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Novel Monomer Free Vinyl Hybrid
Resin for Composite Radomes and
Aerospace Applications
Jim Bono JEC Paris March 12th, 2014
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Background
• Advanced Material Market
• Styrenated Systems are Unacceptable
– Governmental Regulations
– Control Technologies Needed
– Minimize Capital Investment
• Development Need for Reactive Diluent Free Thermoset Resin Systems
– Cost Effective
– Improved Dry/ Wet Tg
– Improved Water Absorption
– Improved Production Rates- approach 3 minute cycle
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Nomenclature
Styrene Free Resins
Reactive Diluent Free Alternative
Reactive
Diluents
VT
• Acrylates
• Others
Solids: “Pre-preg Monomer
Free Hot Melt Vinyl Hybrids”
Liquids: Reactive Oligomers
“Vinyl Hybrid Liquid Resins”
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• ADVALITE™ – Monomer Free Hot Melts
• ADVALITE™ – Vinyl Hybrid Liquid Resins
Chemistry Description: Vinyl Hybrids
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Radomes
5
Functions
• Shield microwave
antenna from adverse
environmental effects
• Minimal effect on
electrical performance
• Withstand Structural
Loads from pressure
differential
Material Property Considerations
• Water Absorption: Water absorbs transmission
energy and increases loss tangent
– Low water absorption is necessary for radomes
• Dielectric Constant: Determine the ability of
insulator to store electrical energy
– Low dielectric constant is necessary for radomes
• Loss Tangent: Ratio of input/output power
through material – Low loss tangent is necessary for radomes
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Radome Resin Candidates
• Cyanate Esters
• Modified Epoxies (BisA Cyanate/Epoxy)
• Epoxy (Accelerated Dicyanamide, 120° C cure)
• ADVALITE™ Vinyl Hybrid
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% Water Absorption Comparisons (64 Hour Boil)
0
0,5
1
1,5
2
2,5
3
3,5
Percent Water Absorption
Epoxy/DICY
X4833-60 (Vinyl Hybrid)
Modified Epoxy
Cyanate Ester
7
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Dielectric Constant Comparison
2,5
2,6
2,7
2,8
2,9
3
3,1
Dry
Epoxy/DICY
X4833-60 (Vinyl Hybrid)
Modified Epoxy
Cyanate Ester
8
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Dielectric Constant Comparisons
Dry vs. Wet
2.60
2.70
2.80
2.90
3.00
3.10
3.20
3.30
Epoxy/ DICY X4833-60
(Vinyl Hybrid)
X4622-47
(Vinyl Hybrid)
X4767-47
(Vinyl Hybrid)
X4759-06
(Vinyl Hybrid)
Die
lect
ric
Co
nst
ant
No Preconditioning 24 Hrs Boiling Water 64 Hrs Boiling Water
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Dissipation Factor/Loss Tangent Comparison
0
0,005
0,01
0,015
0,02
0,025
Dry
Epoxy/DICY
X4833-60 (Vinyl Hybrid)
Modified Epoxy
Cyanate Ester
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Comparison of Dissipation Factor/Loss Tangent
0,000
0,005
0,010
0,015
0,020
0,025
0,030
0,035
0,040
0,045
0,050
Epoxy/ DICY X4833-60(Vinyl Hybrid)
X4622-47(Vinyl Hybrid)
X4767-47(Vinyl Hybrid)
X4759-06(Vinyl Hybrid)
Loss T
an
gen
t
No Preconditioning 24 Hrs Boiling Water 64 Hrs Boiling Water
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ADVALITE™ X4833-60 Radome Resin Clear Cast Mechanical Properties
Property Units ADVALITE™
X4833-60
Flexural Strength M Pa 78,7
Flexural Modulus G Pa 4,14
Tensile Strength M Pa 35,3
Tensile Modulus G Pa 3,54
HDT °C >200
Dry Tg °C 193
Wet Tg °C 172
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Hand Lay-up (Prepreg)
Properties for Optimum Prepreg
• Optimum tack and drape
• Low volatile content
• Low temperature cure
• Long shelf-life
• Low heat of reaction
• Controlled flow
13
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Hand Lay-up
• Heat of reaction of ADVALITE™
Vinyl Hybrids System is roughly half
of a standard 120 °C cure,
accelerated Dicyanamid Bis-A
epoxy, so parts with large cross-
sections can be cured with less risk
of exotherm and cracking
• ADVALITE™ Vinyl Hybrid Systems
offer cure times under 5 minute for
rapid part production
• ADVALITE™ Vinyl Hybrid Systems
are a peroxide-cure, lending itself
well to inline mixing for rapid
prepreg production
• Prepreg produced using
ADVALITE™ VINYL HYBRIDS
systems does not need to be frozen
or refrigerated, lowering the cost of
shipping and handling, and
minimizing scrap due to expired
shelf-life
Typical shelf-life @ 21°C for:
Cyanate ester 14 days
Cyanate/Epoxy 14 days
120 °C cure epoxy 4 to 8 weeks
ADVALITE™
Vinyl Hybrid> 1 year
14
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Radome Resin
Typical Cost/Lb (Formulated)
$0
$10
$20
$30
$40
$50
$60
$70
$80
$90
$100
Cost per Lbs
Epoxy
X4833-60 (Vinyl Hybrid)
Modified Epoxy
Cyanate Ester
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ADVALITE™ 35000-00 Vinyl Hybrid
FR Grade Hot Melt Prepreg Resin Prepreg Thermo-Mechanical Properties
Property Units
ADVALITE™
35000-00
RT
ADVALITE™
35000-00
RT, Wet
ADVALITE™
35000-00
120° C
Tensile Strength M Pa 73 69 51
Tensile Strength
Retention % 94% 70%
Tensile Modulus G Pa 4,6 4,7 4,3
Tensile Modulus
Retention % 102% 93%
Compression
Strength M Pa 64 58
Compression
Modulus G Pa 4,8 4,6
Flexural Strength M Pa 113 100.0 54.0
Flexural Strength
Retention % 89% 48%
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ADVALITE™ Vinyl Hybrid Liquid Resins
Vacuum Infusion Process (VIP)
• Processing Conditions- resin factors
to consider: • Polymer structure
• Viscosity
• Degree of cure-part thickness
Critical to Filling Complex Geometries and Moldability:
• Optimize resin for low viscosity
and good fiber wetting while
retaining good physical properties
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Vacuum Infusion Process
Infusion Flow Rates
0
2
4
6
8
10
12
14
0 20 40 60 80 100 120
Flo
w D
ista
nce
(in
)
Time (min)
Flow Distance vs Time
X4690-86
9102-75
1"
2"
3"
4"
5"
6"
7"
8"
9"
10"
11"
12"
13"
14"
15"
16"
17"
18"
Flow Media
Inlet Line
Laminate
Peel Ply
Vacuum Line
Record Time at
Distance Increments
Start Stopwatch
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Vinyl Hybrid Infusion Trial
Deep vertical draw sections to
ensure proper resin flow rates
Thick section part- 12 mm
Used to study exotherm
conditions and glass wetting
Glass wetting acceptable throughout entire composite part Glass wetting acceptable
throughout entire composite
part
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Mechanical Properties Comparison Neat Resin Clear Cast Results
Property Units ADVALITE™
35065-00 ADVALITE™
35060-00
ADVALITE™
X4830-27 ADVALITE™
X4759-06
Flexural Strength M Pa 159,3 116,9 74,6 117,3
Flexural Modulus G Pa 4,37 3,61 3,52 4,24
Tensile Strength M Pa 80,3 45,6 16,0 31,8
Tensile Modulus G Pa 3,83 3,77 3,63 4,14
Elongation % 2,8% 1,5% 0,5% 0,9%
HDT C 72 155 >200 >200
Dry Tg C 81 170 149 175
Wet Tg C 166
Water Absorption % 0,83% 0,57% 0,16%
Viscosity cps 625 1,200 400 1350
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Conclusions
ADVALITE™ Vinyl Hybrid Systems offer resins capable to produce both prepreg and vacuum infusion molding systems for the Aerospace market which offer the following:
• Excellent retention of properties after exposure to water at elevated temperature
• Superior performance to epoxy regarding; Water Absorption, Dielectric Constant and Dissipation Factor
• Lower heat of reaction than epoxy for rapid cures of thick cross-section parts
• No need for refrigeration of prepreg
• Lower total cost for the manufacture of cost effective commercial radomes
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Questions?
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THANK YOU FOR YOUR ATTENTION!
Visit Reichhold at booth M48 – 7.3