Progress 01/01/05 to 12/31/09
OUTPUTS: Dry milling Corn ethanol industries are expanding at an unprecedented rate in USA. These industries produce ethanol and distillers dried grains with solubles (DDGS), a major co-product in 1:1 quantum ratio. Currently in USA we produce more than 26 billion pounds of DDGS and major uses of these in animal feeds that far exceed this demand. To find responsible as well as value-added engineering uses of DDGS is well realized now for a sustainable development of the corn ethanol industries. Value-added biocomposites of high DDGS content (~75 wt.%) and 25% of castor oil based polyurethane (PU) were developed. Through spectral analysis the urethane-alcohol type bonding was revealed in the biocomposite structure. The dynamic mechanical analysis (DMA), stress-strain curve and scanning electron microscopy studies revealed the toughening mechanism of DDGS-PU biocomposites. The incorporation of the hydrophobic PU improved the water resistance of DDGS in the DDGS-PU composite structure.
Soy meal SM), the byproduct of soy biodiesel industry is mainly used in animal feeds. In finding value-added uses for SM is essential in finding the sustainable growth of the soybean industry. We developed SM-natural rubber (NR) elastic type blends containing around 50 wt.% inexpensive SM in the resulting product through material chemistry and process engineering optimizations. In one of the blend compositions the elongation at break was found out to be 430%. The incorporation of rubber improved the water resistance of soy meal in the blend structure. The interactions between SM and NR helped in increasing the glass transition temperature of the rubber component in the blend as revealed through SEM and DMA studies. The blend compositions revealed a partial compatibility as analyzed through SEM. A novel class of flexible biodegradable plastic films were developed from polyhydroxyalkanoates (PHAs) and thermoplastic starch plastic blends. The extensive process engineering, material
composition optimizations and structure-property correlation studies were adopted in developing these blends that show strong promise in eco-friendly flexible packaging applications. The thermoplastic starch (TPS) was developed by reactive extrusion of corn starch and glycerol (starch plastic) followed by blending with poly-(butylene adipate-co-terephthalate) (PBAT), a tough biodegradable polymer. Starch plastic was found to perform the role of a dual compatibilizer in between the PHA and PBAT phases as revealed through DMA and thermodynamic parameter data analysis. Polylactides (PLA) bioplastics are recently highlighted in packaging uses because of their renewable-resource based origin and biodegradability. One of the major hurdles for their large-scale commercial uses is their inherent brittleness. A nanostructure-controlled PLA was invented by in-situ cross-linking of hyperbranched polymer (HBP) in the PLA through reactive extrusion nano-blending. The TEM analysis showed a less
than 100 nm domain-size of the cross-linked HBP in the PLA matrix.The resultant modified PLA exhibited outstanding stiffness-toughness balance with a percent elongation at break value of more than 800%.
PARTICIPANTS: Y. Parulekar and R. Bhardwaj, Graduate Research Assistant, School of Packaging, Michigan State University, East Lansing, MI-48824. Dr. Q. Wu, Research Specialist, School of Packaging, Michigan State University, East Lansing, MI-48824.
TARGET AUDIENCES: This project would benefit the biobased new materials industries dealing with packaging. The science-based knowledge developed from this project was communicated through conference presentations to the international bioenvironmental polymer society, and the Forest product division of American Institute of Chemical Engineers.
Bioethanol from corn and biodiesel from soybean are coming-up as first generation of biofuels in USA. This is an appropriate time for a bioeconomy to be explored in the context of global warming, greenhouse gas emission, growing environmental threats, depleting petroleum resources and the skyrocketing cost of crude oil surpassing $100 per barrel. For biofuel industries to be sustainable all the components associated with these industries must be sustainable. Currently in US we are producing around 7 billion gallons of ethanol in more than 130 facilities. In dry milling corn ethanol industries ethanol and the co-product distillers' dried grains with solubles (DDGS) are produced in equal quantities. With rapid expansion of corn ethanol industries we will produce more than 40 billion pounds of DDGS annually that far exceed their current major uses as animal feeds. Such voluminous DDGS are predicted to be disposed off to land-filling thus creating additional environmental
threats. The value-added engineering uses of DDGS-polyurethane based biocomposites have opened-up new opportunities of DDGS in composite applications. This provides an enormous impact in material industries where one can find new range of biocomposites that can; not only find value-added uses for DDGS but also can find alternatives and/or supplements to fully petroleum-based composites also thus helping in reducing the use of petroleum and thereby reducing green house gas emission moving towards more greener environment. Both soy meal (SM) and glycerol are byproducts of the emerging soy biodiesel industry. The novel range of SM-natural rubber blends as invented and developed by us has drawn the attention of Ford Motor Company resulting further on-going investigations by Ford for possible elastomeric auto-parts uses. We developed polyhydroxyalkanote (PHA)-thermoplastic starch blends that provide significant potentials in eco-friendly biodegradable packaging materials uses. The product
contained about 70 wt.% of renewable material combining starch, glycerol and PHA bioplastic in the blend composition. This research has attracted the attention of the Cereplast, Inc. a growing US industry dealing with biobased and renewable resource based bioplastics. Our invention on nano-structure controlled PLA has added a new knowledge in the emerging bioplastic and biobased materials research. The use of nanotechnogy in controlling the PLA bioplastic structure resulted in the retention of high stiffness still increasing the toughness of PLA quite significantly. This published research is listed as one of the most-accessed articles during July-September 2007 of the journal "Biomacromelecules" an American Chemical Society publication. This research demonstrated a new industrially relevant methodology to develop a polylactide (PLA) based nanoblend having outstanding stiffness-toughness balance. This approach can foster new opportunities for the bioplastics modification in many new
value-added applications thus creating significant impact the biobased materials development.
- Patent Application: Mohanty, A. K., Bhardwaj, R., 2007, Hyperbranched Polymer Modified Biopolymers, Their Biobased Materials and Process for the Preparation Thereof, US 20060247387 A1 (Patent Pending).
- Journal publications; Mohanty, A. K., Bhardwaj, R., 2007, Modification of Brittle Polylactide (PLA) by Novel Hyperbranched Polymer based Nanostructures, Biomacromolecules 8(8), 2476.
- Wu, Q., Selke, S., Mohanty, A. K., 2007, Processing and Properties of Biobased Blends from Soy Meal and Natural Rubber, Macomolecular Materials & Engineering, 292, 1149.
- Wu, Q., Mohanty, A. K., 2007, Renewable Resource based Biocomposites from Coproduct of Dry Milling Corn Ethanol Industry and Castor Oil based Biopolyurethanes", Journal of Biobased Materials and Bioenergy, 1, 257.
- Mohanty, A. K., Bhardwaj, R., 2007, Advances in the Properties of Polylactide based Materials: A Review, Journal of Biobased Materials and Bioenergy 1, 191.
- Parulekar, Y., Mohanty, A. K., 2007, Extruded Biodegradable Cast Films from Polyhydroxyalkanoate and Thermoplastic Starch Blends: Fabrication and Characterization, Macomolecular Materials & Engineering, 292(12), 1218.
- Conference presentations/publications: Parulekar, Y., Mohanty, A. K., 2007, Biobased Materials from Polyhydroxyalkanoate and Thermoplastic Starch Blends and Their Biocomposites: Opportunities and Challenges, Oral Presentation at AIChE Annual Meeting, Salt Lake City, UT, November, 2007.
- Parulekar, Y., Mohanty, A. K., 2007, Polyhydroxybutyrate-co-valerate (PHBV) and Thermoplastic Starch (TPS) based Blends and Their Talc-filled Biocomposites, Oral Presentation at International Symposium on Polymers and the Environment: Emerging Technology and Science, Hilton Vancouver Washington, October, 2007.
- Mohanty, A. K., Bhardwaj, R., 2007, Nano-structure Controlled Bioplastics and Their Hierachical Nano-Biocomposites, Oral Presentation at SAE 2007 World Congress, Cobo Center, Detroit, Michigan, April, 2007.
- Mohanty, A. K., Bhardwaj, R., 2007, Nanostructure controlled biological polyesters: New opportunities in green materials research, Oral Presentation, Abstracts of Papers, 233rd ACS National Meeting, Chicago, IL, United States, March, 2007.
- Magazine Article: Mohanty, A. K., Bhardwaj, R., 2007, Novel Nanostructured Polylactide Bioplastics for Multifarious Applications, Bioplastics Magazine, Germany,Vol. 2, p.32.
Progress 01/01/06 to 12/31/06
Soy meal and natural rubber blends with about 50 percent soy meal and vulcanized rubber were successfully processed using semi-pilot scale extrusion, two-roll milling and compression molding techniques. The glass transition temperature of the rubber component increased due to the existence of interaction between the rubber component and the soy meal. The value-added biomaterials were developed from distillers' dried grains with solubles (DDGS) and a biopolyurethane. The dynamic mechanical analysis (DMA) and scanning electron microscopy (SEM) studies revealed the toughened nature of these materials. The incorporation of corn stovers into these biomaterials improved the stiffness. Biodegradable nanocomposites for packaging applications have also been developed. Biodegradable multilayer polymer films based on polylactide (PLA) and soy protein isolate were successfully prepared and characterized. The property evaluations of these films revealed strong adhesion of both the
polymers in the multilayer films. Recycled newspaper fibers (RCNF) as well as talc reinforced poly(hydroxybutyrate-co-valerate), PHBV bioplastic based biodegradable biocomposites have been successfully fabricated. The experimental findings were related with the theoretical models. One of the important findings showed better tensile and storage moduli values of PHBV-RCNF biocomposites over polypropylene-RCNF composites. The scanning electron microscopy (SEM) study revealed filler orientation and filler-polymer matrix adhesion of the PHBV-talc biocomposites. In the research on PLA-based materials; biocomposites using reinforcements such as glass fiber and RCNF were developed. The uniform distributions of both types of the fibers in the PLA matrix were indicated through SEM examination. The heat deflection temperature (HDT) of PLA-RCNF composite was found to be comparable to that of PLA-glass fiber composites. Organo-clay and thermoset polymer based nanocomposites are constantly under
development. In our recent work on unsaturated polyester (UPE)-layered silicate nanocomposites the reinforcing effect of delaminated and intercalated clay platelets was evaluated theoretically using the Helpin-Tsai equations. In the development of biobased UPE up to 25 wt.% of the UPE was replaced with a bioresin, epoxidized methyl linseedate (EML). The combination of EML and UPE resulted in a new biobased thermoset polymer with a relatively high glass transition temperature and elastic modulus, which shows the great potential of the replacement of UPE with a biobased resin.
Corn and soybeans are the two of the most important crops of Michigan as well as the US. The corn based bioethanol industries in the US are expanding at an unprecedented rate. The dry milling corn ethanol industries produce ethanol and a co-product, distillers' dried grains with solubles (DDGS) roughly in 1:1 quantum ratio. DDGS is mostly used as a low-cost animal feed (around 5 cents per pound) and we do not have enough livestock for its complete consumption. Similarly, soy meal a byproduct of the soy oil industries is quite inexpensive (around 8 cents per pound) and is also mostly used as animal feed. Biocomposites developed from DDGS and biopolyurethane as well as the green materials developed from soy meal and natural rubber show immense potential of applications in real world. The success of commercialization of these new materials is expected to provide an economic advantage to our agricultural sector. Presently, the production of plastics, composites and
nanocomposites are mostly fossil-fuel based. Petroleum is a finite resource. Our biobased materials research target on the development of renewable resource based materials is to provide sustainable alternatives to petroleum-based polymers and composites. Through our continued research we are gaining new knowledge in the area of biobased materials that can have a substantial impact on the growing bio-economy era.
- Rhim, J-W., Mohanty, A. K., Singh, S. P., Ng, P. K. W., 2006, Preparation and Properties of Biodegradable Multilayer Films Based on Soy Protein Isolate and Polylactide, Industrial & Engineering Chemistry Research, 45, 3059-3066.
- Bhardwaj, R., Mohanty, A. K., Drzal, L.T., Pourboghrat, F., and Misra M., 2006, Renewable Resource based Green Composites from Recycled Cellulose Fiber and Poly (3-hydroxybutyarte-co-3-hydroxyvalerate) Bioplastic, Biomacromolecules, 7(6), 2044-2051.
- Huda, M. S., Drzal, L. T., Mohanty, A. K., Misra, M., 2006, Chopped Glass and Recycled Newspaper as Reinforcement in Injection Molded Poly(lactic acid) (PLA) Composites: A Comparative Studies, Composites Science and Technology, 66(11-12), 1813-1824.
- Miyagawa, H., Mohanty, A. K., Burgueno, R., Drzal, L. T., Misra, M., 2006, Characterization and Thermophysical Properties of Unsaturated Polyester-Layered Silicate Nanocomposites, Journal of Nanoscience and Nanotechnology, 6, 464-471.
- Whaling, A., Bhardwaj, R., Mohanty, A. K., 2006, Novel Talc-Filled Biodegradable Bacterial Polyester Composites, Industrial & Engineering Chemistry Research, 45 (22), 7497-7503.
- Miyagawa, H., Mohanty, A. K., Burgueno, R., Drzal, L. T., Misra, M., 2006, Development of Biobased Unsaturated Polyester Containing Functionalized Linseed Oil, Industrial & Engineering Chemistry Research, 45 (3), 1014-1018.
- Miyagawa, H., Jurek, R.J., Misra, M., Drzal, L. T., A. K. Mohanty, 2006, Biobased Epoxy/Clay Nanocomposites as a new matrix for CFRP, Composite Part A: applied science and manufacturing, A 37 (1), 54-62.
- Rhim, J-W., Mohanty, A.K., Singh, S. P., Ng, P. K. W., 2006, Effect of Processing Methods on Performance of Polylactide (PLA) Films: Thermocompression vs. Solvent Casting Methods, Journal of Applied Polymer Science, 101, 3736-3742.
- Mehta, G., Drzal, L. T., Mohanty, A. K., and Misra, M., 2006, Effect of Fiber Surfaces Treatment on Biocomposites from Nonwoven Industrial Hemp Fiber mats and Unsaturated Polyester resin, J. Applied Polymer Science, 99(3), 1055-1068.
- Aithani, D., Mohanty, A. K., 2006, Value-Added New Materials from Byproduct of Corn Based Ethanol Industries: Blends of Plasticized Corn Gluten Meal and Poly (є-Caprolactone), Industrial & Engineering Chemistry Research, 45(18), 6147-6152.
- Huda, M. S., Drzal, L. T., Mohanty, A. K., Misra, M., 2006, Wood Fiber Reinforced Poly(lactic acid) Composites: Physico-Mechanical and Morphological Properties Evaluation, Journal of Applied Polymer Science, 102, 4856-4869.
- Mohanty, A.K., Wu, Q., 2006, Biobased Compositions from Distillers Dried Grains with Solubles and Methods of Making Those, Application Filed: December 13, 2006.
- Mohanty, A.K., Wu, Q., Selke, S., 2006, Novel Green Materials from Soy Meal and Natural Rubber Blends, Application Filed: December 14, 2006.
- Mohanty, A.K., Parulekar, Y., Chidambarakumar, M., Kasitruangchai, N., Harte, B.R., 2006, Biodegradable Polymeric Nanocomposite Compositions Particularly for Packaging, Application filed: August 11, 2006.
Progress 01/01/05 to 12/31/05
New green materials based on soy meal were developed through blending with natural rubber. These materials, developed using industry prevalent extrusion processing were quite flexible. The applications targeted are bio-rubber bands, sheets and foot-pads etc. Another class of value-added biobased composite materials were fabricated from a combination of an inexpensive co-product of the dry milling corn ethanol industries e.g. distillers dried grains with solubles (DDGS) and biobased polyurethane through extrusion and compression molding processing. These biobased composite materials are likely to be tough, water resistant and will have wide-spread opportunities in applications such as trays, containers and furniture table tops. In another research project, the combination of three materials; a renewable resource-based biodegradable polymer, a petroleum-based biodegradable polymer, and organically modified clay resulted in novel eco-friendly nanocomposites that possess
good barrier properties with balanced stiffness and toughness properties. The renewable resource-based polymers were polylactides (PLA) and polyhydroxybutyrate (PHB). One of the major drawbacks of PLA and PHB is their low percent elongation and brittleness. Such limitations were targeted to be overcome through blending with an aliphatic-aromatic copolyester based tough polymer. The resulting blends were successfully reinforced with organically modified clay. We produced rigid as well as flexible materials. The processing used to develop rigid nanocomposites were extrusion followed by injection molding. The nanocomposites films were developed using extrusion followed by blown film processing. Biobased neat unsaturated polyester materials containing epoxidized methyl soyate and their clay nanocomposites were developed. We also developed biobased epoxy nanocomposites reinforced with organo-montmorillonite and carbon fibers. Our future plan is to use natural fibers to reinforce these
clay-based bio-resins. As a part of our investigations to develop biobased composite materials we were successful in making injection molded green composites from recycled newspaper fibers and polyhydroxyalkanoates (PHAs)as well as PLA. Two PHAs studied were polyhydroxybutyrate and polyhydroxybutyrate-co-valerate. The resulting green composites exhibited improved thermo-mechanical properties.
The bioconversion of corn into ethanol and soy into bio-diesel are approaching industrial viability. However one of the major challenges is to reduce the cost of these products further. Development of value-added applications for the co-products of the corn ethanol industry as well as the soy oil industry will help substantially to improve economic returns to corn and soy growers. The development of new biobased materials will help to substitute and supplement fully petroleum-based materials thereby reducing the adverse environmental impacts and creating job opportunities, especially in rural America. The development of biodegradable nanocomposites films with improved barrier performance and having the desired thermo-mechanical properties will find real world applications. Such practices will help in reducing the packaging wastes generated from nonbiodegradable plastics. Although we look to develop new materials from renewable resources or bio-resources sometimes we
may not get the desired properties. Then it will be acceptable to use a combination of petroleum-based polymer along with a renewable or biobased polymer in order to achieve acceptable cost-performance attributes while reducing the adverse impacts on the environment.
- Miyagawa, H., Mohanty, A.K., Misra, M. and Drzal, L.T., 2005, Novel biobased nanocomposites from functionalised vegetable oil and organically-modified layered silicate clay, Polymer, 46(2), 445-453.
- Miyagawa, H., Misra, M., Drzal, L.T. and Mohanty, A.K., 2005, Biobased Epoxy/Layered Silicate Nanocomposites: Thermophysical Properties and Fracture Behavior Evaluation, Journal of Polymers and the Environment, 13(2), 87-96.
- Huda, M.S., Drzal, L.T., Misra, M., Mohanty, A.K., Williams, K. and Mielewiski, D.F., 2005, A Study on Biocomposite from Recycled Newspaper Fiber and Poly(lactic acid), Industrial & Engineering Chemistry Research, 44 (15), 5593-5601.
- Miyagawa, H., Misra, M., Drzal, L.T. and Mohanty, A.K., 2005, Fracture Toughness and Impact Strength of Anhydride -cured Biobased Epoxy, Polymer Engineering and Science, 45(4), 487-495.
- Huda, M.S., Mohanty, A. K., Drzal, L. T., Schut, E. and Misra, M., 2005, Green composite from recycled cellulose and Poly(lactic acid): Physico-mechanical and morphological evaluation, J. Materials Science, 40 (16), 4221-4229.
- Bhardwaj, R. Mohanty, A.K., Drzal, L.T. and Misra, M., 2005, Novel Green Composites from Recycled Newspaper Fiber and Poly (hydroxyl alkanoates): Studies of Thermo-Mechanical Properties, presented at American Society for Composites 20th Annual Technical Conference September 7-9, 2005 - Philadelphia, PA (Full Paper (Paper No. 151) Published in CD-ROM Edn: Frank Ko, Giuseppe Palmese, Yury Gogotsi, Albert Wang.
- Mohanty, A. K., Miyagawa, H., Burgueno, R. and Misra, M., 2005, Biobased Nanocomposites from Organo-Clay and Blends of Unsaturated Polyester and Functionalized Vegetable Oil, SPE ANTEC 2005, Boston, May 1-5, 2005. (Full paper peer reviewed and published in CD-ROM Conference Proceeding M17- Bio-Nanocomposites, pp. 1310).