3.3.1. Mechanical Testing Results of EPDM/GnPs Composites
The values from the testing of mechanical properties (Young’s modulus, strain at break, stress at tensile strength, M100, and M300) on GnP loadings for EPDM-based composites are provided in
Table S3. As expected, except for the samples reinforced with G4, the Young’s modulus of EPDM/GnPs composites increases linearly with increasing GnPs loading compared to the unfilled EPDM. This increase can be attributed to the higher Young’s modulus, good dispersion, and high aspect ratio of GnPs, and good interfacial adhesion of the filler and matrix. The inclusion of the filler into the matrix can restrict the mobility of polymer chains and increase the crosslink ratio [
44]. Within the experimental range of filler loading, the EPDM-based composites including G4 exhibit lower Young’s modulus values than the unfilled EPDM. This can be attributed to the agglomeration form of G4 (
Figure 3d) and the worse dispersion of G4 (
Figure 4d) into the EPDM matrix. The agglomeration can lead to defects in the composites.
The Young’s modulus of composites increases from 1.61 MPa for the unfilled EPDM to 4.12, 3.53, and 3.73 MPa for the EPDM/G1, EPDM/G2, and EPDM/G3 composites, respectively, and decreases to 0.87 MPa for the EPDM/G4 composites when GnPs content increases from 0 to 20 phr. An increase in Young’s modulus is more noticeable for the EPDM/G1 composites compared to others. This may be due to better dispersion of G1 in the EPDM matrix. When compared in terms of specific surface area, GnPs with lower specific surface area (170 m2/g) give better results than ones with higher (800 m2/g). The reason is the agglomeration of filler with a higher surface area due to higher surface energy because of its smaller dimension. Based on the results, for a fixed specific surface area, Young’s modulus is dependent on the lateral size of GNPs, GnPs with a larger lateral size achieve a higher value of Young’s modulus above 7 phr of GnPs. Up to this concentration, there is no appreciable difference in the values of Young’s modulus among the EPDM/G1, EPDM/G2, and EPDM/G3 composites.
The values of mechanical properties, namely tensile stress, strain at break, as well as moduli M100 and M300 for vulcanizates of EPDM filled with various concentrations of each GnPs are shown in
Figure 7. It is seen that while the concentration dependencies for G1, G2, and G3 are similar or even for some parameters almost identical (e.g., strain at break,
Figure 7b), the dependencies for the G4 substantially differ. Both tensile stress and strain at break are close to double values compared to the three other GnPs, while the values for moduli M100 and M300 are significantly lower for EPDM filled with G4. Surprisingly, the increase in both moduli with rising G4 concentration is almost negligible, unlike the courses for the other three kinds of GnPs.
Figure 7a shows that the tensile strength of the composites with all kinds of GnPs increases with increasing GnPs contents. An unfilled EPDM includes crosslinked molecular chains being kinked, twisted, and coiled. These molecular chains partly straighten, uncoil, and untwist, which leads to elongation in the uniaxial stress direction. The rupture of these chains happens as the loading passes over a critical value, resulting in the strain at fracture. The inclusion of GnPs into the EPDM matrix forms three effects: 1—providing strength and stiffness due to stiffer and stronger GnPs; 2—forming more crosslink points of physical nature to crosslinked molecular chains formed by sulphur during a chemical reaction (vulcanization); and 3—behaving as a connector bridging various EPDM chains, causing an increase in strain at break. Enhancing the strength and stiffness with the addition of GnPs is explained by two former effects. With the increase in GnP loading, the increase in tensile strength is observed because GnPs strengthen and stiffen the EPDM matrix [
22].
At 20 phr of GnPs loading, the enhancements of tensile strength of EPDM-based composites including G1, G2, G3, and G4 were ~171%, 122%, 123%, and 318%, respectively. The EPDM/G4 composites show the highest tensile strength compared to others at different GnP loadings. The tensile strength reaches the maximum at 15 phr of G4 which is 8.43 MPa. Since G4 has the highest specific surface area and the smallest dimension, it exhibits higher surface activity, resulting in better strengthening and stronger adsorption [
5]. At 20 phr of G4, there is an abrupt decrease in the tensile strength of EPDM/G4 composites, but still its value is higher than that of the others at the same concentration. Because of this, the agglomeration form of G4 leads to defects at high concentrations. For types of GnPs with the same thickness (5 nm) and specific surface area (170 m
2/g), the optimum lateral size is approximately 30 µm over 18 and 7 µm above 10 phr of GnPs. Up to this concentration, it is observed that the gradual addition of GnPs into the EPDM matrix progressively increases the tensile strength, however, the values of the EPDM composites with G1, G2, and G3 are more or less the same. Moreover, at all concentrations of the filler loading, G2 and G3 give a nearly identical mechanical performance. Consequently, these results indicate that the specific surface area is a more significant parameter for tensile strength than lateral size.
For all series of EPDM/GnPs composites, regardless of GnPs’ dimensions, while at 1 phr of GnPs, the elongation at break drops down, there is a considerable enhancement in the elongation at break with progressive inclusion of GnPs (
Figure 7b). This can be attributed to C=C on the surface of GnPs, which can participate in the curing process and create additional crosslinks to resist the outside force. Additionally, upon the outside force action, GnPs can be exfoliated. This may be the reason for the initial decrease in elongation at break [
43]. On a comparative basis, the enhancement in elongation at break is found to be ~69%, ~60%, ~53%, and ~147% (from ~363% for the unfilled EPDM to ~612%, ~579%, ~553%, and ~897%) for the EPDM/G1, EPDM/G2, EPDM/G3, and EPDM/G4 composites, respectively. Compared to types of GnPs, it is obvious that the elongation at break exhibits a similar behavior as the tensile strength. The composites with a higher specific surface area have a higher mechanical performance.
Upon loading, GnPs can efficiently share a large stress portion and act as physical crosslinks increasing elastomer density and the total crosslink density. This causes a high strain at break [
21]. The reason for this behavior is almost entirely high specific surface area.
M100 and M300 of unfilled EPDM are 0.95 and 1.38 MPa and are summarized in
Table S3. As seen in
Figure 7c,d, excluding the composites with G4, M100 and M300 increase with the increase in the GnPs loading in the system. Comparing M100 and M300 of the EPDM/GnPs composites at a certain GnPs loading, the highest value was observed in the 20 phr G1 filled system. However, as compared to G2 and G3 reinforced composites, they are close to each other. As compared to GnPs with the same thickness (5 nm) and specific surface area (170 m
2/g), the optimum lateral size is almost 30 µm over 18 and 7 µm above 10 phr of GnPs. The surface area of GnPs influences M100 and M300. The lower the surface area, the higher values of M100 and M300.
The data for M100 and M300 support the certain correlation of moduli with crosslink density [
16], even for M100 this is clearly demonstrated since the material filled with G1 exhibits the highest crosslink concentration, EPDM filled with the G2 and G3 shows almost the same crosslink density, being somewhat lower compared to G1 and the crosslink density of EPDM filled with G4 is the lowest, corresponding with both M100 and M300. The reason for the effect of GnPs on the crosslink density can be possibly seen in the physical interactions of the graphene surface deactivating to a certain extent the activity of the crosslinking system, either the accelerators or perhaps also sulphur. In both cases, the final crosslink density would decrease, as was observed as seen in Table 5 with the crosslink densities data. The data for the M100 and M300 are supported also by values of storage moduli presented in the
supplementary data in
Figure S1.
Consequently, all types of EPDM/GnPs composites exhibit significantly higher mechanical parameters than the unfilled EPDM, a similar observation is made by Lu et al. [
19]. The enhanced mechanical properties can be attributed to the superior mechanical properties of GnPs (tensile strength of 130 GPa and a capability to elongation one-fourth of the original length of GnPs during loading). In addition, there may be an adequate interfacial interaction between matrix and fillers because of good GnPs dispersion in the EPDM matrix, this can enhance the mechanical property through the stress transfer phenomenon [
19]. It can be observed that the size and specific surface area of GnPs have a significant effect on the mechanical properties of EPDM-based composites. While G1 shows better enhancement in Young’s modulus, M100, and M300, G4 gives better results in other properties.
Obviously, the size of GnPs is a less important key factor than the surface area of GnPs, and the ruling parameter for tensile strength as well as the strain at break seems to be the surface area, which is the nearly same for G1, G2, and G3 but substantially larger for G4. On the other hand, during mechanical deformation a certain extent of additional exfoliation may occur which leads to the increase in the surface area available for the interactions with the matrix resulting in the increase in the content of physical crosslinks.
3.3.2. Mechanical Testing Results of Hybrid Composites
Figure 8 demonstrates tensile stress, and strain at break as well as moduli M100 and M300 for the hybrid composites. The values from testing of mechanical properties (Young’s modulus, strain at break, stress at tensile strength, M100, and M300) on GnPs loadings for hybrid composites are provided in
Table S4. Composites with CB at 20 phr exhibit an increase in Young’s modulus, tensile strength, and elongation at break, respectively, by ~11%, ~373% ~46% in comparison with the enhancements ~79%, ~1047%, and ~125% made by filling with CB at 50 phr. These enhancements are attributed to intense specific interactions with the matrix. Additionally, the progressive inclusion of CB leads to a reduction in the distance between CB particles. The transition point of tensile strength as a function of CB content just expresses a critical distance between particle and particle, therefore, the excellent strengthening effect begins. A critical particle–particle distance is considered to be an essential prerequisite for achieving a highly efficient strengthening [
5].
All mechanical properties oscillate and fluctuate with the addition of GnPs into the EPDM/G1 composites. In other words, there is no linear relation between Young’s modulus and GnPs loadings into EPDM/CB composites. The Young’s modulus of the EPDM composites including 50 phr of CB and 5 phr of GnPs is 3.18 MPa, being the highest and 97.5% higher than that of the unfilled EPDM. Excepting 7 phr of GnPs, all hybrid composites including 50 phr of CB show more or less the same level as one with only 50 phr of CB. Similar behavior can be observed in the tensile strength. The addition of 5 phr of GnPs enhances the tensile strength up to ~17% compared to one with 50 phr of CB. The elongation at break decreases with the addition of GnPs into EPDM/CB composites with 50 phr due to the agglomeration of filler, leading to voids in the composites.
In the case of the EPDM hybrid composites with 20 phr of CB, the improvement in tensile properties can be due to a better reinforcement effect of GnPs on EPDM as compared with single CB filler [
45] and homogenous dispersion of CB-GnPs in the EPDM matrix [
6]. In this sense, the improvements in the mechanical properties can also verify the uniform dispersion of GN-CB in the EPDM networks [
6].
The improvement in the stiffness of composites can be attributed to the synergic effect of fillers, as described by Cai et al. [
46]. The enhanced tensile strength of hybrid composites may be attributed to the good dispersion of CB and GnPs through the EPDM-based composites. Small particle sizes of CB can provide a large specific surface area and interact with the matrix, and this can allow more effective stress transfer [
1]. The considerable enhancement in mechanical properties of EPDM/CB composites by the inclusion of GnPs can be attributed to superior mechanical properties of GnPs as well as great interfacial interaction and good dispersion of CB and GnPs [
6].
In the case of hybrid composites with 50 phr of CB, the addition of G1 into the EPDM/CB composites leads to an increase in M100 and M300. These values are slightly influenced by the incorporation of G1 into ones with 20 phr of CB. It can be observed that there is a synergic effect of CB and GnPs on the M100 and M300 for the hybrid composites with 50 phr of CB, in the case of the ones with 20 phr of CB, any synergic effect is not observed.
Briefly, the concentration of the total fillers and each filler are important to achieve considerable improvement in mechanical properties due to the synergic effect of fillers.