HIGH-VALUE PRODUCTS USING CELLULOSE NANOCRYSTAL SCIENCE AND TECHNOLOGY

• Sponsoring Institution: National Institute of Food and Agriculture
• Project Status: COMPLETE
• Funding Source: MCINTIRE-STENNIS
• Reporting Frequency: Annual
• Accession No.: 0220984
• Project Start Date: Feb 1, 2010
• Project End Date: Jan 31, 2015
• Program Code: [(N/A)]- (N/A)

Recipient Organization
OREGON STATE UNIVERSITY
(N/A)
CORVALLIS,OR 97331

Performing Department
Wood Science and Engineering

Non Technical Summary
International competition and globalization have provided motivation to find new high value uses for domestic wood. One such use is cellulose nanocrystals (CNXLs). These are highly crystalline whiskers, or rods, of cellulose that can be extracted from trees or indeed many sources of cellulose. While the size varies with the original species, a typical size for CNXLs is 7 nm in cross section by 150 nm in length. CNXLs have very high properties. They are stronger than steel and stiffer than aluminum. They also have very high surface areas and their surface is easily amenable to chemical modification. CNXLs hold the potential for a great many applications, including as reinforcing fillers in polymer composites, electro-optics applications, biomedical applications, membranes and separation devices and as templates for various nanoscale applications. In this project we will investigate both the fundamental aspects of CNXL science and develop technology for potential applications in the areas of polymer composites, electro-optics and biomedical devices. CNXLs offer bright hope for increased value of forest products as they are utilized to replace petroleum based products and other non-renewable resources. In addition, they offer the prospect of one high value stream from the biorefinery that will add to the overall profitability of the biorefinery concept. Our output will be primarily in the form of scientific publications and various forms of outreach. Our goal is to provide the knowledge foundation upon which others may build commercial enterprises that utilize CNXLs and our wood resource to improve lives and provide for a sustainable and environmentally benign future.

Animal Health Component

(N/A)

Research Effort Categories

Basic

(N/A)

Applied

(N/A)

Developmental

(N/A)

Classification

Knowledge Area (KA)	Subject of Investigation (SOI)	Field of Science (FOS)	Percent
511	0650	2000	100%

Knowledge Area
511 - New and Improved Non-Food Products and Processes;

Subject Of Investigation
0650 - Wood and wood products;

Field Of Science
2000 - Chemistry;

Keywords

cellulose

nanocrystal

polymer

composite

electro-optic

biomedical

aerogel

percolation

Goals / Objectives
We will systematically investigate the fundamental science and technological feasibility of utilizing CNXLs in the fields of 1. Polymer composites; 2. Electro-optic applications; and 3. Biomedical applications. Results will be reported in the peer reviewed scientific literature and, if appropriate, in invention disclosures to the University. In addition, results will be presented at scientific conferences and active collaborations will be pursued with other labs both domestic and international.

Project Methods
Composites fabrication: CNXLs can be incorporated into polymer either by direct mixing in a high shear mixer or by first forming an aerogel and then infusing a polymer solution into the aerogel, then drying and compression molding to form a composite. This "masterbatch" composite than can be further diluted via melt blending to achieve the desired concentration of CNXLs in the polymer matrix. We will examine a variety of polymers, including poly(vinyl alcohol), epoxy, poly(allyl amine), and poly(vinylidene fluoride) and its copolymers. Our effots will be directied towards elucidating and understanding percolation effects in these polymers. We will utilize advanced SEM and TEM imaging techniques to determine the percolatoin threshold in these systems and compare that to macroscale mechanical properties. We will also chemically modify the CNXL surface. This will alter the CNXL-CNXL adhesion and thus the effects of the percolated network on composite properties. The overall goal will be to control the percolation effect and make it "smart," i.e. responsive to various external stimuli. This has already been shown for water, where the modulus was a function of water content in the composite [51]. Electro-optics: CNXLs are extremely birefringent and behave similarly to the liquid crystals used for LCD display devices. We will explore the feasibility of using CNXLs in various display technologies and also will utilize this electro-optic phenomenon in transient electric birefringence (TEB). TEB can be used to measure the size and size distribution of the nanoparticles from their response to an electric field probed by polarized light from a laser. Thus CNXLs electro-optics comprises both technology advancement and nanometrology. We will utilize TEB to characterize CNXL populations. We will also investigate the feasibility of utilizing TEB and similar effects for various display technologies by modifying the CNXL surface and also changing the solvent. Biomedical applications. The advantage here is the non-toxic nature of CNXLs. We plan to explore the potential biomedical applications such as drug delivery and tissue engineering. CNXL aerogels should be a good substrate for containing drugs, since the drug can easily be infused inside the aerogel, then the aerogel compressed to provide for a time release material. CNXL aerogels will also be considered for bone scaffolding with the growth of hydroxyapatite from the aerogel framework.

Progress 02/01/10 to 01/31/15

Outputs
Target Audience: Scientific and technical personnel with an interest in nanocellulose. Changes/Problems: The efforts at electro-optics were unsuccessful. We required significantly more resources to be successful at this technique than we initially expected. The effort at controlled release of pharmaceuticals was also unsuccessful and abandoned. What opportunities for training and professional development has the project provided? We have trained 3 PhDs, 4 Masters students and 9 undergrad students in the course of this project. How have the results been disseminated to communities of interest? Most of the results have been published in the peer reviewed scientific literature. They have also been presented at scientific conferences. What do you plan to do during the next reporting period to accomplish the goals? Nothing Reported

Impacts
What was accomplished under these goals? We have developed a variety of novel polymer composites incorporating nanocellulose. We have looked at cellulose nanocrystals (CNCs) in poly(vinylidene fluoride) and poly(vinylidene fluoride)-co-hexafluoropropylene. We also developed composite films from nanocellulose and additives that are proving to be useful for coating foodstuffs both pre- and post-harvest, and during the processing of colored foods such as blueberries. This is a breakthrough and patent applications have been filed. Composites were also prepared from gluten and its components: glutenin and gliadin. We have also studied CNCs as a reinforcing agent in poly(lactic acid), poly(vinyl acetate), poly(propyelen fumarate) and poly(methyl methacrylate). In all of these we have seen significant reinforcement by the nanocellulose and improvement in the mechanical properties. In addition, we studied the use of CNC aerogels as a drug delivery vehicle, but our material was not superior to existing materials. We also investigated the structure of CNC aerogels and for the first time imaged CNC aerogels in the TEM, which provided information on their shape and the structure of the aerogel. We also collaborated with Prof. John Nairn at OSU in developing the Nairn Model, a mathematical model for the modulus of nanocomposites which is a significant advance over previous models. We also collaborated with David Ji, OSU Chemistry, in utilizing carbonized nanocellulose as an electrode in sodium ion batteries, showing the nanocellulose is superior to existing materials in certain aspects. We collaborated with Reza Shabazian-Yassar at Michigan Tech. Univ. to image CNCs and their composites in the AFM. In collaboration with Prof. Stacey Harper at OSU we developed several different types of nanocellulose for toxicity testing and showed the non-toxic nature of nanocellulose under expected environmental exposures.

Publications

• Type: Journal Articles Status: Published Year Published: 2014 Citation: Rafieian, Fatemeh; Shahedi, Mohammad; Keramat, Javad; Simonsen, John. 2014. Thermomechanical and Morphological Properties of Nanocomposite Films from Wheat Gluten Matrix and Cellulose Nanofibrils. Journal of Food Science, 79(1), N100-N107.
• Type: Journal Articles Status: Published Year Published: 2014 Citation: Smith, Sean, Christian Buesch, Dave Mathews, John Simonsen, John F. Conley. (2014) Improved oxidation resistance of organic/inorganic composite atomic layer deposition coated cellulose nanocrystal aerogels. J. Vac. Sci. Technol. A 32(4), 041508/1-041508/8
• Type: Journal Articles Status: Published Year Published: 2014 Citation: Rafieian, Fatemeh; Simonsen, John. 2014. Fabrication and characterization of carboxylated cellulose nanocrystals reinforced glutenin nanocomposite Cellulose 21(6), 4167-4180.
• Type: Journal Articles Status: Accepted Year Published: 2015 Citation: Fatemeh Rafieian, John Simonsen, (in press) The effect of carboxylated nanocrystalline cellulose on the thermomechanical and barrier properties of cysteine cross linked gliadin nanocomposite. Cellulose.
• Type: Journal Articles Status: Submitted Year Published: 2015 Citation: Jooyeoun Jung, George Cavender, John Simonsen, Yanyun Zhao, (submitted) Mechanisms of metal complexation and cellulose nanofiber/sodium alginate layer-by-layer coating for retaining anthocyanin pigments in thermally processed blueberries, Journal of Agri. Food Chemistry
• Type: Journal Articles Status: Submitted Year Published: 2015 Citation: Virginia Gouw, Jooyeoun Jung, John Simonsen, Yanyun Zhao, (submitted) Optimization of Formulations to Create Apple Pomace Based Biocomposite Boards Using Thermal Compression Molding. Journal of Applied Polymer Sci.
• Type: Journal Articles Status: Submitted Year Published: 2015 Citation: Harper, B., Clendaniel, A., Sinche, F., Adamic, M., Way, D., Hughes, M., Schardt, J., Simonsen, J., Stefaniak, A.B., and S. L. Harper. (submitted) Impacts of chemical modification on the toxicity of diverse nanocellulose materials. Advanced Functional Materials

Progress 01/01/13 to 09/30/13

Outputs
Target Audience: Target audiences for this project are scientists and technicians working in the area of polymer composites, aerogelsand nanocomposites. Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided? the project has provided training opportunities for a number of graduate students and undergraduate student workers. How have the results been disseminated to communities of interest? Publications in peer reviewed journals, presentations at scientific conferences such as the American Chemical Society National conferences and the TAPPI International Conferences on Nanotechnology for Renewable Materials. What do you plan to do during the next reporting period to accomplish the goals? We will continue our efforts in developing aergels, nanocomposites, and new characterization methods. We also hope to become involved in nanocellulose-based coatings of various kinds.

Impacts
What was accomplished under these goals? Sulfate based CNCs from the FPL have improved and we use them routinely in our lab. In addition, we continue to produce carboxylated CNCS using the TEMPO process. We are also developing the ammonium persulfate process. While we have successfully used this process to make CNCs, it is not yet routine in our lab. We have also successfully produced tunicate CNCs using the sulfate process, but the yield was 0.03%. This low yield prohibits the use of tunicates. So this manufacturing process needs more work. The amine modification has been mastered, as has forming quaternary amines on the CNCs using a published method. In addition we have tagged CNCs using rhodamine dye. This is being used in a nanotoxicology study at OSU. We are also developing a method of compatibilizing CNCs for PLA that may result in IP. We have utilized freeze-dried CNF as a template to make carbon fiber and evaluated them as electrodes in sodium ion batteries. This work was published in Journal of Materials Chemistry A and included in their “Hot Article 2013” collection. We have successfully produced CNC aerogels with ionic crosslinking using Dy ions and infused them with PVAc polymer. We are in the process of performing 3D tomography with EDS to identify the CNCs inside the polymer matrix. If we are successful, this will be the first time this has been done. It will provide definitive input for the material point method to evolve the modeling efforts. We have produced C.CNC aerogels, coated them using atomic layer deposition and imaged them using STEM. A conference paper has been published and a further publication has been submitted. We will utilize these images to produce maps of the density and type of contacts between CNCs in the aerogel. We have also developed an optical method to measure the density of aerogels. This is difficult to do manually as the aerogels are easily deformed and difficult to produce in regular geometries (spheres, cylinders, squares, etc.). A publication is in preparation. We will then produce 10 um diameter cylinders (of uncoated CNCs) and collaborate with Siqun Wang at UTK for compression testing on them as a function of temperature and humidity, including full immersion using his custom nanoindenter. This will quantify the percolation effect. Mechanical properties of CNCs in PVDF as a function of alignment are in process and should be done in the near future. Mechanical properties in PVAc and PMMA are underway.

Publications

• Type: Journal Articles Status: Published Year Published: 2014 Citation: Rafieian, F., M. Shahedi, J. Keramat, J. Simonsen. 2014. Mechanical, thermal and barrier properties of nano-biocomposite based on gluten and carboxylated cellulose nanocrystals. Industrial Crops and Products. 53, 282  288.
• Type: Journal Articles Status: Published Year Published: 2014 Citation: Luo, W., Schardt, J., Bommier, C., Wang, B., Razink, J., Simonsen, J. & Ji, X. (2013). Carbon nanofibers derived from cellulose nanofibers as a long-life anode material for rechargeable sodium-ion batteries. J. Mater. Chem. A 1, 10662-10666.

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

Outputs
OUTPUTS: 1) Smith, S.W., H. Chan, C. Buesch, J. Simonsen and J.F. Conley, Jr. 2012. Improved Temperature Stability of Atomic Layer Deposition Coated Cellulose Nanocrystal Aerogels. Proceedings of the Materials Research Society Spring Meeting, April, San Francisco, CA. 2) Simonsen, J. 2012. The future of glycoscience: Grand challenges for materials. Glycoscience. Workshop on the Future of Glycoscience, January 12-13, The National Academies, Washington, D.C. 3) Ding, J., L. Muszynski, J. Nairn and J. Simonsen. 2012. An Improved Method of Evaluating the Essential Work of Fracture in Thin Transparent Film Specimens. Prepared for publication in Polymer Engineering and Science. PARTICIPANTS: Four graduate students worked on this project. They are: Pratish Rao, Han Chan, Jie Ding, Jeremiah Kelley, all of OSU. Collaborations are underway with Reza Shahbazian-Yassar, Michigan Tech Univ., Sandip Basu, Agilent Technologies, Sundar Atre, John Conley and Stacey Harper, all Oregon State University. TARGET AUDIENCES: Target audiences for this project are scientists and technicians working in the area of polymer composites and nanocomposites PROJECT MODIFICATIONS: Nothing significant to report during this reporting period.

Impacts
1. CNC aerogels were fabricated and coated with aluminum oxide via atomic layer deposition. This will provide the ability to obtain TEM tomography images of the aerogel structure. This structure will then be infused with polymer. By this means the new mathematical theory can be utilized to develop predictive principles for polymer nanocomposites for the first time. 2. Methods were developed to fabricate polymer nanocomposites by infusing an aerogel with a polymer solution. 3. The "ionic crosslinking" of aerogels was discovered. This is a means to produce water resistant cellulose nanocrystal materials. 4. Models of fiber networks were developed which will lay the foundation for more sophisticated models in the future. 5. Methods were developed to produce lactic acid oligomers. 6. Electron microscope techniques to successfully image cellulose nanocrystals, which are very beam sensitive, were developed. 7. Atomic force microscopy revealed insights into the nature of the interface in cellulose nanocrystal-poly(vinyl alcohol) composites.

Publications

• Pakzad, A., J. Simonsen, P. Heiden and R. Shahbazian-Yassar. 2012. Observation of Size-Scale Effects on the Nanomechanical Properties of Cellulose I Nanocrystals. Journal of Materials Research 27(3):528-536.
• Pakzad, A., J. Simonsen and R.S. Yassar. 2012. Gradient of nanomechanical properties in the interphase of cellulose nanocrystal composites. Composites Science and Technology 72(2):314-319.

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

Outputs
OUTPUTS: 1. Jeremiah Kelley, Jie Ding, John Simonsen*, Mike Lerner. 2011. Nanocomposites Incorporating Cellulose Nanocrystals with Potential Applications in Lithium Ion Batteries. 2011 TAPPI International Conference on Nano for Renewable Materials, June 6-8, Arlington, VA. 2. Melissa Taylor, John Simonsen*, Wei Kong, William Hetherington. 2011. Transient Electric Birefringence for the Characterization of Cellulose Nanocrystals. 2011 TAPPI International Conference on Nano for Renewable Materials, June 6-8, Arlington, VA. 3. Jeremiah Kelley and John Simonsen,* 2011. Cellulose nanocrystals for battery separators. EPRI-ONAMI Workshop on Nanotechnology, January 12-13, Charlotte, NC. PARTICIPANTS: 1. Graduate Students: Melissa Taylor, Jeremiah Kelley, Han Chan, Pratish Rao, Sean Smith, Anna Prakhzad. 2. Undergrad students: Michelle Romero, Han Chan, Danny Way. 3. Collaborators: Reza Yassar (Michigan Tech. Univ.), John Nairn (OSU), Lech Muszynski (OSU), Vince Remcho (OSU), Larry LeClair (WA State DFW), Steven Allen (BioVision Company). Intern: Sean Pomerory (High School student). TARGET AUDIENCES: The target audience is scientific researchers and technical personnel companies. PROJECT MODIFICATIONS: The effort in transient electric birefringence was abandoned as it was concluded that the method would not yield useful results without an unacceptable amount of money and manpower. The effort to obtain aspect ratio information on CNCs will continue with data from the Nanosight instrument, a novel technology recently available on campus.

Impacts
During this reporting period the mathematical model for cellulose nanocrystal (CNC) composites evolved to a higher level. We also made good progress on developing polymer-infused aerogels, which will be critical components for validating the model. We also successfully isolated tunicate CNCs from a West Coast source of the Steyla Clava species. The surprising ability of CNCs to reinforce poly(vinylidene fluoride)-co-hexafluoropropylene was encouraging for the production of nanocomposites from this material. The results also supported the mechanical model and fell well within its range. The transient electric birefringence effort was abandoned as it proved to require an extraordinary input of money and effort to produce accurate results. Efforts along the same lines will continue with the Nanosight instrument. A new instrument using dynamic light scattering with a novel technology twist. This instrument is now available on campus and our group has access to it.

Publications

• Moon, R., R.A. Martini, J. Nairn, J. Simonsen and J. Youngblood. 2011. Cellulose Nanomaterials Review: Structure, Properties and Nanocomposites. Chemical Society Reviews 40:3941-3994.
• Jovanovic, G., S.V. Atre, B.K. Paul, J. Simonsen, V.T. Remcho and C-H. Chang. 2011 Microfluidic devices, particularly filtration devices comprising polymeric membranes, and method for their manufacture and use. U.S. 7955504.
• Kelley, S.J. 2011. Nanocomposites Incorporating Cellulose Nanocrystals with Potential Applications in Lithium Ion Batteries. Master's Thesis. Materials Science Program. Oregon State University, Corvallis. http://ir.library.oregonstate.edu/xmlui/handle/1957/21774.
• Taylor, M. 2011. Transient Electric Birefringence for the Characterization of Cellulose Nanocrystals and Tobacco Mosaic Virus. PhD Thesis. Materials Science Program. Oregon State University, Corvallis. http://ir.library.oregonstate.edu/xmlui/handle/1957/21778.

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

Outputs
OUTPUTS: Activities: An active research program has been developing a protocol to extract cellulose nanocrystals (CNCs) from tunicates, a sea animal, specifically Didemnun, Styela Clava and Ciona. These tunicates are invasive species in the Pacific Northwest. We have been cooperating with the State of Washington Department of Fisheries and Wildlife, who use scuba divers to collect the animals. Development of protocols for these three species are ongoing. We are studying CNC aerogels and have discovered that when an iron compound is used to gel the dispersions, 2 nm iron nanodots are formed. The mechanism of this structure is currently unknown and unreported in the literature. Investigations are underway. The inclusion of CNCs in poly(vinylidend flouride)-co-hexafluoropropylene has been investigated. This material has potential as a separator film in lithium ion batteries. The inclusion of modified CNCs in poly(lactic acid) is under investigation. We have preliminary results that indicate that our compatibilization method is successful. Confirmatory studies are underway. The utilization of CNC aerogels to make well specified composites is proceeding with the development of a protocol to infuse polymers (specifically poly(methyl methacrylate)) into the aerogel (or organogel) without altering the structure of the aerogel. This is a critical step in developing the ability to fabricate nanocomposites with a precisely known configuration. We are currently working on extending the protocol to additional polymer systems. Work has been ongoing to develop a new instrument and protocol to evaluate the data for our electro-optic project which uses transient electric birefringence (TEB) to determine the size distribution in bulk CNC dispersions. This work has been presented at the American Chemical Society National Meeting in San Francisco, March, 2010 (two talks) and at the EPRI/ONAMI workshop in Charlotte, NC. Jan. 2011 and the 2010 International Conference on Nanotechnology for the Forest Products Industry held September 27-29 in Espoo, Finland. PARTICIPANTS: During this period there were collaborations with: Prof. John Nairn, OSU Prof.; Lech Muszynski, OSU Prof.; Sundar Atre, OSU Prof.; Michael Lerner, OSU Prof.; David Cann, OSU Prof.; William Heatherington, OSU Prof.; Reza Yazzar, Mich. Tech. Univ.; Deepak Srivastava, NASA; Prof. William Tze, Univ. of Minnesota; Prof. Shri Ramaswamy, Univ. of Minnesota; Dr. Wadood Hamad, Paprican Division, FPInnovations, Vancouver, Canada; Prof. Rober Moon, Purdue Univ.; Dr. Bruce Arey, Pacific Northwest National Labs. Graduate students: Melissa Taylor, Jeremiah Kelley, Pratish Rao, Nathan Valmika. Undergraduate Students: John Miles, Han Chan, and Michelle Romero. TARGET AUDIENCES: The target audiences for this work are professional scientists and technologists in a variety of areas. PROJECT MODIFICATIONS: Nothing significant to report during this reporting period.

Impacts
In collaboration with Prof. John Nairn, new equations have been developed which, if validated, could be used to design and develop new and improved nanocomposite materials. Validation work is underway. A new protocol has been developed for the evaluation of TEB data. However, the mathematics is complicated and we are collaborating with the Mathematics Department to attempt to find useful ways to develop the analytical method. As mentioned above, we have developed a new method of producing iron-based nanoparticles, but have not yet fully characterized the particles and have not optimized the method. All of these outcomes should result in peer reviewed articles that will impact the scientific community and eventually affect the commercialization aspects of CNCs.

Publications

• Eichorn, S.J., A. Dufresne, M. Aranguren, N.E. Marcovich, J.R. Capadona, S.J. Rowan, C. Weder, W. Thielemans, M. Roman, S. Renneckar, W. Gindl, S. Veigel, H. Yano, K. Abe, M. Nogi, A.N. Nakagaito, A. Mangalam, J. Simonsen, A.S. Benight, A. Bismarck, L.A. Berglund and T. Peijs. 2010. Review: Current International Research into Cellulose Nanofibres and Nanocomposites. Journal of Materials Science 45(1):1.
• Valmika, N., S. Park, S. Atre, S. Rochefort, R. German and J. Simonsen. 2010. Studies on the Thermal Stability and Degradation Kinetics of Pd/PC Nanocomposites. Journal of Applied Polymer Science 118(6):3602-3611.