Project Accomplishments and Outcomes

Acknowledgements Table of Contents

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

THRUST 3 PROCESSING ......................................................................... 25

THRUST 4 BIOBASED PRODUCTS ........................................................... 29

THRUST 5 MODELING ............................................................................ 35

OUTCOME ................................................................................................... 38

RESEARCH EXPERIENCE FOR UNDERGRADUATES (REU) .......................... 41

CURRENT INDUSTRY MEMBERS AND AFFILIATE MEMBERS ........................ 44

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

2019 Center for Bioplastics and Biocomposites

NDSU does not discriminate in its programs and activities on the basis of age, color, gender expression/identity, 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-rent employee, or veteran status, as applicable. Direct inquiries to Vice Provost, Title IX/ADA Coordinator, Old Main 201, (701) 231-7708,ndsu.eoaa@ndsu.edu.

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, Crystal Leach and Ben Deetz. Published by Washington State University Printing and Creative Services. ©2019 all rights reserved. 159584.4.18

Project Accomplishments and Outcomes

Center for Bioplastics and Biocomposites

3

4 5

From the Directors Introduction

The Center for Bioplastics and Biocomposites (CB2) is a National Science Foundation Industry & University Cooperative Research Center (I/UCRC) that focuses on developing high-value biobased products from agricultural and forestry feedstocks.

The goals of this center are threefold: (1) to improve the basic understanding of the synthesis, processing, properties, and compounding of bioplastic and biocomposite materials; (2) to develop reliable material characteristics data for industrial partners; and (3) to support large-scale implementation of renewable materials. In order to achieve these goals, the activities will be: • Collaboration with industry to develop fundamental knowledge of bioplastics and biocomposites • Dissemination of this knowledge through publications, workshops, and tradeshows • Education of future researchers, engineers, and scientists

Our center’s operational costs are covered by the National Science Foundation (NSF) while the research is funded by our industry partners. The partners start project selection through a well-documented and effective process, including development of seed concepts to serve as topics for a call for proposals from our university partners. The university researchers and their teams submit proposals to address the seed concepts within well-defined thrust areas. Through a multi-step system, our industry partners select the projects for funding based on a vote. Once the projects are funded, they are mentored by the industry partners on a monthly basis. Any intellectual

property that is developed in the course of a CB2 project belongs to the industry partners that fund the execution of the patent royalty free.

While the thrust areas represent general technological and scientific topics where CB2 has unique strengths compared to other research institutes, other technologies outside these thrust areas are also continuously developed to meet the expressed goals of our industry partners. Our goal is to develop viable, science-based, and economically feasible solutions that meet our partners’ needs for a sustainable future. The vision of the center is to develop the knowledge that will allow the production of an array of high-value products, including plastics, coatings, adhesives, and composites from agricultural and forest-based resources that are compatible with current industrial manufacturing systems and thereby promote domestic development.

With a steadily increasing number of companies and institutions setting sustainability goals for their operations, CB2 (Center for Bioplastics and Biocomposites) is well-positioned to support these efforts. CB2 is a collaborative effort by North Dakota State University, Iowa State University, University of Georgia, Washington State University, and industry members to conduct commercially relevant research. As a National Science Foundation (NSF) Industry/University Cooperative Research Center (I/UCRC) we connect a broad spectrum of industry members with university experts. This allows industry to leverage their individual resources to develop new materials, processes, knowledge, and intellectual property, giving them a competitive edge and grow their profitability. While the center creates an environment that fosters partnerships between industry and leading experts from universities, its research focus and the allocation of resources are determined by industry partners. The center’s operation is designed to encourage technology transfer between universities and industry through monthly mentoring meetings, internships, and bi-annual meetings.

The novel technologies and materials resulting from CB2 efforts allow industry to quickly and confidently adopt new and demanding sustainable materials and processes and integrate them seamlessly in their existing operations. The new materials not only meet consumer demands, but also government regulations while supporting corporate goals of environmental stewardship. CB2’s member companies are leading the industry in sustainable materials through their engagement in the renown I/UCRC NSF Center for Bioplastics and Biocomposites.

DAVID GREWELLCB2 Director701-231-5395david.grewell@ndsu.edu

VIKRAM YADAMACB2 Co-Director509-335-6261vyadama@wsu.edu

DEAN WEBSTERCB2 Co-Director701-231-8709dean.webster@ndsu.edu

ERIC COCHRANCB2 Co-Director155-294-0625cochran@iastate.edu

JASON LOCKLINCB2 Co-Director706-542-2359locklin@uga.edu

76

While plastics have greatly increased our quality of life, setting the stage for advances in medical devices, food packaging, consumer goods, and electronics, there are growing reports how these engineered materials are leaving behind a concerning legacy. There are numerous reports about plastics in the oceans and how they impact marine life and our natural ecosystems. In addition, there are concerns regarding micro-plastics in many of today’s consumer goods and even food and beverage products. Also, there is the general concern regarding the large amount of plastics that is simply sent to our waste management infrastructure (i.e. landfills) and the global impacts on countries that lack such infrastructures. In addition, there is the obvious issue of lack of sustainability for plastic derived from fossilized carbon.

What are Bioplastics?

DegradableNon-Degradable

Rene

wab

lePe

troc

hem

ical

Bioplastics Possible zone

Conventional Plastics

Biodegradable

Biobased andBiodegradable

Based on RenewableMaterials

Cellu

lose

Ace

tate

(CA)

Poly

mid

e (P

A)

Poly

buty

lene

Adi

pate

Tere

phth

alat

e (P

BAT)

Poly

buty

lene

Suc

cina

te (P

BS)

Poly

buty

lene

(PE

)

Poly

buty

lene

Tere

phth

alat

e (P

ET)

Poly

hydr

oxy

Alka

noat

es (P

HAs)

Poly

lact

ic A

cid

(PLA

)

Poly

prop

ylen

e (P

P)

Poly

viny

l Chl

orid

e (P

VC)

Poly

uret

hane

(PUS

)

Star

ch B

lend

s (in

pla

stic

com

poun

ds)Av

erag

e Bi

obas

ed C

onte

nt o

f the

Pol

ymer

s, %

Biobased Plastics

0

10

20

30

40

50

60

70

80

90

100

Common Bioplastics and Biobased ContentThe biobased content for various bioplastics can vary depending on the type of plastic as well as the source/manufacturer. The table below summarizes the common bioplastics and their typical biobased content.

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.

Generally, when raw materials for a plastic originates from renewable resources, such as wood or agricultural residues, the resulting material is referred to as a bioplastic. Bioplastics may or may not be biodegradable. Biodegradable plastics can also be produced from petrochemicals. Bioplastics come in many flavors. They canbe designed to be as durable as many petro- chemical plastics or to degrade under certain environmental conditions. This makes them very versatile and able to meet a wide range of industry needs.

Why Bioplastics?

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 solution is also developing novel plastics, coatings, and composites from renewable feedstocks and engineering the products to degrade at the end of life. Renewable feedstocks, that primarily contain 5- and 6-carbon sugars and aromatic polymers, are natural polymers that can yield building blocks for a variety of bio-based products. Synergistic partnerships between researchers and business communities enabled by NSF IUCRCs are critical to reduce the detrimental effects of plastics on our environment and develop fundamental knowledge regarding the mechanical behavior, processing requirements, costs, and life cycle assessment of these materials.

98

31

1 7

15

24

36

39

8

19

14

26, 42

6, 29

9

41

20

40

25

21 4323

12

34

30

24

44

1113

Collaboration

3

2

•Industry Partners†

1 3M 2 ADM 5 BASF 4 Berry Plastics Corporation 5 Boehringer Igelheim 6 Boeing 7 Branson Ultrasonics 8 Byogy Renewables, Inc. 9 CycleWood Solutions Inc. 10 Danimer 11 Diageo 12 Dixie Chemical Company 13 Dukane Ultrasonics 14 EcoProducts 15 EVOLVE GOLF 16 Ford 17 Futamura 18 Hyundai 19 Idaho Forest Group, LLC 20 Inland Packaging 21 John Deere 22 Kimberly-Clark 23 Laurel Biocomposite 24 Minnesota Corn Research 25 GC Innovation 26 Natural Soy Products 27 NatureWorks 28 North Dakota Corn Council 29 Northwest Green Chemistry 30 Powder Coating Research 31 Renewable Energy Group 32 RheTech 33 Rubbermaid 34 RWDC 35 SealedAir 36 SelfEco 37 Shaw Industries Group, Inc. 38 Sherwin Williams 39 Siegwerk USA 40 SuGanit BioRenewables 41 Sunstrand 42 Swamp Fox Chemical LLC 43 Taylor Technologies 44 USDA-ARS-NCAUR 45 Viskase Companies Inc.

• Faculty Members:The NSF Industry & University Cooperative Research Center program is a vehicle for encouraging formal, topical relationships between academic institutions and industry collaborators.

• Industry Members:Companies and organizations interested in bioplastics and biocomposites are invited to join CB2. Becoming a member has many advantages including leveraging research and development efforts through the center’s projects, receiving access to technologies developed by the center and having access to scientists and undergraduate and graduate students for future employment.

• Affiliate Members:In addition to its core funding from the National Science Foundation and industry members, CB2 is supported by affiliate members.

37

†All previous and current industry partners are listed.

8

1632

17

•Institution Partners 1 North Dakota State University 2 Iowa State University 3 Washington State University 4 University of Georgia

5

1022

28

27

344

35

33

2

38

4

3

18

1

10 11

Center Operations

Timeline for project selection

CB2 focuses on five research thrust areas that promote industry-wide acceptance of bioplastics and biocomposites and increase the use of sustainable materials. Each thrust area is listed below.

ResearchCenter Organization

University Policy Committee

Center DirectorDavid Grewell (ISU)

Center CoordinatorYijing Ding

Research

Faculty UGA27 Faculty ISU20 Faculty WSU

Tech Transfer & Education

Synthesis & Compounding Biocomposites Processing Biobased Products Modeling Commercialization

Site Co-DirectorVikram Yadama(WSU)

IndustryAdvisory Board

Center EvaluatorConnie Chang

NSF

12 13

This thrust area develops fundamental understanding of bioplastic synthesis and compounding, including fermentation and polymerization. This includes vegetable oil-based plastics, coatings and adhesives, biobased waxes, monomers, elastomers, poly(ester-amides), protein based plastics, sustainable approaches to advanced functional materials and polymer additives, and feedstock preparation.

SYNTHESIS AND COMPOUNDINGThrust 1

•SYNTHESIS AND COMPOUNDINGThis thrust area develops fundamental understanding of bioplastic synthesis and compounding, including fermentation and polymerization. This includes vegetable oil-based plastics, coatings and adhesives, biobased waxes, monomers, elastomers, poly(ester-amides), protein-based plastics, sustainable approaches to advanced functional materials and polymer additives, and feedstock preparation.

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.

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.

The center affiliates have a proven track record of working with member companies to successfully commercialize biobased products. Because the center offers member companies royalty-free access to intellectual property resulting from center projects, the center is well positioned for direct technology transfer from academia to industry. The center supports the development of Small Business Innovation Research (SBIR) proposals and business plans, facilitates networking, and identifies markets and potential market penetration. This allows member companies to leverage their resources and increase their profits.

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 interactive life cycle assessment software that allows users to easily analyze their current and future products.

•BIOCOMPOSITES

•PROCESSING

•BIOBASED PRODUCTS

•MODELING

•COMMERCIALIZATION

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 biobased composites.

Bioplastic synthesis pilot plant at ISU

Illustration of asperity peak squeeze flow

Students compounding and molding bioplastic material

14 15

Biobased Methacrylates to Replace Styrene as a Reactive Diluent in Thermoset Resins

The objective of this project was to develop low-cost biobased reactive diluents suitable for vinyl ester and vegetable oil-based composites that decrease concentrations of volatile organic compounds (VOC) including styrene, reducing emissions throughout the composite life cycle. We synthesized a range of biobased methacrylates, including methacrylated vanillin (MV), methacrylated vanillyl alcohol (MVA), and methacrylated eugenol (ME), through the reaction between methacrylic anhydride with hydroxyl groups on the biobased precursors. These reactive diluents were blended with high-viscosity thermosetting resins (both vinyl ester and vegetable oil-based resins) and cured via free radical polymerization.

Outcomes1. Successfully synthesized biobased MV, MVA, and ME.

2. Evaluated reactive diluents with CB2 member company’s maleinated acrylated epoxidized soybean oil (MAESO) resin and commercially important vinyl ester resins.

3. Characterized the volatility, viscosity, cure kinetics (gel time and curing extent), thermos-mechanical properties, mechanical properties, and thermal stability as a function of diluent content.

Accomplishments1. Significant reduction of system viscosity (over an order of magnitude) was achieved when 30 wt% of MVA was used.

2. Biobased methacrylates were shown to have great potential to serve as combined reactive diluents for MAESO and vinyl ester resins with decreased viscosity and improved thermal-mechanical properties while maintaining low VOC emission compared to that of commercial styrene resins.

Lead: Michael Kessler, Washington State UniversityStaff Scientist: Yuzhan Li, Washington State UniversityStudent: Yuehong Zhang, Washington State University

Develop Renewable Propylene Using SugarDerived 1,2-Propanediol and Glycerol

Polypropylene (PP) is the second largest polymer produced by volume, used in a wide variety of applications. At present, most of propylene is still obtained from the refining gasoline or produced by splitting, cracking, and reforming hydrocarbon mixtures. However, these processes are still based on petroleum-based feedstock, are performed at high temperatures, and require expensive noble metal catalysts. With the finite stocks of fossil resources and the growing market demand for propylene, development of alternative feedstocks for the production of propylene is an attractive solution. In this work, we developed new and more economic production methods for biobased propylene using sugar-derived 1,2-propanediol (1,2-PDO) and glycerol as feedstocks, respectively.

Outcomes1. Three-step and two-step conversion processes have been designed and fully investigated.

2. Efficient catalysts for each step within thewhole transformation process were

identified and the optimized reaction conditions have been determined, which will be the fundamental data for future scale-up processes.

Accomplishments1. Highly pure propylene was produced with yields higher than 90% based on the whole conversion process.

2. Technical economic analysis (TEA) was initially conducted to predict the production costs of these two conversion processes. The price of renewable propylene produced using our processes is comparable with that of petroleum-based propylene in the marketplace.

Lead: Junna Xin, Washington State University

16 17

PEN Polymers – Next Generation Bottles and Packaging Materials

Poly(ethylene 2,6-naphthalate) (2,6-PEN) exhibits higher dimensional stability, shrinkage resistance, temperature stability and better barrier properties than polyethylene terephthalate (PET). The excellent barrier properties of PENs make them attractive materials for packaging. Unfortunately, limitations on monomer availability and cost significantly affect the commercial expansion of 2,6-PEN, prepared from the oxidation of 2,6-dimethylnaphthalene. Drs. Kraus and Cochran are evaluating structure/function of PENs with the aim to maximize performance and minimize costs of synthesis. While these polymers will initially be more expensive than polymers derived from terephthalic acid, they are expected to exhibit excellent barrier properties and superior mechanical properties and therefore will have applications where PET is less effective or even not usable.

Outcomes1. In 2015 there were 5,971,000,000 pounds of PET bottles sold into the US market.

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.

3. PENs are expected to open up many new markets in the bottling and packaging industries because of their excellent barrier properties and superior mechanical properties.

Accomplishments1. Synthesized three monomers with biobased feedstocks

2. Developed protocols of monomer purification and polymerization

3. Synthesized three new polymers + 2,6-PEN

4. Demonstrated that biobased PEN has a melting temperature > 300 ° C for 2,7 PEN

5. Evaluating potential for value-added properties such as barrier performance through copolymerization with PET

Leads: George Kraus, Eric Cochran, Iowa State University

Glycerol-Based Thermoplastic Elastomers

Our group is interested in the synthesis and characterization of heterogeneous block copolymers and polymer nanocomposites for applications ranging from asphalt modification to adhesives to improved performance biomaterials. Our research team discovered synthetic routes to non-cross linked thermo plastics and thermoplastic elastomers derived from vegetable oils.

We are currently investigating the use of other renewable feedstocks, such as glycerol, as potential replacements for petrochemically derived monomers in specialty polymers, for example biobased, pressure-sensitive adhesives.

Outcomes1. Synthesis of glycerol-based, non-cross linked thermoplastic elastomers.

2. Formulations to produce tackifier-less, pressure sensitive adhesives from renewable feedstocks.

Accomplishments1. Production of glycerol-based, pressure sensitive adhesives with mechanical properties comparable to petroleum-based adhesives.

2. Synthesis of novel transfer agents facilitating the polymerization of triblock copolymers that will improve the mechanical properties of the biobased adhesives.

Lead: Eric Cochran, Iowa State University

18 19

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 biobased composites.

BIOCOMPOSITES

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

Our group is currently performing synthesis and characterization of long-chain unsaturated bioadvantaged Nylon copolymerized with Nylon 6,6. Our research team has found that the incorporation of relatively small amounts of C16:1 Diacid substitution can have dramatic effect on the toughness with minimal negative impact on the strength of the material.

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.

Outcomes1. Synthesis of bioadvantaged Nylon from C16:1 bio-diacids2. Development of mechanically superior Nylon 6,6

Lead: Eric Cochran, Iowa State UniversityStaff Scientist: Michael ForresterUndergraduate Students: Peter Meyer & Nicholas Bloome

AccomplishmentsProduction of Nylon 6,6 with nearly a threefold increase in toughness while retaining >90% of its strength

20 21

Mechanochemically Activated and/or Functionalized Cellulose Powders and Their Reinforced Plastic Composites for Higher Demanding Applications

Cellulose fiber and nanocellulose have the potential for a variety of new applications. However, difficulties in achieving a proper dispersion and a strong interface with the matrix polymer prohibit the realization of this potential. In this research, we hypothesize that wood pulps, composed primarily of cellulose, can be subjected to mechanochemical activation with selected chemicals to prepare surface activated and/or functionalized cellulose powders for reinforcements.

OutcomesThis project evaluated the activation of hydroxyl groups and reducing-end groups on cellulose powder surfaces through the use of a lab-scale planetary 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.

3. Development of techniques and tools for analysis, visualization, and dissemination of different aspects of the research project.

Accomplishments1. Development of solvent-free chemomechanical processes to simultaneously pulverize, activate, and functionalize wood pulp, producing property-tuned meterable cellulose powders.

2. Production of cellulose powders-reinforced polypropylene composites with improved physico-mechanical features.

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

Production of Low-Cost Carbon Fiber from Heavy Fraction of Fast Pyrolysis Bio-Oil

Lead: Xianglan Bai, Iowa State University

Lignin is a promising precursor of low-cost carbon fibers. However, the mechanical properties of carbon fibers produced from melt-spinning of raw lignin are poor, restricted by the randomly cross-linked polymer structures of lignin. In this project, pyrolytic lignin, which is a depolymerized lignin that consists of phenolic monomers and oligomers, was used as the starting material to produce carbon fiber. By repolymerizing the pyrolytic lignin, the modified precursor with improved quality can be obtained.

Outcomes1. Pretreated pyrolytic lignin is turned intoa melt-spinnable carbon fiber precursor withlower glass transition temperature.

2. Carbon fibers with maximum tensile strength of 1040 MPa and modulus of 112 GPa are obtained.

Accomplishments1. Production of carbon fiber from low-costbiorenewable feedstock.

2. A new approach to modify the intrinsic molecular structure of lignin to improve the quality of carbon fibers.

22 23

Lead: Birgitte Ahring and Amir Amelli, Washington State UniversityPostdoctoral Fellows: Jinxue Jiang and Keerthi Srinivas, Washington State University Student: Nahal Aliheidari, Washington State University

Production of Low-Cost Lignin Composite Materials Using Biorefinery Lignin

Carbon fibers form an essential component in automobiles and airplanes, increasing fuel efficiencies and mechanical strength. The increased cost of carbon fibers, however, significantly affects the final product. Our group focuses on research related to the sustainable conversion of lignocellulosic biomass to biofuels and bioproducts and we have been working on modifying the biorefinery lignin stream as a low-cost compound for in-mixing with polyacrylonitrile (PAN). This will reduce the cost of carbon fibers with minimal impact on strength. We use biorefinery lignin, which is highly methoxylated during the upfront pretreatment process that is used to remove carbohydrates from the lignin. These changes make it a better substrate for in-mixing with PAN when compared to commonly available lignins such as Kraft lignin. In this process, the modified lignin (using esterification to increase hydrophobicity) was chemically fused with the PAN through melt spinning to produce carbon fibers with minimal reduction in mechanical characteristics.

Outcomes1. Production of PAN-lignin blends using melt spinning process for further conversion to carbon fibers.

2. Increased in-mixing of PAN-lignin at melt spinning conditions through modification of lignin (by esterification) and using plasticizers without significant impact on mechanical strength.

Accomplishments1. Production of PAN-lignin blends up to 30 wt% in-mixing with mechanical properties similar to those of pure PAN used in carbon fiber production.

2. Melt spinning of PAN-lignin blends using ionic liquid as plasticizer that will facilitate chemical interaction between PAN and lignin, resulting in better lignin-based carbon fibers than currently reported in the literature.

Development of Lignin Thermoplastic Composites

Lead: Reza Montazami, Iowa State University

Biobased composites with mechanical and chemical properties comparable to those of petroleum-based counterparts have considerable economic and environmental advantages. This project investigated the use of a wide range of bio-fillers in combination with petroleum-based matrix polymers to explore the potential of biobased composites that can serve as a one-to-one drop-in for traditional plastics at industrial scale.

Outcomes1. Established the limits of bio-filler content in polymer matrices.

2. Gained an understanding of filler-matrix chemical bonding.

3. Determined mechanical and thermal properties of the resultant biobased composites.

4. Proven economic advantages of the biobased composites using cost analyses.

Accomplishments1. Developed decision-making tools to determine filler type, filler content, and type of polymer matrix to obtain target mechanical properties.

2. The developed knowledge platform facilitates design and manufacturing of parts with biobased composites.

24 25

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.

Thrust 3

PROCESSING

26 27

Odor Control in Agave Fiber-Polypropylene Biocomposites

While biobased plastics provide an environmentally friendly and cost-effective alternative to petroleum-based plastics and are establishing a new consumer-driven market, some challenges still exist in realizing their full integration with consumer goods. One major challenge is the odor of biobased materials. The odor, typically caused by impurities and not inherent to the biomaterials, is conveyed to biocomposites containing bio-fillers and consequently makes them unsuitable for many applications. This project focused on the development of a low-cost and scalable process and formulation for mitigating and eliminating such odors in agave fiber-based composites.

Outcomes1. Developed a scalable process for mitigation of odors in agave fiber composites.

2. Measured the impact of pre-processing conditions of mechanical properties of the biobased composites.

Accomplishments1. Fabricated agave fiber-based polymer composites with no noticeable odor and improved mechanical properties.

2. Developed complete set of preprocessing conditions and formulation for odor-free agave-fiber polymer composites.

3. This is a process that can be adopted for otherbio-fillers.

Lead: Reza Montazami, Iowa State University

Chitin Nanofibers and Chitin Esters: Preparation, Characterization, and Their Transparent Nanocomposite Films and Coatings

Chitin is an abundant biopolymer in nature and can be extracted economically from leftover shells from lobsters, crabs, and shrimp consumed by humans. Chitin in commercially available powder form does not dissolve in water and most common organic solvents, making it difficult to be processed into products industrially. Making chitin dispersible or soluble can increase the scope and value of its applications leading to value-added products and additional revenues for the fishing industry, which in turn decreases the cost of crustacean products.

Outcomes1. Developed mechanochemical methods to convert chitin into chitin nanofibers that can be dispersed uniformly and stably into water and water-based coating systems.

2. Developed methods to convert chitin into chitin esters that can be dissolved in several commercially important organic solvents.

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

Accomplishments1. Demonstrated the potential of chitin nanofibers and chitin esters in applications ranging from inks and films to composites.

2. Used as rheological modifiers or reinforcing additives in water-based or solvent-based ink or coating systems, or as oxygen barrier layer in packaging films.

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

Lead: Jinwu Wang, Michael P. Wolcott, and Hang Liu, Washington State UniversityPostdoctoral Fellow: Tuhua Zhong, Washington State University

28 29

Thermoplastic Starch-Based Thin Films withPolyacrylated Glycerol as Plasticizer

Few biobased thermoplastic materials can successfully compete with their petroleum counterparts, in large part because of a lack in understanding of the fundamental properties of the materials. The use of thermoplastic starches (TPS) has suffered from their inability to maintain 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.

Outcomes1. Developed thermoplastic starch formulations to make films suitable for packaging materials. 2. Improved the water resistance of thermoplastic starch by functionalizing starch.

Accomplishments1. PAG copolymer had 2,000x the ductility of unmodified TPS.

2. Developed functionalized thermoplastic starch resulting in increased moisture resistance.

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 system is a web-based interactive life cycle assessment software that allows users to easily analyze their current and future products.

BIOBASED PRODUCTS

Thrust 4

30 31

Improving Thermoplastic Properties of Starch

Utilizing starch for bioplastic-related applications, i.e., films, adhesives, and molded products among others, requires understanding of the factors that turn it into thermoplastic polymer during extrusion. Factors such as starch composition and structure, plasticizer, temperature of extrusion, moisture content, and nature of blending materials affect resulting starch and film properties. This study investigated those factors, understanding of which allows scientists, designers, engineers, and manufacturers to consider starch for various biobased applications.

Outcomes1. Starch-based cast films were prepared to optimize film formulations and ingredient interactions for desirable film properties.

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.

Accomplishments1. The outcomes allowed stakeholders to produce starch-based films with specific properties.

2. Adding nanomaterials, including biodegradable nano-biofibers, was shown to increase mechanical and barrier properties of starch films.

Lead: Buddhi Lamsal, Iowa State University

Biobased VOC-free Powder Coating Resin Systems

Powder coating has attracted increasing attention in recent years, as it is environmentally friendly and virtually pollution-free. Powder coatings represent more than 15% of the industrial coatings market and is predicted to continue to grow. Current powder coatings, like many other polymer materials, are entirely based on petrochemical feedstocks. We have made a significant effort to develop alternative biobased powder coatings using renewable chemical feedstocks such as rosin acid and dipentene.

Outcomes1. Understanding the design space and limitation of some renewable feedstock for powder coating applications.

2. Introducing promising biobased powder coatings and potential applications.

Accomplishments1. Developed chemical structures and synthesis methods of rosin-derived epoxy powder coatings and rosin-derived curing agents for polyester powder coatings.

2. Determed curing behavior and fundamental performance.

Lead: Jinwen Zhang, Washington State University

32 33

Fully Biobased Degradable Plastic with Insecticide Functionality

The rise of Zika and other insect driven viruses are becoming an epidemic that has been directly impacted by climate change. This is driving a market need for a product that is able to not only prevent insects but also reduce the effects of the spread of these insects. The goal of this project is to develop biodegradable fibers with insecticide functionality for protective garments. Poly (lactic acid) (PLA) is one of the most promising biopolymers able to replace the petroleum-derived polymers for industrial applications. The natural insecticide, pyrethrum, and the repellent DEET were added to a polylactic acid (PLA) fabric via extrusion and spraying. GPC analysis showed that the addition of DEET caused an increase in depolymerization with the increase in DEET concentration. Contact Irritancy Assay (CIA) showed that DEET-treated PLA fabric caused the lowest percentage escape response with an escape frequency of 33.3 ± 3.3%.

This was followed by the extruded natural pyrethrum-treated PLA fabric with an escape frequency of 80 ± 6.3%. Finally, the PLA fabric spray-treated with natural pyrethrum caused an escape frequency of 98.3 ± 1.7%. All treated fabrics caused repellency.

Outcomes1. Compounding of synthetic and natural insect replants with PLA2. Extrusion of compounds into fiber3. Testing mosquito repellency of various fabrics

Accomplishments1. Demonstrated the possibility of compounding synthetic and natural insect repellents with PLA2. Produced fabrics from compounded plastic3. Demonstrated the effectiveness of the various fabric against mosquitosh standardized material characteristics for product design.

Lead: Chunhui Xiang, Iowa State University

Student: Cindu Annandarajah, Iowa State University

Effectiveness and Nutrient Tracking of Biopolymer Horticultural Systems

The extensive use of petroleum-based plastic pots (containers) and synthetic fertilizers in horticulture provides unparalleled effectiveness, but this effectiveness is achieved through heavy consumption of finite fossil resources and with a disproportionate impact on the environment. We evaluated the effectiveness and nutrient efficiency of emerging biopolymer horticultural systems that utilize containers made of biorenewable polymers that provide nutrients to plants by using protein-based biopolymers without synthetic fertilizer.

Outcomes1. Biopolymer horticultural systems were found to be effective and suitable for providing fertilizer nutrients to plants grown in containers and in garden soil.

2. The nutrient efficiency of biopolymer horticultural systems equaled or exceeded the efficiency of synthetic controlled-release fertilizer.

Accomplishments1. Biopolymer horticultural systems are a promising alternative to petroleum-based plastic containers and synthetic fertilizers.

2. Our results demonstrate that they can provide similar functionality, with greatly improved sustainability.

Lead: James Schrader, Iowa State University

34 35

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.

MODELING

Thrust 5

36 37

Development of Life Cycle Assessment Tool for Screening of Trade-offs Among Processing Costs, Environmental Impacts, and End-of-Life Options

Costs and environmental performance of plastics continue to be topics important to both industry and consumers. Our research has focused on life-cycle assessments (LCA) and techno-economic analyses (TEA) in order to understand material and processing costs and environmental impacts of using various fillers in polylactic acid (PLA) composites. We have examined organic fillers such as DDGS, flax, hemp, rice husks, and wood, and compared these against common inorganic fillers such as glass and talc.

Outcomes1. Our work has quantified costs, emissions, and en-ergy intensities associated with raw materials acquisi-tion, processing, transport, and end-of-life treatments.

2. Environmental impacts have included global warming potential, air acidification, air eutrophica-tion, water eutrophication, ozone layer depletion, air smog, carcinogens, and noncarcinogens.

Accomplishments1. Overall we found that use of organic fillers results in lower costs and environmental impacts compared to use of inorganic fillers.

2. This research has shown that utilizing landfill as end-of-life treatment for glass-filled components can be the most environmentally harmful option and resulted in the highest cost.

3. Alternatively, both DDGS and wood filler composites paired with recycling end-of-life treatment were shown to have the lowest environmental impacts and the lowest cost of all PLA composites considered.

Results  -­‐‑ TEA

1

Glass Talc DDGS Flax Hemp Rice  Husks WoodRecycling 9 8.8 8.68 8.78 8.77 8.71 8.68

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

Landfill  +  Methane  Ext. 10.6 10.3 9.82 10.1 10 9.9 9.81

No  End  of  Life  Treatment 10.6 10.1 9.82 10.1 10 9.91 9.82

0

2

4

6

8

10

12

$/k

g

O VE RA LL  CO ST  ($/ KG)  P ER  PART  [0 .01 KG  PA RT  W E IGHT,  100 ,000  KG  L O T  S IZE ,  P L A]

• Overall  Cost  Includes:  material  acquisition,  compounding,  processing,  and  end  of  life  treatment  costs

• Sensitivity  analysis  shown  below:  processing  costs  are  compared  from  published  filler  material  cost  (low  to  high)    

Interfacial Healing of Biopolymers

Interfacial healing of bioplastics is critical in primary processing, such as weld line (net line) formation in injection molding or in secondary operations such as welding and sealing of bioplastic components. Understanding how these novel materials join together provides designers, engineers, and manufacturers with the fundamental knowledge they need to produce biobased, sustainable materials with high quality and consistency that meet the demands of industry.

Outcomes1. This project measured the activation energy of auto-adhesion of several grades of Polylactic acid (PLA) to allow the prediction of healing of PLA interfaces.

2. Transient models based on first order principles were used to predict heat generation in welding and, coupled with finite element models, temperature fields in various welding processes.

Accomplishments1. The outcomes allow designers, engineers, and manufacturers to predict healing of bioplastic interfaces for the sustainable manufacture of plastic products.

2. The coupled models facilitate the production of parts via primary and secondary processes with enhanced quality and consistency. This knowledge gives manufacturers the confidence to utilize novel sustainable materials.

Lead: David Grewell, Iowa State University

Lead: Kurt A. Rosentrater, Iowa State University

1

8600000

8800000

9000000

9200000

9400000

9600000

9800000

kgCO

2eq/kg

PLA -­‐ Incineration   -­‐ GWP  Comparison,   0.01 kg  Part  Weight

Glass Talc DDGS Flax Hemp Rice  Husks Wood

0

500000

1000000

1500000

2000000

2500000

3000000

3500000

4000000

kgCO

2eq/kg

PLA -­‐ Incineration   -­‐ GWP Comparison,   0.1 kg  Part  Weight

Glass Talc DDGS Flax Hemp Rice  Husks Wood

0

500000

1000000

1500000

2000000

2500000

3000000

3500000

kgCO

2eq/kg

PLA -­‐ Incineration   -­‐ GWP Comparison,   1 kg  Part  Weight

Glass Talc DDGS Flax Hemp Rice  Husks Wood

Results  -­‐‑ LCA

3938

Product Outcomes• Agave Fiber Composites

The team worked with Ford Motor Company, Hyundai Motor Group, Diageo, and ARaymond to develop a biobased composite that had superior strength, weight properties, and LCA benefit compared to traditional composites, allowing the automotive industry to manufacture more efficient vehicles and upvaluing coproducts (agave fibers) from the adult beverage industry.

• Multifunctional Biobased Pots

CB2 related projects were instrumental in developing and commercializing a novel pot design for growers. The pots are:

1. Fully biobased2. Degradable3. Self-fertilizing with no petrochemical fertilizer

additions4. 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.

40 41

Research Experience for 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 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 for an independent research project performed with state-of-the-art equipment and facilities, and engage with leading industry experts from the Industrial Advisory Board of the CB2.

Industry contributions leveraged to make a difference

ndsu.edu/centers/cb2

Funded Projects39 Funded Projects valued at over

Workforce Training

Trained postdocs, undergraduate and graduate students

Impact

8 26$2M

Invention Disclosures & Patent Applications

2Bio-basedproducts

brought toproduction

7 100+36+

Theses & Dissertations

44Publications,Book Chapters,& Presentations

Research

A�liates from 4 universities

Industry A�liates

42 43

University of Texas A&M

LeTourneau University

University of Tennessee

Washington State University

University of Montana University of Minnesota

Iowa State University

Bowling Green State University

Stevens Institute of Technology

Stony BrookUniversity

The Pennsylvania State University

1

2

7,13, 15

5, 16 6

3, 28

11, 12, 22, 29

8

410

9

1- Nathan Glandon 4- Daniel Fortino 7- Samantha Trimble 10-Nicholas Van Nest

2- Jacob Bowen 5- Daniel Vincent 8- Anna Treppa

3- Aleesha Slattengren 6- Amelia Cantwell 9- Ryan Funk

11- Mason Moeller

2017 Research Experience Undergraduate (REU) students

12- Ana Miller 15- Hana Gouto 18- Christina Verdi 21-Edgar Varela

13- Jose Velasco 16- Samuel Bigbee-Hansen

19- Andrew Freiburger

14- Zachary Gotto 17- Shelby Bicknell 20- Lexington Peterson

22- Riley Behan

2018 Research Experience Undergraduate (REU) students

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

33- Ian DeBois

25- Alan Ramirez 28- Anna Mikkelsen 31- Thomas Ekstrom

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

2019 Research Experience Undergraduate (REU) students

23- Roman Amorati

34- Kyleigh Rhodes

Boise State University30

University of Michigan

34

South Dakota School of Mines and Technology

32

California State Polytechnic University, Pomona

33

Seattle University

31

Colorado State University - Fort Collins

30

North Carolina State University

University of California, Merced

25

St. Augustine’s University

2418, 26Pittsburg State University

17, 20

Grand Valley State University

19

34

University of Colorado Boulder

University of Wisconsin Platteville

14

The Ohio State University23

4544

Current Industry Members

4746

Notes Affiliate Members

Department of Agricultural and Biosystems Engineering

College of Agriculture and Life Sciences

Center for Crops Utilization Research

College of Engineering

Bioeconomy Institute

Voiland College of Engineering and Architecture

Composite Materials& Engineering Center

New Materials Institute

College of Engineering

Department of Coatings and Polymeric Materials

Department of Mechanical Engineering

Department of Industrial and Manufacturing Engineering

Center for Sustainable Materials Science

ndsu.edu/centers/cb2cb2.iastate.edu

cb2.wsu.edu