Covalently bonded interfaces for polymer/graphene composites

The interface is well known for taking a critical role in the determination of the functional and mechanical properties of polymer composites. Previous interface research has focused on utilising reduced graphene oxide that is limited by a low structural integrity, which means a high fraction is needed to produce electrically conductive composites. By using 4,40-diaminophenylsulfone, we in this study chemically modified high-structural integrity graphene platelets (GnPs) of 2–4 nm in thickness, covalently bonded GnPs with an epoxy matrix, and investigated the morphology and functional and mechanical performance of these composites. This covalently bonded interface prevented GnPs stacking in the matrix. In comparison with unmodified composites showing no reduction in electrical volume resistivity, the interface-modified composite at 0.489 vol% GnPs demonstrates an eight-order reduction in the resistivity, a 47.7% further improvement in modulus and 84.6% in fracture energy release rate. Comparison of GnPs with clay and multi-walled carbon nanotubes shows that our GnPs are more advantageous in terms of performance and cost. This study provides a novel method for developing interface-tuned polymer/graphene composites

Improvement of adhesive toughness measurement

The double cantilever beam (DCB) method for adhesive toughness measurement was improved by incorporating a sufficiently sharp crack made by a wedge-tapping method. A known route to producing cracks via loading–unloading cycles was proved unreliable because the cycles produced plastic deformation in the adhesive where new cracks propagated. Abnormally high toughness values with large standard deviations were obtained with cracks made by embedding a non-sticky insert. Only instantly propagated cracks made by tapping were sufficiently sharp to produce reproducible, accurate tough-ness measurements. However, toughened resin was insensit

Development of polymer composites using modified, high-structural integrity graphene platelets

Previous studies on polymer/graphene composites have mainly utilized either reduced graphene oxide or graphite nanoplatelets of over 10 nm in thickness. In this study we covalently modified 3-nm thick graphene platelets (GnPs) by the reaction between the GnPs’ epoxide groups and the end-amine groups of a commercial long-chain surfactant (Mw = 2000), compounded the modified GnPs (m-GnPs) with a model polymer epoxy, and investigated the structure and properties of both m-GnPs and their epoxy composites. A low Raman ID/IG ratio of 0.13 was found for m-GnPs corresponding to high structural integ-rity. A percolation threshold of electrical conductivity was observed at 0.32 vol% m-GnPs, and the 0.98 vol% m-GnPs improved the Young’s modulus, fracture energy release rate and glass transition tem-perature of epoxy by 14%, 387% and 13%, respectively. These significantly improved properties are cred-ited to: (i) the low Raman ID/IG ratio of GnPs, maximizing the structural integrity and thus conductivity, stiffness and strength inherited from its sister graphene, (ii) the low thickness of GnPs, minimizing the damaging effect of the poor through-plane mechanical properties and electrical conductivity of graphene,(iii) the high-molecular weight surfactant, leading to uniformly dispersed GnPs in the matrix, and (iv) a covalently bonded interface between m-GnPs and matrix, more effectively transferring load/electron across interface

Melt compounding with graphene to develop functional, high-performance elastomers

Rather than using graphene oxide, which is limited by a high defect concentration and cost due to oxidation and reduction, we adopted cost-effective, 3.56 nm thick graphene platelets (GnPs) of high structural integrity to melt compound with an elastomer—ethylene–propylene–diene monomer rubber (EPDM)—using an industrial facility. An elastomer is an amorphous, chemically crosslinked polymer generally having rather low modulus and fracture strength but high fracture strain in comparison with other materials; and upon removal of loading, it is able to return to its original geometry, immediately and completely. It was found that most GnPs dispersed uniformly in the elastomer matrix, although some did form clusters. A percolation threshold of electrical conductivity at 18 vol% GnPs was observed and the elastomer thermal conductivity increased by 417% at 45 vol% GnPs. The modulus and tensile strength increased by 710% and 404% at 26.7 vol% GnPs, respectively. The modulus improvement agrees well with the Guth and Halpin-Tsai models. The reinforcing effect of GnPs was compared with silicate layers and carbon nanotube. Our simple fabrication would prolong the service life of elastomeric products used in dynamic loading, thus reducing thermosetting waste in the environment

Melt compounding with graphene to develop functional, high-performance elastomers

Rather than using graphene oxide, which is limited by a high defect concentration and cost due to oxidation and reduction, we adopted cost-effective, 3.56 nm thick graphene platelets (GnPs) of high structural integrity to melt compound with an elastomer—ethylene–propylene–diene monomer rubber (EPDM)—using an industrial facility. An elastomer is an amorphous, chemically crosslinked polymer generally having rather low modulus and fracture strength but high fracture strain in comparison with other materials; and upon removal of loading, it is able to return to its original geometry, immediately and completely. It was found that most GnPs dispersed uniformly in the elastomer matrix, although some did form clusters. A percolation threshold of electrical conductivity at 18 vol% GnPs was observed and the elastomer thermal conductivity increased by 417% at 45 vol% GnPs. The modulus and tensile strength increased by 710% and 404% at 26.7 vol% GnPs, respectively. The modulus improvement agrees well with the Guth and Halpin-Tsai models. The reinforcing effect of GnPs was compared with silicate layers and carbon nanotube. Our simple fabrication would prolong the service life of elastomeric products used in dynamic loading, thus reducing thermosetting waste in the environment

Interface-tuned epoxy/clay nanocomposites

Though interface has been known for a critical role in determining the properties of conventional composites, its role in polymer nanocomposites is still fragmented and in its infancy. This study synthesized a series of epoxy/clay nanocomposites with different interface strength by using three types of modifiers: ethanolamine (denoted ETH), Jeffamine� M2070 (M27) and Jeffamine� XTJ502 (XTJ). XTJ created a strong interface between clay layers and matrix because it bridged the layers with matrix by a chemical reaction as proved by Fourier transform infrared spectroscopy; M27 produced an interme-diate interface strength due to the molecular entanglement between grafted M27 chains and matrix molecules; the interface made by ETH was weak because neither chemical bridging nor molecular entanglement was involved. The studies of mechanical and thermal properties and morphology at a wide range of magnification show that the strong interface promoted the highest level of exfoliation and dispersion of clay layers, and achieved the most increment in Young’s modulus, fracture toughness and glass transition temperature (Tg) of matrix. With w1.3 wt% clay, the critical strain energy release rate G1c of neat epoxy improved from 179.0 to 384.7 J/m, 115% improvement and Tg enhanced from 93.7 to 99.

Structure-property relations of 55nm particle-toughened epoxy

55-nm rubber particles significantly toughened two epoxy systems without loss of Young’s modulus, tensile strength and glass transition temperature. Transmission Electron Microscopy (TEM) showed that the nanoparticles are uniformly dispersed in matrix and have blurred interface with epoxy. 5 wt% rubber nanoparticles increased the critical strain energy release rate (G1c) of Jeffamine D230 (J230)-cured epoxy from 175 J/m2 to 1710 J/m2 , while the 10 wt% increased G1c of diaminodiphenyl sulfone (DDS)-cured epoxy from 73 J/m2 to 696 J/m2 . This is explained by comparing the surface–surface interparticle distance and total particle surface of nanocomposites with those of composites. The higher the matrix stiffness, the more nanoparticles needed for toughening. Although the 10 wt% J230-cured nanocomposite showed a 50% larger size of stress-whitened zone than the 5 wt% J230-cured nanocomposite, the 5 wt% nano- composite showed a higher toughness. These nanoparticles were found to pose barriers to the vibration of crosslinked matrix molecules, leading to higher glass transition temperatures. While the matrix shear banding caused by nanoparticle expansion and growth is the major toughening mechanism for the J230- cured nanocomposites, the matrix plastic void growth and deformation are most probably the major mechanisms for the DDS-cured system. Under tensile loading, the nanoparticles in the DDS-cured epoxy created fibrils of 100e200 nm in diameter and 3e5 mm in length. TEM analysis in front of a subcritically propagated crack tip showed a number of voids of 30e500 nm in diameter in the vicinity of the crack, implying that rubber nanoparticles expanded, grew and deformed under loading. Unlike conventional epoxy/rubber composites in which all of the rubber particles in the crack front cavitated under loading, only a portion of the nanoparticles in this study expanded to create voids. Huang and Kinloch’s model developed from composites was found not fit well into these nanocomposites

From carbon nanotubes and silicate layers to graphene platelets for polymer nanocomposites

In spite of extensive studies conducted on carbon nanotubes and silicate layers for their polymer-based nanocomposites, the rise of graphene now provides a more promising candidate due to its exceptionally high mechanical performance and electrical and thermal conductivities. The present study developed a facile approach to fabricate epoxy–graphene nanocomposites by thermally expanding a commercial product followed by ultrasonication and solution-compounding with epoxy, and investigated their morphologies, mechanical properties, electrical conductivity and thermal mechanical behaviour. Graphene platelets (GnPs) of 3.5

A facile approach to chemically modified graphene and its polymer nanocomposites

A scalable approach for the mass production of chemically modifi ed graphene has yet to be developed, which holds the key to the large-scale production of stable graphene colloids for optical electronics, energy conversion, and storage materials, catalysis, sensors, composites, etc. Here, a facile approach to fabricating covalently modifi ed graphene and its polymer nanocompos- ites is presented. The method involves: i) employing a common furnace, rather than a furnace installed with a quartz tube and operated in inert gas as required in previous studies, to treat a commercial graphite intercalation compound with thermal shocking and ultrasonication and fabricate graphene platelets (GnPs) with a thickness of 2.51 ± 0.39 nm that contain only 7 at% oxygen; ii) grafting these GnPs with a commercial, long-chain surfactant, which is able to create molecular entanglement with polymer matrixes by taking advantage of the reactions between the epoxide groups of the platelets and the end amine groups of the surfactant, to produce chemically modi- fi ed graphene platelets ( m - GnPs); and iii) solution-mixing m -GnPs with a commonly used polymer to fabricate nanocomposites. These m -GnPs are well dispersed in a polymer with highly improved mechanical properties and a low percolation threshold of electrical conductivity at 0.25 vol%. This novel approach could lead to the future scalable production of graphene and its nanocomposites

Interface modification of clay and graphene platelets reinforced epoxy nanocomposites: a comparative study

The interface between the matrix phase and dispersed phase of a composite plays a critical role in influencing its properties. However, the intricate mecha-nisms of interface are not fully understood, and polymer nanocomposites are no exception. This study compares the fabrication, morphology, and mechanical and thermal properties of epoxy nanocomposites tuned by clay layers (denoted as m-clay) and graphene platelets (denoted as m-GP). It was found that a chemical modification, layer expansion and dispersion of filler within the epoxy matrix resulted in an improved interface between the filler mate-rial and epoxy matrix. This was confirmed by Fourier transform infrared spectroscopy and transmission electron microscope. The enhanced interface led to improved mechanical properties (i.e. stiffness modulus, fracture toughness) and higher glass transition temperatures (Tg) compared with neat epoxy. At 4 wt% m-GP, the critical strain energy release rate G1c of neat epoxy improved by 240 % from 179.1 to 608.6 J/m2 and Tg increased from 93.7 to 106.4 �C. In contrast to m-clay, which at 4 wt%, only improved the G1c by 45 % and Tg by 7.1 %. The higher level of improvement offered by m-GP is attributed to the strong interaction of graphene sheets with epoxy because the covalent bonds between the carbon atoms of graphene sheets are much stronger than silicon-based clay