Dielectric spectroscopic analysis of polyvinyl chloride nanocomposites loaded with Fe2O3 nanocrystals

Iron oxide (α‐Fe₂O₃) nanocrystals powder was successfully synthesized via the sol‐gel method. The microstructural examination of the synthesized nanocrystals confirmed the formation of α‐Fe₂O3 (hematite) structure using X‐ray diffraction and Fourier transform infrared. The synthesized nano‐hematite powder with different weight percentage up to 5 wt% was introduced to polyvinyl chloride (PVC) to fabricate PVC/Fe₂O₃ nanocomposites using the solution‐cast technique. The dielectric spectroscopic analysis for the investigated samples has been studied at room temperature and at different temperatures up to 120°C. The real part of the permittivity (ε^′) exhibited a significant dependence on filler concentrations throughout whole temperature range. However, the dependency of both of the loss tangent (tanδ ) and AC conductivity (σ_ac) on filler concentrations is more pronounced at temperatures higher than room temperature. The obtained values of tan δ for the investigated nancomposites referred to the α‐relaxation around 70°C, which is close to glass transition temperature of the investigated PVC. The dependency of the dielectric strength on Fe₂O₃ nanofiller concentration was observed with enhancement in the dielectric strength reach to 20.5% for PVC/0.7 wt% Fe₂O₃ nanocomposite higher than the recorded value for the pristine PVC.     

Dielectric properties of novel poly(aryl prehnitimide)s

Six different variants of a new type of polyimide, poly(aryl prehnitimide)s, containing various moisture contents have been studied using dielectric relaxation spectroscopy. Dielectric loss measurements show the presence of a double peak near 200 K (depending on frequency) due to water relaxation. The two peaks have been designated γ₁ and γ₂. The γ₂ peak appears as a shoulder on the γ₁ peak at lower temperatures and is very sensitive to moisture content. The γ₁ peak is less sensitive to moisture content and is associated with isolated water molecules coupled to the polymer chains. Both of the γ-relaxation peaks were studied in detail to obtain the associated activation energies. © 1996 John Wiley & Sons, Inc.     

Dielectric,thermal, and mechanical properties of CeO2‐filled HDPE composites for microwave substrate applications

Cerium oxide‐filled high density polyethylene (HDPE) composites for microwave substrate applications were prepared by sigma‐blend technique. The HDPE was used as the matrix and the dispersion of CeO₂ in the composite was varied up to 0.5 by volume fraction, and the dielectric properties were studied at 1 MHz and microwave frequencies. The variations of thermal conductivity (k_eff), coefficient of thermal expansion (α_c) and Vicker's microhardness with the volume fraction of the filler were also measured. The relative permittivity (ε_eff) and dielectric loss (tan δ) were found to increase with increase in CeO₂ content. For 0.4 volume fraction loading of the ceramic, the composite had ε_eff = 5.7, tan δ = 0.0068 (at 7 GHz), k_eff = 2.6 W/m °C, α_c = 98.5 ppm/°C, Vicker's microhardness of 18 kg/mm² and tensile strength of 14.6 MPa. Different theoretical approaches have been used to predict the effective permittivity, thermal conductivity, and coefficient of thermal expansion of composite systems and the results were compared with the experimental data. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 998–1008, 2010     

Preparation and characterization of polypropylene/mesoporous silica nanocomposites with confined polypropylene

Polypropylene (PP)/Ti-MCM-41 nanocomposites were prepared by isospecific propylene polymerization with Ti-MCM-41/Al(i-C₄H₉)₃ catalyst. The cross polarization/magic angle spinning (CP/MAS) ¹³C NMR spectrum of the composite was similar to that of the conventional isotactic PP, and the decrease in the pore volume of Ti-MCM-41 in the nanocomposites, as measured by N₂ adsorption, was consistent with the value calculated from the weight loss in the thermogravimetric analysis (TGA) curve; both these facts attest to propylene polymerization within the mesopores of Ti-MCM-41. Alkali treatment followed by extraction with o-dichlorobenzene allows us to extract the confined PP out of the Ti-MCM-41 mesopores. Although the PP/Ti-MCM-41 nanocomposites do not exhibit a crystalline melting point, the same PP when extracted from the mesopores showed a clear melting point at 154.7 °C; this indicates that the crystallization of PP confined in mesopores is strongly hindered. For the PP polymerized within the confinement, the molecular weight (M_w) and molecular weight distribution (M_w/M_n) were 84,000 and 4.3, respectively; these values were considerably smaller than those of the PP polymerized concurrently outside the Ti-MCM-41 mesopores (M_w = 200,000–450,000, M_w/M_n = 40–75). Therefore, the confinement also has a marked effect on the molecular weight of the PP. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 3324–3332, 2003     

Electrical strength in ramp voltage AC tests of LDPE and its nanocomposites with silica and fibrous and laminar silicates

The electrical strength of a set of LDPE micro and nanocomposites with silica, laminar silicates and fibrous silicates has been studied. A significant 60% increase of the breakdown electrical field is shown by the microsized microdispersed LDPE/montmorillonite composites while only a 20% increase is obtained with a nanosized laminar silicate. Nanosized nanodispersed composites of the spherical silica and fibrous silicate with LDPE show a lower increase of the breakdown electrical field. The data point scatter in repeated tests is very high in the case of the microcomposites, indicating strong morphological heterogeneity, while it is very low in the nanocomposites. This implies that these nanocomposites are remarkably defect‐free as regards electrically “weak” sites. An analysis of the crystalline structure, semicrystalline morphology and inorganic particle size and distribution evidences the importance of the role played not only by the inorganic particles but also by the semicrystalline morphology in the final dielectric performance of the composite. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1301–1311, 2008     

Fe-g-PDEAEMA纳米复合微球的制备及性质研究

由聚N,N-二乙基胺基甲基丙烯酸乙酯(PDEAEMA)与铁纳米颗粒复合制得的纳米铁基复合材料。纳米铁微球表面钝化形成Fe3O4后,将多巴胺基引发剂修饰在Fe3O4的表面,通过表面引发原子转移自由基聚合(SI-ATRP)将DEAEMA单体聚合在修饰了多巴胺基引发剂的表面获得Fe-g-PDEAEMA复合微球。显微结果表明修饰PDEAEMA后,复合微球的分散性得到了一定的提高;XRD数据表明在纳米铁表面生成了一层Fe3O4壳。利用透光率测定研究了复合微球的p H敏感性,表明在酸性条件下悬浮性良好,在碱性条件下发生了沉降,复合微球具有p H敏感性。通过还原降解酸性大红染料,表明Fe-g-PDEAEM复合微球与纳米铁相比,其还原性有所提高,合成的Fe-g-PDEAEMA复合微球可用于氯代烃等氯化物污染的水体保护。     

Synthesis of polyether‐based polyurethane‐silica nanocomposites with high elongation property

The NCO‐terminated prepolymers, prepared by reacting a mixture of poly(tetramethylene glycol) and fumed nanosilica with 4,4′‐diphenylmethane diisocyanate, were chain‐extended with 1,4‐ butanediol to yield polyurethane‐silica nanocomposites. The nanosilica particles were well dispersed in the polyurethane matrix up to 3 wt%. The polyurethane chains in the interfaces were covalently linked to the nanosilica surfaces through urethane bonds. Introduction of the nanosilica into the polyurethane enhanced both tensile strength and elongation of the resulting nanocomposite films. Especially, the elongation at break of the nanocomposite films containing 1 wt% nanosilica was 3.5 times greater than that of the pure polyurethane films. Copyright © 2005 John Wiley & Sons, Ltd.     

Transport properties of organic vapors in nanocomposites of isotactic polypropylene

Isotactic polypropylene nanocomposites were obtained by the melt blending of polypropylene‐graft‐maleic anhydride and organophilic layered silicate (OLS) consisting of synthetic fluorohectorite modified by cation exchange with protonated octadecylamine. The composition of the inorganic clay was varied between 2.5 and 10 wt %, and films of the composites were obtained via hot‐press molding. X‐ray analysis showed that nanocomposites in which silicate layers were either delaminated or ordered as in an intercalated structure were obtained. The elastic modulus of the samples was higher than that of the pure polymer over a wide temperature range and increased with increasing inorganic content. The transport properties, sorption and diffusion, were measured for two organic vapors, dichloromethane and n‐pentane. For both vapors, the sorption was not very different from that of the pure polymer, whereas the zero‐concentration diffusion parameter strongly decreased with increasing OLS content. Therefore, the permeability, that is, the product of sorption and diffusion, decreased for both vapors as a result of the decreased value of the diffusion parameter. The decrease was higher for the less interacting n‐pentane. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1798–1805, 2003     

In situ polymerization of ethylene using metallocene catalysts: Effect of clay pretreatment on the properties of highly filled polyethylene nanocomposites

Highly filled polyethylene (PE)‐based nanocomposites were obtained by insitu polymerization technique. An organically modified montmorillonite, Cloisite® 15A (C15A), was previously treated with methylaluminoxane (MAO) to form a supported cocatalyst (C15A/MAO) before being contacted with a zirconocene catalyst. The main features of C15A/MAO intermediates were studied by elemental analysis, TGA, TGA‐FTIR, WAXD, and TEM. MAO reacts with the clay, replaces most of the organic surfactant within the clay galleries and destroys the typical crystrallographic order of the nanoclay. The catalytic activity in the presence of C15A/MAO is higher than in ethylene polymerization without any inorganic filler and increases with MAO supportation time. This indicates that part of the polymer chains grows within the clay galleries, separates them, and makes it possible to tune the final morphology of the composites. The polymerization results and the influence of C15A pretreatment and polymerization conditions on thermal and morphological properties of the hybrid PE/C15A nanocomposites are presented. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5390–5403, 2008     

Preparation and properties of enhanced nanocomposites based on PLA/PC blends reinforced with silica nanoparticles

In order to lower brittleness of biobased polylactic acid (PLA), its blending with polycarbonate and nanosilica is aimed. In this line, to increase compatibility of the ingredients, dicumyl peroxide (DCP) and Cobalt (II) acetylacetonate (Co) were used as grafting and transesterification catalysts, respectively. The X‐ray diffraction (XRD) spectra demonstrated high compatibility of the ingredients by broadening of the PLA characteristic peaks and, also, good dispersion of nanosilica particles, especially in PLA/PC/Silica/Co sample. The EDX maps confirmed good nanosilica dispersion, too. The silica nanoparticle size was ranged from 20 to 100 nm in transmission electron microscopy (TEM) pictures. All nanocomposites showed improved thermal stability in thermogravimetric analysis (TGA). Differential scanning calorimetry (DSC) results demonstrated lower T_g, T_m, and crystallinity values for the fabricated nanocomposites. Notably, the dynamic mechanical thermal analysis (DMTA) curves confirmed the T_g, T_m, and T_cc trend obtained in DSC; moreover, much higher surface under tan δ peak for PLA/PC/Silica/Co sample was obtained, which implies its higher toughness. The precise tensile study of the samples confirmed significantly higher elongation at break of the nanocomposites, more considerably in PLA/PC/Silica/Co sample, with nearly negligible defect on tensile strength and modulus. In a concise, the obtained results confirmed the higher efficiency of Co catalyst, which leads to the sample with improved characteristics compared with DCP.     

Industrially produced PET nanocomposites with enhaced properties for food packaging applications

Gas permeation of polymers is one of the important factors to be considered in the selection of materials for many packaging applications, such as modified atmosphere packaging (MAP) for foods. Poly (ethylene therephthalate) (PET) is known to exhibit very low gas permeation compared with most polymers such as polystyrene, polyethylene and polypropylene. However, MAP applications require better barrier performance than that of PET. In the present work PET trays reinforced with organically modified sepiolite, fibrillar nanoclay, have been produced at industrial processes. Permeability to water vapour, oxygen and carbon dioxide has been studied in PET nanocomposites as well as their microstructure through transmission electron and scanning electronic microscopy (TEM and SEM), and their mechanical properties. Results show a better performance in barrier properties as well as an increase in tensile strength, and impact resistance when the sepiolite content is lower than 2.5%.     

Alteration of matrix curing characteristics and its role in extension of hydrodynamic equation for predicting viscoelastic properties of nitrile rubber/silica nanocomposites

Neglecting the alteration of matrix curing characteristics in a filled rubber nanocomposite, as a result of possible interactions between the nano filler and curing agent ingredients, leads to inaccurate properties prediction using conventional hydrodynamic equations. In the current work, we present a new empirical extended version of hydrodynamic equation and examine its capability in predicting the viscoelastic properties of NBR/nanosilica system in which the negative influence of the filler on the curing process of the NBR matrix was confirmed through various analyses such as tensile test, rheometry, swelling experiments, and dynamic mechanical analysis. The results showed that the proposed empirical extended model is able to account the contribution of alteration of matrix curing characteristics in changing the composite properties below the filler percolation threshold. It was demonstrated that the extended model provides more accurate prediction of viscoelastic properties of silica‐filled cured NBR nanocomposites above glass transition temperature.     

Preparation and enhanced properties of poly(propylene)/ silica‐grafted‐hyperbranched polyester nanocomposites

A series of poly(propylene) silica‐grafted‐hyperbranched polyester nanocomposites by grafting the modified hyperbranched polyester (Boltorn? H20), possessing theoretically 50% end carboxylic groups and 50% end hydroxyl groups, which endcapped with octadecyl isocyanate (C19), onto the surface of SiO₂ particles (30 nm) through 3‐glycidoxy‐propyltrimethoxysilane (GPTS) was prepared. The effect of silica‐grafted‐modified Boltorn? H20 on the mechanical properties of polypropylene (PP) was investigated by tensile and impact tests. The morphological structure of impact fracture surface and thermal behavior of the composites were determined by scanning electron microscopy (SEM) and differential scanning calorimetry (DSC), respectively. The melt viscosity of composites was investigated by melt flow index (MFI). The obtained results showed that: (1) the modified Boltorn? H20 was successfully grafted onto the SiO₂ surface confirmed by FT‐IR and X‐ray photoelectron spectroscopy (XPS) analysis; (2) the incorporation of silica‐grafted‐modified Boltorn? H20 (3–5 wt% SiO₂) greatly enhanced the notched impact strength as well the tensile strength of the composites; (3) the incorporation of silica‐grafted‐modified Boltorn? H20 had no influence on the melting temperature and crystallinity of PP phase; (4) the MFI of PP composites increased when the silica‐grafted‐modified Boltorn? H20 particles were added compared with PP/SiO₂ or PP/SiO₂‐GPTS composites. Copyright © 2004 John Wiley & Sons, Ltd.     

Poly(methyl methacrylate)/silica/titania ternary nanocomposites with greatly improved thermal and ultraviolet-shielding properties

Poly(methyl methacrylate) (PMMA)/silica/titania ternary nanocomposites with covalent bonding interaction between polymer and inorganic phases have been prepared using a novel non-hydrolytic sol-gel method. Transmission electron microscope (TEM) image of silica/titania binary inorganic component indicates a core-shell-like structure. Scanning electron microscope (SEM) images suggest that the well dispersed silica/titania particles in the hybrid are on the nanometer-scale. The transparencies of nanocomposites are maintained in visible region while the absorption band in ultraviolet (UV) region is red shifted with increasing inorganic content. The thermogravimetric analysis (TGA) results show that the thermal stability of PMMA copolymer increases dramatically with the addition of silica/titania moieties both in nitrogen and in air.     

Melt‐extensional properties and orientation behaviors of polypropylene‐layered silicate nanocomposites

Polypropylene‐layered silicate nanocomposites consisting of three components—pure polypropylene, maleated polypropylene, and organically modified silicate—were prepared by the melt‐intercalation method to investigate melt‐extensional properties such as melt strength, neck‐in test, and orientation behavior. The nanocomposites showed an enhanced tensile modulus, enhanced storage modulus, much enhanced melt tension, and reduced neck‐in during the melt processing as compared with neat polymer. The uniaxial drawing induced the silicate surface to align parallel to the sheet surface. The c and a* axes of the polypropylene crystals were bimodally oriented to the flow direction, and the b axes were oriented to the thickness direction. The bimodal orientation of the polypropylene crystal was enhanced with the concentration of silicates. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 158–167, 2005     

Influence of nanoparticle surface chemistry on the thermomechanical and magnetic properties of ferromagnetic nanocomposites

The effect of nanoparticle surface chemistry on the thermal, mechanical, and magnetic properties of poly(methyl methacrylate) (PMMA) nanocomposites with cobalt ferrite nanofillers was studied by comparing nanofillers coated with oleic acid (OA; which does not covalently bond to the PMMA matrix) and 3‐methacryloxypropyltrimethoxysilane (MPS, which covalently bonds to the PMMA matrix). Thermogravimetric analysis revealed an increase in the thermal degradation temperature of the nanocomposites compared with the neat polymer. The effect of cobalt ferrite nanofiller on the glass transition temperature (T_g) of the nanocomposite was evaluated by differential scanning calorimetry. The T_g value of the material increased when the particles were introduced. Dynamic mechanical analysis indicated an increase in the storage modulus of the nanocomposite because of the presence of nanofiller and a shift in the peak of loss tangent toward higher temperature. Magnetic measurements indicated that both nanocomposites had a small hysteresis loop at 300 K and no hysteresis at 400 K. However, estimates of the nanofiller's rotational relaxation times and measurements of the zero field cooled temperature‐dependent magnetization indicate that the observed lack of hysteresis at 400 K is likely because of particle rotation in the polymer matrix. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

Mechanical properties and structural characteristics of PP/PP‐g‐SBR nanocomposites prepared by dynamical photografting

Poly(propylene) (PP)/PP grafted styrene‐butadiene rubber (PP‐g‐SBR) nanocomposite was prepared by blending PP with PP‐g‐SBR using dynamical photografting. The crystal morphological structure, thermal behavior, and mechanical properties of PP/PP‐g‐SBR nanocomposites have been studied by photoacoustic Fourier transform infrared spectroscopy (PAS‐FT‐IR), wide‐angle X‐ray diffraction (WAXD), scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and mechanical measurements. The data obtained from the mechanical measurements show that the PP‐g‐SBR as a modifier can considerably improve the mechanical properties of PP/PP‐g‐SBR nanocomposites, especially for the notched Izod impact strength (NIIS). The NIIS of the nanocomposite containing 2 wt% PP‐g‐SBR measured at 20°C is about 2.6 times that of the control sample. The results obtained from PAS‐FTIR, WAXD, SEM, and DSC measurements revealed the enhanced mechanism of impact strength of PP/PP‐g‐SBR nanocomposites as follows: (i) the β‐type crystal of PP formed and its content increased with increasing the photografting degree of PP‐g‐SBR; (ii) the size of PP‐g‐SBR phase in the PP/PP‐g‐SBR nanocomposites obviously reduced and thus the corresponding number of PP‐g‐SBR phase increased with increasing the photografting degree of PP‐g‐SBR. All the earlier changes on the crystal morphological structures are favorable for increasing the compatibility and enhancing the toughness of PP at low temperature. Copyright © 2004 John Wiley & Sons, Ltd.     

Polypropylene multifilament yarn filled with clay and/or graphite: Study of a potential synergy

In this study, clay and/or graphite particles have been added in various quantities to polypropylene matrix by melt blending. The morphology and more particularly the dispersion of particles in these composites have been compared by transmission electron microscopy (TEM). Their thermal stability has also been studied by thermogravimetric analysis (TGA). The experimental results reveal that the addition of 5 wt % of graphite particles or clay improves the thermal stability in air of the matrix by about 50 and 90 °C, respectively. In a second step, these blends have been melt‐spun to produce multifilament yarns. The experiments have shown that the addition of graphite particles up to 5 wt % do not reduce the spinnability of the polypropylene, while the incorporation of more than 1 wt % of clay was causing difficulties for the spinning and more particularly for the drawing step. However, a slight improvement of the Young's modulus of the filaments reinforced with 1 wt % of Cloisite®15A is observed when the filaments are drawn up. The flammability of the different blends used as knitted fabrics has finally been evaluated with a mass loss calorimeter at 35 kW/m². An atypical behavior has been highlighted for all blends and will be discussed. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1185–1195, 2010     

Preparation, morphology and properties of nanocomposites of polyacrylamide copolymers with monodisperse silica

To improve oil recovery (IOR) performance of polyacrylamide polymer media, the paper presented the nanocomposites (PA-B-S) of acrylamide-styrene-AMPS copolymers (PA-S) with monodisperse SiO₂ particles. The monodisperse particles from 17 to 100 nm with low size deviation were adopted as an inorganic phase, and their nanocomposite properties and morphology were investigated with viscosity measurements, thermal degradation (TGA), flooding test and transmission electron microscopy (TEM) techniques. For 66.7 nm SiO₂ particles at 0.5 wt% load, the nanocomposites produced viscosity enhancement at critical concentration, high salt-tolerance behavior, and the high degradation temperature at 411 °C, which were obviously higher than those of pure PA-S copolymers. These inorganic-organic synergistic or nano size effects were shown in a series of prepared nanocomposite samples. TEM morphology proved that PA-B-S solution at LCST formed uniform dispersion of the SiO₂ particles encapsulated with this associating copolymer and formed stable drop-like emulsion patterns.In flooding experiments, the PA-B-S solutions at critical viscosity gave the resistance factor of 9.38 and residual resistance factor of 3.39, compared with those of 5.20, 1.51 for pure PA-S, respectively. Such improved properties of PA-B-S were suitable for producing high shearing behavior and sweep volume in IOR or EOR. As the controllable characters of monodisperse SiO₂ particles, the results from their nanocomposites were the good references to the multi-disperse particles acted as IOR media.