Chemical modification of waste oil fly ash for improved mechanical and thermal properties of low density polyethylene composites

In this paper, oil fly ash (OFA), a by-product generated by the combustion of oil in power plants, was used as a filler for the preparation of low density polyethylene (LDPE) composite. Four different loadings of filler in the range 1–10%wt were used. Both mechanical and thermal properties were studied using tensile measurements and Differential Scanning Calorimetery. The effect of surface modification of OFA by functionalization with COOH group and the effect of polyethylene-grafted-maleic anhydride as a compatibilizer were also examined. Improvement in Young’s modulus and yield strength of OFA was obtained in the range 1–2% as a result of chemical modification and mainly in the range 5–10%w due to compatiblization. However, a decrease in toughness and elongation at break was also observed. In general, functionalization and compatiblization improved small strain mechanical properties and failed to do the same for large strain properties of composites. No considerable effect for fly ash on melting point, on-set temperature and crystallization peaks was observed. Coupling of functionalization and compatiblization can enhance modulus and tensile strength mechanical properties of composites of LDPE and waste ash.     

Positive temperature coefficient effect and interaction based on low‐density polyethylene/graphite powder composites

In this article, the positive temperature coefficient (PTC) and interaction based on low‐density polyethylene (LDPE) filled with the loading of graphite (G) powder have been investigated. The dependence of the room temperature resistivity on filler content showed the significant decrease. The PTC behavior enhanced with increasing graphite content but this was not always the case. The maximum PTC effect was observed in LDPE/G composites (G, 45 wt %) with the relatively low room temperature resistivity. The thermal behavior was measured by differential scanning calorimetry (DSC). The structure characteristic for LDPE/G composites was examined by X‐ray diffraction (XRD), field‐emission scanning electron microscopy (SEM), and stress–strain test. The fact was revealed that the slight interaction between LDPE matrix and graphite may lead to change the thermal‐electric properties of the PTC materials. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Rheological,thermal, and morphological properties of low‐density polyethylene/ultra‐high‐molecular‐weight polyethylene and linear low‐density polyethylene/ultra‐high‐molecular‐weight polyethylene blends

The dynamic rheological behavior of low‐density polyethylene (LDPE)/ultra‐high‐molecular‐weight polyethylene (UHMWPE) blends and linear low‐density polyethylene (LLDPE)/UHMWPE blends was measured in a parallel‐plate rheometer at 180, 190, and 200°C. Analysis of the log–additivity rule, Cole–Cole plots, Han curves, and Van Gurp curves of the LDPE/UHMWPE blends indicated that the blends were miscible in the melt. In contrast, the rheological properties of LLDPE/UHMWPE showed that the miscibility of the blends was decided by the composition of LLDPE. The differential scanning calorimetry results and scanning electron microscopy photos of the LLDPE/UHMWPE blends were consistent with the rheological properties, whereas with regard to the thermal and morphological properties of LDPE/UHMWPE blends, the results reveal three endothermic peaks and phase separation, which indicated a liquid–solid phase separation in the LDPE/UHMWPE blends. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Dynamic rheology and morphology of HDPE‐fumed silica composites: Effect of interface modification

In the present study, high density polyethylene (HDPE)‐based composites containing different amounts of fumed silica (FS) were prepared by melt compounding in a corotating twin screw extruder. Polyethylene‐g‐maleic anhydride copolymer (PE‐g‐MA) containing 1 wt% maleic anhydride was used for interface modification between filler and polymer. The interaction between the surface hydroxyl groups of fumed silica nanoparticles with maleic anhydride groups of PE‐g‐MA led to a finer dispersion of the filler in the HDPE matrix. The terminal complex viscosity and terminal storage modulus were highest at 1 wt% filler loading due to widely spread network formation by FS nanoparticles. This filler network plausibly got disturbed at higher filler content and/or interface modification which was reflected in their stress relaxation behavior also. The dynamic rheological behavior of the composites was explained in terms of morphological observations. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Graphene Oxide as a Prospective Graft in Polyethylene Glycol for Enhancing the Toughness of Epoxy Nanocomposites

Polyethylene glycol (PEG) was successfully grafted onto the surface of graphene oxide (GO) by the “grafting to” technique. PEG, GO as well as the PEG grafted GO (GO-g-PEG) was successfully incorporated into an epoxy matrix and subsequently cured using diethylenetoluenediamine (DETDA) to make epoxy nanocomposites. Mechanical, thermal, and rheological properties of the epoxy nanocomposites were studied to check the effectiveness of these fillers in the epoxy matrix. An improvement of 255% and 334% at a very low filler loading of about 0.1 wt% was observed in the fracture toughness of GO and GO-g-PEG loaded systems versus the neat epoxy. Toughening mechanisms are also explained by analyzing SEM images of the fractured surface. Modeling of rheological properties was carried out by following time-independent Newtonian model. The homogeneity of the epoxy filler systems are explained with the help of Cole–Cole plots. The thermal stability of the filler loaded epoxy composites was examined in detail by TGA. Improvements in mechanical properties reveal the potential benefit of the grafting process in epoxy toughening. POLYM. ENG. SCI., 60:773–781, 2020. © 2020 Society of Plastics Engineers     

Melt fracture and rheology of linear low density polyethylene ‐ calcium carbonate composites

Rheological behavior and melt fracture of linear low‐density polyethylene (LLDPE) calcium carbonate (CaCO₃) composites were investigated. Two types of commercial inorganic fillers were used, unmodified and modified with stearic acid. Rheological capillary studies were conducted to assess the influence of inorganic filler incorporation as well as chemical treatment on the rheological properties and instability sequence of polyethylene‐based composites. Strong suppression of melt flow instabilities was observed for both types of composites. Mooney analysis was applied to examine the influence of mineral filler addition and stearic acid modification on the wall slip. Moreover, chemical treatment of calcium carbonate allows to obtain better dispersion of the inorganic filler in a polymeric matrix. POLYM. ENG. SCI., 57:998–1004, 2017. © 2016 Society of Plastics Engineers     

Mechanical and thermal properties of low density polyethylene composites filled with dye‐loaded shell powder

To achieve reinforcement and coloring in one combined process of polymer production, a dye‐loaded shell powder (DPSP) based on Congo red and pearl shell powder was prepared and used as a versatile bio‐filler in low‐density polyethylene (LDPE). The DPSP was characterized by means of X‐ray diffraction, Fourier transform infrared spectroscopy and thermogravimetric analysis. The mechanical, thermal, and colorimetric properties of prepared LDPE/DPSP composites were investigated as well. Adding DPSP could significantly increase the strength and stiffness of LDPE composites while giving an outstanding coloring performance. Moreover, the impact strength of LDPE composites was improved at lower filler loading rate, and the maximum incorporation content could reach 10 wt % with a good balance between toughness and stiffness of LDPE composites. The thermal performance studies confirmed an increase in thermal stability and heat resistance of LDPE composites with the incorporation of DPSP. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44118.     

Electrical conductivity and rheological behavior of multiphase polymer composites containing conducting carbon black

Multiphase polymer composites of carbon black (CB), polypropylene (PP) and low density polyethylene (LDPE) were prepared by melt‐mixing method to reduce the amount of CB in the conductive composites. SEM images showed that CB preferably located in LDPE phase and formed electrically conductive path. The measurement of conductive properties showed that the ternary materials possessed lower percolation than binary composites of CB/PP or CB/LDPE, the former was ～6 wt% and the latter was 9–10 wt%. Positive temperature coefficient (PTC) effects of the binary and ternary composites were investigated, indicating that the latter exhibited a relatively high PTC intensity. A rheological percolation estimated by a power law function is 2.66 wt% of CB loading, suggesting an onset of solid‐like behavior at low frequencies. This difference between the electrical and rheological percolation thresholds may be understood in terms of the smaller CB–CB distance required for electrical conductivity as compared with that required to impede polymer mobility. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Dynamic mechanical analysis and morphological studies of fly ash/mica reinforced poly(ether‐ether‐ketone)‐based hybrid composites

Hybrid composites based on poly(ether‐ether‐ketone) (PEEK) were fabricated with fly ash and mica. Nearly 5, 10, and 15 wt% of fly ash were replaced by mica of the optimized fly ash reinforced composites and were subjected to dynamical mechanical analysis to determine the dynamic properties as a function of temperature. The storage modulus E′ was found to decrease with the increase of weight fraction of mica. Loss modulus was also found to decrease with loading while the damping property was found to increase marginally. Peak height of tan δ for hybrid composites were decreased by varying combinations of fly ash with mica. It is probably due to improved crystallinity of PEEK and strong interaction between the fillers and PEEK matrix. Cole–Cole analysis was made to understand the phase behavior of the composite samples. Kubat parameter was calculated to study the adhesion between matrix and filler of the fabricated composites. Without surface modification for inorganic fillers, the distribution of two different shape filler particles appears to be reasonably uniform. The use and limitation of various theoretical equations to predict the tan δ and storage modulus of filler reinforced composites have been discussed. Addition of both fillers opens up new opportunities for development of high‐performance multifunctional materials suitable for industrial applications. Scanning electron micrographs of tensile fracture surfaces of composites demonstrated filler–matrix bonding. POLYM. COMPOS., 35:68–78, 2014. © 2013 Society of Plastics Engineers     

Preparation and characterization of functionalized low density polyethylene matrix biocomposites

The incorporation of cellulosic fibers into polyethylene matrices was studied in this work, by dispersion of fluff pulp from maritime pine in a hot polymer solution, followed by co‐precipitation of the solid components by cooling at room temperature. The above method was found suitable for proper wetting and dispersion of fibers in the polymeric matrix, as compared with melt compounding. Unmodified low density polyethylene [LDPE], modified LDPE with maleic anhydride grafted linear low density polyethylene [M‐LLDPE] and a copolymer of acrylic acid and n‐butyl acrylate polyethylene [(AA/n‐BA)‐LDPE], were used as matrices for the preparation of fiber reinforced composites. The thermal properties of these composites were determined using differential scanning calorimetry and thermogravimetric analysis. The incorporation of cellulosic fibers results in a decrease of the crystallinity of the polymer matrix, as they act as inert material. In addition, the appropriate tests were run in order to determine the density and tensile properties of the composite specimens prepared by compression molding, with filler content ranging from 10 to 40% (w/w). Composites based on modified LDPE showed improved mechanical properties. The Takayanagi model, applied to predict the Young's modulus of composites, was in very good agreement with the experimental data obtained in this work. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Surface modification of microcrystalline cellulose (MCC) and its application in LDPE‐based composites

Microcrystalline cellulose (MCC) was modified by grafting onto its surface ferulic acid, methacryloyl chloride and oleoyl chloride. The efficacy of the chemical modification was confirmed by X‐ray photoelectron spectroscopy. In addition, the size distribution of the cellulosic particles was investigated by optical microscopy and laser granulometry and its hydrophobicity was evaluated using a contact angle method. Finally, to investigate the affinity of modified MCC with a nonpolar polymer and to assess its potential as a biobased reinforcing filler, the modified MCC was compounded into low‐density polyethylene. An organic peroxide, dicumyl peroxide, was added at selected formulations to see if it could further enhance mechanical bonding between the polymer and the particulates. The dispersion was assessed by scanning electron microscopy. Mechanical properties were investigated through tensile testing while the melt rheology of the composites was monitored by small angle oscillatory shear rheology. The acylation modification of the MCC improved the dispersion within LDPE and enhanced the mechanical properties of the composites. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44348.     

Effects of silane coupling agent and maleic anhydride‐grafted polypropylene on the morphology and viscoelastic properties of polypropylene–mica composites

In this study, morphology, and dynamic and mechanical properties of polypropylene–mica (PP–Mica) composites were investigated. To enhance the adhesion between PP and mica, maleic anhydride‐grafted PP (MAPP) and treated mica with silane coupling agent were used. MAPP (as a compatibilizer) and silane coupling agent (as a filler surface modifier) caused an interfacial bonding in the mica filled polypropylene composites. The effect of mica content, MAPP, and treated mica with silane coupling agent on the morphological properties were investigated by Scanning Electron Microscopy (SEM). The results showed that with increasing MAPP or silane coupling agent, dispersion of filler and adhesion between PP and filler were improved. Mechanical data showed that with increasing MAPP and mica treated with silane coupling agent, tensile modulus and flextural strength of composites were enhanced. Dynamic rheological behavior of composites was also investigated within the domain of linear viscoelasticity. The rheological observations indicated that the complex viscosity, storage and loss moduli increased, and tan δ decreased with increasing mica content. POLYM. COMPOS. 27:491–496, 2006. © 2006 Society of Plastics Engineers.     

Enhancing interfacial adhesion performance by using poly(vinyl alcohol) in (low‐density polyethylene)/(natural rubber)/(water hyacinth fiber) composites

The effects of (a) the chemical modification of water hyacinth fiber by poly(vinyl alcohol) (WHF‐_PVA) and (b) loading on the properties of low‐density polyethylene (LDPE)/(natural rubber (NR))/(water hyacinth fiber (WHF)) composites were studied. Mechanical properties, water absorption behavior, morphology, and thermal properties were examined; X‐ray diffraction and infrared spectroscopic analysis were done. The results indicated that LDPE/NR/WHF‐_PVA composites had higher values of tensile strength, Young's modulus, melting temperature, and water absorption resistance but lower elongation at break than LDPE/NR/WHF composites. The LDPE/NR/WHF‐_PVA composites had better interfacial adhesion between the matrix and the fibers than LDPE/NR/WHF composites, as shown by SEM results. The LDPE/NR/WHF‐_PVA composites exhibited lower interparticle spacing than LDPE/NR/WHF composites, a feature which enhanced the interparticle interaction between the water hyacinth fibers and the LDPE/NR matrix. J. VINYL ADDIT. TECHNOL., 19:47–54, 2013. © 2012 Society of Plastics Engineers     

Melt rheological studies of polypropylene filled with coconut water treated and untreated fly ash

The melt rheology of polypropylene (PP) filled with fly ash (FA) before and after treatment with coconut water (CW) was studied for different concentration of the filler. The fly ash after coconut water treatment clearly showed additional peaks in the infrared (IR) spectra corresponding to the hydroxyl and carbonyl groups indicating good adsorption of CW on FA. The X‐ray diffraction of melt compounded PP filled with CW‐treated (CWT) FA showed large reduction of the main silica peak of FA and considerable broadening of Mullite and hematite peaks suggesting formation of fine particles by this treatment. Scanning electron microscopy (SEM) confirmed the drastic reduction of particle size in these composites. The melt rheological studies for these composites indicated considerable increase in viscosity at low filler loading for CW treated FA. The concentration dependence of melt viscosity did not follow any of the theoretical equations suggested in literature. Although, the behavior was similar to nanoparticle‐filled polymers, there were some differences especially above the critical concentration of 4.5% by volume. The frequency dependence of storage and loss modulus indicated crossover point clearly, which was greatly affected by CW treatment. The Cole–Cole plots of real and imaginary part of melt viscosity brought out the broad distribution of relaxation time for the CW treated FA. The CW treated FA melt compounded with PP gave rise to nanocomposites with uniform dispersion. However, above 4.5% by volume, there appears to be agglomerate formation along with a thin interfacial layer, which assists the melt flow even at high filler loading. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43900.     

Effect of surface functionalization on the properties (rheological,mechanical, and dielectric) and microtopography of PEN/CPEN‐f‐CNTs nanocomposites

Novel carboxylic poly(arylene ether nitrile)s (CPEN) functionalized carbon nanotubes (CPEN‐f‐CNTs) were successfully prepared by a simple and effective solvent–thermal route. The CPEN‐f‐CNTs were subsequently used as the novel filler for preparation of high performance poly(arylene ether nitrile)s (PEN) nanocomposites. The SEM characterization of the PEN nanocomposites revealed that the CPEN‐f‐CNTs present better dispersion and interfacial compatibility in the PEN matrix, which was confirmed by the linear rheological analysis (Cole–Cole plots) as well. Consequently, the improved thermal stability (increased initial and maximum decomposition temperature) and enhanced mechanical properties (tensile strength and modulus) were obtained from nanocomposites using CPEN‐f‐CNTs. More importantly, the PEN/CPEN‐f‐CNTs nanocomposites not only show a high dielectric constant but also have low dielectric loss. For example, a dielectric constant of 39.7 and a dielectric loss of 0.076 were observed in the PEN composite with 5 wt% CPEN‐f‐CNTs loading at 100 Hz. Therefore, the flexible PEN/CPEN‐f‐CNTs nanocomposites with outstanding mechanical, thermal and dielectric properties will find wide application in the high energy density capacitors. POLYM. COMPOS., 37:2622–2631, 2016. © 2015 Society of Plastics Engineers     

Green composites based on high‐density polyethylene and Saccharum spontaneum: Effect of filler content on morphology,thermal, and mechanical properties

Here we report the preparation and characterization of a green composite based on high‐density polyethylene and Kaans grass (Saccharum spontaneum). The composites were prepared by conventional melt‐mixing method, using maximum loading of Kaans grass in powder form (KG‐filler) to achieve acceptable range of required properties. Maleic anhydride grafted polyethylene was used as compatibilizer to achieve effective interaction for improved surface adhesion which was confirmed by FT‐IR spectroscopy. Morphological studies revealed good interaction between the base polymer matrices and the KG‐fillers that improved the mechanical and thermal properties of the composites up to certain (10 phr) KG‐filler loading. Study on water absorption property revealed moderate increase in weight at higher KG‐filler loadings. Thermogravimetric analysis (TGA) and melt flow index (MFI) studies indicated retention of thermal stability and flow property of the HDPE/KG‐filler composite at lower filler loadings. POLYM. COMPOS., 36:2157–2166, 2015. © 2014 Society of Plastics Engineers     

Effects of filler–filler and polymer–filler interactions on rheological and mechanical properties of HDPE–wood composites

High‐density polyethylene (HDPE)–wood composite samples were prepared using a twin‐screw extruder. Improved filler–filler interaction was achieved by increasing the wood content, whereas improved polymer–filler interaction was obtained by adding the compatibilizer and increasing the melt index of HDPE, respectively. Then, effects of filler–filler and polymer–filler interactions on dynamic rheological and mechanical properties of the composites were investigated. The results demonstrated that enhanced filler–filler interaction induced the agglomeration of wood particles, which increased the storage modulus and complex viscosity of composites and decreased their tensile strength, elongation at break, and notched impact strength because of the stress concentration. Stronger polymer–filler interaction resulted in higher storage modulus and complex viscosity and increased the tensile and impact strengths due to good stress transfer. The main reasons for the results were analyzed. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Studies on High Density Polyethylene Reinforced with Phosphate Ore Particles: Thermal,Rheological, Mechanical and Morphological Properties

Calcareous phosphate ore can be utilized as a cost-effective alternate to other inorganic fillers for polymer-based composites. In this study, composites of high-density polyethylene and phosphate rock ore particles were prepared by melt blending and injection-molding techniques. The thermomechanical, rheological, and mechanical properties of these composites were studied to investigate the effect of filler loading on their functionality. The reduction in the crystallinity of phosphate ore/high-density polyethylene composites was observed compared to that of the neat high-density polyethylene. The relative crystallinity of the neat high-density polyethylene decreases from 53 to 30% by the addition of 2.5–15 wt% of ore, respectively. Comparison of the linear dynamic viscoelasticity for the neat high-density polyethylene and the ore-filled composites shows t a monotonic increase in both storage modulus and loss modulus with the increasing frequency. The viscoelastic behavior at high frequencies remains unaffected. However, at lower frequencies, both G′ and G″ exhibit diminished frequency dependence. It was also observed that higher filler content decreased the tensile and impact strength, whereas the Young's modulus of the composites increased. The morphological analysis shows relatively weak interaction between the fillers and the matrix because of agglomeration which in turn adversely affects the mechanical properties of the composites.     

Melt Rheological Behavior and Thermal Properties of Low-Density Polyethylene/Palm Kernel Shell Composites: Effect of Polyethylene Acrylic Acid

The melt flow behavior and thermal properties of low-density polyethylene (LDPE)/palm kernel shell (PKS) composites were studied. Polyethylene acrylic acid (PEAA) was used as a compatibilizer in the composites. The results showed that the increasing of PKS loading had decreased MFI values of LDPE/PKS composites. The presence of PEAA increased the MFI values of the LDPE/PKS composites. The apparent viscosity of the composites was found to exhibit a linear relationship with the reciprocal of the temperature. Thermal properties showed that higher filler loading tended to reduce the onset temperature as the PKS possessed lower degradation temperature compared to the LDPE. The presence of the PKS in the LDPE polymeric matrix improved the thermal stability of the composites. The addition of PEAA into the composites provided better interfacial bonding between the LDPE matrix and PKS filler, while higher onset temperature and lower total weight loss were observed of LDPE/PKS composites. The activation energy of the LDPE/PKS composites was increased with increasing filler loading. At similar filler loading, the presence of PEAA increased the activation energy of the LDPE/PKS composites.     

Studies on LDPE—Cyanoethylated lignocellulosics blends using epoxy functionalized LDPE as compatibilizer

Rubberwood flour and cellulose have been plasticized by cyanoethylation and then blended with low‐density polyethylene (LDPE). A small quantity of epoxy functionalized polyethylene i.e., polyethylene‐co‐glycidyl methacrylate (PEGMA) has been added to further enhance the mechanical properties. The mechanical properties were measured according to the standard ASTM methods. SEM analysis was performed for both fractured and unfractured blend specimens. The mechanical properties were improved by the addition of PEGMA compatibilizer. LDPE blends with cyanoethylated wood flour (CYWF) showed higher tensile strength and modulus than cyanoethylated cellulose CYC‐LDPE blends. However CYC‐LDPE blends exhibited higher relative elongation at break values as compared with the former. The TGA analysis showed lowering of thermal stability as the filler content is increased and degradation temperature of LDPE is shifted slightly to lower temperature. DSC analysis showed loss of crystallinity for the LDPE phase as the filler content is increased for both types of blends. Dielectric properties of the blends were similar to LDPE, but were lowered on adding PEGMA. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 219–237, 2006