The design of crosslinks in different vulcanized systems to improve crack growth resistance for carbon black/graphene oxide/ natural rubber composites

doi:10.21203/rs.3.rs-2563295/v1

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The design of crosslinks in different vulcanized systems to improve crack growth resistance for carbon black/graphene oxide/ natural rubber composites

https://doi.org/10.21203/rs.3.rs-2563295/v1

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published 15 Apr, 2023

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Herein, the carbon black/graphene oxide/natural rubber composites (CB/GO/NR) with different crosslink networks were prepared through the latex co-precipitation approach. Meanwhile, the type of crosslinks on the crack propagation resistance and fatigue life in different vulcanized systems were investigated. As a result, CB/GO/NR composites dominated by polysulfide in conventional vulcanization (CV) system exhibited the improved tear strength (71.6 KN/m) and lowest crack growth rate (64.1 nm/cycle), the developed crosslink network and polysulfide based crosslink structure in CV system were the key factors to improve the crack propagation resistance. In addition, the relationship between viscoelasticity and dynamic crack propagation behavior of CB/GO/NR was studied, and the CV system had the lowest loss compliance modulus( J "), thus more energy dissipation occurred in the crack propagation region and the crack propagation resistance of CV system was improved. Importantly, this work can provide the guideline for designing the rubber-based composites in the practical engineering applications.

Graphene oxide

Fatigue life

Natural rubber

Crack growth resistance

Natural rubber (NR), as an extremely important strategic resource, has been widely applied in tires and conveyor belts for the transportation, aerospace, construction[1–5]. The unique strain induced crystallization ability can endow it with the excellent mechanical strength, wear resistance, high elasticity and other characteristics[6–9]. However, the relatively short fatigue lives of NR-based composites still limit its further practical applications. Crack comes from the initiation as well as propagation of micro-cracks and become a risk factor in deteriorating the fatigue life, which were generate by the agglomeration defects of fillers and the weak interaction of NR molecules[10, 11]. Noticeably, the micro-cracks will gradually enlarge into macroscopic cracks and eventually result in fatigue failure in rubber components under the special environment of cyclic deformation or high impact force[12–14]. Thus, it become an important research issue to improve fatigue life by developing crack propagation resistance for the NR-based composites in recent years[15].

In the rubber industry, carbon black (CB) and silica (SiO₂) are always used as the conventional reinforcing filler to improve the anti-crack growth performance[16–21]. Previous works demonstrated that the crack growth rate could be obviously reduced when CB added into the NR matrix due to the increased crystallization zones[22, 23]. However, the high filler content makes it easy to agglomerate in the composites, thus generating stress concentration and micro-cracks. Nowadays, in order to reduce the amount of CB, new carbon materials such as graphene and carbon nanotubes were aroused research appetite to replace part of conventional fillers. The large specific surface area, low density and high strength properties make it easier to build the filler networks and scatter the stress[24, 25]. Guo and co-workers took advantage of small amount GO to change the crack propagation path and reduce the crack growth rate due to the improved strain induced crystallization capacity and branch on the crack tip[26]. Therefore, it is a feasible way to improve the crack propagation resistance and fatigue life by using novel reinforcing filler for the NR-based composites.

Additionally, the crosslink networks which include crosslink density and structure of NR matrix were another decisive factor on the crack propagation resistance and fatigue life properties[27, 28]. The related reports verified that the crosslink density and type of crosslink bonds could be designed through the different vulcanized systems. According to the ratio of sulfur/accelerator (S/A), it could be divided into common conventional (CV), semi-effective (SEV), effective (EV) systems[29–31]. Honorato et al. investigated the different crosslink structures in influencing the mechanical properties of NR composites, which demonstrated that CV system had the well-developed crosslink networks and improved tear strength through Penny effect and Gibbs free energy method[32]. Larpkasemsek and co-workers also demonstrated the highest crosslink density with CV system owned the good mechanical properties and the fastest vulcanized rate for epoxied NR composites[33]. The above results illustrated that the CV system with high ratio of S/A had the higher crosslink density, which could provide longer flexible polysulfide crosslinking (C-S_X-C, X > 3) and good physical and mechanical properties due to the rearrangement characteristics of crosslink bonds. Although it had made some progress in theoretical analysis, the research on the crack propagation resistance and fatigue life properties for NR-based composites remain to be further studied.

In this work, the carbon black/graphene oxide/natural rubber composites (CB/GO/NR) with different vulcanized systems were prepared by the latex co-precipitation method. The effect of crosslink networks in differently vulcanized systems on the crack propagation resistance and fatigue life were investigated in detail.

As a result, CB/GO/NR composites with CV system owned the highest crosslink density and improved tear strength (71.6 KN/m). Meanwhile, the crack growth rate of CB/GO/NR composites with CV system under uniaxial cyclic load was also the lowest (64.1 nm/cycle), which was less than that of semi-efficient vulcanization (SEV, 83.7 nm/cycle, 30.6%) and efficient vulcanization (EV, 101 nm/cycle, 57.6%) system. In addition, the relationship between viscoelasticity and dynamic crack propagation behavior of CB/GO/NR was studied. More importantly, this work could provide the basic data and possible solutions for the NR-based composites in engineering applications.

2.1 Materials

Natural rubber latex (NRL) was purchased from Hainan Natural rubber Industry Group. GO dispersion was provided by Changzhou Sixth Element Technology Company. Carbon black (N330) was offered from Cabot Company. N-cyclohexyl-2-benzothiazolyl sulfonamide (CZ), zinc oxide (ZnO) and stearic acid (SA) were obtained from China Aladdin Chemical Co., LTD. Antioxidant (4010 NA) and sulfur (S) are industrial grade products. Acetone, toluene, n-heptane, 2-propane mercaptan, and 1-hexanethiol were used as analytical reagents.

2.2 Preparation of CB/GO/NR composites

CB/GO/NR composites with different vulcanized systems were prepared by the latex co-precipitation method. Firstly, GO dispersion (5mg/mL) was sonicated until to form the uniform solution. Then, a certain amount of GO dispersion was added into NRL and mechanically stirred for 30 mins. Subsequently, the flocculants calcium chloride dispersion (CaCl₂, 1.0 wt%) was added to the above solution to obtain the graphene oxide/natural rubber (GO/NR) masterbatch and washed by the deionized water for 5 times. After drying for 24 h in an oven at 60 ℃, the different content of CB and additives were added into the GO/NR masterbatch by the mechanical blending. Finally, the compounds were vulcanized to obtain the composites. The characteristic vulcanization value of composites was mainly depended on the rubber process analyzer rheometer at 150 ℃. While the optimum vulcanized time (Tc 90) was at the condition of 150 ℃⋅15 MPa. The formula of materials was shown in Table 1 as follows:

Table.1 the formulae of different NR-based composites

Samples	CV	SEV	EV
NR	100	100	100
ZnO	5	5	5
SA	2	2	2
CB	50	50	50
GO	0.5	0.5	0.5
4010 NA	1	1	1
S	3	2	1
CZ	1	2	3

2.3 Characterization

Rubber processing analyzer (PRA-8000-H, Gotech, China) was used to characterize the packing networks of different CB/GO/NR composites at a frequency of 1 Hz ⋅ 60 ℃. Mechanical property was tested at a speed of 500mm·min^− 1 by the tensile testing machine (Al-7000-SGD, Gotech, China). The morphology of fillers, distribution and crack propagation path were observed by field-emission scanning electron microscopy (FESEM, Hitachi SU8010, Japan), carbon black particle size disperser (Alpha-500, USA) and atomic force microscopy (AFM, Cypher ES from AsylumResearch, USA), respectively.

The crosslink density of NR-based composites is determined by equilibrium swelling method and can be calculated according to Flory-Rehneer equation, where the solvent was toluene[34–36]:

$${\text{V}}_{\text{e}}=\frac{-\text{ln}\left(1-{V}_{r}\right)+{V}_{r}+{\chi }{{\text{V}}_{r}}^{2}}{{V}_{1}({{V}_{r}}^{\frac{1}{3}}-{V}_{r}/2)}$$

where V_e is the crosslink density of composites, V_r presents volume fraction of NR, V₁ is the molar volume of solvent (V₁ = 106.3 cm3/mol), and X is the interaction parameter between solvent and rubber (χ = 0.391)[37].

While V_r can be obtained from Eq. (2):

$${V}_{r}=\frac{({m}_{2}/\rho )}{[\frac{{m}_{2}}{\rho }+({m}_{1}-{m}_{2})/{\rho }_{s}]}$$

where m₁ is the mass of composites after swelling, m₂ represents the mass of composites after drying, ρ_s is the density of composites, ρ is the density of toluene.

The crosslinking of mono-, di- and polysulfide crosslink in composites were tested by chemical detection reagent.

The glass transition temperature (Tg) with different vulcanization systems CB/GO/NR composites was measured by differential scanning calorimeter (DSC, Mettler Toledo, Switzerland) at a heating rate of 10℃/min. While dynamic mechanical properties were analyzed by dynamic thermo-mechanical analysis (DMA, TA, USA). The test sample size was 40 mm×5 mm×1mm spline. The dynamic strain was 0.5% and the temperature range is -80℃~80℃ with heating rate of 3 ℃/min.

Uniaxial cyclic load tests were performed by the tensile testing machine, which the specimen was 40×6×2 mm and the pre-cut depth was 1.5 mm. Meanwhile, the high-speed camera (Imetrum, USA) was used to observe the crack propagation process and calculate its length. The tearing energy of composites can be calculated by the following Eq. (3)[38] :

$$G=W{h}_{0}$$

where G is tearing energy (J/m²), W means strain energy density, and h₀ is sample height. Under the condition of pure shear pattern, the tearing energy is independent of the crack length and the above equation can be simplified as Eq. (4) [39]:

$$G=\frac{{E}_{f}}{S}=\frac{{E}_{f}}{L\times e}$$

in which, S is the cross-sectional area (m²), e and L are the width (m) and thickness (m) of the sample respectively. E_f is the strain energy (J).

3.1 Mechanism of different crosslink process for CB/GO/NR composites

As shown in Fig. 1, the crosslink way in different vulcanized process for NR-based composites was mainly contained four steps. Firstly, the accelerator CZ could be decomposed into promoting base (M) and active groups at the vulcanized temperature. Subsequently, the M could automatically catalyze CZ to produce dimer of M (MSSM). Then, MSSM could be reacted with sulfur to produce persulfide (MSS_xSM) under the action of ZnO catalyzer. Finally, MSS_xSM crosslinked with the chain of NR, including three crosslink structures by designing the different S/A ratio, where the crosslinks were polysulfide and monosulfide in CV and EV system, respectively. While the SEV system showed the little difference in the three crosslink structures because of the equal ratio of S/A.

3.2 Characterization of filler and its dispersion in NR matrix

The filler structures and distributions in the NR matrix had a great influence on the crack propagation resistance and fatigue life properties. As shown in Fig. 2 (a), raw GO had the transparently lamellar structures and wrinkled edges with a micrometer size. Figure 2 (b) showed that CB particles were spherical and easily stick together to form dendritic chains. Figure 2 (c) was the curve of energy storage modulus (G’) to the strain, where the similar tendency of G' in different three vulcanized systems indicated the basically same strength of filler networks and the dispersion properties. Figure 2 (d, e, f) represented fractured surface SEM images of CB/GO/NR composites with CV, SEV and EV system, respectively. It observed that both GO and CB were uniformly dispersed without obvious agglomeration, demonstrating that the vulcanized systems had little influence on the dispersion of fillers. As shown in Fig. 2 (g, h, i), CB dispersion level of CB/GO/NR composites was further investigated to verify the filler dispersion ability. According to the distribution of CB, it could be seen that the size distribution was about 0–30 µm and the largest was about 8.6 µm, which were accounted for 18.2%, 17.2% and 19.4% in CV, SEV and EV systems, respectively. The result verified that the dispersion degree of reinforcing fillers in the three vulcanization systems was similar. According to these basic data, it can be concluded that the dispersion ability of composites with different vulcanized systems is similar. And the determinants affecting the crack propagation resistance and fatigue life of composites with different curing systems still need to be explored.

3.3 Vulcanization parameters of CB/GO/NR composites

In order to explore the vulcanized properties in different vulcanized systems, characteristic parameters of CB/GO/NR composites were studied by the torque rheometer. As shown in Fig. 3 (a, b, c), compared with SEV and EV systems, the positive vulcanization with CV system was the shortest and its corresponding vulcanized efficiency was the fastest as well, which could be ascribed to the large amount of sulfur obviously increased the available sites and thus accelerated the vulcanized rate. In addition, the highest ΔM of composites (the difference between the maximum and minimum torque) belong to CV system, reflecting its the highest crosslink density. Figure 3 (d) displayed the exactly crosslink density and crosslink structure distribution through using the equilibrium swelling method. It could be obtained that crosslink density of CB/GO/NR composites with CV system reached 3.72×10^− 4mol/cm³, which was higher than that of the SEV (3.61×10^− 4mol/cm³) and EV (3.35×10^− 4mol/cm³) system. Meanwhile, the crosslink structure was dominated by polysulfide instead of monosulfide (EV) as well as three crosslinks evenly distributed (SEV). Furthermore, the relaxation of CB/GO/NR composites was investigated to test crosslink density, where the crosslinked and un-crosslinked composites were corresponded to short and long relaxation time, respectively[40–42]. From Fig. 3 (e), it could be seen that the crosslinked proportion of CV system was the largest, indicating that a large number of crosslinks were generated during the vulcanization process. Also, the glass transition temperature (T_g) of CB/GO/NR composites was measured by DSC. As shown in Fig. 3 (f), the T_g of CV system increased to 60.7 ℃, which resulted from the enhanced fragment restriction caused by the higher crosslink density in CV system. Thus, it could be inferred that the highest crosslink density and structure dominated by polysulfide were existed in CV system.

3.4 Static mechanical properties of CB/GO/NR composites

Figure 4 showed the static mechanical properties of CB/GO/NR composites with different three vulcanized systems. From Fig. 4 (a, b and c), it could be seen that CB/GO/NR composites with CV system owned the highest tensile strength (27.5 MPa), elongation at break (362.5%), modulus at 100% and 300% elongation (4.2, 19.5 MPa), tear strength (71.6 KN/m) and hardness (69 A) because of the developed crosslink networks. And the high tear strength of CV system indicates that the developed crosslink networks was beneficial to prevent crack propagation and improve the tear resistance of rubber composites. Meanwhile, as for NR-based composites, the high strain-induced crystallization ability was helpful to improve the crack deflection, passivation, branching and fatigue resistance, which could be evaluated by Mooney-Rivlin equation from stress-strain curves as follows:[43, 44]

σ*=σ/2(λ-λ⁻²)=C₁ + C₂λ⁻¹

where σ represented the stress, λ was the tensile ratio, C1 and C2 were Mooney-Rivlin constants respectively. As shown in Fig. 4 (e), the upturn point of tensile ratio gradually shifts to the right of X-axis from EV to CV system, where the larger X, the greater strain-induced crystallization ability. The largest upturn point and elastic modulus were CV system, which mainly because the large number of polysulfide crosslinks with low bond energy, thus, in the stretching process, the early fracture could make molecular chains stretch and lead to the easy orientation as well as crystallization.

3.5 Crack propagation resistance growth under cyclic loading

Crack growth rate of composites was the most important method to monitor the dynamic crack propagation resistance and fatigue life performance, which was mainly influenced by the tear energy[45]. As shown in Fig. 5 (a), it could be seen that composites with CV system required the highest tear energy under the same displacement and deformation. Figure 5 (b) reflected that the lowest crack growth rate (64.1 nm/cycle) in CV system and also showed an upward trend with the increase of tear energy, which was obviously lower than that of EV (101 nm/cycle, 57.6%) and SEV (83.7 nm/cycle, 30.6%) system at 2000 J/m². As shown in Fig. 5 (c, d), it could be seen that composites with CV system owned the highest storage modulus (E') in the whole testing range, indicating the improved interactions among the NR chains[46]. Figure 5 (e) showed the relationship between loss factor (tanδ) and temperature, where the tanδ value was significantly reduced in CV system, demonstrating that the developed crosslink networks restricted the movement ability of NR molecular chains. In addition, the relationship between crack propagation behavior and viscoelasticity could be obtained according to the theory proposed by Persson and Brener, which expressed as follows:[47, 48]

$$G\left(v\right)={G}_{0}+{G}_{0}f(v,T)$$

$$G\left(v\right)={G}_{0}[1+\frac{2}{\pi }{E}_{0}{\int }_{0}^{2\pi v/a}d\omega \frac{F\left(\omega \right)}{\omega }{J}^{{\prime }{\prime }}{]}^{-1}$$

$${J}^{{\prime }{\prime }}=\frac{\text{tan}\delta }{{E}^{{\prime }}+{E}^{{\prime }}{tan}^{2}\delta }$$

where G (v) was tear energy at a certain crack growth rate (v), G₀ represented the threshold energy to crack growth at the crack tip, G₀f (v, T) expressed as the bulk dissipation in the linear viscoelastic region and mainly contributed G(v)[49]. According to the time-temperature equivalence principle, G (v) could be also expressed as formular (2), F(ω) was a function of frequency (ω), crack-tip diameter (a), and crack velocity (v). J" was loss compliance modulus relating to the viscoelastic parameter and could be measured as formular (3). Figure 5 (f) displayed the change of loss compliance modulus various temperature[50]; it could be seen that the CB/GO/NR composites with CV system had the lowest J", according to the relationship between crack growth behavior and viscoelastic formula in Fig. 5 (g), J" decreases, leading to G₀f (v, T) increases, indicating that the crack tip of CV system has higher energy dissipation (hysteretic loss) during dynamic crack growth. When the tearing energy is fixed, the increase of G₀f (v, T) will cause the decrease of G₀, and the energy applied to crack growth will be reduced. Therefore, the crack growth rate of CV system will be reduced.

The energy dissipation value can be obtained by calculating the area of the strength-strain curve[51, 52].The energy consumed (E_diss) per unit crack propagation length could more intuitively study the viscoelastic behavior at the tip of rubber composites, which was established as follows:

$${E}_{diss}=\frac{E}{dc/dN}$$

From Fig. 6 (a-d), the cyclically stress-strain curves and hysteresis loss of CB/GO/NR composites with different vulcanized systems under various tear energy was characterized. It could be found that composites with CV system had the little hysteresis loss at the same tear energy. As shown in Fig. 6 (f), it observed that the Ediss of CV system was the largest, indicating that more energy was consumed in the dynamic process of crack propagation and finally improved the crack propagation resistance and fatigue life.

The crack growth path could further help understand the influence on the dynamic fatigue life and crack propagation resistance property[53]. It could be seen that CB/GO/NR composite exhibited the different paths in the crack propagation process from the same initial crack length. As shown in Fig. 7 (a-a2), the crack propagation path of CV system had obvious migration phenomenon and passivation as well as branching also appeared at the crack tip. Meanwhile, the SEM images of fatigue tear sections in Fig. 7 (a3) were the rough and had a deeper sense of hierarchy complex, which demonstrated that the more energy was dissipated and reduced the stress concentration, thus delaying the crack growth rate and improving the dynamic fatigue life of composites. While for the SEV (b-b3) and EV (c-c3) system, the crack growth path was basically obvious deviation and consistent with the initial crack. Also, the SEM images of fatigue tear sections were relatively simple and smooth, which made the crack subjected to less resistance and had an adverse effect on crack propagation and fatigue life.

Additionally, AFM was also used to characterize the change of interface morphology of CB/GO/NR composites after crack propagation. Figure 8 (a, d, g) was the AFM scan of cross-section of CV, SEV and EV vulcanization system after 20000 cyclic tests, respectively. It could be seen that the roughness was distinctly different. From Fig. 8 (b, e, h), it found that the composites with CV system owned large surface variation and the maximum height difference was about 300 nm, which was higher than that of SEV (184 nm) and EV (120 nm) system. As shown in Fig. 8 (c, f, i), 3D maps of the surface roughness verified that the CV system had the great surface fluctuation when compared with SEV and EV system. The results demonstrated that the rearrangement of polysulfide bonds and stress dredging characteristics in the CV system made its surface roughness larger, which effectively diffused the external strength during the crack propagation process and improved the crack propagation resistance.

Figure 9 was the typically schematic of crack propagation for CB/GO/NR composites with CV system. Herein, according to the above results, it could be known that CV system mainly contained polysulfide crosslinks with low bond energy, which led to the stress release and the crosslinks exchange rearrangement reaction to improve the crack propagation resistance and fatigue life property of CB/GO/NR composites. The specific procedures were as follows[54]: (1) the fracture of polysulfides made the molecular chain stretch easily, improving the strain induced crystallization and the passivation of crack tip ability. (2) The polysulfides had the function of exchange rearrangement, which made it form a new crosslink and change the uneven degree in the initial vulcanization network to a certain extent, reducing the crack growth rate and improving the crack growth resistance. Therefore, CB/GO/NR composites with CV system had the excellent crack propagation resistance and fatigue life property.

In summary, the CB/NR/NR composites with different vulcanized systems were successfully prepared by the latex co-precipitation method and the effect of crosslink density and crosslink structures on static and dynamic properties were studied. As a result, the composites with CV system owned the developed crosslink networks and improved tear strength (71.6 KN/m) because of the composition of polysulfide bonds. Under the dynamic cyclic testing, composites with CV system showed the lowest crack growth rate (64.1 nm/cycle), which was less than that of SEV (83.7 nm/cycle, 30.6 %) and EV (101 nm/cycle, 57.6 %) system. In addition, the relationship between viscoelasticity and crack propagation property was established logicality. The SEM and AFM characterizations demonstrated that CV system were more prone to migration and branching in the process of crack growth due to its large number of polysulfide crosslink networks, resulting in a lower crack growth rate. More importantly, this work could provide the basic data and possible solutions for the NR-based composites in engineering applications.

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Author Contributions Statement

Zhiwei Li: Conceptualization, Formal analysis, Writing – original draft. Dong An: Formal analysis. Rizheng He: Investigation. Zhijian Sun: Investigation. Jiaxiong Li: Investigation. Zhiyi Zhang: Formal analysis. Yaqing Liu: Supervision. Chingping Wong: Writing – review & editing.

Funding

The authors received financial support from Natural Science Foundation of Shanxi Province (Grant No. 20210302124430) and the Shanxi Provincial Science and Technology Major Project (Grant No. 20181101010).

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The design of crosslinks in different vulcanized systems to improve crack growth resistance for carbon black/graphene oxide/ natural rubber composites

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Abstract

Figures

1. Introduction

2. Experimental Section

2.1 Materials

2.2 Preparation of CB/GO/NR composites

2.3 Characterization

3. Results And Discussion

3.1 Mechanism of different crosslink process for CB/GO/NR composites

3.2 Characterization of filler and its dispersion in NR matrix

3.3 Vulcanization parameters of CB/GO/NR composites

3.4 Static mechanical properties of CB/GO/NR composites

3.5 Crack propagation resistance growth under cyclic loading

Conclusion

Declarations

References

Additional Declarations

Supplementary Files

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