Abstract
The frictional behaviors of methyl oleate (MO), methyl palmitate (MP), methyl laurate (ML), and methyl stearate (MSt) as additives in hexadecane have been examined in a boundary lubrication test regime using steel contacts. It was found that the transient attributes of coefficient of friction (COF)-time spectra are a sensitive measure of adsorption equilibria. Critical additive concentrations were defined and used to perform novel and simple Langmuir analyses that provide an order of adsoprtion energies: MSt>MP>MO≥ML. Application of Langmuir, Temkin, and Frumkin-Fowler-Guggenheim adsorption models via nonlinear fitting of a general cooperative model demonstrates the necessary inclusion of cooperative effects in the applied model. In agreement with the qualitative features of steady-state COF-concentration plots, MSt modeling requires minimal cooperative interaction terms. However, MO, MP, and ML data require large attractive interaction terms to be adequately fitted. Primary adsorption energies calculated via the cooperative model are necessarily decreased, whereas total adsorption energies correlate well with values obtained via critical concentration analyses. These results and comparisons with previous adsorption studies of MO and MSt suggest that primary (ester-surface) and secondary (alkyl-surface) adsorbate-adsorbent, adsorbate-adsorbare, and (free-additive) adsorpt-adsorpt interactions collectively determine both the calculated primary and the cooperative interaction energies.
This is a preview of subscription content, log in via an institution to check access.
We’re sorry, something doesn't seem to be working properly.
Please try refreshing the page. If that doesn't work, please contact support so we can address the problem.
References
Erhan, S.Z., and J.M. Perez, Biobased Industrial Fluids and Lubricants, AOCS Press, Champaign, 2002, 135 pp.
Bhushan, B., Introduction to Tribology, John Wiley & Sons, New York, 2002, 752 pp.
Biresaw, G., A. Adhvaryu, and S.Z. Erhan, Friction Properties of Vegetable Oils, J. Am. Oil Chem. Soc. 80:697–704 (2003).
Biresaw, G., A. Adhvaryu, S.Z. Erhan, and C.J. Carriere, Friction and Adsorption Properties of Normal and High-Oleic Soybean Oils, 79:53–58 (2002).
Rowe, C.N., Role of Additive Adsorption in the Mitigation of Wear, ASLE Trans. 13:179–188 (1970).
Langmuir, I., The Adsorption of Gases on Plane Surfaces of Glass, Mica, and Platinum, J. Am. Chem. Soc. 40:1361–1403 (1918).
Steinfeld, J.I., J.S. Francisco, and W.L. Hase, Chemical Kinetics and Dynamics, Prentice Hall, Upper Saddle River, NJ, 1999, 560 pp.
Jahanmir, S., and M. Beltzer, An Adsorption Model for Friction in Boundary Lubrication, ASLE Trans. 29:423–430 (1986).
Bowden, F.P., J.N. Gregory, and D. Taboi, Adsorption of Nitrogen and the Mechanism of Ammonia Decomposition Catalysts, J. Am. Chem. Soc. 64:751–758 (1942).
Butt, H.-J., K. Graf, and M. Kappl, Physics and Chemistry of Interfaces, John Wiley & Sons, New York, 2003, 373 pp.
Wright, E.H.M., Adsorption of Methyl Laurate and Related Methyl Esters from Solution by Oxide Absorbents, Trans. Faraday Soc. 61:1764–1770 (1965).
Standard Test Method for Determination of the Coefficient of Friction of Lubricants Using the Four-Ball Wear Test Machine, Annual Book of ASTM Standards 5:164–167 (2001) D 5183-95.
Kingsbury, E.P., The Heat of Adsorption of a Boundary Lubricant, ASLE Trans, 3:30–33 (1960).
Frewing, J.J., The Heat of Adsorption of Long-Chain Compounds and Their Effect on Boundary Lubrication, Proc. R. Soc. Lond. A 182:270–285 (1944).
Sharma, J.P. R.C. Malhotra, and A. Cameron, Heat of Adsorption and Critical Temperature Studies of Boundary Lubricants on Steel Surfaces, Wear 25:281–297 (1973).
Cowley, C.W., C.J. Ultee, and C.W. West, Influence of Temperature on Boundary Lubrication, ASLE Trans. 1:281–286 (1958).
Huheey, J.E., E.A. Keiter, and R.L. Keiter, Inorganic Chemistry, Harper Collins College, New York, 1993.
Mori, S., and Y. Imaizumi, Adsorption of Model Compounds of Lubricant on Nascent Surfaces of Mild and Stainles Steels Under Dynamics Conditions, Trib. Trans. 31:449–453 (1988).
Miller, R., V.B. Fainerman, E.V. Aksenenko, V.V. Makievski, J. Kragel, L. Liggieri, F. Ravera, R. Wustneck, and G. Loglio, Surfactant Adsorption Kinetics and Exchange of Matter for Surfactant Molecules with Changing Orientation Within the Adsorption Layer, Proceedings of the Symposium on Emulsions, Foams, and Thin Films, (University Park, PA, June 21–24, 1998), Marcel Dekker, New York, 2000, pp. 313–327.
Fukuzaki, S., H. Urano, and M. Hiramatsu, Study of the Conformation of Protein Adsorbed on Stainless Stell Surfaces, J. Surface Finishing Jpn 49:1237–1238 (1998).
Author information
Authors and Affiliations
Corresponding author
About this article
Cite this article
Kurth, T.L., Biresaw, G. & Adhvaryu, A. Cooperative adsorption behavior of fatty acid methyl esters from hexadecane via coefficient of friction measurements. J Amer Oil Chem Soc 82, 293–299 (2005). https://doi.org/10.1007/s11746-005-1069-2
Received:
Accepted:
Issue Date:
DOI: https://doi.org/10.1007/s11746-005-1069-2