The Design of Biocomposite Materials

Chad A. Ulven, PhD Associate Professor

M echanical Engineering Departm ent
North Dak ota State University (NDSU)
Fargo, ND 58102 USA

Biopolymers & Biocomposites Workshop - August 14, 2012

Iowa State University, Ames, IA
 Biocomposite Development
at North Dakota State Univ.
Collaborators:
D. Webster, L. Jiang, D. Wiesenborn, S. Pryor, B. Chisholm, M. Sibi,
D. Bajwa, S. Huo North Dakota State University
S. McKay, S. Potter, M. Alcock, S. Meatherall Composites
Innovation Centre (CIC)
R. Plagemann, N. Ravindran Tecton Products
J. Hertsgaard, S. Geiger SpaceAge Synthetics, Inc.
J. Hogue FlaxStalk, Natural Fiber Solutions
J. Peterson AGCO Corporation
J. Dworshak Steinwall, Inc.
J. Olson, B. Briggs John Deere Co.
A. Hill Bobcat Co.
W. Welland, J. Myers - Hyundai-Kia America Technical Center, Inc.

Current NDSU Students:

J. Lattimer, B. Nerenz, S. Munusamy, J. Flynn, N. Hosseini, C. Taylor,
R. Whitacre, T. Krosbakken, B. Lisburg, & K. Luick
 Biocomposite Research
Approach at NDSU
A multidisciplinary team has been assembled focused on
improving the growth, harvesting, treatments, and
development of new agri-based precursors for processing
structural biocomposites in local and regional composite
manufacturing facilities for use in a wide range of applications
Commercial Applications
Vegetable
Proteins

Natural Fibers
Twin Screw
Extrusion

Biobased
Vegetable Oil Composite
Materials
Plant Breeding &
Processing Liquid Molding
Processing
 Motivation for Biocomposites
Research
Biocomposite materials will emerge as an important
engineering material as the technology evolves through
strong collaboration by several facets of the entire production

Plastics & University &

Composite Industry
Manufacturers Researchers

Farmers & Commodity

Processors Groups
 Biocomposite Project Areas

Short Natural Fiber Research

Utilization of waste cellulose fiber:
DDGS, sunflower hull, sugar beet pulp, oat hull, etc.
Long Natural Fiber Research
Utilization of residual flax, hemp, grasses, etc.:
Aspect Ratios (L/D) >2000
Biopolymer Development Research
Utilization of different vegetable oils, proteins, starches,
etc. as building blocks for new resins
 Biocomposites Investigated
To-Date at NDSU
*Fibers:
flax, flax shive, hemp,
sugar beet pulp,
sunflower hull, DDGS,
corn chaff, corn cob,
oat hull, etc.
*Polymers:
polypropylene,
polyethylene,
acrylonitrile butadiene
styrene, polymethyl
methacrylate, polyvinyl
*Fiber volume fractions from 5-50% chloride, nylon, vinyl
*Multitude of chemical treatments ester, epoxy,
polyurethane, etc.
 Design Approach with
Biocomposites
Provide a means for interested companies, research groups,
and other faculty to work towards developing polymer matrix
composite solutions for a wide variety of applications
Function ? Material Selection
/ Part Design
Process
Design
Recognition &
Specifications

With composites, one

must design the material
for a specific application
and/or function Prototype Creation
& Verification
Production Feasibility Study
Implementation

???
Data Sheet Generation for
Biocomposites at NDSU
 Biocomposite Project Areas

Short Natural Fiber Research

Utilization of waste cellulose fiber:
DDGS, sunflower hull, sugar beet pulp, oat hull, etc.
Long Natural Fiber Research
Utilization of residual flax, hemp, grasses, etc.:
Aspect Ratios (L/D) >2000
Biopolymer Development Research
Utilization of different vegetable oils, proteins, starches,
etc. as building blocks for new resins
 Hybridization

DDGS SFH SBP OH

Biom ass Supply Stability Hybrid Biofiller

 Hybridization Strategy

Focus on the influence constituent content has upon

the strength and modulus of a single loaded polymer

Various blends to isolate role of individual

constituents, as well as validate whether blend
hybridization is feasible
Ash Protein Lignin Cellulose Hemicellulose Starch Calcium Phosphorus Fat
(%) (%) (%) (%) (%) (%) (%) (%) (%)
Oat Hull 6.87 5.5 5.19 26.86 30.3 5.43 0.07 0.17 1.95
Sunflower Hull 2.77 4.6 21.68 42.37 16.69 0 0.17 0.1 1.7
DDGS 4.05 25.88 1.73 9.27 28.53 1.43 0.02 0.76 11.04
Sugarbeet Pulp 6.89 7.01 1.68 23.06 18.76 0 1.15 0.08 0.01
Corn Cob 3.48 2.43 4.54 30.83 34.52 5.56 0.03 0.06 0.16
Corn Chaff 0.86 11.49 1.03 8.76 25.85 39.47 0.05 0.21 3.5
*Initial study *Compounded
conducted in PP, ABS, &
with 20 w/w PP w/MAPP
 Hybridization Elastic Modulus
Potential

ABS

PP
 Hybridization Tensile Strength
Potential

ABS

PP
 Hybridization Tensile Strength
Potential with Compatibilizer

Maleic anhydride grafted PP (MAPP)

Maleic anhydride (MA) reacts with
hydroxyl groups in cellulose, forming CO
bonds
PP in MAPP co-crystallizes with matrix PP

PP with MAPP
 Predictive Model Production

Examined two filler types at 10, 20, 30 and 40 w/w

loading
Ash Protein Lignin Cellulose Hemicellulose Starch Calcium Phosphorus Fat
(%) (%) (%) (%) (%) (%) (%) (%) (%)
DDGS 4.05 25.88 1.73 9.27 28.53 1.43 0.02 0.76 11.04
Corn Cob 3.48 2.43 4.54 30.83 34.52 5.56 0.03 0.06 0.16

5 base polymer matrices:

Polypropylene (PP)
with and without MAPP compatibilization
Linear Low Density Polyethylene (LLDPE)
with and without MAPE compatibilization
Acrylonitrile Butadiene Styrene (ABS)
Poly(methyl methacrylate) (PMMA)
Polylactide (PLA)
 Elastic Modulus Model

Where Ec,ideal is a modified version of Einsteins linear predictive single

phase model, and Ec,FP is the change in modulus due to fat and protein
content

where d is a function of the

matrix elastic modulus

and

where FP is the combined fat

and protein content
 Modulus Model Fitting

ABS PMMA

PLA
 Modulus Model Fitting -
Polyolefins

PP LDPE
 Strength Fitting Model
Development

Most promising modeling approach is a hyperbolically

modified exponential model developed by Puknszky et
al. out of Budapest University of Technology and
Economics

Relies upon an empirical constant, B, which is used to

adjust (without any direct correlation) for interfacial
adhesion, particle surface area, and particle density
Adjustment of this constant allows the model to be tailored to
make adequate fits on nearly all of the biobased specimens
However the constant can not be predictably determined easily
 Strength Model Development

B inherently must be tied to empirical

measurements, however it can be modified to
adjust for any given lignocellulosic filler

for non-modified

for compatibilized
where Cell is the cellulose content

These yield final equations which, when applied to

the exponential model, can be used to predict for
any change in filler type after
 Tensile Strength Model Fitting

ABS PMMA

PLA
 Tensile Strength Model Fitting -
Polyolefins

PP

LDPE
 Torrefaction Strategy

Torrefying biomass for storage or energy purposes is not

a new concept...
However, torrefying biomass for the purposes of high
temperature biocomposites is new.
Allows us to compound biomass into Nylon, ABS, PS, etc.
Flexural Property Results: TFS
Heat Deflection Temperature:
TFS
Moisture Uptake: TFS
 Biocomposite Product Trials
To-Date
Biocomposite materials from NDSU are being/have been
evaluated by different molding facilities throughout the U.S.
Mellet Plastics, Fargo, ND
Steinwall Incorporated, Coon Rapids, MN
General Pattern, Blaine, MN
Falcon Plastics, Brookings, SD
Great Plains Plastic Molding, Fargo, ND
*Trial structural step parts produced with NDSU
biocomposite material by Great Plains Plastic Molding
 Biocomposite Trial:
John Deere Company
Developing biocomposite injection molded
handles for John Deere tractor equipment
Steinwall, Inc. is the molder for several
John Deere parts (35,000 lb/yr)

The latest trial

incorporated
30wt% ag filler
in polypropylene
 Biocomposite Trial:
Shur-Co
Falcon Plastics (Brookings, SD)
currently molds the Shur-Co
(Yankton, SD) handle out of
Nylon 6,6 (5,000 lb/yr)
These handles are used on a
variety of roll-tarp applications
for agricultural transportation
equipment
The handle must be impact
and weather resistant as well
as self-lubricating to rotate
over a metallic central core

Handles have been molded

and are now being tested for
performance and endurance
 Biocomposite Trial:
Bobcat Company
Developing and analyzing biocomposite
material solutions to existing and future
Bobcat skid steer loader equipment
Role in the Collaboration
Identify candidate
biocomposite material
applications
Develop biocomposite
formulations for interior
applications
Perform physical tests on
biocomposite materials and
designs for verification
Prototype biocomposite parts
for field testing
 Hyundai Project

Meetings with Hyundai have generated a high level of

interest.
The Composites Innovation Centre (CIC) of Winnipeg, MB,
Canada is managing the project.
A target part has been identified and we are currently
formulating two biocomposite materials for trial.
 Biocomposite Project Areas

Short Natural Fiber Research

Utilization of waste cellulose fiber:
DDGS, sunflower hull, sugar beet pulp, oat hull, etc.
Long Natural Fiber Research
Utilization of residual flax, hemp, grasses, etc.:
Aspect Ratios (L/D) >2000
Biopolymer Development Research
Utilization of different vegetable oils, proteins, starches,
etc. as building blocks for new resins
 Biocomposite Trial:
AGCO Corporation
Development of Sprayer Boom Tip Prototypes
lightweight
sprayer booms 10 ft Composite Boom

10 ft Steel Boom

30 Boom Design in FEA

Less Soil Compaction

Improved Fuel
Economy
Longer Spans
Corrosion Resistant
Biocomposites Strategy for
Pultruded Composites
 Hybridization of Long Fiber
Biocomposites

Layer Areal Fiber volume fractions

Layer Thickness (%)
Lay-up Density
(mm)
(g/m2) Flax:Carbon
Carbon Fiber Flax Fiber
Carbon fiber 0.48 448 Weight Ratio
Flax fiber 1.03-2.54 320-972 0.5:1 24 15
1:1 17 21
Carbon Fiber 0.48 448
1.5:1 12 24
Flax Fiber 1.03-2.54 320-972 Plain Carbon 52 0
Carbon Fiber 0.48 448 Plain Flax 0 29

Carbon Fibers

Flax Fibers
 Testing Results vs. Theory

Prediction of Tensile Modulus based on simple

rule-of-mixtures approach
 Additional Results

3pt Bend Flexural Results

Impact Results
 Biocomposite Project Areas

Short Natural Fiber Research

Utilization of waste cellulose fiber:
DDGS, sunflower hull, sugar beet pulp, oat hull, etc.
Long Natural Fiber Research
Utilization of residual flax, hemp, grasses, etc.:
Aspect Ratios (L/D) >2000
Biopolymer Development Research
Utilization of different vegetable oils, proteins, starches,
etc. as building blocks for new resins
 Epoxidation of Sucrose Ester
Resins
Prilezhaev reaction
Near 100% conversion of double bonds to epoxies
No side reactions
O

O O
O O
O
OO O OO O
O O
H2O2 , Acetic acid
O O O O O
O O O O
O O
O O O O
O O O
O O O O O O
O O

Amberlite 120H O

O
O
O
O O

Epoxy The average Average Epoxide Epoxide Viscosity Density

degree of molecular equivalent functionality (mPa-s) (g/cm3)
sucrose weight, MW weight, EEW per molecule
substitution (g/mol) (g/eq.)
ESL 7.7 2,700 183 15.0 8000 1.05
ESSF 7.7 2,645 230 11.6 5000 1.04
ESS 7.7 2,628 248 10.6 2200 1.02
ESSB6 6 2,048 256 8.0 5500 1.03
ESO
(Control) 3 993 231 4.3 420 0.99
 ESE Resins: A Platform
Technology

O O

O O
O

O O
O O O
O
O

O
O

O
O

O
O
O O Photo-
O

Polyols O
O

O
O
O

O
polymerization

Crosslinking
(Meth)acrylates

Thermal
Crosslinking -
Anhydrides
 Anhydride Curing of ESS
Resins

O O
O
Crosslinker:
Methyl
hexahydrophthalic
anhydride (MHHPA)

Catalyst:
N 1,8-diazabycyclo
[5.4.0] undec-7-
N
ene (DBU)
 Tensile Properties MHHPA
Cured ESS Resins

Tensile
Epoxy Epoxide/anhydride Modulus Elongation
strength
compound (equivalent ratio) (MPa) at break (%)
Epoxy Modulus Tensile Elongation Tensile (MPa)
compound (MPa) strength at break toughness (J) ESS 1:0.5 170.8 12.8 7.8 0.4 11.0 1.8
(MPa) (%) X 103
ESL 1395 191 45.8 5.4 5.7 2.6 8.44 3.5 ESS 1:0.75 595.1 8.2 21.8 1.4 6.2 1.0

ESSF 909 179 31.5 3.2 8.5 2.7 11.5 6.3 ESSB6 1:0.5 231.8 40.5 8.9 1.6 10.4 2.2

ESS 497 38 20.3 4.3 21.7 7.8 29.4 9.2 ESSB6 1:0.75 643.9 26.1 19.6 5.7 4.5 0.7
ESSB6 1002 52 35.1 3.6 5.4 0.7 9.1 3.8 ESO
1:0.5 5.0 0.16 1.2 0.1 27.9 3.6
(Control)
ESO
65 10 10.2 2.5 167 19 97 13.8 ESO
(Control) 1:0.75 97.7 28.7 6.0 0.5 28.7 5.6
(Control)
 Center for Biocomposite
Research & Engineering
To kick-start the development of the CBRE at NDSU,
$265,000 from the ND Corn Council was secured to
purchase a large, production scale twin-screw extruder and
accessories to support current biocomposite trials with JD,
Shur-Co, AGCO, Bobcat, etc.
Several other entities are being be solicited to contribute to
the CBRE for other equipment, but ND Corn Council
contribution is the seed to launch the center.
 CBRE - Pilot Plant Vision
Large Scale R&D Biocomposite Compounding Facility
5,000 sqft (Location SpaceAge Synthetics, Inc., Fargo, ND)
1-2 Technicians + Research Students (Research Funding)
Major Equipment
Biomass & Polymer Storage
Biomass Milling/Grinding
Biomass Drying/Mixing/Metering
Pressurized Conveying System
Compound Extruder w/ Pelletizer
Pultrusion Line
Natural Fiber Mat Production Line
Biocomposite Drying
Biocomposite Metering/Bagging
Dust Vacuum System
Large Air Compressor
Microwave Ashing Unit
 Acknowledgements and
Continued Partners
NDSU College of Engineering & Architecture/Mechanical Engineering
Department
Existing equipment and facilities will be included in the center
Educational and research time of interested faculty will be encouraged
NDSU College of Agriculture, Food Systems and Natural Resources/NDSU
Extension and Experiment Station
Existing Agricultural Pilot Plant facilities will closely collaborate with the center
Sharing of ag-based materials knowledge and knowhow
SpaceAge Synthetics Contribution (Fargo, ND)
Space allocation for the biocomposite pilot plant facilities
Continued collaboration regarding biobased foam and biocomposite technology
Tecton Products (Fargo, ND)
Collaboration regarding pultrusion technology for various companies
Composites Innovation Centre (Winnipeg, MB)
Continued collaboration on biocomposite development for various companies
Other existing companies we have been working with
AGCO, John Deere Co., Steinwall, Inc., Shur Co., Falcon Plastics, Inc., GVL Poly, etc.
Other commodity groups
AmeriFlax, Soybean Council, Oilseed Council, Sugarbeet Growers, etc.