BIOBIOBASED Nano/Micro BASED Nano/Micro COMPOSITE MATERIALS: COMPOSITE MATERIALS: COMPOSITE MATERIALS: COMPOSITE MATERIALS:
CHALLENGES and OPPORTUNITIESCHALLENGES and OPPORTUNITIES
Professor Lawrence T. DrzalProfessor Lawrence T. Drzal
Dept of Chemical Engineering and Materials ScienceDept of Chemical Engineering and Materials ScienceComposite Materials and Structures CenterComposite Materials and Structures Center
2100 Enginee ing B ilding2100 Enginee ing B ilding2100 Engineering Building2100 Engineering BuildingMichigan State UniversityMichigan State UniversityEast Lansing, MIEast Lansing, MI--4882448824
[email protected]@EGR.MSU.EDU
BioPolymers come from…BioPolymers come from…
SugarSugar FermentationFermentation
Future:
Lactic Acid
Mo o eMo o eFuture: Monomer Monomer ProductionProduction
LactideLactide
Polymer Polymer ProductionProductionPolymerPolymer ProductionProduction
PLA
Polymer Polymer ConversionConversion
Ref.: B. S. Glasbrenner (Natureworks) Antec 2005 Ref.: B. S. Glasbrenner (Natureworks) Antec 2005
BioBioBased Polymers Based Polymers Commercial ProductsCommercial Products Commercial ProductsCommercial Products
Poly(lactic acid)Poly(lactic acid) ‘‘Natureworks’Natureworks’ ((Cargill) & Mitsui ChemicalsCargill) & Mitsui ChemicalsStarch plasticsStarch plastics Novamont, National StarchNovamont, National StarchCellulosic PlasticCellulosic Plastic Eastman ChemicalEastman Chemical FromFromCellulosic PlasticCellulosic Plastic Eastman ChemicalEastman ChemicalBacterial polyesterBacterial polyester ‘Telles’ Metabolix‘Telles’ Metabolix--ADMADM
Aliphatic / aliphaticAliphatic / aliphatic--aromatic copolyesteraromatic copolyester
RenewablesRenewables
p pp p p yp yEaster BioEaster Bio EastmanEastmanBiomax DuPontBiomax DuPontEcoflex BASFEcoflex BASFBAK BayerBAK Bayer
FromFromPetroleumPetroleum
BAK BayerBAK BayerBionolle Showa High PolymerBionolle Showa High Polymer
Petroleum blend with Renewable ResourcesPetroleum blend with Renewable Resources FromFromSorona (DuPont)Sorona (DuPont)BioBio--based polyurethanesbased polyurethanesBioBio--based Epoxy/Polyesterbased Epoxy/Polyester
FromFromBioBio--+ Petro+ Petro
Ref. A. K. Mohanty, M. Misra, G. Hinrichsen, Macromol. Mater. Sci. Eng. 276/277, 1-24 (2002)
BioBioBased Structural Polymer Composites Based Structural Polymer Composites th M t i l f th 21 th M t i l f th 21stst C t !C t !are the Materials for the 21are the Materials for the 21stst Century!Century!
• Advantages of Bio-Based Polymers:– Biodegradable, made from renewable, sustainable Resources– Very Good processability, Good mechanical properties– Eco-friendly
• Shortcomings:• Shortcomings:– Biodegradable, Brittle, Water Sensitive, Low HDT– Thermally Degrade, inherent variability in composition,
properties, quality– primarily for textiles, packaging and disposables
• Bio-based Structural polymer composite materials have both properties and performance:
Bi C it M t i l– Bio-Composite Materials• Addition of reinforcing fibers or nanoparticles to improve mechanical,
thermal properties and durability– Control of reinforcement orientation and concentration
‘optimizes’ properties‘optimizes’ properties– Adding biobased reinforcing fibers reduces cost
REINFORCEMENTSREINFORCEMENTS
Motivation for BioFibersWeight savings
1.3
2.62
3
4
y, g
/cm
3
Cost comparison
70
6080
100120
Cen
ts/lb
.
1.3
0
1
Glass Biofiber
Den
sity
25
0204060
Glass Biofiber
U.S
. C
Energy savings
23,500
15 00020,00025,00030,000
/1 lb
. fib
er
6,500
05,000
10,00015,000
Glass Kenaf
E (B
TUs)
/
Biodegradable Biodegradable M t i lM t i l
- Mechanical PERFORMANCE- Biodegradable and Recyclable- CO2 Neutral & Sequesterization
MaterialsMaterials
2 q
BIOFIBER REINFORCEMENTS from BIOFIBER REINFORCEMENTS from BIOFIBER REINFORCEMENTS from BIOFIBER REINFORCEMENTS from PLANTSPLANTS
Non-woodBioFibers
StrawBioFibers
WoodBioFibers
CelluloseNano-whiskers
BAST LEAF SEED/FRUIT
Corn,Wheat,Rice Straw Wood
& Non-wood
Kenaf, Flax,Jute,Hemp, Cotton, Coir
& Non-woodFibers Through
AFEX
Grasses
Sisal, Henequen,
Cotton, Coir
ConiferousD idPineapple Leaf Fiber Deciduous
Hierarchical StructureHierarchical StructureBast Fiber Bast Fiber
microfibril
nanowhisker
H. L. BOS, et al., J. MATER SCI 39 (2004) 2159 – 2168
BioBioFIBERSFIBERSFLAXFLAX “Industrial” HEMP“Industrial” HEMP KENAFKENAF
COICOIRR
JUTEJUTE HENEQUENHENEQUEN
Woven Woven JUTE ClothJUTE Cloth
BioComposite Manufacturing BioComposite Manufacturing Process Requirements Process Requirements
WOODWOOD GrassGrassCorCor• Preserve BioFiber Mechanical Properties
– minimize attrition – minimize mixing degradation
P i t t 200 C– Processing temperature <200oC• High Degree of BioFiber Dispersion and
Wettability• Maximize BioFiber Volume Fraction• Control BioFiber Orientation• Control BioFiber Orientation• High Speed• Low Cost• Environmentally Benign
No organic solvent – No organic solvent – Water process or Dry process
• Low energy consumption
K f Pl t Fib /S Pl ti Bi itK f Pl t Fib /S Pl ti Bi itKenaf Plant Fiber/Soy Plastic BiocompositesKenaf Plant Fiber/Soy Plastic Biocomposites
6 2
11
9
12
MPa
)
370
2892.7
2.0250
300
350
400
th (J
/m)
2
2.5
3
n Im
pact
m
m)
Impact strengthFiber length on impact surface
2.9 3
4.65.9 6.2
3
6
Mod
ulus
(M
50
125
184
920.8
1.2
0.750
100
150
200
250
mpa
ct s
tren
g
0.5
1
1.5
ber l
engt
h on
surf
ace
(m
0
A B C D E F
A= 30% kenaf 6mm fiber/ soy composites injection molding
0.20
50
A B C D E F
Im
0 Fib
A= 30% kenaf 6mm fiber/ soy composites injection molding B= 33% Kenaf 6mm fiber/ soy compression molding C= 55% Kenaf 2mm fiber/ soy compression molding D= 56% Kenaf 6mm fiber/ soy compression molding E= 57% Kenaf 2 inch fiber /soy compression molding F= 54% Kenaf long fiber/ soy compression molding
Microfibrillated Cellulose (MFC)Microfibrillated Cellulose (MFC)Microfibrillated Cellulose (MFC)Microfibrillated Cellulose (MFC)Cellulose Nanowhiskers (CNW)Cellulose Nanowhiskers (CNW)
Di i t t dDisintegrated cellulose microfibrils - MFC
Crystalline region
Extracted cellulose
Crystalline region
Paracrystalline region
crystals - CNWs
The fringe-micelle modelA schematic of wood cell The fringe micelle model of cellulose microfibrils **
* Yamamoto, H., et al., Journal of Biomechanical Engineering, 124(2002), 432-440** Muhlethaler, Annu. Rev. Plant. Physiol., 1967, 18: 1-24
A schematic of wood cell wall ultrastructure *
Advantages of MFC and CNWAdvantages of MFC and CNW
Raw materials are abundant, cheap, and renewable
Biodegradable
High aspect ratio. Diameter from 3 to 20 nm; Length can be several g p 3 ; ghundreds of nanometers.
Large relative surface area
Less energy required in production compared with glass and carbon fibersgy q p p g
High modulus, high strength and low density
Density (g/cm3)
Tensile strength (GPa)
Young’s Modulus (GPa)
E glass fiber [1] 2.54 - 2.62 ~3.4 at 21 °C ~72.4 at 21 °C
Jute fiber [2] 1 3 1 45 0 39 0 77 13 26Jute fiber [2] 1.3 - 1.45 0.39 - 0.77 13 - 26
SiC whisker [3] 3.2 21.0 (max) 700 (max)
Cellulose nanowhisker [4]
1.5 ~10 ~150[4]
[1] Strong, Fundamentals of Composites Manufacturing: Materials, Methods and Applications, Society of Manufacturing Engineers, 1989[2] Mohanty, Misra, and Hinrichsen, Macromolecular Materials and Engineering, 2000, 276/277, 1-24[3] Kelly and Macmillan, Strong Solids, 3rd edition, Oxford University Press, New York, 1986 [4] Helbert, Cavaille, Dufresne, Polymer Composites, 1996, 17, 4, 604-611
Cellulose Micro+Nanowhiskers Cellulose Micro+Nanowhiskers Wheat StrawWheat StrawCellulose Micro+Nanowhiskers Cellulose Micro+Nanowhiskers -- Wheat StrawWheat Straw
Availability of wheat straw1.3-1.4 lb of straw per lb of wheat grain*58.7 million tons of wheat were produced in the US in 2004**627 1 million tons produced wordwide627.1 million tons produced wordwidePartial removal of straw does not hurt soil fertility
Straw as a low-cost feedstock for celluloseContains about 35-40 % celluloseIs being used for cellulosic ethanol production
MFC and CNW extraction strategy in our labMFC and CNW extraction strategy in our labPeracetic acid and alkali treatments High pressure homogenization (MFC)Acid hydrolysis, dialysis and ultrasonication (CNW)
* B.C. Saha and M.A. Cotta, Biotechnol. Prog, 2006,22, 449–453 ** Chen, et al, Appl. Biochem. Biotechnol, 2007, 142:276–290
Microfibrillated Cellulose (MFC) extracted from wheat strawextracted from wheat straw
2μm 100nm
The web-like structure of the MFC The width of the individual microfibrils is about 15 nm.
Cellulose Nanowhiskers (CNW)extracted from wheat strawextracted from wheat straw
500nm 200nm
The length and width of the extracted nanowhiskers are in the range of 100-200nm and 5-10nm respectively.
Aspect ratio: 20+, Modulus ~130 GPa, Strength ~10 GPap g
Polyvinyl Alcohol (PVOH) CompositesPolyvinyl Alcohol (PVOH) Composites
Advantages: PVOH is ater sol blePVOH is water solublePVOH is biodegradableEasy to process
DisadvantagesHygroscopic. Material properties affected by moisture content.Difficult to make bulk samples
Polyvinyl Alcohol (PVOH) CompositesPolyvinyl Alcohol (PVOH) Composites
i i Fil tiCNW suspension
S i ti
A simple solution - film casting method was used:
mixing Film-casting
PVOH water solution
Sonication
Ad tAdvantages: PVOH is water solublePVOH is biodegradableEasy to processy p
DisadvantagesHygroscopic. Material properties affected by moisture content.Difficult to make bulk samples
The thickness of the films was controlled to be approximately 100 micrometers. The films were conditioned in 20% relative humidity
Difficult to make bulk samples
Transparent Composite Films
WS-MFC / PVOH Films0% 1% 3% 5% 10%
WS-CNW / PVOH Films0% 1% 3% 5% 10%
f f % % C/ OAll films reinforced with cellulose nanowhiskers were transparent.
The 5wt% and 10wt% MFC/PVOH films were a little opaque.
WellWellDispersed MFC in compositesDispersed MFC in composites
1 wt% MFC/PVOH 3 wt% MFC/PVOH
5 wt% MFC/PVOH 10 wt% MFC/PVOH
Excellent Dispersion of CNW in CompositesExcellent Dispersion of CNW in Composites
1 wt% CNW/PVOH 3 wt% CNW/PVOH
5 wt% CNW/PVOH 10 wt% CNW/PVOH
CNW/PVOH and MFC/PVOHCNW/PVOH and MFC/PVOHPlasma etched surfacesPlasma etched surfacesPlasma etched surfacesPlasma etched surfaces
With the polymer etched away by Oxygen Plasma, the fillers are exposed ...
10 t% MFC/PVOH 10 t% CNW/PVOH10 wt% MFC/PVOH 10 wt% CNW/PVOH
Notice the network structure formed by the MFC in the polymer matrix.
The white dots - CNWs.
Wheat Straw MFC/PVOH Composites Dynamic Mechanical AnalysisDynamic Mechanical Analysis
1 0 0 0 0
1 0 0 0 0 0
MPa
)
N e a t PV O H
1 w t% M F C /PV O H
3 w t% M F C /PV O H
5 w t% M F C /PV O H
1 0 w t% M F C /PV O H 0 .3
0 .4 N e a t PV O H
1 w t% M F C /PV O H
3 w t% M F C /PV O H
5 w t% M F C /PV O H
1 0 w t% M F C /PV O H
1 0 0
1 0 0 0
1 0 0 0 0
- 4 0 - 2 0 0 2 0 4 0 6 0 8 0 1 0 0
Stor
age
mod
ulus
(M
0
0 .1
0 .2
- 4 0 - 2 0 0 2 0 4 0 6 0 8 0 1 0 0
Tan The
reinforcement effect became more significant above the
Storage modulus Tan δ
T e m p e r a t u r e ( °C ) T e m p e r a t u r e ( °C )
Wheat Straw Wheat Straw CNWCNW/PVOH Composites/PVOH Composites
significant above the Tg of the polymer.
The improvement Wheat Straw Wheat Straw CNWCNW/PVOH Composites/PVOH Composites Dynamic Mechanical AnalysisDynamic Mechanical Analysis
1 0 0 0 0 0
Pa)
N e a t P VO H1 w t% C N W /P VO H3 w t% C N W /P VO H
5 w t% C N W /P VO H 0 .3 0
0 .4 0 N e a t P VO H
1 w t% C N W /P VO H
3 w t% C N W /P VO H
5 w t% C N W /P VO H
1 0 w t% C N W /P VO H
of the storage modulus was much greater for the MFC filled PVOH than for
1 0 0
1 0 0 0
1 0 0 0 0
Stor
age
mod
ulus
(MP 1 0 w t% C N W /P VO H
0 0 0
0 .1 0
0 .2 0
Tan
Del
ta
1 0 w t% C N W /P VO H filled PVOH than for the CNW filled PVOH films.
1 0 0-4 0 -2 0 0 2 0 4 0 6 0 8 0 1 0 0
Te m pe r a ture (°C)
0 .0 0-4 0 -2 0 0 2 0 4 0 6 0 8 0 1 0 0
T e m p e r atu r e ( °C )
Storage modulus Tan δ
Comparison of the storage moduli at 20 Comparison of the storage moduli at 20 °°C + 85 C + 85 °°C C Storage modulus at 20 °C
6000
70008000
9000
us (M
Pa)
Storage modulus at 85 °C
400
500
600
s (M
Pa)
240% increase
0
10002000
30004000
5000
Stor
age
mod
ul
0
100
200
300
Stor
age
mod
ulus
Neat PVOHfilm
1wt% WS-MFC/PVOH
3wt% WS-MFC/PVOH
5wt% WS-MFC/PVOH
10wt% WS-MFC/PVOH
0Neat PVOH
film1wt% WS-MFC/PVOH
3wt% WS-MFC/PVOH
5wt% WS-MFC/PVOH
10wt% WS-MFC/PVOH
Storage modulus at 20 °C Storage modulus at 85 °C
Wheat Straw MFC / PVOH
Storage modulus at 20 C
50006000700080009000
ulus
(MP
a)
Storage modulus at 85 C
400
500
600
ulus
(MP
a)96% increase
010002000300040005000
Neat PVOH 1wt% WS- 3wt% WS- 5wt% WS- 10wt% WS-
Sto
rage
mod
u
0
100
200
300
Neat PVOH 1wt% WS- 3wt% WS- 5wt% WS- 10wt% WS-
Stor
age
mod
u
film CNW/PVOH CNW/PVOH CNW/PVOH CNW/PVOH film CNW/PVOH CNW/PVOH CNW/PVOH CNW/PVOH
Wheat Straw CNW / PVOH
BioBased Materials are a Value AddedBioBased Materials are a Value AddedProduct of a BIOREFINERY
Origin Processing Refining Intermediates Products
Feedstocks
Modifiedstarches
Citric acidItaconateL i
LubricantsCoatingsPolyols
Origin Processing Refining Intermediates Products
FeedstocksCornSoyWheat
Carbohydrate
Glucose
Fermentationfeedstocks
LysineLactic acidEthanolIsosorbide
PolyolsPlasticizersThermoplasticsUrethanesP lCanola
SugarFlaxSunflower
OilsFatty acids
IsosorbidePolyestersPlastic
intermediatesBioCompositesSunflower
GrassesBiomass
GlycerolBioComposites
BioFibersBioFibersMFC & CNW
Wheat Straw Ethanol Production ResidueWheat Straw Ethanol Production ResidueWheat Straw Ethanol Production ResidueWheat Straw Ethanol Production Residue
Cellulosic Ethanol from Wheat StrawCellulosic Ethanol from Wheat Straw Fuel from a waste instead of from foodAmmonia Fiber Expansion (AFEX) pretreatment at MBI and MSUAt 50-60% glucan conversion, what can we do with the rest of the cellulose in the residue ?
Possible applications of the fermentation residueBurnt to produce thermal energyBurnt to produce thermal energyPyrolysed to produce organic acids and other chemicalsProcessed into fertilizer or animal feed, etc.A possible cheap feedstock for MFC and CNWs ?
Ongoing effort of extracting MFC and CNW from the residue in our lab
Characterization of the residue (morphological and chemical)( p g )MFC and CNW extraction from the residueComposite preparation and characterization
Morphology ChangesMorphology Changes
Untreated wheat straw After Ethanol production
After being used for ethanol production, the cellular structure of the wheat straw is still largely preserved.
But the surface of the cell wall has become rougher and more heterogeneousBut the surface of the cell wall has become rougher and more heterogeneous.
MFC extracted from the residue
1μm 500nm
Surface Chemistry ChangesSurface Chemistry Changes
Raw Wheat Straw
1731
The peak at 1731 cm-1, which is characteristic of hemicellulose, disappeared.
A
AFEX+SSF Residue
1505
145814201593
More prominent peaks at 1420 cm-1, 1458 cm-1, 1505 cm-1 and 1593 cm-1, which are all characteristic peaks of
4000.0 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 650.0cm-1
lignin .
The theoretical values of O/C
O/C C1 % C2 % C3 %
Raw wheat 0.17 81.8 13.5 4.8
The theoretical values of O/C ratios for cellulose, hemicellulose, lignin and extractives are 0.83, 0.80, 0.33 and 0.04-0.12 respectively *.
straw
Residue 0.30 62.7 32.6 4.7 The untreated wheat straw is covered by extractives on the surface, while the AFEX+SSF residue has high concentration of lignin on the surface.
Opportunities…Opportunities…Plant Derived Fiber and Crop Derived PlasticsPlant Derived Fiber and Crop Derived Plastics
Biopolymer growth is expected to exceed~+25% per year over the next 3 yearsp y y
Global demand for biopolymers is forecast ~338,000 tons by 2012 with U.S. market ~$845 million
Structural composites (consumer) ~2-3 million tons by 2008 p ( ) yMarket demand for bio-based composites is being driven by:
Replace/Substitute Petroleum Based Composites Compete on a modulus, strength and impact basis p , g pRequire less energy to produce and processRenewability, Biodegradable, RecyclabilityMore competitive price structurep pGovernment / legislative tractionConsumer education & adoptionExpanded Market - Agricultural Industry p g y
Summary:Summary:yyCellulose Fibers from Plant have potential to replace Glass Fibers as Reinforcements in Polymer CompositesMicrofibrillated Cellulose (MFC) and Cellulose Nanowhiskers (CNW) from Wheat Straw have excellent mechanical propertiesmechanical properties
Stiffness, Strength Impact, Transparency
Challenges:Challenges:ggProperties of MFC and CNW after AFEX PretreatmentCost Effective Process for MCF and CNW Fibers Modification of Manufacturing Technology