Synergistic effect of hybrid graphene nanoplatelet and multi-walled carbon nanotube fillers on the thermal conductivity of polymer composites and theoretical modeling of the synergistic effect

We found that the thermal conductivity of polymer composites was synergistically improved by the simultaneous incorporation of graphene nanoplatelet (GNP) and multi-walled carbon nanotube (MWCNT) fillers into the polycarbonate matrix. The bulk thermal conductivity of composites with 20 wt% GNP filler was found to reach a maximum value of 1.13 W/m K and this thermal conductivity was synergistically enhanced to reach a maximum value of 1.39 W/m K as the relative proportion of MWCNT content was increased but the relative proportion of GNP content was decreased. The synergistic effect was theoretically estimated based on a modified micromechanics model where the different shapes of the nanofillers in the composite system could be taken into account. The waviness of the incorporated GNP and MWCNT fillers was found to be one of the most important physical factors determining the thermal conductivity of the composites and must be taken into consideration in theoretical calculations.     

Effects of poly(oxyethylene)-block structure in polyetheramines on the modified carbon nanotube/poly(lactic acid) composites

The hybrids of multi-walled carbon nanotube and poly(lactic acid) (MWCNT/PLA) were prepared by a melt-blending method. In order to enhance the compatibility between the PLA and MWCNTs, the surface of the MWCNTs was covalently modified by Jeffamine® polyetheramines by functionalizing MWCNTs with carboxylic groups. Different molecular weights and hydrophilicity of the polyethermaines were grafted onto MWCNTs with the assistance of a dehydrating agent. The results showed that low-molecular-weight Jeffamine® polyetheramine modified MWCNTs can effectively improve the thermal properties of PLA composites. On the other hand, high-molecular-weight and poly(oxyethylene)-segmented polyetheramine could render the modified MWCNTs of well dispersion in PLA, and consequently affecting the improvements of mechanical properties and conductivity of composite materials. With the addition of 3.0 wt% MWCNTs, the increment of E′ of the composite at 40 °C was 79%. For conductivity, the surface resistivity decreased from 1.27 × 10¹² Ω/sq for neat PLA to 8.30 × 10⁻³ Ω/sq for the composites.     

Water absorption behavior,mechanical and thermal properties of nano TiO2 enhanced glass fiber reinforced polymer composites

Nano TiO₂ particle is one of the promising inorganic nano fillers used in polymer matrix composites to enhance the mechanical properties. However, reliability of this type of nano composites is yet to be ensured in hydrothermal environment. The present work investigates the addition of nano TiO₂ filler on water sorption, residual strength and thermal properties of glass fiber reinforced polymer (GFRP) composites. The results revealed that addition of 0.1 wt% TiO₂ has reduced water diffusion coefficient by 9%, improved residual flexural strength by 19% and residual interlaminar shear strength by 18% among all the nano TiO₂ modified composites. The improvement of mechanical properties in hydrothermal environment creates opportunity and reliability to be used in different engineering applications. Weibull design parameters are evaluated and found a good agreement between Weibull stress-strain curves and experimental one. Fractographic analysis confirmed the various failures and strengthening mechanisms of nano composites in dry and hydrothermal environment.     

Characterization and properties of transparent cellulose nanowhiskers-based graphene nanoplatelets/multi-walled carbon nanotubes films

Transparent cellulose nanowhiskers (CNW)/graphene (GN) and CNW/multi-wall carbon nanotube (MWCNT) films were obtained by ultrasonication assisted mechanically stirring followed by solvent casting methods. GN has more significant influence on the properties of CNW film than MWCNT does because GN exhibits strong interaction with CNW by its adsorption on the surface of GN. Thermal behaviors of CNW-based composite films were greatly affected by addition of GN or MWCNT. The melting peak and initial degradation temperature increase by 23.5 and 24 °C, and by 78 °C and 94 °C for the composite films containing 5 wt% MWCNT and 5 wt% GN, respectively. The composites show the contact angles of 61.9° for GN included film and 46.9° for MWCNT included film, which is higher than that of pure CNW film (42.8°).     

Strong and optically transparent biocomposites reinforced with cellulose nanofibers isolated from peanut shell

Cellulose nanofibers–reinforced PVA biocomposites were prepared from peanut shell by chemical–mechanical treatments and impregnation method. The composite films were optically transparent and flexible, showed high mechanical and thermal properties. FE-SEM images showed that the isolated fibrous fragments had highly uniform diameters in the range of 15–50 nm and formed fine network structure, which is a guarantee of the transparency of biocomposites. Compared to that of pure PVA resin, the modulus and tensile strength of prepared nanocomposites increased from 0.6 GPa to 6.0 GPa and from 31 MPa to 125 MPa respectively with the fiber content as high as 80 wt%, while the light transmission of the composite only decreased 7% at a 600 nm wavelength. Furthermore, the composites exhibited excellent thermal properties with CTE as low as 19.1 ppm/K. These favorable properties indicated the high reinforcing efficiency of the cellulose nanofibers isolated from peanut shell in PVA composites.     

The thermal conductivity of Al(OH)3 covered MWCNT/epoxy terminated dimethyl polysiloxane composite based on analytical Al(OH)3 covered MWCNT

Aluminum-hydroxide-covered multi-walled carbon nanotubes (A–MWCNT) were fabricated as a thermally conductive material. The thermal conductivity of A–MWCNT was estimated based on Casimir theory. The effective thermal conductivity of A–MWCNT was estimated at about ∼26 W/mK. The thermal conductivity of A–MWCNT/epoxy-terminated polydimethylsiloxane (ETDS) composite was examined as a function of A–MWCNT loading, and the results showed the maximum value at 1.5 wt% of A–MWCNT loading, above which it decreased slightly. The effective medium approximation (EMA) developed by Maxwell–Garnett (M–G) was used to analyze the thermal conducting behavior of the composite. The experimental results showed negative deviation from the expected thermal conductivity, k_e, beyond 1.5 wt% of A–MWCNT loading, because the composites containing A–MWCNT were strongly affected by interfacial resistance. The interfacial resistance value calculated from M–G approximation increased when filler loading was higher than 1.5 wt% because of the folded and partially agglomerated A–MWCNT along with insufficient interfacial interactions.     

Enhanced conductivity behavior of polydimethylsiloxane (PDMS) hybrid composites containing exfoliated graphite nanoplatelets and carbon nanotubes

Polydimethylsiloxane (PDMS) hybrid composites consisting of exfoliated graphite nanoplatelets (xGnPs) and multiwalled carbon nanotubes functionalized with hydroxyl groups (MWCNTs-OH) were fabricated, and the effects of the xGnP/MWCNT-OH ratio on the thermal, electrical, and mechanical properties of polydimethylsiloxane (PDMS) hybrid composites were investigated. With the total filler content fixed at 4 wt%, a hybrid composite consisting of 75% × GnP/25% MWCNT-OH showed the highest thermal conductivity (0.392 W/m K) and electrical conductivity (1.24 × 10⁻³ S/m), which significantly exceeded the values shown by either of the respective single filler composites. The increased thermal and electrical conductivity found when both fillers are used in combination is attributed to the synergistic effect between the fillers that forms an interconnected hybrid network. In contrast, the various different combinations of the fillers only showed a modest effect on the mechanical behavior, thermal stability, and thermal expansion of the PDMS composite.     

The optimal formulation of recycled polypropylene/rubberwood flour composites from experiments with mixture design

A mixture design was used in experiments, to determine the optimal mixture for composites of rubberwood flour (RWF) and reinforced recycled polypropylene (rPP). The mixed materials were extruded into panels. Effects were determined of the mixture components rPP, RWF, maleic anhydride-grafted polypropylene (MAPP), and ultraviolet (UV) stabilizer, on the mechanical properties. The overall composition significantly affected flexural, compressive, and tensile properties. The fractions of recycled polypropylene and rubberwood flour increased all the mechanical material properties; however, increasing one fraction must be balanced by decreasing the other, and the rubberwood flour fraction had a higher effect size. The fraction of MAPP was best kept in mid-range of the fractions tested, while the UV stabilizer fraction overall degraded the mechanical properties. Our results suggest that the fraction of UV stabilizer should be as small as possible to minimize its negative influences. The models fitted were used for optimization of a desirability score, substituting for the multiple objectives modeled. The optimal formulation found was 50.3 wt% rPP, 44.5 wt% RWF, 3.9 wt% MAPP, 0.2 wt% UV stabilizer, and 1.0 wt% lubricant; the composite made with this formulation had good mechanical properties that closely matched the model predictions.     

Facile synthesis of lanthanum hypophosphite and its application in glass-fiber reinforced polyamide 6 as a novel flame retardant

This work developed flame retarded glass fiber reinforced polyamide 6 (FR-GFPA) composites with excellent mechanical properties, thermal stability and flame retardancy using a novel flame retardant, lanthanum hypophosphite (LaHP). The flame-retarded properties of FR-GFPA composites were characterized by limiting oxygen index, Underwriters Laboratories 94 testing and cone calorimeter test. FR-GFPA composite with 20 wt% LaHP reached V-0 rating and a high LOI value (27.5 vol%). The mechanical performance analysis showed that both the storage modulus and tensile strength increased and then decreased with the increase of LaHP loading. For FR-GFPA composite with 15 wt% LaHP loading, the storage modulus was 164% higher than that of glass fiber reinforced polyamide 6 (GFPA). Thermogravimetric analysis (TGA) and char residue characterization showed that the addition of LaHP can promote the formation of compact physical char barrier, reduce the mass loss rate and thus improve the flame retardancy of FR-GFPA composites.     

Preparation,morphology and properties of acid and amine modified multiwalled carbon nanotube/polyimide composite

The precursor of polyimide, polyamic acid, was prepared by reacting 4,4′-oxydianiline (ODA) with 3,3′,4,4′-benzophenone tetracarboxylic dianhydride (BTDA). Unmodified, acid-modified and amine-modified multiwall carbon nanotubes (MWCNT) were separately added to the polyamic acid and heated to 300 °C to produce polyimide/carbon nanotube composite. Scanning electron microscopic (SEM) and transmission electron microscopic (TEM) microphotographs reveal that acid-modified MWCNT and amine-modified MWCNT were dispersed uniformly in the polyimide matrix. The effect of the acid and amine-modified MWCNTs on the surface and volume electrical resistivities of MWCNT/polyimide composites were investigated . The surface electrical resistivity of the nanocomposites decreased from 1.28 × 10¹⁵ Ω/cm² (neat polyimide) to 7.59 × 10⁶ Ω/cm² (6.98 wt% unmodified MWCNT content). Adding MWCNTs influenced the glass transition temperatures of the nanocomposites. Modified MWCNTs significance enhanced the mechanical properties of the nanocomposites. The tensile strength of the MWCNT/polyimide composite was increased from 102 MPa (neat polyimide) 134 MPa (6.98 wt% acid modified MWCNT/polyimide composites).     

Thermal and mechanical properties of phenolic-based composites reinforced by carbon fibres and multiwall carbon nanotubes

The thermal, mechanical and ablation properties of carbon fibre/phenolic composites filled with multiwall carbon nanotubes (MWCNTs) were investigated. Carbon fibre/phenolic/MWCNTs were prepared using different weight percentage of MWCNTs by compression moulding. The samples were characterized by scanning electron microscopy (SEM), flexural tests, thermal gravimetric analysis and oxyacetylene torch tests. The thermal stability and flexural properties of the nanocomposites increased by increasing MWCNTs content (wt% ⩽1), but they decreased when the content of MWCNTs was 2 wt%. The linear and mass ablation rates of the nanocomposites after modified with 1 wt% MWCNTs decreased by about 80% and 52%, respectively. To investigate the material post-test microstructure, a morphological characterization was carried out using SEM. It was shown that the presence of MWCNTs in the composite led to the formation of a strong network char layer without any cracks or opening.     

Manufacture and characterisation of thermoplastic composites made from PLA/hemp co-wrapped hybrid yarn prepregs

PLA/hemp co-wrapped hybrid yarns were produced by wrapping PLA filaments around a core composed of a 400 twists/m and 25 tex hemp yarn (Cannabis sativa L) and 18 tex PLA filaments. The hemp content varied between 10 and 45 mass%, and the PLA wrapping density around the core was 150 and 250 turns/m. Composites were fabricated by compression moulding of 0/90 bidirectional prepregs, and characterised regarding porosity, mechanical strength and thermal properties by dynamic mechanical thermal analysis (DMTA) and differential scanning calorimetry (DSC). Mechanical tests showed that the tensile and flexural strengths of the composites markedly increased with the fibre content, reaching 59.3 and 124.2 MPa when reinforced with 45 mass% fibre, which is approximately 2 and 3.3 times higher compared to neat PLA. Impact strength of the composites decreased initially up to 10 mass% fibre; while higher fibre loading (up to 45 mass%) caused an increase in impact strength up to 26.3 kJ/m², an improvement of about 2 times higher compared to neat PLA. The composites made from the hybrid yarn with a wrapping density of 250 turns/m showed improvements in mechanical properties, due to the lower porosity. The fractured surfaces were investigated by scanning electron microscopy to study the fibre/matrix interface.     

Preparation and characterization of carbon nanotube/polyetherimide nanocomposite films

Multi-walled carbon nanotube (MWCNT)/polyetherimide (PEI) nanocomposite films have been prepared by casting and imidization. A homogeneous dispersion of MWCNTs throughout the PEI matrix is observed by scanning electron microscopy of fracture surfaces, which shows not only a fine dispersion of MWCNTs but also strong interfacial adhesion with the matrix, as evidenced by the presence of many broken but strongly embedded carbon nanotubes (CNTs) in the matrix and by the absence of debonding of CNTs from the matrix. Differential scanning calorimetry and dynamic mechanical analysis show that the glass transition temperature of PEI increases by about 10 °C by the addition of 1 wt% MWCNTs. Mechanical testing shows that for the addition of 1 wt% MWCNTs, the elastic moduli of the nanocomposites are significantly improved by about 250% while the tensile strength is comparable to that of the matrix. This improvement is due to the strong interfacial interaction between the MWCNTs and the PEI matrix which favors stress transfer from the polymer to the CNTs.     

Using response surface methodology for modeling and optimizing tensile and impact strength properties of fiber orientated quaternary hybrid nano composite

In current study, weight percentage of nano silica and nano clay and also fiber orientation have been chosen as independent variables and the affect of these variables on tensile and izod impact strength of epoxy/glass fiber/SiO₂/clay hybrid laminate composite has been investigated. Central composite design (CCD) which is subset of response surface methodology has been employed to present mathematical models as function of physical factors to predict tensile and impact behavior of new mentioned hybrid nano composite and also optimizing mentioned mechanical properties. Totally 20 experiments were designed with 6 replicates at center point. The maximum and minimum value of tensile strength were 450.90 MPa and 158.16 MPa which occurred in design levels 1 and 14 respectively, also the maximum and minimum of izod impact strength were 10.47 kJ/m² and 2.56 kJ/m² which occurred in design levels 13 and 14 respectively. The optimization results using optimization part of Minitab software showed that the best tensile strength was obtained 488.53 MPa and occurred in 3.5 wt% of nano silica, 1.1 wt% of nano clay and 9° of fiber orientation and after preparing and testing five samples average value of tensile strength was obtained about 480 MPa. Also the results showed that the best impact strength obtained from software was 11.35 kJ/m² and occurred in 4.03 wt% of nano clay, 5 wt% of nano silica and 0° of fiber orientation. The optimization results also showed that tensile and impact strength at optimum values improved up to 6.4% and 203.5% compared to level 1 and 14 and 6.02% and 303.6% compared to level 13 and 14 respectively. In addition, the fracture surface morphologies of the quaternary nano composites were investigated by scanning electron microscopy (SEM).     

The effect of interfacial interactions on the mechanical properties of polypropylene/natural zeolite composites

The effect of interfacial interactions on the mechanical properties of polypropylene (PP)/natural zeolite composites was investigated under dry and wet conditions. Interfacial interactions were modified to improve filler compatibility and mechanical properties of the composites by surface treatment of natural zeolite with a non-ionic surface modifier; 3 wt% polyethylene glycol (PEG) and three different types of silane coupling agents; 3-aminopropyltriethoxysilane (AMPTES), methyltriethoxysilane (MTES) and 3-mercaptopropyltrimethoxysilane (MPTMS), at four different concentrations (0.5–2 wt%). PP composites containing (2–6 wt%) zeolite were prepared by an extrusion technique. The tensile properties of the composites determined as a function of the filler loading and the concentration of the coupling agents were found to vary with surface treatment of zeolite. Silane treatment indicated significant improvements in the mechanical properties of the composites. According to the dry and wet tensile test results, the maximum improvement in the mechanical properties was obtained for the PP composites containing 1 wt% AMPTES treated zeolite. The improvement in the interfacial interaction was confirmed using a semi-empirical equation developed by Pukanszky. Good agreement was obtained between experimental data and the Pukanszky model prediction. Scanning electron microscopy studies also revealed better dispersion of silane treated filler particles in the PP matrix.     

Influence of compatibilizing system on morphology,thermal and mechanical properties of high flow polypropylene reinforced with short hemp fibers

Simultaneous influence of polypropylene-graft-maleic anhydride (MAPP) and silane-treated hemp fibers (HF) on morphology, thermal and mechanical properties of high-flow polypropylene (PP) modified with poly[styrene-b-(ethylene-co-butylene)-b-styrene] (SEBS) was studied in this paper. The addition of SEBS reduced the efficiency of MAPP in PP composites with HF, thus silane-treated fibers (HFs) were used to improve polymer–fiber interface. Thermal stability of HF was improved after silane treatment and less than 2% weight loss was observed at 240 °C in composites with 30 wt% HF. Better dispersion of fibers and better efficiency in enhancing static and dynamic mechanical properties of PP, doubling its strength and stiffness were observed in composites with treated fibers compared to untreated ones. High ability to absorb and dissipate energy and well-balanced strength and stiffness were showed by PP modified with SEBS and MAPP containing 30 wt% HFs. These composites were studied as an alternative to conventional PP/glass fibers composites for injection molding of small to medium auto parts.     

Highly thermally conductive POSS-g-SiCp/UHMWPE composites with excellent dielectric properties and thermal stabilities

Polyhedral oligomeric silsesquioxane grafting thermally conductive silicon carbide particle (POSS-g-SiCp) fillers, are performed to fabricate highly thermally conductive ultra high molecular weight polyethylene (UHMWPE) composites combining with optimal dielectric properties and excellent thermal stabilities, via mechanical ball milling followed by hot-pressing method. The POSS-g-SiCp/UHMWPE composite with 40 wt% POSS-g-SiCp exhibits relative higher thermal conductivity, lower dielectric constant and more excellent thermal stability, the corresponding thermally conductive coefficient of 1.135 W/mK, the dielectric constant of 3.22, and the 5 wt% thermal weight loss temperature of 423 °C, which holds potential for packaging and thermal management in microelectronic devices. Agari’s semi-empirical model fitting reveals POSS-g-SiCp fillers have strong ability to form continuous thermally conductive networks.     

Influence of the process parameters on the mechanical properties of engineering biocomposites using a twin-screw extruder

The utilization of bio-based engineering polymers as a matrix material for cellulosic fiber reinforced composites has become an important focus in materials research. This is due to a rising demand for sustainable materials from renewable resources. In addition to this aspect, the bio-based materials provide an advantage for lightweight applications with their lower density. In this investigation, the completely bio-based polyamide 10.10, with a melting point above 200 °C, was used as a polymer matrix. Chopped man-made cellulose fibers (Cordenka CR-Type) were investigated as reinforcement for use in injection molded applications. A co-rotating twin-screw extruder with a screw-diameter of 18 mm was used for compounding. It was verified that reinforcing polyamide 10.10 with 20 wt% and 30 wt% cellulosic fibers is possible, resulting in an increase of impact and tensile properties. Furthermore, it was shown that the temperatures and screw-configurations of the twin-screw extruder only result in different fiber length distributions but in minor differences of the morphological structure and mechanical properties of PA 10.10 with 20 wt% fibers. Compounds with 30 wt% cellulose fibers show significant higher impact properties that those with 30 wt% glass fibers.     

Improvement of ternary recycled polymer blend reinforced with date palm fibre

This paper investigates the study and preparation of date palm fibre reinforced recycled polymer blend composites. This is the first paper which describes the recycled polymer ternary blends of (1) recycled low density polyethylene (RLDPE), (2) recycled high density polyethylene (RHDPE) and (3) recycled polypropylene (RPP). The date palm fibre reinforced composites (C_D00) were prepared by maintaining constant weight% of fibre of 20 wt% without any fibre treatment. Maleic anhydride (MA) was used as the compatabilizer (1 and 2 wt%) and the effect of compatabilizer on the blend matrix composites was studied. The mechanical, thermal, morphological properties, water absorption and chemical resistance properties were evaluated for these composites and also studied for pure blend matrix (C₀₀). Date palm fibre improved the tensile strength and hardness of recycled polymer blend matrix. Further improvement was achieved with 1% MA (C_D1), which showed that 1% MA treated composites (C_D1) had higher tensile strength, modulus and hardness properties. Thermal stability and water absorption were improved by 1% MA. These improvements were demonstrated at the nanoscale level by the decrease in roughness appearing in Atomic Force Spectroscopic Microscopy analysis indicating that flow is better under this concentration. The SEM analysis also showed that the fibre matrix adhesion improved by adding 1 wt% (C_D1) of MA. The melting and crystallisation temperatures of the blends did not change with the addition of date palm fibre and MA, indicating that the additives did not influence the melting and crystallisation properties of the composites. The chemical resistance test results showed that these composites are resistance to all chemicals but more weight gain observed in solvents. 2 wt% of MA (C_D2) caused poor adhesion between the polymer chains and fibres as well as polymer chain scission.     

Micro-crack behavior of carbon fiber reinforced thermoplastic modified epoxy composites for cryogenic applications

Three different types of thermoplastics, poly(ether imide) (PEI), polycarbonate (PC), and poly(butylene terephthalate) (PBT) were used to modify epoxy for cryogenic applications. Carbon fiber reinforced thermoplastic modified epoxy composites were also prepared through vacuum-assisted resin transfer molding (RTM). Dynamic mechanical analysis (DMA) shows that the storage moduli of PEI, PC, and PBT modified epoxies are 30%, 21%, and 17% higher than that of the neat epoxy respectively. The impact strength of the modified epoxies at cryogenic temperature increases with increasing thermoplastic content up to 1.5 wt.% and then decreases for further loading (2.0 wt.%). The coefficient of thermal expansion (CTE) values of the PBT, PEI, and PC modified epoxies also decreased by 17.76%, 25.42%, and 30.15%, respectively, as compared with that of the neat epoxy. Optical microscopy image analysis suggests that the presence of PEI and PC in the carbon fiber reinforced epoxy composites can prevent the formation of micro-cracks. Therefore, both the PEI and PC were very effective in preventing micro-crack formation in the composites during thermal cycles at cryogenic condition due to their low CTE values and high impact strength.