Cellulose Reinforced High Density...
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Cellulose Reinforced High Density Polyethylene
Presented by
Velu Palaniyandi
M.S. Thesis DefenseAdvisors:
Dr.John SimonsenDr.Ralph Busch
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Contents
Background IntroductionObjectivesMaterials and MethodsResultsConclusionsAcknowledgements
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Source : Reinforced Plastics, Feb 2004
Background
Natural Fiber Reinforced Composites (NFRP) applications in Car Interiors
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Some More ApplicationsHeat deflection temperatureGas barrier / permeability
Packaging materialsElectrical conductivity
Electronics ,Housing appliances Flame retardancy
Source :Plastic technology ,Feb 2004
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0
20
40
60
80
100
120
140
160
E-glassHemp
Flax
Jute
Sisal
CoirCotton
cellulose nanocrysta
lDouglas F
ir
Ponderosa Pine
Stiff
ness
/Spe
cifi S
tiffn
ess(G
pa) Stiffness
Specific Stiffness
Property Comparison Among the Commonly Used Reinforced Fibers
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IntroductionWhy cellulose-reinforced thermoplastics?
Property enhancement at lower density and cost than synthetic fiber materials (glass, carbon)Non-abrasive and easily recyclable compared to inorganic fillersHigh strength to weight ratioSound abatement capabilityLow energy for processing
(6500 BTU/lb of kenaf ; 23,500BTU/lb of glass fiber)
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Matrix
σ 1
strain,ε
Fiber
εmεf =εc
Compositeσ1
σ1
decreases ε, increases E
Role of fiber and Matrix in FRP
Fiber
High stiffness
Brittle
Matrix
Medium for stress transfer
Binds the fiber togetherStress-Strain curve
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Fiber Reinforced Composite - Issues
Fiber dispersionDispersing agent
Interfacial adhesionCompatabilizer or coupling agentsSurface modification of fibers
Effect of filler on the crystallization behavior of polymer
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Compatabilizer – Function and Mechanism
CelluloseOH
OH
OH
OH
OH
Matrix
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ObjectivesTo prepare nanocrystalline cellulose with high aspect ratioTo investigate the material properties of nanocrystalline cellulose (NCC) filled high density polyethylene (HDPE)To use microcrystalline cellulose (MCC) as a model filler for NCCTo disperse MCC using a coupling agent systemTo study the non-isothermal crystallization kinetics of the filled composites
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MaterialsMatrix: High Density Polyethylene Filler
Cellulose nanocrystal from CottonMicrocrystalline cellulose (FMC Corp, NJ)
Coupling agent:MAPE (Optipak 210)
Developed by Kaichang Li’s labAKD (Aquapel 364)PMDI (Rubinate 1840)
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Experimental MethodsAmorphous region
Individual cellulose microfibrils
Crystalline regions
Acid hydrolysis
Individual crystallites
Schematic of acid hydrolysis of cellulose
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Brabender PlasticorderMelt mixing HDPE and NCC/MCC at 180 oC for 10 minMAPE (0.4 wt%) and AKD-PMDI (1.0 wt%) was added during mixing
Carver Hot pressCompression molding at 185 oC at 348.5 kPa for 10 min
Composite Preparation Method
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Mechanical testing –Sintech 1G, Universal testing machine
Flexural strength (MOR) and Flexural modulus (MOE) were measured according to ASTM D 790-02
Thermal AnalysisDifferential Scanning Calorimetry, TA Instruments DSC 2920
-Temperature range – 20-200oC- Heating/cooling rate – 5, 10, 12.5, 15oC/min
Thermo gravimetric analysis , TA Instruments, Q500
- Temperature range – 40-600oC- Heating rate –10oC/min
Composite Characterization Techniques
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Results – TEM Characterization/Mechanical Testing
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Transmission Electron Micrograph From Cellulose Nanocrystal Suspension Negatively Stained With
Ammonium Molybdate
Mag -100,000X
Diameter – 4nm
Length – 120 – 160 nm
Aspect ratio – 30-40
LAspect ratio =L/d
d
Mag -100,000X
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Flexural Strength (MOR)
20
22
24
26
28
30
32
34
-5 0 5 10 15 20 25
Wt % MCC/NCC content
MOR
(MPa
)
MCC-HDPE20
22
24
26
28
30
32
34
36
-5 0 5 10 15 20 25
Wt % MCC/NCC content
MOR
(MPa
)
MCC-HDPE
MCC_MAPE_HDPE
20
22
24
26
28
30
32
34
36
38
-5 0 5 10 15 20 25
Wt % MCC/NCC content
MO
R (M
Pa)
MCC-HDPE
MCC-AKD-PMDI-HDPE5%NCC-HDPE
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0.600
0.700
0.800
0.900
1.000
1.100
1.200
1.300
1.400
1.500
1.600
-5 0 5 10 15 20 25
Wt % MCC/NCC CONTENT
MOE
(GPa
)
MCC-HDPEMCC-MAPE-HDPEMCC-AKD-PMDI-HDPE5%NCC-HDPE
Flexural Stiffness
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1.0
1.5
2.0
2.5
3.0
3.5
4.0
0 5 10 15 20 25Wt % of MCC
Asp
ect
rati
o (
L/D
)Aspect ratio with No MAPE
Aspect ratio with MAPE
Low aspect ratio due to agglomeration
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Light Microscopy Image of the Cross Section Perpendicular to the Length
of the Samples
Mag-20x
Mag-10x
Agglomerated cellulose fibers in
5%NCC-HDPE composite
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Light Microscopy Image of the Cross Section Perpendicular to the Length
of the Samples
Mag-20x
Dispersed cellulose fibers in 5%MCC-AKD—PMDI-HDPE sample
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THERMAL ANALYSIS Differential Scanning Calorimetry/
Thermal Gravimetric Analysis
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Polymer Crystallization
Isothermal Crystallization Constant temperature processAvrami, Ozawa,Kissinger
Non- Isothermal crystallizationConstant cooling rate processSimulates real processing conditions Modified Avrami, Kissinger
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Kissinger Method –Activation Energy (Ea)
d (ln ϕ/Tp2) /d(1/Tp) = -∆E/R
ϕ– Cooling rate (ok/min)Tp – Crystallization peak temperature (k)∆E – Activation energy (kJ/mole)R- Universal gas constant (= 8.314 j/mol k)
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dQ/dT
Crystallization
Heating
Cooling
End
othe
rmic
Exo
ther
mic
High temp
High temp
Low temp
Tp
Matrix Crystallinity= ∆Hc/∆Hoc
Low temp
Melting
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RESULTS
Thermal Analysis
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Crystallization Peak TemperatureC r y s t a l l i z a t i o n p e ak t e mp e r a t u r e a t 1 0 pe r m i n
3 8 7
3 8 7 . 5
3 8 8
3 8 8 . 5
3 8 9
3 8 9 . 5
3 9 0
3 9 0 . 5
0 5 10 15 20 25
%M CC
M C C - H D P E
C r y s t a l l i z a t i o n p e a k t e m p e r a t u r e a t 1 0 p e r m i n
3 8 6
3 8 6 . 5
3 8 7
3 8 7 . 5
3 8 8
3 8 8 . 5
3 8 9
3 8 9 . 5
3 9 0
3 9 0 . 5
3 9 1
0 5 10 15 20 25
%M C C
M C C - HD P E
M C C - M A P E - H DP E
C r y s t a l l i z a t i o n p e a k t e mp e r a t u r e a t 1 0 p e r mi n
3 8 5
3 8 6
3 8 7
3 8 8
3 8 9
3 9 0
3 9 1
0 5 10 15 20 25
%M CC
M C C - H D P E
A K D - P M D I - H D P E
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Percent Matrix Crystallinity
40
45
50
55
60
65
70
75
-5 0 5 10 15 20 25
Wt % MCC
Perc
ent c
ryst
allin
ity(%
)
MCC_HDPE
40
45
50
55
60
65
70
75
80
-5 0 5 10 15 20 25
Wt % MCC
Per
cent
Cry
stal
linity
(%)
MCC_HDPE
MCC-MAPE-HDPE
40
45
50
55
60
65
70
75
80
85
-5 0 5 10 15 20 25
Wt % MCC
Perc
ent C
ryst
allin
ity (%
)
MCC_HDPE
MCC-AKD-PMDI-HDPE
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Activation Energy
MCC-HDP E
70
90
110
130
150
170
190
-5 0 5 10 15 20 25
% MCC content
Act
ivat
ion
Ener
gy (k
j/mol
e) MCC-HDPE
70
90
110
130
150
170
190
-5 0 5 10 15 20 25
% MCC content
Act
ivat
ion
Ener
gy (k
j/mol
e)
MCC-HDPE
MCC-MAPE-HDPE
70
90
110
130
150
170
190
-5 0 5 10 15 20 25
% MCC content
Act
ivat
ion
Ener
gy (k
j/mol
e)
MCC-HDPE
MCC-AKD-PMDI-HDPE
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1.00
1.10
1.20
1.30
1.40
1.50
1.60
-5 0 5 10 15 20 25
Wt %MCC
Avr
ami e
xpon
ent,n
MCC-MAPE-HDPE
AKD-PMDI-HDPE
Avrami Exponent
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0
2
4
6
8
10
12
14
16
0 50 100 150 200 250 300 350 400 450 500 550 600 650
Te mpe rature (oC)
Wei
ght l
oss
rate
(%/m
in)
20%MCC-HDPE
20%MCC-AKD-PMDI-HDPE
Derivative Thermogravimetric (DTG) Curves
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0
2
4
6
8
10
12
20 70 120 170 220 270 320 370 420 470 520 570
Temp
Wei
ght l
oss
rate
(%/m
in)
Pure Cellulose
Cellulose nanocrystal Sulfate groups
decrease onset degradation temperature
Ea=113.53kj/mole
Ea=153.1kj/mole
(oC)
Derivative Thermogravimetric (DTG) Curves
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ConclusionsCoupling agents increase strength.Fillers alter nucleation behavior PMDI-AKD increases crystallinity.PMDI-AKD changes the activation energy and peak crystallization temperatureDegradation behavior of the composite is not altered in the presence of compatabilizer.Grafted sulfate groups decreases the activation energy and onset degradation temperatureThe concept of compatabilizer systems can be extended to nanocomposites
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AcknowledgementsThis project was funded by a grant from the USDA National Research Initiative Competitive Grants ProgramAdvisors
Dr.John SimonsenDr.Ralph Busch
Committee membersDr.Joe KarchesyDr.Sundar V.AtreDr.Jeffrey K.Stone
Thanks to my colleagues in my group and to folks in WSE dept