polyurethane in composites presentation at sandia...
TRANSCRIPT
![Page 1: Polyurethane in Composites Presentation at SANDIA …energy.sandia.gov/wp-content//gallery/uploads/2A-B-4-Younes1.pdf• R Ratio = 0.15 • Frequency = 3 Hz P. Interlaminar Fracture](https://reader031.vdocuments.us/reader031/viewer/2022012923/5ac091527f8b9a357e8ba48d/html5/thumbnails/1.jpg)
Polyurethane in Composites
Presentation at SANDIAMay 31, 2012Usama Younes
![Page 2: Polyurethane in Composites Presentation at SANDIA …energy.sandia.gov/wp-content//gallery/uploads/2A-B-4-Younes1.pdf• R Ratio = 0.15 • Frequency = 3 Hz P. Interlaminar Fracture](https://reader031.vdocuments.us/reader031/viewer/2022012923/5ac091527f8b9a357e8ba48d/html5/thumbnails/2.jpg)
DOE project Objectives
• Carbon Nanotube Reinforced Polyurethane Composites for Wind Turbine BladesDOE Award Number DE-EE0001361
1. Determine if polyurethane based composites offer performance advantages over incumbent materials (epoxy, vinyl ester) used in the manufacture of wind turbine blades.
2. Determine if carbon nanotubes can be used to strengthen both incumbent and experimental polyurethane systems.
![Page 3: Polyurethane in Composites Presentation at SANDIA …energy.sandia.gov/wp-content//gallery/uploads/2A-B-4-Younes1.pdf• R Ratio = 0.15 • Frequency = 3 Hz P. Interlaminar Fracture](https://reader031.vdocuments.us/reader031/viewer/2022012923/5ac091527f8b9a357e8ba48d/html5/thumbnails/3.jpg)
Challenges
• Polyurethane– Speed of Reaction– Viscosity– Moisture Sensitivity
• Carbon Nanotubes– Dispersion– Re-agglomeration– Viscosity
![Page 4: Polyurethane in Composites Presentation at SANDIA …energy.sandia.gov/wp-content//gallery/uploads/2A-B-4-Younes1.pdf• R Ratio = 0.15 • Frequency = 3 Hz P. Interlaminar Fracture](https://reader031.vdocuments.us/reader031/viewer/2022012923/5ac091527f8b9a357e8ba48d/html5/thumbnails/4.jpg)
Resins
Epoxy Vinyl ester Polyester Polyurethane
PU RTM PU/Soy
![Page 5: Polyurethane in Composites Presentation at SANDIA …energy.sandia.gov/wp-content//gallery/uploads/2A-B-4-Younes1.pdf• R Ratio = 0.15 • Frequency = 3 Hz P. Interlaminar Fracture](https://reader031.vdocuments.us/reader031/viewer/2022012923/5ac091527f8b9a357e8ba48d/html5/thumbnails/5.jpg)
PU Development
• Developed two PU systems specifically designed for Wind – Conventional– Soy based
• Low viscosity • Long gel time >2 hours• Infusion time >50 minutes• Compared performance with Epoxy and Vinyl Ester Composites
![Page 6: Polyurethane in Composites Presentation at SANDIA …energy.sandia.gov/wp-content//gallery/uploads/2A-B-4-Younes1.pdf• R Ratio = 0.15 • Frequency = 3 Hz P. Interlaminar Fracture](https://reader031.vdocuments.us/reader031/viewer/2022012923/5ac091527f8b9a357e8ba48d/html5/thumbnails/6.jpg)
• Why Soy?– Adds renewable content to the PU– Reduces moisture sensitivity of the system
• Synthesized a new soy polyol– Viscosity; Reactivity
Soy based polyols
![Page 7: Polyurethane in Composites Presentation at SANDIA …energy.sandia.gov/wp-content//gallery/uploads/2A-B-4-Younes1.pdf• R Ratio = 0.15 • Frequency = 3 Hz P. Interlaminar Fracture](https://reader031.vdocuments.us/reader031/viewer/2022012923/5ac091527f8b9a357e8ba48d/html5/thumbnails/7.jpg)
Improve water sensitivity with soy
PU Soy PU
Initial sp. gr. g/cc 1.127 1.167
sp. gr. g/cc after 4 weeks
0.973 1.124
% reduction in sp. gr. 13 3.7
Soy Polyol shows improved water sensitivity vs. commercial polyol
![Page 8: Polyurethane in Composites Presentation at SANDIA …energy.sandia.gov/wp-content//gallery/uploads/2A-B-4-Younes1.pdf• R Ratio = 0.15 • Frequency = 3 Hz P. Interlaminar Fracture](https://reader031.vdocuments.us/reader031/viewer/2022012923/5ac091527f8b9a357e8ba48d/html5/thumbnails/8.jpg)
Viscosity rise over time PU RTM and PU Soy
DOE Work (PU vs Epoxy vs Vinyl Ester)
200
300
400
500
600
700
800
900
1,000
2 5 10 15 20 25 30 40 50
Reaction Time (min)
Visc
osity
(cps
)
PU SoyPU EpoxyVinyl Ester
![Page 9: Polyurethane in Composites Presentation at SANDIA …energy.sandia.gov/wp-content//gallery/uploads/2A-B-4-Younes1.pdf• R Ratio = 0.15 • Frequency = 3 Hz P. Interlaminar Fracture](https://reader031.vdocuments.us/reader031/viewer/2022012923/5ac091527f8b9a357e8ba48d/html5/thumbnails/9.jpg)
PU system and the effect of heat on cure
0
1,000
2,000
3,000
4,000
5,000
6,000
2 5 10 15 20 25 30 40 50 60 70 80 90
Visc
osity
(cps
)
Time (min)
Reaction Viscosity of PU RTM @ Various Reaction Temperatures
25ºC
5ºC
15ºC
35ºC
![Page 10: Polyurethane in Composites Presentation at SANDIA …energy.sandia.gov/wp-content//gallery/uploads/2A-B-4-Younes1.pdf• R Ratio = 0.15 • Frequency = 3 Hz P. Interlaminar Fracture](https://reader031.vdocuments.us/reader031/viewer/2022012923/5ac091527f8b9a357e8ba48d/html5/thumbnails/10.jpg)
Thick Laminate, Long-Flow Infusion
Infusion flow distance (inches)
Epoxy infusion time (minutes)
PU infusion time, min PU Soy infusion time,min
12 1 0.5 1
24 4 1 2
36 8 4 5
48 16 8 12
60 26 16 24
![Page 11: Polyurethane in Composites Presentation at SANDIA …energy.sandia.gov/wp-content//gallery/uploads/2A-B-4-Younes1.pdf• R Ratio = 0.15 • Frequency = 3 Hz P. Interlaminar Fracture](https://reader031.vdocuments.us/reader031/viewer/2022012923/5ac091527f8b9a357e8ba48d/html5/thumbnails/11.jpg)
Epoxy, Vinyl ester, and PU 21 ply Root Ring Moldings
![Page 12: Polyurethane in Composites Presentation at SANDIA …energy.sandia.gov/wp-content//gallery/uploads/2A-B-4-Younes1.pdf• R Ratio = 0.15 • Frequency = 3 Hz P. Interlaminar Fracture](https://reader031.vdocuments.us/reader031/viewer/2022012923/5ac091527f8b9a357e8ba48d/html5/thumbnails/12.jpg)
Faster Infusion
![Page 13: Polyurethane in Composites Presentation at SANDIA …energy.sandia.gov/wp-content//gallery/uploads/2A-B-4-Younes1.pdf• R Ratio = 0.15 • Frequency = 3 Hz P. Interlaminar Fracture](https://reader031.vdocuments.us/reader031/viewer/2022012923/5ac091527f8b9a357e8ba48d/html5/thumbnails/13.jpg)
Reinforcements Used
• E-Glass– Vectorply E-BX 2400-5– 820 g/m2 biax weave– Multi-compatible sizing
• Carbon Fiber– Vectorply C-BX 1800-5– 580 g/m2 biax weave
• Carbon Fiber unidirectional– Toray– Toho
![Page 14: Polyurethane in Composites Presentation at SANDIA …energy.sandia.gov/wp-content//gallery/uploads/2A-B-4-Younes1.pdf• R Ratio = 0.15 • Frequency = 3 Hz P. Interlaminar Fracture](https://reader031.vdocuments.us/reader031/viewer/2022012923/5ac091527f8b9a357e8ba48d/html5/thumbnails/14.jpg)
Composite TensileJ Mater Sci (2008) 43:4487–4492
• 6 ply biax, tested at 45º • Accutek testing labs
Sample Ultimate Tensile Str. MPa
Epoxy 133.3
Vinyl Ester 129.5
Polyurethane 155.3
![Page 15: Polyurethane in Composites Presentation at SANDIA …energy.sandia.gov/wp-content//gallery/uploads/2A-B-4-Younes1.pdf• R Ratio = 0.15 • Frequency = 3 Hz P. Interlaminar Fracture](https://reader031.vdocuments.us/reader031/viewer/2022012923/5ac091527f8b9a357e8ba48d/html5/thumbnails/15.jpg)
Tensile-Tensile Fatigue
• Tested 45º to fiberdirection
• R Ratio = 0.15• Frequency = 3 Hz
P
![Page 16: Polyurethane in Composites Presentation at SANDIA …energy.sandia.gov/wp-content//gallery/uploads/2A-B-4-Younes1.pdf• R Ratio = 0.15 • Frequency = 3 Hz P. Interlaminar Fracture](https://reader031.vdocuments.us/reader031/viewer/2022012923/5ac091527f8b9a357e8ba48d/html5/thumbnails/16.jpg)
Interlaminar Fracture Toughness -G1C
• ASTM D5528• Interlaminar fracture toughness• 6 ply biax glass tested at 45º to
fiber direction
![Page 17: Polyurethane in Composites Presentation at SANDIA …energy.sandia.gov/wp-content//gallery/uploads/2A-B-4-Younes1.pdf• R Ratio = 0.15 • Frequency = 3 Hz P. Interlaminar Fracture](https://reader031.vdocuments.us/reader031/viewer/2022012923/5ac091527f8b9a357e8ba48d/html5/thumbnails/17.jpg)
Superior Interlaminar Fracture Toughness
• Biax Glass fabric
• Tested at 45º to fiber
• P value = 0.007
Sta
ble
Del
amin
atio
n
Resin G1C J/m²
Bayer 3798
Epoxy 1918
Vinyl ester 1377
P
![Page 18: Polyurethane in Composites Presentation at SANDIA …energy.sandia.gov/wp-content//gallery/uploads/2A-B-4-Younes1.pdf• R Ratio = 0.15 • Frequency = 3 Hz P. Interlaminar Fracture](https://reader031.vdocuments.us/reader031/viewer/2022012923/5ac091527f8b9a357e8ba48d/html5/thumbnails/18.jpg)
Fatigue crack growth
• ASTM E647• R Ratio 0.1, 10 Hz• Notch direction 45º to fiber direction• Epoxy - At 24ksi/in stress crack
growth Rate 2.4E-05 in/cycle• Polyurethane - At 24ksi/in stress
crack growth Rate 1.7E-06 in/cycle
Test coupon shown above
![Page 19: Polyurethane in Composites Presentation at SANDIA …energy.sandia.gov/wp-content//gallery/uploads/2A-B-4-Younes1.pdf• R Ratio = 0.15 • Frequency = 3 Hz P. Interlaminar Fracture](https://reader031.vdocuments.us/reader031/viewer/2022012923/5ac091527f8b9a357e8ba48d/html5/thumbnails/19.jpg)
Better Adhesion to Glass Fiber
• Bayer PU Resin • Epoxy Resin
P
![Page 20: Polyurethane in Composites Presentation at SANDIA …energy.sandia.gov/wp-content//gallery/uploads/2A-B-4-Younes1.pdf• R Ratio = 0.15 • Frequency = 3 Hz P. Interlaminar Fracture](https://reader031.vdocuments.us/reader031/viewer/2022012923/5ac091527f8b9a357e8ba48d/html5/thumbnails/20.jpg)
Polyurethane/carbon fiber composites
• ASTM D5528 Mode 1• Interlaminar fracture
toughness with unidierctionalcarbon
• Epoxy 1512 J/m²• Polyurethane 3116 J/m²
![Page 21: Polyurethane in Composites Presentation at SANDIA …energy.sandia.gov/wp-content//gallery/uploads/2A-B-4-Younes1.pdf• R Ratio = 0.15 • Frequency = 3 Hz P. Interlaminar Fracture](https://reader031.vdocuments.us/reader031/viewer/2022012923/5ac091527f8b9a357e8ba48d/html5/thumbnails/21.jpg)
Tensile-Tensile FatigueUni Carbon Fiber
• Tested 0º to fiberdirection
• R Ratio = 0.15• Frequency = 3 Hz
P
![Page 22: Polyurethane in Composites Presentation at SANDIA …energy.sandia.gov/wp-content//gallery/uploads/2A-B-4-Younes1.pdf• R Ratio = 0.15 • Frequency = 3 Hz P. Interlaminar Fracture](https://reader031.vdocuments.us/reader031/viewer/2022012923/5ac091527f8b9a357e8ba48d/html5/thumbnails/22.jpg)
• Using uni- S glass – Comp str. PU = 840 MPa Epoxy 630 MPa
• Using E glass Unidirectional– In fiber direction Comp Str. PU = 650 MPA E- Modulus= 45 kMPa
– Perpendicular fiber Comp Str. PU = 210 MPa, E-Modulus = 15 kMPa
Compressive Data
![Page 23: Polyurethane in Composites Presentation at SANDIA …energy.sandia.gov/wp-content//gallery/uploads/2A-B-4-Younes1.pdf• R Ratio = 0.15 • Frequency = 3 Hz P. Interlaminar Fracture](https://reader031.vdocuments.us/reader031/viewer/2022012923/5ac091527f8b9a357e8ba48d/html5/thumbnails/23.jpg)
Results and Conclusions - Polyurethane
• Developed Two Polyurethane systems designed for vacuum infusion– Conventional polyether and Soy based polyols
• Glass and Carbon fiber reinforced Polyurethane composites are superior to epoxy , polyester, and vinyl ester composites
– Fatigue resistance; Fracture toughness; Tensile strength; Fatigue crack growth resistance, Impact, and elongation.
– Lower Shrinkage– 42 meter Blade Root Ring Molding Demonstrated– Faster Demold than Epoxy– Potentially a reduction in the cost of making a blade
![Page 24: Polyurethane in Composites Presentation at SANDIA …energy.sandia.gov/wp-content//gallery/uploads/2A-B-4-Younes1.pdf• R Ratio = 0.15 • Frequency = 3 Hz P. Interlaminar Fracture](https://reader031.vdocuments.us/reader031/viewer/2022012923/5ac091527f8b9a357e8ba48d/html5/thumbnails/24.jpg)
MWCNT Challenges
Dispersion
Re-agglomeration
Viscosity limitations
Performance advantages
![Page 25: Polyurethane in Composites Presentation at SANDIA …energy.sandia.gov/wp-content//gallery/uploads/2A-B-4-Younes1.pdf• R Ratio = 0.15 • Frequency = 3 Hz P. Interlaminar Fracture](https://reader031.vdocuments.us/reader031/viewer/2022012923/5ac091527f8b9a357e8ba48d/html5/thumbnails/25.jpg)
Non Functionalized and Functionalization CNT
CO
OH
C OHO
H2NNH2
UV/Ozone
CO
NH
NH2
C NO H
NH2
CO
NH
NNH2
H
NH2N
NH
CO
H
H2NNH
NH2
![Page 26: Polyurethane in Composites Presentation at SANDIA …energy.sandia.gov/wp-content//gallery/uploads/2A-B-4-Younes1.pdf• R Ratio = 0.15 • Frequency = 3 Hz P. Interlaminar Fracture](https://reader031.vdocuments.us/reader031/viewer/2022012923/5ac091527f8b9a357e8ba48d/html5/thumbnails/26.jpg)
Re-agglomeration on CNT in Polyurethane
![Page 27: Polyurethane in Composites Presentation at SANDIA …energy.sandia.gov/wp-content//gallery/uploads/2A-B-4-Younes1.pdf• R Ratio = 0.15 • Frequency = 3 Hz P. Interlaminar Fracture](https://reader031.vdocuments.us/reader031/viewer/2022012923/5ac091527f8b9a357e8ba48d/html5/thumbnails/27.jpg)
Block Copolymers as Dispersing Agents
+
Lyophobic
Lyophilic
BlockCopolymer
Dispersed CNTs+
J. Cho, I. M. Daniel / Scripta Materialia 58 (2008) 533–536
![Page 28: Polyurethane in Composites Presentation at SANDIA …energy.sandia.gov/wp-content//gallery/uploads/2A-B-4-Younes1.pdf• R Ratio = 0.15 • Frequency = 3 Hz P. Interlaminar Fracture](https://reader031.vdocuments.us/reader031/viewer/2022012923/5ac091527f8b9a357e8ba48d/html5/thumbnails/28.jpg)
Effect of additives on Re-agglomeration on Carbon nanotubes in polyurethane
![Page 29: Polyurethane in Composites Presentation at SANDIA …energy.sandia.gov/wp-content//gallery/uploads/2A-B-4-Younes1.pdf• R Ratio = 0.15 • Frequency = 3 Hz P. Interlaminar Fracture](https://reader031.vdocuments.us/reader031/viewer/2022012923/5ac091527f8b9a357e8ba48d/html5/thumbnails/29.jpg)
Fatigue of Neat Epoxy nanotubesmeasured at CASE
103 104 105 106
25
30
35
40
45
50
55
Log (Cycles to fail, N)
Max
imum
stre
ss (
max
, MP
a)
Epoxy Epoxy + CNTs R2=0.95 R2=0.95
![Page 30: Polyurethane in Composites Presentation at SANDIA …energy.sandia.gov/wp-content//gallery/uploads/2A-B-4-Younes1.pdf• R Ratio = 0.15 • Frequency = 3 Hz P. Interlaminar Fracture](https://reader031.vdocuments.us/reader031/viewer/2022012923/5ac091527f8b9a357e8ba48d/html5/thumbnails/30.jpg)
CASE Tensile Neat PU and PU/CNT
0 1 2 3 4 5 6 7 8 9 10 11 12 130
10
20
30
40
50
60
70
80
Strain (%)
Stre
ss (M
Pa)
PU* - Neat PU*3-L-7602 in Polyol PU*4-L-76026 in Isocyanate
Representative stress‐strain curves for the polyurethane based nano‐composites. The CNTs amount is 0.1 wt.% in relation to polyol whereas the dispersing agent amount is 10X the amount of CNTs.
![Page 31: Polyurethane in Composites Presentation at SANDIA …energy.sandia.gov/wp-content//gallery/uploads/2A-B-4-Younes1.pdf• R Ratio = 0.15 • Frequency = 3 Hz P. Interlaminar Fracture](https://reader031.vdocuments.us/reader031/viewer/2022012923/5ac091527f8b9a357e8ba48d/html5/thumbnails/31.jpg)
Tension-Tension Fatigue of glass reinforced Epoxy Resins with and without MWCNT
50.0
55.0
60.0
65.0
70.0
75.0
80.0
85.0
90.0
10,000 100,000 1,000,000
Peak Stress (MPa
)
# of Cycles (Log)
944281‐ECNT
980272‐1E
![Page 32: Polyurethane in Composites Presentation at SANDIA …energy.sandia.gov/wp-content//gallery/uploads/2A-B-4-Younes1.pdf• R Ratio = 0.15 • Frequency = 3 Hz P. Interlaminar Fracture](https://reader031.vdocuments.us/reader031/viewer/2022012923/5ac091527f8b9a357e8ba48d/html5/thumbnails/32.jpg)
Tension-Tension Fatigue of Polyurethane Composites with and without MWCNT
50.0
55.0
60.0
65.0
70.0
75.0
80.0
85.0
90.0
10,000 100,000 1,000,000
Peak Stress (MPa
)
# of Cycles (Log)
944281‐PCNT
944281‐PCNCT
980272‐3P
![Page 33: Polyurethane in Composites Presentation at SANDIA …energy.sandia.gov/wp-content//gallery/uploads/2A-B-4-Younes1.pdf• R Ratio = 0.15 • Frequency = 3 Hz P. Interlaminar Fracture](https://reader031.vdocuments.us/reader031/viewer/2022012923/5ac091527f8b9a357e8ba48d/html5/thumbnails/33.jpg)
MWCNT further improves Interlaminar Fracture Toughness in PU
• Biax Glass fabric
• Tested at 45º to fiber
• P value = 0.142
• Resin + 0.38% MWCNT
Resin G1C J/m²
Bayer 3798
Bayer + MWCNT
5617
Bayer + FMWCNT
4222
Stab
leD
elam
inat
ion
![Page 34: Polyurethane in Composites Presentation at SANDIA …energy.sandia.gov/wp-content//gallery/uploads/2A-B-4-Younes1.pdf• R Ratio = 0.15 • Frequency = 3 Hz P. Interlaminar Fracture](https://reader031.vdocuments.us/reader031/viewer/2022012923/5ac091527f8b9a357e8ba48d/html5/thumbnails/34.jpg)
Interlaminar Fracture Toughness in Epoxy ANOVA, P value = 0.162
![Page 35: Polyurethane in Composites Presentation at SANDIA …energy.sandia.gov/wp-content//gallery/uploads/2A-B-4-Younes1.pdf• R Ratio = 0.15 • Frequency = 3 Hz P. Interlaminar Fracture](https://reader031.vdocuments.us/reader031/viewer/2022012923/5ac091527f8b9a357e8ba48d/html5/thumbnails/35.jpg)
Results and Conclusions Carbon Nanotubes
• Carbon nanotubes dispersion stability is dependent on dispersing aids• Carbon nanotubes reinforces the neat resin properties of polyurethane,
epoxy and vinyl ester– Improved Tensile and Fatigue
• Carbon nanotubes reinforced glass fiber reinforced composites
– Improves fracture toughness (G1C) both in epoxy and polyurethane systems
– Improvement in fiber reinforced composites is largely dependent on what dominates properties Fiber or Resin
– Improves electric and thermal conductivity of composites
![Page 36: Polyurethane in Composites Presentation at SANDIA …energy.sandia.gov/wp-content//gallery/uploads/2A-B-4-Younes1.pdf• R Ratio = 0.15 • Frequency = 3 Hz P. Interlaminar Fracture](https://reader031.vdocuments.us/reader031/viewer/2022012923/5ac091527f8b9a357e8ba48d/html5/thumbnails/36.jpg)
The Technical Collaboration Team
• Bayer MaterialScience• Usama Younes, Eric Giles, Robert Gastinger, Mike Wellman, Stephen Bailey,
Al Magnotta, Tom Sekelek.• Serkan Unal, Robert Hunt, Jennifer Nau.
• Case Western Reserve University • Marcio Loos, Jingting Yang, Donald L. Feke, Ica Manas-Zloczower.
• Molded Fiber Glass• Frank Bradish, Peter Emrich, Richard Sesco
![Page 37: Polyurethane in Composites Presentation at SANDIA …energy.sandia.gov/wp-content//gallery/uploads/2A-B-4-Younes1.pdf• R Ratio = 0.15 • Frequency = 3 Hz P. Interlaminar Fracture](https://reader031.vdocuments.us/reader031/viewer/2022012923/5ac091527f8b9a357e8ba48d/html5/thumbnails/37.jpg)