Open access peer-reviewed chapter

Processing of Graphene/Elastomer Nanocomposites: A Minireview

Written By

Mohammed A. Sharaf and Andrzej Kloczkowski

Submitted: 16 March 2022 Reviewed: 07 April 2022 Published: 14 July 2022

DOI: 10.5772/intechopen.104849

From the Edited Volume

Nanocomposite Materials for Biomedical and Energy Storage Applications

Edited by Ashutosh Sharma

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Abstract

Since the isolation and identification of graphene, the academic and industrial communities are utilizing its superior properties. This minireview deals with the processing of graphene-based fillers/elastomer nanocomposites. The incorporation of graphene in an elastomeric matrices has significant effects on the properties of nanocomposites. The dispersion of graphene in elastomers is discussed. The processing of graphene/elastomer nanocomposites is discussed. The mechanical properties of the elastomeric matrix can be enhanced due to the presence of graphene. In this review and due to space limitations, we will present an example of improvements in the mechanical characteristics of graphene/styrene-butadiene (SBR) elastomer nanocomposites.

Keywords

  • elastomers; graphene-based filers; dispersion
  • interfacial interactions
  • mechanical characteristics
  • mechanical percolation

1. Introduction

1.1 Elastomers

Elastomers exhibit rubber-like behavior [1, 2, 3, 4]. They are characterized by weak intermolecular forces, ease of deformation at ambient temperatures, low modulus of elasticity, and can stretch to high ultimate strains. Also, elastomers manifest good heat resistance. To sum up, elastomers are characterized by: (i) their amorphous high molecular mass molecular chains that are randomly coiled; (ii) bonds in the elastomer molecules freely rotate or extend in response to any applied strain; (iii) glass transition temperature for elastomers ought to be lower than their service temperatures; and (iv) a low degree of vulcanization to control shape [1, 2, 3, 4].

Elastomers have low mechanical, thermal, and electrical conductivity properties. Compounding elastomeric materials with fillers results in composites with an average mix of properties of the original constituents. Owing to their properties and their low cost, they have established their niche in several technological applications that include automotive, aerospace, military, conveyor belts, packaging, healthcare, and numerous others.

Elastomers constitute the polymeric matrix in the production of elastomer-based nanocomposites that possess improved properties [5, 6, 7, 8, 9, 10, 11, 12]. On the other hand, elastomeric nanocomposites demand different preparative and processing procedures as compared with polymer-based nanocomposites. The process of their cross-linking is different and requires the use of an activator.

The incorporation of inorganic fillers such as silica nanoparticles, layered silicates (clay), carbon black, carbon nanotubes, and other nanomaterials results in the production of high-performance elastomeric nanocomposites [6, 13, 14, 15, 16, 17, 18]. The final properties of the nanocomposite are affected by the type of filler involved due to differences in their structural and geometrical characteristics.

1.2 Graphene

Graphene (GE) is 2D a carbon allotrope consisting of sp2 hybridized carbons, which are arranged in a honeycomb lattice [19, 20]. It is a single-atom-thick nanostructured sheet that is considered the basic building block for graphene-based fillers [21, 22, 23]. Because of its unique exceptional properties, graphene has emerged as a very promising nanomaterial. It is one of the strongest materials and a good conductor of heat and electricity; it is optically transparent and impermeable to gases [24, 25, 26]. In Figure 1, the graphene hexagonal honeycomb chemical structure is represented [27]. Some notable properties of graphene are listed in Table 1 [28].

Figure 1.

Graphene hexagonal honeycomb chemical structure and its remarkable physical properties. The black dots are carbon atoms [27].

PropertyExperimental valuesRefs.
Elastic modulus∼1 TPa[29]
Tensile strength∼130 GPa
Fatigue resistance109 cycles at mean stress of 71 GPa[30]
Thermal conductivity∼5300 W m−1 K−1[31]
Thermal stability∼2600 K[32]
Electrical conductivity6000 S cm−1[33]

Table 1.

Some notable properties of graphene [28].

Once the mass-produced graphene has qualities comparable to those produced in research laboratories, it will be of greater interest in applications [33, 34, 35]. However, there are still various barriers and risks to overcome [36].

Polymer nanocomposites reinforced by a single- and few-layer graphene have demonstrated significant improvements in various properties [37]. Another encouraging factor in the use of graphene in polymer nanocomposites is that it has been realized that a minute quantity of can leads to significant enhancements in properties, Undoubtedly, graphene is a favorite candidate for the use in nanocomposites. Emphasis will be given here to the techniques used in the preparation of graphene, elastomers, and nanocomposites, along with the physicochemical aspects and attributes reported and the applications of the final materials.

This chapter will be concerned with the processing and properties of graphene/elastomer nanocomposites.

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2. Some considerations concerning the processing graphene-based/elastomer nanocomposites

2.1 Filler dispersion

The efficient preparation of an elastomeric nanocomposite requires appropriate dispersion of the filler in the elastomeric matrix. Whence, there is a need for the filler and matrix to be compatible, physically and/or chemically. Most properties of nanocomposites depend on the nanofillers structure in the matrix. Therefore, such intimate nanofiller/elastomeric matrix interactions are dependent on the filler size, morphology, surface treatment, and activity. Undoubtedly, the fine dispersion of nanosized particles would lead to a very large interfacial area. Undoubtedly, the reinforcement changes with the specific interfacial area, for fillers with the same chemical nature [38, 39, 40]. As a result, the filler-matrix interactions and bonding will increase, in the meantime, the filler-filler interactions will decrease, and/or the platelet interlayer distance will increase [41, 42, 43, 44, 45]. They permit lower loadings, weight reduction of the fillers, and allow for the nanoparticles of ≤1 μm size the formation of a sort of colloidal suspensions. In the specific case of graphite-based fillers, because of the positive effect of aromatic rings, they would allow for the establishment of an intimate interaction between the nanofiller and the rubber matrix [40, 46, 47, 48]. One should note that elastomeric polymers possess high viscosity and thus necessitate intensive mixing and blending to achieve an even dispersion and distribution.

During the dispersive step, in the mixing process, large components undergo size reduction through erosion and rupture into smaller fragments that are then separated into the matrix [49, 50, 51]. These two last phases most likely happen rather simultaneously [49, 52]. Ideal dispersion of platelets-like (lamellar) nanofillers requires that all layers should be separated from each other, i.e., complete exfoliation. However, the strong interlayer interactions need to be circumvented, more often through intercalations to facilitate exfoliation [53, 54, 55].

Graphite is like montmorillonite clay (MMT), and researchers applied similar procedures for the dispersion of graphene-based fillers [56, 57, 58]. Intercalated and exfoliated compounds are in common usage. To reduce the strong p-p interactions between graphene platelets, graphene sheets are customarily surface-modified [56, 57, 58]. For the classification of graphene-based fillers, for example, a stack of few-layer graphene is called graphene nanoplatelets (GNP) [27, 59, 60].

Figure 2b is a representation of stacked, expanded, and exfoliated graphite platelets in an elastomeric matrix. Exfoliation of GNPs into an elastomer is desired to enhance the properties of the final material. Most exfoliation processes are performed in suspension rather than during bulk processing, during which, high shear is reported to break the platelets rather than exfoliate them [27, 59, 60].

2.2 Surface functionalization

For surface functionalization of graphene sheets, there is firstly a non-covalent and secondly a covalent approach. Non-covalent functionalization is primarily based on hydrophobic, van der Waals, and electrostatic interactions [61, 62, 63, 64, 65]. Covalent functionalization is dependent on the oxygen functional groups on the graphene surface. They can be utilized to change the surface functionality of graphene. The main functional groups are the carboxylic acid at the edges and epoxy and hydroxyl groups on the basal plane [66, 67, 68, 69].

A comprehensive summary of the functionalization of graphene has been reviewed in the literature [70, 71, 72, 73, 74].

2.3 Graphene-based fillers in the reinforcement of elastomer nanocomposites

Fillers have been employed as reinforcing agents for ages. Fillers, depending on their activity, can be categorized as extenders, which increase the volume of materials. On the one hand, reinforcing fillers leads to improve certain physical and mechanical properties. The reinforcing ability of fillers is dependent on the particle shape, size, agglomeration (dispersion), surface properties, and most importantly, the degree of interaction between the filler and the matrix.

2.3.1 Graphene oxide (GO) as a reinforcing filler

The research community focused attention on the field of polymer nanocomposites on graphene oxide (GO). This could be attributed to the variety of chemical functional groups available on the surface of GO that make it tunable, hydrophilic, and relatively low-cost as compared with pristine graphene. Its interaction with polar polymeric matrices is improved by the presence of such hydrophilic functional groups.

Improving the interfacial adhesion of GO and the host polymers through covalent bonding has been the subject of several studies [75, 76, 77]. Thus, GO becomes intertwined as a single phase with the host chains. In consequence, the superior properties of GO are transferred to the matrix, and thus improvements in the final properties of the composites will ensue. Various approaches have been explored for producing GO-polymer nanocomposites through covalent bonding [78, 79, 80, 81, 82, 83]. These methods normally involve the incorporation of thermally reduced GO (TrGO) [84, 85] or in situ chemically reduced GO (CrGO) in the rubber matrix [86, 87]. Homogeneity of TOGO in the rubber matrix is assisted by ultrasonication or high shear mixing. A strong polymer-filler interaction is critical for GO to act as a successful reinforcement agent [88, 89, 90, 91, 92]. For GO, the change in the degree of oxidation may significantly impact the physicochemical structure of the GO surface.

2.3.2 Other reinforcing fillers

Conventionally, the most widely used and effective conventional reinforcing filler for rubber is carbon black (CB). It provides a notable improvement in the properties of elastomers, in general. The drawback, in some cases, is when colored rubber compositions are needed. Due to its high specific surface area, silicon dioxide (SiO2) is known to be the most effective reinforcing non-black fillers. it is reported that about 90% of the worldwide production of CB is employed and applied in the tire industry, enhancing tear strength, modulus, and wear characteristics of the tires [93]. Recently, nanofillers have gained momentum both in fundamental and industrial fields. This is mainly due to the high specific surface area and quite often to their high aspect ratio that can be dispersed in the elastomeric matrix. There exist interactions at the molecular level between the elastomeric matrix and the nanofiller. As a result, extraordinary properties are achieved compared with conventional filler materials. Based on their dimensions in host matrices, nanofillers are classified into three categories: spherical nanoparticle fillers, elongated structure with only two dimensions is in the nanometer scale, and the third is larger, e.g., nanotubes and whiskers, and layered structures with only one dimension of the filler is in the nanometer scale, such as graphene that is the subject of our study. One notes that these nanofillers have a strong tendency to form aggregates and agglomerates, owing to their high surface energies.

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3. Mechanical characteristics

3.1 Effects of a covalent interphase

Many graphene-based polymer composites with significantly improved properties have been prepared and tested. Graphene with its possession of remarkable physical properties have been proposed as an efficient reinforcement agent for elastomers [94, 95, 96, 97, 98, 99, 100]. To make the best out of graphene in reinforcement, improved dispersion of graphene and higher interfacial interactions are important [101, 102, 103, 104].

Graphene oxide is efficiently reduced by tannin derivatives. At the same time, ortho-quinone derivatives produced during the reduction of graphene oxide are adsorbed on the graphene surface [105, 106]. The quinones are reactive toward thiols via Michael addition [107, 108]. Polythiols are usually produced during the sulfur-cure of an elastomer [108, 109]. The ortho-quinone derivatives are quite suitable for constructing covalent interphase cross-linking between graphene and the rubber matrix.

In a study by Yang et al. [106], graphene/styrene-butadiene rubber (SBR) nanocomposites were prepared by latex co-coagulation of SBR latex with a suspension of graphene. They pursued a strategy to construct a strong interface in graphene/SBR nanocomposites. The ortho-quinone covalent interphase was realized in the graphene/rubber system. The main feature was superior dispersion and controlled reinforcement properties with the quinone-modified graphene in the rubber matrix. In this nanocomposites system, the energy loss by a tire was lower compared with those for carbon black-filled elastomers. Figure 2 represents the manufacture of graphene/SBR nanocomposite and the mechanism of formation of covalent interphase between graphene and the SBR Matrix. The developed nanocomposites were applied to a dynamic elastomeric product, the auto tires. The very low rolling resistance coefficient is considered a great advancement in the production of tires.

Figure 2.

Fabrication of graphene/SBR nanocomposites and a schematic illustration of proposed formation mechanism of covalent interface between graphene and rubber matrix [109].

3.2 Mechanical behavior of a graphene/SBR nanocomposite

With the introduction of covalent interphase, the dispersion status of graphene in the rubber matrix and the interfacial interaction between graphene and SBR were remarkably enhanced. The stress-strain isotherms of SBR and SBR nanocomposites are illustrated in Figure 3. The effect of graphene on the mechanical properties of graphene/SBR nanocomposites is apparent. For purposes of comparison, a stress-strain isotherm of 10% graphite-filled SBR composite was also made. The presented results indicate much higher efficiency in the reinforcement of SBR. In Figure 4, the effect of graphene loading on the mechanical properties of the nanocomposites is demonstrated. Compared with the neat SBR, the tensile strength of graphene/SBR nanocomposites with only 1.1 phr of graphene has increased by 223%. With the incorporation of 5.6 phr of graphene, the tensile strength of the nanocomposite can reach 21.5 MPa, which is over ninefold that of the neat SBR. This is a marked enhancement in reinforcement compared with other 2D reinforcing fillers such as clay [110, 111, 112].

Figure 3.

Stress-strain curves of SBR/graphene nanocomposites [107].

Figure 4.

Tensile modulus and strength of graphene/SBR nanocomposites [107].

As an additional confirmation of reinforcement, a percolation phenomenon is observed in Figure 5 in the tensile strength with graphene loading, as has been reported earlier [106, 113, 114, 115, 116, 117, 118]. Although for CNT-filled composites, 0.001 wt% percolation concentrations have been reported. In other studies, 2 wt% concentrations are reported that depend on the processing, alignment, chemistry of the CNTs, and matrix compatibility [116, 117, 118].

Figure 5.

Percolation phenomena of SBR nanocomposites, the intersections of the dash lines represent the percolation point [107].

In what would be considered the first stage, below the percolation threshold volume fraction of graphene, the phenomenon could be explained by the rubber strengthening mechanism that graphite nanofillers induce the formation of straightened polymer chains during the stretching process [119]. In the second stage, when the distance between the fillers decreases to a specific threshold, chains attached to the adjacent fillers will form straightened rubber chains that will enhance and strengthen the rubber [119]. In Figure 5, the tensile stress of the composites could be observed to initially increase slightly and then shows an abrupt increase. The percolation point of graphene/SBR nanocomposite appears surprisingly at as low as 0.42 phr, which is far below that of CB/SBR composite (5.1 phr), as seen in Figure 5. The ultralow percolation threshold of graphene/SBR composites might be ascribed to the excellent dispersion of ultrathin graphene layers and the strong covalent interface. The different result obtained for graphene and carbon black (CB) in the reinforcement of SBR composites is evidence that graphene possesses significantly higher reinforcing efficiency toward SBR [106].

The effect of the presence of the nanostructures on the thermal stability of natural rubber was evaluated using thermogravimetric analysis (TGA). The results indicated that the presence of GO does not affect the thermal stability of the rubber [106, 119].

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4. Conclusions

Graphene-based fillers have features such as relatively high mechanical properties. They are incorporated as fillers in polymeric materials such as elastomers nanocomposites due to their pronounced differences in properties. Several parameters such as processing conditions that affect these enhancements were highlighted. Morphologies of the corresponding nanocomposites were observed to be affected by processing. One of the major challenges concerning graphene is the industrial-scale production of inexpensive graphene-based nanocomposites. This would require newer processing techniques able to prepare low-thickness stacks with higher specific areas. A crucial aspect that we addressed is the better dispersion of graphene-based fillers in an elastomeric matrix. Covalent functionalization of graphene-based sheets proved to be indeed significant in the improvement of the interfacial filler dispersion and its exfoliation in the matrix. That is why other efforts should be made to exploit graphene-based fillers at the nanoscale by creating a nanostructural organization of graphene sheets that would ensure a lower percolation threshold and consequently more pronounced enhancement in reinforcement.

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Written By

Mohammed A. Sharaf and Andrzej Kloczkowski

Submitted: 16 March 2022 Reviewed: 07 April 2022 Published: 14 July 2022