CHEMICAL SYSTEMS FOR SOYBEAN OIL CONVERSION TO INDUSTRIAL PRODUCTS

Knowledge Area (KA)	Subject of Investigation (SOI)	Field of Science (FOS)	Percent
511	1820	2000	90%
511	1899	2000	10%

Progress 08/09/04 to 06/14/09

Outputs
Progress Report Objectives (from AD-416) Establish different reaction protocols to insert branching and transesterification on triglyceride molecule of vegetable oil for use in the formulation of industrial/automotive lubricants with better lubricity, friction, wear, oxidation and low temperature properties. Such fluids include, but are not restricted to: (a) Bio-based Greases; (b) Synthetic Lubricants/Metalworking Fluids/Gear Oils/Under-carriage Oils; (c) Bio- based Specialty Additives. Investigate and develop economically feasible polymeric products from vegetable oils (with emphasis on soybean oil) and thus, expand their domestic and export markets. These biobased polymeric materials include, but are not restricted to: (a) Soybased composites reinforced with flax fibers; (b) Nanoclay reinforced soybased composites; (c) Polymeric surfactants derived from soybean oil; (d) Soybased hydrogel for controlled delivery system; and (e) Energy absorbing materials. Approach (from AD-416) Research will focus on establishing different reaction protocols to insert branching and trans-esterification, on triglycerid molecule of soybean oil that will be used in the formulation of biobased grease, synthetic lubricants, metal-working fluids, biobased specialty additives with better lubricity, friction, wear, oxidation and low temperature properties. Research will also utilize the principles of organic chemistry and polymer science to synthesize more reactive soybean oil based monomers. New types of polymers and composites will be developed. Resulting polymers will be used in controlled delivery systems and energy absorbing materials formulations. Significant Activities that Support Special Target Populations The accomplishments in this project over the term have continued toward the goal of developing technology to increase the suitability and acceptability of vegetable oil based products in non-traditional applications. All of the milestones set for this year have been accomplished. Additionally, the work has resulted in a total of four docket disclosures. These disclosures cover a variety of materials, including a new polymeric form of vegetable oil which can be used in chewing gum production and a new selection of additives which will improve the extreme pressure lubrication properties of bio-based lubricants. Two of the disclosures were accepted, and are in the docket of the patent committee awaiting patent preparation. The others both received deferments, indicating that they are suitable to be patented with some additional information. Samples of lubrication products have been sent out to several companies, which are hopeful in using these products in their formulations. In work that is complimentary to these milestones, a new method utilizing low resolution nuclear magnetic resonance (NMR) spectroscopy in order to determine the physical properties of a polymer was developed and published. Although these technologies are too new to judge completely, the amount of interest that they are drawing from industrial companies is promising. If put into practice, there is potential for the gum material to enter into a market which is both highly valued, and highly visible. The lubrication fluids are vying for a less visible market, but one that is also quite large. They bring the added benefit that in addition to being bio-based themselves, these fluids are designed to work with lubricants that are also bio-based. All of these are steps towards the new agriculturally based economy of the future. Technology Transfer Number of Active CRADAS: 1 Number of New/Active MTAs(providing only): 12 Number of Invention Disclosures submitted: 4

Impacts
(N/A)

Publications

Doll, K.M., Erhan, S.Z. 2008. Synthesis of cyclic acetals (ketals) from oleochemicals using a solvent free method. Green Chemistry. 10(6):712-717.
Doll, K.M., Kenar, J.A., Erhan, S.Z. 2008. Carbonates from oleochemicals: Biobased materials to value added green chemicals. Chemistry Today/Chimica Oggi. 25(6):7-10.
Doll, K.M., Sharma, B.K., Suarez, P.A., Erhan, S.Z. 2008. Comparing biofuels obtained from pyrolysis, of soybean oil or soapstock, with traditional soybean biodiesel: density, kinematic viscosity, and surface tensions. Energy and Fuels. 22(3):2061-2066.
Sharma, B.K., Doll, K.M., Erhan, S.Z. 2008. Biobased greases: soap structure and composition effects on tribological properties. In: Biresaw, G., Mittal, K.L., editors. Surfactants in Tribology. Boca Raton, FL: CRC Press. p. 309-323.
Sharma, B.K., Perez, J.M., Erhan, S.Z. 2007. Soybean oil-based lubricants: a search for synergistic antioxidants. Energy and Fuels. 21:2408-2414.
Doll, K.M., Sharma, B.K., Erhan, S.Z. 2007. Synthesis of branched methyl hydroxy stearates including an ester from bio-based levulinic acid. Industrial and Engineering Chemistry Research. 46:3513-3519.
Kurth, T.L., Sharma, B.K., Doll, K.M., Erhan, S.Z. 2007. Adsorption behavior of epoxidized fatty esters via boundary lubrication coefficient of friction measurements. Chemical Engineering Communications. 194:1065- 1077.
Kurth, T.L., Byars, J.A., Cermak, S.C., Sharma, B.K., Biresaw, G. 2007. Non-linear adsorption modeling of fatty esters and oleic estolides via boundary lubrication coefficient of friction measurements. Wear. 262(5-6) :536-544.
Sharma, B.K., Doll, K.M., Erhan, S.Z. 2008. Ester hydroxy derivatives of methyl oleate: tribological, oxidation and low temperature properties. Bioresource Technology. 99(15):7333-7340.
Xu, J., Liu, Z., Erhan, S.Z. 2008. Viscoelastic properties of a biological hydrogel produced from soybean oil. Journal of the American Oil Chemists' Society. 85(3):285-290.
Carrao-Panizzi, M.C., Erhan, S.Z. 2007. Environmental and genetic variation of soybean tocopherol content under Brazilian growing conditions. Journal of the American Oil Chemists' Society. 84:921-928.
Sharma, B.K., Liu, Z., Adhvaryu, A., Erhan, S.Z. 2008. One-pot synthesis of chemically modified vegetable oils. Journal of Agricultural and Food Chemistry. 56:3049-3056.
Biswas, A., Sharma, B.K., Willett, J.L., Erhan, S.Z., Cheng, H.N. 2008. Room-temperature self-curing ene reactions involving soybean oil. Green Chemistry. 10(3):298-303.
Biresaw, G., Liu, Z., Erhan, S.Z. 2008. Investigation of the surface properties of polymeric soaps obtained by ring-opening polymerization of epoxidized soybean oil. Journal of Applied Polymer Science. 108(3):1976- 1985.
Liu, Z., Erhan, S.Z., Akin, D.E., Barton Ii, F.E., Onwulata, C.I., Mckeon, T.A. 2008. Modified flax fibers reinforced soy-based composites: mechanical properties and water absorption behavior. Composite Interfaces. 15:207-220.
Suarez, P.A., Pereira, M.S., Doll, K.M., Sharma, B.K., Erhan, S.Z. 2009. Epoxidation of Methyl Oleate using Heterogeneous Catalyst. Journal of Industrial and Engineering Chemical Research. 48:3268-3270.
Doll, K.M., Erhan, S.Z. 2009. Polyol and Amino Acid-Based Biosurfactants, Builders, and Hydrogels. In: Hayes, D.G., Kitamomo, D., Solaiman, D.K.Y., Ashby, R.D., editors. Biobased Surfactants and Detergents: Synthesis, Properties, and Applications. Urbana, IL: AOCS Press. p. 425-448.
Erhan, S.Z., Sharma, B.K., Doll, K.M. 2009. Opportunities for Industrial Uses of Agricultural Products. Chemistry Today/Chimica Oggi. 27(1):38-41.
Erhan, S.Z., Sharma, B.K., Doll, K.M. 2009. Production of Agricultural Commodities in the United States. Chemistry Today/Chimica Oggi. 27(1):34- 36.
Doll, K.M. 2009. A Convenient Low-Resolution NMR Method for the Determination of the Molecular Weight of Soybean Oil-Based Polymers. Journal of the Association for Laboratory Automation. 14(4):185-189.
Doll, K.M., Sharma, B.K., Erhan, S.Z. 2008. Friction reducing properties and stability of epoxidized oleochemicals. Clean. 36(8):700-705.
Biswas, A., Sharma, B.K., Willett, J.L., Erhan, S.Z., Cheng, H. 2008. Soybean Oil as a Renewable Feedstock for Nitrogen-Containing Derivatives. Energy and Environmental Science. 1:639-644. Available: http://xlink.rsc. org/?doi=B809215J.
Liu, Z., Erhan, S.Z. 2008. A new soy-based hydrogels: development, viscoelastic properties, and application for controlled drug release. In: Parris, N., Liu, L.S., Song, C. and Shastri, V.P., editors. New Delivery Systems for Controlled Drug Release from Naturally Occurring Materials. American Chemical Society Symposium Series 992, Chapter 2. Washington, DC: ACS Press. p. 17-38.
Liu, Z., Erhan, S.Z. 2009. Synthesis of Soy Polymers Using a "Green" Processing Method. In: Celina, M.C., Wiggins, J.S., Billingham, N.C., editors. Polymer Degradation and Performance. Chapter 7. Washington, DC: American Chemical Society. p. 70-87.
Liu, Z., Erhan, S.Z. 2008. "Green" composites and nanocomposites from soybean oil. Materials Science and Engineering A. 483-484(1-2c):708-711.
Doll, K.M., Moser, B.R., Sharma, B.K., Erhan, S.Z. 2007. Current uses of vegetable oil in the surfactant, fuel, and lubrication industries. Chemistry Today/Chimica Oggi. 24(6):41-44.

Progress 10/01/06 to 09/30/07

Outputs
Progress Report Objectives (from AD-416) Establish different reaction protocols to insert branching and transesterification on triglyceride molecule of vegetable oil for use in the formulation of industrial/automotive lubricants with better lubricity, friction, wear, oxidation and low temperature properties. Such fluids include, but are not restricted to: (a) Bio-based Greases; (b) Synthetic Lubricants/Metalworking Fluids/Gear Oils/Under-carriage Oils; (c) Bio- based Specialty Additives. Investigate and develop economically feasible polymeric products from vegetable oils (with emphasis on soybean oil) and thus, expand their domestic and export markets. These biobased polymeric materials include, but are not restricted to: (a) Soybased composites reinforced with flax fibers; (b) Nanoclay reinforced soybased composites; (c) Polymeric surfactants derived from soybean oil; (d) Soybased hydrogel for controlled delivery system; (e) Energy absorbing materials. Develop economically feasible polymeric products from vegetable oils (with emphasis on soybean oil) and thus, expand their domestic and export markets. Approach (from AD-416) Research will focus on establishing different reaction protocols to insert branching and trans-esterification, on triglycerid molecule of soybean oil that will be used in the formulation of biobased grease, synthetic lubricants, metal-working fluids, biobased specialty additives with better lubricity, friction, wear, oxidation and low temperature properties. Research will also utilize the principles of organic chemistry and polymer science to synthesize more reactive soybean oil based monomers. New types of polymers and composites will be developed. Resulting polymers will be used in controlled delivery systems and energy absorbing materials formulations. Accomplishments Development of a new synthetic method to make vegetable oil-based industrial fluids. With annual global lubricant demand at more than 30 million tons, alternatives to petroleum-based lubricants are needed. Many currently available lubricant additives contain materials which may be harmful to the environment. We have developed a method to synthesize a new fluid from bio-based materials using green methodology. Our compounds have been characterized and shown to have the properties necessary to be effective lubricant additives. A patent was filed, on March 13, 2007: Method of Making Fatty Acid Ester Derivatives, S.N. 11/717,524 (Docket #0071.06). This accomplishment addresses Component 2 of the National Program 306, "New Processes, New Uses, and Value-Added Foods and Biobased Products." Technology Transfer Number of New CRADAS and MTAS: 5 Number of Active CRADAS and MTAS: 6 Number of Patent Applications filed: 1 Number of U.S. Patents granted: 1 Number of new Commercial Licenses granted: 1 Number of Non-Peer Reviewed Presentations and Proceedings: 32 Number of Newspaper Articles,Presentations for NonScience Audiences: 1

Impacts
(N/A)

Publications

Sharma, B.K., Adhvaryu, A., Perez, J.M., Erhan, S.Z. 2006. Biobased grease with improved oxidation performance for industrial application. Journal of Agricultural and Food Chemistry. 54:7594-7599.
Sharma, B.K., Sharma, C.D., Tyagi, O.S., Bhagat, S.D., Erhan, S.Z. 2007. Structural characterization of asphaltenes and ethyl acetate insoluble fractions of petroleum vacuum residues. Petroleum Science and Technology. 25:121-139.
Liu, Z., Sharma, B.K., Erhan, S.Z. 2006. From oligomers to molecular giants of soybean oil in supercritical carbon dioxide medium: 1. Preparation of polymers with lower molecular weight from soybean oil. Biomacromolecules. 8:233-239.
Sharma, B.K., Adhvaryu, A., Erhan, S.Z. 2006. Synthesis of hydroxy thio- ether derivatives of vegetable oil. Journal of Agricultural and Food Chemistry. 54:9866-9872.
Sharma, B.K., Sharma, C.D., Bhagat, S.D., Erhan, S.Z. 2007. Maltenes and asphaltenes of petroleum vacuum residues: Physico-chemical characterization. Petroleum Science and Technology. 25:93-104.
Biswas, A., Adhvaryu, A., Stevenson, D.G., Sharma, B., Willett, J.L., Erhan, S.Z. 2007. Microwave irradiation effects on the structure, viscosity, thermal properties and lubricity of soybean oil. Industrial Crops and Products. 25:1-7.
Erhan, S.Z., Sharma, B.K., Perez, J.M. 2006. Oxidation and low temperature stability of vegetable oil-based lubricants. Industrial Crops and Products. 24:292-299.
Doll, K.M., Erhan, S.Z. 2006. Synthesis and performance of surfactants based on epoxidized methyl oleate and glycerol. Journal of Surfactants and Detergents. 9:377-383.
Wong, H.L., Rauth, A.M., Bendayan, R., Manias, J.L., Ramaswamy, M., Liu, Z. , Erhan, S.Z., Wu, X.Y. 2006. A new polymer-lipid hybrid nanoparticle system increases cytotoxicity of doxorubicin against multidrug-resistant human breast cancer cells. Pharmaceutical Research. 23(7):1574-1585.
Sharma, B.K., Doll, K.M., Erhan, S.Z. 2007. Oxidation, friction reducing, and low temperature properties of epoxy fatty acid methyl esters. Green Chemistry. 9:469-474.
Biswas, A., Sharma, B.K., Willett, J.L., Vermillion, K., Erhan, S.Z., Cheng, H.N. 2007. Novel modified soybean oil containing hydrazino-ester: synthesis and characterization. Green Chemistry. 9:85-89.
Erhan, S.Z., Sharma, B.K. 2007. Vegetable oil-based biodegradable industrial lubricants. In: Hou, C., Shaw, J.-F., editors. International Symposium on Biocatalysis and Biotechnology for Functional Food and Industrial Products, 2nd edition. Boca Raton, FL: CRC Press. p. 349-362.
Erhan, S.Z., Sharma, B.K. 2007. Lubricants. In: Gunstone, F.D., Harwood, J. L., Dijkstra, A.J., editors. Non Food Uses of Oils and Fats, Lipid Handbook, 3rd Edition, Chapter 9. Boca Raton, FL: CRC Press. p. 591-635.
Liu, Z., Erhan, S.Z., Calvert, P. 2007. Solid freeform fabrication of epoxidized soybean oil/epoxy composite with bis or polyalkyleneamine curing agents. Composites: Part A 38:87-93.

Progress 10/01/05 to 09/30/06

Outputs
Progress 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? Why does it matter? The major use of vegetable oils (such as soybean oil) is directed to food products, salad and cooking oils, shortenings, and margarines in particular. Less than 3% is utilized in non-food applications, since a number of former vegetable oil markets are lost to petroleum products. In the years following World War II, petroleum derived products rapidly displaced vegetable oil-based materials. Certain performance and technical properties can be easily achieved using seed oil derivatives. Such products based on agro raw materials are at par with available petroleum based products in the market. The importance of natural products for industrial applications becomes very clear with increasing social emphasis on the issues of environment, waste disposal, and depleting non-renewable resources. Seed oils and products based on seed oil derivatives suffer from some technical drawbacks such as oxidation, cold flow behavior and extended stability. For applications such as composites, lubricants, plastics, fuel, and chemical intermediates; soybean oil and other vegetable oils are too viscous and too reactive toward atmospheric oxygen to establish significant markets. Limitations in molecular weight and crystallization properties restrict the uses of vegetable oils in solvents, plastics, fuels, and industrial fluids. In addition to above problems, this research project will address low volatile organic chemicals (VOC), high biodegradability in ink formulations, and low or no VOC improved oxidative stability/low temperature properties in biodegradable lubricants. This project contributes to National Program 306 on "Quality and Utilization of Agricultural Products." U.S. Environmental Protection Agency (EPA), Clean Air Act Amendment, and U.S. Department of Labor, Occupational Safety & Health administration, (OSHA) regulations exert ever growing pressure on the graphic arts (inks, paints, coatings), lubricants and hydraulic oils, detergents, emulsifiers, and the polymer industries on limiting the use of organic solvents, creating less toxic waste, using a renewable resource, and producing more biodegradable products. Parties affected by these regulations and parties interested in enhanced marketability of soybean (American Soybean Association, United Soybean Board) and other oilseed crops will use the results and/or products of this research project to expand the market for these commodities. 2. List by year the currently approved milestones (indicators of research progress) First Year FY2005: 1. Seed oil-based metalworking fluid for aluminum hot rolling will be formulated. 2. Complete initial preparation of grease samples with Li metal, fatty acids and check for consistency and smooth paste like texture conforming to NLGI specifications. 3. Complete preparation of synthetic lubricant basestocks using epoxidized vegetable oils, long chain/branched alcohols and catalyst; and further reaction on above product using acid anhydrides. 4. Complete the reaction optimization of vegetable oils with different sulfur compounds (which may or may not contain an amine functionality) using a catalyst (perchloric acid) to obtain biobased additives in higher yields and characterization using NMR, FTIR and PDSC. 5. Complete initial preparation of composites samples with non-coated flax fibers using compression molding method and study their mechanical and water absorption properties. 6. Complete the samples preparations of Nano-clay Reinforced Soybased Composites. Thermo and mechanical properties will be studied. 7. Soybased Hydrogels prepared from ring-opening polymerization and hydrolysis of obtained polymers will be studied for their temperature sensitive and pH sensitive properties. 8. ESO will be cured with polyamine compounds to form Energy Absorbing Materials sheets for mechanical, thermophysical properties tests. 9. Ring opening polymerization will be carried out using Lewis catalysts for preparing soybean oil based polymeric surfactants. Second Year FY2006: 1. Seed oil-based metalworking fluid for aluminum hot rolling will be tested for various performance and tribochemical properties in-house. 2. Characterization of grease samples for their Penetration, oxidation and thermal stability using PDSC, micro-oxidation, oven test, RBOT. 3. Complete ring-opening reaction of epoxidized seed oil followed by esterification of resulting hydroxyl group to give lubricant base fluid. Characterize the chemically modified vegetable oil fluids for their oxidative stability and pour point and check to see if the process significantly improved the low temperature fluidity and thermal stability of the oil. 4. Complete the reactions of vegetable oils with different amines using same catalyst to synthesize bio-based anti-wear, anti-oxidants additives and characterization using NMR, FTIR and PDSC. 5. To prepare composites samples reinforced with coated flax fibers and to characterize their binding properties using TEM. Three point bend and tensile tests will be performed on samples fabricated under task 1 (first year) using noncoated fibers and coated fibers. Compare their mechanical and water absorption properties. Evaluate polyamine curing agents. 6. Optimum clay loading, curing conditions and study the structures of clay dispersion in the host polymers for Nano-clay Reinforced Soybased Composites. 7. Study drug loading and release rate of Soybased Hydrogels. Effect of dissolution media such as temperature, pH on the release rate will be investigated. 8. Complete material selection and formulation of Energy Absorbing Materials. Glass transition temperatures (Tgs) will be determined using DSC. 9. Initiator evaluation for ring opening polymerization will be performed. Optimization of polymerization conditions necessary to obtained soybean oil based polymeric surfactants in high yield will also be investigated. Synthesis of other derivatives of epoxidized methyl esters such as epoxidized methyl oleate, epoxidized methyl linoleate, and epoxidized linolenate. Third Year FY2007: 1. Tribochemical evaluation and physical property determination of metal working fluids will continue based on feed back from CRADA partner. 2. Develop methods to study wear-friction properties of grease samples. Try to establish structure-property relationship using above data. 3. Complete the formulation and blending of chemically modified vegetable oil fluids with other seed oils and suitable PPD, anti-oxidant and anti-wear additives. Evaluate the final products for pour point, viscosity, viscosity index, oxidative stability using PDSC, friction and wear characteristics using Falex to study the effect of structural variation in the oil molecules. 4. Complete the reactions of vegetable oils with different alcohol- amines using same catalyst to synthesize bio-based anti-wear, anti- oxidants additives and characterization using NMR, FTIR and PDSC. Synthesis of vegetable oil analogs using carboxylic acids using base catalysis. 5. Optimization of curing agents for epoxidized soybean oil and curing conditions such as pressure, temperature, and reaction time; study of fiber loading influence on the mechanical properties of composites; and analysis of water swelling data of composites. 6. Work will continue on the characterization of Nano-clay Reinforced Soybased composites using x-ray and TEM. 7. Study drug release kinetics followed Fickian law or nonFickian law for Soybased Hydrogels. 8. Damping and falling weight properties of soybased energy absorbing materials will be evaluated. 9. Hydrolysis of obtained soybean oil based polymers using sodium hydroxide to remove glycerin small molecule, purification of the samples for GPC analysis. Surface tension and contact angle measurements of soybean oil based polymeric surfactants are performed. The critical micelle concentration(CMC) will be determined. Synthesis of small molecule surfactants derived from vegetable oil and the carboxylic acids and esters of vegetable oil. Fourth Year FY2008: 1. Using established structure - property relationship and optimized conditions such as metal, fatty acid content, base oil amount to complete preparation/formulation of NLGI grade 2 grease with AO, AW, EP additives. Formulation will be tested by industrial CRADA partners. 2. Complete scale up in 20L reactor to prepare 6 lbs of synthetic lubricant base fluids and optimization of reaction variables for economically producing the environmentally friendly ester-based lubricants from epoxidized vegetable oil; following test by industrial CRADA partners. 3. Complete development of PDSC and Falex methods to test effectiveness (anti-oxidant and anti-wear behavior) of synthesized bio-based additive compounds, comparison with industrially available additives and screening for potential bio-based anti-oxidant and anti-wear additives. 4. Complete development of composites which are reinforced by natural fiber and nano clay. Industrial CRADA partner finishes their site tests. 5. A soybased drug controlled release system will be developed. Industrial partners will test this system. 6. New energy absorbing materials with good damping and energy absorbing properties will be developed from soybean oil. 7. Finish studies on soybean oil based polymeric surfactants. Further evaluation and comparison of vegetable oil based small molecule surfactants with available products. Synthesis of bio-based surfactants using vegetable oil based esters and other biological small molecules such as sugars and glycerides. Evaluation of the surfactants for CMC and surface tension reduction. Fifth Year FY2009: 1. Complete bio-based grease studies, patent/transfer technology. 2. Complete final evaluation of Synthetic Lubricants/Metal working Fluids/Gear Oils/Under-carriage oils after analyzing data obtained from industrial CRADA partners, offer recommendations for changes in final formulation and patent/transfer technology. 3. Finish studies on Bio-based Speciality Additives, complete patents/paper writing. 4. Technical paper will be written for publication for studies on Soybased Composites Reinforced with Flax Fibers and Nano-clay Reinforced Soybased Composites. 5. Complete patent/paper writings and patent filing on the soybased hydrogels for controlled release systems. 6. Related scientific papers will be written on energy absorbing material developed from soybean oil. 7. Complete patent/paper writing on polymeric surfactants derived from soybean oil. 4a List the single most significant research accomplishment during FY 2006. Developing soybased hydrogels. Polymeric drug delivery systems have attracted increasing attention during the last two decades. Amphiphilic block copolymers have been widely studied due to their potential application in drug delivery systems as they are capable of forming aggregates in aqueous solutions. These aggregates comprise of a hydrophobic core and hydrophilic cell. They are good vehicles for delivering hydrophobic drugs, since the drugs are protected from possible degradation by enzymes. The soy-based amphiphilic polymers are prepared in our lab. Hydrogels formulated from these polymers are studied in controlled release systems. This work is intended to develop and evaluate a new polymer-lipid hybrid nanoparticle system that can efficiently load and release water-soluble anticancer drug doxorubicin hydrochloride (Dox) and enhance Dox toxicity against multidrug-resistant (MDR) cancer cells. Dox-SLN were prepared with a drug encapsulation efficiency of 60-80% and a particle size range of 80-350 nm. About 50% of the loaded drug was released in the first few hours and an additional 10-20% in 2 weeks. Treatment of the MDR cells with Dox-SLN resulted in over 8-fold increase in cell kill when compared to Dox solution treatment at equivalent doses. The blank SLN and the excipients exhibited little cytoxicity. The biological activity of the released Dox remained unchanged from fresh, free Dox. The new polymer-lipid hybrid nanoparticle system is effective for delivery of Dox and enhances its efficacy against MDR breast cancer cells. The patent "Soy-based Thermosensitive Hydrogels for Controlled Release Systems" is pending. The paper of "A New Polymer-Lipid Hybrid Nanoparticle System Increases Cytotoxicity of Doxorubicin Against Multidrug Resistant Human Breast Cancer Cells," coauthored with the University of Toronto, was accepted by the journal of "Pharmaceutical Research." This accomplishment is under NP 306, Component 2, "New Processes, New Uses, and Value-Added Foods and Biobased Products." 4b List other significant research accomplishment(s), if any. Development of vegetable oil based lubricants. Two CRADA's have been signed in the area of lubricant research. Metal working fluid developed under a CRADA is being used by one of the CRADA partners in their two commercial plants in the U.S. and being tested for use in their Australia and England plants. This accomplishment is part of NP 306, Component 2, "New Processes, New Uses, and Value-Added Foods and Biobased Products." 5. Describe the major accomplishments to date and their predicted or actual impact. Technologies developed by the involved scientists and currently undergoing commercial development include biobased lubricants and composites. U.S. Patent (6,583,302) has been awarded for Chemically Modified Vegetable Oil Based Industrial Fluids. Another U.S. Patent (6, 528,571) has been awarded for Extrusion Freeform Fabrication of Soybean Oil-based composites by Direct Deposition. Total non-food use of soybean oil is only 300 million pounds per year. The above technologies alone present an opportunity to triple the market. Chemically modified vegetable oil based lubricants technology has been licensed to Agrilube Inc./Bunge an Indiana-based company and licensing and technology transfer activities are continuing (with great interest from domestic and international companies) for other technologies. A soy oil based elevator hydraulic fluid technology was developed based on a request from National Park Service (Statue of Liberty, Ellis Island, NY). The bio-based fluid was developed at the NCAUR facility of USDA and independently evaluated by industrial partner (OTIS elevator). Subsequently the fluid was scaled up and retrofitted in the Statue of Liberty elevator and has been successfully operating for nearly 2 years. Collaborative efforts will continue to license our ink, grease, lubricants and composite work. Based on this technology development activity, the NCAUR/USDA team has been awarded the FLC-2004 award for "Excellence in Technology Transfer." Bunge Oil/Agrilube, Inc. licensed three patent technologies for the soybean oil-based hydraulic elevator fluid and printing inks. The collaborators (CRADA Partners) in Alcoa Technology were provided with 150 gallons of USDA's soy oil based base oil for metalworking fluid, which they used in their formulation and tried in one of their pilot plants at Reno, NV. The plant trial was a huge success and USDA's bio- based lubricant outperformed the equivalent control lubes. In quality of metal, USDA's bio-based lube without scratch-brushes outperformed control with scratch-brush (use of scratch-brush improves rolled metal quality). In productivity, USDA's bio-based lube allowed incrased reduction that was unattainable with existing dispersion lubes. As far as operator exposure is concerned, EHS conducted tests and found that USDA's bio- based lube outperformed control lubes, i.e., exposure was minimum with bio-based lubes. They also did a price evaluation of the cost to make a hot rolling lubricant using USDA's base oil. They conclude that USDA's base oil makes this formulation very attractive even though its cost is much higher than mineral oil. The reason for this is that the cost of the overall package is actually slightly less than many of their commercial hot mill lubricants because boundary additives are not needed for USDA formulation. They will conduct a trial or two for their large rolling mills in coming months (one in Europe and one in USA). 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? Ink and Hydraulic Elevator Fluid Technologies have been transferred to a company. One Cooperative Research and Development Agreement was signed. Two Cooperative Research and Development Agreements are in progress. Two U.S. Patents are pending. One U.S. Patent application is in the process. Four Material Transfer Agreements have been signed. 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). 1. Statue of Liberty Goes Green With Soy-Based Elevator Fluid http://www.agclassroom.org/teen/ars_pdf/tech/2004/10soy.pdf http://www.findarticles.com/p/articles/mi_m3741/is_10_52/ai_n6276559 http://www.ars.usda.gov/is/AR/archive/oct04/soy1004.htm http://www.thesoydaily.com/BiodieselBiobased/liberty10052004.asp 2. Biodegradable Lube for Metalworking Operations was published in the May 2006 issue of Agricultural Research magazine. http://www.ars.usda.gov/is/AR/archive/may06/lube0506.htm 3. Soy Oil-Based Metalworking Lubricant Earns High Marks from Alcoa was published on 5/9/2006 issue of Soyatech eNews Daily http://www.soyatech.com/bluebook/news/viewarticle.ldml?a=20060509-8

Impacts
(N/A)

Publications

Erhan, S.Z., Sharma, B.K. 2005. Biodegradable industrial lubricants [abstract]. International Symposium on Biocatalysis and Biotechnology, Functional Foods and Industrial Products. p. 49.
Doll, K.M., Holser, R.A., Erhan, S.Z. 2006. Surface tension studies of chemically modified oleochemical glycerides. 97th American Oil Chemists' Society Annual Meeting and Expo. p. 72-73.
Adhvaryu, A., Biresaw, G., Sharma, B.K., Erhan, S.Z. 2006. Friction behavior of some seed oils: Bio-based lubricant applications. Industrial and Engineering Chemistry Research. 45(10):3735-3740.
Adhvaryu, A., Erhan, S.Z., Perez, J.M. 2005. Preparation of soybean oil- based greases: Effect of composition and structure on physical properties. Journal of Agricultural and Food Chemistry. 52(21):6456-6459.
Erhan, S.Z., Sharma, B.K. 2005. Development and tribochemical evaluation of biobased antiwear additive. In: Proceedings of the American Society of Mechanical Engineers (ASME). International Mechanical Engineering Congress and Exposition, November 5-11, 2005, Orlando, Florida. p. 1-5.
Erhan, S.Z., Sharma, B.K., Adhvaryu, A. 2005. Biobased lubricants: Improvement in oxidation and low temperature stability. In: Pascual- Villalobos, M.J., Nakayama, F.S., Bailey, C.A., Correal, E., Schoman, Jr., W.W., editors. Proceedings of the 2005 Annual Meeting of the Association for the Advancement of Industrial Crops. International Conference on Industrial Crops and Rural Development, September 17-21, 2005, Murcia, Spain. p. 737-746.
Erhan, S.Z., Sharma, B.K. 2005. High oleic vegetable oil based lubricants. In: Proceedings of the United States/Japan Natural Resources (UJNR) Food and Agriculture Panel Meeting, October 23-29, 2005, Fuji, Japan. p. 129- 135.
Biswas, A., Adhvaryu, A., Gordon, S.H., Erhan, S.Z., Willett, J.L. 2005. Synthesis of diethylamine functionalized soybean oils. Journal of Agriculture and Food Chemistry. 53(24):9485-9490.
Liu, Z., Erhan, S.Z., Akin, D.E., Barton II, F.E. 2006. Green composites from renewable resources: Preparation of epoxidized soybean oil and flax fiber composites. Journal of Agricultural and Food Chemistry. 54:2134-2137.
Erhan, S.Z. 2006. The use of soybean oil in biobased products. In: Proceedings of the 3rd Edition of the Mercosur Congress of Soybean (MERCOSOJA 2006), June, 27-30, 2006, Rosario, Argentina. p. 23-25.
Erhan, S.Z., Sharma, B.K. 2005. Environmentally friendly biobased lubricants [abstract]. PacifiChem 2005, December 15-20,2005, Honolulu, Hawaii. p. 877.
Erhan, S.Z., Liu, Z. 2005. Development of thermosensitive polymers for control release systems [abstract]. PacifiChem 2005, December 15-20, 2005, Honolulu, Hawaii. p. 685.
Sharma, B.K., Perez, J.M., Erhan, S.Z. 2006. Synthesis and characterization of biobased lubricant additives [abstract]. 97th American Oil Chemists' Society Annual Meeting and Expo. p. 73.
Sharma, B.K., Perez, J.M., Erhan, S.Z. 2006. Friction and wear behavior of biobased lubricant additives [abstract]. 61st Annual Meeting of the Society of Tribologist and Lubrication Engineers (STLE). p. 232.
Erhan, S.Z., Sharma, B.K. 2006. Vegetable oil based biodegradable lubricants for industrial applications [abstract]. BIO 2006 International Convention, Innovative Corridor Poster Session. p. 21.
Liu, Z., Erhan, S.Z. 2006. "Green" composites and nanocomposites from soybean oil [abstract]. 14th International Conference on the Strength of Materials (ICSMA14). p. 103.
Carrao-Panizzi, M.C., Rennick, K.A., Erhan, S.Z. 2006. Phytosterol concentration of soybean cultivars sowed in different locations of Brazil [abstract]. 97th American Oil Chemists' Society Annual Meeting and Expo. p. 90.
Erhan, S.Z., Liu, Z. 2006. Soy-based thermosensitive polymers for control release systems [abstract]. BIO 2006 International Convention, Innovative Corridor Poster Session. p. 39.
Liu, Z., Sharma, B.K., Erhan, S.Z. 2006. From oligomer to molecular giants of soybean oil in supercritical carbon dioxide medium [abstract]. 97th American Oil Chemists' Society Annual Meeting and Expo. p. 73.
Doll, K.M., Erhan, S.Z. 2006. Synthesis of cyclic carbonates from fatty materials using supercritical carbon dioxide [abstract]. 10th Annual Green Chemistry and Engineering Conference, Designing for a Sustainable Future. p. 24.
Song, B., Chen, W., Liu, Z., Erhan, S.Z. 2006. Dynamic compressive behavior of epoxidized soybean oil/clay nanocomposites [abstract]. U.S. Congress Of Theoretical and Applied Mechanics (USNCTAM), University of Colorado at Boulder. p. 59.
Erhan, S.Z., Sharma, B.K., Adhvaryu, A. 2005. Industrial lubricants based on high oleic vegetable oils [abstract]. 26th World Congress and Exhibition of the International Society of Fats (ISF). p. 82.
Erhan, S.Z., Adhvaryu, A., Sharma, B.K. 2006. Chemically functionalized vegetable oils. In: Rudnick, L.R., editor. Synthetics, Mineral Oils, and Bio-Based Lubricants, Chemistry and Technology. Boca Raton, FL: CRC Press. p. 361-387.
Castro, W., Perez, J.M., Erhan, S.Z., Caputo, F. 2006. A study of the oxidation and wear properties of vegetable oils: Soybean oil without additives. Journal of the American Oil Chemists' Society. 83(1):47-52.
Song, B., Chen, W., Liu, Z., Erhan, S.Z. 2006. Compressive properties of soybean oil-based polymers at quasi-static and dynamic strain rates. Journal of Applied Polymer Science. 99:2759-2770.
Hwang, H., Erhan, S.Z. 2006. Synthetic lubricant basestocks from epoxidized soybean oil and guerbet alcohols. Industrial Crops and Products. 23:313-317.
Rudnick, L.R., Erhan, S.Z. 2006. Natural oils as lubricants. In: Rudnick, L.R., editor. Synthetics, mineral oils, and bio-based lubricants. Chapter 21. Boca Raton, FL: CRC Press. p. 353-360.
Sharma, B.K., Adhvaryu, A., Liu, Z., Erhan, S.Z. 2006. Chemical modification of vegetable oils for lubricant applications. Journal of the American Oil Chemists' Society. 83(2):129-136.
Adhvaryu, A., Sharma, B.K., Erhan, S.Z. 2005. Current developments of biodegradable grease. In: Erhan, S.Z., editor. Industrial Uses of Vegetable Oils. Chapter 2. Champaign, IL: AOCS Press. p. 14-30.
Liu, Z., Erhan, S.Z., Xu, J. 2005. Preparation, characterization and mechanical properties of epoxidized soybean oil/clay nanocomposites. Polymer. 46:10119-10127.
Doll, K.M., Erhan, S.Z. 2005. Synthesis of carbonated fatty methyl esters using supercritical carbon dioxide. Journal of Agricultural and Food Chemistry. 53(24):9608-9614.
Doll, K.M., Erhan, S.Z. 2005. The improved synthesis of carbonated soybean oil using supercritical carbon dioxide at a reduced reaction time. Green Chemistry. 7:849-854.
Adhvaryu, A., Sharma, B.K., Hwang, H., Erhan, S.Z., Perez, J.M. 2006. Development of bio-based synthetic fluids: Application of molecular modeling to structure-physical property relationship. Industrial and Engineering Chemistry Research. 45(3):928-933.

Progress 10/01/04 to 09/30/05

Outputs
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? The major use of vegetable oils (such as soybean oil) is directed to food products, salad and cooking oils, shortenings, and margarines in particular. Less than 3% is utilized in non-food applications, since a number of former vegetable oil markets are lost to petroleum products. In the years following World War II, petroleum derived products rapidly displaced vegetable oil-based materials. Certain performance and technical properties can be easily achieved using seed oil derivatives. Such products based on agro raw materials are at par with available petroleum based products in the market. The importance of natural products for industrial applications becomes very clear with increasing social emphasis on the issues of environment, waste disposal, and depleting non-renewable resources. Seed oils and products based on seed oil derivatives suffer from some technical drawbacks such as oxidation, cold flow behavior and extended stability. For applications such as composites, lubricants, plastics, fuel, and chemical intermediates; soybean oil and other vegetable oils are too viscous and too reactive toward atmospheric oxygen to establish significant markets. Limitations in molecular weight and crystallization properties restrict the uses of vegetable oils in solvents, plastics, fuels, and industrial fluids. In addition to above problems, this research project will address low Volatile Organic Chemicals (VOC), high biodegradability in ink formulations, and low or no VOC, improved oxidative stability/low temperature properties in biodegradable lubricants. U.S. Environmental Protection Agency (EPA), Clean Air Act Amendment, and U.S. Department of Labor, Occupational Safety & Health Administration, (OSHA) regulations exert ever growing pressure on the graphic arts (inks, paints, coatings), lubricants and hydraulic oils, detergents, emulsifiers, and the polymer industries on limiting the use of organic solvents, creating less toxic waste, using a renewable resource, and producing more biodegradable products. Parties affected by these regulations and parties interested in enhanced marketability of soybean (American Soybean Association, United Soybean Board) and other oilseed crops will use the results and/or products of this research project to expand the market for these commodities. 2. List the milestones (indicators of progress) from your Project Plan. First Year FY2005: 1. Seed oil-based metalworking fluid for aluminum hot rolling will be formulated. 2. Complete initial preparation of grease samples with Li metal, fatty acids and check for consistency and smooth paste like texture conforming to National Lubricant Grease Index (NLGI) specifications. 3. Complete preparation of synthetic lubricant base stocks using epoxidized vegetable oils, long chain/branched alcohols and catalyst; and further reaction on above product using acid anhydrides. 4. Complete the reaction optimization of vegetable oils with different sulfur compounds (which may or may not contain an amine functionality) using a catalyst (perchloric acid) to obtain biobased additives in higher yields and characterization using Nuclear Magnetic Resonance (NMR), Fourier Transform Infrared (FTIR) and Pressurized Differential Scanner Calorimetry (PDSC). 5. Complete initial preparation of composites samples with non-coated flax fibers using compression molding method and study their mechanical and water absorption properties. 6. Complete the samples preparations of nano-clay reinforced soybased composites. Thermo and mechanical properties will be studied. 7. Soybased Hydrogels prepared from ring-opening polymerization and hydrolysis of obtained polymers will be studied for their temperature sensitive and pH sensitive properties. 8. Epoxidized Soybean Oil (ESO) will be cured with polyamine compounds to form energy absorbing materials sheets for mechanical, thermophysical properties tests. 9. Ring opening polymerization will be carried out using Lewis catalysts for preparing soybean oil based polymeric surfactants. Second Year FY2006: 1. Seed oil-based metalworking fluid for aluminum hot rolling will be tested for various performance and tribochemical properties in-house. 2. Characterization of grease samples for their penetration, oxidation and thermal stability using PDSC, micro-oxidation, oven test, Rotary Bound Oxidation Test (RBOT). 3. Complete ring-opening reaction of epoxidized seed oil followed by esterification of resulting hydroxyl group to give lubricant base fluid. Characterize the chemically modified vegetable oil fluids for their oxidative stability and pour point and check to see if the process significantly improved the low temperature fluidity and thermal stability of the oil. 4. Complete the reactions of vegetable oils with different amines using same catalyst to synthesize bio-based anti-wear, anti-oxidants additives and characterization using NMR, FTIR and PDSC. 5. Prepare composites samples reinforced with coated flax fibers and to characterize their binding properties using a Transmission Electron Microscope (TEM). Three point bend and tensile tests will be performed on samples fabricated under task 1 (first year) using noncoated fibers and coated fibers. Compare their mechanical and water absorption properties. Evaluate polyamine curing agents. 6. Optimum clay loading, curing conditions and study the structures of clay dispersion in the host polymers for nano-clay reinforced soybased composites. 7. Study drug loading and release rate of soybased hydrogels. Effect of dissolution media such as temperature, pH on the release rate will be investigated. 8. Complete material selection and formulation of energy absorbing materials. Glass transition temperatures (Tgs) will be determined using DSC. 9. Initiator evaluation for ring opening polymerization will be performed. Optimization of polymerization conditions necessary to obtained soybean oil based polymeric surfactants in high yield will also be investigated. Synthesis of other derivatives of epoxidized methyl esters such as epoxidized methyl oleate, epoxidized methyl linoleate, and epoxidized linolenate. Third Year FY2007: 1. Tribochemical evaluation and physical property determination of metal working fluids will continue based on feedback from Cooperative Research and Development Agreement (CRADA) partner. 2. Develop methods to study wear-friction properties of grease samples. Try to establish structure-property relationship using above data. 3. Complete the formulation and blending of chemically modified vegetable oil fluids with other seed oils and suitable Pour Point Depressant (PPD), Anti-Oxidant (AO) and Anti-Wear (AW) additives. Evaluate the final products for pour point, viscosity, viscosity index, oxidative stability using PDSC, friction and wear characteristics using Falex to study the effect of structural variation in the oil molecules. 4. Complete the reactions of vegetable oils with different alcohol-amines using same catalyst to synthesize bio-based anti-wear, anti-oxidants additives and characterization using NMR, FTIR and PDSC. Synthesis of vegetable oil analogs using carboxylic acids using base catalysis. 5. Optimization of curing agents for epoxidized soybean oil and curing conditions such as pressure, temperature, and reaction time; study of fiber loading influence on the mechanical properties of composites; and analysis of water swelling data of composites. 6. Work will continue on the characterization of nano-clay reinforced soybased composites using X-ray and TEM. 7. Study drug release kinetics followed Fickian law or nonFickian law for Soybased Hydrogels. 8. Damping and falling weight properties of soybased energy absorbing materials will be evaluated. 9. Hydrolysis of obtained soybean oil based polymers using sodium hydroxide to remove glycerin small molecule, purification of the samples for Gel Permeation Chromatography (GPC) analysis. Surface tension and contact angle measurements of soybean oil based polymeric surfactants are performed. The Critical Micelle Concentration (CMC) will be determined. Synthesis of small molecule surfactants derived from vegetable oil and the carboxylic acids and esters of vegetable oil. Fourth Year FY2008: 1. Using established structure - property relationship and optimized conditions such as metal, fatty acid content, baseoil amount to complete preparation/formulation of NLGI grade 2 grease with AO, AW, Extreme Pressure (EP) additives. Formulation will be tested by industrial CRADA partners. 2. Complete scale up in 20L reactor to prepare 6 lbs of synthetic lubricant base fluids and optimization of reaction variables for economically producing the environmentally friendly ester-based lubricants from epoxidized vegetable oil; following test by industrial CRADA partners. 3. Complete development of PDSC and Falex methods to test effectiveness (anti-oxidant and anti-wear behavior) of synthesized bio-based additive compounds, comparison with industrially available additives and screening for potential bio-based anti-oxidant and anti-wear additives. 4. Complete development of composites which are reinforced by natural fiber and nano clay. Industrial CRADA partner finishes their site tests. 5. A soybased drug controlled release system will be developed. Industrial partners will test this system. 6. New energy absorbing materials with good damping and energy absorbing properties will be developed from soybean oil. 7. Finish studies on soybean oil based polymeric surfactants. Further evaluation and comparison of vegetable oil based small molecule surfactants with available products. Synthesis of bio-based surfactants using vegetable oil based esters and other biological small molecules such as sugars and glycerides. Evaluation of the surfactants for CMC and surface tension reduction. Fifth Year FY2009: 1. Complete bio-based grease studies, patent/transfer technology. 2. Complete final evaluation of synthetic lubricants/metal working fluids/gear oils/under-carriage oils after analyzing data obtained from industrial CRADA partners, offer recommendations for changes in final formulation and patent/transfer technology. 3. Finish studies on bio-based speciality additives, complete patents/paper writing. 4. Technical paper will be written for publication for studies on soybased composites reinforced with flax fibers and nano-clay reinforced soybased composites. 5. Complete patent/paper writings and patent filing on the soybased hydrogels for controlled release systems. 7. Related scientific papers will be written on energy absorbing material developed from soybean oil. 8. Complete patent/paper writing on polymeric surfactants derived from soybean oil. 3a List the milestones that were scheduled to be addressed in FY 2005. For each milestone, indicate the status: fully met, substantially met, or not met. If not met, why. 1. Seed oil-based metalworking fluid for aluminum hot rolling will be formulated. Milestone Fully Met 2. Complete initial preparation of grease samples with Li metal, fatty acids and check for consistency and smooth paste like texture conforming to NLGI specifications. Milestone Fully Met 3. Complete preparation of synthetic lubricant base stocks using epoxidized vegetable oils, long chain/branched alcohols and catalyst; and further reaction on above product using acid anhydrides. Milestone Fully Met 4. Complete the reaction optimization of vegetable oils with different sulfur compounds (which may or may not contain an amine functionality) using a catalyst (perchloric acid) to obtain biobased additives in higher yields and characterization using NMR, FTIR and PDSC. Milestone Fully Met 5. Complete initial preparation of composites samples with non-coated flax fibers using compression molding method and study their mechanical and water absorption properties. Milestone Fully Met 6. Complete the samples preparations of nano-clay reinforced soybased composites. Thermo and mechanical properties will be studied. Milestone Fully Met 7. Soybased Hydrogels prepared from ring-opening polymerization and hydrolysis of obtained polymers will be studied for their temperature sensitive and pH sensitive properties. Milestone Fully Met 8. ESO will be cured with polyamine compounds to form energy absorbing materials sheets for mechanical, thermophysical properties tests. Milestone Fully Met 9. Ring opening polymerization will be carried out using Lewis catalysts for preparing soybean oil based polymeric surfactants. Milestone Fully Met 3b List the milestones that you expect to address over the next 3 years (FY 2006, 2007, and 2008). What do you expect to accomplish, year by year, over the next 3 years under each milestone? Second Year FY2006: 1. Seed oil-based metalworking fluid for aluminum hot rolling will be tested for various performance and tribochemical properties in-house. 2. Characterization of grease samples for their penetration, oxidation and thermal stability using PDSC, micro-oxidation, oven test, RBOT. 3. Complete ring-opening reaction of epoxidized seed oil followed by esterification of resulting hydroxyl group to give lubricant base fluid. Characterize the chemically modified vegetable oil fluids for their oxidative stability and pour point and check to see if the process significantly improved the low temperature fluidity and thermal stability of the oil. 4. Complete the reactions of vegetable oils with different amines using same catalyst to synthesize bio-based anti-wear, anti-oxidants additives and characterization using NMR, FTIR and PDSC. 5. To prepare composites samples reinforced with coated flax fibers and to characterize their binding properties using TEM. Three point bend and tensile tests will be performed on samples fabricated under task 1 (first year) using noncoated fibers and coated fibers. Compare their mechanical and water absorption properties. Evaluate polyamine curing agents. 6. Optimum clay loading, curing conditions and study the structures of clay dispersion in the host polymers for nano-clay reinforced soybased composites. 7. Study drug loading and release rate of soybased hydrogels. Effect of dissolution media such as temperature, pH on the release rate will be investigated. 8. Complete material selection and formulation of energy absorbing materials. Glass transition temperatures (Tgs) will be determined using DSC. 9. Initiator evaluation for ring opening polymerization will be performed. Optimization of polymerization conditions necessary to obtained soybean oil based polymeric surfactants in high yield will also be investigated. Third Year FY2007: 1. Tribochemical evaluation and physical property determination of metal working fluids will continue based on feedback from CRADA partner. 2. Develop methods to study wear-friction properties of grease samples. Try to establish structure-property relationship using above data. 3. Complete the formulation and blending of chemically modified vegetable oil fluids with other seed oils and suitable PPD, anti-oxidant and anti- wear additives. Evaluate the final products for pour point, viscosity, viscosity index, oxidative stability using PDSC, friction and wear characteristics using Falex to study the effect of structural variation in the oil molecules. 4. Complete the reactions of vegetable oils with different alcohol-amines using same catalyst to synthesize bio-based anti-wear, anti-oxidants additives and characterization using NMR, FTIR and PDSC. 5. Optimization of curing agents for epoxidized soybean oil and curing conditions such as pressure, temperature, and reaction time; study of fiber loading influence on the mechanical properties of composites; and analysis of water swelling data of composites. 6. Work will continue on the characterization of nano-clay reinforced soybased composites using X-ray and TEM. 7. Study drug release kinetics followed Fickian law or nonFickian law for soybased hydrogels. 8. Damping and falling weight properties of soybased energy absorbing materials will be evaluated. 9. Hydrolysis of obtained soybean oil based polymers using sodium hydroxide to remove glycerin small molecule, purification of the samples for GPC analysis. Surface tension and contact angle measurements of soybean oil based polymeric surfactants are performed. The CMC will be determined. Fourth Year FY2008: 1. Using established structure - property relationship and optimized conditions such as metal, fatty acid content, baseoil amount to complete preparation/formulation of NLGI grade 2 grease with AO, AW, EP additives. Formulation will be tested by industrial CRADA partners. 2. Complete scale up in 20L reactor to prepare 6 lbs of synthetic lubricant base fluids and optimization of reaction variables for economically producing the environmentally friendly ester-based lubricants from epoxidized vegetable oil; following test by industrial CRADA partners. 3. Complete development of PDSC and Falex methods to test effectiveness (anti-oxidant and anti-wear behavior) of synthesized bio-based additive compounds, comparison with industrially available additives and screening for potential bio-based anti-oxidant and anti-wear additives. 4. Complete development of composites which are reinforced by natural fiber and nano clay. Industrial CRADA partner finishes their site tests. 5. A soybased drug controlled release system will be developed. Industrial partners will test this system. 6. New energy absorbing materials with good damping and energy absorbing properties will be developed from soybean oil. 7. Finish studies on soybean oil based polymeric surfactants. Anticipated impact/outcomes/results of the research: 1. A vegetable oil-based metalworking fluid for aluminum hot rolling will be available for use by Alcoa Technology in its plant operations. 2. Will have a technology to prepare bio-based greases for various end use applications having higher oxidation stability and good friction and wear properties compared to commercially available bio-based greases and at par properties to commercial mineral oil-based greases. 3. A two-step and one-step processes for chemical modification of vegetable oils will result from this research. These chemically modified vegetable oils will have improved oxidation stability and low temperature properties. 4. Bio-based additives having sulfur and/or nitrogen functionalities will be made, that have good antiwear, antioxidant properties along with their biodegradable nature will be prepared. 5. The water absorption properties of soy-based composites reinforced with protein and lipid coated flax fibers will be improved. The mechanical properties of these composites will be comparable to the composites reinforced with uncoated flax fibers. The fiber length will affect the mechanical properties of composites. 6. Swelling kinetics of soy-based hydrogels and release kinetics of loaded drugs will be studied and measured. Swelling and release behavior will show the temperature and pH dependence. 7. Glass transition temperatures (Tgs) of soy-based rubber materials prepared with different aromatic and aliphatic amines will be determined. It is anticipated that the soy-based materials with aromatic amine curing agents will show the higher Tgs than with aliphatic amine curing agents. 8. Ring opening polymerization of epoxidized soybean oil with anionic and cationic initiators will be investigated. Optimization of polymerization conditions will be studied. Surface activities of these polymers will be examined. 9. Surface activities and CMC of small molecule surfactants will be studied. Important variables will be solution pH, solution salinity, the number of introduced branching points in the hydrophobe, and the number of units in the polyglyceride or carbohydrate hydrophilic unit. 4a What was the single most significant accomplishment this past year? The collaborators (CRADA Partners) in Alcoa Technology were provided with 150 gallons of USDA's soy oil based base oil for metalworking fluid, which they used in their formulation and tried in one of their pilot plants at Reno, NV. The plant trial was a huge success and USDA's bio- based lubricant outperformed the equivalent control lubes. In quality of metal, USDA bio-based lube without scratch-brushes outperformed control with scratch-brush (use of scratch-brush improves rolled metal quality). In productivity, USDA's bio-based lube allowed increased reduction that was unattainable with existing dispersion lubes. As far as operator exposure are concerned, EHS conducted tests and found that USDA bio-based lube outperformed control lubes, i.e., exposure was minimum with bio- based lubes. They also did a price evaluation of the cost to make a hot rolling lubricant using USDA's base oil. They conclude that USDA's base oil makes this formulation very attractive even though its cost is much higher than mineral oil. The reason for this is that the cost of the overall package is actually slightly less than many of their commercial hot mill lubricants because boundary additives are not needed for USDA formulation. They will conduct a trial or two for their large rolling mills in coming months (one in Europe and one in USA). 4b List other significant accomplishments, if any. 1. Invention report. Erhan, S. Z., Liu, Z. and McKeon, T. "Soybased Thermosensitive Hydrogels for Controlled Release Systems." 2. Invention Report. Erhan, S. Z., Sharma, B. K. and Adhvaryu, A. "Process Development of Bio-based Grease for Industrial Applications." 3. Patent Pending. Erhan, S. Z. Adhvaryu, A. and Sharma, B. K. "Poly(hydroxylthioether) Vegetable Oil Derivatives Useful as Lubricant Additives." 4. CRADA with Advanced Ceramics Research, Tucson, AZ, (soybased composition) continuing. 5. CRADA with Alcoa Technology, PA, (hot and cold rolling fluid for metal processes) continuing. 6. CRADA with Caterpillar Inc. (Under carriage lubricants) is in final stage of development. 7. CRADA with Caterpillar Inc., IL (Antisticking coating) is in final stage of development. 8. CRADA with Anderson Development Co., MI (Boron based lubricants) is in final stage of development 9. MTA with University of Toronto, CA; Sullair Corp, IN, Cephalon Inc., UT, The Valvoline Company, KY, is in place. 10. Confidentiality Agreement with Anesta Corp., UT. 4d Progress report. We are developing the synthesis of carbonated methyl esters and carbonated soybean oil from their corresponding epoxides and supercritical carbon dioxide. These carbonates will be useful as starting materials for ester based surfactants and polymers. We have synthesized one previously unreported compound and our synthesis of carbonated soybean oil is 3x faster than a reported literature synthesis. 5. Describe the major accomplishments over the life of the project, including their predicted or actual impact. Accomplishments through September 2004 related to industrial uses of vegetable oils can be found in the last progress report of the terminated project 3620-41000-101-00D. The collaborators (CRADA Partners) in Alcoa Technology were provided with 150 gallons of USDA's soy oil based base oil for metalworking fluid, which they used in their formulation and tried in one of their pilot plants at Reno, NV. The plant trial was a huge success and USDA's bio-based lubricant outperformed the equivalent control lubes. In quality of metal, USDA bio-based lube without scratch- brushes outperformed control with scratch-brush (use of scratch-brush improves rolled metal quality). In productivity, USDA's bio-based lube allowed increased reduction that was unattainable with existing dispersion lubes. As far as operator exposure are concerned, EHS conducted tests and found that USDA bio-based lube outperformed control lubes, i.e., exposure was minimum with bio-based lubes. They also did a price evaluation of the cost to make a hot rolling lubricant using USDA's base oil. They conclude that USDA's base oil makes this formulation very attractive even though its cost is much higher than mineral oil. The reason for this is that the cost of the overall package is actually slightly less than many of their commercial hot mill lubricants because boundary additives are not needed for USDA formulation. They will conduct a trial or two for their large rolling mills in coming months (one in Europe and one in USA). 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? Ink and Hydraulic Elevator Fluid Technology licensing procedure is in final stage (Bunge/AgriLube Inc. is in process of licensing). One patent is pending and two patent applications are in process. In two to three years products through CRADA partners should be available to the public. 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). a. Statue of Liberty Goes Green with Soy-Based Elevator Fluid http://www.agclassroom.org/teen/ars_pdf/tech/2004/10soy.pdf Agricultural Research, October 2004, pg. 22. b. ARS's Soy-Based Hydraulic Fluid Powers Lady Liberty's Elevator Federal Technology Transfer, 2005, pg. 12. c. Statue of Liberty to use Biolubricants Lubricants World, September/October, 2004, pg. 10.

Impacts
(N/A)

Publications

Xu, J., Liu, Z., Erhan, S.Z., Carriere, C.J. 2004. Cross-linkers control the viscoelastic properties of soybean oil based biomaterials. Journal of the American Oil Chemists' Society. 81(8):813-816.
Sharma, B.K., Adhvaryu, A., Erhan, S.Z. 2005. Vegetable oil-based lubricants: improvement in oxidation and low temperature stability. Annual Meeting and Expo of the American Oil Chemists' Society. p. 66.
Doll, K.M., Erhan, S.Z. 2005. The improved synthesis of carbonated soybean oil in supercritical carbon dioxide. American Chemical Society Abstracts. p.74.
Erhan, S.Z., Sharma, B.K., Adhvaryu, A. 2005. Biobased lubricants for industrial applications. World Oleochemical Conference. p. 89.
Liu, Z., Erhan, S.Z. 2005. Development of soy composites by direct deposition. In: Erhan, S.Z., editor. Industrial Uses of Vegetable Oils. Champaign, IL: AOCS Press. Chapter 7. p. 131-142.
Adhvaryu, A., Erhan, S.Z. 2005. Fatty acids and antioxidant effects on grease microstructures. Industrial Crops and Products. 21:285-291.
Erhan, S.Z. 2005. The use of vegetable oils as lubricants and hydraulic fluids. In: Murrell, S., editor. Bailey's Industrial Oil and Fats Products. 6th edition. Hoboken, NJ: John Wiley & Sons, Inc. p. 259.
Liu, Z., Erhan, S.Z., Calvert, P.D. 2004. Solid freeform fabrication of soybean oil based composites reinforced with clay and fibers. Journal of the American Oil Chemists' Society. 81(6):605-610.
Adhvaryu, A., Liu, Z., Erhan, S.Z. 2005. Synthesis of novel triacylglycerol molecule with improved high and low temperature behavior. Industrial Crops and Products. 21:113-119.
Panizzi, M., Kwanyuen, P., Erhan, S.Z. 2005. Environmental and genetic variation of beta-conglycinin and glycinin content in brazilian soybean cultivars. Annual Meeting and Expo of the American Oil Chemists' Society. p. 100.
Liu, Z., Erhan, S.Z., Akin, D.E., Barton Ii, F.E. 2005. Development of soybean oil/flax fiber based composites by compression molding method. Annual Meeting and Expo of the American Oil Chemists' Society. pg. 106
Doll, K.M., Erhan, S.Z. 2005. Synthesis of carbonated methyl oleate from methyl oleate epoxide (EMO) in supercritical carbon dioxide. Annual Meeting and Expo of the American Oil Chemists' Society. p. 89.
Erhan, S.Z., Sharma, B.K., Adhvaryu, A. 2005. Additive-additive interactions in vegetable oil: the search for synergistic antioxidant using pdsc. Society of Tribologists and Lubrication Engineers. p. 189.
Liu, Z., Erhan, S.Z. 2005. Preparation of epoxidized soybean oil/clay nanocomposites. World Oleochemical Conference. p. 145.
Doll, K.M., Erhan, S.Z. 2005. Improved synthesis of carbonated soybean oil in supercritical carbon dioxide. American Chemical Society National Meeting. p. 191.
Liu, Z., Akin, D.E., Barton Ii, F.E., Onwulata, C.I., Erhan, S.Z. 2004. Preparation of soy-based composites reinforced with protein coated flax fiber. UJNR Food & Agricultural Panel Proceedings. p. 134.
Erhan, S.Z., Sharma, B.K., Adhvaryu, A. 2005. Biobased lubricants: improvement in oxidation and low temperature stability. Association for the Advancement of Industrial Crops Conference. p. 204.
Erhan, S.Z. 2005. Printing inks. In: Erhan, S.Z., editor. Industrial Uses of Vegetable Oils. Champaign, IL: AOCS Press. Chapter 9. p. 163-169.