Thermal stability and dynamic mechanical behavior of exfoliated graphite nanoplatelets‐LLDPE nanocomposites

The objective of this research was to investigate thermal stability and dynamic mechanical behavior of Exfoliated graphite nanoplatelets (xGnP™)‐Linear Low‐Density Poly Ethylene (LLDPE) nanocomposites with different xGnP loading content. The xGnP‐LLDPE nanocomposites were fabricated by solution and melt mixing in various screw rotating systems such as co‐, counter‐, and modified‐corotating. The storage modulus (E′) of the composites at the starting point of −50°C increased as xGnP contents increased. E′ of the nanocomposite with only 7 wt% of xGnP was 2.5 times higher than that of the control LLDPE. Thermal expansion and the coefficient of thermal expansion of xGnP‐loaded composites were much lower than those of the control LLDPE in the range of 45–80°C (299.8 × 10⁻⁶/°C) and 85–100°C (365.3 × 10⁻⁶/°C). Thermal stability of the composites was also affected by xGnP dispersion in LLDPE matrix. The xGnP‐LLDPE nanocomposites by counter‐rotating screw system showed higher thermal stability than ones by co‐rotating and modified‐co‐rotating system at 5 wt% and 12 wt% of xGnP. xGnP had a great effect on high thermal stability of xGnP‐LLDPE composites to be applied as tube and film for electrical materials. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers     

Reinforcement of graphene nanoplatelets on plasticized poly(lactic acid) nanocomposites: Mechanical,thermal, morphology,and antibacterial properties

Plasticized poly(lactic acid) (PLA)‐based nanocomposites filled with graphene nanoplatelets (xGnP) and containing poly(ethylene glycol) (PEG) and epoxidized palm oil (EPO) with ratio 2 : 1 (2P : 1E) as hybrid plasticizer were prepared by melt blending method. The key objective is to take advantage of plasticization to increase the material ductility while preserving valuable stiffness, strength, and toughness via addition of xGnP. The tensile modulus of PLA/2P : 1E/0.1 wt % xGnP was substantially improved (30%) with strength and elasticity maintained, as compared to plasticized PLA. TGA analysis revealed that the xGnP was capable of acting as barrier to reduce thermal diffusion across the plasticized PLA matrix, and thus enhanced thermal stability of the plasticized PLA. Incorporation of xGnP also enhanced antimicrobial activity of nanocomposites toward Escherichia coli, Salmonella typhimurium, Staphylococcus aureus, and Listeria monocytogenes. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41652.     

Preparation and thermal degradation behavior of room temperature vulcanized silicone rubber-g-polyhedral oligomeric silsesquioxanes

Room temperature vulcanized (RTV) silicone rubber-g-polyhedral oligomeric silsesquioxanes (POSS) was prepared and its thermal degradation behavior and thermo-oxidative stability were investigated by thermogravimetric analysis (TGA). The results demonstrated that the chemical incorporation of POSS into polydimethylsiloxane (PDMS) chains significantly enhanced thermal stability of RTV silicon rubber in both nitrogen and air atmosphere. The degradation behavior was further monitored by TGA coupled with real time Fourier transform infrared spectra (FTIR), and the residues were characterized by FTIR and X-ray photoelectron spectroscopy (XPS). It was found that the remarkable improvement in thermal stability could be attributed to the following reasons: (1) the branched structure of RTV silicone rubber-g-POSS and interaction between POSS molecules and PDMS chains; (2) POSS traps generated and grafted or cross-linked structure formed; (3) intumescent ceramic protective barrier formed; (4) the perfect distribution of POSS in RTV silicone rubber-g-POSS.     

Enzymatic degradation,electronic, and thermal properties of graphite- and graphene oxide-filled biodegradable polylactide/poly(ε-caprolactone) blend composites

Commodity polymers are the most widely used materials for electronic packaging applications. However, they are nondegradable and causing serious environmental damage. Addressing this challenge, the relative effects of graphite (G) and graphene oxide (GO) dispersion on the enzymatic degradation, electronic properties, thermal degradation, and crystallization behavior of enzyme degradable polylactide/poly(ε-caprolactone) blend composites is investigated. Owing to the oxygenated surface functionalities and excellent thermal conductivity arising from the carbon structure, the randomly dispersed GO particles do not provide electrical pathways and facilitate large enhancements in the electrical resistivity (126%) and thermal conductivity (72%) of the blend composites. However, while the G particles enhanced the thermal conductivity of the composites, they had little effect on enzymatic degradation. Furthermore, they reduced the electrical resistivity, particularly at high concentration (0.25 wt % G), as a result of the conducting delocalized electrons in the G structure and due to network formation. We also find that the energy required to initiate and propagate the thermal degradation process for GO-filled blend composites is relatively lower than that of G-filled blend composite. However, the former composites show higher crystallization rate coefficients value than that of G-filled composites and the neat blend, thereby providing better crystallization ability and miscibility with the matrix. In summary, the GO-filled blend composites are observed to show potential for use in sustainable materials for thermal management applications. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47387.     

Kinetic parameters of thermal degradation of polyethylene glycol‐toughened novolac‐type phenolic resin

The miscibility and thermal degradation of poly(ethylene glycol) (PEG)‐toughened novolac‐type phenolic resin were investigated. Differential scanning calorimetry (DSC) results confirmed that the phenolic resin/PEG blend was blended completely. Infrared spectra show that hydrogen bonding existed in the blends. Thermal degradation of PEG blended with novolac‐type phenolic resin was studied utilizing a dynamic thermogravimetric technique in a flowing nitrogen atmosphere at several heating rates (i.e., 5, 10, 20, 40°C/min). Thermal degradation of phenolic resin/PEG blends takes place in multiple steps. The thermal behavior and the thermal stability affected the thermal degradation, which coincided with the data from the thermal degradation of novolac‐type phenolic resin/PEG blends by thermogravimetric analysis (TGA). © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 188–196, 2001     

Synthesis and thermal oxidative degradation of a novel amorphous polyamide/nanoclay nanocomposite

A novel amorphous polyamide/montmorillonite nanocomposite based on poly(hexamethylene isophthalamide) was successfully prepared by melt intercalation. Wide angle X-ray diffraction and transmission electron microscopy showed that organoclay containing quaternary amine surfactant with phenyl groups was delaminated in the polymer matrix, resulting in well-dispersed morphologies even at high montmorillonite content. Thermal oxidation behavior of the polymer nanocomposites was studied by thermogravimetric analysis (TGA), and the chemical evolution in the solid residue was monitored by elemental analysis and Fourier transform infrared spectroscopy (FTIR). TGA results showed that the addition of well-dispersed organoclay resulted in a substantial increase (30 °C) in the onset degradation temperature of the nanocomposites as compared to the homopolymer. Elemental analysis on the solid residue indicated that the presence of nanoclay resulted in char formation with greater thermal stability. FTIR spectra showed that thermal degradation in air occurred via both oxidative and non-oxidative mechanisms simultaneously. In the homopolymer, the oxidative mechanism was more dominant. However, with the addition of well-dispersed organoclay, the non-oxidative pathway became more significant. Hence the presence of delaminated nanoclay layers could effectively retard thermo-oxidative degradation of the amorphous polymer by constraining the polymer chains and slowing down the rate of oxygen diffusion through the nanocomposites, but it was not as effective in hindering the non-oxidative degradation reaction pathway.     

Thermo-oxidative degradation of poly(ethylene glycol)/poly( -lactic acid) blends

The thermo-oxidative degradation of poly(ethylene glycol)/poly( -lactic acid) (PEG/PLLA) blends was studied by infra-red spectroscopy (IR), differential scanning calorimetry (DSC), gel permeation chromatography (GPC) and thermogravimetry (TGA). The thermo-oxidative degradation of PEG occurred after a period time of aging in air at 80 °C. The mechanism of thermo-oxidative degradation of PEG was found to be the random chain scission of the main chain. As PEG blending with PLLA, the existence of PLLA appeared to enhance the thermo-oxidative degradation of PEG. The enhancement of thermo-oxidative degradation increased first and then decreased with the increase of PLLA. The results could be attributed to the ease of abstraction of the carboxylic hydrogen (–COOH) of PLLA, which enhanced the thermo-oxidative degradation of PEG. Also, the dilution effect of PLLA on the concentration of free radicals was an important factor of the thermo-oxidative degradation.     

Thermal and photochemical degradation of PPO/HIPS blends

In general, polymer blends show a degradation behavior different from a simple combination of the individual components, making any forecast difficult without experiments. Interactions between polymers can sensibilize or stabilize the blend against degradation. In this work, the thermal and photooxidative degradation of blends of poly(2,6‐dimethyl‐1,4‐phenylene oxide) (PPO) and high impact polystyrene (HIPS) have been studied under accelerated conditions. The extent of degradation was accompanied by infrared spectroscopy (FTIR) and Raman spectroscopy (FT‐Raman) and impact resistance and strain–stress testing followed its influence on the macroscopic properties of the blends. The results showed that HIPS and the blend containing 60 wt % of PPO are more susceptible to thermal and photochemical degradation, while the blends containing 40 and 50 wt % of PPO are more stable. Infrared and Raman spectroscopic analyses showed that the degradation of HIPS and its blends is caused not only by degradation of the polybutadiene phase. Effects of interactions, such as exchange of energy in excited state between the PPO and PS components of the polymeric matrix may also be responsible for the degradation and loss of mechanical properties of the PPO/HIPS blends. The chemical degradation directly affects the mechanical properties of the samples with photodegradation being more harmful than the thermal degradation at 75°C. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Contribution of compatibilizer backbone to degradation and retained functionality of multiple extruded polypropylene/poly(ethylene terephthalate) blends

This study assesses thermal and morphological stabilization of three compatibilizers during mechanical recycling of polymer blends. Polypropylene/poly(ethylene terephthalate) blends compatibilized with three different maleic anhydride grafted compatibilizers were extruded five times via single-screw extrusion. The backbones of the compatibilizers are (1) polypropylene-based, (2) an elastomer block copolymer poly(styrene-co-[ethylene-butylene]-styrene), and (3) a polyolefin elastomer. The degradation and retained functionality of these compatibilizers was assessed by means of simultaneous thermo-gravimetric analysis, melt flow index, a morphology study, differential scanning calorimetry and tensile testing. The results show that degradation of the compatibilized blends during multiple processing is low, although the core stability of the blends depends on the initial stability of all of the components in the blend. The thermal stability across the five extrusions was the most favorable for the matrix based grafted compatibilized blend. The functionality of the compatibilizers did show minor morphological destabilization but did not affect the mechanical properties.     

Thermal stabilization of poly(3‐hydroxybutyrate) by poly(glycidyl methacrylate)

Poly(3‐hydroxybutyrate) (PHB)/poly(glycidyl methacrylate) (PGMA) blends with the PGMA content up to 30 wt % were prepared by a solution‐precipitation procedure. The thermal decomposition of PHB/PGMA blends was studied by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and differential thermal analysis (DTA). The thermograms of PHB/PGMA blends contained a two‐step degradation process, while that of pure PHB sample exhibited only one‐step degradation process. This degradation behavior of PHB/PGMA blends, which have a higher thermal stability as measured by maximum decomposition temperature or residual weight after isothermal degradation for 1 h, is probably due to crosslinking reactions of the epoxide groups in the PGMA component with the carboxyl chain ends of PHB fragments during the degradation process, and the occurrence of such reactions can be assigned to the exothermic peaks in their DTA thermograms. An isothermal study of these blends at 200–250°C for 1 h indicated that the residual weight was directly correlated with the amount of epoxide groups in the PHB/PGMA blends. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2945–2952, 2002; DOI 10.1002/app.10318     

Morphology and thermal degradation studies of melt‐mixed PLA/PHBV biodegradable polymer blend nanocomposites with TiO2 as filler

The morphology and thermal stability of melt‐mixed poly(lactic acid) (PLA)/poly(hydroxybutyrate‐co‐valerate) (PHBV) blends and nanocomposites with small amounts of TiO₂ nanoparticles were investigated. PLA/PHBV at 50/50 w/w formed a co‐continuous structure, and most of the TiO₂ nanoparticles were well dispersed in the PLA phase and on the interface between PLA and PHBV, with a small number of large agglomerates in the PHBV phase. Thermogravimetric analysis (TGA) and TGA–Fourier‐transform infrared spectroscopy was used to study the thermal stability and degradation behavior of the two polymers, their blends, and nanocomposites. The thermal stability of PHBV was improved through blending with PLA, whereas that of the PLA was reduced through blending with PHBV, and the presence of TiO₂ nanoparticles seemingly improved the thermal stability of both polymers in the blend. However, the degradation kinetics results revealed that the nanoparticles could catalyze the degradation process and/or retard the volatilization of the degradation products, depending on their localization and their interaction with the polymer in question. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42138.     

Improving the thermal conductivity and shape-stabilization of phase change materials using nanographite additives

Improvements in the thermal conductivity and shape-stability of paraffin phase change materials (PCMs) by adding exfoliated graphite nanoplatelets (xGnP) or graphene were compared. The composite PCMs were fabricated by mixing paraffin with xGnP or graphene in hot toluene, followed by solvent evaporation and vacuum drying. A larger increase in thermal conductivity was observed for paraffin/xGnP, with a 10 wt.% xGnP loading producing a more than 10-fold increase. Graphene shows a lower electrical percolation threshold and offers a much larger increase in the electrical conductivity of paraffin than xGnP. However, its thermal conductivity increase is much lower. Despite the excellent thermal conductivity of single-flake graphene, the large density of nanointerfaces due to the small size of the graphene flakes significantly impedes heat transfer. We also found that graphene is much more effective than xGnP as a shape-stabilizing filler. At 2 wt.% graphene loading, paraffin maintains its shape up to 185.2 °C, well above the operating temperature range of paraffin PCMs, while the paraffin/xGnP counterpart is shape-stable up to 67.0 °C only. Small amounts of graphene and xGnP can be used in combination as a low-cost and effective improver for both the heat diffusion and shape-stabilization of paraffin PCMs.     

Thermally conductive high-density polyethylene as novel phase-change material: Application-relevant long-term stability

The long-term stability of thermally conductive high-density polyethylene (HDPE)-based compounds as phase-change material (PCM) is investigated. For this purpose, the HDPE's thermal conductivity (TC) is first enhanced via compounding two different filler types (expanded graphite and aluminum) into the polymeric matrix. Bulky specimens of these compounds are then stored in air for up to 7289 h in the melt state to investigate the compounds' long-term stability as PCM. Their thermo-oxidative/thermal stability and their ability to maintain the isotropic material character (homogeneous distribution of the incorporated particles) is investigated. The compounds' degradation behavior is monitored via Fourier-transform infrared spectroscopy and the maintenance of the homogeneous filler distribution is examined via a combined differential scanning calorimetry/thermogravimetric analysis mapping of each exposed specimen. The storage capacity decreases minimally after 7289 h of exposure. Furthermore, the incorporated filler particles enhance the thermo-oxidative stability of HDPE as PCM. Consequently, thermally conductive HDPE is a highly interesting PCM. © 2019 The Authors. Journal of Applied Polymer Science published by Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48269.     

Multifunctional polypropylene composites produced by incorporation of exfoliated graphite nanoplatelets

The potential of using exfoliated graphite nanoplatelets, xGnP^TM, as a reinforcement that can produce multifunctional polymer composites was explored. xGnP-polypropylene (PP) composites fabricated by melt mixing using a twin-screw extruder followed by injection molding were investigated for their thermal, viscoelastic and barrier properties as a function of xGnP concentration and aspect ratio. These properties of the xGnP-PP composites were compared to the properties of composites made with PAN-based carbon fibers, VGCF, carbon black and nanoclay. Results indicate that when oriented properly, the xGnP will not only stiffen the composite but also reduce the coefficient of thermal expansion in two directions rather than in one as in the case of aligned fiber composites. Furthermore, the large aspect ratio of xGnP, even at low loadings, increases the oxygen barrier of PP at least as effectively as the commonly used nanoclays and finally, addition of xGnP significantly enhances the thermal conductivity of the polymer matrix.     

Photodegradation of thermodegraded polypropylene/high‐impact polystyrene blends: Mechanical properties

The influence of the addition of high‐impact polystyrene (HIPS) on polypropylene (PP) photodegradation was studied with blends obtained by extrusion with and without styrene–butadiene–styrene (SBS) copolymer (10 wt % with respect to the dispersed phase). The concentrations of HIPS ranged from 10 to 30 wt %. The blends and pure materials were exposed for periods of up to 15 weeks of UV irradiation; their mechanical properties (tensile and impact), fracture surface, and melt flow indices were monitored. After 3 weeks of UV exposure, all of the materials presented mechanical properties of the same order of magnitude. However, for times of exposure greater than 3 weeks, an increasing concentration of HIPS resulted in a better photostability of PP. These results were explained in light of morphological observations. This increase of photostability was even greater when SBS was added to the blends. It was more difficult to measure the melt flow index of the binary PP/HIPS blends than that of PP for low concentrations of HIPS; this was most likely due to energy transfer between the blend domains during photodegradation. This phenomenon was not observed for the ternary blends. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Thermal and phase-separation behavior of injection-molded poly(<Emphasis Type="SmallCaps">l</Emphasis>-lactic acid)/poly(<Emphasis Type="SmallCaps">d</Emphasis>-lactic acid) blends with moderate optical purity

l-Lactide-rich poly(l-lactide) (LR-PLLA)/d-lactide-rich poly(d-lactide) (DR-PDLA) blends with moderate optical purity were prepared by conventional extrusion and followed by injection-molding process in this study. Thermal properties, crystalline structure, spherulite morphology, melt degradability, and thermal mechanical property were investigated by means of DSC, WAXD, POM, TG, and DMA. In comparison with LR-PLLA/DR-PDLA blends with higher optical purity, stereocomplex with less perfect structure was partially formed from the LR-PLLA/DR-PDLA blends with various compositions and showed lower melting temperature. Surprisingly, double melting peaks have appeared in blends with 40 or 50 wt% DR-PDLA. Annealing at higher temperature for blends with 50 wt% DR-PDLA resulted in three melting peaks. It is assumed that the optical purity would play a critical role, thus, producing limited amount of stereocomplex with less imperfect structure. Annealing would also induce the micro-phase separation behavior in LR-PLLA/DR-PDLA blends and significantly influence the thermal and degradable properties of blends.     

Effect of the graphite nanoplatelet size on the mechanical,thermal, and electrical properties of polypropylene/exfoliated graphite nanocomposites

Polypropylene (PP)/exfoliated graphite nanoplatelet (xGnP) nanocomposites with various intrinsic aspect ratios of graphite nanoplatelets (GnPs; large and small in diameter) were prepared by a melt‐mixing procedure. Transmission electron microscopy showed that all types of xGnP were well‐dispersed in the polymer matrix. The effects of the dimensions and loading of the xGnPs on the morphology, mechanical reinforcement, and electrical properties of PP/xGnP were studied. A differential scanning calorimetry study of the PP/xGnP morphology indicated that all types of xGnP additives were heterogeneous nucleation sites for PP crystallization. Tensile testing, DMA, and thermogravimetric analysis of PP/xGnPs with different types of GnP additives showed enhancements in their mechanical properties, heat resistance, and thermal stability compared to plain PP. We also found a significant increase in the conductivity of PP/xGnP. The PP/xGnP with a large diameter of GnPs demonstrated the lowest percolation threshold, equal to 4 vol % of the xGnP loading. The mechanical properties were estimated by means of micromechanical modeling. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Overview of Various Sorts of Polymer Nanocomposite Reinforced with Layered Silicate

Polymer/layered silicate nanocomposites represent an important class of materials in which polymer is hardened by homogeneously dispersed inorganic particles. The most widely used nanoclay is bentonite which mainly consists of montmorillonite. Nanoclays are known to form composites with epoxy resin, polystyrene, poly(methyl metacraylate), polyvinyl chloride, and ternary blends. An outline of advancement in polymer-layered silicate nanocomposite is presented with different preparation methods such as in situ polymerization, solution-induced intercalation, and melt processing. The property enhancement comprises increased strength, decreased flammability, higher modulus, thermal stability, and barrier properties. Thermal, mechanical, and nonflammability property improvement has resulted in automotive and industrial applications.     

Crystallization of poly(3‐hydroxybutyrate) by exfoliated graphite nanoplatelets

Poly(3‐hydroxybutyrate) (PHB) has been shown to be efficiently nucleated by exfoliated graphite nanoplatelets (xGnP). The nucleating effect of xGnP was investigated using differential scanning calorimetry, optical microscopy and atomic force microscopy. Nonisothermal crystallization of PHB from the melt required lower activation energies for PHB containing 1 wt % and 3 wt % xGnP (?214 and ?102 kJ/mol respectively) than for pure PHB (?60 kJ/mol). A kinetic study of the PHB/xGnP crystallization employing a modified form of the Avrami equation revealed that the presence of xGnP increased the PHB crystallization temperature, as well as the crystallization rates, and generated smaller and more numerous spherulites. Optical microscopy and atomic force microscopy confirmed the incorporation of xGnP into the lamellar structure of the PHB spherulites and provided insight into the influence of xGnP on spherulite size and lamellae thickness. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Effect of LCP and rPET as reinforcing materials on rheology,morphology, and thermal properties of in situ microfibrillar‐reinforced elastomer composites

Microfibrillar‐reinforced elastomer composites based on two dispersed phases, liquid crystalline polymer (LCP) and recycled poly(ethylene terephthalate)(rPET), and styrene‐(ethylene butylene)‐styrene (SEBS) were prepared using extrusion process. The rheological behavior, morphology, and thermal stability of SEBS/LCP and SEBS/rPET blends containing various dispersed phase contents were investigated. All blends and LCP exhibited shear thinning behavior, whereas Newtonian fluid behavior was observed for rPET. The incorporation of both LCP and rPET into SEBS significantly improved the processability by bringing down the melt viscosity of the blend system. The fibrillation of LCP dispersed phase was clearly observed in as‐extruded strand with addition of LCP up to 20–30 wt %. Although the viscosity ratio of SEBS/rPET system is very low (0.03), rPET domains mostly appeared as droplets in as‐extruded strand. The results obtained from thermogravimetric analysis suggested that an addition of LCP and rPET into the elastomer matrix improved the thermal resistance significantly in air but not in nitrogen. The simultaneous DSC profiles revealed that the thermal degradation of all polymers examined were endothermic and exothermic in nitrogen and in air, respectively. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009