novel monomer free vinyl hybrid resin for composite ... 2014 novel...radomes 5 functions • shield...

Novel Monomer Free Vinyl Hybrid

Resin for Composite Radomes and

Aerospace Applications

Jim Bono JEC Paris March 12th, 2014

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

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”

• ADVALITE™ – Monomer Free Hot Melts

• ADVALITE™ – Vinyl Hybrid Liquid Resins

Chemistry Description: Vinyl Hybrids

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

Radome Resin Candidates

• Cyanate Esters

• Modified Epoxies (BisA Cyanate/Epoxy)

• Epoxy (Accelerated Dicyanamide, 120° C cure)

• ADVALITE™ Vinyl Hybrid

% 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

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

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

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

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

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

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

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

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

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%

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

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

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

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

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

Questions?

THANK YOU FOR YOUR ATTENTION!

Visit Reichhold at booth M48 – 7.3