3.1 ESEM Characterization
ESEM images of GMRG sample are illustrated in Fig. 1. Figure 1a displays an image of the sample without influence of magnetic field, Fig. 1b for sample under pre-treated with magnetic field of 0.1T, and Fig. 1c to show the enlarged views of microstructure CIPs and graphite in GMRG sample.
Generally, the CIPs and graphite were randomly distributed in grease medium in the absence of magnetic field (Fig. 1a). Then, with influence of magnetic field, the CIPs were attracted to each other through dipole-dipole force and start to align to the direction of applied magnetic field. Simultaneously, graphite particles vibrate together with magnetically influence CIPs thus involves during aligning process to form more stronger columnar chain structure (Fig. 1b). Moreover, by referring to Fig. 1c, it is confirmed that the utilized CIPs and graphite are in spherical and irregular shape, respectively. However, few graphite was captured due to the small amount of weight percent of graphite compared to CIPs. It was also observed that graphite showed a good dispersion in the grease matrix without existence of any agglomeration.
In terms of ESEM results as illustrated in Fig. 2b, an EDX analysis was performed at selected area, spectrum 16 (Fig. 2a) to confirm the elemental composition in GMRG sample.
Three types of chemical element namely, carbon, oxygen and iron were obtained as listed in Table 2 that displays weight (%) and atomic (%) of each element composition in the sample.
Table 2
GMRG elemental compositions
Element
|
Weight (%)
|
Atomic (%)
|
C
|
75.34
|
89.26
|
O
|
7.02
|
6.24
|
Fe
|
17.64
|
4.49
|
Carbon exhibited the largest proportion, which was around 75.34 wt.%, and followed by iron and oxygen with the proportion of 17.64 and 7.02 wt.%, respectively. As elemental carbon in 2-dimesional structure of graphite have the lowest energy state, it was the most stable form of carbon in standard condition (ambient temperature and pressure), therefore it reflected to the highest constituent in the result20. Besides, large proportion of carbon was due to the hydrocarbon chain from grease matrix, where, in addition, contributed to the proportion of oxygen as well. This was due to the fact that the type of grease being utilized in this study was based on Lithium-12-hydrostearate thickener that consisted of hydroxyl (-OH) and carboxylate (-COO−) functional groups21,22. Furthermore, the second highest constituent of Fe was contributed from the CIPs that normally made up of pure Iron.
3.1 Effect of Graphite on MRG under rotational mode.
Figure 3 represents the apparent viscosity of MRG and GMRG as function of shear rate at various magnetic field strengths.
It can be observed that both samples, MRG and GMRG experienced shear-thinning phenomenon under the absence and presence of magnetic fields23,24. The apparent viscosity of both samples declined along with increasing shear rate. This phenomenon related to the destruction of CIPs alignments as well as alteration of grease medium under the influence of high shear force25. Furthermore, it can be seen, that the apparent viscosity of both samples increased as the applied current increased from 0 to 3A, corresponding to the formation of strong columnar chain between CIPs along with the direction of applied magnetic fields5.
Apart from that, it can be realized GMRG exhibited a higher value of apparent viscosity at each magnetic field strength as compared with MRG by increasing shear rate. For an example, at off-state condition, the value of initial apparent viscosity of GMRG showed an increment about 0.049 MPa.s as compared to the MRG sample. In absence of magnetic field, the apparent viscosity of MRG was merely depended on the fibrous structure of grease matrix8,23. However, with addition of graphite in GMRG has brought into thickening effect in the grease matrix26, as employment of graphite has increased the number of solid content in sample GMRG that also contained CIPs. Consequently, a greater number of particles to polymer interaction occurred and as a results, the flow resistance of the medium increased27. Even so, the increment of the apparent viscosity in GMRG was still considered low. The reason was because of the low density of utilized graphite as compared to CIPs, which about 4 times differences.
Nevertheless, with the presence of magnetic field, GMRG depicted a slightly increased on apparent viscosity compared to MRG. From the result obtained, it can be proved that although graphite is non-magnetic particles, yet it can involve in the process of alignment with CIPs to form more stronger structures with the presence of magnetic fields. The result is in agreement with Zhang et al.28. Furthermore, such finding was consistent with the previous studies that utilized graphite in improving the rheological properties of MR material17,18. However, GMRG exhibited unstable apparent viscosity in applied current of 3A due to the formation of thicker structure that attributed from graphite particles along with increasing of magnetic field strength. Thus, the formation might contribute to the slip of parallel plate rheometer at high shear rate29.
The shear stress assessment with shear rate range from 0.01 to 100 s− 1 at varied applied magnetic field strength is demonstrated in Fig. 4.
A fluctuating shear stress trend was remarked on GMRG at off-state condition. The increasing of solid content in the GMRG caused extra collisions happened between the particles and the medium under the influence of shear force. Furthermore, larger size and irregular shape owned by graphite has led to the disorder motion in the grease medium. Nonetheless, the shear stress trend of GMRG was more stable upon an application of magnetic field. Besides, at low shear rate, it was observed that both samples showed a linear increment of shear stress. This might be happened due to the CIPs in medium were not stable at low shear rate as the formation of columnar chain structure was initiated but hindered due to shear force. However, the shear stress at a higher shear rates depicted a stable trend owing to the strong dipole-dipole interaction between the CIPs, which perpendicular to the direction of shear flow. It was known that the shear stress of MR suspension manageably improved with the implementation of high shear rate30.
Additionally, the experimental results of GMRG demonstrated high value of shear stress compared to MRG in off-state condition. This result corresponded by the additional particles in GMRG that attributed form CIPs and graphite, which participated in the process of shear. The addition of graphite has contributed to increase the number of interactions between the particle-particle and particle-medium, however, resulted in more frictions between the particles and the medium. Subsequently, the interactions have induced the flow resistance of the medium and as a consequence the shear stress of GMRG sample increases27. Interestingly, an effect of graphite on shear stress was also obviously seen with presence of magnetic field. It was observed that GMRG exhibited a higher shear stress compared to MRG at all magnetic field strengths. Noted here that, as the applied magnetic field strength increases, a thicker columnar chain structure between CIPs has been formed. Simultaneously, the existing irregular-shaped graphite with high surface contact area has promoted the agglomeration of CIPs around their surface31. Subsequently as the density of graphite was much lower than CIPs, graphite was easily being escorted by CIPs in the alignment process. As the outcome, graphite particles were indirectly involved in the formation of columnar chain structure to develop more robust and stable structure, which reflected to the result of increment in the shear stress of GMRG.
From relationship between shear stress and shear rate, yield stress for both samples can be acquired through extrapolation at zero shear rate. Figure 5 shows yield stress of MRG and GMRG as a function of varying applied current from 0 to 3 A.
A linear trend of enhancement in the yield stress was observed at both samples, MRG and GMRG towards increasing magnetic field. The yield stress of MRG has shown an improvement from 1.375 to 36.051 kPa, while 4.0167 to 50.048 kPa for GMRG as increasing the applied current from 0 to 3A. The increment of yield stress was resulted from the formation of stable chain structures within the medium with escalating of magnetic field strength. This owing to the fact that the stiffness of both samples increased along with the magnetic field strength, thus hindered the free movement of CIPs within the medium. From the results, it showed that the growth of yield stress in GMRG was about 32.7% higher as compared to MRG from 0A to 3A. Hence, it proved that graphite could help to expand the range of yield stress of MRG due to their strengthen effect.
Apart from that, as can be seen from Fig. 5, the addition of graphite in GMRG shows an improvement to the yield stress at all applied currents. It was noted that the yield stress of MRG has increased from 36.051 to 50.048 kPa with an increment of 38.8% with 10 wt% of graphite at 3A. Furthermore, the yield stress of GMRG showed a dramatic increment starting from 2 to 3A, which appeared to be a different trend compared to MRG. With further increment of magnetic field strength, the CIPs in the medium that already formed thicker and stronger chain structures, has reached a stable formation of structures. As consequences, a higher force was required to break the new structure, which directly caused sudden rise in the yield stress of GMRG.
3.2 Effect of Graphite on MRG under oscillatory mode
At the beginning of applied strain, the storage modulus of both samples was independent with strain amplitude, this was known as dynamic properties of linear viscoelastic (LVE) material. However, the effect of strain showed a non-linear trend as strain amplitude increases due to change in their dynamic properties at high strain32,33. This finding related to the destruction of the microstructure of the samples resulting from a strong distance dependence of dipole-dipole interaction, which known as Payne effect33,34. Generally, it is important to identify the LVE region of the material in order to be used in specific applications.
Referring to Fig. 6a, the graph shows the storage modulus, G’ of MRG has increased from 0.77 to 1.74 MPa by increasing the applied current from 0 to 1A. The dramatic increment of storage modulus, G’ caused from strong columnar chain structures that were formed at a stronger magnetic field. Comparing with Fig. 6b, the different gaps of storage modulus, G’ between 0 and 1A for GMRG samples was lower compared to MRG samples. It was acknowledged that by the addition of in GMRG sample has increased the stiffness of the medium due to their high surface contact area that led to a stronger interaction between the grease medium and CIPs. Simultaneously, it would affect the mobility of the CIPs in the medium16. Nevertheless, it was observed that the storage modulus, G’ for each sample was slightly increased along with escalated magnetic field strength.
Figure 7 illustrates the comparison between MRG and GMRG samples under shear strain at off- and on-state conditions.
The storage modulus, G’ of GMRG displayed a higher value compared with MRG at all magnetic field strengths. This finding reflected to a strong viscoelastic behaviour exhibited by GMRG samples. Meanwhile, the addition of graphite as in sample GMRG has shorten the range of LVE region in off-state condition. It was because graphite contributed to a stiffer GMRG, thus sensitive to a low strain, which could cause microstructural damage. However, a broaden LVE region (< 0.1%) was observed in the GMRG sample compared to MRG sample (< 0.03%) at on-state condition. This was because the irregular shape of graphite contributed to good wettability between graphite and grease, which led to an excellent dispersion of graphite in grease medium31. As a result, graphite was also involved in the alignment process together with CIP, thus provided more stable structures at high magnetic field strength.
Additionally, Fig. 8 presents the loss modulus, G’’ of MRG and GMRG at small strain ranging from 0.001 to 10% at different applied currents.
The loss modulus, G’’ for each sample showed a lower value at strain < 0.1% but increased dramatically at strain > 0.1%. Both samples displayed fluctuating loss modulus at high magnetic fields strength in a low applied strain, < 0.1%. Moreover, the peak of the graph becoming more obvious with increased of magnetic field strength. This suggested that at high magnetic field strength, more energy dissipated through heat that promoted to more inter-particle interactions between CIPs35. On the other hand, the increasing loss modulus at a higher magnetic field might due to the complicated structure attributed from combination of grease’s matrix fibre structure with induced-magnetizable chain structure36.
On the other hand, the comparison of loss modulus, G’’ between both samples in off- and on-state conditions are illustrated in Fig. 9.
It was observed that in absence of magnetic field, the loss modulus of GMRG was higher than MRG, indicated that more heat was dissipated by GMRG. In contrast, with presence of magnetic field, it was noticed that MRG sample displayed a higher and more fluctuated loss modulus compared to GMRG at a very low strain (< 0.1%). The possible reason might relate to the stable structure acquired by GMRG at escalated applied magnetic field strength caused by the existing of graphite particles. However, at strain > 0.1%, GMRG showed a much higher value of loss modulus compared to MRG due to strong Payne effect experienced by GMRG.
Based on above results, it can predict that the addition of graphite has a significant effect towards the interaction between CIPs and grease medium. It was assumed that some of the CIPs have attracted to the graphite to establish bonding between them (Fig. 1b). Furthermore, the positive improvement on rheological properties of GMRG was related to the excellent interfacial interaction of graphite with grease medium. Mechanism of the movement of graphite during CIPs alignment under the presence of magnetic field in GMRG is illustrated in Fig. 10.
Without an application of magnetic field, the spherical CIPs and irregular shape graphite were dispersed randomly16 in grease medium as shown in Fig. 10a. At this stage, the viscosity of the samples was primarily depended on the fibrous structure of the grease matrix. Due to a good adhesion of graphite with grease medium, the apparent viscosity and shear stress of GMRG was supposed to be higher, however, it has a drawback by the low density of graphite. Thus, resulted in a small difference with MRG.
Conversely, with an application of magnetic field, the CIPs were magnetized and started to attract to each other as displayed in Fig. 10b. The movement of CIPs was according to the direction of magnetic field and at the same time, the gap between the particles was reduced. The process of alignment was involved the CIPs, where the graphite was also followed by the movement of CIPs that attached to it. With further increased of magnetic field, the inter-particle interactions were stronger due to the closer gap between the CIPs, resulted in a thick columnar chain structure driven from dipole-dipole force. In the meantime, more CIPs accumulated around the graphite’s surface due to rough and high surface area contact of irregular graphite31. Consequently, the graphite tended to ‘move’ together with magnetizable CIPs and thus, involved in the formation of columnar structure within the matrix as shown in Fig. 10c. Apparently, a stronger interaction structure between CIPs, graphite and matrix led to the improvement of the rheological properties in the GMRG sample.