EVOH‐g‐PCL were prepared by a solvent‐free reactive extrusion process using a co‐rotating twin screw extruder. Kinetic simulations were made of selected reaction conditions at 185 °C. Changes in the screw rotation rate resulted in evolution of the residence time distribution and slightly changed the monomer conversion. An increase of the [OH]0/[Cl]0 ratio made the reactive system more viscous and decreased the overall pumping capacities of the extruder. Increase of the mean residence time, combined with a positive kinetic effect of [OH]0 increase, leaded to an important increase in conversion. For all the conducted experiments, equivalent distribution dispersions and good agreements between calculated conversion and those measured were obtained. An increase in temperature from 185 to 200 °C resulted in total conversion.
Poly(ε‐caprolactone) (PCL) was grafted to the surface of starch nanocrystals (StN) via microwave‐assisted ROP. The resultant nanoparticles were then incorporated into a poly(lactic acid) matrix to produce fully‐biodegradable nanocomposites with good mechanical properties. A loading level of 5 wt.‐% StN‐g‐PCL resulted in simultaneous enhancements of strength and elongation. The StN‐g‐PCL self‐aggregated as rubbery microparticles to enhance the elongation by ca. 10‐fold over that of neat PLA. Meanwhile, the grafted PCL chains were miscible with PLA and formed a stress‐transferring interface to the StN, providing a reinforcing function.
Chemical modification of EVOH in the molten state at 185 °C by a grafting from process of poly(ε‐caprolactone) in batch was studied. 1H NMR was used to characterize the structure evolutions of PCL grafts. In addition to grafting reactions, dynamic covalent transesterification reactions between EVOH residual alcohols and the polyester grafts led to a redistribution of the PCL grafts length. up to 27 and SR up to 80% were obtained. Experiments made in a corotating mini twin‐screw extruder also confirmed these results. The effect of the alcohol to caprolactone ratio and catalyst concentration (SnOct2) on kinetic evolution showed that few minutes were necessary to complete the polymerization. A kinetic model was proposed and adequate conditions for the synthesis by reactive extrusion were defined.
A comparative study of the preparation and properties of composites of PCL with cellulose microfibres (CFs) containing butanoic‐acid‐modified cellulose (CB) or PCL grafted with maleic anhydride/glycidyl methacrylate as compatibilizers, is reported. The composites are obtained by melt mixing and analyzed using SEM, DSC, TGA, XRD, FT‐IR, NMR and tensile tests. An improved interfacial adhesion is observed in all compatibilized composites, as compared to PCL/CF. The crystallization behavior and crystallinity of PCL is largely affected by CF and CB content. Composites with PCL‐g‐MAGMA display higher values of tensile modulus, tensile strength and elongation at break.
The influence of talc loading on phase morphology of PLA/PCL/talc composites and improvement in resulting properties are reported. Talc‐based composites of PLA/PCL blends were prepared by melt blending. SEM analysis demonstrates that PLA appears as discrete domain phase, while PCL acts as a bulk phase in the blend. Talc addition decreases PLA domain sizes and voids in the matrix. This results in significant improvement of oxygen and water vapor barrier properties of composite by 33 and 25%, respectively, at 3 wt.‐% talc loading. DSC shows that talc acted as nucleating agent for PCL phase in the composite and improves its crystallinity. Various theoretical models based on dispersion and filler geometry are used to predict the tensile modulus and oxygen permeability.
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.
Nanoparticles based on Al(III) and Zr(IV) melamine phosphate and sulfate, respectively, are prepared. Cone calorimeter measurements reveal that compared to an unfilled polyacrylate matrix the polyacrylate‐based nanocomposites containing the novel nanoparticles display significantly improved flame‐retardant properties as evidenced by the corresponding values for the peak heat release rate, the time‐to‐ignition, the values for the peak rate of heat release, the total heat evolved, the time to the CO peak and the CO yield. Concomitantly, the mechanical properties of the acrylate‐based composite coatings, i.e., the Martens and surface hardness, can also be significantly improved.
Copolymers of poly(2,5‐benzimidazole) (ABPBI) and poly[2,2′‐(p‐phenylene)‐5,5′‐bibenzimidazole] (pPBI) were synthesized for use as fuel cell membranes to take advantage of the properties of both constituents. The composition of the copolymers were controlled by changing the feed ratio of 3,4‐diaminobenzoic acid and terephthalic acid with 3,3′‐diaminobenzidine in the polycondensation reaction. The copolymer membranes showed higher conductivities, better mechanical properties, and larger acid absorbing abilities than commercial poly[2,2′‐(m‐phenylene)‐5,5′‐bibenzimidazole] membranes.
A method that combines UV irradiation and pausing was developed to manipulate the regularity and the length scales of the morphology generated by phase separation in full‐interpenetrating polymer networks of polystyrene and poly(methyl methacrylate). Upon increasing the pause time of photopolymerization and photo‐crosslink processes, the morphology gradually changes from hexagonal‐like packing to random structures. The width of the loss tan δ obtained for these phase‐separated materials changes with the morphological regularity, suggesting a potential technique for fabrication of mechanical bandgap materials.
Cyano‐OPV moieties were covalently incorporated into a PETG backbone to create ductile amorphous polymers which change their PL and absorption color as a function of deformation. The cyano‐OPV concentration was systematically varied, and the composition was related to the material's optical response. This approach afforded PETG/dye copolymers which upon annealing display characteristics of aggregated dye molecules. The materials exhibit a significant color change upon compression, consistent with disassembly of the dye aggregates. This mechanochromic response is irreversible and can be detected by the unassisted eye.
The influence of the flow history experienced during injection molding on the mechanical properties of amorphous polymers is investigated. It is demonstrated that flow‐induced molecular orientation only causes a small anisotropic effect on the yield stress, which can be regarded as insignificant with respect to its absolute value. Its influence on the post‐yield strain‐hardening response is also shown to be imperceptible, in contrast to a orientation which is applied during deformation below the glas transition.
Epoxy‐networked materials containing N,N'‐dioctadecylimidazolium iodide are prepared by curing a mixture of DGEBA and different ratios of the ionic liquid with MCDEA at high temperature. The presence of ionic liquid results in an increase of the storage modulus and a decrease of the glass transition temperature, as indicated by DMA. Also, the onset curing temperature decreases as the amount of IL increase indicating that IL also takes part on the curing process. DSC and FTIR analyses confirm that the imidazolium‐based ionic liquid is able to promote the crosslink of the epoxy pre‐polymer without the presence of external curing agent.
The consumption of 10‐undecene‐1‐olate (UOA) during its continuous re‐feeding in the metallocene‐catalyzed copolymerization with propene was investigated by ATR‐FTIR spectroscopy in‐line monitoring through evaluation of the integral absorbances of the characteristic IR bands. For the quantitative determination of the comonomer concentration during the copolymerization reaction with and without continuous re‐feeding of UOA, multiple calibration functions based on the chemometric partial least squares method were applied. For the first time, a direct correlation between the consumption of an olefin and the addition of a polar comonomer during a metallocene‐catalyzed copolymerization was demonstrated. By means of this technique, a relatively constant molar stoichiometric ratio of the comonomer and propene over the whole polymerization time was achieved, which is very important in obtaining copolymers with defined random structure and, thus, from the point of view of reaction engineering, constant product quality.
The nucleating effect of zinc phenylphosphonate (PPZn) was investigated on the as‐bacterially synthesized poly(3‐hydroxybutyrate) [P(3HB)] and poly[(3‐hydroxybutyrate)‐co‐(3‐hydroxyhexanoate)]s [P(3HB‐co‐3HHx)s] in order to improve their crystallization rate. PPZn is found an efficient nucleating agent on the crystallization of P(3HB) and P(3HB‐co‐3HHx) with low 3HHx unit content. The nucleation mechanism is proposed to be epitaxial nucleation. Both the comonomer‐unit composition and its distribution of P(3HB‐co‐3HHx)s were found exhibiting significant effect on the nucleating effect of PPZn. It is found that PPZn is more efficient on nucleating the crystallization of P(3HB‐co‐3HHx) with a broader comonomer‐unit compositional distribution than that with a narrower distribution.
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.
Isotactic PP nanocomposites filled with Fe@FeO nanoparticles are fabricated by a facile ex situ method. The nanofillers are dispersed in a boiling PP/xylene solution. X‐ray diffraction is used to determine the nanofiller effects on the crystallinity of PP. The crystallinity along the (040) plane is found to decrease with the incorporation of nanoparticles. Thermal properties and crystallinity are studied by TGA and DSC, respectively. Enhanced thermal stability and influenced crystallinity are observed in the PP nanocomposites compared with those of pure PP. An increased dielectric property without percolation threshold is observed. In addition, the nanocomposites are found to exhibit ferromagnetic properties.
The application of computationally inexpensive modeling methods for a predictive study of powder mixing is discussed. A multidimensional population balance model is formulated to track the evolution of the distribution of a mixture of particle populations with respect to position and time. Integrating knowledge derived from a discrete element model, this method can be used to predict residence time distribution, mean and relative standard deviation of the API concentration in a continuous mixer. Low‐order statistical models, including response surface methods, kriging, and high‐dimensional model representations are also presented. Their efficiency for design optimization and process design space identification with respect to operating and design variables is illustrated.
The solid and thermally instable azoinitiators V‐65 and VR‐110 were embedded within a polymer particle by using the miniemulsion process and afterwards quickly decomposed by thermal treatment below the glass temperature of the polymer. The resulting nitrogen gas overpressure inside the particles leads to a disruption of the polymer particle and a possible sudden release of encapsulated substances. It is shown, by electron microscopic measurements, that the number of burst particles correlates with the applied temperatures as well as the heating time. The surface deformation could be verified by scanning electron microscope analyses.
An in situ lubrication dispersion method is developed to achieve electrical conductivity in PP containing a small amount of MWCNTs. Good dispersion of the MWCNTs in PP is observed even after a short mixing time because the interactions between the entangled nanotubes are reduced. By in situ lubrication dispersion, the electrical percolation threshold of the PP nanocomposite can be as low as 0.5–0.7 wt% MWCNT. Rheological data also support percolation at 0.5 wt% MWCNT. With 0.5 wt% MWCNT, the slope of G′ at low frequency approaches unity and shows non‐terminal behavior. The proposed dispersion method enhances the wetting of MWCNTs and improves MWCNT dispersion compared to both direct mixing of MWCNT powder with a polymer melt and conventional master batch dilution.
Glass fiber biobased composites have been prepared by ROMP of a commercially available vegetable oil derivative possessing an unsaturated bicyclic moiety, and DCPD. The resins and the corresponding composites have been characterized thermophysically and mechanically. Higher DCPD content yields materials with higher glass transition temperatures. Glass fibers significantly improve the tensile modulus of the resin from 28.7 to 168 MPa. These biobased composites utilize only a limited amount of a petroleum‐based monomer, while employing substantial amounts of a renewable resource.
