Polyurethane in Composites

Presentation at SANDIA
May 31, 2012
Usama Younes
 DOE project Objectives

• Carbon Nanotube Reinforced Polyurethane Composites for Wind Turbine

Blades
DOE 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.
 Challenges

• Polyurethane
– Speed of Reaction
– Viscosity
– Moisture Sensitivity
• Carbon Nanotubes
– Dispersion
– Re-agglomeration
– Viscosity
 Resins

 Epoxy
 Vinyl ester
 Polyester
 Polyurethane
 PU RTM
 PU/Soy
 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
 Soy based polyols

• Why Soy?
– Adds renewable content to the PU
– Reduces moisture sensitivity of the system
• Synthesized a new soy polyol
– Viscosity; Reactivity
 Improve water sensitivity with soy

PU Soy PU

Initial sp. gr. g/cc 1.127 1.167

sp. gr. g/cc after 4 0.973 1.124

weeks

% reduction in sp. gr. 13 3.7

Soy Polyol shows improved water

sensitivity vs. commercial polyol
Viscosity rise over time PU RTM and PU Soy

DOE Work (PU vs Epoxy vs Vinyl Ester)

1,000

900
Viscosity (cps)

800

700 PU Soy
PU
600
Epoxy
500 Vinyl Ester

400

300

200
2 5 10 15 20 25 30 40 50

Reaction Time (min)

 PU system and the effect of heat on cure

Reaction Viscosity of PU RTM @ Various

Reaction Temperatures

6,000

5,000
Viscosity (cps)

4,000 25ºC
5ºC
3,000
15ºC
2,000 35ºC

1,000

0
2 5 10 15 20 25 30 40 50 60 70 80 90

Time (min)
 Thick Laminate, Long-Flow
Infusion

Infusion flow distance Epoxy infusion time PU infusion time, min PU Soy infusion time,
(inches) (minutes) min

12 1 0.5 1

24 4 1 2

36 8 4 5

48 16 8 12

60 26 16 24
Epoxy,Vinyl ester, and PU 21 ply Root
Ring Moldings
Faster Infusion
 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
 Composite Tensile
J 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
 Tensile-Tensile Fatigue

• Tested 45º to fiber

direction
• R Ratio = 0.15
• Frequency = 3 Hz

P
 Interlaminar Fracture Toughness -G1C

• ASTM D5528
• Interlaminar fracture toughness
• 6 ply biax glass tested at 45º to
fiber direction
 Superior Interlaminar Fracture Toughness

• Biax Glass fabric

• Tested at 45º to fiber

Delamination
• P value = 0.007

Stable
Resin G1C J/m²
Bayer 3798
Epoxy 1918
Vinyl ester 1377

P
 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

 Better Adhesion to Glass Fiber

• Bayer PU Resin • Epoxy Resin

P
 Polyurethane/carbon fiber composites

• ASTM D5528 Mode 1

• Interlaminar fracture
toughness with unidierctional
carbon
• Epoxy 1512 J/m²
• Polyurethane 3116 J/m²
 Tensile-Tensile Fatigue
Uni Carbon Fiber

• Tested 0º to fiber
direction
• R Ratio = 0.15
• Frequency = 3 Hz

P
 Compressive Data

• 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
 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
 MWCNT Challenges

 Dispersion
 Re-agglomeration
 Viscosity limitations
 Performance advantages
Non Functionalized and Functionalization CNT

O
C OH
O H
C N
NH2
NH 2
UV/Ozone H 2N

C OH NH2
O C N
O H

H 2N NH2 O H
NH
C N NH2
N
H

H
N
C N NH2
O H
Re-agglomeration on CNT in Polyurethane
Block Copolymers as Dispersing Agents

Lyophilic
Lyophobic

Block Dispersed
+ CNTs
Copolymer

J. Cho, I. M. Daniel / Scripta Materialia 58 (2008) 533–536

Effect of additives on Re-agglomeration on
Carbon nanotubes in polyurethane
 Fatigue of Neat Epoxy nanotubes
measured at CASE

55
Epoxy
Maximum stress (max, MPa) 50 Epoxy + CNTs
2
R =0.95
45 2
R =0.95

40

35

30

25
3 4 5 6
10 10 10 10
Log (Cycles to fail, N)
 CASE Tensile Neat PU and PU/CNT

80

70

60

50
Stress (MPa)

40

30

20
PU* - Neat
10 PU*3-L-7602 in Polyol
PU*4-L-76026 in Isocyanate
0
0 1 2 3 4 5 6 7 8 9 10 11 12 13
Strain (%)
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. 
 Tension-Tension Fatigue of glass reinforced
Epoxy Resins with and without MWCNT

90.0

85.0

80.0
Peak Stress (MPa)

75.0
944281‐ECNT
70.0

65.0 980272‐1E
60.0

55.0

50.0
10,000 100,000 1,000,000
# of Cycles (Log)
 Tension-Tension Fatigue of Polyurethane
Composites with and without MWCNT

90.0

85.0

80.0
Peak Stress (MPa)

75.0
944281‐PCNT
70.0
944281‐PCNCT
65.0
980272‐3P
60.0

55.0

50.0
10,000 100,000 1,000,000
# of Cycles (Log)
 MWCNT further improves Interlaminar
Fracture Toughness in PU

• Biax Glass fabric

• Tested at 45º to fiber

• P value = 0.142

Delamination
Stable
• Resin + 0.38% MWCNT

Resin G1C J/m²

Bayer 3798
Bayer + 5617
MWCNT
Bayer + 4222
FMWCNT
Interlaminar Fracture Toughness in Epoxy
ANOVA, P value = 0.162
 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
 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