Temperature effects on the fracture behavior and tensile properties of silane-treated clay/epoxy nanocomposites

We investigated the effects of clay silane treatment on the fracture behaviors of clay/epoxy nanocomposites by comparing the compliance, critical fracture load, and fracture toughness of silane-treated samples with those of untreated samples. The fracture toughnesses of untreated and silane-treated clay/epoxy nanocomposites were 8.52 J/m² and 15.55 J/m², respectively, corresponding to an 82% increase in fracture toughness after clay silane treatment. Tensile tests were performed at ?30 °C, 25 °C, 40 °C, and 70 °C. Tensile strength and elastic modulus were higher at ?30 °C than at 25 °C for both samples. However, the tensile properties decreased as temperature increased for both samples. In particular, at 70 °C, the tensile properties were less than 10% of the original value at room temperature, independent of surface treatment. The fracture and tensile properties of silane-treated clay/epoxy nanocomposites increased due to good dispersion of the clay in epoxy and improvement in interfacial adhesive strength between epoxy and clay layers.     

Mechanical performance of epoxy matrix hybrid nanocomposites containing carbon nanotubes and nanodiamonds

A novel class of epoxy matrix hybrid nanocomposites has been developed containing multiwalled carbon nanotubes (MWCNTs) and nanodiamonds (NDs) to explore the combined effect of nanoreinforcements on the mechanical performance of nanocomposites. Both the nanofillers were functionalized before incorporating into epoxy matrix to promote interfacial interactions. The concentrations of both MWCNTs and NDs in the nanocomposites were increased systematically, i.e. 0.05 wt.%, 0.1 wt.% and 0.2 wt.% while composites containing individual nanoreinforcements were also manufactured for comparison. The developed nanocomposites were characterized microstructurally by scanning electron microscopy (SEM) and mechanically by tensile, flexural, impact and hardness tests. Homogeneous dispersion of MWCNTs and NDs was observed under SEM, which resulted in the enhancement of mechanical properties of nanocomposites. The composites containing 0.2 wt.% MWCNTs and 0.2 wt.% NDs showed 50% increase in hardness while tensile strength and modulus enhanced to 70% and 84%, respectively. Flexural strength and modulus also showed a rise of 104% and 56%, respectively. Interestingly, fracture strain also increased in both the tensile and flexural testing. The impact resistance increased to 161% showing a significant improvement in the toughness of hybrid nanocomposites.     

Synergetic effect of thermal conductive properties of epoxy composites containing functionalized multi-walled carbon nanotubes and aluminum nitride

This study investigates the thermal conductivity of epoxy composites containing two hybrid fillers which are multi-walled carbon nanotubes (MWCNTs) and aluminum nitride (AlN). To form a covalent bonds between the fillers and the epoxy resin, poly(glycidyl methacrylate) (PGMA) were grafted onto the surface of nano-sized MWCNTs via free radical polymerization and micro-sized AlN was modified by zirconate coupling agent. Results show that functionalized fillers improve thermal conductivity of epoxy composites, due to the good dispersion and interfacial adhesion, which is confirmed by scanning electron microscope. Furthermore, the hybrid fillers provide synergetic effect on heat conductive networks. The thermal conductivity of epoxy composites containing 25 vol.% modified AlN and 1 vol.% functionalized MWCNTs is 1.21 W/mK, comparable to that of epoxy composites containing 50 vol.% untreated AlN (1.25 W/mK), which can reduce the half quantity of AlN filler used.     

Methoxypolyethylene glycol functionalized carbon nanotube composites with high permittivity and low dielectric loss

High relative permittivity and low dielectric loss were simultaneously achieved in the percolative nanocomposites with methoxypolyethylene glycol (mPEG) modified multi-walled carbon nanotubes (MWCNTs). The dense mPEG layer with a thickness of approximately 1.7 nm was continuously coated on the surface of MWCNTs. MWCNTs exhibited excellent dispersibility after being functionalized by mPEG (mPEG@MWCNTs), the mPEG@MWCNTs/ethanol suspension was still turbid even when the suspension was deposited for two months. A high permittivity of 69.7 and a low dielectric loss of 0.042 were simultaneously achieved in the poly(vinylidene fluoride-co-hexafluoropropylene) (P(VDF-HFP)) nanocomposite with 4.02 vol% mPEG@MWCNTs at 1 kHz. The improved dielectric properties in the nanocomposite is mainly ascribed to the following reasons: (i) the increased microcapacitors formed by MWCNTs and insulated dielectric composite; (ii) the enhanced interfacial polarization due to the homogeneous dispersion of mPEG@MWCNTs in the nanocomposites and tight adhesion between mPEG@MWCNTs and P(VDF-HFP) matrix.     

Oxygen plasma processing and improved interfacial adhesion in PBO fiber reinforced epoxy composites

The effects of oxygen plasma processing on the improved interfacial adhesion properties of poly(1,4-phenylene-cis-benzobisoxazole) (PBO) fiber reinforced epoxy composites have been investigated in this paper. Both As-spun (AS) and high-modulus (HM) PBO fiber systems were studied. The characterization techniques included microscopy, surface analysis, and composite interfacial adhesion tests. The results showed that the high-modulus fiber surface free energy could be increased significantly by 42.2% from 46.2 to 65.7 mJ/m², while the tensile strength was only slightly decreased by 3.4% from 5.87 to 5.67 GPa. In addition, the interfacial adhesion strength of PBO fiber reinforced epoxy composite was improved by 37.5% from 32.5 to 44.7 MPa for the HM fiber system. The improvement has been attributed to the enhanced cohesive failure that dissipated more fracture energy.     

Montmorillonite/polypyrrole nanocomposites. The effect of organic modification of clay on the chemical and electrical properties

Montmorillonite/polypyrrole (MMT/PPy) nanocomposites, with 15% mass loading of PPy, were prepared by the in situ polymerization of pyrrole in the presence of montmorillonite (MMT) or organo-modified montmorillonite (oMMT) in aqueous solutions containing an oxidant and an anionic surfactant. The morphology of MMT/PPy nanocomposites distinctly differs from that of the untreated MMT as shown by SEM. X-ray photoelectron spectroscopy showed that the MMT/PPy nanocomposite has an MMT-rich surface, whereas the oMMT/PPy nanocomposite surface has a rather organic nature. Due to the organic modification of MMT by the alkylammonium chloride, polymerization of pyrrole at the surface of oMMT is much more efficient in producing a conductive adlayer resulting in an enhancement of conductivity of the oMMT/PPy nanocomposites (1.1 S cm^− 1) compared to MMT/PPy (3.1 × 10^− 2 S cm^− 1). The difference in the behaviour of oMMT/PPy and MMT/PPy is interpreted in terms of surface energy minimization by the alkylammonium ions present at the surface of organo-modified MMT. Indeed, the dispersive contribution to the surface energy (γ_s^d), as determined by inverse gas chromatography at 150 °C, was estimated to be 34.0 mJ/m² for oMMT, much lower than the value of 216 mJ/m² determined for MMT.     

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).     

Reduction of thermal residual stresses of laminated polymer composites by addition of carbon nanotubes

This paper studies the effects of multi-walled carbon nanotubes (MWCNTs) on the thermal residual stresses in polymeric fibrous composites. Reinforced ML-506 epoxy nanocomposites with different amounts of homogeneously dispersed MWCNTs (0.1 wt.%, 0.5 wt.% and 1 wt.%) were fabricated using the sonication technique. Thermo-mechanical analysis and tensile tests of the specimens were carried out to characterize the thermal and mechanical properties of MWCNTs/epoxy composites. Due to the negative thermal expansion and high modulus of MWCNTs, addition of MWCNTs resulted in a great reduction of the coefficient of thermal expansion (CTE) of epoxy. The MWCNTs also moderately increased the Young’s modulus of the epoxy. Then, the effects of adding MWCNTs on micro and macro-residual stresses in carbon fiber (CF)/epoxy laminated composites were investigated using the energy method and the classical lamination theory (CLT), respectively. The results indicated that the addition of low amounts of MWCNTs leads to a considerable reduction in thermal residual stress components in both micro and macro levels.     

Surface structural changes,surface energy and antiwear properties of polytetrafluoroethylene induced by proton irradiation

In this work, the polytetrafluoroethylene (PTFE) surface was modified with 25 keV proton beam irradiation in vacuum condition. Multiple characterization techniques including X-ray photoelectron spectroscopy, Raman spectroscopy and infrared spectroscopy were employed for research on microstructure changes in the PTFE surface. The changes in the surface energy and antiwear properties of PTFE were evaluated using contact angle analysis and a ball-on-disk tribometer, respectively. Experimental results showed that the surface energy of PTFE obviously increased from 13.17 mJ/m² to 33.73 mJ/m² and the wear rate decreased from 8.9 × 10^− 3 mm³/Nm to 5.8 × 10^− 4 mm³/Nm after proton irradiation for 15 min. Moreover, TRIM simulation indicated that the H⁺ ions cannot penetrate through the PTFE block and only stop at a depth of about 730 nm from the material surface. Proton irradiation has been proved to be a simple, rapid and effective measure for the surface modification of PTFE with distinctly improved surface energy and antiwear properties, and the possible reaction mechanism taking place in PTFE was also discussed in this paper.     

Synergistic flame retardancy effect of graphene nanosheets and traditional retardants on epoxy resin

Novel non-toxic halogen-free flame retardants are replacing traditional flame retardants in polymer and polymer matrix composite structures. In this study, graphene nanosheet (GNS) is investigated in combination with traditional layered double hydroxide (LDH), layered rare-earth hydroxide (LRH), and phosphorus-based flame retardant (DOPO) to enhance the flame retardancy of epoxy resin. A synergistic flame retardancy effect is achieved in GNS/LDH and GNS/DOPO systems where combined GNS and LDH increased the viscosity of the epoxy melt, and limited the flame propagation through inhibition of dripping. The limiting oxygen index of epoxy increased from 15.9 to 23.6 with addition of 0.5 wt.% each of GNS and LDH. With the addition of 2.5 wt.% of both GNS and LDH, the total heat release of epoxy resin also reduced from 33.4 MJ/m² to 24.6 MJ/m². The synergistic effect of GNS and DOPO adopted a different mechanism. The addition of 2.5 wt.% of GNS and DOPO reduced the peak heat release rate from 1194 kW/m² to 396 kW/m², and the total heat release rate from 72.5 MJ/m² to 48.1 MJ/m². The synergistic mechanisms of the flame retardants were closely analyzed and correlated with the flame retardant properties.     

Potentiometric urea biosensor based on multi-walled carbon nanotubes (MWCNTs)/silica composite material

A novel potentiometric urea biosensor has been fabricated with urease (Urs) immobilized multi-walled carbon nanotubes (MWCNTs) embedded in silica matrix deposited on the surface of indium tin oxide (ITO) coated glass plate. The enzyme Urs was covalently linked with the exposed free –COOH groups of functionalized MWCNTs (F-MWCNTs), which are subsequently incorporated within the silica matrix by sol–gel method. The Urs/MWCNTs/SiO₂/ITO composite modified electrode was characterized by Fourier transform infrared (FTIR) spectroscopy, thermal gravimetric analysis (TGA) and UV–visible spectroscopy. The morphologies and electrochemical performance of the modified Urs/MWCNTs/SiO₂/ITO electrode have been investigated by scanning electron microscopy (SEM) and potentiometric method, respectively. The synergistic effect of silica matrix, F-MWCNTs and biocompatibility of Urs/MWCNTs/SiO₂ made the biosensor to have the excellent electro catalytic activity and high stability. The resulting biosensor exhibits a good response performance to urea detection with a wide linear range from 2.18 × 10^? 5 to 1.07 × 10^? 3 M urea. The biosensor shows a short response time of 10–25 s and a high sensitivity of 23 mV/decade/cm².     

Fabrication and characterization of a zirconia/multi-walled carbon nanotube mesoporous composite

A zirconia/multi-walled carbon nanotube (ZrO₂/MWCNT) mesoporous composite was fabricated via a simple method using a hydrothermal process with the aid of the cationic surfactant cetyltrimethylammonium bromide (CTAB). Transmission electron microscopy (TEM), N₂ adsorption–desorption, Fourier transform infrared spectroscopy (FT-IR) and X-ray diffraction (XRD) techniques were used to characterize the as-made samples. The cubic ZrO₂ nanocrystallites were observed to overlay the surface of MWCNTs, which resulted in the formation of a novel mesoporous–nanotube composite. On the basis of a TEM analysis of the products from controlled experiment, the role of the acid-treated MWCNTs and CTAB was proposed to explain the formation of the mesoporous–nanotube structure. The as-made composite possessed novel properties, such as a high surface area (312 m² · g^? 1) and a bimodal mesoporous structure (3.18 nm and 12.4 nm). It was concluded that this composite has important application value due to its one-dimensional hollow structure, excellent electric conductivity and large surface area.     

An investigation on post-fire behavior of hybrid nanocomposites under bending loads

This work focuses on residual bending properties of hybrid nanocomposites after intense heat conditions. Carbon fiber/epoxy-nanoclay and carbon fiber/epoxy-graphene nanosheets were manufactured. The nanoparticles employed were Cloisite 30B nanoclay and surface modified graphene nanosheets. The epoxy system was RemLam M/HY956. For short beam samples exposed to 800 KW/m² heat flux, for a various period of time up to 120 s, the addition of nanoparticles (nanoclay and graphene nanosheets) increased the unburned thickness from 0.16 mm (original) to 2.63 mm and 2.74 mm, respectively. When the two-dimensional (plates) samples were tested, the improvement on heat performance was reduced. The unburned thickness improved close to 10% with the presence of nanoclay. The addition of graphene nanosheets leads to a decrease in unburned thickness of 12.8%. This result can be due to the good thermal protection properties of the graphene nanosheets. Using SEM analysis, it was observed that when the hybrid nanocomposites were subjected to a large heat flux, nanoparticles remained trapped inside the char layers. Finally, the proposed model seems to overestimate the residual bending response by 8%.     

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.     

Effect of chemical functionalization of multi-walled carbon nanotubes with 3-aminopropyltriethoxysilane on mechanical and morphological properties of epoxy nanocomposites

Nanocomposites based on epoxy resin and different weight percentages of unmodified, oxidized, and silanized multi-walled carbon nanotubes (MWCNTs) were prepared by cast molding method. Effects of MWCNTs content on the flexural properties were examined. The results showed that as the loading of the MWCNTs increased, improved flexural strength and flexural modulus were observed. The mechanical properties decreased when the MWCNTs content exceeded 0.2 wt.% due to agglomeration of MWCNTs. These results prove the effect of functionalization on the interfacial adhesion between epoxy and MWCNTs. This was further confirmed by morphology study of fractured surfaces of nanocomposites by SEM and TEM.     

Facile preparation,characterization and performance of noncovalently functionalized graphene/epoxy nanocomposites with poly(sodium 4-styrenesulfonate)

Graphene was noncovalently functionalized with poly(sodium 4-styrenesulfonate) (PSS) and then successfully incorporated into the epoxy resin via in situ polymerization to form functional and structural nanocomposites. The morphology and structure of PSS modified graphene (PSS-g) were characterized with transmission electron microscopy, X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy. The effects of PSS-g additions on tensile, electrical and thermal properties of the epoxy/graphene nanocomposites were studied. Noncovalent functionalization improved interfacial bonding between the epoxy matrix and graphene, leading to enhanced tensile strength and modulus of resultant nanocomposites. The PSS-g additions also enhanced electrical properties of the epoxy/PSS-g nanocomposites, resulting in a lower percolation threshold of 1.2 wt%. Thermogravimetric and differential scanning calorimetric results showed the occurrence of a two-step decomposition process for the epoxy/PSS-g nanocomposites.     

Thermally reduced graphene oxide acting as a trap for multiwall carbon nanotubes in bi-filler epoxy composites

The effect of thermally reduced graphene oxide (TRGO) on the electrical percolation threshold of multi wall carbon nanotube (MWCNT)/epoxy cured composites is studied along with their combined rheological/electrical behavior in their suspension state. In contrast to MWCNT and carbon black (CB) based epoxy composites, there is no prominent percolation threshold for the bi-filler (TRGO–MWCNT/epoxy) composite. Furthermore, the electrical conductivity of the bi-filler composite is two orders of magnitude lower (∼1 × 10⁻⁵ S/m) than the pristine MWCNT/epoxy composites (∼1 × 10⁻³ S/m). This result is primarily due to the strong interaction between TRGO and MWCNTs. Optical micrographs of the suspension and scanning electron micrographs of the cured composites indicate trapping of MWCNTs onto TRGO sheets. A morphological model describing this interaction is presented.     

Improving the mechanical properties of epoxy using multiwalled carbon nanotubes functionalized by a novel plasma treatment

Achieving both uniform dispersion and good interfacial adhesion have been long-term challenges in optimizing the properties of carbon nanotube reinforced polymer nanocomposites. A novel and effective plasma method, which combines continuous and pulsed plasma modes in a nitrogen and hydrogen gas mixture (15% H₂), has been developed to better meet this need. It has yielded high levels of primary amines on the surface of multiwalled carbon nanotubes which improved their dispersion and interfacial bonding with an epoxy resin. By adding just 0.1 wt% of these nanotubes to Bisphenol F epoxy resin, the mechanical properties of the nanocomposites, from nano to macro, were significantly improved. Nanoindentation tests showed that the hardness and elastic modulus increased by 40% and 19%, respectively, using the functionalized nanotubes. Macro-mechanical properties from thermo-mechanical and flexural analysis were also enhanced, with a nearly 40% improvement in toughness.     

Effect of surface functionalization on mechanical properties and decomposition kinetics of high performance polyetherimide/MWCNT nano composites

In this investigation, Polyetherimide (PEI) reinforced with multi-walled carbon nanotube (MWCNT) using novel melt blending technique. Surface of MWCNTs are modified by acid treatment as well as by plasma treatment. PEI nano composites with 2 wt% treated MWCNT shows about 15% improvement in mechanical properties when compared to unfilled PEI. The thermal decomposition kinetics of PEI/MWCNT nano composites has been critically analyzed by using Coats – Redfern model. The increase in activation energy for thermal degradation by 699 kJ/mol for 2 wt% MWCNT implies improvement in the thermal properties of PEI. Studies under Fourier Transform Infrared Spectroscopy (FTIR) and Transmission Electron Microscopy (TEM) depict significant interfacial adhesion with uniform dispersion of MWCNT in polymer matrix due to surface functionalization. 0.5 wt% chemically modified MWCNT shows typical alignment of MWCNT. There is a significant improvement in mechanical properties and thermal properties for surface functionalized MWCNT reinforced.     

Comparison of carbon nanofiller-based polymer composite adhesives and pastes for thermal interface applications

Graphite nanoplatelets (GNP), carbon black (CB) and carbon nanotubes are extensively researched to produce thermal interface materials (TIMs). This work reports comparison of interfacial thermal conductance (ITC) of carbon nanofiller-based polymer composite adhesives and pastes. The results show that total thermal contact resistance (TTCR) of GNP/rubbery epoxy composite was the same as that of an equivalent glassy epoxy composite. Although CB-based rubbery epoxy and silicone composites can be applied as thin bondlines, their TTCRs were significantly higher than GNP/rubbery epoxy. GNP incorporation into CB/rubbery epoxy composite improves the ITC of the CB/rubbery epoxy composites but the performance of CB/GNP/rubbery epoxy was inferior to GNP/rubbery epoxy. The thermal paste of GNP/polyetheramine had TTCR of 4.8 × 10^− 6 m²·K/W which is comparable to commercial TIM-paste. The paste produced with silicone had relatively poor ITC versus that prepared with polyetheramine. The paste having smaller particle sized GNPs offers lower TTCR than that prepared with large sized GNPs. The GNP/rubbery epoxy adhesives produced from precursor pastes gave the lowest TTCRs in comparison with the other adhesives. This study suggests that GNPs offer potential for enhancing ITC of TIMs and that ITC of adhesives depends on fillers' thermal conductivity and their interfacial contact with substrates.