2005 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.
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, 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.
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.
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.
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. Vegetable oils as lubricants, hydraulic fluids, and inks. In: Shahidi, F., editor. Bailey's Industrial Oil and Fat Products: Industrial and Nonedible Products from Oils and Fats. Chapter 7, 6th edition. Indianapolis, IN: John Wiley & Sons, Inc. p. 259-278.
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. 2006. Synthesis of carbonated methyl oleate from methyl oleate epoxide (EMO) in supercritical carbon dioxide [abstract]. 97th American Oil Chemists' Society Annual Meeting and Expo. 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.
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.