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Tribology International 42 (2009) 397402

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Tribology International
journal homepage: www.elsevier.com/locate/triboint

Tribological properties of uorine-containing additives of silicone oil

Guotuan Gu a,, Zhishen Wu a, Zhijun Zhang a, Fengling Qing b
a b

College of Chemistry and Chemical Engineering, Henan University, 85 Minlun Street, Kaifeng 475001, China College of Chemistry and Chemical Engineering, Donghua University, 2999 North Remin Road, Songjiang District, Shanghai 201620, China

a r t i c l e in fo
Article history: Received 14 December 2007 Received in revised form 8 July 2008 Accepted 18 July 2008 Available online 30 August 2008 Keywords: Silicone oil Anti-wear Friction-reduction Fluoro acid amine salt

abstract
An oil soluble uorine-containing octadecylamine salt of decapentyluorooctanoic acid was synthesized and characterized by Fourier transform infrared spectroscopy (FTIR), 1H-nuclear magnetic resonance (1H NMR) and 19F NMR. The thermal stability of octadecylamine salt of decapentyluorooctanoic acid was measured by a thermogravimetric (TG) analysis. The anti-wear and friction-reducing properties of the amine salt as a silicone-based lubricating oil additive were evaluated using a four-ball tribotester. The results indicated that both the wear resistance and the load-carrying capacity of a silicone-based lubricating oil 4609 shock absorption liquid were improved and the friction coefcient was decreased by the additive. The wear scar, after being cleaned using an ultrasonic bath in petroleum ether, was characterized with scanning electron microscopy (SEM) and X-ray photoelectron spectrometry (XPS). It was found that the boundary lm on the worn surface was composed of uorinecontaining organic lm and iron uoride such as FeF2, which provided the oil with improved anti-wear and friction-reducing properties. & 2008 Elsevier Ltd. All rights reserved.

1. Introduction Polydimethylsiloxanes are basic components of one of the most popular and widely applied synthetic polymer materials silicones. Their unique properties such as wide-range thermal stability, resistance to oxidation, low surface tension, gas permeability, excellent dielectric properties, physiological inertness and moisture resistance [13] are the reasons for a wide application of silicones to many branches of industry [4,5]. Silicone uids have a uniquely low-temperature coefcient of viscosity, which make them of interest as lubricant. However, silicones also have a serious drawback: they are very poor lubricants under conditions of boundary lubrication and particularly when the rubbing surfaces are of steel. Under such conditions, the use of silicones as lubricants leads to high friction and wear, galling and seizing [6]. Anti-wear and friction-reducing additives are necessary to improve the boundary lubricating properties of silicone oil. But, most of the conventional anti-scuff and anti-wear additives developed for use in mineral lubricating oils are not soluble in liquid silicones, and most of those that do dissolve in silicones do not give the expected benet. Fluorinated and partially uorinated organic compounds may be used as anti-wear additives in lubricating oils. Fluorinated organic compounds, particularly esters and ethers [710], have

been suggested as lubricants for magnetic media. Fluorinated organic compounds are thought to protect metal surfaces from wear by forming metal uorides on the coated surfaces through tribochemical reactions. Metal uorides such as iron uoride are known to have good properties as solid lubricants. Although some uorinated materials such as PTFE, PFPE, uorinated esters are used as lubricants themselves, but their very low solubility in conventional lubricant base uids makes it extremely difcult to use them as additives in lubricant formulations. Therefore, this investigation aims to synthesize an oil and silicone uid soluble uorine-containing octadecylamine salt of decapentyluorooctanoic acid and evaluate their tribological properties as an antiwear and friction-reducing additives for silicone-based lubricant formulations.

2. Experimental 2.1. Preparation of octadecylamine salt of decapentyluorooctanic acid Octadecylamine salt of decapentyluorooctanic acid, CF3 CF2 5 CF2 COO NH3 CH2 CH2 16 CH3 was prepared according to the literature [6]. The following procedures were used. Separate solutions were made of (1) 0.01 mole (2.695 g) of octadecylamine (CH3(CH2)16CH2NH2, Fluka, with hexadecylamine p10%, average molecular weight 269.52) in

Corresponding author.

E-mail address: guotuan-gu@henu.edu.cn (G. Gu). 0301-679X/$ - see front matter & 2008 Elsevier Ltd. All rights reserved. doi:10.1016/j.triboint.2008.07.012

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15 mL tetrahydrofuran and (2) 0.01 mole (4.770 g) of decapentyluorooctanic acid (CF3(CF2)5CF2COOH, Dupont) in 20 mL tetrahydrofuran. The acid solution was slowly added at room temperature to the amine solution, with stirring. The temperature rose from 25 to 30 1C. The tetrahydrofuran was then distilled using a R-210 (Buchi) rotatory evaporator (RPM, 100 r/min, temperature, 50 1C) under vacuum (vacuum pressure, 0.05 Mpa). The nal product was an amber, viscous uid, and waxy solid below 20 1C, soluble in hydrocarbons and silicone uids. 2.2. Characterization of octadecylamine salt of decapentyluorooctanic acid The chemical structure of octadecylamine salt of decapentyluorooctanic acid was characterized by FTIR and 1H and 19F NMR. The FTIR spectrum was recorded on a Nicolet IR-380 spectrometer. 1 H and 19F NMR were recorded on an AV400 (Bruker) nuclear magnetic resonance detector. Chemical shifts of the 1H spectrum were related to the CHCl3 signal at 7.24 ppm. And chemical shifts of the 19F spectra were related to the CFCl3 signal at 0 ppm. To evaluate the thermal stability, thermogravimetric analysis was carried out on a NETZSCH TG 209 F1 thermoanalyzer, under N2 atmosphere, with a heating rate of 10 1C/min. 2.3. Measurement of tribological properties The prepared octadecylamine salt of decapentyluorooctanic acid was added to a silicone-based lubricating oil (commercial brand 4609 shock adsorption liquid, PetroChina Company Limited) with heating (about 40 1C) and stirring. The blends are clear and show no signs of haze or settling even after 2 months storage. The anti-wear and friction-reducing properties of octadecylamine salt of decapentyluorooctanic acid in silicone were tested on a MS-10A four-ball tribotester, which provides a point contact conguration. The steel balls (j12.7 mm, Shanghai Steel Ball Company) used in the test are made of GCr15 bearing steel (composition: C, 0.951.05%; Si, 0.150.35%; Mn, o0.250.45%; P,

o0.25%; S,o0.25%; Cr, 1.401.65%; Ni, and Cu o0.025%) with Rockwell C hardness (HRC) 6164. The base stock 4609 shock adsorption liquid had a viscosity of 11.92 mm2/s at 100 1C and 1209 mm2/s at 40 1C. Before each test, the balls and specimen holders were ultrasonically cleaned in a petroleum ether bath (normal alkane with a boiling point of 6090 1C). Each test was repeated three times so as to minimize data scatter. All tests were conducted at room temperature under the following conditions: room temperature, load 147 N, rotation rate 1450 rpm, test duration 60 min. At the end of each test, the mean wear-scar diameter on the three lower balls was measured using a digitalreading optical microscope to an accuracy of 0.01 mm. The average wear-scar diameter of the three identical tests was calculated as the wear-scar diameter. 2.4. Analysis of the rubbed surface The morphologies of the rubbed surfaces were observed using a JEOL JSM-5600LV scanning electron microscope (SEM). The binding energies of typical elements on the worn surface were measured using a Perkin-Elmer PHI-5702 multi-technique X-ray photoelectron spectrometer (XPS) using a pass energy of 29.35 eV and a MgKa line excitation source with the reference of C1s at 284.6 eV.

3. Results and discussion 3.1. Characteration of octadecylamine salt of decapentyluorooctanic acid FTIR spectra were recorded on a Nicolet IR-380 spectrometer. Solid powders of octadecylamine were mixed with KBr powders and pressed into tablet. The specimen of octadecylamine salt of decapentyluorooctanic acid was dissolved in acetone and coated on a cleaned KBr tablet. Both spectra of octadecylamine and octadecylaminealt of decapentyluorooctanic acid are shown in

100 % Transmittance % Transmittance 80 60 40 20 -0

100 80 60 40 20 4000 3500 3000 2500 2000 wavenumber (cm-1) 1500 1000 500

Fig. 1. FTIR spectra of octadeylamine (top) and octadecylamine salt of decapentyluorooctanic acid (bottom).

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c
e d c b a f g h i C F 3 C F 2 (CF 2 ) 4 C F 2 CO O -+ N H 3 CH 2 (C H 2 ) 15 CH 2 CH 3

e
2.51 1.28

d
1.90 0.62 1.76 1.83 23.27 3.00

4 ppm

g h 1.20 3.00 2.15 7.16

-60

-70

-80

-90

-100 ppm

-110

-120

-130

Fig. 2. 1H NMR (top) and 19F NMR (bottom) of octadecylamine salt of decapentyluorooctanic acid.

Fig. 1. We clearly see that the band of NH (st) near 3334 cm1 disappeared completely after reaction with decapentyluorooctanic acid. In the IR spectrum of octadecylamine salt of decapentyluorooctanic acid, bands at 2929 and 1467 cm1 are +NH3(st) and + NH3(d), respectively. And the band at 1685 cm1 attributed to carbonyl CQO (st) of COO group. No bands of OH(st) are near 3400 cm1 of COOH group of raw material decapentyluorooctanic acid. This means all the amine and the acid used are changed to amine salt (Fig. 2): 1 H-NMR (CDCl3): 7.79 (d, 3H, +NH3), 1.95 (d, 2H, NCH2), 0.87 (d, 3H, CH3), 1.65 (d, 2H, CH2CH3), 1.29 (d, 24H, all other CH2). 19 F NMR (CDCCl3): 77.8 (m, 3F, CF3), 73.81 (m, 2F, CF3CF2), 119.18 (m, 2F, CF2COO), 128.11 (m, 8F, all other CF2 signals). This indicated that amine salt octadecylamine salt of decapentyluorooctanic acid was prepared successfully. To evaluate the volatility and the thermal stability of octadecylamine salt of decapentyluorooctanic acid, the thermogravimetric analysis was carried out on a NETZSCH TG 209 F1 thermoanalyzer, under N2 atmosphere, with a heating rate of

10 1C/min. As shown in Fig. 3, below 150 1C, almost no weight loss was found, and when the temperature increased to 200 1C, only about 5% weight loss was found. This means octadecylamine salt of decapentyluorooctanic acid liquid has a very low volatility. Sharp weight loss takes place at about 215 1C. This indicated the thermal decomposition of octadecylamine salt of decapentyluorooctanic acid.

3.2. Measurement of tribological properties The tribological properties of octadecylamine salt of decapentyluorooctanic acid prepared as additive for silicone-based lubricating oil were tested on a four-ball tribotester. Fig. 4 shows the effect of concentration of octadecylamine salt of decapentyluorooctanic acid on the wear-scar diameter of lubricating oil. The test conditions are as follows: room temperature, load 147 N, rotation rate 1450 rpm, test duration 60 min. Clearly, the addition of octadecylamine salt of decapentyluorooctanic acid can improve the anti-wear property of base oil. With the increase of additive content from 0 wt% (base oil) to 0.5 wt%,

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-5.23 100

215.3

Flow/ (mL/min) 250 -0 -5 200 DTG (%/min) base oil oil with 0.5wt% additive -10

80

TG/%

60

150 100

-15 -20 -25

40

20 229 50 100 150 200 250 300 350 400 450 500

50 -30 0

Temperature C
Fig. 3. The TG curve of octadecylamine salt of decapentyluorooctanic acid, with N2 atmosphere, heating rate 10 1C.

0.50 Wear Scar Diameter (mm) 0.48 Friction coefficient 0.0 0.5 1.0 concentration (%)
Fig. 4. The effect of concentration of octadecylamine salt of decapentyluorooctanic acid on the wear-scar diameter (room temperature, load 147 N, 60 min, 1450 rpm).

0.18 0.17 0.16 0.15 0.14 0.13 0.12 0.11 0.10 1.5 2.0 0.09 0.08 0 10 20 30 40 Friction time (minute) 50 60

0.46 0.44 0.42 0.40

0.56 Wear Scar Diameter (mm)

Fig. 6. Effect of octadecylamine salt of decapentyluorooctanic acid on the friction coefcient of silicone-based lubricating oil (load, 245 N, room temperature, 1450 rmp, 60 min).

0.52
slightly high WSD. This means higher contents of additive are not helpful to improve the anti-wear property of the base oil. Small amount of the additive about 0.5 wt% is suitable for the lubricating oil formulation. Fig. 5 shows the WSD of 4609 shock absorption liquid (base oil) and of 4609 shock absorption liquid with 0.5 wt% of additive, as a function of applied load. The test conditions are: room temperature, 1450 rpm, 60 min. It can be seen that, for base oil only, the wear-scar diameters are relatively higher than that of base oil with 0.5 wt% additive. At the highest load (245 N), the test had to be stopped right away because of the high friction and excessive noise. On the other hand, base oil-containing additive ran smoothly at all loads and gave relatively low wear-scar diameters. This means octadecylamine salt of decapentyluorooctanic acid as an additive can improve the anti-wear property of the siliconebased lubricating oil. The friction-reduction effect of octadecylamine salt of decapentyluorooctanic acid as an additive for silicone-based

0.48

0.44 oil with 0.5% additive base oil 147 196 Load (N) 245

0.40

Fig. 5. The wear-scar diameter with and without additive under different normal load (room temperature, 60 min, 1450 rpm).

the wear-scar diameter (WSD) decreases from 0.498 to 0.398 mm. The lowest wear-scar diameter was found when the content was about 0.5 wt%. Higher concentrations of the additive resulted a

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Fig. 7. SEM morphologies of the worn surface lubricated with: (a) 4609 shock adsorption liquid, 200 ; (b) 4609 shock adsorption liquid, 1000 ; (c) 4609 shock adsorption liquid with 0.5 wt% of octadecylamine salt of decapentyluorooctanic acid , 200 ; (d) 4609 shock adsorption liquid with 0.5 wt% of octadecylamine salt of decapentyluorooctanic acid, 1000 . (conditions: 147 N, 1450 rpm, room temperature, 60 min).

lubricating oil 4609 shock adsorption liquid is shown in Fig. 6. It can be seen clearly that the friction coefcient measured using the oil with 0.5 wt% additive is slightly lower than that of the base oil only during the initial stage of the test. As friction time increased, both of them showed a tendency to decrease. As a result, the friction coefcient of the oil-containing octadecylamine salt of decapentyluorooctanic acid additive was markedly less than that of the base oil. This indicates octadecylamine salt of decapentyluorooctanic acid as an additive for silicone-based lubricating oil can reduce the friction coefcient of the oil. The results of the tribological properties of octadecylamine salt of decapentyluorooctanic acid as an additive for silicone-based lubricating oil show that the silicone oil itself gave high friction and wear. Adding a small amount of the additive prepared can reduce the friction and the wear of the base oil.

3.3. A discussion of the anti-wear and friction-reduction mechanism of octadecylamine salt of decapentyluorooctanic acid The wear-scar morphologies of balls running in base oil and in the oil with octadecylamine salt of decapentyluorooctanic acid additive are given in Fig. 7. Both balls were ultrasonically cleaned in a petroleum ether bath 5 min before SEM observations. Severe wear is found on the former wear scar, and the latters are smoother and only slight wear is found. This means octadecylamine salt of decapentyluorooctanic acid additive is helpful in protecting the friction surface from wear under severe friction conditions. We suppose that octadecylamine salt of decapentyluorooctanic acid could be easily adsorbed on the sliding surfaces of frictional pairs. Subsequently, an effective boundary lm would form thereon to reduce the friction and the wear. Furthermore, under severe friction conditions, octadecylamine salt of decapentyluorooctanic acid will decompose to

form anti-scratch components such as iron uorides. Evidence of deposition can be found on the latter worn surface. Moreover, it seems that the wear scar appeared like a platform made by the deposition process. The elemental compositions of the worn surfaces after testing lubrications with base stock oil and with oil-containing octadecylamine salt of decapentyluorooctanic acid additive were analyzed using XPS (Fig. 8). No uorine signals were detected on the worn surface lubricated with the base stock oil (Fig. 8a). Meanwhile, uorine signals were detected on the worn surface lubricated with oil-containing additives (Fig. 8b), peaks at about 685.4 eV correspond to iron uorides, and peaks at about 680 eV to organic uorides. The Fe2p3/2 spectra (Fig. 8c) exhibit photoelectron intensity at a binding energy consistent with FeF2 at about 711 eV [11]. Thus, it can be concluded that complicated tribochemical reactions were involved during the friction process. Hence, it can be inferred that octadecylamine salt of decapentyluorooctanic acid as lubricant additive for silicone base oil, could mainly function by tribochemical reaction, with the generation of a surface protective lm composed of organic uoride and inorganic uoride on the lubricated metal surface.

4. Conclusion Silicone liquid oil-soluble octadecylamine salt of decapentyluorooctanic acid was synthesized. The anti-wear and frictionreduction properties of the uorine-containing amine salt used as a silicone-based lubricating oil additive were evaluated. The wear resistance of a commercially available silicone-based oil 4609 shock adsorption liquid were improved and its friction coefcient decreased by a small amount addition of octadecylamine salt of decapentyluorooctanic acid. Tribochemical reactions took place under severe friction conditions, which resulted in the formation

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Acknowledgments

280 260 240 Intensity 220 200 180 160 140 695 690 685 680 675 Binding energy (eV)

F1s

The authors would like to thank Professor Huizhong Huang and Dr. Jingwei Zhang of Henan University for XPS analysis and helpful discussion. The authors are also grateful to the National Postdoctoral Science Foundation of China (Grant no. 2005038411) and Henan University Science Foundation (Grant no. XK052DZR007) for the nancial support. References
[1] Clarson SJ, Semlyen JH, editors. Siloxane polymers. New York: Prentice-Hall; 1993. [2] Kircheldorf HR, editor. Silicon in polymer synthesis. Berlin: Springer; 1996. [3] Yilgor I, McGrath JE. Adv Polym Sci 1998;86:1. [4] KirkOthmer encyclopedia of chemical technology, 4th ed., vol. 22, New York: Wiley; 1997. [5] Rappoport Z, Apeloig Y, editors. The chemistry of organic silicon compounds. Chichester: Wiley; 1998. [6] US patent 3565926. [7] US patent 5578387. [8] Japanese patent 01122026. [9] US patent 4203856; 5066412; 4039301. [10] US patent 3124533. [11] Hara H, Nishigachi I, Sagi S, Tsuboi S. Tribol Lett 2001;10:143.

670

280 260 Intensity 240 220 200 180 160 140 695 690 685 680 675 685.4

F1s

670

Binding enegy (eV)

400 350 Intensity 300 250 200 150 100 740 730 720

711

Fe2p3/2

710

700

Binding energy (eV)

Fig. 8. XPS spectra of F1s worn surface lubricated by silicone-based oil (a); F1s (b) and Fe2p3/2 (c).

of boundary lubrication lms consisting iron uorides, which improves the boundary lubrication behavior of the silicone-based lubricating oil.