Rheological and morphological properties of high‐density polyethylene and poly(ethylene–octene) blends

The rheological and morphological properties of blends based on high‐density polyethylene (HDPE) and a commercial ethylene–octene copolymer (EOC) produced by metallocene technology were investigated. The rheological properties were evaluated in steady and dynamic shear experiments at 190°C in shear rates ranging from 90 s^?1 to 1500 s^?1 and frequency range between 10^?1 rad/s and 10² rad/s, respectively. These blends presented a high level of homogeneity in the molten state and rheological behavior was generally intermediate to those of the pure components. Scanning electron microscopy (SEM) showed that the blends exhibit dispersed morphologies with EOC domains distributed homogeneously and with particle size inferior to 2 μm. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2240–2246, 2002     

Melt processing of nanocomposites of cellulose nanocrystals with biobased thermoplastic polyurethane

Nanocomposites of thermoplastic polyurethane (TPU) with cellulose nanocrystals (CNC) without and with surface treatment are obtained by melt processing. Nanocomposites are obtained with nanofiller weight content near of the theoretical percolation threshold (3.9 wt%). Visual observation of CNC agglomerates is sufficient to prove the inefficiency of the mixing in systems with untreated CNC. The crystallization kinetics of the TPU changes with the addition of CNC and this is confirmed by differential scanning calorimetry analysis. Thermogravimetric analysis prove that the addition of CNC increases the thermal stability of the TPU. From the rheological analysis it is possible to verify the absence of percolation and an intermediate state of sol–gel transition in the nanocomposites. CNC/TPU nanocomposites with 5 wt% of treated CNC present better mechanical performance than de neat TPU and the other processed nanocomposites and display around 130% increase in Young's modulus while retaining significant values of toughness, tensile strength and elongation at break.     

An algorithm for computerized automatic tuning of power system stabilizers

The main objective of this paper is to relieve the power system engineers from the burden of the complex and time-consuming process of power system stabilizer (PSS) tuning. To achieve this goal, the paper proposes an automatic process for computerized tuning of PSSs, which is based on an iterative process that uses a linear matrix inequality (LMI) solver to find the PSS parameters. It is shown in the paper that PSS tuning can be written as a search problem over a non-convex feasible set. The proposed algorithm solves this feasibility problem using an iterative LMI approach and a suitable initial condition, corresponding to a PSS designed for nominal operating conditions only (which is a quite simple task, since the required phase compensation is uniquely defined). Some knowledge about the PSS tuning is also incorporated in the algorithm through the specification of bounds defining the allowable PSS parameters. The application of the proposed algorithm to a benchmark test system and the nonlinear simulation of the resulting closed-loop models demonstrate the efficiency of this algorithm.     

Elaboration and properties of novel biobased nanocomposites with halloysite nanotubes and thermoplastic polyurethane from dimerized fatty acids

Nanocomposites of biobased thermoplastic polyurethane (TPU) from dimer fatty acids and halloysite nanotubes (HNT) were elaborated by different melt processing routes such as direct mixing (1 step process) and masterbatch/dilution (2 steps process), at different temperatures (150 and 180 °C). Rheological and transmission electron microscopy (TEM) analyses indicated that the HNT distribution and dispersion were dependent on the processing conditions: the 2 steps process produced well dispersed nanocomposites and the masterbatch dilution at 180 °C improved the HNT distribution through the TPU. Consequently, a high reinforcement was achieved, with a 40% increase in the elastic modulus and 8 °C increase in the relaxation temperature related to the glass transition of the TPU soft segments. Furthermore, a percolated network was attained, even if a large extent of HNT breaking was observed during processing, suggesting that a synergistic effect between the HNT particles and the TPU's hard segments in the molten state occurred. Thus, HNT nanotubes can be seen as highly reinforcing nanofillers when good dispersion and distribution are achieved through the polymeric matrix.     

Nanocomposites of PBAT and cellulose nanocrystals modified by in situ polymerization and melt extrusion

Cellulose nanocrystals (CNC) were successfully grafted with a low molecular weight poly(butylene glutarate) through an in situ polymerization procedure. The grafting treatment decreased the CNC hydrophilic character and increased the onset of their thermal degradation by approximately 20°C, thus increasing the possibilities of CNC application. Composites of grafted and nongrafted CNC with a poly(butylene‐adipate‐co‐terephthalate) (PBAT) matrix were prepared by melt extrusion. The CNC addition led to an increase of 50% of the tensile elastic modulus of the PBAT. In addition, dynamic mechanical thermal analysis showed that the composite with CNC retained its high modulus even at temperatures far above the glass transition temperature of PBAT. At 60°C the storage modulus of the composite with CNC was approximately 200% higher than that of the pure PBAT. Thus, in this work, nanocomposites of improved properties were obtained through a combination of in situ polymerization and melt extrusion. POLYM. ENG. SCI., 56:1339–1348, 2016. © 2016 Society of Plastics Engineers     

Miscibility and morphology of poly p-phenylene sulphide–liquid crystal polymer blends

Blends of poly p-phenylene sulphide (PPS) and a liquid crystalline polymer (LCP) were made by two methods: (i) mixing and capillary extrusion (samples A), and (ii) injection moulding (samples B). To study miscibility in the melt and solid states and the resulting morphology, techniques like polarized light optical microscopy, capillary rheometry, dynamic mechanical thermal analysis and scanning electron microscopy with X-ray microanalysis were used. It was observed that the miscibility of the amorphous fractions of both polymers increased with increasing intensity (rates and stresses) of deformational flow (shear and elongational). Samples A had a morphology composed of fibrils of both polymers, but a matrix made of only one polymer i.e. PPS. Samples B had a mainly fibrillar morphology, with no observable matrix, made of both polymers. Formation of pure LCP fibrils was not observed neither in the extruded blends nor in the injection moulded samples. The addition of LCP to PPS improved its mechanical properties. At a molecular level, these blends can be considered to be molecular composites.     

Blends of a bottle‐grade polyethylene terephthalate copolymer with a liquid crystalline polymer. Part II: Thermal and transport properties

In this work the thermal and transport properties of dichloromethane in blends of a bottle‐grade polyethylene terephthalate copolymer, PET, and a liquid crystalline polymer, LCP, were measured. Thermal characterizations of the blends were made by modulated differential scanning calorimetry and dynamic mechanical thermal analyses. An approximated LCP “bulk orientation” was also calculated by wide angle X‐ray diffraction. The morphology was analyzed by scanning electron microscopy. The resulting sorption curves of pure PET, and the B20, B40 and B60 blends were sigmoid type curves, while the sorption curve of the B80 blend was a two‐stage type curve. The diffusion coefficients of the B20 and B40 blends were found to be the lowest of all the blends. These low diffusivities were attributed to the occurrence of strong long‐range and short‐range interactions between the PET and the LCP in the B20 and B40 blends, and also to the perfection of the PET crystals in the B20 blend.     

Chain extension reaction in solid‐state polymerization of recycled PET: The influence of 2,2′‐bis‐2‐oxazoline and pyromellitic anhydride

Conventional and chain extended‐modified solid‐state polymerization (SSP) of postconsumer poly(ethylene terephthalate) (PET) from beverage bottles was investigated. SSP was carried out at several temperatures, reaction times, and 2,2′‐bis‐2‐oxazoline (OXZ) or pyromellitic anhydride (ANP) concentrations. The OXZ was added by impregnation with chloroform or acetone solution. Higher molecular weights were reached when the reaction was carried out with OXZ, resulting in bimodal distribution. The molecular weights of the flakes reacted at 230°C for 4 h were 85,000, 95,000, and 100,000 for samples impregnated with 0, 0.5, and 1.25 wt % OXZ solution, respectively. In the case of reactions with ANP, branched chains were obtained. The thermal and thermal‐mechanical‐dynamic properties of these high‐molecular‐weight recycled PET were determined. For OXZ‐reacted samples, the reduction of crystallinity was observed as the reaction time was increased, becoming evident the destruction of the crystalline phase. The chain extended samples did not show changes in thermal relaxations or thermal degradation behavior. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Remarkable change in the broadband electrical behavior of poly(vinylidene fluoride)–multiwalled carbon nanotube nanocomposites with the use of different processing routes

Poly(vinylidene fluoride) (PVDF) nanocomposites have plenty of applications in the electronic realm. In this study, we produced nanocomposites based on PVDF and multiwalled carbon nanotubes (MWCNTs), with various MWCNT loadings, using three different processing routes: solution mixing, melt mixing, and electrospinning. The broadband electrical behavior of these nanocomposites was studied and compared via impedance spectroscopy. The morphologies of the nanocomposites were characterized by transmission electron microscopy and scanning electron microscopy. The results reveal that the electrical behaviors of the samples were completely different according to the processing route used. Solution mixing was the most suitable method for producing nanocomposites with the highest conductivities, at low MWCNT loadings, whereas electrospinning was the most suitable method for producing nanocomposites with the lowest dielectric permittivity. These differences were attributed to the different arrangements of the MWCNTs caused by the different processes. Although the solution-mixed samples exhibited long and twisted MWCNTs, the melt-mixed samples had shorter MWCNTs, and the electrospun samples had MWCNTs embedded and aligned inside the insulating polymer nanofibers. Thus, these results project a vast horizon for tailoring the structure and thereby the broadband electrical behavior of PVDF–MWCNT nanocomposites for different types of applications. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47409.     

Blends of polypropylene resins with a liquid crystalline polymer. I. Isothermal crystallization

The isothermal crystallization kinetics of blends of different polypropylene (PP) resins and a liquid crystalline polymer (LCP) after two different melting conditions (200 and 290°C) were studied by DSC and polarized light optical microscopy. The resins were a homopolymer (hPP), a random copolymer with ethylene (cPP), and a maleic anhydride grafted PP (gPP). The LCP was Vectra A950, a random copolymer made of 75 mol % of 4‐hydroxybenzoic acid and 25 mol % of 2‐hydroxy,6‐naphthoic acid. It was observed that the overall crystallization rates of all the blends after melting at 200°C were higher than those after melting at 290°C. The LCP acted as a nucleating agent for all the PP resins; however, its nucleating effect was stronger for the hPP than for the cPP and gPP resins. After both melting conditions, an increase was observed in the overall crystallization rate of the hPP and gPP resins with the increase in the amount of LCP, but not in the cPP crystallization rate. The fold surface free energy σ_e of hPP and cPP in the blends decreased, but increased in the gPP blends. Finally, all the PP resins formed transcrystallites on the LCP domain surfaces. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 916–930, 2003