2005 Annual Report 1.What major problem or issue is being resolved and how are you resolving it (summarize project aims and objectives)? How serious is the problem? What does it matter? In order to expand the utilization of plant products, new markets and applications need to be developed. Of critical importance in such development is the ability to manufacture a product with acceptable performance characteristics in a cost-effective manner. This is particularly true of bio-based metalworking lubricants, which must compete against petroleum-based products that have been developed and optimized over several decades. In order to successfully develop and commercialize biobased metalworking lubricants, first a research program aimed at understanding the tribochemistry of biobased raw materials will be undertaken. Knowledge gained from such a program will then be used to develop new biobased metalworking lubricants. Complex tribochemical reactions occur during metalworking operations, which are responsible for the observed friction and wear (which affect productivity), as well as for the characteristics of the products (e.g. ability to wet and clean, adhesion, reflectance, etc) and co-products tribopolymers, hazardous air pollutants (HAPS), etc. Understanding, predicting and controlling tribochemical reactions is key to a successful development of biobased metalworking lubricants. Currently, there is a large oversupply of biobased raw materials relative to worldwide demand. This has depressed the price of agricultural products and, hence, the revenue to U.S. farmers. One way of increasing demand is through the development of new bio-based products. Metalworking fluids constitute a multi-billion dollar a year industry worldwide. Currently, almost all metalworking fluids are petroleum-based. Successful development of biobased lubricants that effectively compete against petroleum-based metalworking lubricants will result in new markets for millions of pounds of agricultural products, and thereby improve the income of U.S. farmers. This research falls under National Program 306 - Quality and Utilization of Agricultural Products; Component 2 - New processes, New Uses, and Value Added Foods and Biobased Products; Problem Area 2A - New Product Technology and Problem Area 2C - New and Improved Processes and Feedstocks. 2.List the milestones (indicators of progress) from your Project Plan. (1) Investigate the tribological properties of ag-based products of interest in metalworking lubricant formulation (a) Lubricity [boundary, hydrodynamic, elasthydrodynamic (EHD), mixed] & fluid property investigations (b) Film thickness investigations (c)Tribochemical investigations (d) Tribosimulation evaluations (e) Prototype tests (f) Pilot-scale blending (g) Production plant trial/implementation (h) Commercialize bio-based metalworking fluid (2) Develop and apply tribological predictive models for ag-based raw materials of interest in metalworking lubricant formulation. (a) Process parameter evaluation (Al rolling, steel drilling) (b) Evaluation of existing [boundary, hydrodynamic, mixed lubrication] models (c) Predictive model development (d) Predictive model evaluation/refinement (e) Predictive model application 4a.What was the single most significant accomplishment this past year? Development of a cheaper and quicker procedure for evaluating the boundary properties of ag-based raw materials. The method uses interfacial tension measurements between water and a non-polar oil to characterize the adsorption behavior of ag-based materials. The method is not limited to ag-based materials, but is applicable to any polar material that is soluble in non-polar oils. Previous methods used by us and other groups involved duplicate measurements over several concentrations that consumed a lot of rather expensive specimen. Our study showed that the interfacial method gave similar results as the friction method, faster, and at a much lower cost. 4b.List other significant accomplishments, if any. Commissioned several new tribotest instruments, and developed and implemented test protocols for investigating the boundary, extreme pressure (EP), hydrodynamic, EHD, traction, and other properties of ag-based materials and their blends. This has allowed the Current Research and Information System (CRIS) to play a key role in a USDA-Caterpillar collaborative research program aimed at developing biobased undercarriage lubricants. 4c.List any significant activities that support special target populations. None. 5.Describe the major accomplishments over the life of the project, including their predicted or actual impact. (1) Investigated the boundary properties of vegetable oils as a function of vegetable oil chemistry, which is critical to their development in metalworking lubricant formulations. (2) Studied the friction and wear properties of FanteskTM (starch-oil composites). These composites have the potential to be developed as solid lubricants for forming sheet metal. (3) Characterized the tribological properties of commercial and experimental ag-based raw materials that led to the development of promising water-free and water-based metalworking formulations. (4) Evaluated and extended existing adsorption models. Such work is critical in the development of predictive tribological models. (5) Investigated the hydrodynamic and elasto-hydrodynamic properties of various commercial and non-commercial seed oils. Such investigations are essential in the development of ag-based metalworking lubricants and the development of predictive models. (6) Investigated the boundary and hydrodynamic properties of various estolides. Estolides are oils synthesized from ag-based raw materials, and have been found to possess several useful characteristics of interest in lubrication. (7) Developed and implemented the interfacial method of investigating the boundary properties of ag-based materials. 6.What science and/or technologies have been transferred and to whom? When is the science and/or technology likely to become available to the end-user (industry, farmer, other scientists)? What are the constraints, if known, to the adoption and durability of the technology products? This CRIS is a critical component of the Cooperative Research and Development Agreement (CRADA) with Aluminum Company of America (Alcoa) to develop biobased aluminum rolling formulations (3620-41000-101-04T - Vegetable Oil Based Hot and Cold Rolling Metalworking Lubricants, S.Z. Erhan). This CRADA attained a major milestone this year when a jointly develop biobased lubricant was used by Alcoa in a hot rolling trial at a plant near Reno, NV. According to a preliminary report from Alcoa, the trial showed promising results for the biobased hot rolling lubricant in several areas including: product quality, productivity, and safety (operator exposure). Some of the environmental data collected during the trial was analyzed and reported at the conference of Society of Tribologists and Lubrication Engineers (STLE). Knowledge developed in this CRIS is currently being applied in a USDA-Caterpillar (CAT) collaborative research program aimed at developing biobased undercarriage lubricants for tractors. The USDA team in this collaboration involves personnel from three units at the National Center for Agricultural Utilization Research (NCAUR), and a CRADA is currently being finalized. In order to improve the chances of commercialization of the technology developed in this CRIS, we are continuing our effort to identify and interact with key private companies related to the metalworking industry. Our objective is to get them interested in a collaborative program where they can play a variety of roles in the development of biobased metalworking fluids, including providing access to their bench and pilot scale evaluation facilities. To this end, we have continued our interactions with companies that supply biobased ingredients to metalworking lubricant formulators, formulate and supply metalworking fluids, and use metalworking fluids. In addition, findings of this program have been transferred through timely presentations and publications to farm groups, private industry, and to other scientists working in academia and industry. Over the last reporting year we have made formal/informal presentations to farmer and industry groups (Cargill). Our results have also been presented at several national and international scientific meetings, and published in peer-reviewed journals. We will continue to report our findings as quickly as we obtain verifiable results. We also plan to continue identifying and interacting with potential collaborators in order to be able to evaluate and commercialize biobased metalworking lubricants. 7.List your most important publications in the popular press and presentations to organizations and articles written about your work. (NOTE: List your peer reviewed publications below). None. Review Publications Kurth, T.L., Biresaw, G., Adhvaryu, A. 2005. Cooperative adsorption behavior of fatty acid methyl esters from hexadecane via coefficient of friction measurements. Journal of the American Oil Chemists' Society. 82(4):293-299. Biresaw, G. 2004. Compatibility in polymer blends comprising biodegradable polyesters. In: Proceedings of International Conference on Polymers for Advanced Technologies, December 15-17, 2004, Thiruvananthapuram, India. 2004 CDROM. Shogren, R.L., Biresaw, G. 2005. Surface properties of water soluble starch esters [abstract]. American Chemical Society. p.1 of 2, cell 27. Dunlap, C.A., Biresaw, G., Jackson, M.A. 2005. Cell surface properties of blastospores of the entomopathogenic fungus paecilomyces fumosoroseus [abstract]. XLV Annual Meeting, American Phytopathological Society-Caribbean Division/VI National Phytopathological Meeting. Abstract #14. Biresaw, G., Carriere, C.J. 2004. Surface energy parameters of polymers from directly measured interfacial tension with probe polymers. Journal of Adhesion Science and Technology. 18(14):1675-1686. Biresaw, G., Gordon, S.H. 2005. Spectroscopic investigation of polymer interactions in model bioblends. Proceedings of Adhesion Society. p.428-430. Biresaw, G., Isbell, T., Cermak, S.C. 2005. Film-forming properties of estolides. Proceedings of World Tribology Congress III. Available: http://www.conferencetoolbox.org/WTC05/index.cfm. Kurth, T.L., Cermak, S.C., Biresaw, G. 2005. Adsorption behavior of fatty esters and oleic estolides from hexadecane via coefficient of friction measurements [abstract]. World Tribology Congress III. Available: http://www.conferencetoolbox.org/WTC05/index.cfm. Biresaw, G. 2004. Compatibility in polymer blends comprising biodegradable polyesters [abstract]. Biodegradable Polyesters International Conference on Polymer Science and Technology. p.28. Biresaw, G., Gordon, S.H. 2005. Spectroscopic investigation of polymer interactions in model bioblends [abstract]. Adhesion Society. p.17. Biresaw, G. 2005. Elastohydrodynamic properties of biobased ingredients [abstract]. Society of Tribologists and Lubrication Engineers. p.81. Kurth, T.L., Adhvaryu, A., Biresaw, G. 2005. FFG adsorption behavior of methyl esters from hexadecane [abstract]. Society of Tribologists and Lubrication Engineers. p.171. Kurth, T.L., Biresaw, G. 2005. Cooperative adsorption behavior of methyl fatty esters from hexadecane via coefficient of friction measurements [abstract]. American Oil Chemists' Society Meeting. p. 57.