2004 Annual Report 1.What major problem or issue is being resolved and how are you resolving it (summarize project aims and objectives)? How serious is the problem? What does it matter? The U.S. produces much more wheat than can be marketed domestically. Historically, much of the surplus grain was exported to foreign buyers. However, countries that were once large importers are now more self-sufficient or are exporting grain themselves. There is a need to develop new domestic markets for wheat. Efforts are being made to resolve the problem by developing new food and industrial products that utilize wheat. A second aspect of this problem is the management of crop residues such as wheat and rice straw. Farmers are no longer allowed to burn straw in increasing number of states. There is a need to develop new products that utilize straw. 2.List the milestones (indicators of progress) from your Project Plan. Milestones and Outcomes; Objective 1 Fractionation of rice/wheat straws --- Determine success of novel fractionation processes for rice straw. Quantify silica fraction in untreated and pulped rice straw. Complete chemical analyses of organic constituents & characterize surface properties of rice/wheat straws. Apply lignocellulose fractions in packaging products. Assess utility. Patent and/or publish data. Complete CF economic analysis. Complete lignin fraction analyses and assess potential as adhesive/composite binder. Microfibril/clay nanomaterials --- Complete isolation of nanoscale cellulose microfibrils. Complete rheological tests of native particles. Begin scale-up of isolation; Complete characterization of microfibril and clay nanocomposites; benchmark their utility. Publish/patent data. Complete determination of surface interactions of nanoparticles within composites. Select optimal surface modifications. Establish CRADA with industrial partner and transfer technology on nanocomposites. Milestones and Outcomes; Objective 2 Chemical/enzyme modified starch and fiber --- Complete creation of crosslinked & enzyme modified biobased materials. Select target composites for use. Field test the polymer complexes developed for controlling soil erosion. Create a CRADA partnership to utilize (1) charged polymers as soil additive, and (2) modified biopolymers in films. Transfer technology and publish results on effect of polymer complexes in controlling soil erosion. Milestones and Outcomes; Objective 3 Baked foam and expanded-bead containers --- Transfer technology on baked foams using wheat starch, and optimal selection of fibers, fillers, coatings. Complete lab-scale techniques & formulations for starch-based foam beads. Adapt expanded foam bead technology to commercial-scale EPS molding equipment. Transfer technology on expanded starch bead molding. File appropriate patents. Pulping/use of straws --- Complete pilot scale test for pretreatment of straws for Regale. Transfer technology to Regale's full-scale plant. Complete sophisticated CF pulping techniques. Recover the liquor, assess value of silica. Transfer technology and/or file appropriate patents for straw pulp fiber process. Assess the value of each fraction from straws. Find appropriate outlets for each fraction. Lightweight Concrete --- Complete tests of alkaline resistant starch blends in lightweight concrete. Patent process. Transfer technology on alkaline resistant starch-based lightweight concrete. Establish expanded starch-based aggregate in lightweight concrete. Transfer technology on expanded starch-based aggregate in lightweight concrete. Soluble films --- Complete development of water soluble biobased films and substrates. Transfer technology and publish data from biobased films and substrates. Create crosslinked films to act as non-woven cleaners. Transfer technology on films and substrates to industrial partners. Milestones and Outcomes; Objective 4 Biodegradability/aging; performance of bioproducts --- Establish respirometry at WRRC as tool to test biodegradability of market-targeted bioproducts. Transfer information to industrial partners of biodegradability of starch/fiber based composite materials. Continue to provide data on biodegradability of materials developed by other scientists within the group. Benchmark the biodegradability of each new biomaterial against standard ASTM results. Publish data. 3.Milestones: A. Activities concerning the milestones listed for FY 2004 were as follow: Milestones scheduled to be addressed in 2004/2005. This project terminated during 2004. Objective 1 Fractionation of rice/wheat straws --- Determine success of novel fractionation processes for rice straw. Quantify silica fraction in untreated and pulped rice straw; Accomplishment: The quantity of silica in untreated rice straw has been measured as a function of the fractionation method (publication for Inglesby et al.) Methods of pulping rice straw are being tested. Microfibril/clay nanomaterials --- Complete isolation of nanoscale cellulose microfibrils. Complete rheological tests of native particles. Begin scale-up of isolation. Accomplishment: Starch nanocomposites were formulated and produced by extrusion. Rheological properties were characterized and results were summarized and submitted for publication (Chiou et al.). Other work with microfibrils is ongoing. Objective 2 Chemical/enzyme modified starch and fiber --- Complete creation of crosslinked & enzyme modified biobased materials. Select target composites for use. Accomplishment: Several cross-linking reactions have been tested to modify starch/fiber surface properties. Results are preliminary, but cross-linked foams have been presented to CRADA partner as part of joint work. Objective 3 Baked foam and expanded-bead containers --- Transfer technology on baked foams using wheat starch, and optimal selection of fibers, fillers, coatings. Accomplishment: Formulations for baked foams made of wheat starch were developed and transferred to CRADA partner and are being commercially applied in their Northern California industrial plant. Preliminary studies on expanded beads were obtained. Pulping/use of straws --- Complete pilot scale test for pretreatment of straws for Regale. Transfer technology to Regale's full-scale plant. Accomplishment: Pre-treated rice straw was pre-treated and utilized by Regale in their slurry-pulp industrial process. Samples were tested as packaging by their customers. Lightweight Concrete --- Complete tests of alkaline resistant starch blends in lightweight concrete. Patent data. Accomplishment: One study on alkaline resistant starch blends was completed and results were submitted to journal for publication. The data is not patentable because of the existing patent. Soluble films --- Complete development of water soluble biobased films and substrates. Accomplishment: Water-soluble films with abrasive surface properties have been developed and are being tested. A patent disclosure has been approved by the patent committee and been filed. Objective 4 Biodegradability/aging; performance of bioproducts --- Establish respirometry at WRRC as tool to test biodegradability of market- targeted bioproducts; Accomplishment: Respirometer has been purchased and has just been installed. First tests are being carried out. B. Milestones to address over the next 3 years. Objective 1 Fractionation rice/wheat straws. Year (2005) Determine success of novel organo-solv and traditional processes for rice straw. Quantify silica fraction in untreated and pulped rice straw. Year (2006) Complete chemical analyses of organic constituents & characterize surface properties of rice/wheat straws. Year (2007) Apply lignocellulose fractions in packaging products and assess utility. Patent and/or publish data. Microfibril/clay nanomaterials. Year (2005) Complete isolation of nanoscale cellulose microfibrils. Complete rheological tests of native particles. Begin scale-up of isolation. Year (2006) Yr. 2006. Complete characterization of microfibril and clay nanocomposites and benchmark their utility. Publish/patent data. Year (2007) Complete determination of surface interactions of nanoparticles within composites. Select optimal surface modifications. Objective 2 Chemical/enzyme modified starch and fiber (Imam/ Inglesby/Chiou/Orts). Year (2005) Complete creation of crosslinked & enzyme modified biobased materials. Select target composites for use. Year (2006) Field test the polymer complexes developed for controlling soil erosion. Year (2007) Create a CRADA partnership to utilize (1) PECs as soil additive, and (2) modified biopolymers in films. Objective 3 Baked foam and expanded-bead containers (Glenn/ Imam/Chiou/Wood). Year (2005) Complete lab-scale techniques & formulations for starch-based foam beads. Year (2006) Adapt expanded foam bead technology to commercial-scale EPS molding equipment. Year (2007) Transfer technology on expanded starch bead molding. File appropriate patents. Pulping/use of straws. Year (2005) Complete pilot scale test for pretreatment of straws for Regale. Transfer technology to Regale's full scale plant. Year (2006) Complete sophisticated CF pulping techniques. Recover the liquor, assess value of silica. Year (2007) Transfer technology and/or file appropriate patents for straw pulp fiber process. Lightweight Concrete. Year (2005) Complete tests of alkaline resistant starch blends in lightweight concrete. Transfer technology on alkaline resistant starch-based lightweight concrete. Year (2006) Establish expanded starch-based aggregate in lightweight concrete. Year (2007) Transfer technology on expanded starch-based aggregate in lightweight concrete. Soluble films. Year (2005) Complete development of water soluble biobased films and substrates. Year (2006) Transfer technology and publish data from biobased films and substrates. Year (2007) Create crosslinked films to act as non-woven cleaners; Transfer technology on films and substrates to industrial partners. Milestones and Outcomes; Objective 4 Biodegradability/aging; performance of bioproducts (Imam/Glenn/Orts) Year (2005) Establish respirometry at WRRC as tool to test biodegradability of market-targeted bioproducts. Test target products. Year (2006) Transfer information to industrial partners of biodegradable starch/fiber based composite materials, and use this information to design industrial biodegradable biopolymers. Year (2007) Continue to provide data on biodegradability of materials developed by other scientists within the group. 4.What were the most significant accomplishments this past year? A. Creating new markets for surplus crops and underutilized agricultural fibers is critical for U. S. farmers to stay competitive in the global marketplace. Scientists in the Biobased Chemistry and Engineering Research Unit, WRRC, in Albany, CA, developed novel wheat starch- and straw-based industrial packaging materials. Wheat starch was incorporated into starch-based single-use food wraps, plates and trays, allowing CRADA partner to create industrial packaging products that are less expensive and more flexible than their present starch-based industrial materials. More specifically, basic knowledge of the structure/ properties relationship of wheat starch and its associated trace proteins was applied to provide an industrial process that had no objectionable odor and allowed EarthShell, Inc. to cut material costs by more than 50%. This breakthrough will enable starch-based packaging to take a more competitive position in the $10 billion single-use packaging market, and will help expand the non-food markets for wheat starch and fiber. B. Other signifiant accomplishments(s), if any Since the ban on the open-field burning, agricultural residues from crops continue to accumulate roughly one million tons annually and remain severely underutilized. Research at WRRC in collaboration with Dr. Buschle-Diller of Auburn University and in cooperation with Regale Inc. (CRADA) was carried out to understand the chemical composition, fractionation, material processing and the extraction of nano-fibers and the associated novel minerals contents from wheat straw. Efforts led to fundamental knowledge and utilization of fibers and minerals as novel materials and nano-composites. Utilization of agriculturally derived fibers and nano-fibers will facilitate their use in the development of high performance and much improved conventional building materials for domestic use where building materials (over a $20 billion market) are currently made from mostly imported wood or wood substitutes. To improve farm economy and make U.S. agriculture globally competitive, new markets for surplus commodities underutilized crop residues are needed. Scientists in the Bioproduct Chemistry and Engineering Research Unit, Albany, CA in collaboration a CRADA partner have developed several product prototypes for home and office cleaning utilizing renewable materials. Prototypes were made available to the CRADA partner for in-home consumer testing and feedback. Technologies or products will be available for marketing through exclusive licenses to the CRADA partner. Seed potatoes are susceptible to fungal infection, and seeds are conventionally stored and shipped in the presence of a powder containing harmful fungicides raising concern for the safety of the farm workers. In collaboration with scientists from the ARS laboratory, Kimberley, ID, scientists at the Bioproduct Chemistry and Engineering research Unit, Albany, CA developed Seed Potato coatings with encapsulated commercial fungicide. In the lab-scale studies these coatings effectively prevented the fungal growth destructive to seeds. Technology will help farm workers from direct exposure to harmful chemicals. C. None D. Agriculturally derived polymers and commodity chemicals are produced in surplus and are underutilized. As part of this CRIS (now Project No. 5325-4100-044-00D), research at the WRRC under the CRADA partner was conducted to develop biobased cleaning products for consumer use. Research is ongoing and 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. Currently, cleaning products from CLOROX with an estimated $ 8 billion annual sale are made from corrosive chemicals and petrochemicals. The use of eco-compatible plant polymers in cleaning products will help the American farmer by opening new markets for surplus crops, reduce our dependence on petroleum, and ensure safer environment. This report serves to document research conducted under a CRADA partner. Additional details can be found in the report for the parent CRIS Project No. 5325-4100-044-00D. A pilot plant and testing facility has been built at the WRRC. Prototype plates are being made of cereal starches. The results obtained in the pilot plant will be used to in a commercial production facility that will open in October 2004. The facility will provide an important new market for cereal starches. 5.Describe the major accomplishments over the life of the project, including their predicted or actual impact. Previous accomplishments include the development and patenting of starch-based microcellular foams. The starch foam had high compressive strength, very low thermal conductivity, low density, and small pore-size. In addition the foams were able to absorb high quantities of oils and to encapsulate flavors and odors. The foams performed as well or better than cyclodextrins for encapsulating several important flavor compounds. Because cyclodextrins are expensive and are not approved for food use in the U.S. the foams have good commercial potential as a flavor carrier and could create a new market for wheat starch. A patent protecting this technology has issued. Three manuscripts describing the physical, morphological and mechanical properties of the foams have been published. The most recent progress with this product is reported in the answer to question 4. The use of microcellular foams in the controlled release of agricultural compounds could benefit farmers and help reduce the overall quantities of pesticides needed. This research is consistent with milestones listed under objective 1 of the Project Plan. Previous work had focused on developing wheat starch-based containers based on a baking technology. The work began with support from the Washington and Idaho wheat commissions followed by work with Penford Products Co. An in situ method of laminating the baked containers was developed in our laboratory during the current project. The technique allowed the baking and laminating process to be accomplished in a single step thus imparting the product with moisture and grease resistance as well as providing printable surface. We have discussed with a packaging manufacturer, the possibility of using the laminating process to increase the throughput of package production. Further accomplishments in this work were reported in the answer to question 4. This discovery could help broaden the number of products that can be made using the baking technology which has only recently been commercialized. This research is consistent with milestones in the Project Plan listed under objective 2. 6.What science and/or technologies have been transferred and to whom? When is the science and/or technology likely to become available to the end-user (industry, farmer, other scientists)? What are the constraints, if known, to the adoption and durability of the technology products? Technology pertaining to wheat-starch based food packaging has been transferred to the CRADA partner for industrial-scale product manufacturing. The CRADA partner has already launched starch-based food containers for marketing through Walmart Super Stores. Several bio-based cleaning product prototypes were delivered to the CRADA partner that were in-home tested by consumer panels to provide feedback for product development. Once developed, products will be manufactured by the CRADA partners and made available to consumers all over the world. In collaboration with scientists from the Hayden Bee Research Center, Tucson, AZ biopolymer based slow-release delivery system for miticide was developed and field tested. A company which holds the licensing agreement with the ARS on the exclusive use of this miticide is very encouraged by these initial field trials. These systems will be commercially available for the Bee industry throughout to combat mites impacting the bee population. An equipment manufacturer and a Seed supplier from Idaho has shown considerable willingness to field-test coated seed potatoes and the technology will be transferred at the time of seed harvesting. Scientists associated with this CRIS project have been involved in the analyses and evaluation of soil binding properties of natural polymers and their mixtures for use as a substitute for polyacrylamide (PAM) in preventing soil erosion in irrigated fields. Several companies (Tate and Lyle Company, Decatur, IL, Folia, Inc., and Innovium Corporation) are collaborating in these studies and have sent numerous samples for evaluation. 7.List your most important publications in the popular press and presentations to organizations and articles written about your work. Rice Straw: come hell or high water. Chemsitry World News, May 2004, Issue 5. USDA-EarthShell Crada Developments (Cybercast). Recording is available on internet archive at WWW.EarthShell.com. June 28, 2004. In Search of the Perfect Clamshell. March 3, 2004. Published in on-line magazine (Salon-Technology at WWW.salon.com) Technology transfer efforts were apparent in the following on-site visits and pilot plant demonstrations: U.S. China MOST delegation visit/tour Rohm and Haas visit U.C. Davis faculty visit National Wheat Growers Association visit/tour Washington Tree Fruit Commission visit/tour Cargill Ventures American Express Venture Group The group also participated in out-reach programs to high school students (Academic Workshop) and hosted other visiting high school and grade school visitors. The group also participated in meetings to foster cooperation and technology transfer. The meetings include the following: U.S. Japan Natural Resources -Protein panel held in Tsukuba City, Japan. Rice Straw Exposition (Sacramento, CA) Rice Field Day (Central Valley) U.C. Irvine visit with Director for Materials Characterization Center Review Publications Orts, W.J., Sojka, R.E. 2003. Polymer application in irrigation water to reduce erosion and better manage water infiltration. Encyclopedia of Water Science. B.A. Stewart and Terrt A, Howell, Editors. 449-453p. Glenn, G.M., Klamczynski, A., Chiou, B., Wood, D.F., Orts, W.J., Imam, S.H. 2004. Lightweight concrete containig alkaline resistent starch-based aquagels. Journal of Polymers and the Environment, 12(3):189-196. Liang, C., Gordon, S.H., Imam, S.H. 2003. Starch graft poly(methyl acrylate) loose-fill foam: preperation, properties and degradation. American Chemical Society. Biomacromolecules, 5(1):238-244. Emo, C., Patricia, C., Federica, C., Imam, S.H. Feature article: environmentally degradable bio-based polymeric blends and composites. 2004. Macromolecular Bioscience,4:218-231. Glenn, G.M., Imam, S.H., Orts, W.J., Klamczynski, A. 2004. Fiber reinforced extruded starch form. ANTEC, Chicago, IL. 2484-2488. Cinelli, P., Lawton, Jr J.W., Gordon, S.H., Imam, S.H., Chiellini, E. 2003. Injection moled hybrid composites based on corn fibers and poly(vinyl alchol). Macromolecular Symposium. (197)115-124. Imam, S.H., Glenn, G.M., Shey, J., Klamczynski, A., Nguyen, T.T., Cornish, K., Orts, W.J. 2004. Characterization and performance of starch-poly-(vinyl alcohol) (pva) blends with agricultural waste fiber. Society of Plastics Engineers Proceedings. 2437-2441. CINELLI, P., CHIELLINI, E., GORDON, S.H., IMAM, S.H. CHARACTERISTICS AND DEGRADATION OF HYBRID COMPOSITE FILMS PREPARED FROM PVA, STARCH AND LIGNOCELLULOSTICS. MACROMOLECULAR SYMPOSIA. 2003. v. 197. p. 143-155. Imam, S.H., Glenn, G.M., Orts, W.J. 2004. Renewable starch polymer: property, modification, processing and product development. International Union of Pure and Applied Chemistry World Polymer Congress Proceedings. 128. Salazar, R., Imam, S.H., Morales, L., Galan, L., Arevalo, K. 2004. Characterization of Natural Polyelectrolytes and their Application in Environmental Biotechnology, Polyelectrolytes, Gels and Complex Fluids. Proceedings of the 40th IIUPAC World Polymer Congress, July 4-9, Paris, France. 134. Inglesby, M.K., Wood, D.F., Gray, G.M. 2003. Non-conventional pulping effect on si02 in oryza sativa. Characterization of the Cellulosic Cell Wall. Inglesby, M.K., Buschle-Diller, .G., Guttman, M.E., Gray, G.M., Wood, D.F., Bailey, D.A. 2003. Cellulosic fibers as reinforcing agents. 225th American Chemical Society National Meeting, March 2003, New Orleans, Lousianana. Inglesby, M.K., Gray, G.M., Wood, D.F., Gregorski, K.S. 2004. Rice straw utilization in building materails: Characterization of surfaces and biomineral distribution. 227th National Meeting of the American Chemical Society, Anaheim, CA. Buschie-Diller, G., Inglesby, M.K., Wu, Y. 2004. Physicochemical properties of chemically and enzymatically modified cellulosic surfaces. Colloids and Surfaces A: Physicochemical and Engineering Aspects. Orts, W.J., Nobes, G.A.R., Glenn, G.M., Inglesby, M.K., Gray, G.M. 2003. Agriculturaly-derived polymer-fiber (nano) composites. 225th ACS National Meeting, New Orleans, LA, March 2003. Orts, W.J., Imam, S.H., Glenn, G.M., Wong, D., Inglesby, M.K., Guttman, M.E., Samac, D.A. 2004. Envisioning biorefineries based on utilization of lignocellulosic straws and bagassess. 227th National Meeting of the American Chemical Society, Anaheim, CA.