High-density polyethylene reinforced by low loadings of electrochemically exfoliated graphene via melt recirculation approach

The purpose of the paper is to demonstrate the effectiveness of high-aspect ratio electrochemically exfoliated graphene (EEG) as a filler in high-density polyethylene (HDPE); we use an industrially viable polymer processing technique (melt blending with melt recirculation) to ensure excellent dispersion and reinforcement at low loadings. The effects of nanofiller loading were evaluated for two different HDPE grades with two different melt flow indices (MFI) based on crystallization, tensile, and rheological properties. The findings indicate improvements in mechanical properties (tensile modulus and tensile strength) for all HDPE/EEG nanocomposite samples; however, the reinforcement was more pronounced at 0.2 wt% loading, indicating a transition from excellent dispersion at lower loadings to aggregated at higher loadings. The low and high MFI HDPE/EEG nanocomposites at 0.2 wt% EEG loading displayed an improvement of 31% and 40% in tensile modulus and 19% and 33% in tensile strength, respectively. The improved mechanical response with higher MFI nanocomposites is likely due to enhanced dispersion associated with the lower melt viscosity. Similarly, the rheological results also showed maximum increase in storage and loss modulus at a loading of 0.2 wt% EEG. In conclusion, EEG can be an effective filler if proper dispersion is achieved, which is challenging at high loadings.     

Development of waste tire‐derived graphene reinforced polypropylene nanocomposites with controlled polymer grade,crystallization and mechanical characteristics via melt‐mixing

In the present work, single layer graphene nanoplatelets (GNPs) derived from waste tires by recycling and upcycling approaches were integrated in homopolymer (Homo‐) and copolymer (Copo‐) polypropylene (PP) matrices by fast and efficient mixing in the melt phase. The effect of GNP content on crystallization and mechanical behaviors was investigated in detail at different loading levels. Regarding isothermal and non‐isothermal crystallization experiments, GNPs significantly accelerated the nucleation and growth of crystallites, and the crystallization degree in Homo‐PP nanocomposites was slightly higher than that of Copo‐PP based nanocomposites. Also, there was significant improvement in mechanical and thermal properties of GNP reinforced polymers compared to neat polymers. As the GNP concentration increased from 1 to 5 wt%, there was a gradual increase in flexural modulus and strength values. In tensile tests, an increase in GNP content in both polymer grades led to a slight increase in yield strength coming from the proper distribution of nano‐reinforcement by creating stress concentration sites. After the yield point, Homo‐PP based nanocomposites showed higher strain hardening than GNP reinforced Copo‐PP owing to a high crystallization degree and linear chains of Homo‐PP. This work showed that functionalized graphene can act as both nucleating and reinforcing agent in the compounding process and its exfoliation through polymer chains is much better in homopolymers at a faster and high shear rate. © 2020 Society of Chemical Industry     

Enhancement of the surface and bulk mechanical properties of polystyrene through the incorporation of raw multiwalled nanotubes with the twin‐screw mixing technique

In this article, we present the effects of incorporated multiwalled nanotubes (MWNTs) on a metal surface and the bulk mechanical properties of as‐synthesized polystyrene (PS)–MWNT composites prepared with the twin‐screw mixing technique. The MWNTs used for preparing the composites were raw compounds that were not treated with any surface modifications. The morphology for the dispersion capability of the MWNTs in the PS matrix was subsequently characterized with transmission electron microscopy. Surface mechanical property studies (i.e., wear resistance and hardness) showed that the integration of MWNTs led to a distinct increase in the wear resistance and also the micro/nanohardness with up to a 5 wt % MWNT loading in the composites. Moreover, the enhancement of the wear resistance of the as‐prepared composites, in comparison with pure PS, was further identified with scanning electron microscopy observations of the surface morphology after testing. On the other hand, for bulk mechanical property studies (i.e., the tensile strength and flexural strength), the composites containing a 3 wt % concentration of MWNTs in the PS matrix exhibited the best performance with respect to the tensile strength and flexural strength. This means that this composition of MWNTs exhibited good compatibility with the PS matrix, and this can be attributed to the π–π interacting forces existing between the aromaticity of the MWNTs and PS matrix. Furthermore, at higher MWNT loadings (e.g., 5 wt %), raw MWNTs were aggregated in the polymer matrix, as observed by transmission electron microscopy. Also, this led to an obvious decrease in the tensile strength and flexural strength. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Influence of structure of amines on the properties of amines‐modified reduced graphene oxide/polyimide composites

Graphene oxide (GO), as an important precursor of graphene, was functionalized using alkyl‐amines with different structure and then reduced to prepare reduced amines grafted graphene oxide (RAGOs) by N₂H₄ · H₂O. The successful chemical amidation reaction between amine groups of alkyl‐amines and carboxyl groups of GO was confirmed by Fourier transform infrared (FTIR), X‐ray photoelectron spectroscopy (XPS), and thermal gravimetric analysis (TGA). Then RAGOs/polyimide nanocomposites were prepared via in situ polymerization and thermal curing process with different loadings of RAGOs. The modification of amine chains lead to homogenous dispersion of RAGOs in the composites and it formed strong interfacial adhesion between RAGOs and the polymer matrix. The mechanical and electrical properties of polyimide (PI) were significantly improved by incorporation of a small amount of RAGOs, the influence of structure of amines grafted on RAGOs on the enhancement effects of composites was discussed. The research results indicated that the proper structure of amine could effectively enhance the properties of composites. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43820.     

Structural and mechanical properties of YBCO‐polystyrene composites

Microcrystalline powders of yttrium barium copper oxide [YBa₂Cu₃O₇] have been prepared by conventional ceramic preparation technique. The powder belong to orthorhombic symmetry with unit cell dimensions ‘a’=3.8214 Å, ‘b’=3.8877 Å and ‘c’=11.693 Å. XRD and SEM studies revealed that its particle size is in the micrometer range. Micro composites of polystyrene with different loading of yttrium barium copper oxide fillers were prepared by melt mixing in a brabender plasticorder at a rotor speed of 60 rpm. The lattice parameters of the constituent phases are the same in all the composites. Mechanical properties such as stress–strain behavior, Young's modulus, and tensile strength were studied as a function of filler loading. Addition of filler enhances the Young's modulus of the polymer. Because of the poor filler‐matrix adhesion, tensile strength and strain at break decreases with filler loading. To explore more carefully the degree of interfacial adhesion between the two phases, the results were analyzed by using models featuring an adhesion parameter. Finally experimental results were compared with theoretical predictions. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Fabrication and Characterization of Soluble Multi‐Walled Carbon Nanotubes Reinforced P(MMA‐co‐EMA) Composites

Summary: Soluble multi‐walled carbon nanotubes (s‐MWNTs), obtained via amidation reaction of octadecylamine with purified multi‐walled carbon nanotubes (p‐MWNTs), were solution‐mixed with P(MMA‐co‐EMA) at various loadings. Compared to the p‐MWNTs/P(MMA‐co‐EMA) composites, the s‐MWNTs/P(MMA‐co‐EMA) composites showed great improvement both in Young's modulus and tensile strength. With the addition of 10 wt.‐% s‐MWNTs, the Young's modulus and tensile strength of s‐MWNTs/P(MMA‐co‐EMA) composite have 135% and 49% increase over the pure P(MMA‐co‐EMA), respectively, and a 9.2% increase in Young's modulus and 12.8% increase in tensile strength over that of 10 wt.‐% p‐MWNTs composite. With the increase of MWNTs content, the T_g increases from 89 to 106 °C. SEM studies show that the s‐MWNTs are well dispersed in the polymer matrix. Good dispersion of s‐MWNTs in polymer matrix and great interfacial bonding between s‐MWNTs and P(MMA‐co‐EMA) may be the key reason for the improvement of the mechanical properties.

Stress‐strain curves of the MWNTs and P(MMA‐co‐EMA) composites.     

Photochemical aging and processability of life‐time‐controlled polystyrene/high‐impact polystyrene blends

This work investigated the influence of the addition of acetophenone and benzophenone (2.5 and 5%) on the photodegradability of polystyrene/high‐impact polystyrene blends (50/50 w/w) prepared by sheet extrusion, aiming to improve their decomposition during exposure to a natural environment. The modified materials were submitted to photodegradation under controlled conditions, and the extent of degradation was monitored by suitable characterization techniques, such as infrared and ultraviolet–visible spectroscopy, viscosimetry, and measurements of the mechanical properties. The processability of the modified blends was also studied by capillary and oscillatory rheometry. Evidence for the formation of hydroperoxides and carbonyl groups, the occurrence of chain scission, and the loss of mechanical properties was achieved, being greater for samples with benzophenone. It was also observed that for the same ketone level, benzophenone caused greater changes in the mechanical properties, and this was in agreement with the decrease in the molecular weight observed. Thus, the addition of this type of chemical compound could enhance the photodegradability of polystyrene/high‐impact polystyrene blends without a significant effect on their processability and mechanical performance. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Highly antibacterial and toughened polystyrene composites with silver nanoparticles modified tetrapod‐like zinc oxide whiskers

In this work, high‐performance multifunctional composites were obtained by melt blending silver deposited tetrapod‐like zinc oxide whiskers (Ag‐ZnOw) with polystyrene (PS). The chemical, spectroscopic, antibacterial, mechanical, and morphological properties of the PS/Ag‐ZnOw composites were carefully investigated and discussed. The obtained PS/Ag‐ZnOw composites characterized remarkable antibacterial activity against Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus). Moreover, it is found that impact strength of the composite increase with increasing nanofiller concentration (up to 0.25 wt %). Morphological characterization of the impact fractured surface of composites revealed that toughening was achieved through uniform filler distribution in the polymer matrix, and anchoring effect was imparted by the tetrapod‐like shape of ZnO whiskers. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40900.     

Thermal and electrical conductivity of melt mixed polycarbonate hybrid composites co‐filled with multi‐walled carbon nanotubes and graphene nanoplatelets

In this work, we present thermoplastic nanocomposites of polycarbonate (PC) matrix with hybrid nanofillers system formed by a melt‐mixing approach. Various concentrations of multi‐walled carbon nanotubes (MWCNT) and graphene nanoplatelets (GnP) were mixed in to PC and the melt was homogenized. The nanocomposites were compression molded and characterized by different techniques. Torque dependence on the nanofiller composition increased with the presence of carbon nanotubes. The synergy of carbon nanotubes and GnP showed exponential increase of thermal conductivity, which was compared to logarithmic increase for nanocomposite with no MWCNT. Decrease of Shore A hardness at elevated loads present for all investigated nanocomposites was correlated with the expected low homogeneity caused by a low shear during melt‐mixing. Mathematical model was used to calculate elastic modulus from Shore A tests results. Vicat softening temperature (VST) showed opposite pattern for hybrid nanocomposites and for PC‐MWCNT increasing in the latter case. Electrical conductivity boost was explained by the collective effect of high nanofiller loads and synergy of MWCNT and GnP. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42536.     

Thermal and mechanical properties of wood flour–polystyrene blends from postconsumer plastic waste

Polystyrene (PS) from packing materials and plastic cups was reinforced with 30 and 50% wood flour through a blending process with and without a commercial compatibilizing agent. The processability of the pure recycled polystyrene (rPS) and wood–rPS composites was studied in terms of the torque of the mixing process; this was then compared with that of a commercial virgin multipurpose PS. The physical and mechanical properties were compared with those of the virgin PS reinforced with 30 and 50% wood flour. The results show that the mechanical properties of the pure and reinforced rPS did not decrease with respect to the virgin PS, and in terms of the impact strength, the rPS was superior to the virgin plastic. The mechanical properties were not affected by the commercial compatibilizing agent, but the torque of the blends was significantly lower with the compatibilizer. Differential scanning calorimetry (DSC) and dynamic mechanical analysis were used to study the glass‐transition temperature (T_g) of both the pure virgin PS and pure rPS and the wood flour–PS composites. The T_g values of the rPS and wood–rPS composites were higher than those of the virgin PS and wood–virgin PS composites. The use of rPS increased the stiffness and flexural modulus of the composites. Thermogravimetric analysis revealed that the thermal stability of rPS and its composites was slightly greater than that of the virgin PS and its composites. These results suggest that postconsumer PS can be used to obtain composite materials with good mechanical and thermal properties. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Enhanced permittivity by the adhesion of conducting and low‐loss insulating ceramics in polystyrene

Ca[(Li_1/3Nb_2/3)_0.8Ti_0.2]O_3?δ (CLNT)–polystyrene–La_0.5Sr_0.5CoO_3?δ (LSCO) three‐phase composites were prepared by a two‐step mixing and hot‐molding method. The dielectric properties of polystyrene–CLNT composites were in agreement with the theoretical predictions. The dielectric properties of the three‐phase composites were investigated in terms of the volume fraction of LSCO and the frequency. The relative permittivity of the composites increased with LSCO loading. These composites with low processing temperatures showed a maximum relative permittivity of the order of 10⁴. These composites, with a giant permittivity with a broad smearing region, can find application in electrostrictive, decoupling capacitors and embedded passive devices. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Development of Ethylene‐Vinyl Acetate Composites Reinforced with Graphene Platelets

Composites of ethylene‐vinyl acetate (EVA) reinforced with graphene platelets are fabricated. Morphological, thermal, mechanical, electrical properties as well as moisture absorption of the composites are characterized. Transmission electron microscopy shows a good dispersion of graphene platelets in the matrix. The unidirectional orientation of graphene platelets parallel to the surface of the composites is revealed by field emission scanning electron microscopy and is validated using the Halpin–Tsai model. Tensile strength and elongation of the composites are respectively improved by 109 and 83%, after the addition of 3 wt% graphene platelets. The incorporation of 5 wt% graphene platelets enhances the char residue of the composites from 0.544% for pure EVA to 6.63% for the composites. The electrical conductivity of the composite with 3 wt% graphene platelets is two orders of magnitude higher than that of pure EVA with 10⁻¹³ S cm^–1 electrical conductivity.

     

Preparation and properties of styrene‐butadiene rubber nanocomposites blended with carbon black‐graphene hybrid filler

Graphene has become an attractive reinforcing filler for rubber materials, but its dispersion in rubber is still a big challenge. In this work, a novel carbon black‐reduced graphene (CB‐RG) hybrid filler was fabricated and blended with styrene‐butadiene rubber (SBR) via simple two‐roll mill mixing. The prepared CB‐RG hybrids had a microstructure with small CB agglomerates adsorbed onto graphene surfaces. CB acted as a barrier preventing the RG sheets from restacking even after drying. Homogeneous dispersion of graphene sheets in SBR matrix was observed by the mechanical mixing method based on the application of the CB‐RG hybrid fillers. Dynamic mechanical analysis showed that Tg of the SBR/CB‐RG blend was higher than that of the SBR/CB blend indicating strong interfacial interactions between RG and SBR due to the high surface area of graphene and the π‐π interaction between SBR and graphene. The tensile properties of SBR/CB‐RG composites improved significantly and the volume resistivity decreased compared with the SBR/CB blends. The thermal stability of SBR composites filled with CB and CB‐RG showed slight difference. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41309.     

Rice husk powder–filled polystyrene/styrene butadiene rubber blends

Natural fibers are rich in cellulose and they are a cheap, easily renewable source of fibers with the potential for polymer reinforcement. The presence of large amounts of hydroxyl groups makes natural fibers less attractive for reinforcement of polymeric materials. Composites made from polystyrene (PS)/styrene butadiene rubber (SBR) blend and treated rice husk powder (RHP) were prepared. The RHP was treated by esterification and acetylation. A similar series of composites was also prepared using maleic anhydride–polypropylene (MA–PP) as a coupling agent. The processing behavior, mechanical properties, effect of thermooxidative ageing, and surface morphology of untreated and chemically modified RHP were studied. There was a decrease in tensile strength (except MA–PP composites), elongation at break, and Young's modulus in chemically treated RHP composites. The postreaction process during thermooxidative ageing enhanced the tensile strength and Young's modulus of the esterified and MA–PP composites. Acetylation treatment was effective in reducing the percentage of water absorption in RHP/PS–SBR composites. In general chemically treated RHP/PS–SBR composites and MA–PP showed a better matrix phase and filler distribution. However, the degree of filler–matrix interaction was mainly responsible for the improvement of mechanical properties in the composites. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3320–3332, 2004     

Comparative study on the exfoliated expanded graphite nanosheet‐PES composites prepared via different compounding method

Composites made of polyethersulfone (PES) reinforced with exfoliated graphite nanoplatelets are fabricated by melt mixing, polymer solution, and coating. Coating is an efficient compounding method emphasized in this research, where expanded graphite (EG) and PES powder are premixed in isopropyl alcohol using sonication to disperse the EG by coating individual PES powder particles. The microstructure and property of EG/PES composites were investigated by X‐ray diffraction, scanning electron microscope, thermal gravimetric analysis, differential scanning calorimetric, and electronic tensile tester. The electrical conductivity was confirmed using electrochemical tester. It is found that the coating method is more effective than the polymer solution and directly melt mixing methods widely used, in terms of increasing the electrical conductivity and lowering the percolation threshold of thermoplastic composites, and enhancing the probability that the large platelet morphology of EG can be preserved in the final composite. The research reported here provides an understanding on how the compounding method used during the fabrication of composites is important to achieving the optimal mechanical properties, thermal properties, electrical conductivity, and percolation threshold. This method should have wide applicability to all thermoplastic matrix composite systems. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Enhanced mechanical and thermal properties of biodegradable poly(butylene succinate‐co‐adipate)/graphene oxide nanocomposites via in situ polymerization

Poly(butylene succinate‐co‐butylene adipate) (PBSA)/graphene oxide (GO) nanocomposites were synthesized via in situ polymerization for the first time. Atomic force microscopy demonstrated the achievement of a single layer of GO, and transmission electron microscopy proved the homogeneous distribution of GO in the PBSA matrix. Fourier transform infrared spectroscopy results showed the successful grafting of PBSA chains onto GO. With the incorporation of 1 wt % GO, the tensile strength and flexural modulus of the PBSA were enhanced by 50 and 27%, respectively. The thermal properties characterized by differential scanning calorimetry and thermogravimetric analysis showed increases in the melting temperatures, crystallization temperatures, and thermal stability. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 4075–4080, 2013     

Morphology and properties of polystyrene/agave fiber composites and foams

In this work, agave fibers were blended with polystyrene to produce foamed and unfoamed composites. The effect of fiber size and density reduction on the morphological, thermal, mechanical, and rheological properties, as well as crystallinity and water absorption kinetics of the composites was assessed. The results show that Young's modulus and tensile strength increased with increasing fiber content, but decreased with density reduction. Increasing fiber content and decreasing the size of the fibers both increased crystallinity of the composites. Finally, water uptake and diffusion coefficient were found to increase with increasing fiber content for all sizes. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Visualizing phase separation in polystyrene/polystyrene homo‐IPNs via sulfonation

BACKGROUND: Polystyrene/polystyrene (PS/PS) interpenetrating polymer networks (IPNs) represent ideal homo‐IPNs. Whether phase separation occurs in this system has been a long‐standing problem, which is closely related to the self‐organization mechanism in IPN formation and is important to the exploration of new polymer morphologies and properties by topological isomerism. RESULTS: A series of bead samples of PS/PS sequential IPNs with the same nominal divinylbenzene contents were synthesized by suspension polymerization, followed by sulfonation. Scanning electron micrographs and energy‐dispersive X‐ray mapping show unique distinctive topography on both surfaces and fractured surfaces and large heterogeneity in sulfonation of the PS/PS IPN beads, which for the first time provide visual evidence for dual‐phase continuity in PS/PS IPNs. CONCLUSION: The phase separation behavior is proposed to be due to hydrodynamic screening, architectural asymmetry and excluded volume interactions between network I and the precursor chains of network II. This is considered to represent pure IPN effects in sequential formation and may shed light on the general constitution mechanism and molecular design of IPN materials. Copyright © 2009 Society of Chemical Industry     

Synthesis of iron oxides intercalated montmorillonite and α‐zirconium phosphate particles and their applications in polystyrene composites

Three kinds of particles of organically modified montmorillonite (OMT) intercalated with iron oxides (Fe‐OMT), hexadecyltrimethylammonium bromide (CTAB) and ethylamine (EA)‐modified zirconium phosphate (ZrP) intercalated with iron oxides, named as Fe‐ZrP(CTAB) and Fe‐ZrP(EA), respectively, were synthesized through a simple route. Characterization of these particles showed that they had a mesoporous lamellar structure with high specific surface area and mesoporous volume. The influence of these particles on the thermal properties and combustion effluents of polystyrene (PS) were comparatively studied with the widely used OMT. The results suggested that the presence of Fe‐OMT, Fe‐ZrP(CTAB), and Fe‐ZrP(EA) imparted PS with an increased thermal degradation onset temperature and a higher glass transition temperature, but they could not increase the thermo‐oxidative stability remarkably as OMT did. Meanwhile, Fe‐ZrP(CTAB) and Fe‐ZrP(EA) exhibited stronger acidity and higher efficiency in preventing the condensed phase oxidation than either OMT or Fe‐OMT, since they imparted the PS composites with a higher ratio of CO/CO₂ in the combustion effluents. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42737.     

Bead‐to‐fiber transition in electrospun polystyrene

The morphological transition, namely bead‐to‐fiber transition, of electrospun polymer was examined for polystyrene, with its molecular weight ranging from 19,300 to 1,877,000 g/mol. Tetrahydrofuran and N,N‐dimethylformamide were used as solvents to examine the effects of solvent properties on the morphological variations. Polymer molecular weight and solvent properties had a significant effect on the morphology of beads as well as fibers. Observation of fiber diameter and its distribution suggested that the effect of molecular weight and solvent may be independent. The critical concentrations at which incipient and complete fibers were observed were found to decrease significantly with molecular weight, as can be expected. The effect of solvents on these critical concentrations was minimal for moderate to high‐molecular‐weight (>100,000 g/mol) solutions. For low‐molecular‐weight solutions, the transition occurred at concentrations much lower than those predicted by a model, based exclusively on chain entanglements. Rapid solidification of jet which is expected to occur with concentrated solutions may play a vital role in establishing stable fibers during electrospinning. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007