Project Accomplishments and Outcomes Acknowledgements Table of Contents

The content of this booklet was supported by the National Science Foundation’s Center for Bioplastics and Project Accomplishments and Outcomes Biocomposites under grant number 1439639 and 1738417. We would like to thank our many stakeholders and industry partners for their contributions to the project. Center for Bioplastics and Biocomposites

FROM THE DIRECTORS...... 4 INTRODUCTION...... 5

WHAT IS BIOPLASTICS?...... 6 MEMBER MAP...... 6 CENTER OPERATIONS...... 10 RESEARCH ...... 11 THRUST 1 SYNTHESIS AND COMPOUNDING...... 13

THRUST 2 BIOCOMPOSITES...... 19

2019 Center for Bioplastics and Biocomposites THRUST 3 PROCESSING...... 25

NDSU does not discriminate in its programs and activities on the basis of age, color, gender expression/identity, THRUST 4 BIOBASED PRODUCTS...... 29 genetic information, marital status, national origin, participation in lawful off-campus activity, physical or mental disability, pregnancy, public assistance status, race, religion, sex, sexual orientation, spousal relationship to cur- THRUST 5 MODELING...... 35 rent employee, or veteran status, as applicable. Direct inquiries to Vice Provost, Title IX/ADA Coordinator, Old Main 201, (701) 231-7708,[email protected]. OUTCOME...... 38 This book was produced by David Grewell, Director. and site directors Vikram Yadama, Eric Cochran, Jason Locklin and Dean Webster of the Center for Bioplastics and Biocomposites, with assistance from Sarah Dossey, RESEARCH EXPERIENCE FOR UNDERGRADUATES (REU)...... 41 Crystal Leach and Ben Deetz. Published by Washington State University Printing and Creative Services. ©2019 all rights reserved. CURRENT INDUSTRY MEMBERS AND AFFILIATE MEMBERS...... 44 159584.4.18

3 From the Directors Introduction

With a steadily increasing number of companies The Center for Bioplastics and Biocomposites (CB2) is property that is developed in the course of a CB2 and institutions setting sustainability goals for their a National Science Foundation Industry & University project belongs to the industry partners that fund the operations, CB2 (Center for Bioplastics and Cooperative Research Center (I/UCRC) that focuses execution of the patent royalty free. Biocomposites) is well-positioned to support these on developing high-value biobased products from efforts. CB2 is a collaborative effort by North Dakota agricultural and forestry feedstocks. While the thrust areas represent general State University, Iowa State University, University of technological and scientific topics where CB2 has Georgia, Washington State University, and industry The goals of this center are threefold: (1) to improve unique strengths compared to other research members to conduct commercially relevant research. the basic understanding of the synthesis, processing, institutes, other technologies outside As a National Science Foundation (NSF) Industry/ properties, and compounding of bioplastic and these thrust areas are also continuously University Cooperative Research Center (I/UCRC) biocomposite materials; (2) to develop reliable developed to meet the expressed we connect a broad spectrum of industry members material characteristics data for industrial partners; goals of our industry partners. Our goal DAVID GREWELL VIKRAM YADAMA with university experts. This allows industry to leverage CB2 Director CB2 Co-Director and (3) to support large-scale implementation of is to develop viable, science-based, their individual resources to develop new materials, 701-231-5395 509-335-6261 renewable materials. In order to achieve these goals, and economically feasible solutions processes, knowledge, and intellectual property, [email protected] [email protected] the activities will be: that meet our partners’ needs for a giving them a competitive edge and grow their sustainable future. profitability. While the center creates an environment • Collaboration with industry to develop The vision of the center is to develop the that fosters partnerships between industry and leading fundamental knowledge of bioplastics and knowledge that will allow the production of experts from universities, its research focus and the biocomposites an array of high-value products, allocation of resources are determined by industry • Dissemination of this knowledge through including plastics, coatings, partners. The center’s operation is designed to publications, workshops, and tradeshows adhesives, and composites encourage technology transfer between universities • Education of future researchers, engineers, and from agricultural and forest- and industry through monthly mentoring meetings, scientists based resources that are internships, and bi-annual meetings. compatible with current Our center’s operational costs are covered by the industrial manufacturing The novel technologies and materials resulting from National Science Foundation (NSF) while the research systems and thereby promote CB2 efforts allow industry to quickly and confidently is funded by our industry partners. The partners start domestic development. adopt new and demanding sustainable materials project selection through a well-documented and and processes and integrate them seamlessly in their effective process, including development of seed existing operations. The new materials not only meet concepts to serve as topics for a call for proposals DEAN WEBSTER ERIC COCHRAN JASON LOCKLIN consumer demands, but also government regulations from our university partners. The university researchers CB2 Co-Director CB2 Co-Director CB2 Co-Director while supporting corporate goals of environmental and their teams submit proposals to address the seed 701-231-8709 155-294-0625 706-542-2359 stewardship. CB2’s member companies are leading concepts within well-defined thrust areas. Through [email protected]@iastate.edu [email protected] the industry in sustainable materials through their a multi-step system, our industry partners select the engagement in the renown I/UCRC NSF Center for projects for funding based on a vote. Once the Bioplastics and Biocomposites. projects are funded, they are mentored by the industry partners on a monthly basis. Any intellectual

4 5 What are Bioplastics? Why Bioplastics?

Generally, when raw materials for a plastic Based on Renewable Biobased and While plastics have greatly originates from renewable resources, such Materials Biodegradable

Renewable increased our quality of life, as wood or agricultural residues, the resulting setting the stage for advances material is referred to as a bioplastic. in medical devices, food Bioplastics may or may not be biodegradable. packaging, consumer goods, Biodegradable plastics can also be produced and electronics, there are Conventional Biodegradable from petrochemicals. Plastics growing reports how these Bioplastics come in many flavors. They can engineered materials are leaving be designed to be as durable as many petro- behind a concerning legacy. chemical plastics or to degrade under certain Petrochemical There are numerous reports about environmental conditions. This makes them very plastics in the oceans and how Non-Degradable Degradable versatile and able to meet a wide range of they impact marine life and our industry needs. natural ecosystems. In addition, Bioplastics Possible zone there are concerns regarding Common Bioplastics and Biobased Content micro-plastics in many of today’s The biobased content for various bioplastics can vary depending on the type of plastic as well as the source/ consumer goods and even food manufacturer. The table below summarizes the common bioplastics and their typical biobased content. and beverage products. Also, 100 there is the general concern 90 regarding the large amount 80 of plastics that is simply sent 70 to our waste management 60 infrastructure (i.e. landfills) and 50 the global impacts on countries

40 that lack such infrastructures. In 30 addition, there is the obvious 20 issue of lack of sustainability for 10 plastic derived from fossilized 0 carbon.

Average Biobased Content of the Polymers, % of the Polymers, Biobased Content Average Worldwide and on the national scale, there are numerous efforts to recycle, reuse, and repurpose plastics which offer ways to mitigate the negative effects of persistent plastic materials. Part of the

Polymide (PA) Polymide solution is also developing novel plastics, coatings, and composites from renewable feedstocks Polybutylene (PE) Polybutylene

Polypropylene (PP) Polypropylene and engineering the products to degrade at the end of life. Renewable feedstocks, that primarily Polyurethane (PUS) Polyurethane Polylactic Acid (PLA) Acid Polylactic Cellulose Acetate (CA) Acetate Cellulose contain 5- and 6-carbon sugars and aromatic polymers, are natural polymers that can yield Polyvinyl Chloride (PVC) Polyvinyl building blocks for a variety of bio-based products. Synergistic partnerships between researchers Polybutylene Succinate (PBS) Succinate Polybutylene Polyhydroxy Alkanoates (PHAs) Polyhydroxy and business communities enabled by NSF IUCRCs are critical to reduce the detrimental effects Polybutylene Terephthalate (PET) Terephthalate Polybutylene

Starch Blends (in plastic compounds) Starch of plastics on our environment and develop fundamental knowledge regarding the mechanical Biobased Plastics behavior, processing requirements, costs, and life cycle assessment of these materials. Polybutylene Adipate Terephthalate (PBAT) Terephthalate Adipate Polybutylene

Source: Dammer L, Carus M, Raschka A, and Scholz L (2013) Market Developments of and Opportunities for Biobased Products and Chemicals, nova-Institute for Ecology and Innovation, Germany. 6 7 •Institution Partners •Industry Partners† 1 North Dakota State University 1 3M 2 Iowa State University 2 ADM 3 Washington State University 5 BASF Collaboration 4 University of Georgia 4 Berry Plastics Corporation 5 Boehringer Igelheim • Faculty Members: 6 Boeing The NSF Industry & University 6, 29 7 Branson Ultrasonics 19 Cooperative Research Center 8 Byogy Renewables, Inc. program is a vehicle for encouraging 3 9 CycleWood Solutions Inc. formal, topical relationships between 10 Danimer 1 academic institutions and industry 28 11 Diageo

25 collaborators. 24 12 Dixie Chemical Company 13 Dukane Ultrasonics 27 36 20 7 • Industry Members:

1 14 EcoProducts

Companies and organizations

4 15 EVOLVE GOLF

32 16 Ford interested in bioplastics and 31 16 2 34 17 Futamura biocomposites are invited to join 38 2 39 13 18 Hyundai CB . Becoming a member has many 24 21 11 23 43 19 Idaho Forest Group, LLC advantages including leveraging 26, 42 30 20 Inland Packaging research and development efforts 40 44 2 21 John Deere through the center’s projects, 8 14 receiving access to technologies 41 22 Kimberly-Clark 23 Laurel Biocomposite developed by the center and 24 Minnesota Corn Research having access to scientists and 25 GC Innovation undergraduate and graduate 35 15 26 Natural Soy Products students for future employment. 33 27 NatureWorks 37 18 9 4 28 North Dakota Corn Council • Affiliate Members: 5 17 34 29 Northwest Green Chemistry In addition to its core funding from 30 Powder Coating Research the National Science Foundation and 31 Renewable Energy Group industry members, CB2 is supported by 10 32 RheTech affiliate members. 22 33 Rubbermaid 34 RWDC 35 SealedAir 36 SelfEco 12 37 Shaw Industries Group, Inc. 3 38 Sherwin Williams 39 Siegwerk USA 40 SuGanit BioRenewables 41 Sunstrand

†All previous and current industry partners are listed. 42 Swamp Fox Chemical LLC 43 Taylor Technologies 88 44 USDA-ARS-NCAUR 9 45 Viskase Companies Inc. Center Operations Research CB2 focuses on five research thrust areas that promote industry-wide acceptance of bioplastics and Center Organization biocomposites and increase the use of sustainable materials. Each thrust area is listed below.

University Policy Committee

Center Director Site Co-Director NSF David Grewell (ISU) Vikram Yadama(WSU)

Center Evaluator Industry Connie Chang Advisory Board

Center Coordinator Yijing Ding

Research Tech Transfer & Education

20 Faculty WSU 27 Faculty ISU Faculty UGA

Synthesis & Compounding Biocomposites Processing Biobased Products Modeling Commercialization

Timeline for project selection

10 11 •SYNTHESIS AND COMPOUNDING •COMMERCIALIZATION This thrust area develops fundamental understanding The center affiliates have a proven track record of Thrust 1 of bioplastic synthesis and compounding, including working with member companies to successfully fermentation and polymerization. This includes commercialize biobased products. Because the center SYNTHESIS AND COMPOUNDING vegetable oil-based plastics, coatings and adhesives, offers member companies royalty-free access to biobased waxes, monomers, elastomers, poly(ester- intellectual property resulting from center projects, the amides), protein-based plastics, sustainable center is well positioned for direct technology transfer This thrust area develops fundamental approaches to advanced functional materials and from academia to industry. The center supports the understanding of bioplastic synthesis and polymer additives, and feedstock preparation. development of Small Business Innovation Research compounding, including fermentation and (SBIR) proposals and business plans, facilitates BIOCOMPOSITES polymerization. This includes vegetable networking, and identifies markets and potential • oil-based plastics, coatings and adhesives, Knowledge of biocomposites, including fiber synthesis, market penetration. This allows member companies to biobased waxes, monomers, elastomers, biobased resin systems, and biobased fiber systems, leverage their resources and increase their profits. is developed in this thrust. These areas include self- poly(ester-amides), protein based plastics, healing composites, fiber production from lignin, nano- sustainable approaches to advanced technologies as well as biobased composites. functional materials and polymer additives, and feedstock preparation. •PROCESSING This thrust focuses on the specific requirements of biobased polymers and composites during vital processing operations. This includes melt processing, extrusion, and molding, as well as secondary operations Illustration of asperity peak squeeze flow such as cutting, welding, and coating. •BIOBASED PRODUCTS This thrust focuses on developing biobased products, such as plastics or composite products, that are drop-in substitutes for petroleum-based products currently in the market. It also includes determining sustainability metrics such as environmental impact. Part of the

center’s already existing system is a web-based Bioplastic synthesis pilot plant at ISU interactive life cycle assessment software that allows users to easily analyze their current and future products. •MODELING This thrust studies energy and mass transfer for typical processing techniques such as extrusion and injection molding. The long-term goal is to develop models based on fundamental principles that can be used across a wide range of applications. Students compounding and molding bioplastic material

12 13 Biobased Methacrylates to Replace Styrene Develop Renewable Propylene Using Sugar as a Reactive Diluent in Thermoset Resins Derived 1,2-Propanediol and Glycerol

Lead: Michael Kessler, Washington State University Lead: Junna Xin, Washington State University Staff Scientist: Yuzhan Li, Washington State University Student: Yuehong Zhang, Washington State University

Polypropylene (PP) is the second largest polymer identified and the optimized reaction conditions have The objective of this project was to develop low-cost 3. Characterized the volatility, viscosity, cure kinetics produced by volume, used in a wide variety of been determined, which will be the fundamental biobased reactive diluents suitable for vinyl ester (gel time and curing extent), thermos-mechanical applications. At present, most of propylene is still data for future scale-up processes. and vegetable oil-based composites that decrease properties, mechanical properties, and thermal obtained from the refining gasoline or produced concentrations of volatile organic compounds (VOC) stability as a function of diluent content. by splitting, cracking, and reforming hydrocarbon Accomplishments including styrene, reducing emissions throughout mixtures. However, these processes are still based on 1. Highly pure propylene was produced with yields the composite life cycle. We synthesized a range of Accomplishments petroleum-based feedstock, are performed at high higher than 90% based on the whole conversion biobased methacrylates, including methacrylated 1. Significant reduction of system viscosity (over an temperatures, and require expensive noble metal process. vanillin (MV), methacrylated vanillyl alcohol (MVA), order of magnitude) was achieved when 30 wt% of catalysts. With the finite stocks of fossil resources and methacrylated eugenol (ME), through the MVA was used. and the growing market demand for propylene, 2. Technical economic analysis (TEA) was initially reaction between methacrylic anhydride with development of alternative feedstocks for the conducted to predict the production costs of these hydroxyl groups on the biobased precursors. 2. Biobased methacrylates were shown to have great production of propylene is an attractive solution. In two conversion processes. The price of renewable These reactive diluents were blended with high- potential to serve as combined reactive diluents for this work, we developed new and more economic propylene produced using our processes is viscosity thermosetting resins (both vinyl ester and MAESO and vinyl ester resins with decreased viscosity production methods for biobased propylene using comparable with that of petroleum-based propylene vegetable oil-based resins) and cured via free radical and improved thermal-mechanical properties while sugar-derived 1,2-propanediol (1,2-PDO) and glycerol in the marketplace. polymerization. maintaining low VOC emission compared to that of as feedstocks, respectively. commercial styrene resins. Outcomes Outcomes 1. Successfully synthesized biobased MV, MVA, and ME. 1. Three-step and two-step conversion processes have been designed and fully investigated. 2. Evaluated reactive diluents with CB2 member company’s maleinated acrylated epoxidized 2. Efficient catalysts for each step within the soybean oil (MAESO) resin and commercially whole transformation process were important vinyl ester resins.

14 15 PEN Polymers – Next Generation Bottles and Glycerol-Based Thermoplastic Elastomers Packaging Materials Lead: Eric Cochran, Iowa State University Leads: George Kraus, Eric Cochran, Iowa State University

Poly(ethylene 2,6-naphthalate) (2,6-PEN) exhibits 3. PENs are expected to open up many new markets in Our group is interested in the synthesis and Accomplishments higher dimensional stability, shrinkage resistance, the bottling and packaging industries because of their characterization of heterogeneous block copolymers 1. Production of glycerol-based, pressure sensitive temperature stability and better barrier properties excellent barrier properties and superior mechanical and polymer nanocomposites for applications adhesives with mechanical properties comparable to than polyethylene terephthalate (PET). The excellent properties. ranging from asphalt modification to adhesives to petroleum-based adhesives. barrier properties of PENs make them attractive improved performance biomaterials. Our research materials for packaging. Unfortunately, limitations Accomplishments team discovered synthetic routes to non-cross linked 2. Synthesis of novel transfer agents facilitating the on monomer availability and cost significantly affect 1. Synthesized three monomers with biobased feedstocks thermo plastics and thermoplastic elastomers derived polymerization of triblock copolymers that will improve the commercial expansion of 2,6-PEN, prepared from vegetable oils. the mechanical properties of the biobased adhesives. from the oxidation of 2,6-dimethylnaphthalene. Drs. 2. Developed protocols of monomer purification and Kraus and Cochran are evaluating structure/function polymerization We are currently investigating the use of other of PENs with the aim to maximize performance and renewable feedstocks, such as glycerol, as potential minimize costs of synthesis. While these polymers will 3. Synthesized three new polymers + 2,6-PEN replacements for petrochemically derived monomers initially be more expensive than polymers derived in specialty polymers, for example biobased, pressure- from terephthalic acid, they are expected to exhibit 4. Demonstrated that biobased PEN has a melting sensitive adhesives. excellent barrier properties and superior mechanical temperature > 300 ° C for 2,7 PEN properties and therefore will have applications where Outcomes PET is less effective or even not usable. 5. Evaluating potential for value-added properties such 1. Synthesis of glycerol-based, non-cross linked as barrier performance through copolymerization with thermoplastic elastomers. Outcomes PET 1. In 2015 there were 5,971,000,000 pounds of PET 2. Formulations to produce tackifier-less, pressure bottles sold into the US market. sensitive adhesives from renewable feedstocks.

2. This work resulted in a cost competitive and fully sustainable path to the superior PEN, a 5-10% displacement of the PET volume would be highly significant.

16 17 Unsaturated Diacids for the Synthesis of Bio-Enhanced Nylon-6,6 Thrust 2

Lead: Eric Cochran, Iowa State University BIOCOMPOSITES Staff Scientist: Michael Forrester Undergraduate Students: Peter Meyer & Nicholas Bloome Knowledge of biocomposites, including fiber synthesis, biobased resin systems, and biobased fiber systems, is developed in this thrust. These areas include self- healing composites, fiber production from lignin, nano-technologies as well as Our group is currently performing synthesis and Outcomes biobased composites. characterization of long-chain unsaturated 1. Synthesis of bioadvantaged Nylon from C16:1 bio- bioadvantaged Nylon copolymerized with Nylon 6,6. diacids Our research team has found that the incorporation 2. Development of mechanically superior Nylon 6,6 of relatively small amounts of C16:1 Diacid substitution can have dramatic effect on the toughness with Accomplishments minimal negative impact on the strength of the Production of Nylon 6,6 with nearly a threefold material. increase in toughness while retaining >90% of its strength We are currently investigating the limits and reproducibility of this modification as well as understanding whether the unsaturation or the carbon length is the major contributing factor to this change in mechanical properties.

18 19 Mechanochemically Activated and/or Production of Low-Cost Carbon Fiber from Heavy Functionalized Cellulose Powders and Their Fraction of Fast Pyrolysis Bio-Oil Reinforced Plastic Composites for Higher Demanding Applications Lead: Xianglan Bai, Iowa State University

Lead: Michael Wolcott, Washington State University Postdoctoral Fellow: Mohammadali Azadfar, Washington State University Students: Lang Huang and Max Graham, Washington State University

Cellulose fiber and nanocellulose have the potential 3. Development of techniques and tools for analysis, Lignin is a promising precursor of low-cost carbon Outcomes for a variety of new applications. However, visualization, and dissemination of different aspects of fibers. However, the mechanical properties of carbon 1. Pretreated pyrolytic lignin is turned into difficulties in achieving a proper dispersion and a the research project. fibers produced from melt-spinning of raw lignin a melt-spinnable carbon fiber precursor with strong interface with the matrix polymer prohibit are poor, restricted by the randomly cross-linked lower glass transition temperature. the realization of this potential. In this research, we Accomplishments polymer structures of lignin. In this project, pyrolytic hypothesize that wood pulps, composed primarily of 1. Development of solvent-free chemomechanical lignin, which is a depolymerized lignin that consists 2. Carbon fibers with maximum tensile strength of 1040 cellulose, can be subjected to mechanochemical processes to simultaneously pulverize, activate, and of phenolic monomers and oligomers, was used MPa and modulus of 112 GPa are obtained. activation with selected chemicals to prepare surface functionalize wood pulp, producing property-tuned as the starting material to produce carbon fiber. activated and/or functionalized cellulose powders for meterable cellulose powders. By repolymerizing the pyrolytic lignin, the modified Accomplishments reinforcements. precursor with improved quality can be obtained. 1. Production of carbon fiber from low-cost 2. Production of cellulose powders-reinforced biorenewable feedstock. Outcomes polypropylene composites with improved physico- This project evaluated the activation of hydroxyl mechanical features. 2. A new approach to modify the intrinsic molecular groups and reducing-end groups on cellulose powder structure of lignin to improve the quality of carbon surfaces through the use of a lab-scale planetary fibers. ball mill in dry media chemical reaction systems to demonstrate functionalization of cellulose powder.

1. Preparation of size-reduced and activated cellulose powders.

2. Formulations to improve the interfacial adhesion between filling cellulose powders and polypropylene matrices.

20 21 Production of Low-Cost Lignin Composite Development of Lignin Thermoplastic Materials Using Biorefinery Lignin Composites

Lead: Birgitte Ahring and Amir Amelli, Lead: Reza Montazami, Iowa State University Washington State University Postdoctoral Fellows: Jinxue Jiang and Keerthi Srinivas, Washington State University Student: Nahal Aliheidari, Washington State University

Carbon fibers form an essential component in Outcomes Biobased composites with mechanical and chemical Accomplishments automobiles and airplanes, increasing fuel efficiencies 1. Production of PAN-lignin blends using melt spinning properties comparable to those of petroleum-based 1. Developed decision-making tools to determine and mechanical strength. The increased cost of process for further conversion to carbon fibers. counterparts have considerable economic and filler type, filler content, and type of polymer matrix to carbon fibers, however, significantly affects the final environmental advantages. This project investigated obtain target mechanical properties. product. Our group focuses on research related 2. Increased in-mixing of PAN-lignin at melt spinning the use of a wide range of bio-fillers in combination to the sustainable conversion of lignocellulosic conditions through modification of lignin (by with petroleum-based matrix polymers to explore the 2. The developed knowledge platform facilitates biomass to biofuels and bioproducts and we have esterification) and using plasticizers without significant potential of biobased composites that can serve as a design and manufacturing of parts with biobased been working on modifying the biorefinery lignin impact on mechanical strength. one-to-one drop-in for traditional plastics at industrial composites. stream as a low-cost compound for in-mixing with scale. polyacrylonitrile (PAN). This will reduce the cost of Accomplishments carbon fibers with minimal impact on strength. We 1. Production of PAN-lignin blends up to 30 wt% in-mixing Outcomes use biorefinery lignin, which is highly methoxylated with mechanical properties similar to those of pure PAN 1. Established the limits of bio-filler content in polymer during the upfront pretreatment process that is used used in carbon fiber production. matrices. to remove carbohydrates from the lignin. These changes make it a better substrate for in-mixing with 2. Melt spinning of PAN-lignin blends using ionic liquid 2. Gained an understanding of filler-matrix chemical PAN when compared to commonly available lignins as plasticizer that will facilitate chemical interaction bonding. such as Kraft lignin. In this process, the modified lignin between PAN and lignin, resulting in better lignin- (using esterification to increase hydrophobicity) was based carbon fibers than currently reported in the 3. Determined mechanical and thermal properties of chemically fused with the PAN through melt spinning literature. the resultant biobased composites. to produce carbon fibers with minimal reduction in mechanical characteristics. 4. Proven economic advantages of the biobased composites using cost analyses.

22 23 Thrust 3 PROCESSING

This thrust focuses on the specific requirements of biobased polymers and composites during vital processing operations. This includes melt processing, extrusion, and molding, as well as secondary operations such as cutting, welding, and coating.

24 25 Odor Control in Agave Fiber-Polypropylene Chitin Nanofibers and Chitin Esters: Preparation, Biocomposites Characterization, and Their Transparent Nanocomposite Films and Coatings Lead: Reza Montazami, Iowa State University Lead: Jinwu Wang, Michael P. Wolcott, and Hang Liu, Washington State University Postdoctoral Fellow: Tuhua Zhong, Washington State University

While biobased plastics provide an environmentally Accomplishments Chitin is an abundant biopolymer in nature and Accomplishments friendly and cost-effective alternative to petroleum- 1. Fabricated agave fiber-based polymer composites can be extracted economically from leftover shells 1. Demonstrated the potential of chitin nanofibers based plastics and are establishing a new consumer- with no noticeable odor and improved mechanical from lobsters, crabs, and shrimp consumed by and chitin esters in applications ranging from inks and driven market, some challenges still exist in realizing properties. humans. Chitin in commercially available powder films to composites. their full integration with consumer goods. One major form does not dissolve in water and most common challenge is the odor of biobased materials. The 2. Developed complete set of preprocessing organic solvents, making it difficult to be processed 2. Used as rheological modifiers or reinforcing odor, typically caused by impurities and not inherent conditions and formulation for odor-free agave-fiber into products industrially. Making chitin dispersible additives in water-based or solvent-based ink to the biomaterials, is conveyed to biocomposites polymer composites. or soluble can increase the scope and value of its or coating systems, or as oxygen barrier layer in containing bio-fillers and consequently makes them applications leading to value-added products and packaging films. unsuitable for many applications. This project focused 3. This is a process that can be adopted for other additional revenues for the fishing industry, which in on the development of a low-cost and scalable bio-fillers. turn decreases the cost of crustacean products. process and formulation for mitigating and eliminating such odors in agave fiber-based composites. Outcomes 1. Developed mechanochemical methods to convert Outcomes chitin into chitin nanofibers that can be dispersed 1. Developed a scalable process for mitigation of uniformly and stably into water and water-based odors in agave fiber composites. coating systems.

2. Measured the impact of pre-processing 2. Developed methods to convert chitin into chitin conditions of mechanical properties of the esters that can be dissolved in several commercially biobased composites. important organic solvents.

3. Characterized chitin nanofibers and chitin esters as well as their coating formulations and films.

Water dispersible chitin nanofibers and organo-soluble chitin propionate for coatings and films

26 27 Thermoplastic Starch-Based Thin Films with Polyacrylated Glycerol as Plasticizer Thrust 4

BIOBASED PRODUCTS Lead: Nacu Hernandez, Iowa State University This thrust focuses on developing biobased products, such as plastics or composite products, that are drop-in substitutes for petroleum-based products currently in the market. It also includes determining sustainability metrics such as environmental impact. Part of the center’s already existing Few biobased thermoplastic materials can Accomplishments system is a web-based interactive life cycle successfully compete with their petroleum 1. PAG copolymer had 2,000x the ductility of counterparts, in large part because of a lack in unmodified TPS. assessment software that allows users to understanding of the fundamental properties of easily analyze their current and future the materials. The use of thermoplastic starches 2. Developed functionalized thermoplastic starch products. (TPS) has suffered from their inability to maintain resulting in increased moisture resistance. thermoplasticity as the material ages.

As they age, TPS undergo retrogradation where the starch recrystallizes and the water molecules and other plasticizers are pushed out, making the material harder and less flexible. If TPS retrogradation can be controlled, many commercial applications will become available. In particular, our interest is focused on the creation of “green” films with controlled oxygen and water permeability for use in food applications. Also desirable is the ability for the material to accept dye, e.g., from printing processes.

Outcomes 1. Developed thermoplastic starch formulations to make films suitable for packaging materials.

2. Improved the water resistance of thermoplastic starch by functionalizing starch.

28 29 Biobased VOC-free Powder Coating Resin Improving Thermoplastic Properties of Starch Systems Lead: Buddhi Lamsal, Iowa State University Lead: Jinwen Zhang, Washington State University

Powder coating has attracted increasing attention Accomplishments Utilizing starch for bioplastic-related applications, Accomplishments in recent years, as it is environmentally friendly and 1. Developed chemical structures and synthesis i.e., films, adhesives, and molded products among 1. The outcomes allowed stakeholders to produce virtually pollution-free. Powder coatings represent methods of rosin-derived epoxy powder coatings and others, requires understanding of the factors that turn starch-based films with specific properties. more than 15% of the industrial coatings market and rosin-derived curing agents for polyester it into thermoplastic polymer during extrusion. Factors is predicted to continue to grow. Current powder powder coatings. such as starch composition and structure, plasticizer, 2. Adding nanomaterials, including biodegradable coatings, like many other polymer materials, are temperature of extrusion, moisture content, and nano-biofibers, was shown to increase mechanical entirely based on petrochemical feedstocks. We 2. Determed curing behavior and fundamental nature of blending materials affect resulting starch and barrier properties of starch films. have made a significant effort to develop alternative performance. and film properties. This study investigated those biobased powder coatings using renewable chemical factors, understanding of which allows scientists, feedstocks such as rosin acid and dipentene. designers, engineers, and manufacturers to consider starch for various biobased applications. Outcomes 1. Understanding the design space and limitation Outcomes of some renewable feedstock for powder coating 1. Starch-based cast films were prepared to optimize applications. film formulations and ingredient interactions for desirable film properties. 2. Introducing promising biobased powder coatings and potential applications. 2. Optimized film formulations were extruded in a twin- screw extruder at various processing conditions for sheet films and pertinent properties of resulting films, e.g., strength, barrier properties, hydrophobicity, glass- transition, and thermal degradation, were compared.

30 31 Effectiveness and Nutrient Tracking of Fully Biobased Degradable Plastic with Biopolymer Horticultural Systems Insecticide Functionality

Lead: James Schrader, Iowa State University Lead: Chunhui Xiang, Iowa State University

Student: Cindu Annandarajah, Iowa State University

The extensive use of petroleum-based plastic pots Accomplishments The rise of Zika and other insect driven viruses are This was followed by the extruded natural pyrethrum- (containers) and synthetic fertilizers in horticulture 1. Biopolymer horticultural systems are a promising becoming an epidemic that has been directly treated PLA fabric with an escape frequency of 80 ± provides unparalleled effectiveness, but this alternative to petroleum-based plastic containers and impacted by climate change. This is driving a market 6.3%. Finally, the PLA fabric spray-treated with natural effectiveness is achieved through heavy consumption synthetic fertilizers. need for a product that is able to not only prevent pyrethrum caused an escape frequency of 98.3 ± of finite fossil resources and with a disproportionate insects but also reduce the effects of the spread of 1.7%. All treated fabrics caused repellency. impact on the environment. We evaluated the 2. Our results demonstrate that they can provide these insects. The goal of this project is to develop effectiveness and nutrient efficiency of emerging similar functionality, with greatly improved biodegradable fibers with insecticide functionality Outcomes biopolymer horticultural systems that utilize containers sustainability. for protective garments. Poly (lactic acid) (PLA) 1. Compounding of synthetic and natural insect made of biorenewable polymers that provide is one of the most promising biopolymers able to replants with PLA nutrients to plants by using protein-based biopolymers replace the petroleum-derived polymers for industrial 2. Extrusion of compounds into fiber without synthetic fertilizer. applications. The natural insecticide, pyrethrum, 3. Testing mosquito repellency of various fabrics and the repellent DEET were added to a polylactic Outcomes acid (PLA) fabric via extrusion and spraying. GPC Accomplishments 1. Biopolymer horticultural systems were found to be analysis showed that the addition of DEET caused 1. Demonstrated the possibility of compounding effective and suitable for providing fertilizer nutrients an increase in depolymerization with the increase in synthetic and natural insect repellents with PLA to plants grown in containers and in garden soil. DEET concentration. Contact Irritancy Assay (CIA) 2. Produced fabrics from compounded plastic showed that DEET-treated PLA fabric caused the 3. Demonstrated the effectiveness of the various 2. The nutrient efficiency of biopolymer horticultural lowest percentage escape response with an escape fabric against mosquitosh standardized material systems equaled or exceeded the efficiency of frequency of 33.3 ± 3.3%. characteristics for product design. synthetic controlled-release fertilizer.

32 33 Thrust 5

MODELING

This thrust studies energy and mass transfer for typical processing techniques such as extrusion and injection molding. The long- term goal is to develop models based on fundamental principles that can be used across a wide range of applications.

34 35 Interfacial Healing of Biopolymers Development of Life Cycle Assessment Tool for Screening of Trade-offs Among Processing Lead: David Grewell, Iowa State University Costs, Environmental Impacts, and End-of-Life Options

Lead: Kurt A. Rosentrater, Iowa State University

Interfacial healing of bioplastics is critical in primary Accomplishments Costs and environmental performance of plastics 2. This research has shown that utilizing landfill as end- processing, such as weld line (net line) formation in 1. The outcomes allow designers, engineers, and continue to be topics important to both industry and of-life treatment for glass-filled components can be injection molding or in secondary operations such manufacturers to predict healing of bioplastic consumers. Our research has focused on life-cycle the most environmentally harmful option and resulted as welding and sealing of bioplastic components. interfaces for the sustainable manufacture of plastic assessments (LCA) and techno-economic analyses in the highest cost. Understanding how these novel materials join products. (TEA) in order to understand material and processing together provides designers, engineers, and costs and environmental impacts of using various 3. Alternatively, both DDGS and wood filler manufacturers with the fundamental knowledge they 2. The coupled models facilitate the production fillers in polylactic acid (PLA) composites. We have composites paired with recycling end-of-life need to produce biobased, sustainable materials with of parts via primary and secondary processes with examined organic fillers such as DDGS, flax, hemp, treatment were shown to have the lowest high quality and consistency that meet the demands enhanced quality and consistency. This knowledge rice husks, and wood, and compared these against •environmentalOverall Cost Includes: impacts material acquisition, and the compounding, lowest processing, cost and of end all of life treatment costs PLA of industry. gives manufacturers the confidence to utilize novel common inorganic fillers such as glass and talc. •compositesSensitivity analysis considered. shown below: processing costs are compared from published filler material cost (low to high) sustainable materials. Results -­‐‑ TEA OVERALL COST ($/KG) P ER PART [0.01 KG PART W EIGHT, Outcomes Outcomes 100,000 KG LOT PLA SIZE, ] PLA -­‐ Incineration -­‐ GWP Comparison, 0.01 kg Part Weight 1. This project measured the activation energy of 1. Our work has quantified costs, emissions, and en- 12 9800000 10 9600000 auto-adhesion of several grades of Polylactic acid ergy intensities associated with raw materials acquisi- 8 6 9400000 $/kg (PLA) to allow the prediction of healing of PLA tion, processing, transport, and end-of-life treatments. 4 9200000 2 interfaces. kgCO2eq/kg 0 9000000 Glass Talc DDGS Flax Hemp Rice Husks Wood Recycling 9 8.8 8.68 8.78 8.77 8.71 8.68 2. Environmental impacts have included global 8800000 Incineration 10.4 9.95 9.65 9.9 9.87 9.73 9.64 Landfill 10.8 10.3 10 10.3 10.2 10.1 10 2. Transient models based on first order principles warming potential, air acidification, air eutrophica- 8600000 Landfill + Results Methane Ext. 10.6 10.3 9.82-­‐‑ LCA10.1 10 9.9 9.81 were used to predict heat generation in welding and, tion, water eutrophication, ozone layer depletion, air No End of Life Treatment 10.6 10.1 9.82 10.1 10 9.91 9.82 Glass Talc DDGS Flax Hemp Rice Husks Wood coupled with finite element models, temperature smog, carcinogens, and noncarcinogens. PLA -­‐ Incineration -­‐ GWP Comparison, 0.1 kg Part Weight 1 PLA -­‐ Incineration -­‐ GWP Comparison, 1 kg Part Weight fields in various welding processes. 4000000 3500000 3500000 3000000 Accomplishments 3000000 2500000 2500000 1. Overall we found that use of organic fillers results in 2000000 2000000

kgCO2eq/kg 1500000

lower costs and environmental impacts compared to 1500000 kgCO2eq/kg use of inorganic fillers. 1000000 1000000 500000 500000

0 0 Glass Talc DDGS Flax Hemp Rice Husks Wood Glass Talc DDGS Flax Hemp Rice Husks Wood 1 36 37 Product Outcomes

• Agave Fiber Composites • Multifunctional Biobased Pots

The team worked with Ford Motor Company, Hyundai CB2 related projects were instrumental in developing Motor Group, Diageo, and ARaymond to develop and commercializing a novel pot design for growers. a biobased composite that had superior strength, The pots are: weight properties, and LCA benefit compared to traditional composites, allowing the automotive 1. Fully biobased industry to manufacture more efficient vehicles and 2. Degradable upvaluing coproducts (agave fibers) from the adult 3. Self-fertilizing with no petrochemical fertilizer beverage industry. additions 4. Able to increase vegetable yield by 100% because of enhanced root ball morphology (stops root circling)

The team included center researchers, Laurel Biocomposites, and SelfEco which now sells the product through Walmart and Amazon. The project was leveraged with a USDA, Specialty Crops Research Initiative (award # 2011-51181-30735) grant.

38 39 Research Experience for Industry contributions leveraged to make a difference Undergraduates (REU)

Each year, 10 students (recruited primarily from academic institutions with limited STEM research programs) work on research conducted by the CB2, with 5 students conducting their research at ndsu.edu/centers/cb2 Washington State University and 5 students doing their research projects at Iowa State University.

During the program, the students participate in a series of bioplastics short courses, take on responsibility Impact Workforce Training for an independent research project performed with Research state-of-the-art equipment and facilities, and engage with leading industry experts from the Industrial Invention Disclosures & 2 Patent Applications Industry Trained postdocs, Advisory Board of the CB . A liates undergraduate and 8 36+ graduate students Publications, Book Chapters, 26 & Presentations 44 Funded Projects Theses & Dissertations 39 Funded Projects valued at over

Bio-based A liates from 4 universities+ products 100 7 brought to $ production2 2M

40 41 2017 Research Experience Undergraduate (REU) students Seattle University

31 1- Nathan Glandon 4- Daniel Fortino 7- Samantha Trimble 10-Nicholas Van Nest 5, 16 6 University of Montana University of Minnesota The Pennsylvania Washington State State University University South Dakota School of Grand Valley

Mines and Technology 3, 28 State University 9 2- Jacob Bowen 5- Daniel Vincent 8- Anna Treppa 11- Mason Moeller 30 University of Wisconsin 10 33

19 4 Stony Brook

Platteville 34

Boise State University 14 University of Stevens Institute University 11, 12, 8 of Technology Colorado State University - Fort Collins 22, 29 Michigan Iowa State Bowling Green University of California, Merced 23 State University 3- Aleesha Slattengren 6- Amelia Cantwell 9- Ryan Funk 30 University 34 The Ohio State University 25 University of Colorado Boulder St. Augustine’s California State Polytechnic 17, 20 University 24 University, Pomona Pittsburg State University 18, 26 7, 2018 Research Experience Undergraduate (REU) students 13, 15 North Carolina State University 32 University of Tennessee

12- Ana Miller 15- Hana Gouto 18- Christina Verdi 21-Edgar Varela 2 LeTourneau University University of Texas A&M 1 13- Jose Velasco 16- Samuel 19- Andrew Freiburger 22- Riley Behan Bigbee-Hansen

14- Zachary Gotto 17- Shelby Bicknell 20- Lexington Peterson 23- Roman Amorati

2019 Research Experience Undergraduate (REU) students

24- Abib Hooker 27- Peter Meyer 30- Jiamin 33- Ian DeBois (Carmen) Wu

25- Alan Ramirez 28- Anna Mikkelsen 31- Thomas Ekstrom 34- Kyleigh Rhodes

26- Anna Schraufnagel 29- Liam Herbst 32- Rogine Gomez

42 43 Current Industry Members

44 45 Notes Affiliate Members

Department of Coatings and Department of Agricultural Polymeric Materials and Biosystems Engineering Voiland College of Engineering and Architecture Department of Mechanical College of Agriculture Engineering and Life Sciences Composite Materials & Engineering Center Department of Industrial and Center for Crops Manufacturing Engineering Utilization Research

Center for Sustainable College of Engineering Materials Science Bioeconomy Institute

New Materials Institute

College of Engineering

46 47 ndsu.edu/centers/cb2 cb2.iastate.edu cb2.wsu.edu