafine fibers are fabricated at optimized concentrations, while large compact aggregates caused by hydrophobic interactions have a negative effect on the formation of continuous protein fibers. Moreover, hordein fibers show a lower cytotoxicity than gliadin and zein fibers.
Preparation and analysis of morphologic and electrical properties of high‐performance multiwalled carbon nanotube/polyamide 6 nanocomposites was achieved. The MWNTs were surface‐coated by in situ polymerization of ethylene as catalyzed directly from the nanotube surface previously treated by a highly active metallocene‐based complex. The so‐produced polyethylene‐coated MWNTs were melt‐mixed with the PA6 matrix. Pristine MWNTs were also dispersed in PA6. The in situ ethylene polymerization/coating reaction allowed the destructuring of the native bundle‐like aggregates leading to the preparation of nanocomposites with improved properties even at very low nanofiller content.
The present work provides a critical review of polymer crystallization studies using SALS; experimental methods, analysis techniques, observations and their relations with respect to other techniques are discussed. Furthermore, the fact that nucleation might be accompanied by large scale density fluctuations has been investigated for the flow‐induced crystallization of iPB. SALS was applied to measure density and orientation fluctuations, whereas complementary results were obtained from optical microscopy. The observations from both crystallization and melting experiments seem to indicate that the detected density fluctuations result from the presence of weakly anisotropic structures, rather than being an indication of densification before the onset of crystallization.
Near‐monodisperse, size‐controllable, poly(methyl methacrylate)‐pigment nanoparticle composites were produced using electrohydrodynamic atomization (EHDA). The geometric mean diameters of the composite particles were in the 0.91 to 1.90 µm‐diameter range with geometric standard deviations of approximately 1.05 to 1.12. Increasing the polymer volume fraction and liquid flow‐rate resulted in an increase in the diameter of the composite particles, which agreed well with droplet scaling relations for EHDA. The results here demonstrate that EHDA can be used for polymer‐nanoparticle‐composite production and as an alternative to conventional inkjet printing.
A new, nickel‐coated graphite resistance‐change‐based method for gel‐point determination for epoxy‐based thermoset resins is presented and compared with DSC and rheological methods. Gelation times determined by this new method are in very good agreement with conventional techniques; this new method is potentially simpler and less time consuming than existing ones.
