Progress 08/01/09 to 09/30/12

Outputs
OUTPUTS: While the original plan was to engage other institute to form collaboration on wood products, using bio-based adhesives developed at ISU, because the funding source was discontinued when ISU joined the program, these planned meetings never occurred. Thus, this report detailed the activities at ISU that are related to bio-based materials that could be utilized with wood based products. Multiple grants from multiple sources were funded with a total award over $6 million. The funding sources include, USDA Office of Energy Policy and New Uses, USDA, the United Soybean Board, Grow Iowa Value Funds, as well as other sources. Following is a list of awarded grants: Food Packing Sealing; CAREER: Multifunctional Biorenewable Polymers; Ultrasonic Sealing and Cutting of Bioplastic Films; Application of a Continuous Welding Using a Radial Tool for Sealing of PLA Plastic Films; Soy Protein Plastics Formulation Development to Reduce Water Solubility; Development and Commercialization of Soy/Corn/Linseed Oil Bioplastics; Practical Waterborne Agricultural Oil-Based Coatings; Biorenewable Composites Reinforced with Under-used Co-products from Ethanol Production; Novel Renewable Bio-based Rubber Composites from Plant Oils and Agricultural Co-products; Fiberglass Reinforced Polymers from Agricultural Oils. FEASIBILITY STUDIES: Recycling and Recovery of Lactic Acid from Post-consumer PLA Products Utilizing Energy Efficient Ultrasonic Depolymerizing System; Using Water-stable, High-strength Soy-based Plastic for Horticulture Crop Containers; Feasibility Study of the Use of DDGs Plastic Composites for Structural Components in Window Framing; Life Cycle Cost Model Development of Bioplastics; Comparison of Plastics from Corn Zein; PLA Mechanical Test; Soy Protein Plastics Formulation Development for Enhanced Mechanical Strength and Reduced Water Solubility; Characterization of Commercial Biodegradable Plastics for Biodegradation and Compostability; Benchmark Compostability Testing Services; Scale-up and Technology Transfer of Protein-based Plastic Products; Pultruded Window Frames from Agricultural Oils (2); Commercialization of a Corn/Soy Oil-Based Composite Hog Feeder; Development and Commercialization of Soy / Corn / Linseed Oil Bioplastics. In addition, over 20 journal articles were published as well as over 25 conference papers were published as a related to the this project over its duration. The team also attended and had a booth at several bio-plastics trade shows and organized three highly successful and well-attended bioplastics workshops in 2008, 2010, and 2012. The team has applied for and has been awarded or has pending more than 5 patents. In February 2013, the team was awarded a planning grant by the National Science Foundation (NSF) to lead a multi-institutional Industry/University Cooperative Research Center (I/UCRC) in bioplastics (the Center for Bioplastics and Biocomposites, or CB2). Over the course of the project a software package was developed and posted on the web that allows users to compare bioplastics and petrochemical plastics in conjunction with Nypro and M-Base in terms of costs, greenhouse gas generation, and energy usage. PARTICIPANTS: ISU Participants: David Grewell -- Associate Prof.; Mike Kessler -- Associate Prof.; Maria Baboi -- Research Scientist; Gowrishankar Srinivasan -- Post-Doc; Julius Vogel -- PhD Student; Joe Vanstrom -- MS student. Non-ISU Participants: Roy Taylor of SoyWorks/RT Technologies. TARGET AUDIENCES: Engineers, scientists working with bioplastics; including processors, manufacturers and compounders. PROJECT MODIFICATIONS: While the original plan was to engage other institute to form collaboration on wood products, using bio-based adhesives developed at ISU (such a binders with wood chips to form wood paneling), because the funding source was discontinued when ISU joined the program, these planned meetings never occurred. Thus, this report detailed the activities at ISU that are related to bio-based materials that could be utilized with wood based products.

Impacts
Over the duration of this project the outcomes of the project included the *Prototype production of plant protein plastic products, including pots for plants, lawn care products and animal drug delivery systems. *New knowledge was gained that allows lignin to be converted into low cost high value graphite fibers. *New knowledge on the pathways to polymerize renewable oils into structural bioplastics. *The development of chemical pathways to depolymerize polyesters, such as PLA. *Patent applications/Patents issued: 1) Depolymerization of Polylactic Acid, ISURF Docket #3950, ISU, November 2011, G. Srinivasan, D. Grewell. 2) Heat Element and Ultrasonic - Hybrid Welding, ISURF Docket #3926, ISU, November 2011, J. Vogel, D. Grewell. 3) Wet Spinning Process of Lignin for Fiber Production, ISURF Docket #3959, ISU, December 2011, D. Grewell. 4) Compositions Including Esterified Lignin and Poly(lactic acid) and Carbon Fibers Produced Therefrom, M. Thunga, b K. Chen, b M. R. Kessler, U.S. Patent Application, October 9, 2012. 5) Polyisocyanates from Fused Bicyclic Polyols and Polyurethanes Therefrom, J. Chen, M. R. Kessler, M. Zenner, b, Invention Disclosure, Iowa State University Research Foundation (ISURF), U.S. Patent Application, October 15, 2012. 6) Thermoset Polymers via Ring Opening Metathesis Polymerization of Functionalized Oils, R. C. Larock, P. H. Henna, and M. R. Kessler, United States Patent 8,318,876, Issued November 27, 2012.

Publications

• P. J. Gramann, J. C. Cruz, D. Grewell, T. Wang, M. Montablo-Lomboy, Effects of Glycerin Antifreeze on CPVC, 100th Annual Technical Conference for the Society of Plastic Engineers Proceedings (2013), Society of Plastic Engineers, Brookfield, CT, Accepted January 2013
• M. Montablo-Lomboy, D. Grewell, T. Wang, P. J. Gramann, J. C. Cruz Effects of Biodiesel on Plastics, 100th Annual Technical Conference for the Society of Plastic Engineers Proceedings (2013), Society of Plastic Engineers, Brookfield, CT, Accepted January 2013
• D. Grewell, G. Srinivasan, J. Schrader, W. Graves, M.Kessler, Sustainable Materials for Horticultural Application, 100th Annual Technical Conference for the Society of Plastic Engineers Proceedings (2013), Society of Plastic Engineers, Brookfield, CT, Accepted January 2013
• P. Badrinarayanan, b M. K. Rogalski, c M. R. Kessler a: Carbon Fiber Reinforced Cyanate Ester / Nano-ZrW2O8 Composites with Tailored Thermal Expansion, ACS Applied Materials and Interfaces, 2012, 4(2), 510-517 (doi: 10.1021/am201165q) (special issue: Forum on Polymers for Aerospace Applications).
• J. Schrader , G. Srinivasan , D. Grewell, W. Graves, Fertilizer Effects of Soy-plastic Containers during Production and Transplant Establishment of Tomato and Pepper, American Society of Horticultural Science, August 2012, Miami Fl
• V. Akumar, S., S. Jung, D. Grewell , S. Clark. . Poster presentation. Effects of thermosonication on total plasmin and characteristics of skim milk and cream. Annual Mtg. Institute of Food Technologists (IFT), Las Vegas, NV. 2012. Sakthi placed 5th in Dairy Foods Division graduate poster competition
• W. X. Sun, W. Z. Sun, M. R. Kessler, N. Bowler, K. W. Dennis, R. W. McCallum, Q. Li, X. Tan: Multifunctional properties of cyanate ester composites with SiO2 coated Fe3O4 fillers, ACS Applied Materials and Interfaces, 2013, In Press (doi: 10.1021/am302520e).
• D. M. Kadam, M. Thunga,b S. Wang, M. R. Kessler, D. Grewell, B. Lamsal, C. Yu: Preparation and Characterization of Whey Protein Isolate Films Reinforced with Porous Silica Coated Titania Nanoparticles, Journal of Food Engineering, 2013, In Press (doi: 10.1016/j.jfoodeng.2013.01.046).
• D. Vennerberg,b R. Quirino,b M. R. Kessler a: A Novel Microwave-Assisted Carbothermic Route for the Production of Copper-Carbon Nanotube Metal Matrix Composites Directly from Copper Oxide, Advanced Engineering Materials, 2012, In Press (doi: 10.1002/adem.201200250).
• S. A. Madbouly,b Y. Xia,b M. R. Kessler a: Rheokinetics of Ring Opening Metathesis Polymerization of Bio-Based Castor Oil Thermosets, Macromolecules, 2012, 45(19), 7729-7739 (doi: 10.1021/ma301458n).
• Y. Xia,b Z. Zhang, M. R. Kessler, B. Brehm-Strecher, R. C. Larock: Antimicrobial Soybean Oil-Based Cationic Polyurethane Coatings Prepared from Different Amino Polyols, ChemSusChem, 2012, 5(11), 2221-2227 (doi: 10.1002/cssc.201200352)
• M. R. Kessler: Polymer Matrix Composites: A Perspective for a Special Issue of Polymer Reviews, Polymer Reviews, 2012, 52(3), 229-233 (doi: 10.1080/15583724.2012.708004).
• W. Sun, J. E. De Leon, b C. Ma, X. Tan,a M. R. Kessler: Novel Si/Cyanate Ester Nanocomposites with Multifunctional Properties, Composites Science and Technology, 2012, 72, 1692-1696 (doi: 10.1016/j.compscitech.2012.06.023).
• H. Cui,b M. R. Kessler a: Glass fiber reinforced ROMP-based bio-renewable polymers: Enhancement of the interface with Silane Coupling Agents, Composites Science and Technology, 2012, 72, 1264-1272 (doi: 10.1016/j.compscitech.2012.04.013).
• T. C. Mauldin,b J. Leonard,c K. Earl,b J. K. Lee, and M. R. Kessler a: A Modified Rheokinetic Technique to Enhance the Understanding of Microcapsule-based Self-healing Polymers, ACS Applied Materials & Interfaces, 2012, 4(3), 1831-1837 (doi: 10.1021/am300133n).
• J. Vogel, M. R. Kessler, S. Sriram, D. Grewell: Activation Energy for Diffusion and Welding of PLA Films, Polymer Engineering and Science, 2012, 52(8), 1693-1700 (doi: 10.1002/pen.23120).
• M. Thunga, b Y. Xia, U. Gohs, G. Heinrich, R. C. Larock, M. R. Kessler a: Influence of Electron Beam Irradiation on Mechanical Properties of Vegetable Oil-based Biopolymers, Macromolecular Materials and Engineering, 2012, 297(8), 799-806 (doi: 10.1002/mame.201100339).
• X. Liu, J. K. Lee, M. R. Kessler: Microencapsulation of Self-healing Agents with Malamine-Urea-Formaldehyde by the Shirasu Porous Glass (SPG) Emulsification Technique, Macromolecular Research, 2011, 19(10), 1056-1061 (doi: 10.1007/s13233-011-1009-3).
• P. Badrinarayanan b and M. R. Kessler a: Zirconium Tungstate/Cyanate Ester Nanocomposites with Tailored Thermal Expansivity, Composites Science and Technology, 2011, 71, 1385-1391 (doi: 10.1016/j.compscitech.2011.05.004).
• G. C. Huang, J. K. Lee, M. R. Kessler: Evaluation of Norbornene-Based Adhesives to Amine Cured Epoxy for Self-Healing Applications, Macromolecular Materials and Engineering, 2011, 296, 965-972 (doi: 10.1002/mame.201100016) .
• E. A. Stefanescu,b X. Tan, Z. Lin, N. Bowler, M. R. Kessler a: Multifunctional Fiberglass-Reinforced PMMA-BaTiO3 Structural/Dielectric Composites, Polymer, 2011, 52, 2016-2024 (doi: 10.1016/j.polymer.2011.02.050).

Progress 01/01/11 to 12/31/11

Outputs
OUTPUTS: Several projects are currently active developing and characterizing plant protein plastics. Funding sources include the USDA Office of Energy Policy and New Uses and the United Soybean Board. Experiments conducted to study various grades of polylactic acid (PLA) included welding and sealing of PLA films and measuring activation energy for welding of PLA films. Experiments conducted to study the welding of polylactic acid (PLA) included process optimization of ultrasonic welding, and process optimization of impulse welding. An ASTM compositing system was constructed and finalized to test products for biodegradability. The setup included anaerobic digestion and aerobic digestion. A software package was developed and posted on the web that allows users to compare bioplastics and petrochemical plastics in conjunction with Nypro and M-Base in terms of costs, greenhouse gas generation, and energy usage. Events this period included: continued chair position of ISU's Bioplastics, Biocomposites Research Team; served as US delegate for the International Institute of Welding and shared results on welding of PLA; Invited lecturer Bioplastics and Renewable Fuels, POET, Sioux Falls, SD, October 2011; Invited lecture: D. Grewell, Maria Baboi, Gowrishankar Srinivasan, Investigating Protein Based Plastic Composites for Industrial Applications, 18th International Composites Conference, Jeju Island, South Korea, August 21, 2011; Work with Insite on bioplastic ground cover; Work with Creative Composites on lubrication product. Dissemination this period included a paper at the Annual Technical Conference of the Society (ANTEC) of Plastic Engineers (SPE). Patent Applications: 1) Depolymerization of Polylactic Acid, ISURF Docket # 3950, ISU, November 2011, G. Srinivasan, D. Grewell. 2) Heat Element and Ultrasonic - Hybrid Welding, ISURF Docket # 3926, ISU, November 2011, J. Vogel, D. Grewell. 3) Wet Spinning Process of Lignin for Fiber Production, ISURF Docket # 3959, ISU, December 2011, D. Grewell. PARTICIPANTS: ISU Participants: David Grewell -- Associate Prof.; Mike Kessler -- Associate Prof.; Maria Baboi -- Research Scientist; Gowrishankar Srinivasan -- Post-Doc; Julius Vogel -- PhD Student; Joe Vanstrom -- MS student. Non-ISU Participants: Roy Talyor of SoyWorks. TARGET AUDIENCES: Engineers, scientists working with bioplastics; including processors, manufacturers and compounders. PROJECT MODIFICATIONS: Nothing significant to report during this reporting period.

Impacts
The outcomes of the work included the prototype production of plant protein plastic products, including pots for plants and animal drug delivery systems. In addition, new knowledge was gained that will allow future polymer chemists to know which processing steps of bioplastic correspond to the highest costs and allow them to direct their efforts to these costs. Work on process optimization of ultrasonic welding, and process optimization of impulse welding results in knowledge that allows others to weld/join PLA for applications such as food packaging with confidence and knowledge of the proper parameters. This in terms will promote the wide acceptance of PLA and reduce our dependence on petrochemical plastics and decrease our impact on the enviromennt. The software package developed allows others to decide the economical and environmental benefits of bioplastics compared to petrochemical plastics. This will also promote the use of bioplastics and also reduce our implact on the environment.

Publications

• Vogel, J., D. Grewell, M. Kessler, D. Drummer, and M. Menacher. 2011. Ultrasonic and impulse welding of polylactic acid films. Polymer Engineering & Science, 51(6), pp. 1059-1067.
• D. Grewell, D. Fuchs, Krishna Rajan, M. Schemme, P. Karlinger, M. R. Kessler, 2011. Vacuum Infusion Processing of Self-Healing Composites with Reinforcement Bound Microcapsules, Journal of Plastics Technology,2011/01, 2-16.
• Julius Vogel, D. Grewell. Weldability of Bioplastics, Plastics Decorating, 55(2)33-36, February 2011.
• J.Vogel, D.Grewell. 2011. Ultrasonic cutting of biodegradable polylactic acid (PLA) films, 98th Annual Technical Conference for the Society of Plastic Engineers Proceedings, Society of Plastic Engineers, Brookfield, CT.

Progress 01/01/10 to 12/31/10

Outputs
OUTPUTS: Several projects are currently active developing and characterizing plant protein plastics. Funding sources include USDA Office of Energy Policy and New Uses, United Soybean Board, and POET Biorefining. 1) Experiments were conducted to study various grades polylactic acid (PLA) funded by the USDA. These studies included strength, impact strength, toughness, and thermal stability. 2) Experiments were conducted to study the welding of polylactic acid (PLA) funded by the USDA. These studies included process optimization of ultrasonic welding and process optimization of impulse welding. 3) An ASTM compositing system was constructed to test products for biodegradability. The setup included anaerobic digestion and aerobic digestion. 4) Data were collected on the life cycle analyzes of key bioplastics and petrochemical plastics. A software package was developed and posted on the web that allows user to compare bioplastics and petrochemical plastics in terms of costs, green house gas generation, and energy usage. 5) Dissemination this period included three papers submitted and accepted at the Annual Technical Conference (ANTEC) of the Society of Plastic Engineers (SPE), and Corn Utilization and Technology Conference, Atlanta, 2nd prize in poster competition. PARTICIPANTS: Iowa State University: David Grewell, Assist. Prof.; Mike Kessler, Assist. Prof.; Maria Baboi, Research Scientist; Gowrishankar srinivasan, PhD Stuent; Julius Vogel, PhD Student; Joe Vanstrom, MS student. SoyWorks: Roy Talyor. TARGET AUDIENCES: Engineers, scientist working with bioplastics; including processor, manufacturers and compounders. PROJECT MODIFICATIONS: Nothing significant to report during this reporting period.

Impacts
The outcomes of the work included the prototype production of plant protein plastic products, including pots for plants and animal drug delivery systems. In addition, new knowledge was gained that will allow future polymer chemist to know which processing steps of bioplastic correspond to highest costs and allow them to direct their efforts to these costs. Other outcomes were the setup of an ASTM test cell for compostibility (to be fully functional 2011).

Publications

• J.Vogel , D. Grewell, Weldability of Bioplastics, 68th Annual Technical Conference for the Society of Plastic Engineers Proceedings (2010), Society of Plastic Engineers, Brookfield, CT.
• D. Grewell, J. Vogel, R. Anex, Comparison of Life Cycle Greenhouse Gas and Energy profiles of bio-plastics and petroleum based plastics, GPEC 2010 Conference, Orlando, FL, Society of Plastics Engineers, Brookfield, CT.
• D. Grewell, Julius Vogel, Calculation of the Activation Energy for Self Diffusion and Molecular Healing in PLA Films, Annual International Polymer Processing Society Conference, Banff, Canada, July 2010, Invited Lecture.
• J.Vogel, D.Grewell, Calculation of the Activation Energy for Self Diffusion, 68th Annual Technical Conference for the Society of Plastic Engineers Proceedings (2010), Society of Plastic Engineers, Brookfield, CT.
• G. Srinivashan, S. Carolan, D. Grewell, Enhanced water stability of soy protein plastics using acid anhydrides, 68th Annual Technical Conference for the Society of Plastic Engineers Proceedings (2010), Society of Plastic Engineers, Brookfield, CT.