2007 Annual Report 1a.Objectives (from AD-416) 1)Use cereal or tuber starches to make polymer composites for non-food products. 2)Develop methods of processing starch composites into molded articles. 3)Convert agricultural fibers into biodegradable packaging, building materials and slurry-molded products. 4)Isolate cellulose, lignin and hemicellulose components from ag-fibers by applying environmentally friendly fractionation methods. 5)Promote technology transfer of these innovations. Conduct more basic studies of the structure and properties of microfibrils from cereal products and crop residues, which could lead to their eventual use in building and packaging foams, nanocomposites and related products. 1b.Approach (from AD-416) Starch will be blended with other polymers to produce resins with useful functional properties for making renewable products. Blend compatibility will be enhanced by use of starch derivatives and compatibilizers. Resins will be molded into marketable items using current and novel processing technologies, accompanied by physical and mechanical testing.Fiber reinforced packaging materials will be made via a foam-baking process, extrusion, injection molding and thermoforming. Advantageous functional properties of agriculturally-derived fibers used in these packages will be correlated to fiber length, aspect ratio, freeness, surface properties, and miscibility. Ag-derived fibers will be pulped using novel procedures, such as hot-compressed water (HCW) treatment, an environmentally friendly method of isolating cellulose, lignin and hemicellulose via super-heated water. Processed fibers will be optimized by chemical, enzymatic and chemoenzymatic modification. Methods for isolating and characterizing cellulose microfibrils as nanocomposites will be developed/exploited. Formerly 5325-41000-039-00D (6/04). 3.Progress Report Agriculturally derived polymers and commodity chemicals are produced in surplus and are underutilized. As part of this CRIS, research at the WRRC along with CRADA partner, Clorox, was conducted to develop biobased cleaning products and charcoal for consumer use. Research has already led to the development of several prototypes for cleaning, scrubbing as well as moisture and odor-removing non-woven substrates generated from totally biodegradable plant materials. The use of cereal-based binders in charcoal products could save a partner an estimated $5 million each year. The use of eco-compatible plant polymers in cleaning products and charcoal will help the American farmer by opening new markets for surplus crops, reduce our dependence on petroleum, and ensure safer environment. As part of completion of a CRADA agreement with EarthShell Corp., a pilot plant and testing facility for creating biodegradable single-use items, such as plates, bowls and cups, was finalized at the WRRC so that technology could be transferred to third-party commercial producers. Prototype plates from formulations derived at WRRC were made of cereal starches and transferred to commercial partners such as Renewable Products Incorporated (RPI) to facilitate their industrial process. RPI is currently operating a production facility located in Springfield, MO that is expanding and marketing packages from cereal starches. Final efforts are being made to develop formulations for making a hot cup product. 4.Accomplishments Most significant accomplishment: Biofuels and Bioproducts from Under-Utilized Ag-Fibers. Producing biofuels and bioproducts from under-utilized Agricultural Fibers and residues is critical to meet U.S. strategic goals. Biorefinery operations in support of a biofuels program, aimed at utilizing ag-derived waste fibers was established by the ARS, WRRC scientists in Albany, CA. WRRC Researchers showed that ethanol and energy can be derived efficiently from cellulosic biomass by combining high-pressure steam fractionation of lignocellulosic materials with suitable enzymatic hydrolysis and fermentation. Ag-derived waste fibers, co-mingled with municipal solids waste, were hydrolyzed and converted into ethanol at large lab-scale and then pilot scale in collaboration with industrial partner, CR3. The potential outcome of this work is a viable biorefinery process for converting ag-derived waste fiber into fuel ethanol thus, reducing U.S. dependece on Foreign oil. This research aligns with NP 307 - BioEnergy Alternatives: Component 1 Ethanol and NP 306 - Quality and Utilization of Agricultural Products: Component II. (d) New and Improved Processes and Feedstocks. Other accomplishments: Biomaterials to Control Parasitic Bee Mites. Parasitic mites are threatening the honeybee industry which directly and indirectly accounts for $14 billion of agricultural products. Starch foam microspheres and film coatings and envelopes were developed by BCE scientists, Albany, CA for delivery of volatile plant oils that control parasitic mites in honeybees when ingested. The starch-based microspheres coated with benign, edible films were developed in WRRC, Albany, CA and tested at the Hayden Bee Labs, AZ. Preliminary field trials show that commercial production of the films/foam composites could have a large impact on the honeybee industry as well as on the dry Fruit and Citrus Industry in the Pacific West Area of the United States. This research aligns with NP 307 - BioEnergy Alternatives: Component 1 Ethanol and NP 306 - Quality and Utilization of Agricultural Products: Component II. (d) New and Improved Processes and Feedstocks. Renewable Packaging, Plates and Bowls. Development of Biodegradable food packaging from renewable plant materials is needed to promote new uses for surplus farm commodities, and help American farmers as well as agro-industry. WRRC Researchers, as part of a CRADA agreement with EarthShell Corp. commercialized single-use items, such as plates, bowls and cups, derived from cereal starches and fiber composites. Technical transfer to third party licensees, such as Renewable Products Incorporated (RPI), facilitated start-up of commercial processes, including a commercial production facility located in Springfield, MO. This facility is providing an expanding market for renewable, biodegradable single-use items from cereal starches. This research aligns with NP 307 - BioEnergy Alternatives: Component 1 Ethanol and NP 306 - Quality and Utilization of Agricultural Products: Component II. (d) New and Improved Processes and Feedstocks. Lightweight Concrete from Ag-Materials. Developing non-food uses of surplus farm products and residues is critical for helping farmning communities and American Agro-industry. WRRC Researchers have created novel cereal-based lightweight concrete with improved strength and resiliency, with uniform pore density relative to typical lightweight commercial concretes. They discovered a novel method of dispersing cellulose fiber in a matrix of concrete which maximizes surface exposure of individual fibers, therefore increasing strength. Not only does this provide for lighter concrete, but it allows for easier construction because nails and screws can be driven directly into this composite, providing alternative building materials with greater fire resistance and low cost. This research aligns with NP 307 - BioEnergy Alternatives: Component 1 Ethanol and NP 306 - Quality and Utilization of Agricultural Products: Component II. (d) New and Improved Processes and Feedstocks. New Uses for Alaskan Fish Wastes. Fish gelatin, in contrast to other types of gelatin, is not currently used in biomedical applications because of its poor properties at room temperature. Team of scientists at the Western Regional Research Center, Albany, CA in collaboration with ARS scientists in Fairbanks, Alaska have extracted gelatin from the skins of Alaska Pollock and pink salmon. The team has successfully cross-linked the fish gelatin and improved its properties at room temperature. This finding could help develop a new niche market for fish waste-a growing concern to the Alaska fishing industry. This research aligns with NP 307 - BioEnergy Alternatives: Component 1 Ethanol and NP 306 - Quality and Utilization of Agricultural Products: Component II. (d) New and Improved Processes and Feedstocks. Conductive, Stable Nanocomposites. A team of scientists at WRRC, in collaboration with EMBRAPA scientists from Brazil are creating electroconductive nanofibrils for new application in coatings and electronic packaging. Nanocrystalline cellulose fibrils derived from agricultural residues were polymerized with conducting polymers and applied as rust-resistant paints and additives. Chemically modifying surfaces by azidation of both the cellulose and biopolymer components has proven to improve nanocomposite stability Azide modified starches and cellulose are less moisture sensitive and tend to retrograde less than native starches, and provide an interesting matrix for the conductive nanofibril materials. This research aligns with NP 307 - BioEnergy Alternatives: Component 1 Ethanol and NP 306 - Quality and Utilization of Agricultural Products: Component II. (d) New and Improved Processes and Feedstocks. Green Cleaning Agents. Agriculturally derived polymers and commodity chemicals are produced as part of biorefinery operation and will be a main economic driver in realization of viable cellulose ethanol production. As part of this CRIS (Project No. 5325-4100-044-00D), research at the WRRC with CRADA partner, Clorox, was conducted to develop biobased cleaning products, charcoal, odor-removing non-woven substrates, and biodegradable cleaning substrates that are “flushable” and still effective at scrubbing. The use of eco-compatible plant polymers in cleaning products and charcoal creates “greener”, more economical products for Clorox and aids the American farmer by opening new markets for surplus crops, reduces our dependence on petroleum, and minimizes the carbon footprint of single-use products. This research aligns with NP 307 - BioEnergy Alternatives: Component 1 Ethanol and NP 306 - Quality and Utilization of Agricultural Products: Component II. (d) New and Improved Processes and Feedstocks. Novel Biocontrol Applications to Control Coddling Moth. WRRC Researchers, in collaboration with ARS Entomologists in Wapato, WA, developed a sprayable foam that controls coddling moth which is sprayed around tree trunks as biocontrol agent in apples and pears. The foam consists of low cost materials, such as straw and bagasse, and contains bioactive agents for insect control. This obviates the need to spray the fruit directly, thus having widespread application in organic orchards, an important growing market. Field trials are on-going. This research aligns with NP 307 - BioEnergy Alternatives: Component 1 Ethanol and NP 306 - Quality and Utilization of Agricultural Products: Component II. (d) New and Improved Processes and Feedstocks. 6.Technology Transfer Number of active CRADAs and MTAs 7 Number of patent granted 2 Number of newspaper articles and other presentations for non-science audiences 2 Review Publications Inglesby, M.K., Wood, D.F., Gray, G.M. 2006. Effect of chemical fractionation treatments on silicon dioxide content and distribution in oryza sativa. In: Characterization of the Cellulosic Cell Wall, D.D. Stokke and L.H. Groom, eds, Blackwell Publishing, Ames, IA, pp 192-212. Ibanez-Carranza, A.M., Wood, D.F., Yokoyama, W.H., Park, I.M., Tinoco, M.A., Hudson, C.A., McKenzie, K.S., Shoemaker, C.F. 2007. Viscoelastic Properties of Waxy and Non-Waxy Rice Flours, Their Fat and Protein-Free Starch, and the Microstructure of Their Cooked Kernels. Journal of Agricultural and Food Chemistry. 55(16):6761-6771. Sojka, R.E., Bjorneberg, D.L., Entry, J.A., Lentz, R.D., Orts, W.J. 2007. Polyacrylamide (PAM) in agriculture and environmental land management. Advances in Agronomy. 92:75-162. Orts, W.J., Roa-Espinosa, A., Sojka, R.E., Glenn, G.M., Imam, S.H., Erlacher, K., Pedersen, J. 2007. Use of synthetic polymers and biopolymers for soil stabilization in agricultural, construction and military applications. Journal of Materials in Civil Engineering. 19(1):58-66. Chiou, B., Yee, E., Glenn, G.M., Orts, W.J. 2005. Rheology of starch-clay nanocomposites. Carbohydrate Polymers. 59: 467-475 (2005) Ogawa, Y., Wood, D.F., Orts, W.J., Glenn, G.M. 2006. Compression deformation and structural relationships of cooked rice. Cereal Chemistry. 83 (6): 635-640. (2006) Chiou, B., Avena Bustillos, R.D., Shey, J., Yee, E., Bechtel, P.J., Imam, S.H., Glenn, G.M., Orts, W.J. 2006. Rheological and mechanical properties of cross-linked fish gelatins. Polymer. 47(18):6379-6386. Shey, J., Holtman, K.M., Wong, R.Y., Gregorski, K.S., Klamczynski, A., Orts, W.J., Glenn, G.M., Imam, S.H. 2006. The azidation of starch. Carbohydrate Polymers. 65 (4): 529-534 (2006) Glenn, G.M., Klamczynski, A., Shey, J., Chiou, B., Holtman, K.M., Hoffman, G.D., Wood, D.F. 2007. Controlled release of volatile liquids using starch gel matrices and films. Polymers for advanced technologies. 18 (8): 636:642. (2007) Orts, W.J., Nobes, G.A., Glenn, G.M., Gray, G.M., Imam, S.H., Chiou, B. 2007. Blends of starch with ethylene vinyl alcohol copolymers: effect of water, glycerol and amino acids as plasticizers. Polymers for Advanced Technologies. 18 (8): 629-635. (2007) Mao, J., Holtman, K.M., Scott, J.T., Kadia, J.F., Schmidt-Rohr, K. 2007. Differences between Lignin in Unprocessed Wood, Milled Wood, Mutant Wood, and Extracted Lignin Detected by 13C Solid-State NMR. Journal of Agricultural and Food Chemistry. 59 (26): 9677-9686. (2007).