Progress 05/01/03 to 04/30/06
Outputs
Research and commercialization efforts within this project included characterization of ethanol-biodiesel-diesel fuel blends, improving the thermal stability of soybean oil as a lubricant, characterization of starch acetate as a water resistant packaging/insulating foam, understanding the extrusion/expansion of starches and modeling the extrusion of starch. Stable blends of ethanol, biodiesel and diesel fuel were identified as a function of temperature. Another biodiesel project was a study to strategically locate new soybean oil extraction/expression capabilities and biodiesel production facilities in Nebraska. An electronic model will be available to identify the distribution of fats and oils resourses and existing markets for the same. Studies of the effects of hydroxylation and nitroxylation of soybean oil were initiated. The results, to date, suggest that both thermal and oxidative stabilities have been improved. The development of a technique to make a highly
substituted starch (DS between 2 and 3)was done in a previous project. The highly modified starch was shown to be highly resistant to water after extrusion-expansion to form a foamed product. The acetylation process was studied to fully understand the requirements of the conversion and to determine the functionality of the starch acetates. The addition of natural fibers at low levels were found to make the starch acetate foams more functional interms of strength, texture and physical characteritics. Selected aspects of the extrusion process were mathematically modeled to better understand the expansion of starches with the goal of ultimately being able to provide for feedback control of the process.
Impacts
Our effort to develop a model which will allow us to determine strategic locations for soybean and biodiesel facilities in Nebraska will greatly reduce the time it takes for individual communities to do feasibilitiy studies. Investors will be able to see readily the extent of the opportunities across the state. Our ethanol-biodiesel-diesel fuel blend research will avoid engine problems and marketing setbacks for the newly developing biodiesel industry. Successful commercialization of technologies that with contribute to value-added processing of agricultural commodities is the goal of everyone working in this arena. The challenges are great and the number of successes have been few but they are growing as the portfolio of technology grows. We have ongoing comecialization activities with respect to our starch-polymer blends and modified starch technologies.
Publications
- Wang, L., G.M. Ganjyal, D.D. Jones, C.L. Weller and M.A. Hanna. 2005. Modeling of bubble growth dynamics and non-isothermal expansion in starch-based foams during extrusion. Advances in Polymer Technology. 24(1):29-45.
- Xu, Y., Y. Dzenis and M. Hanna. 2005. Water solubility, thermal characteristics and biodegradability of extruded starch acetate foams. Industrial Crops and Products. 21(3):361-368.
- Xu, Y. and M. Hanna. 2005. Physical, mechanical and morphological characteristics of extruded starch acetate foam. J. Polymers and the Environment. 13(3).
- Guan, J. and M.A, Hanna. 2004. Extruded foams from corn starch acetate and native corn starch. Biomacromolecules. 5(6):2329-2339.
- Guan, J., K. Eskridge and M.A. Hanna. 2004. Functional properties of extruded acetylated starch-cellulose foams. J. of Polymers and the Environment. 12(3):113-121. Guan, J., Q. Fang and M.A. Hanna. 2004. Selected functional properties of extruded starch acetate-natural fiber foams. Cereal Chemistry. 81(2):199-206.
- Guan, J., Q. Fang and M.A, Hanna. 2004. Functional properties of extruded starch acetate blends. J. Polymers and the Environment. 12(2):57-63.
- Guan. J., Q. Fang and M.A. Hanna. 2004. Marcomolecular characteristics of starch acetate extruded with natural fibers. Trans. of ASAE. 47(1):205-212.
- Wang, L., G.M. Ganjyal, D.D. Jones. C.L. Weller and M.A. Hanna. 2004. Finite element modeling of fluid flow, heat transfer and melting of biomaterials in a single screw extruder. J. Food Sci. 69(5):E212-223.
- Xu, Y., V. Miladinov and M. Hanna. 2004. Synthesis and characterization of starch acetate with high degree of substitution. Cereal Chemistry. 81(6):735-740.
- Zhou, J. and M.A Hanna. 2004. Extrusion of starch acetate with mixed blowing agents. Starke. 56(10):484-494.
- Fernando, S. and M.A. Hanna. 2005. Phase behavior of the ethanol-biodiesel-diesel microemulsion system. Trans. of the ASAE. 48(3):903-908.
- Guan, J.J. and M.A. Hanna. 2005. Selected morphological and functional properties of extruded acetylated starch-polylactic acids foams. Industrial Engineering and Chemistry Research. 44(9):3106-3115.
- Guan, J., K. Eskridge and M. A. Hanna. 2005. Acetylated starch-polylactic acid loose-fill packaging materials. Industrial Crops and Products. 22(2):109-123.
- Ganjyal, G. and M.A. Hanna. 2004. Effects of extruder die nozzle dimensions on expansion and micrographic characteristics of acetylated starch. Starke. 56(3-4):108-117.
- Fernando, S. and M.A. Hanna. 2003. Oxidation characteristics of soybean oils as water pump lubricants. Trans. of the ASAE. 45(6):1715-1719.
- Guan, J.J. and M.A, Hanna. 2003. Post extrusion steaming of starch acetate foams. Trans. of the ASAE. 46(6):1613-1624.
- Fernando, S. and M.A. Hanna. 2004. Development of a biofuel blend using ethanol-biodiesel-diesel micro-emulsions: EB-diesel. Energy and Fuels. 18:1695-1703.
- Ganjyal, G.M., Reddy, N., Yang, Y. and Hanna M.A. 2004 Biodegradable packaging foams of starch acetate blended with corn stalk fibers. J. Appl. Polym. Sci. 93(6):2627-2633.
- Guan, J. and M.A. Hanna. 2004. Functional properties of extruded foam composites of starch acetate and corn cob fiber. Ind. Crops and Products. 19(3):255-269.
- Xu, Y. and M.A. Hanna. 2005. Preparation and properties of biodegradable foams form starch acetate and poly(tetremethylene adipate-co-terephthalate). Carbohydrate Polymers. 59(4):521-529.
- Xu, Y., V. Miladinov and M. Hanna. 2005. Starch acetate-maleate mixed ester synthesis and characterization. Cereal Chemistry. 82(3):336-340. JSN 14810. Zhou, J. and M.A. Hanna. 2005. Effects of the properties of blowing agents on processing and performance of extruded starch acetate. J. Applied Polymer Science. 97:1880-1890.
- Fernando, S. and M.A. Hanna. 2006. A review of test criteria for evaluating two-stroke engine lubricants and performance of soybean oil based lubricant in two-stroke engines. J. Agric. Engr. Res. In review.
- Guan, J.J. and M.A. Hanna. 2006. Selected morphological and functional properties of extruded starch-cellulose foams. Bioresource Tech. In press.
- Guan, J.J. and M.A. Hanna. 2006. Physical, mechanical and macromolecular peoperties of starch acetate during extrusion foaming transformations. Industrial Engineering and Chemistry Research. Submitted.
- Hanna, M., J. Guan and Y. Xu. 2006. Starch-based biodegradable packaging. (Chapter). Encyclopedia of Agricultural, Food and Biological Engineering. In press.
- Hanna, M.A., L. Isom and J. Campbell. 2005. Biodiesel: Current Perspectives and Future. J. Scientific and Industrial Research. 64(11):854-857.
- Julson, J. L., J. Guan, S. Raghavachari, M. Hanna. 2006. Physical properties of extruded corn flour-polystyrene foams. Industrial Crops and Products. Submitted.
- Kumar, A., G.M. Ganjyal, D.D. Jones and M.A. Hanna. 2006. Digital image processing for measurement of residence time distribution in a laboratory extruder. J. Food Process Engineering. 75:237-244.
- Wang, L., D. D. Jones, C.L. Weller and M.A. Hanna. 2006. Modeling of transport phenomena and melting kinetics of starch in a co-rotating twin screw extruder. Adv. Polymer Tech. 25(1)1-19.
- Xu, Y. and M. Hanna. 2006. Physical, mechanical and morphological characteristics of extruded starch acetate foam. J. Polymers and the Environment. 13(3):221-230.
|
Progress 10/01/04 to 09/30/05
Outputs
Two manuscripts were published on ethanol-biodiesel-diesel fuel blends. The specifics of this research was reported previously. Current efforts in the area of biodiesl include assessing the opportunities for soybean and biodiesel processing facilities in Nebraska, meetng with community economical development groups to discuss the same, and participating in workshops to inform producer groups and investors of opportunities and challenges associated with becoming a biofuel producer. Continuing research efforts have contributed to our understanding of the expansion of extruded, stach-based, biopolymer systems. The roles of nucleating agents and blowing agents are better understood in terms of why a material expands as it exits an extruder and also why, and how much, the same material shrinks subsequent to the initial expansion. Significant progress has been made toward the commercialization of our starch-polystrene, starch-polylactic acid and starch acetate extruded foam
technologies. Emphasis is curently on the starch-polystrene technology because it is the most cost competitive and because it appears to have a niche in the loose fill market. Producing a thermoformable sheet using all of these tehnologies is still a goal to enter the markets for retail packages such as egg cartons and wet and dry goods trays and construction materials such as insulation.
Impacts
Our effort to develop a model which will allow us to determine strategic locations for soybean and biodiesel facilities in Nebraska will greatly reduce the time it takes for individual communities to do feasibilitiy studies. Investors will be able to see readily the extent of the opportunities across the state. Successful commercialization of technologies that with contribute to value-added processing of agricultural commodities is the goal of everyone working in this arena. The challenges are great and the number of successes have been few but they are growing as the portfolio of technology grows.
Publications
- Fernando, S. and M.A. Hanna. 2004. Development of a biofuel blend using ethanol-biodiesel-diesel micro-emulsions: EB diesel. Energy and Fuels. 18:1695-1703.
- Guan, J. and M.A. Hanna. 2004. Functional properties of extruded foam composites of starch acetate and corn cob fiber. Ind. Crops and Products. 19(3):255-269.
- Guan, J. and M.A, Hanna. 2004. Extruded foams from corn starch acetate and native corn starch. Biomacromolecules. 5(6):2329-2339.
- Xu, Y., V. Miladinov and M. Hanna. 2004. Synthesis and characterization of starch acetate with high degree of substitution. Cereal Chemistry. 81(6):735-740.
- Zhou, J. and M.A Hanna. 2004. Extrusion of starch acetate with mixed blowing agents. Starke. 56(10):484-494.
- Fernando, S. and M.A. Hanna. 2005. Design and development of a threshing chamber and pneumatic conveying and cleaning units for soybean harvesting. Trans. of the ASAE. 48(5):1681-1688.
- Fernando, S. and M.A. Hanna. 2005. Phase behavior of the ethanol-biodiesel-diesel microemulsion system. Trans. of the ASAE. 48(3):903-908.
- Guan, J.J. and M.A. Hanna. 2005. Selected morphological and functional properties of extruded acetylated starch-polylactic acids foams. Industrial Engineering and Chemistry Research. 44(9):3106-3115.
- Guan, J., K. Eskridge and M. A. Hanna. 2005. Acetylated starch-polylactic acid loose-fill packaging materials. Industrial Crops and Products. 22(2):109-123.
- Xu, Y., Y. Dzenis and M. Hanna. 2005. Water solubility, thermal characteristics and biodegradability of extruded starch acetate foams. Industrial Crops and Products. 21(3):361-368.
- Xu, Y. and M.A. Hanna. 2005. Preparation and properties of biodegradable foams form starch acetate and poly(tetremethylene adipate-co-terephthalate). Carbohydrate Polymers. 59(4):521-529.
- Xu, Y., K. Kim, M. Hanna and D. Nag. 2005. Chitosan-starch composite films preparation and characterization. Industrial Crops and Products. 21:185-192.
- Xu, Y., V. Miladinov and M. Hanna. 2005. Starch acetate-maleate mixed ester synthesis and characterization. Cereal Chemistry. 82(3):336-340.
- Zhou, J. and M.A. Hanna. 2005. Effects of the properties of blowing agents on processing and performance of extruded starch acetate. J. Applied Polymer Science. 97:1880-1890.
|
Progress 10/01/03 to 10/01/04
Outputs
This project generally addresses research and commercialization of biopolymers, biofuels and biopower. Specifically, one part of the proposal is to develop a better understanding of how the functionality of native and modified starches are changed with the addition of nucleating and blowing agents and by changing the extrusion processing conditions. The biodegradability of highly modified starches is part of this study. Also, an aside of this project has been the development of a commercial extrusion process to manufacture a sheet of expanded (native, modified and blended) starch that can be thermoformed into consumer products such as egg cartons, meat trays and clam shells. Another part of the proposal is to develop a template for the production of stable blends of ethanol, biodiesel and diesel fuel. Biodiesel is proposed as an emulsifier for otherwise immiscible ethanol and diesel fuel blends. A phase diagram for the three component fuel has been developed and
presented graphically, clearly showing the 1-2 and the 2- 3 phase boundaries for the three component blends. Overall, we have made significant advances on the objectives. Numerous manuscripts have been published and proposals have been written to the USDA-NRI, DOE and NSF competitive grants programs on starch biopolymers and ethanol-biodiesel-diesel fuel blends.
Impacts
The melt characteristics and water resistance of acetylated starch make it attractive in plastic-like applications. Extrusion processing is the most common technique for expanding starches. Selection of appropriate blowing agents to maximize the expansion of starches and starch blends is imprecise because of different solubilities. As a result, significant shrinkage of extrusion expanded products is common. The net result is the products are denser, more costly and less functional otherwise. The results of our work clarify the role of blowing agents and the importance of selecting the proper agent(s) for a given polymer or polymer blend.
Publications
- Ganjyal, G. and M.A. Hanna. 2004. Effects of extruder die nozzle dimensions on expansion and micrographic characteristics of acetylated starch. Starke. 56(3-4):108-117.
- Ganjyal, G.M., Reddy, N., Yang, Y. and Hanna M.A. 2004 Biodegradable packaging foams of starch acetate blended with corn stalk fibers. J. Appl. Polym. Sci. 93(6): 2627-2633.
- Xu, Y., J. Zhou, and M.A. Hanna. 2004. Melt-intercalated starch acetate nanocomposite foams as affected by type of organoclay. Cereal Chemistry. 82(1):105-110.
- Ali, Y., V. Ghorpade, R. Weber and M.A. Hanna. 2004. A Method for Mulching an Agricultural Soil Bed using a Biodegradable Protein Material and a Mulched Agricultural Crop Growing Plot Produced Thereby. Patent Number 6,672,001 issued on 1/6/04.
|
Progress 10/01/02 to 09/30/03
Outputs
Starch acetates with degrees of substitution (DS) of 0.57, 1.11, 1.68, and 2.23 were prepared and extruded with water or ethanol. Microstructure, radial expansion ratio [RER], unit density, spring index [SI], compressibility[C], and crystalline structure of foams were investigated. When water was used as the solvent with low DS starch, the foams were pale yellow, with rough and uneven surfaces. The cells were dense, with thick cell walls. When ethanol was used as solvent, the snow-white foams had smooth surfaces, uniform cells, and smooth cell walls. High RER and SI, and low unit density and C were observed. Changes in SI and C with RER depended on the type of solvent. A crystalline pattern was observed because of the formation of well-ordered structures during extrusion. To decrease hydrophilicity of starch and cost of modified starch foams, native corn starch was blended with starch acetate and extruded. Melting temperature of extruded starch acetate/native starch
foam was 216 C as compared to 193.4 for starch acetate and 78.4 for native starch. Strong X-ray diffractogram peaks for extruded starch acetate/native starch foam suggested new crystalline regions were formed. Optimum conditions for high RER, high C, low specific mechanical energy requirement and low water absorption index were 46.0% native starch content, 163 rpm screw speed and 148 C barrel temperature. Starch acetate (DS2) was extruded with ethanol and propanol, as blowing agents, at concentrations of 0, 2, 5, 10, 15 and 25 % at 150 C, at a screw speed of 140 rpm and through a 4 mm dia and 16.2 mm long die nozzle to study the role of blowing agents on expansion of extrudates. Extrudates with 0 % blowing agent, shrank considerably after exiting the die. RER of extrudates increased with increase in ethanol concentration to an optimum value of 18.0 at 5 % (db) ethanol content and decreased with further increase in ethanol content. RER increased to a maximum of 17.0 as the
concentration of propanol was increased to 25 % (db). Blowing agents aided in releasing the heat and pressure generated during extrusion by flashing off. The faster the extrudate cooled, the less likely it was to shrink. To obtain an extrudate with high expansion and lower density, propanol at 15 - 25 % (db) was found most suitable. In another study to understand how physiochemical properties of blowing agents affect plasticization and expansion processes, starch acetate was extruded with water, ethanol, and ethyl acetate. Evaporation rate, surface tension, boiling point (B.P.), solubility index, latent heat of vaporization (hv) of blowing agents, extrusion temperature, and nucleating and blowing agents concentrations were studied. Properties of blowing agents and operating conditions affected solubility of matrix polymer, the nucleation process, and cell growth, which affected foam density and specific volume. High temperature increased cell density and specific volume when water and
ethanol were used, since high temperature increased solubility of starch acetate in water and ethanol and promoted nucleation. High temperature reduced melting strength, thereby reducing cell density and specific volume.
Impacts
The melt characteristics and water resistance of acetylated starch make it attractive in plastic-like applications. Extrusion processing is the most common technique for expanding starches. Selection of appropriate blowing agents to maximize the expansion of starches and starch blends is imprecise because of different solubilities. As a result, significant shrinkage of extrusion expanded products is common. The net result is the products are denser, more costly and less functional otherwise. The results of our work clarify the role of blowing agents and the importance of selecting the proper agent(s) for a given polymer or polymer blend.
Publications
- Guan, J.J. and M.A, Hanna. 2003. Post extrusion steaming of starch acetate foams. Trans. of the ASAE. 46(6):xxxxx.
- Guan, J. and M.A. Hanna. 2004. Functional properties of extruded foam composites of starch acetate and corn cob fiber. Ind. Crops and Products. In press.
- Guan, J., K. Eskridge and M.A. Hanna. 2004. Functional properties of extruded acetylated starch-cellulose foams. J. of Polymers and the Environment. Accepted for publication.
- Guan, J., Q. Fang and M.A. Hanna 2004. Selected functional properties of extruded starch acetate-natural fiber foams. Cereal Chemistry. Accepted for publication.
- Guan, J., Q. Fang and M.A, Hanna. 2004. Functional properties of extruded starch acetate blends. J. Polymers and the Environment. 12(2):57-63.
- Xu, Y. and M. Hanna. 2004. Physical, mechanical and morphological characteristics of extruded starch acetate foam as affected by DS values and solvent type. J. Polymers and the environment. Submitted. Xu, Y., V. Miladinov and M. Hanna. 2004. Synthesis and characterization of starch acetate with high degree of substitution. Cereal Chemistry. Submitted.
- Zhou, J. and M.A Hanna. 2004. Extrusion of starch acetate with mixed blowing agents. Starke. Submitted.
- Zhou, J. and M.A. Hanna. 2004. Effects of blowing agents properties on processing and performance of extruded starch acetate. J. Applied Polymer Science. Submitted.
- Guan. J., Q. Fang and M.A. Hanna. 2004. Marcomolecular characteristics of starch acetate extruded with natural fibers. Trans. of ASAE. 47(1):xxxxx.
|
|