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This work covers the synthesis and characterization of in-reactor Ultra-High Molecular Weight Polyethylene/High Density Polyethylene, UHMWPE/HDPE, blends by in situ polymerization in a single reactor, through dual catalyst immobilization. These blends are synthesized combining two different catalysts (one for each targeted molar mass) co-immobilized in mesoporous Santa Barbara Amorphous, SBA-15, particles. First, the ethylene polymerization behavior is investigated, under different polymerization conditions. Then, studies on the thermal, mechanical and rheological characteristics of the produced in-reactor blends are presented and their performance is compared and discussed in a comprehensive way. Moreover, the effect of different filler contents on the properties exhibited by the resulting materials is investigated. Results have shown that these in-reactor UHMWPE/HDPE blends exhibit a complex thermal, mechanical and rheological behavior, which depends mainly on the proportion between the two polymer components and on the amount of SBA-15.
In this work, we studied the parameters affecting the localization of hydrophobic nanosilica particles and its impact on morphology development of polyethylene/polystyrene/poly (methyl methacrylate) (HDPE/PS/PMMA) ternary blends, which originally have a thermodynamically preferred core–shell type morphology, by means of a combination of rheology and electron microscopy. An attempt was also made to compare the experimental results with thermodynamic predictions. The ternary blend samples with the same blend ratio but varying in nanosilica loadings were prepared by melt compounding using a laboratory internal mixer. It was demonstrated that the nanosilica localization which could be controlled by the sequence of feeding, would play a significant role in determining the morphology development of the nanofilled ternary blend samples. It was shown that in contrary to thermodynamic prediction of a core shell morphology for the nanofilled samples, the highly enhanced melt elasticity of nanosilica filled polystyrene phase did not allow the PS phase to form a complete encapsulating shell.
Ternary composites of rigid polyurethane foam (RPUF)/glass fiber/silica as well as RPUF/glass fiber have been fabricated from glass fiber, silica, polymeric 4,4′-di-phenylmethane diisocyanate (PMDI) and polyol using HFC 365mfc as blowing agent. Foam formation kinetics, morphology, thermal conductivity, glass transition temperature, decomposition temperatures as well as the mechanical strengths of the foam have been studied. With the addition an increasing amount of glass fiber cream time, rise time, gel time, tack free time, density, compression strength, thermal conductivity (k) monotonically increased while the glass transition temperature showed a maximum at 2%. At constant glass fiber content (2%), addition of silica further increased the process times, density and compression strength while the Tg and thermal decomposition temperature showed a maximum at 3% silica. The k value of RFUF/glass fiber composite decreased with the addition of silica up to 3%, where it was even lower than the virgin RPUF. However, beyond the content k value increased. Overall, the variation of k value with silica content showed identical tendency with cells size and closed cells content.
Linseed (LO) and soybean oil (SO) were in–situ epoxidized with peracetic acid to produce different degree of epoxidized LO and epoxidized SO. For comparison purpose, commercial epoxidized linseed oil (ELO®) and epoxidized soybean oil (ESO®) were also included in the study. The effect of epoxidation degree on the copolymerization reaction between epoxidized oils and vinyl acetate (VAc) was investigated. Results showed that a copolymer can be formed between VAc and epoxidized LO with high epoxy content, while no reaction occurred between VAc and SO or its epoxidized derivatives. As the most reactive monomer among the studied oils, the epoxidized LO with highest epoxy content (i.e. ELO®) was mixed with VAc and then impregnated into the wood using three different ELO®/VAc formulations either as solution or as emulsions. After curing, the impact of the resulting copolymer issued from the three tested formulations on the wood durability was evaluated. Results showed that the formulation comprising VAc, ELO®, H2O, K2S2O8 and alkaline emulsifier (Formulation 3) can significantly improve wood’s durability against white rot- (Trametes versicolor) and brown rot fungi (Postia placenta and Coniophora puteana). Treated wood of 8% weight percentage gain (WPG) was sufficient to ensure decay resistance against the test fungi with less than 5% mass loss.
Nanocomposites of bisphenol A polycarbonate with organically modified clays have been prepared for the first time by in-situ polymerization using bis(methyl salicyl) carbonate as activated carbonate. The use of the activated carbonate permits to conduct the polymerization reaction at lower temperature and with shorter polymerization time with respect to those necessary for traditional melt methods that uses diphenyl carbonate, affording a nanocomposite with improved color. Moreover, an imidazolium salt with two long alkyl chains has been used to modify the montmorillonite, providing an organically modified clay with high thermal stability and wide d-spacing. The addition of ionic groups at the end of the polymer chain increases the interaction between the clay surface and the polymer producing a better dispersion of the clay. The presence of the clay increases the thermal stability of the polymer.
A new numerical model considering nanofiller random distribution in a porous polymeric matrix was developed to predict electrical percolation behavior in systems incorporating 1D-carbon nanotubes (CNTs) and/or 2D-graphene nanoplatelets (GNPs). The numerical model applies to porous systems with closed-cell morphology. The percolation threshold was found to decrease with increasing porosity due to filler repositioning as a result of foaming. CNTs were more efficient in forming a percolative network than GNPs. High-aspect ratio (AR) and randomly oriented fillers were more prone to form a network. Reduced percolation values were determined for misaligned fillers as they connect better in a network compared to aligned ones. Hybrid CNT-GNP fillers show synergistic effects in forming electrically conductive networks by comparison with single fillers.
To avoid the interference of electromagnetic radiation from other devices, an electronic device needs to be fabricated with flexible and light weight electromagnetic interference (EMI) shielding materials with high efficiency. According, highly flexible porous poly(vinylidene fluoride) (PVDF)/PFR (Fe3O4 decorated polyaniline/RGO composite) composite was prepared through solution blending of PVDF with pre-synthesized PFR conductive composite that involves in-situ oxidative polymerization of aniline in the presence of reduced graphene oxide (RGO) using FeCl3 as oxidant. The porous morphology of the composite was created by leaching out of mixed NaCl from the composite. Polyaniline and RGO were mutually decorated by chemically in-situ synthesized ferrosoferric oxide (Fe3O4) using the Fe source of FeCl3. A homogeneous dispersion of PFR in insulated PVDF matrix resulted in a highly electrical conductive composite (PVDF-PFR) material through formation of three dimensional continuous conductive networks of polyaniline-RGO in the matrix phase. The composite shows an outstanding EMI shielding effectiveness (EMI SE) property due to the porous structure and the presence of conductive network and ferromagnetic Fe3O4 nanoparticles. The PVDF-PFR composite (0.5 mm thickness) depicts a great permittivity and permeability value and achieve high EMI SE value (≈–28.18 dB) and conductivity value of ≈1.10·10–1 S·cm–1 at very low loading (5 wt%) of RGO.