Correlation between rheological,electrical, and microstructure characteristics in polyethylene/aluminum nanocomposites

Polyethylene (PE)/aluminum (Al) nanocomposites with various filler contents were prepared by a solution compounding method. We investigated the influence of the surface modification of Al nanoparticles on the microstructure and physical properties of the nanocomposites. The silane coupling agent octyl‐trimethoxysilane was shown to significantly increase interfacial compatibility between the polymer phase and Al nanoparticles. Rheological percolation threshold values were determined by analyzing the improvement in storage modulus at low frequencies depending on the Al loadings. Lower percolation threshold values were obtained for the composites prepared with the original nanoparticles than those prepared with the silane‐modified Al nanoparticles. A strong correlation between the time and concentration dependences of dc conductivity and rheological properties was observed in the different nanocomposite systems. The rheological threshold of the composites is smaller than the percolation threshold of electrical conductivity for both of the nanocomposite systems. The difference in percolation threshold is understood in terms of the smaller particle–particle distance required for electrical conduction when compared with that required to impede polymer mobility. It was directly shown by SEM characterization that the nanoparticle surface modification yielded better filler dispersion, as is consistent with our rheological and electrical analysis. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2143–2154, 2008     

ZnO nanoparticles as chain elasticity reducer and structural elasticity enhancer: Correlating the degradating role and localization of ZnO with the morphological and mechanical properties of PLA/PP/ZnO nanocomposite

The main purpose of this study was to investigate the effect of zinc oxide (ZnO) nanoparticles on the morphological, mechanical, thermal, and rheological properties of PLA/PP blend. In this regard, nanocomposites containing 1, 3, and 5 wt% of ZnO nanoparticles were prepared by melt mixing. In addition, three different mixing procedures were adopted to study their effects on the microstructure of nanocomposites. The rheological behaviors demonstrated a higher elasticity and less compatibility for two phases in the case of nanocomposites containing nanoparticles in harmony with the morphological observations. Accordingly, it was correlated to the elasticity originating from the interphase, anticipated coalescence of dispersed particles as a result of degradation of PLA chains triggered by ZnO nanoparticles (ZnO‐NPs) and also agglomeration of ZnO‐NPs depending on the content of nanoparticles and chosen mixing procedure. It was also found that mixing method puts a remarkable influence on the microstructure and rheological behavior of nanocomposites. Results of mechanical characterizations and thermogravimetric analysis (TGA) also confirmed the degradation induced by ZnO nanoparticles.     

Investigation of the electrical properties of XLPE/SiC nanocomposites

The interface between nanoparticles and the polymer matrix, which dominates the electrical properties of nanocomposites, can effectively improve the DC breakdown and suppress space charge accumulation in nanocomposites. To research the interface characteristics, XLPE/SiC nanocomposites with concentrations of 1 wt%, 3 wt% and 5 wt% were prepared. The DC breakdown, dielectric properties and space charge behavior were examined using pulsed electro-acoustic (PEA) equipment and a dielectric analyzer. The test results show that the nanocomposites with concentrations of 1 wt% and 3 wt% have higher DC breakdown field strength than neat XLPE. In contrast, there is a lower DC breakdown strength at a concentration of 5 wt%, possibly due to the agglomeration of nanoparticles. Nanoparticle doping increases the real and imaginary permittivities over those of neat XLPE. Furthermore, with increasing concentration, a larger increase in the permittivity amplitude was observed. Based on the space charge behavior, all nanocomposites could suppress space charge accumulation, but the nanocomposite with a concentration of 1 wt% exhibited the best effect. Meanwhile, heterocharge accumulation near electrodes was observed in neat XLPE and the nanocomposite with a concentration of 5 wt%. In contrast, homocharge accumulation near electrodes was observed in the nanocomposite with a concentration of 3 wt%. This phenomenon may be due to different amounts of shallow traps in nanocomposites with different concentrations, which might lead to differing electron or hole mobility.     

Preparation of magnetic polyurethane rigid foam nanocomposites

Super paramagnetic Fe₃O₄@SiO₂ nanoparticle was incorporated into polyurethane rigid foams in order to prepare new corresponded magnetic nanocomposite foams via one-shot method. The core–shell-structured nanoparticles were prepared by sol–gel method and characterized by transmission electron microscopy, X-ray diffraction, as well as Fourier transform infrared spectroscopy techniques. Magnetic nanoparticles were used up to 3 % in the foam formulations and the samples prepared successfully. Thermal, mechanical, and magnetic properties of nanocomposites were studied and the results showed superior properties in comparison with pristine foams.     

Thermally stimulated dielectric properties of polyvinylidenefluoride–zinc oxide nanocomposites

Thirty-micrometer thick polyvinylidenefluoride (PVDF)–zinc oxide (ZnO) nanocomposite samples in the mass ratio of ZnO (1–6% (w/w)) have been prepared by solution mixing method. The nano- and microstructures of PVDF–ZnO nanocomposite of different mass ratios were characterized by using high-resolution techniques such as atomic force microscopy (AFM) and scanning electron microscopy (SEM). The SEM and AFM images show the presence of different components such as nanoparticles, amorphous and crystalline phases in nanocomposite samples. Dielectric properties of polymer nanocomposite based on PVDF and ZnO of different mass/% compositions have been studied to understand the molecular motion at different frequencies in the temperature range from 300 to 500 K. The permittivity of the nanocomposites decreases with frequency, while increases with the increasing temperature and ZnO content. The loss peak that disappeared at higher frequency is the remarkable result of this study.     

Effect of ZnO nanoparticles on the thermal and mechanical properties of epoxy-based nanocomposite

Effect of ZnO nanoparticles particles on the mechanical properties and the curing behavior of an epoxy nanocomposite were studied. Nanocomposites were prepared using different loadings of pre-dispersed ZnO nanoparticles having an average size of 40 nm. The surface topography and morphology of the nanocomposites were studied using atomic force microscope (AFM). The mechanical properties of nanocomposites were studied using analytical techniques including dynamic mechanical thermal analysis and micro-Vickers hardness. Effects of ZnO nanoparticles on the curing behavior of these nanocomposites were investigated utilizing isothermal and non-isothermal differential scanning calorimeter techniques. In addition, chemical compositions of coatings containing different ZnO nanoparticles contents were studied using a Fourier transform inferred. It was found that, ZnO nanoparticles can effectively influence the mechanical properties of epoxy coating. In addition, lower curing degrees, and therefore crosslinking density of epoxy coating including higher ZnO nanoparticles were obtained. This effect was completely different at low and high loadings of the particles.     

Preparation,characterization, and permeability of novel poly (lactic acid)-based blends filled with thymol and ZnO

Novel thin sheets based on poly (lactic acid)/poly (caprolactone)/thermoplastic starch ternary blends were fabricated by incorporating thymol, zinc oxide nanoparticles (ZnO-NPs) and thymol/ZnO-NPs at different concentrations (6, 9, 12 wt% thymol and 1, 3, 5 wt% ZnO). The gas/water vapor barrier properties of the nanocomposites comprising the effects of polar and non-polar molecules and their leading mechanisms were thoroughly discussed. Moreover, the localization preference of ZnO-NPs, morphology along with mechanical, and thermal properties of the nanocomposites were investigated. A significant improvement of 58% in the water vapor impermeability by 5 wt% ZnO and 12 wt% thymol loading was achieved. Finally, the fitting of the Maxwell model on the experimental data revealed that this model cannot correctly predict the permeation behavior of ZnO-filled nanocomposites. Results suggested that these nanocomposites could be capable of being used as the packaging materials with high barrier performance.     

Nanoflower-like composites of ZnO/SiO2 synthesized using bamboo leaves ash as reusable photocatalyst

In this study, the synthesis of ZnO/SiO₂ nanocomposites using bamboo leaf ash (BLA) and tested their photocatalytic activity for rhodamine B decolorization have been conducted. The nanocomposites were prepared by the sol–gel reaction of zinc acetate dihydrate, which was used as a zinc oxide precursor, with silica gel obtained from the caustic extraction of BLA. The effect of the Zn content (5, 10, and 20 wt%) on the physicochemical characteristics and photocatalytic activity of the nanocomposites was investigated. The results of X-ray diffraction, scanning electron microscopy, gas sorption, and transmission electron microscopy characterization confirmed the mesoporous structure of the composites containing nanoflower-like ZnO (wurtzite) nanoparticles of 10–30 nm in size dispersed on the silica support. Further, the nanocomposites were confirmed to be composed of ZnO/SiO₂ by X-ray photoelectron spectroscopy analysis. Meanwhile, diffuse-reflectance UV–visible spectrophotometry analysis of the nanocomposites revealed band gap energies of 3.38–3.39 eV. Of the tested nanocomposites, that containing 10 wt% Zn exhibited the highest decolorization efficiency (99%) and fastest decolorization rate. In addition, the degradation efficiencies were not reduced significantly after five repeated runs, demonstrating the reusability of the nanocomposite catalysts. Therefore, the ZnO/SiO₂ nanocomposite obtained from BLA is a promising reusable photocatalyst for the degradation of dye-polluted water.     

Multi walled carbon nanotubes induced viscoelastic response of polypropylene copolymer nanocomposites: Effect of filler loading on rheological percolation

Polypropylene random copolymer nanocomposites having 0.2–7.0 vol% multi-walled carbon nanotubes (MWCNTs) were prepared via melt processing. Transmission electron microscopy (TEM) was employed to determine the nano scale dispersion of carbon nanotubes. Linear viscoelastic behavior of these nanocomposites was investigated using parallel plate rheometry. Incorporation of carbon nanotubes in the polymer matrix resulted in higher complex viscosity (η*), storage (G′) and loss modulus (G″) as compared to neat polymer, especially in the low-frequency region, suggesting a change from liquid to solid-like behavior in the nanocomposites. By plotting storage modulus vs. carbon nanotube loading and fitting with a power law function, the rheological percolation threshold in these nanocomposites was observed at a loading of ∼0.27 vol% of MWCNTs. However, electrical percolation threshold was reported at ∼0.19 vol% of MWCNTs loading. The difference in the percolation thresholds is understood in terms of nanotube connectivity with nanotubes and polymer chain required for electrical conductivity and rheological percolation.     

Poly(lactic acid)/organoclay nanocomposites: Thermal,rheological properties and foam processing

In this study, polymer nanocomposites based on poly(lactic acid) (PLA) and organically modified layered silicates (organoclay) were prepared by melt mixing in an internal mixer. The exfoliation of organoclay could be attributed to the interaction between the organoclay and PLA molecules and shearing force during mixing. The exfoliated organoclay layers acted as nucleating agents at low content and as the organoclay content increased they became physical hindrance to the chain mobility of PLA. The thermal dynamic mechanical moduli of nanocomposites were also improved by the exfoliation of organoclay; however, the improvement was reduced at high organoclay content. The dynamic rheological studies show that the nanocomposites have higher viscosity and more pronounced elastic properties than pure PLA. Both storage and loss moduli increased with silicate loading at all frequencies and showed nonterminal behavior at low frequencies. The nanocomposites and PLA were then foamed by using the mixture of CO₂ and N₂ as blowing agent in a batch foaming process. Compared with PLA foam, the nanocomposite foams exhibited reduced cell size and increased cell density at very low organoclay content. With the increase of organoclay content, the cell size was decreased and both cell density and foam density were increased. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 689–698, 2005     

Preparation of PLA-based nanocomposites modified by nano-attapulgite with good toughness-strength balance

Polylactic acid (PLA) was modified by poly (butylene adipate-co-terephthalate) (PBAT) and nano-attapulgite (AT) using the melt blending technique. Ethylene-butyl acrylate-glycidyl methacrylate (E-BA-GMA) was used as a compatibilizer which can bond the AT nanoparticles with PLA/PBAT matrix by interaction between the epoxy and hydroxyl groups. The effects of the AT content on the mechanical properties, thermal properties, crystallinity and morphology of PLA/PBAT/ATT nanocomposites were investigated. The results showed that the tensile strength, elongation at break and impact strength of PLA/PBAT could be simultaneously increased by incorporating AT nanoparticles. PLA/PBAT/AT nanocomposites possessed higher thermal stability than pure PLA/PBAT. In the ternary composite system of PLA/PBAT/AT, AT acted as a heterogeneous nucleating agent and was able to increase the crystallization temperature. When the AT content was low (≤2.5 wt%), AT nanoparticles could uniformly disperse in the PLA/PBAT matrix. In general, AT was an effective filler to reinforce and toughen PLA/PBAT blend simultaneously, and the PLA/PBAT/AT nanocomposite with 2.5 wt% AT exhibited a good combination of strength and toughness.     

Nutmeg filler as a natural compound for the production of polyurethane composite foams with antibacterial and anti-aging properties

Polyurethane (PU) composite foams were successfully reinforced with different concentrations (1 wt%, 2 wt%, 5 wt%) of nutmeg filler. The effect of nutmeg filler concentration on mechanical, thermal, antimicrobial and anti-aging properties of PU composite foams was investigated. PU foams were examined by rheological behavior, processing parameters, cellular structure (Scanning Electron Microscopy analysis), mechanical properties (compression test, impact test, three-point bending test, impact strength), thermal properties (Thermogravimetric Analysis), viscoelastic behavior (Dynamic Mechanical Analysis) as well as selected application properties (thermal conductivity, flammability, apparent density, dimensional stability, surface hydrophobicity, water absorption, color characteristic). In order to Disc Diffusion Method, all PU composites were tested against selected bacteria (Escherichia coli and Staphylococcus aureus). Based on the results, it can be concluded that the addition of 1 wt% of nutmeg filler leads to PU composite foams with improved compression strength (e.g. improvement by ~19%), higher flexural strength (e.g. increase of ~11%), improved impact strength (e.g. increase of ~32%) and comparable thermal conductivity (0.023–0.034 W m⁻¹ K⁻¹). Moreover, the incorporation of nutmeg filler has a positive effect on the fire resistance of PU materials. For example, the results from the cone calorimeter test showed that the incorporation of 5 wt% of nutmeg filler significantly reduced the peak of heat release rate (pHRR) by ca. 60% compared with that of unmodified PU foam. It has been also proved that nutmeg filler may act as a natural anti-aging compound of PU foams. The incorporation of nutmeg filler in each amount successfully improved the stabilization of PU composite foams. Based on the antibacterial results, it has been shown that the addition of nutmeg filler significantly improved the antibacterial properties of PU composite foams against both Gram-positive and Gram-negative bacteria.     

Preparation and Rheological Characterization of Polymer Nanocomposites Based on Expanded Graphite

A new type of conductive filler, namely expanded graphite (EG), was used to prepare novel nanocomposites. The EG was incorporated into several rather different polymers, specifically polycarbonate (PC), low‐density polyethylene (LDPE), isotactic polypropylene (PP), and polystyrene (PS), using melt mixing in a small‐scale DACA‐Microcompounder. The EG content was varied between 1 and 20 wt%. The rheological properties and morphologies of the nanocomposites were characterized by melt rheology and scanning electron microscopy (SEM), respectively. The melt‐state linear viscoelastic properties were investigated using an ARES rheometer, with the measurements performed in the dynamic mode at various temperatures over a wide range of frequencies. Addition of the EG increased the linear dynamic moduli and melt viscosity of the materials. Up to a certain critical concentration of EG, the materials exhibited a simple liquid‐like behavior. Above this concentration, however, significant changes in the frequency dependences of the moduli and viscosity were observed. In addition, the moduli showed a liquid‐solid transition resulting in a second plateau in the low frequency‐regime, and the complex viscosity revealed shear‐thinning behavior. Specific values of this percolation concentration were found to be at around 4 wt% in the case of PC/EG, 9 wt% for PP/EG and PS/EG, and 12 wt% for PE/EG. This critical concentration was correlated to a network‐like structure formed through interactions between the EG platelets and the polymers. The extent of these complications was found to vary from polymer to polymer, presumably due to different degrees of EG exfoliation and dispersion arising from different EG‐polymer interactions and from variable shearing forces dependent on the polymer viscosities. The formation of network‐like structures is very sensitively displayed using van Gurp‐Palmen plots, which are most suitable for identifying “rheological percolation” in our investigated systems.     

Facile Fabrication of PBS/CNTs Nanocomposite Foam for Electromagnetic Interference Shielding

In order to reduce the pollutants of environment and electromagnetic waves, environment friendly polymer foams with outstanding electromagnetic interference shielding are imminently required. In this paper, a kind of electromagnetic shielding, biodegradable nanocomposite foam was fabricated by blending poly (butylene succinate) (PBS) with carbon nanotubes (CNTs) followed by foaming with supercritical CO₂. The crystallization temperature and melting temperature of PBS/CNTs nanocomposites with 4 wt % of CNTs increased remarkably by 6 °C and 3.1 °C compared with that of pure PBS and a double crystal melting peak of various PBS samples appeared in DSC curves. Increasing the CNT content from 0 to 4 wt % leads to an increase of approximately 3 orders of magnitude in storage modulus and nearly 9 orders of magnitude in enhancement of electrical properties. Furthermore, CNTs endowed PBS nanocomposite foam with adjustable electromagnetic interference (EMI) shielding property, giving a specific EMI shielding effectiveness of 28.5 dB cm³/g. This study provides a promising methodology for preparing biodegradable, lightweight PBS/CNTs foam with outstanding electromagnetic shielding properties.     

The synergistic reinforcing effects of halloysite nanotube particles and polyolefin elastomer-grafted-maleic anhydride compatibilizer on melt and solid viscoelastic properties of polylactic acid/ polyolefin elastomer blends

The effect of halloysite nanotube (HNTs) particles and polyolefin elastomer-graft-maleic anhydride (POE-g-MA) in the polylactic acid (PLA) and polyolefin elastomer (POE) blend with a constant weight percentage composition have been studied using the scanning electron microscopy, rheometry, dynamic mechanical thermal analysis (DMTA) as well as the thermogravimetric testing. Through these, it was found that the simultaneous presence of POE-g-MA and HNT significantly improves the melt and solid viscoelastic properties and thermal stability of PLA/POE. This improvement is attributed to the increased interactions and improved interfacial adhesion between the present components. The microscopic images of PLA/POE-g-MA/POE (80/8/12) blend containing 4 wt% HNT showed a microstructure similar to the interconnected morphology due to the enhanced compatibility and better dispersion of nanoparticles. The rheological behavior was significantly changed for the PLA/POE blend containing POE-g-MA and 4 wt% HNT. This dramatic increase in the rheological properties was consistent with the morphological results. Only one glass transition temperature was observed in the DMTA plot of PLA/POE-g-MA/POE blend, which was a sign of a homogeneous, fully compatible system. In addition, a very strong reinforcing effect of HNT particles was observed in the presence of POE-g-MA for the nanocomposites. Finally, the thermogravimetric analysis showed a completely different trend for thermal degradation of PLA/POE-g-MA/POE nanocomposite containing 4 wt% HNT, which could be an indication of microstructural development.     

Filler network structure in graphene nanoplatelet (GNP)-filled polymethyl methacrylate (PMMA) composites: From thermorheology to electrically and thermally conductive properties

In this work, graphene nanoplatelet (GNP) filled polymethyl methacrylate (PMMA) composites were prepared using solution method via a specially designed route and relatively high thermal conductivities of the composites were achieved at a low GNP loading. The effect of GNP content on rheological behavior, thermal and electrical conductivity of the composites was intensively investigated. Thermorheological complexity was displayed at elevated GNP loading, and the rheological percolation threshold of GNP in PMMA decreased from 7.96 wt% at 220 °C to 4.02 wt% at 260 °C according to Winter-Chambon method, suggesting that GNP was more likely to form a seepage network at higher temperature. The DMTA results showed that the increase in moduli of the composites should be ascribed to the formation of the GNP-GNP network structure. The electrical conductivity of the composites underwent a sudden jump by seven orders of magnitude, which also indicated the formation of a GNP conductive pathway in the matrix with an electrical percolation threshold of 2–4 wt%. The results of transient temperature measurement were in good consistent with the thermal conductivity versus GNP loading, which was compared with various thermal conduction models with a modified Agari model presenting an acceptable evaluation of the dispersion status of GNP in the matrix. The experimental electrical and thermal conductivities as a function of GNP content could well be interpreted by the filler network structure as observed in morphological studies.     

On the synthesis and characterization of ZnO/MgO nanocomposite by thermal evaporation technique

ZnO/MgO nanocomposites have been synthesized by an easy and cost effective thermal evaporation technique. Various growth temperatures ranging from 800 to 900 °C were tried. It is observed that the process temperature plays a key role in the formation of ZnO/MgO nanocomposite and the proper formation of ZnO/MgO nanocomposite occurs at 875 °C temperature as confirmed by X-ray diffraction studies. Scanning electron microscopic images indicate that the ZnO/MgO nanocomposite is formed as agglomerated nanoparticles distributed over a large area. Energy dispersive X-ray analyses also reveal that the Mg composition in the synthesized nanocomposite strongly depends on the process temperature. Photoluminescence (PL) spectrum exhibits a blue shift for the ZnO/MgO nanocomposite synthesized at 875 °C indicating the incorporation of Mg into the ZnO crystal lattice. A higher PL intensity ratio of band-edge to deep band emission has been observed for this sample indicating the presence of low crystalline defects.     

Nanoperlite effect on thermal,rheological, surface and cellular properties of poly lactic acid/nanoperlite nanocomposites for multipurpose applications

In this study, poly lactic acid (PLA) based nanocomposites containing perlite nanoparticles were prepared by melt mixing method. Various characterization techniques were employed to evaluate the performance PLA/nanoperlite nanocomposites. The nanocomposites were characterized via FTIR to investigate the functional groups and chemical structure of the nanocomposites. Thermal properties of the nanocomposites, examined by DSC, showed that the increase of nano-perlite content in the PLA matrix reduces the crystallinity and melting temperature of the nanocomposites. The rheological studies indicated that both of storage and loss modulus are increased when the nanoperlite is added up to 5 wt%. However, the modulus is reduced in samples containing more than 5 wt% nanoparticle due to their agglomeration. The in-vitro degradation studies of the nanocomposites at elevated and normal temperatures showed hydrolytic degradation around 13–15 months. The surface behavior results implied that the water contact angle values exhibit a reducing trend when the nanoperlite content increases up to 3 wt%, which can be related to the decreased crystallinity of PLA and also to the hydrophilic nature of perlite. Moreover, the adhesion of osteoblast cells and their viability on an electrospun scaffold, made of optimized sample, showed the initial implications of potential applications of the nanocomposites in bone regeneration and biomedical applications. These multipurpose nanocomposites can also be used for packaging applications.     

Organo-modified montmorillonite/poly(?-caprolactone) nanocomposites prepared by melt intercalation in a twin-screw extruder

Nanocomposites based on biodegradable poly(?-caprolactone) organo-modified clay have been prepared by melt intercalation using a twin-screw extruder. The screw configuration developed allowed us to obtain an intercalated/exfoliated nanocomposite structure using a modified montmorillonite containing no polar groups, in contrast to previous work using mainly alkyl ammonium containing hydroxyl polar groups in poly(?-caprolactone). Montmorillonite nanocomposites were prepared using a specific extrusion profile from a 30 wt% masterbatch of organo-modified clay, which was then diluted at 1, 3 and 5%. Intercalated and/or exfoliated nanocomposites structures were assessed using rheological procedures and confirmed by transmission electron microscopy analysis. Mechanical and thermal properties were found to be strongly dependent on morphology and clay percentage. Crystallinity was only slightly affected by the clay addition. Effect of exfoliation on Young's modulus and thermal stability was investigated. Young's modulus increased significantly and onset degradation temperature measured by TGA was significantly reduced for an exfoliated nanocomposite composition containing 5 wt% organoclay.     

In situ polymerized poly(butylene succinate)/silica nanocomposites: Physical properties and biodegradation

A series of poly(butylene succinate)/silica (PBS/silica) nanocomposites were prepared by in situ polymerization. Solid-state ²⁹Si NMR and FTIR analysis indicated that silanol-bonded carbonyl groups are established within PBS/silica nanocomposite materials. Rheological effects inherent to the silica filler were evaluated by melt rheological analysis as a function of shear force in the molten state. Despite high shear force, PBS/silica nanocomposites maintained a relatively high melt viscosity, attributable to a network structure resulting from covalent bonding between silica and the polymer chain. Nanocomposite material containing 3.5 wt% silica exhibited greatly improved mechanical properties. The tensile strength at break and elongation were ca. 38.6 MPa and 515%, while those of the parent PBS were 26.3 MPa and 96%, respectively. PBS/silica nanocomposites showed composition dependency on biodegradation ascribable to reduced crystallinity and preferential microbial attack.