2006 Annual Report
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.
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.
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).
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
Hwang, H., Erhan, S.Z. 2006. Synthetic lubricant basestocks from epoxidized soybean oil and guerbet alcohols. Industrial Crops and Products. 23:313-317.
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.
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.
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.
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.
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., 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.