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Tribol Lett (2011) 41:209215 DOI 10.

1007/s11249-010-9702-5

ORIGINAL PAPER

Modication of Graphene Platelets and their Tribological Properties as a Lubricant Additive


Jinshan Lin Liwei Wang Guohua Chen

Received: 18 April 2010 / Accepted: 20 September 2010 / Published online: 6 October 2010 Springer Science+Business Media, LLC 2010

Abstract Graphene platelets were chemically modied in a reux reaction with stearic and oleic acids. Examination of the surface features of the graphene platelets before and after modication by infrared spectroscopy and ultraviolet visible spectrophotometer revealed that the modication led to an improvement in the dispersion of graphene platelets in base oil. The tribological behavior of the lubricating oil containing modied graphene platelets (MGP) was further investigated using a four-ball machine. The results indicated that the oil containing only 0.075 wt% of MGP clearly improved the wear resistance and load-carrying capacity of the machine. Scanning electron microscopy and energy dispersive spectrometer performed to analyze the wear scar surfaces after friction conrmed that the outstanding lubrication performance of MGP could be attributed to their small size and extremely thin laminated structure, which allow the MGP to easily enter the contact area, thereby preventing the rough surfaces from coming into direct contact. Keywords Graphene platelets Surface modication SEM TEM Additive-deposited lms

1 Introduction Graphene platelets have been the focus of interest in both theoretical research and in studies on practical applications due to their unique structure and remarkable properties [15]. Recent studies have shown that graphene platelets have
J. Lin L. Wang G. Chen (&) Institute of Polymer and Nanomaterials, Huaqiao University, Quanzhou 362021, China e-mail: hdcgh@hqu.edu.cn

extraordinary electronic transport properties when they were incorporated in composite materials and distributed homogeneously throughout the matrix [68]. Graphene has also been used to fabricate a number of simple electronic devices, such as eld-effect transistors [9, 10] and resonators [11], due to its fundamental electronic properties and semimetallic nature. Moreover, graphene platelets are promising candidates as components in applications such as organic photovoltaic cells [12], energy-storage materials [13], paperlike materials [14, 15], and liquid crystal devices [16]. However, very few studies on the tribological applications of graphene platelets have been reported. Peterson et al. [17] pointed out that effective solid lubricants generally have a number of basic properties, such as thermal stability, low shear strength, surface adherence, and characteristics of lamellar structure. A number of researchers have reported that graphite [18] and some graphite derivatives [19, 20] as well as other lubricant materials [21, 22] together have the above desirable properties. Graphene platelets are the building block of the common macroscopic solid lubricant graphite, and they also are characterized by possessing the above-mentioned advantages [23]. Huang et al. [24] investigated the tribological properties of graphite nanosheets as an oil additive. They found that the load-carrying capacity and antiwear ability of the lubricating oil were improved when graphite nanosheets were added to the parafn oil at the optimal concentration. Filleter et al. [25] explored friction and dissipation in epitaxial graphene lms, revealing that bilayer graphene as a lubricant outperforms even graphite due to reduced adhesion. Wang [26] suggested the thin lms of solid lubricant materials would be an outstanding solid lubricant at temperatures ranging from -270 to more than 1,000C. Based on these results, it can be inferred that graphene platelets would be an effective solid lubricant.

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Graphene platelets that are derived from graphite generally bear hydroxyl and carboxyl functional groups on their sheet edges [2], which make graphene platelets strongly hydrophilic and easy to coagulate in oil. Hence, when graphene platelets are added to the base oil as a lubricant additive, it is necessary to ensure uniform dispersion without any agglomeration of graphene platelets in the base oil. Two main approaches are currently used to solve the suspension problem. One is that the graphene platelets and effective dispersant are mixed with the base oil. It has been proven that the dispersant can enwrap one nanoparticle to repel another and thereby form a uniform suspension [24, 27]. Nevertheless, due to this action, excessive or too little dispersant may greatly affect the effectiveness of the suspension [27]. The second approach is to modify the graphene platelets with a proper modier. It has been demonstrated [2830] that modifying nanoparticles with the appropriate modier is an effective way to prevent the coagulation of nanoparticles in suspension. Chen et al. [31] reported that multi-walled carbon nanotubes (MWNTs) modied with stearic acid under the inuence of gravity could be suspended homogeneously in base lubricant for over 6 months at room temperature, whereas the nonmodied MWNTs were entirely coagulated at the bottom after 2 months. Structurally, MWNTs consist of multigraphene cylinders with end seamless caps. Here, we report on our use of the second approach to improve the stability of graphene platelets in oil. However, in our approach, the selection of an appropriate modier is the key. We therefore tested a large number of surface modiers, such as sodium dodecyl benzene sulfonate, stearic acid, dodecyl trimethyl ammonium chloride, oleic acid, sorbitan monooleate, as well as polysorbate and others, which involved a considerable research effort. Our results demonstrated that stearic and oleic acids are the most suitable modiers for graphene platelets. We then modied the graphene platelets with a certain proportion of stearic and oleic acids and subsequently added the modied graphene platelets (MGP) into the oil to enhance tribological properties of lubricating oil. The surface features of the graphene platelets before and after modication were examined by Fourier transformed infrared spectroscopy (FTIR) and ultravioletvisible spectrophotometry (UVVIS). Scanning electron microscopy (SEM) and energy dispersive spectrometry (EDS) were used to analyze wear scar surfaces after friction.

Graphite Co.(China). Base oil SN350 was supplied by the Shishi Zerun Lubricating Oil Co. (China). Stearic acid was purchased from Shanghai Reagent General Plant (Shanghai, China). Oleic acid, cyclohexane, petroleum ether, ethanol, and acetone, all analytical reagent grade, were purchased from the Shantou Xilong Chemical Co. (Shantou, China). 2.2 Chemical Modication of Graphene Platelets and Natural Flake Graphite Stearic and oleic acids (mass ratio 3:5) were mixed by sonication in 40 ml cyclohexane for 30 min. Dried graphene platelets were added to the above solution and the suspension sonicated for 30 min at ambient temperature. The suspension of graphene platelets was then stirred and reuxed at 80C for 5 h, then cooled to ambient temperature. To remove the residual stearic and oleic acids, the resulting graphene platelets were ltered and washed with acetone. The nal step was to dry the products under vacuum at 100C. For comparison, natural ake graphite was also modied using the above process. 2.3 Stability Test of Modied Graphene Platelets The 350SN base oil was used as base lubricant in this test. The MGP were dispersed in 350SN base oil by sonication followed by stirring with a magnet for 1 h at 80C (rotate speed R = 600 r/min). To evaluate the stabilization of the MGP in base oil, following the dispersion of the MGP as described above, the MGP lubricant was diluted 50 times with pure base oil and precipitated by centrifugation at 1,000 rpm. The supernatant uid was then decanted at 30-min intervals to evaluate absorbance using a UVVIS spectrophotometer. Based on the LambertBeer law, absorbance is proportional to concentration. The concentration of graphene platelets in the supernatant uid is an indicator of the suspension property, with higher concentrations associated with better suspension properties. Therefore, the dispersion stability of MGP in base oil was evaluated by assessing the absorbance. For comparison, pristine graphene platelets were obtained by the same process. 2.4 Tribological Properties of MGP as an Oil Additive The maximum nonseized load (PB), friction coefcient and the wear rate of the lubricating oil with MGP were tested on a MS-10A four-ball machine (Xiamen Tenkey Automation Co., China) and compared to those of the base oil and the oil with modied natural ake graphite (MNFG). The PB of the lubricating oil was determined according to the ASTM D2783 standard method. The machine was

2 Experimental 2.1 Materials The graphene platelets and natural ake graphite (particle size: 25 lm) were provided by the Fujian Kaili Specialty

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conducted at a drive shaft speed of 1,450 rpm and in the temperature range 1835 C. The friction and wear tests were carried out according to the ASTM D4172-82 standard method and conducted at a rotating speed of 1,200 rpm and under a constant load of 147 N for a test duration of 60 min; a temperature of 75 2C was maintained throughout the whole test process. The 12.7mm diameter test balls used in this study were made of GCr15A bearing steel (AISI 52100) with a hardness of 64 HRC. Before each test, all test-section components were cleaned ultrasonically with petroleum ether, rinsed in ethanol, and dried. The wear scar diameters on the steel balls were measured using an optical microscope. The worn surfaces of the balls after the friction test were examined with SEM and EDS.

3 Results and Discussion 3.1 Characterization of Graphene Platelets Figure 1 is a typical SEM image of graphene platelets and shows that the graphene platelets retain their original laminated structure, with an average diameter of 1.2 lm. The thickness of the graphene platelets is about 1015 nm (Fig. 2) as determined by transmission electron microscopy (TEM). 3.2 Characterization of MGP The FTIR spectrum of graphene platelets before and after modication is shown in Fig. 3. Pure graphene platelets only showed a weak peak at 1,629 cm-1, which refers to C=C bonds. After modication with stearic and oleic acids, the peak at 1,629 cm-1 was strengthened, likely due to the absorption of oleic acids on the graphene platelets.
T(%)

Fig. 2 Transmission electron microscopy image of graphene platelets

25 20 15 10

after modification
1629 3485 2921 2862

5 0 -5 4000 3500

before modification
3000 2500 2000

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1629

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Wavenumber(cm-1)

Fig. 3 Infrared spectrum of modied graphene platelets (MGP) and pristine graphene platelets

Fig. 1 Scanning electron microscopy image of graphene platelets

Simultaneously, three new peaks at approximately 2,862, 2,921, and 3,485 cm-1 were clearly observed. The peaks at 2,862 and 2,921 cm-1 are attributed to CH3 and CH2 stretching mode, respectively, while the broad peak at 3,485 cm-1 can likely be attributed to -OH bonds. Coates [32] reported that the impact of hydrogen bonding could produce signicant band broadening as well as lower the mean absorption frequency, as shown in Fig. 3. Therefore, we concluded that the surfaces of graphene platelets were chemically modied by stearic and oleic acids. Figure 4 shows the suspension stability of the two lubricating oils as evaluated by UVVIS spectrophotometry, which measured the UV intensity of the lubricating oil

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1.00 0.95

pristine graphene platelets modified graphene platelets

700 650

Relative Concentration

oil with modified graphene platelets oil with modified natural flake graphite

0.90 0.85 0.80 0.75 0.70 0.65

PB(N)
0 50 100 150 200 250

600 550 500 450

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400 0.00 0.02 0.04 0.06 0.08 0.10 0.12

Time(min)

C(wt%)
Fig. 5 Effect of MGP and modied natural ake graphite (MNFG) concentration on maximum nonseizure load of the oil

Fig. 4 Suspension stability of the lubricating oils with MGP and graphene platelets as determined by ultravioletvisible light (UV VIS) spectrophotometry

solution by evaluating the rate of nanoparticle sedimentation. The relative concentration was calculated by the ratio of the particle concentration intensity of the supernatant uid at each measurement time divided by the initial concentration intensity of the suspension. A value of 1.0 at the relative concentration means excellent stability of the lubricating oil solution without particle sedimentation. Figure 4 shows that the particle concentration of the two different suspensions was nearly equal before centrifugation. Following a long period of centrifugation, rapid precipitation was observed for the suspension with the pristine graphene platelets, indicating that unmodied graphene platelets were heavily agglomerated in base oil. In contrast, little MGP precipitation was observed in the suspension with the MGP. This result indicates that the addition of MGP to the lubricating oil had produced an excellent stable suspension and that this improvement could be attributed to the effectiveness of the surface modication. Following the modication of the graphene platelets with stearic and oleic acids, the hydrophilic segments of the stearic and oleic acids molecules were anchored onto the surface of the graphene platelets. When the MGP were dispersed in the base oil, the long hydrocarbon segments easily stretched into the base oil and therefore produced a typical steric hindrance effect [31], which effectively helped to separate the graphene platelets from each other. At the same time, the steric hindrance force could conquer gravity and prevent the graphene platelets from coagulating. Therefore, the lubricating oil with MGP formed a uniform and stable suspension. 3.3 Tribology Tests of the Lubricating Oil with MGP or MNFG Bartz [33] pointed out that an optimal concentration of solid additive, such as graphite, exists in liquid lubricant. In

1.2 1.1 1.0 0.9

oil with modified natural flake graphite oil with modified graphene platelets pure base oil

Wear rate(%)

0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 10 20 30 40 50 60

Friction time(min)
Fig. 6 Wear rate as a function of friction time (four-ball, 1,200 rpm, 147 N, 60 min, 75 2C)

order to determine the concentration of additive giving the best tribological behavior, we tested several dispersions of MGP (0.015, 0.035, 0.055, 0.075, 0.095, and 0.105 wt%) and MNFG. Figure 5 shows the inuence of MGP and MNFG concentration on maximum nonseizure load (PB) of the oil. The PB represents the load-carrying capacity of the lubricating oil; in the pure base oil with 0 wt% of graphite particles, the PB value was 418.5 N. There was a remarkable increase in the PB values of the lubricating oil with the addition of increased concentrations of MGP and MNFG, respectively, to the base oil. When the concentration of MGP and MNFG reached 0.075 wt%, both PB values reached their maximum, but the largest PB value of the oil with MGP was 627.2 N, which was much higher than that of oil with MNFG (523 N). These results indicate that the oil with MGP had a better load-carrying capacity than the base oil and oil with MNFG. When the concentration was

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0.22 0.21 0.20

oil with modified graphene platelets pure base oil oil with natural flake graphite

0.19 0.18 0.17 0.16 0.15 0.14 0.13 0.12 0.11 0 10 20 30 40 50 60

Friction time(min)

Fig. 7 Friction coefcient as a function of friction time (four-ball, 1,200 rpm, 147 N, 60 min, 75 2C)

higher than 0.075 wt%, excessive MGP also resulted in a decrease in the PB value of the oil. One possible explanation is that some coagulation of graphene platelets and metallic debris occurred at higher concentrations of MGP/ MNFG owing to the friction effect, which made the friction unstable or caused vibration, leading to a decrease in the maximum nonseized load [34]. Figure 6 shows the wear rate of lubricating oils as a function of friction time, with MGP and MNFG concentrations of 0.075 wt% and a load of 147 N for 60 min at a speed of 1,200 rpm. It can be seen that the wear rates increased with increasing friction time. However, the wear rate of the oil with MGP increased to a lesser degree and more gradually than that of the base oil and the oil with MNFG. A similar tendency was observed in Fig. 7, which displays the friction coefcient as a function of friction time. With increasing friction time, the friction coefcients

Fig. 8 The worn surface of the steel ball and the corresponding energy dispersive spectrometry analysis. a Lubricated with base oil, b lubricated with base oil containing MNFG, c lubricated with base oil containing MGP

Friction coefficient

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of both the base oil and the oil with MNFG increased remarkably; in comparison, the friction coefcient of the oil with MGP was relatively steady throughout the test. Moreover, the friction coefcient of the oil with MGP was much lower than that of the base oil and oil with MNFG. The excellent anti-wear properties of MGP may possibly be attributed to their small diameter and extremely thin laminated structure, which allows MGP to easily enter the contact area and deposit a continuous protective lm that prevents direct contact with the rough face. The MNFG was unable to perform this efciency due to the large size of its lamellae.

additive to stably disperse in oil. The wear resistance and load-carrying capacity of the lubricating oil were greatly improved with the addition of MGP at an optimal content of 0.075 wt%. The friction coefcient of the oil with MGP was much lower than that of the base oil and oil with MNFG. In summary, the overall lubricious properties of the lubricating oil were notably improved, and this improvement can be attributed to the addition of MGP.
Acknowledgments This work is supported by National Science Foundation of China (No. 20574025), Natural Science Foundation of Fujian Province (E0820001), and Fujian Key Laboratory of Polymer Materials (Fujian Normal University).

3.4 Surface Analysis The lubricating oil containing MGP presents excellent anti-wear and friction-reducing properties, which were conrmed by the results of the SEM and EDS analysis. Figure 8 shows the SEM images of the rubbing surfaces lubricated by three lubricating oils as well as the corresponding EDS analysis. As shown in Fig. 8a, the metal surface has been severely scratched due to the poor antiwear property of the pure base oil. The EDS analysis showed that the content of C element on the metal surface was only 3.6 wt%, which may be due to the basal component of the steel ball and carbonizations of the oil layer. The rubbing surface shown in Fig. 8b was smoother than that in Fig. 8a, but it still showed obvious scratches and extensive furrows. Correspondingly, the EDS analysis displayed a content of C element of 10.2%, just a little higher than that found in Fig. 8a. This result indicates that natural ake graphite was barely deposited on the rubbing surface, which conrms that this graphite has difculty entering the contact area and, consequently, forming a continuous protective lm. In contrast, it can be seen in Fig. 8c that many graphene platelets were distributed on the metal surface and that the surface had nearly none of wear and scratch traces observed in Fig. 8a and b. In addition the content of C element was up to 27.86%, which is nearly ninefold and 2.7-fold higher than that shown in Fig. 8a and b, respectively. This result clearly proves that graphene platelets in oil easily form protective deposited lms to prevent the rubbing surfaces from coming into direct contact and, thereby, improve the entirely tribological behavior of the oil.

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