High thermal and mechanical properties enhancement obtained in highly filled polybenzoxazine nanocomposites with fumed silica

Highly filled polybenzoxazine nanocomposites filled with nano-SiO₂ particles were investigated for their mechanical and thermal properties as a function of filler loading. The nanocomposites were prepared by high shear mixing followed by compression molding. A very low A-stage viscosity of benzoxazine monomer gives it excellent processability having maximum nano-SiO₂ loading as high as 30 wt% (18.8 vol%) with negligible void content. Moreover, thermal analysis of the curing process of the compound of the PBA-a/nano-SiO₂ composites was found to be autocatalytic in nature with average activation energy of 79–92 kJ mol⁻¹. Microscopic analysis (SEM) performed on the PBA-a/nano-SiO₂ composite fracture surface indicated a nearly homogeneous distribution of the nano-scaled silica in the polybenzoxazine matrix. In addition, the enhancement in storage modulus of the nano-SiO₂ filled polybenzoxazine composites was found to be significantly higher than that of the recently reported nano-SiO₂ filled epoxy composites. The dependence of the nanocomposites’ modulus on the nano-SiO₂ particles content is well fitted by the generalized Kerner equation. Furthermore, the relatively high micro-hardness of the PBA-a/nano-SiO₂ composites up to about 600 MPa was achieved. Finally, the substantial enhancement in the glass transition temperature (T_g) of the PBA-a/nano-SiO₂ composites was also observed with the ΔT_g up to 16 °C at the nano-SiO₂ loading of 30 wt%. The resulting PBA-a/nano-SiO₂ composite is a highly attractive candidate as coating material in electronic packaging or other related applications.     

Synthesis of polypyrrole nanocomposites decorated with silver nanoparticles with electrocatalysis and antibacterial property

Polypyrrole nanowire/silver nanoparticle composites (PPy/Ag) are obtained in aqueous media through a one-pot method without any external stimulus. PPy nanowires were assembled on the reactive self-degraded template of the complex of AgNO₃ and methyl orange (MO). During the synthesis process in the dark surrounding, Ag nanoparticles could be uniformly decorated onto the surface of PPy nanowires in situ by the redox reaction of pyrrole and AgNO₃. Neither additional reducing agents for the growth of silver nanoparticles nor oxidizing agents for the polymerization of pyrrole are utilized. The formation mechanism, morphologies, structural characteristics, and conductivity of the obtained PPy/Ag nanocomposites are reported. The as-prepared PPy/Ag nanocomposites exhibit well-defined response to the electrochemical reduction of hydrogen peroxide. Moreover, the preliminary antibacterial assays indicate that the PPy/Ag nanocomposites also possess antibacterial abilities against Escherichia coli.     

Widely dispersed PEI-based nanocomposites with multi-wall carbon nanotubes by blending with a masterbatch

High performance poly(etherimide) (PEI)-based nanocomposites (PNs) with multi-walled carbon nanotubes (MWCNT) were obtained via melt mixing. To achieve this, PEI was mixed with a well-dispersed commercial poly(butylene terephthalate) (PBT)/MWCNT master-batch in an attempt to transfer the dispersed MWCNTs to a PEI matrix. A broad and homogeneous dispersion of MWCNTs throughout the PEI-based matrix was obtained. The electrical percolation threshold (p_c) was reached at only 1 wt.% MWCNT. This p_c showed a power law dependence of conductivity on filler concentration, with a critical exponent of 1.92, which indicates that a three dimensional percolated structure was achieved. The glass transition temperature and the pressure at the output end of the extruder decreased when the master-batch was added, indicating that the processability of PEI was improved. In addition to this, the modified PEI-based PNs presented ductile behaviour and an ameliorated (12% with 5 wt.% MWCNT) elastic modulus compared with pure PEI.     

Influence of morphology on the dynamic mechanical characteristics of PP-EP/EVA/organoclay nanocomposites

A study on the dynamic mechanical properties of polypropylene copolymer/ethylene–vinyl acetate/organoclay (PP-EP/EVA/C20A) nanocomposites is presented. Nanocomposites were obtained by melt blending. Morphology consisting of intercalated–exfoliated clay nanolayers preferentially located within the EVA phase was observed by transmission electron microscopy (TEM) and wide angle X-ray diffraction (WAXD). Polar groups of vinyl acetate in the EVA facilitated the polymer–clay interactions. Changes in the glass transition temperature (T_g) were correlated with changes in the clay intercalation–exfoliation levels. The highly reinforced with intercalated–exfoliated clay layers EVA phase was considered as the origin of the improvement on mechanical properties of the ternary nanocomposites and is associated with the increase on viscosity, heat deflection temperature (HDT), and storage modulus.     

Engineering the coefficient of thermal expansion and thermal conductivity of polymers filled with high aspect ratio silica nanofibers

The thermomechanical properties of epoxy filled with two different types of silica nanofillers: spherical nanoparticles and nanofibers were investigated as a function of silica nanofiller aspect ratio and concentration. Results indicated that at room temperature and at 8.74% silica nanofiber concentration (by volume) the thermal conductivity of epoxy increased twofold and coefficient of thermal expansion (CET) decreased by ∼40%. Silica nanofiber filled epoxy showed 1.4 times greater CET and 1.5 times greater thermal conductivity compared to spherical nanoparticle filled epoxy. The significant changes observed in thermomechanical properties of silica nanofiber filled epoxy were attributed to its high aspect ratio by constraining the polymer matrix as well as reducing the phonon scattering due to the formation of a continuous fiber network within the matrix. In addition to being electrically insulating, the improved properties of silica nanofiber filled epoxy make it an extremely attractive material as underfill and encapsulant in advanced electronic packaging industry.     

Prediction of failure properties of injection-molded short glass fiber-reinforced polyamide 6,6

This study simulates the tensile failure of injection-molded short glass fiber-reinforced polyamide 6,6 (GF/PA66). Tensile tests of unreinforced PA66 are first conducted and the material properties are obtained by fitting a simulated stress–strain curve to the experiment result. Using the obtained material properties, failure simulations of GF/PA66 composites are performed for four types of specimens with various fiber lengths and fiber orientation distributions. In the simulations, multiscale mechanistic model, which can simulate micromechanical damage, and Micromechanics Model (MM), which has very low computational cost, are adapted and the results are compared with experiments. Both models reproduce the experiment results well. Considering the computational cost, MM is the better model for predicting the failure properties of GF/PA66 composites.     

Improved electrical insulating properties of LDPE based nanocomposite: Effect of surface modification of magnesia nanoparticles

Three silane coupling agents with amino, long alkyl chain or vinyl functional groups were used to modify magnesia (MgO) nanoparticles. The modified nanoparticles were then mechanically mixed with low-density polyethylene (LDPE) to fabricate insulating nanocomposites. The average size of the modified MgO aggregates dispersed in LDPE matrix was below 100 nm. The pulsed electroacoustic method indicated that the MgO nanoparticles regardless of surface modification were effective to suppress the packet-like charge injection and accumulation in the LDPE sample, decrease the permittivity and tan δ, and also improved the direct-current breakdown strength of LDPE at different temperatures. The best insulating properties were found in the case of vinyl-silane-modified-MgO/LDPE samples probably owing to the improved interfacial adhesion. A multi-core model was used to discuss the results obtained.     

Dynamic mechanical analysis of fumed silica/cyanate ester nanocomposites

Fumed silica particles with average primary particle diameters of 12 and 40 nm were combined with a low viscosity bisphenol E cyanate ester resin to form composite materials with enhanced storage modulus and reduced damping behavior, as evidenced by dynamic mechanical analysis (DMA). The storage modulus increased with volume fraction of fumed silica in both the glassy and rubbery regions, but the increase was more pronounced in the rubbery region. The maximum increase in storage modulus in the glassy region was 75% for 20.7 vol% of 40 nm fumed silica, while the same composition showed a 231% increase in the rubbery storage modulus. Furthermore, decreases in damping behavior were used to estimate the effective polymer-particle interphase thickness. The glass transition temperature of the nanocomposites was not changed significantly with increasing volume fraction.     

Thermo-mechanical properties enhancement of bio-polyamides (PA10.10 and PA6.10) by using rice husk ash and nanoclay

Composites consisting of fully (PA10.10) and partially (PA6.10) bio-based polyamides and 10–20 wt.% rice husk ash (RHA) was prepared by melt compounding. The mechanical analysis data showed that RHA induced significant improvement in Young’s modulus, a slight reduction in the tensile strength and a large decrease in the deformation at break. Pukanszky’s model was used to evaluate the filler–matrix interactions. The two PAs exhibited similar filler–matrix load transfer with RHA and better performance than polylactic acid (PLA). The addition of modified clay (Cloisite 30B) to the systems with 10 wt.% of RHA gave the best mechanical properties and filler–matrix interactions, notwithstanding the matrix used. Finally, DMT analyses demonstrated that the addition of RHA caused an increase in the heat deflection temperature (HDT) compared to the neat PA matrices. Furthermore, the simultaneous presence of RHA and clay provided the best results.     

Synthesis and characterization of novel waterborne polyurethane nanocomposites with magnetic and electrical properties

The novel nanocomposites derived from waterborne polyurethane and nano-Fe₃O₄ (WPU/Fe₃O₄) have been successfully synthesized by in situ polymerization progress. The nano-Fe₃O₄ particles prepared by co-precipitation method were modified by using oleic acid (OA) to improve their compatibility with monomers. The chemical structures, morphology, thermal behavior, mechanical properties, magnetic properties and electrical properties of the WPU/Fe₃O₄ nanocomposites were investigated by Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), X-ray diffraction (XRD), atomic force microscope (AFM), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMA), vibrating sample magnetometer (VSM) and high resistance meter respectively. The results indicated that the Fe₃O₄ nanoparticles modified by oleic acid could be homogeneously dispersed in the WPU and the introduction of ones was obviously improving the thermal properties, magnetic properties and electrical properties of WPU/Fe₃O₄ nanocomposites. The resulting WPU/Fe₃O₄ nanocomposites would be having the potential applications in microwave absorption.     

Tensile properties of fumed silica filled polydimethylsiloxane networks

Tensile properties of fumed silica filled hydroxylated polydimethylsiloxane (PDMS) networks were investigated in the current work. Similar to unfilled bimodal networks, unimodal networks filled with concentrated fumed silica exhibit non-Gaussian effect and improved ultimate tensile properties. The concept of “hierarchical network” was proposed to depict the networks exhibiting non-Gaussian effect at sufficiently high strains. It was found that the reinforcing effect originates from both the effective volume effect from filler volume and polymer–filler interaction and the synergistic effect between network chains within the “hierarchical network”. Experimental results showed that filler’s dispersion, concentration, specific surface area and surface chemistry have a great influence on the tensile properties, which could be interpreted by analyzing the variation of both effective volume effect and synergistic effect.     

Aligning carbon nanotubes using bulk acoustic waves to reinforce polymer composites

Bulk acoustic waves (BAWs) are used to align multi-walled carbon nanotubes (MWCNTs) in polymer composite materials. MWCNTs are first dispersed in the liquid state of a thermoset resin and aligned using standing BAWs. Cross-linking of the resin fixates the aligned MWCNTs in the polymer matrix material. We have quantified the alignment obtained with this method on the macro, micro, and nanoscale, and it is found to be similar to other alignment techniques such as stretching, slicing, and wet spinning. The elastic modulus and ultimate tensile strength of composite material specimens with aligned MWCNTs, fabricated using this technique, are evaluated and compared with specimens consisting of randomly oriented MWCNTs and resin material without MWCNTs. Different MWCNT loading rates are considered. The elastic modulus of composite material specimens with only 0.15 weight percent aligned MWCNTs is observed to be 44% higher than specimens with randomly oriented MWCNTs, and 51% higher than specimens without MWCNTs. However, further increasing the MWCNT loading rate does not significantly increase the elastic modulus and ultimate tensile strength, likely because of insufficient dispersion of MWCNTs in the thermoset matrix material.     

Effects of functional groups on the graphene sheet for improving the thermomechanical properties of polyurethane nanocomposites

Dispersibility of graphene sheets in polymer matrices and interfacial interaction are challenging for producing graphene-based high performance polymer nanocomposites. In this study, three kinds nanofillers; pristine graphene nanoplatelets (GNPs), graphene oxide (GO), and functionalized graphene sheet (FGS) were used to prepare polyurethane (PU) composite by in-situ polymerization. To evaluate the efficacy of functional groups on the graphene sheets, PU reinforced with GNPs, GO, and FGS were compared through tensile testing and dynamic mechanical thermal analysis. The Young's moduli of 2 wt% GO and FGS based PU nanocomposites were found significantly higher than that of same amount of GNPs loading as an evidence of the effect of functional groups on graphene sheets for the mechanical reinforcement. The strong interaction of FGS with PU was responsible to exhibit notably high modulus (25.8 MPa) of 2 wt% FGS/PU composite than the same amount of GNPs and GO loading even at elevated temperature (100 °C).     

Extraction of cellulose nanocrystals from plant sources for application as reinforcing agent in polymers

In the last few decades, the usages of plant sources-based stiff fillers as reinforcement material in polymer composites have attracted significant interests of researchers. The crystalline part of the semicrystalline cellulose chains as found in the plant cell walls represents the most highly potential reinforcing agents for polymer. This review systematically covers the extraction of nano-sized cellulose crystals from plant cell wall which involving the applications of several highly effective techniques. The topic about the derivation of products functionality at each stage as well as their influences on the final reinforcing capability is also covered. Apart from these, a detailed overview of current knowledge on the surface modification of nanocellulose has been provided also. Inasmuch, this paper is desired to encourage the emergence of preparation of cellulose derivative nanocrystals with controlled morphology, structure and properties, so that enable positive development of biocompatible, renewable and sustainable reinforcing materials for polymer composites field.     

Dynamic mechanical analysis and thermal properties of LLDPE/EVA/modified silica nanocomposites

The effect of hexamethylene disilazane modified nanosilica on the dynamic mechanical analysis (DMA), crystallization, melting and thermal degradation behavior of linear low density polyethylene/ethylene vinyl acetate copolymer (LLDPE/EVA) blends are explored.Detailed DMA analysis is carried out in order to investigate the reinforcing behavior of nanosilica adopting Kerner–Nielson model. Oxidative degradation and thermal stabilities of samples are also studied by the thermogravimetery analysis. The high content of nanosilica particles results in significant shift of degradation temperature to higher temperatures in the oxygen atmosphere. This behavior might be attributed to the barrier properties of nanoparticles against oxygen and gaseous degradation products. However, incorporation of modified nanosilica into LLDPE/EVA blend is decreased the onset of degradation temperature of the unfilled system. In nitrogen atmosphere, no changes are observed in the thermal degradation range and only a reduction is documented in the onset of degradation temperature. Considering important role of onset of degradation temperature, activation energy of starting of degradation temperature is calculated utilizing Kissinger-Ozawa model in both oxygen and nitrogen atmospheres. Results showed that activation energy of degradation reaction is decreased by ∼ 20 kJ/mol. This decrease is owing to the release of modifiers from the nanoparticles.     

Helium gas permeability of montmorillonite/epoxy nanocomposites

Helium gas permeability of silicate clay (montmorillonite) particles/epoxy nanocomposites was examined. The incorporation of increasing amounts of montmorillonite particles reduced the helium gas permeability. Based on Fick’s law, gas permeation behavior of the nanocomposite was evaluated. With the increase of montmorillonite loading, gas diffusivity decreased, while gas solubility increased. Helium diffusion behavior is in agreement to the numerical results based on the Hatta–Taya–Eshelby theory. It has been revealed that dispersion of nanoscale platelets in polymer is effective in improving gas barrier property.     

Effect of surface treatment on thermal stability of the hemp-PLA composites: Correlation of activation energy with thermal degradation

The thermal behavior of hemp-poly lactic acid composites with both untreated and chemically surface modified hemp fiber was characterized by means of activation energy of thermal degradation. Three chemical surface modification employed were; alkali, silane and acetic anhydride. Model-free isoconversion Flynn–Wall–Ozawa method was chosen to evaluate the activation energy of composites. The results indicated that composites prepared with acetic anhydride modified hemp had 10–13% higher activation energy compared to other composites. Further, among the three surface modifications, acetic anhydride resulted in higher activation energy (159–163 kJ/mol). Fourier transform infrared spectroscopy supported the findings of thermogravimetric analysis results, wherein surface functionalization changes were observed as a result of surface modification of hemp fiber. It was concluded that, higher bond energy results in higher activation energy, which improves thermal stability. The activation energy data can aid in better understanding of the thermal degradation behavior of composites as a function of composite processing.     

Molecular characterizations,mechanical properties and anti-algal activities for PVC and wood/PVC composites containing urea- and triazine-based algaecides

Material behaviors and anti-algal performances of PVC and wood PVC composites (WPVCs) were examined after adding commercial algaecides of different types and contents. Three different wood types commonly found in tropical climates – namely, Xylia kerrii Craib and Hutch.; Hevea brasiliensis Muell.; and Mangifera indica Linn. – were of interest. Isoproturon (3-(4-isopropylphenyl)-1,1-dimethylurea), a urea-based algaecide, and Terbutryn (N²-tert-butyl-N⁴-ethyl-6-methylthio-1,3,5-triazine-2,4-diamine), a triazine-based algaecide, were used as anti-algal agents in this study; concentrations in the specimens varied from 0 to 1500 ppm. Surface color, thermal properties, chemical structure and mechanical properties of the materials were also monitored. The results revealed that addition of Isoproturon tended to considerably change the surface color of the materials, particularly for PVC which had the highest ΔE^* value, whereas addition of Terbutryn did not. The effect of wood types was found to influence the initial surface color of the materials. Evidence based on DSC, FT-IR and contact angle testing indicated that Isoproturon had a strong molecular interaction with PVC and could induce PVC degradation. The mechanical properties of PVC and WPVC were affected by the addition of wood, but not by algaecide addition. The results of the growth inhibition zone and chlorophyll-a content in Chlorella vulgaris TISTR 8580 suggested that Terbutryn exhibited better anti-algal performance than Isoproturon with a recommended dosage of 1000 ppm while Isoproturon at 1500 ppm could act as an effective coupling agent in WPVC composites.