Brief Summary of Minutes of Annual Meeting

This multi-state research project is addressing the nation’s research priority of bioenergy and biobased products by developing renewable fibrous materials and innovative technologies for eco-friendly and sustainable textile products that have an impact on improving environment and quality of living. Four research objectives are defined: (1) to develop novel biobased polymeric materials; (2) to develop and evaluate biobased fibrous products for eco-friendly crop protection; (3) to develop and evaluate biobased products for health and safety applications; and (4) to develop and evaluate methods to remove dyes and finishing chemicals from textile waste water. The research progress is made through cooperation among the participants from nine universities in the states of CA, GA, MT, NE, NY, TN, TX, WA, and WI.

Objective 1 University of Nebraska-Lincoln (NE) continued to work on improving properties of polylactide from the molecular level via the study of PLLA-PDLA interlocked structure and their nanocomposites for the better applications of PLA in textiles and plastics industry. One focus was on studying the steam flash-explosion to extract biofibers from cotton stalks with high aspect ratios for textiles and composites uses. Another focus was on chemical grafting of proteins, and polysaccharides to turn these biopolymers into thermoplastics for industrial applications. A technical advancement in dissolving highly-crosslinked proteins such as keratin, camelina and sorghum proteins was achieved. This technology enabled producing water-stable fibers and films with good mechanical properties via controlled de-crosslinking and disentanglement. Cornell University (NY) has been working on biodegradable resins and composites using proteins and starches from agricultural products. A novel water based reaction scheme was developed to crosslink the protein from soy flour (SF) without using any external crosslinker. This technology included a series of steps to separate, oxidize, and crosslink sugars from SF. The resulted soy protein resin had enhanced mechanical and thermal properties and reduced moisture absorption. When reinforced with strong microfibrillated cellulose the crosslinked SF could produce fully sustainable and biodegradable green composites. The developed technology might be extended to produce biobased plastics with enhanced properties by crosslinking natural flours with the similar composition to that of SF. Green composites were also developed by blending waxy maize starch (WMS) with micro- and nano-fibrillated cellulose (MFC/NFC). An environmentally-friendly crosslinker, 1,2,3,4-butanetetracarboxylic acid (BTCA), was used to crosslink WMS to fabricate crosslinked starch-based composites. This allowed using a benign and convenient method to produce crosslinked thermoset starch-based composite films, comparable to commercially available plastic sheets. The process could be easily scaled up for commercial production. In this work industrially pregelatinized WMS was used to obtain smooth, transparent and defect-free films. Crosslinking improved mechanical properties of the films and helped reduce film moisture absorption and increase film water insolubility. The University of Georgia (GA) has focused on the development of biothermoplastics and thermosets from the algal proteins. A study on development of Spirulina microalgae based bioplastics and thermoplastic blends was conducted. A method of thermomechanical process was used to develop bioplastics and Spirulina (blue-green microalgae) and its blends. Spirulina biomass was processed into bio-plastics by means of plasticization, blending and compatibilization. The extracted protein content and its molecular weight were determined using BCA assay and sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE), respectively. Thermal, mechanical, and morphological properties of the above biobased plastics were tested to assess their performance and possible end-use applications. The optical observation of Spirulina powder and its extracted pellets along with protein precipitation using trichloroacetic acid (TCA) confirmed the cell rupture/break. A study on producing biodegradable polyesters from Algal sources was also accomplished. Polyhydroxyalkanoates (PHAs) are a family of linear biodegradable thermoplastic polyesters that are synthesized in nature by bacterial fermentation. The formation is triggered by deficiency of nutrients and the excessive supply of carbon sources. In spite of high yield of PHAs via bacterial fermentation, it is not an economically viable route due to high costs incurred by expensive carbon sources and rich oxygen supply during bacterial fermentation. In order to reduce the cost of PHA, photoautotrophic production is thought to be a desired route. Cyanobacteria are one of the only prokaryotic species that naturally produces PHAs (under stress conditions) by photosynthesis and requires fewer resources for growth and biomass production. The mixotrophic biosynthesis of PHB (poly 3–hydroxy butyrate) in cyanobacteria (blue green algae) (Nostoc sp.) was investigated, and the biosynthesized polymer was extracted using a methanol-chloroform solvent technique. Tested results suggested that the Nostoc sp. culture was a viable candidate for the PHB production. This research demonstrated that PHA could be produced photoautotrophically and mixotrophically in cyanobacterial species, as PHB was accumulated in Nostoc sp. The University of Texas at Austin (TX) UT has continued the research on the echo-friendly fabrication of regenerated cellulose fiber from cellulosic biomass. Different solvent systems were compared in terms of cellulose solubility, spinning conditions, and regenerated cellulose fiber properties. Polymeric structure of the regenerated cellulose fiber was characterized using advanced instrumental methods. The developed research data helped determine a better spinning solvent. The research effort was also made for producing regenerated cellulose fiber and film covalently bound with a protein. The study exhibited that a synthesis of enzyme conjugation on cellulose could be undertaken in a controlled manor, enabling an immobilization of a desired amount of protein. The research was also done on the analysis of creep behavior and crack propagation of kenaf/ polypropylene nonwoven composite. Nonwoven composites made of natural and polypropylene fiber have been increasingly used in many industrial sectors. To meet different requirements of end uses, the time-dependent and temperature-dependent mechanical properties of the composite need to be improved. This study modeled the fiber composite behavior of creeping and cracking using a numerical approach and finite element method. At the University of California, Davis (CA), scientists have derived highly crystalline nanocellulose from under-utilized agricultural by-products. Cellulose nanofibrils (CNFs) derived from rice straw have been self-assembled into hydrogels and aerogels. The ultra-light (as low as 1.7 mg/cm3) and ultra-porous (99.5 to 99.9%) aerogels exhibited excellent wet-resiliency, super-absorbency and amphiphilicity, absorbing 210 and 375 times by mass of water and chloroform, respectively, far superior to any previously reported cellulose aerogels. These aerogels could be tuned to be more hydrophobic and oleophilic, capable of absorbing up to 356 times of non-polar hydrocarbons, polar aprotic solvents and oils, surpassing all previously reported polymeric, cellulosic and carbonaceous aerogels by up to 20 times. Rice straw CNFs have also been used as dual capping and shape regulating agent for silver nanoprism synthesis. CNF-bound Ag nanoprisms with 80-320 nm truncated edges were light blue in color and exhibit sharp out-of-plane quadruple resonance peak at 334 nm and prominent in-plane dipole resonance peaks at 762-900 nm. Objective 2 University of Tennessee (TN) has advanced the development of robust biodegradable agricultural mulches (BDMs) to alleviate concerns about the long-term environmental impact of debris formed during weathering of conventional polyethylene-based mulches. The research team investigated the performance of several different inexpensive amendments (e.g., mushroom compost and switchgrass biochar) that could be applied to the mulches at the end of their service life, to help “open up” their structure, to enhance biodegradation when the mulches are subsequently plowed into the soil. The tests were performed on BDMs prepared from polylactic acid (PLA) and PLA-polyhydroxyalkanoate (PHA) blends via meltblown nonwoven processing, composed of micron-sized fibers. Several analyses of differential scanning calorimetry, molecular weight analysis via gel permeation chromatography, and tensile strength demonstrated that fertilizer and mushroom compost were the most effective amendments. The research team also assembled a biodegradability apparatus that can be used to measure biodegradability under ambient soil and composting conditions, via ASTM D5988 and D5338, respectively. The apparatus would be used to measure the biodegradability and compostability of several commercially available and experimental BDMs, both before and after weathering. Through a major USDA Specialty Crop Research Initiative (SCRI) grant received by (Project Director) Hayes, Wadsworth, Belasco, and collaborators at the University of Tennessee, Washington State University, and Montana State University, the long-term implications of deploying on soil quality, the soil microbial community, specialty crop production, pests and diseases, and consumers would be investigated via a transdisciplinary approach. Objective 3 Reported from CA, cellulose nanofibrils (CNFs) derived from rice straw have been used as nanotemplates to synthesize silver nanoparticles (AgNPs) via electrostatic binding of Ag+ on negatively charged, 2 nm wide CNF surfaces, followed by the reduction to atomic silver and AgNPs. At 150 mM equivalent Ag+ concentration, CNF-AgNPs induced the production of EPS-like material, causing clustering of bacteria in solution indicating potential use in concentrating and collection of microbs. At a higher 450 mM equivalent Ag+ concentration, CNF-AgNPs prohibited significant bacterial growth. NE developed a novel dry-electrospinning technology for making 3D randomly oriented ultrafine fibers materials, which could be used effectively for cartilage repair and have potential of being a major electrospinning method.

Xu, H., Shi, Z., Reddy, N., and Yang*, Y. Intrinsically Water-Stable Keratin Nanoparticles and Their In Vivo Biodistribution for Targeted Delivery. Journal of Agricultural and Food Chemistry. 62(37) 9145-9150 (2014). Shi, Z., Reddy, N., Hou, X., and Yang*, Y. Development and Characterization of Thermoplastics from Corn Distillers Grains Grafted with Various Methacrylates. Industrial & Engineering Chemistry Research. 53(36) 13963-13970 (2014). Hou, X., Sun, F., Zhang, L., Luo, J., Lu, D., and Yang*, Y. Chemical-free extraction of cotton stalk bark fibers by steam flash explosion. BioResources. 9(4) 6950-6967 (2014). Hou, X., Sun, F., Yan, D., Xu, H., Dong, Z., Li, Q., and Yang*, Y. Preparation of Lightweight Polypropylene Composites Reinforced by Cotton Stalk Fibers from Combined Steam Flash-Explosion and Alkaline Treatment. Journal of Cleaner Production. 83. 454-462 (2014). Dong, Z., Hou, X., Sun, F., Zhang, L., and Yang*, Y. Textile grade long natural cellulose fibers from bark of cotton stalks using steam explosion as a pretreatment. Cellulose. 21(5) 3851-3860 (2014). Xu, H., Ma, Z. and Yang*, Y. Dissolution and Regeneration of Wool via Controlled Dis-integration and Dis-entanglement of Highly-Crosslinked Keratin. Journal of Materials Science. 49(21) 7513-7521 (2014). Reddy, N., Jiang, J., Yang*, Y., Biodegradable Composites Containing Chicken Feathers as Matrix and Jute Fibers as Reinforcement. Journal of Polymers and the Environment. 22(3) 310-317 (2014). Shi, Z., Reddy, N., Shen, L. Hou, X., and Yang*, Y. Grafting Soyprotein Isolates with Various Methacrylates for Thermoplastic Applications. Industrial Crops and Products. 60, 168-176 (2014). Xu, H., Cai, S. and Yang*, Y. Water-stable three dimensional ultrafine fibrous scaffolds from keratin for cartilage tissue engineering. Langmuir. 30(28), 8461-8470 (2014). Xu, H., Cai, S., Sellers, A. and Yang*, Y. Electrospun ultrafine fibrous wheat glutenin scaffolds with three-dimensionally random organization and water stability for soft tissue engineering. Journal of Biotechnology.184. 179-186 (2014). Shi, Z., Reddy, N., Hou, X., and Yang*, Y. Tensile Properties of Thermoplastic Feather Films Grafted with Different Methacrylates. ACS Sustainable Chemistry & Engineering. 2(7), 1849-1856 (2014). Shi, Z., Reddy, N., Shen, L., Hou, X., and Yang*, Y. Effects of Monomers and Homopolymer Contents on the Dry and Wet Tensile Properties of Starch Films Grafted with Various Methacrylates. Journal of Agricultural and Food Chemistry. 62(20), 4668-4676 (2014). Xu, H., and Yang*, Y. Controlled de-crosslinking and disentanglement of feather keratin for fiber preparation via a green process. ACS Sustainable Chemistry & Engineering. 2(6) 1404-1410 (2014). Xu, H., Cai, S., Sellers, A., and Yang*, Y. Intrinsically water-stable electrospun three-dimensional ultrafine fibrous soy protein scaffolds for soft tissue engineering using adipose derived mesenchymal stem cells. RSC Advances. 4 (30), 15451–15457 (2014). Kang, Y., Chen, Z., Wang, B., and Yang*, Y. Synthesis and mechanical properties of thermoplastic films from lignin, sebacic acid and poly(ethylene glycol). Industrial Crops and Products. 56, 105-112 (2014). Hou, X., Xu, H., Shi, Z., Ge, M., Chen, L., Cao, X., and Yang*, Y. Hydrothermal pretreatment for the preparation of wool powders. Journal of Applied Polymer Science. 131(8), 40173 (10pgs) (2014). Zhao, Y., Jiang, Q., Xu, H., Reddy, N., Xu, L., and Yang*, Y., Cytocompatible and water-stable camelina protein films for tissue engineering. Journal of Biomedical Materials Research: Part B - Applied Biomaterials. 102B(4), 729-736 (2014). Reddy, N., Chen, L., Zhang, Y., Yang*, Y., Reducing Environmental Pollution of the Textile Industry Using Keratin as Alternative Sizing Agent to Poly(vinyl alcohol). Journal of Cleaner Production. 65. 561-567(2014). Jiang, Q., Xu, H., Cai, S. and Yang*, Y. Ultrafine fibrous gelatin scaffolds with deep cell infiltration mimicking 3D ECMs for soft tissue repair. Journal of Materials Science: Materials in Medicine. 25(7), 1789-1800 (2014). Reddy, N., Shi, Z., Temme, L., Xu, H., Xu, L., Hou, X., and Yang*, Y. Development and Characterization of Thermoplastic Films from Sorghum Distillers Dried Grains Grafted with Various Methacrylates. Journal of Agricultural and Food Chemistry. 62(11), 2406-2411(2014). Shi, X., Chen, Z., and Yang*, Y. Toughening of Poly(L-lactide) with Methyl MQ Silicone Resin. European Polymer Journal. 50 243–248 (2014). Qiu, K. and Netravali A. N., A Review of Bacterial Cellulose and Bacterial cellulose based Nanocomposites. Polymer Reviews, 54 (4), pp. 598-626, 2014. DOI:10.1080/15583724.2014.896018 Vieira, R. K., Vieira, A. K., Kim, J. T. and Netravali, A. N., Characterization of Amazonic White Pitch (Protium heptaphyllum) for Potential use as a ‘Green’ Adhesive. Journal of Adhesion Science & Technology, 28 (10), pp. 963-974, 2014. DOI: 10.1080/01694243.2014.880220 Ghosh-Dastidar, T. and Netravali, A. N., Crosslinked Waxy Maize Starch based ‘Green’ Nanocomposites, Carbohydrate Polymers, ACS Sustainable Chemistry and Engineering, 1 (12), pp. 1537-1544, 2013. DOI: 10.1021/sc400113a Ghosh-Dastidar, T. and Netravali, A. N., Novel Thermosetting Resin from Soy Flour Crosslinked using Green Technology, Green Chemistry, 15 (11), pp. 3243-3251, 2013. DOI: 10.1039/C3GC40887F Banerjee, A., and Sharma, S. (2014). Study of biodegradable polyesters from algal sources for use in future textile fiber applications. American Association of Textile Chemists and Colorists (AATCC) International Conference. Banerjee, A. (2013, November). Project Title: Study of biodegradable polyesters from algal sources for use in textile fiber applications. This graduate research project was funded by the AATCC Foundation under Graduate Research Proposals Competition. Wang, K. (2014) Masters Thesis: “Bioplastic Potential of Spirulina Microalgae." Sharma, S., Zeller, M. A., Hunt, R.W., and Jones, A. Bioplastics and their thermoplastic blends from Spirulina and Chlorella microalgae. Journal of Applied Polymer Science, 2013, 130(5), 3263-3275. Chen, J.Y., Sun, L., Jiang, W., and Lynch, V. Using ionic liquid to fabricate regenerated cellulose/nanosilver fiber with antimicrobial and no-leaching performance. Journal of Bioactive and Compatible Polymers, 2014, DOI: 10.1177/0883911514556960. Hao, A., Chen, Y., and Chen J.Y. Creep and Recovery Behavior of Kenaf/Polypropylene Nonwoven Composites. Journal of Applied Polymer Science, 2014, DOI: 10.1002/app.40726. Chen, J.Y. and Jiang, N. Fabrication and Characterization of Carbonized and Activated Cotton Nonwovens. Journal of Industrial Textiles, 2014, 43(3), 338-349. Chen, J.Y. Chapter 4 Man-made fibres: regenerated cellulose fibres. in Textiles and fashion: materials, design and technology, Rose Sinclair Ed. Woodhead Publishing Ltd., Cambridge, England. 2014, pp 79-96. Elodie Hablot, Satiskumar Dharmalingam, Douglas G. Hayes, Larry C. Wadsworth, Christopher Blazy, Ramani Narayan, and Debra A. Inglis. Effect of simulated weathering on physico-chemical properties and inherent biodegradation of PLA/PHA nonwoven-based mulches. Journal of Polymers and the Environment, 2014, 22(4), 417-429. Sathiskumar Dharmalingam, Douglas G. Hayes, Larry C. Wadsworth, Rachel N. Dunlap, Jennifer M. DeBruyn, Jaehoon Lee, Annette L. Wszelaki, Soil degradation of polylactic acid / polyhydroxyalkanoate-based nonwoven mulches. Journal of Polymers and the Environment, 2014, in review. Jiang, F., Y.-L. Hsieh, Amphiphilic superabsorbent cellulose nanofibril aerogels, Journal of Materials Chemistry A, 2014, 2, 6337-6342. Jiang, F. and Y.-L. Hsieh, Synthesis of cellulose nanofibril bound silver nanoprism for surface enhanced Raman scattering, Biomacromolecules, 20141, 5(10), 3608-3616. Shen, W., Y.-L. Hsieh, Biocompatible sodium alginate fibers by aqueous processing and physical crosslinking, Carbohydrate Polymers, 2014, 102, 893-900. Wang, M.S., F. Jiang, Y.-L. Hsieh, N. Nitin, Cellulose nanofibrils improve dispersibility and stability of silver nanoparticles and induce production of bacterial extracellular polysaccharides, Journal of Materials Chemistry B, 2014, 2(37), 6226-6235.